0% found this document useful (0 votes)

6 views33 pages

Organic Cathodes for Aluminum-Ion Batteries

This review discusses the potential of organic electrode materials (OEMs) for rechargeable aluminum-ion batteries (RAIBs), highlighting their structural diversity and advantages over traditional cathode materials. The paper examines various types of OEMs, their electrochemical performance, and the challenges faced in improving their application in RAIBs. It aims to provide insights and guidelines for the development of high-capacity and stable organic cathode materials for future energy storage solutions.

Uploaded by

daniel limenew

We take content rights seriously. If you suspect this is your content, claim it here.

Available Formats

Download as PDF, TXT or read online on Scribd

0% found this document useful (0 votes)

6 views33 pages

Organic Cathodes for Aluminum-Ion Batteries

Uploaded by

daniel limenew

We take content rights seriously. If you suspect this is your content, claim it here.

Available Formats

Download as PDF, TXT or read online on Scribd

Review

ChemSusChem [Link]/10.1002/cssc.202202358

[Link]
Very Important Paper
Organic Cathode Materials for Rechargeable Aluminum-Ion
Batteries
Zhen Huang,[a] Xianfeng Du,*[a] Mingbo Ma,[a] Shixin Wang,[a] Yuehong Xie,[a] Yi Meng,[a]
Wenzhi You,[a] and Lilong Xiong*[a]

ChemSusChem 2023, 16, e202202358 (1 of 33) © 2023 Wiley-VCH GmbH

Organic electrode materials (OEMs) have shown enormous discusses the uses of conductive polymers, carbonyl com-
potential in ion batteries because of their varied structural pounds, imine polymers, polycyclic aromatic hydrocarbons,
components and adaptable construction. As a brand-new organic frameworks, and other organic materials as the
energy-storage device, rechargeable aluminum-ion batteries cathodes of RAIBs, as well as energy-storage mechanisms and
(RAIBs) have also received a lot of attention due to their high research progress. It is hoped that this Review can provide the
safety and low cost. OEMs are expected to stand out among design guidelines for organic cathode materials with high
many traditional RAIB cathode materials. However, how to capacity and great stability used in aluminum-organic batteries
improve the electrochemical performance of OEMs in RAIBs on and develop more efficient organic energy storage cathodes.
a laboratory scale is still challenging. This work reviews and

1. Introduction is generally ionic liquid. Although ionic liquid electrolyte is

sensitive to water and air, the battery can still work properly
The most mature modern battery technology is lithium-ion under closed conditions. Moreover, because the dendrite
batteries (LIBs), which are considered to be the most suitable problem in RAIBs is not too serious, there are few studies on
batteries for electronic portable devices and electric vehicles aluminum anodes. With suitable electrolytes and the high
owing to their high energy density. However, due to the limited energy density of the aluminum anode, the important remain-
and expensive Li and Co resources, the long-term and large- ing limitation of the development of RAIBs is the cathode.[21]
scale application of LIBs seems to be problematic.[1] Moreover, However, traditional metal ion batteries are usually based on
due to the dendrites generated during the charging and inorganic electrode materials, such as carbon-based materials,
discharging process of LIBs, it is easy to cause a short circuit, transition metal oxides, transition metal chalcogenides and
resulting in fire or explosion. Considering safety and sustain- elemental sulfur, which have their advantages and disadvan-
ability, researchers have begun looking for other battery devices tages. When used in aluminum secondary batteries, carbon
to partially replace LIBs, such as alkali metal ion batteries and materials have high working voltage, good rate performance,
multivalent metal ion batteries (such as Na +,[2] K +,[3,4] Mg2 +,[5] and cycle stability but low discharge capacity, generally 60–
Ca2 +,[6] Zn2 +,[7] Al3 + [8] batteries). Meanwhile, nonmetal chloride 110 mAh g 1.[8,22] Oxides and sulfides exhibit higher discharge
ion batteries and fluoride ion batteries also appeared.[9,10] capacities than carbon materials, but poor reversibility and
Among them, aluminum is the most abundant metal element cycling stability.[23–27]
in the earth’s crust (Table 1). Rechargeable aluminum-ion Different from traditional electrode materials, OEMs show
batteries (RAIBs) have become candidates for the next gen- great application potential due to their high theoretical capacity
eration of energy storage systems due to their high theoretical (most of which only contain light elements, such as C, H, O, N,
specific capacity. and S), flexible structural design, and environmental
Currently reported aluminum batteries are divided into two friendliness.[28,29] Organic molecules as electrode materials for
categories: aqueous batteries (aqueous Al-rocking chair and LIBs and sodium-ion batteries (NIBs) have shown the advan-
primary Al-air batteries) and non-aqueous batteries (aluminum tages of high energy density, high power density, structural
graphite dual-ion batteries (AGDIBs), Al-organic dual-ion bat- diversity, flexibility, and sustainability.[30–32] However, the appli-
teries (AODIBs), rocking chair Al-S battery).[1] The primary cation of OEMs in RAIBs lags behind its application in LIBs. The
batteries have limited utilization because they can only high solubility, low intrinsic conductivity, large volume change,
discharge once. Secondary rechargeable batteries can be widely and low tap density of OEMs in the electrolyte are the main
used for a long time because they can achieve reversible challenges for their application in RAIBs. If the above problems
conversion of electrical energy and chemical energy through can be solved, the organic cathode and aluminum anode can
electrochemical reactions.[11–13] Therefore, RAIBs become the become ideal pairs, aluminum metal anode-organic cathode
focus of researchers. In the past few years, the development of battery is expected to become an efficient energy storage
RAIBs has made significant progress in different components. equipment based on rich and sustainable materials.[33] Xie and
Special types of separators and current collectors have also Zhang[34] reviewed organic materials used in multivalent metal
become a fixed match for RAIBs.[14–16] The electrolyte of RAIBs is ion rechargeable batteries. Du et al.[35] reviewed the polymer
not limited to the molten salt electrolyte working at a high electrode materials for LIBs. Zhao et al.[31] reviewed organic-
temperature,[1,13,17] and various electrolytes that can operate at based cathode materials in NIBs. The applications of OEMs in
room temperature have appeared.[18–20] The electrolyte of RAIBs potassium, magnesium, and zinc ion batteries are also reviewed
in detail.[36–38] Inspired by these, this work reviews the aluminum
storage mechanisms of different organic cathode materials and
[a] Z. Huang, Prof. X. Du, M. Ma, S. Wang, Y. Xie, Y. Meng, W. You, the research progress of aluminum-organic batteries. It is hoped
Prof. L. Xiong
Engineering Research Center of Energy Storage Materials and Devices, that the design of high capacity and high voltage organic
Ministry of Education, School of Chemistry cathode materials will provide fundamental guidance for the
Xi’an Jiaotong University future development of organic-based rechargeable aluminum-
Xi’an 710049 (P. R. China)
E-mail: xianfengdu@[Link] ion batteries.
lilongxiong@[Link]

ChemSusChem 2023, 16, e202202358 (2 of 33) © 2023 Wiley-VCH GmbH

Table 1. A comparison of different metal anodes.

Metal Number of elec- Molar mass Density Gravimetric capacity[a] Volumetric capacity[b] Earth crust Electrode potential
anode trons (x) [g mol 1] [g cm 3] [mAh g 1] [mAh cm 3] abundance[39] [%] [V] vs. SHE

Li 1 6.941 0.534 3861 2062 0.002 3.05

Na 1 22.99 0.968 1166 1128 2.3 2.71
Mg 2 24.31 1.740 2205 3836 2.3 2.37
Al 3 26.98 2.702 2980 8052 8.2 1.66
K 1 39.10 0.862 685 591 2.1 2.93
Ca 2 40.08 1.550 1337 2073 4.1 2.87
Zn 2 65.41 7.140 819 5851 0.0075 0.76

[a] Gravimetric capacity = x × F/M. [b] Volumetric capacity = x × F × 1/M, where F = 26.8 × 103 mAh mol 1 (Faraday constant); x = number of electrons [mol]
used to oxidize/reduce 1 mol of the active material, 1 = density of metal [g cm 3], M = molar mass of active material [g mol 1].

2. Aluminum Storage Mechanisms of Organic the main materials to accommodate carrier ions.[42] The energy
Cathodes storage mechanism of traditional layered carbon and metal
halide-based aluminum ion batteries (AIBs) cathodes is usually
Organic cathode materials can be divided into n-type, p-type, based on AlCl4 and Al3 + intercalation/delamination.[8,22,43]
and bipolar-type according to their redox mechanisms, accom- However, due to the large size of AlCl4 and the high charge
panied by cations and anions involved in charge compensation density of trivalent Al3 +, their corresponding reversible capacity
during charge and discharge.[35,40,41] In this Review, according to is difficult to improve.[44]
the structure of the organic cathode, the organic cathode Recently, the storage mechanism of cationic aluminum
materials are divided into conductive polymers (CPs), carbonyl complexes ([AlClx](3 x), x = 1 or 2) proposed by aluminum
compounds (COCs) and imine polymers (IPs), polycyclic aro- organic batteries is different from that of traditional AlCl4 or
matic hydrocarbons (PAHs), covalent organic frameworks Al3 +. The specific form of aluminum complex ion [AlClx](3 x) is
(COFs), metal–organic frameworks (MOFs), and other organic related to the electrolyte, the structure of cathode materials,
cathodes. The charge storage mechanisms of different organic whether a redox reaction occurs, and the charge carried by the
cathode materials are discussed, and compared with the group. For the commonly used aluminum trichloride ionic liquid
traditional cathode materials of RAIBs, hoping to provide a basis electrolyte, rich Cl can coordinate with Al3 + to form AlCl4
for the vigorous development of aluminum-organic batteries. anion, so Al3 +, Cl , and AlCl4 are potential ionic charge
Figure 1 summarizes the aluminum storage mechanisms of six carriers.[45,46] Figure 2 shows the formation of [AlClx](3 x) ion in an
types of organic cathode materials. aluminum-organic battery and the reaction of [AlClx](3 x) on the
The charge storage mechanism determines the specific cathode. When x is 4, the positive electrode is p-type; when x is
capacity, redox potential, rate performance, and cycle stability 0 or 1, or 2, the positive electrode is n-type; otherwise, it is
of cathode materials, which seriously affects the electrochemical bipolar. Different from the traditional cathodes, it can be seen
performance of RAIBs. To study the reaction mechanism of Al- from Table 2, small aluminum cations (such as AlCl2 + and
organic batteries, it is necessary to figure out the Al-storage AlCl2 +) in organic small molecules can achieve reversible
structures of cathode electrode materials. Layered materials are intercalation/deintercalation due to their different functional

Zhen Huang is a Master’s student at the Lilong Xiong is an associate professor of the
School of Chemistry, Xi’an Jiaotong University School of Chemistry at Xi’an Jiaotong Univer-
(P.R. China). She received her [Link]. degree sity. He received his Ph.D. degree from Xi’an
from Kunming University of Science and Jiaotong University in 2011. His research
Technology in 2020 (P.R. China). Her research focuses on lithium-ion batteries, aluminum-
focuses on organic cathode materials design ion batteries, supercapacitors, novel dielectric
and the electrochemical reaction mechanisms capacitors, and smart sensor devices.
research of rechargeable aluminum batteries.

Xianfeng Du is a professor of the School of

Chemistry at Xi’an Jiaotong University. He
received his Ph.D. degree from Xi’an Jiaotong
University in 2008. In 2011–2012, he worked
as a visiting scholar at the University of
Michigan (USA). His research focuses on
electrolytic capacitors, lithium/sodium/alumi-
num-ion batteries, supercapacitors, flexible
devices, catalysis

ChemSusChem 2023, 16, e202202358 (3 of 33) © 2023 Wiley-VCH GmbH

Figure 1. Aluminum storage mechanism of six categories of organic cathodes: a) CPs; b) COCs and IPs; c) PAHs; d) COFs; e) MOFs; and f) other organic
cathodes.

through functional groups (Figure 1). PAHs and COFs usually

exhibit the characteristics of p-type organic cathode material
and are combined with AlCl4 during charging. MOFs exhibit a
variety of aluminum storage mechanisms due to their structural
diversity. The organic cathodes in the aqueous RAIBs realize the
rocking chair storage of multivalent ion Al3 + or [Al(OTF)]2 +.

3. Research Progress of Aluminum-Organic

Batteries

3.1. Conductive polymers

The most notable p-type organic cathode material is CPs, so it

is usually combined with anionic AlCl4 for energy storage. As
Figure 2. Redox reactions of aluminum–organic batteries. a) Positive elec-
trode reaction. b) Negative electrode reaction. cathode materials for RAIBs, CPs usually include polyaniline
(PANI), polythiophene (PTh), polythiophene derivative poly(3,4-
ethylenedioxythiophene) (PEDOT), polypyrrole (PPy), polypyr-
ene and polyphenylene. Their aluminum storage reaction
groups ( C=O; C=N ), resulting in rapid kinetic conversion in mechanisms are shown in Figure 3.
the electrochemical process. Organic electrodes usually experi-
ence the storage mechanism of “ion coordination”, which is in
sharp contrast to the slow kinetics of some inorganic com- 3.1.1. Polyaniline
pounds, because there is no strong coulomb interaction
between organic electrodes and aluminum carrier ions.[47] Polyaniline (PANI) is an ordinary conductive polymer. PANI has
Unfortunately, the poor conductivity of small organic molecules a long-range conjugated structure with the possibility of storing
and serious dissolution problem in the electrolyte limit their [AlClx](3 x) ions and merit of good electrical conductivity (up to
long-cycle performance. Organic CPs as typical p-type cathode 1 × 103 S cm 1).[87] However, bare polyaniline cannot fully realize
materials exhibit superior electrical conductivity and enhanced the full utilization of active materials, researchers usually
chemical stability due to their conjugated chemical-bonds and combine PANI with some carbon materials to further enhance
long-range conjugated structures compared with organic small its active sites and conductivity.[48–50] These carbon materials
molecules.[48] The n-type cathode material COCs and IPs include ordered mesoporous carbon (OMC), single-walled
coordinate with cations (AlCl2 + or AlCl2 + or [AlCl2(urea)2] +) carbon nanotubes (SWCNTs), and graphene oxide (GO). The

ChemSusChem 2023, 16, e202202358 (4 of 33) © 2023 Wiley-VCH GmbH

Table 2. Summary of organic cathodes for rechargeable Al-ion batteries.
Cathode[Ref.] Structure Insertion ion Electrolyte[d] (molar Electrode compo- Separator Current Cell type Voltage Capacity Cyclability (ca-
ratio) sition (mass ratio) collector window [mAh g 1]/ pacity
(AM[a]/CA[b]/bind- [V] rate [mAh g 1]/
er) [mA g 1] cycles/rate
ChemSusChem

[mA g 1])

8 : 1 : 1 (AM/car- Whatman Swagelok- 140/100

PANI/OMC[49] AlCl4 AlCl3/[EMIm]Cl = 1.3 Mo 0.1–2.45 106/5000/1000
bon black/PVDF) GF/D type 118/2000

glass fiber 200/1000

PANI(H +)@SWCNTs[48] AlCl2 + AlCl3/[EMIm]Cl = 1.3 free-standing Mo Soft-package 0.3–2.0 90/8000/10000
(GF/A) 75/40000

ChemSusChem 2023, 16, e202202358 (5 of 33)

6 : 3 : 1 (AM/
Whatman Swagelok- 180/1000
G-PANI[50] AlCl4 AlCl3/[EMIm]Cl = 1.3 acetylene black/ Mo 0.1–2.3 180/4000/1000
934-AH type 155/2000
PVDF)
152.5/500
8 : 1 : 1 (AM/car- Whatman CR2025 coin 85.7/500/2000
PTh/G[51] AlCl4 AlCl3/[EMIm]Cl = 1.3 Mo 0.01–2.4 113.5/
Review

bon black/PVDF) 934-AH cells 75.5/500/5000

1000
8 : 1 : 1 (AM/
glass fiber Swagelok- 130/1000
Pth@GO[52] AlCl4 AlCl3/[EMIm]Cl = 1.3 acetylene black/ Mo 0.1–2.4 100/4000/1000
paper type 86/5000
PVDF)
5.5 : 3 : 1.5 (AM/ carbon 190/2000 80/100000/
PT[53] AlCl4 AlCl3/ET3NHCl = 1.5 glass fiber –[c] 0.5–2.5
Super P/PVDF) paper 127/5000 10000
stainless-
PTh/MWCNT
PTh/MWCNT[54] AlCl4 AlCl3/[EMIm]Cl = 1.5 – steel – 0–2.2 216/32.5 ~ 120/300/130
composite
mesh
90 : 5 : 5 (AM/ stainless-
AlCl4 &
MoS2/PTh[55] AlCl3/[EMIm]Cl = 1.5 acetylene black/ – steel – 0–2.5 ~ 240/75 ~ 150/8/75
Al3 +
[Link]/10.1002/cssc.202202358

PVDF) mesh

glass fiber
PEDOT[56] AlCl4 AlCl3/[EMIm]Cl = 2 PEDOT film – – 0.5–2.2 191/0.8 C /
(Whatman)

5 : 4 : 1 (AM/CB/ Whatman Custom-

Polypyrene[57] AlCl4 AlCl3/[EMIm]Cl = 1.3 W 1.05–2.2 70/200 70/300/200
PVDF) GF/D made cell

Poly(nitropyrene-co- 5 : 4 : 1 (AM/CB/ Whatman custom- ~ 85/1000/200

AlCl4 AlCl3/[EMIm]Cl = 1.3 W 1.05–2.2 ~ 105/200
pyrene)[57] PVDF) GF/D made cell ~ 48/500/2000

6 : 1 : 3 (AM/SP Glassy
Whatman Swagelok-
Polypyrrole[58] AlCl4 AlCl3/[EMIm]Cl = 1.5 carbon black/Ky- carbon 0.8–2.0 ~ 66/20 ~ 55/100/20
GF/D type
nar Flex 2801) rod
6 : 3 : 1 (AM/ 92/100 82/1000/1000
Whatman Swagelok-
Polyphenylene[59] AlCl4 AlCl3/[EMIm]Cl = 1.3 acetylene black/ Mo 0.01–2.0 79/500 70/30000/
glass fiber type
PVDF) 75/5000 10000

© 2023 Wiley-VCH GmbH

1864564x, 2023, 9, Downloaded from [Link] by Ecole De Technologie Superieur, Wiley Online Library on [19/06/2024]. See the Terms and Conditions ([Link] on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Table 2. continued
Cathode[Ref.] Structure Insertion ion Electrolyte[d] (molar Electrode compo- Separator Current Cell type Voltage Capacity Cyclability (ca-
ratio) sition (mass ratio) collector window [mAh g 1]/ pacity
(AM[a]/CA[b]/bind- [V] rate [mAh g 1]/
er) [mA g 1] cycles/rate
ChemSusChem

[mA g 1])

7 : 2 : 1 (AM/ 133/200
Whatman carbon Swagelok-
PVBPX[60] AlCl4 AlCl3/[EMIm]Cl = 1.3 acetylene black/ 0.1–2.0 110/1000 88/50000/5000
GF/A cloth type
PVDF) 60/10000

ChemSusChem 2023, 16, e202202358 (6 of 33)

6 : 3 : 1 (AM/Prin-
Whatman
AQ[33] AlCl2 + AlCl3/[EMIm]Cl = 1.5 tex carbon black/ Mo pouch cells 0.3–1.6 100/0.2 C 83/50/0.2 C
GF/A
PTFE)
Review

6 : 3 : 1 (AM/Prin-
Whatman Swagelok- 160/0.5 C
PAQS/MWCNT[33] AlCl2 + AlCl3/[EMIm]Cl = 1.5 tex carbon black/ W 0.4–1.8 120/500/0.5 C
GF/A type 130/10 C
PTFE)

6 : 3 : 1 (AM/CB/ Whatman Swagelok- 165/0.5 C

PAQS/MWCNTs[61] AlCl2 + AlCl3/[EMIm]Cl = 1.5 W 0.4–1.8 /
PTFE) GF/C type 133/20 C
[Link]/10.1002/cssc.202202358

8 : 1 : 1 (AM/ 229/20
CR2016 coin
AQ[62] Al3 + AlCl3/[EMIm]Cl = 1.5 acetylene black/ glass fiber Mo 0.1–2.1 211/100 192/200/100
cells
PTFE) 166/500

Super P-
7 : 1 : 2 (AM/car- 137/20
modified CR2032 coin 0.01–
BDTD[63] AlCl2 + AlCl3/TMAHCl = 1.8 bon black/So- Mo 65/40 50/100/20
Whatman cells 1.80
dium alginate) 26/100
GF/A

5 : 3 : 2 (AM/
MXene@BDTO[64] Al3 + AlCl3/[EMIm]Cl = 1.3 acetylene black/ – Mo – 0.1–2.4 229.8/500 134.9/500/500
PVDF)

© 2023 Wiley-VCH GmbH

[mA g 1])

[EMIm][AlCl4]/ 3 : 5 : 2 (AM/Denka Whatman Swagelok- 110/100 82/200/200

PQ-Δ[65] AlCl2 + Ta 0.8–1.75
AlCl3 = 1.5 black/PVDF) GF/D type 70/10000 53/5000/2000

ChemSusChem 2023, 16, e202202358 (7 of 33)

PQ-Δ-HY[65] / AlCl2 + & [EMIm][AlCl4]/ 8 : 1 : 1 (AM/Denka Whatman Ta Swagelok- 0.7–2.35 114/200 114/500/200
AlCl4 AlCl3 = 1.5 black/PVDF) GF/D type 107/500
92/2000
Review

polymer- 80/600
7 : 2 : 1 (AM/ glass fiber
TPB[44] AlCl2(urea)2 + AlCl3/urea = 1.3 coated Pouch cells 0.1–2.4 70/800 175/250/100
Super P/PVDF) filter paper
Ni bars 50/1000

5 : 1 : 3 : 1 (AM/gra- Whatman
150/100/20
TPBQ[66] AlCl2 + AlCl3/[EMIm]Cl = 1.3 phene/Ketjen glass fi- Mo pouch cells 0.5–2.3 125/200
[Link]/10.1002/cssc.202202358

91/3000/1000
black/PTFE) bers

5 : 4 : 1 (AM/con-
Whatman Swagelok- 0.25–
TDK[67] AlCl2 + AlCl3/[EMIm]Cl = 1.5 ductive agent/ Ta 350/20 170/300/100
GF/D type 2.25
PVDF)

8 : 1 : 1 (AM/ 110/100
CR2016 coin
PTCDA-SP[68] Al3 + AlCl3/[EMIm]Cl = 1.5 acetylene black/ glass fiber Mo 0.4–2.0 95/200 108/1200/100
cells
PTFE) 72/1000

© 2023 Wiley-VCH GmbH

[mA g 1])

6 : 3 : 1 (AM/Ketjen 295/100
glass fibers Swagelok-
PYTQ-CNT[47] AlCl2(urea)2 + AlCl3/urea = 1.3 black/carboxyl Mo 0.2–2.1 153/500 85/4000/1000
(Whatman) type
methyl cellulose) 85/2000

ChemSusChem 2023, 16, e202202358 (8 of 33)

Whatman
6 : 3 : 1 (AM/Ketjen
PHATN[69] AlCl2 + AlCl3/[BMIm]Cl = 1.5 glass fi- – Pouch cells 0.2–1.2 145/50 92/100/50
black/PTFE)
bers
Review

101/100
6 : 3 : 1 (AM/con-
glass fiber Swagelok- 88/200
H2TPP[70] AlCl2 + AlCl3/[EMIm]Cl = 1.3 ductive carbon Mo 0.5–2.2 75/5000/200
filter paper type 80/300
black/PVDF)
74/500
[Link]/10.1002/cssc.202202358

21/100
6 : 3 : 1 (AM/con-
glass fiber Swagelok- 16/200
H2TCPP[70] AlCl2 + AlCl3/[EMIm]Cl = 1.3 ductive carbon Mo 0.5–2.2 ~ 20/5000/200
filter paper type 14/300
black/PVDF)
12/500

glassy
7 : 2 : 1 (AM/Ketjen glass fibers Swagelok- 83/1000
PI/MOFs[71] AlCl2 + AlCl3/[EMIm]Cl = 1.3 carbon 0.1–2.4 73/1800/1000
black/PVDF) (Whatman) type 40/4000
electrode

© 2023 Wiley-VCH GmbH

[mA g 1])

Whatman
Inconel Swagelok-
PI@CNT[72] Al3 + AlCl3/[EMIm]Cl = 1.5 Free-standing glass fi- 0.2–1.1 130/150 110/100/150
alloy type
bers

112.3/400/200
[73] + 5 : 4 : 1 (AM/NG/ glass fiber Swagelok- 92.1/8000/500
PNA AlCl2 AlCl3/[EMIm]Cl = 1.5 Mo 0.5–2.3 175/50

ChemSusChem 2023, 16, e202202358 (9 of 33)

sodium alginate) (Whatman) type 72.5/10000/
2000
6 : 3 : 1 (AM/
glass fiber Swagelok- 157/100
anthracene[74] AlCl4 AlCl3/[EMIm]Cl = 1.3 acetylene black/ Mo 0.1–2.3 130/800/100
film type 82/500
PVDF)
Review

307/100
7 : 2 : 1 (AM/ Whatman CR2032 coin 245/500
TpBpy-COF[75] AlCl4 AlCl3/[EMIm]Cl = 1.3 Mo 0.01–2.3 150/3000/2000
Super P/PVDF) GF/D cells 162/1000
113/5000
[Link]/10.1002/cssc.202202358

8 : 1 : 1 (AM/car- Whatman
COF-derived NPC[76] AlCl4 AlCl3/[EMIm]Cl = 1.3 – pouch cells 0.5–2.43 90/2000 80/30000/5000
bon black/PVDF) 934-AH

© 2023 Wiley-VCH GmbH

[mA g 1])

6 : 3 : 1 (AM/
2D Cu-based AlCl4 or Whatman Swagelok- 147/200
AlCl3/[EMIm]Cl = 1.3 acetylene black/ Ta 0.1–2.2 155/1000/200
MOF@rGO[77] AlCl2 + GF/A type 65/500
PVDF)

ChemSusChem 2023, 16, e202202358 (10 of 33)

6 : 3 : 1 (AM/
120/200
TCNQ[78] AlCl2 + AlCl3/[EMIm]Cl = 1.3 acetylene black/ ABMS Ta pouch cells 0.01–2.3 115/2000/500
100/500
PVDF)
Review

CuPc@graphite[79] / AlCl4 AlCl3/[EMIm]Cl = 1.4 50 : 45 : 5 (graph- Whatman Ni pouch cells 1.0–2.82 120/320 90/1000/320
ite/CuPc/LA132) GF/A

8 : 1 : 1 (AM/ W or car- 136/50

glass fiber Swagelok-
N4[80] AlCl4 AlCl3/[EMIm]Cl = 1.3 Super P/sodium bon 0.2–1.85 124/1000 116/4000/1000
(GF/C) type
alginate) cloth 116/2000
[Link]/10.1002/cssc.202202358

7 : 2 : 1 (AM/car- glass fiber CR2032 coin 132/50

PZ[81] Al(OTF)2 + 5 M Al(OTF)3 – 0.2–1.0 101/300/50
bon black/PVDF) (Whatman) cells 41/200

400/100
6 : 3 : 1 (AM/Ketjen Whatman Ti steel CR2032 coin
C4Q[82] [Al(OTF)]2 + 1 m Al(OTF)3 0.4–1.4 371/200 269/50/200
black/PTFE) GF/D mesh cells
300/800

6 : 3 : 1 (AM/ 147/200
carbon CR2032 coin
TCQ[83] Al3 + 1 m Al(OTf)3 acetylene black/ – 0.5–1.8 116/400 70/200/2000
paper cells
PVDF) 80/1000

© 2023 Wiley-VCH GmbH

1864564x, 2023, 9, Downloaded from [Link] by Ecole De Technologie Superieur, Wiley Online Library on [19/06/2024]. See the Terms and Conditions ([Link] on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
1864564x, 2023, 9, Downloaded from [Link] by Ecole De Technologie Superieur, Wiley Online Library on [19/06/2024]. See the Terms and Conditions ([Link] on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Review
ChemSusChem [Link]/10.1002/cssc.202202358

Cyclability (ca- average discharge potentials of the Al/PANI cells are in the
range of 1.0–1.5 V. Liao et al.[49] developed a new RAIBs system

110/1000/5 C

165/300/100
47/100/500
cycles/rate
[mAh g 1]/
based on prickly polyaniline/ordered mesoporous carbon

[a] Active material. [b] Conductive additive. [c] Not applicable, the information is not able to be obtained or estimated from reference studies. [d] [EMIm]Cl is the abbreviation of 1-ethyl-3-methylimidazolium
[mA g 1]) composite (PANI/OMC) as cathode material. Pricked polyaniline
pacity

grew orderly on the surface of mesoporous carbon (Figure 4a),

resulting in more exposed active sites. A high capacity of
[mAh g 1]/

122/5000
~ 53/500

127/10 C
Capacity

120 mAh g 1 can be obtained at 1000 mA g 1. The synergistic

[mA g 1]

42/1000
29/2000

185/100
156/5 C
effect of OMC and polyaniline reduce the ohmic resistance and
rate

increase the conductivity. The self-regulation of the polyaniline

chain improves the way for ions to enter the interior of
window
Voltage

0.95–
0.1–1.2

0.1–1.6
polyaniline during cycling, resulting in a stable discharge
0.8
[V]

capacity of 121 mAh g 1, long cycle life of 5000 cycles (Fig-

trode config-

ure 4b). PANI with special morphology increases the interface

CR2025 coin

CR2032 coin
three-elec-

between PANI and electrolyte, resulting in the effective

Cell type

uration

utilization of active sites of PANI and good rate performance.

cells

The combination of PANI and OMC effectively improves the

mechanical durability of PANI when it is repeatedly doped/
collector

graphite
Ti mesh
Current

carbon

dedoped with anions (e. g. AlCl4 ), thus obtaining excellent

paper
plate

cyclic stability. Protonated PANI(H +)@SWCNT composite mem-

brane was synthesized by Wang et al.[48] PANI and SWCNT are
chloride, [BMIm]Cl is the abbreviation of 1-butyl-3-methylimidazolium chloride, TMAHCl is the abbreviation of trimethylamine hydrochloride.
Whatman

Whatman
Separator

arranged in a cross shape, showing a porous network structure

GF/A

(Figure 4c). Because of protonation, more NH + active sites

–

can be obtained, thus PANI(H +)@SWCNT electrode shows a

Electrode compo-
sition (mass ratio)

stronger redox peak than PANI@SWCNT cathode (Figure 4d).

(AM[a]/CA[b]/bind-

bon black/PTFE)
8 : 1 : 1 (AM/car-

Therefore, the discharge capacity of Al/PANI(H +) battery is twice

Free-standing

that of the initial composite film. PANI(H +)@SWCNT electrode

also displays low cell over-potential and excellent rate capability
er)

(Figure 4e). The structure of PANI(H +)@SWCNT not only facili-

tates electron transfer but also provides an open channel for
Al(ClO4)3 · 9H2O/suc-
Electrolyte[d] (molar

ion diffusion. With the increase of protonation time, the

cinonitrile = 1 : 12

quinone rings were further converted into benzene rings, and

1 m Al2(SO4)3

0.25 m AlCl3

the crystallinity of PANI was improved due to the structural

rearrangement during the protonation process. PANI(H +) elec-
ratio)

trode materials exhibits reversible AlCl2 + intercalation/deinter-

calation due to the protonation of PANI. Theoretical calculations
Insertion ion

show that AlCl4 prefers to combine with the hydrogen atom of

NH in the polyaniline chain through electrostatic interaction
Al3 +

Al3 +

rather than forming chemical bonds. Wang et al.[50] in situ

synthesized PANI on the surface of GO and obtained uniformly
dispersed PANI/GO composites (G-PANI) (Figure 4f). G-PANI
achieved a very high specific capacity (180 mAh g 1 at
1000 mA g 1) (Figure 4g), and excellent cycle stability over 4000
cycles. Because of the strong interaction between GO sheets
and PANI, the spacing in G-PANI-8 may widen, which is also
conducive to the deintercalation of AlCl4 during the charge
and discharge process. The intensity of C=N and C N peaks
increase when the AlCl4 approaches the NH group (Fig-
ure 4h).
Structure

3.1.2. Polythiophene and derivatives

Table 2. continued

Polythiophene (PTh) is a common long chain polymer con-

ductive polymer material. The composites of inorganic layered
Cathode[Ref.]

materials and CPs have good electrical/electrochemical proper-

SPANI[86]
PoPD[85]
AQ[84]

ties and dimensional stability. Zhao et al.[51] synthesized poly-

thiophene/graphite composite (PTh/G). PTh/G showed a high

Figure 3. Aluminum storage reactions of conductive polymers. a) PANI, b) PTh, c) PEDOT, d) PPy, e) polypyrene, f) polyphenylene.

Figure 4. a) TEM image of PANI/OMC and galvanostatic charge–discharge curves of OMC, PANI, and PANI/OMC at 1000 mA g 1. b) Cycling performance of the
PANI/OMC (Preparation schematic of PANI/OMC, inset). Reproduced with permission.[49] Copyright 2020, Elsevier. c) HRTEM image of PANI(H +)@SWCNT. d) The
CV curves of Al/PANI batteries. e) Discharge capacity, cell overvoltage, and rate capability of PANI@SWCNT and PANI(H +)@SWCNT electrode. Reproduced with
permission.[48] Copyright 2019, Wiley-VCH. f) SEM image of G-PANI-8. g) Typical charge–discharge voltage profiles of the GOA, PANI, and G-PANI-8 at
1000 mA g 1. h) FTIR spectra of PANI and AlCl4 -doped PANI calculated by DFT-GGA (The abbreviation of Density Functional Theory-Generalized Gradient
Approximation). Reproduced with permission.[50] Copyright 2020, Springer Nature.

capacity of 113.5 mAh g 1 at 1 A g 1. α-α-Polythiophene pro- stability of PTh structure during charge and discharge. However,
vides a host for AlCl4 intercalation and deintercalation (Fig- graphite hindered the migration of AlCl4 to polythiophene to
ure 5a). Graphite in the composite electrode maintains the some extent. With the increase of cycles, the number of AlCl4

Figure 5. a) Structure and connections of PTh. Reproduced with permission.[51] Copyright 2019, The Royal Society of Chemistry. b) Synthesis of Pth@GO. c)
Galvanostatic charge–discharge curves from GO, Pth, and Pth@GO-3 at 1000 mA g 1. (SEM images of Pth@GO-3, inset). d) Capacity retention and coulombic
efficiency of Pth@GO-3. Reproduced with permission.[52] Copyright 2020, American Chemical Society. e) Representative GCD cycles of Al-PTh/MWCNT cells
(Representative high-resolution TEM image of PTh/MWCNT composite, inset). Reproduced with permission.[54] Copyright 2020, Elsevier. f) FESEM (The
abbreviation of Field Emission Scanning Electron Microscope) images recorded and representative GCD cycle recorded for the MoS2, MoS2/PTh A (The
thiophene monomer was added after the oxidant), and MoS2/PTh B (The thiophene monomer was added before the oxidant). Reproduced with permission.[55]
Copyright 2021, American Chemical Society. g) Characteristic GCD cycle and schematic illustration of an Al-PEDOT battery. Reproduced with permission.[56]
Copyright 2020, Elsevier.

ions that cannot be released into PTh increases, resulting in an discharge (GCD) produces a high discharge capacity of
increase in charge transfer resistance and a decrease in ion 216 mAh g 1. The electrochemical reaction mechanism on the
diffusion ability. Therefore, graphene and polythiophene can be PTh/MWCNT composite working electrode is a combination of
mixed in subsequent studies, and the stability of polythiophene two redox processes, which are considered to occur simulta-
structure should be better maintained. This idea was imple- neously in a typical cycle, leading to the oblique charge-
mented by Kong et al.[52] in 2020, where polythiophene was discharge curves. The active polymer sites oscillate between
polymerized on the surface of graphene oxide (Figure 5b). positive and neutral states when the battery is charged and
Polythiophene in Pth@GO composite is uniformly coated on the discharged, and the MWCNT also helps to embed AlCl4 . Raju
surface of graphene oxide, which makes the electrode have et al.[55] combined sulfide with polythiophene to explore the
high Pth active site exposure, high electrical conductivity, and effect of different oxidant addition sequences on MoS2/PTh
high structural stability, and provides a high discharge specific hierarchical structure. CPs increase the electronic conductivity
capacity (~ 130 mAh g 1) and excellent cycle stability (above and specific capacity of the composites, replacing the tradi-
100 mAh g 1 after 4000 cycles) (Figure 5c,d). The first-principles tional conductive carbon for electrodes. Although the two
calculation shows that AlCl4 is stored on Pth@GO by the MoS2/PTh had a higher initial discharge specific capacity of
electrostatic attraction induced by β-hydrogen in Pth. Zhang about 200 mAh g 1 (at 75 mA g 1) compared with MoS2 (Fig-
et al. proved that the α-α polythiophene broke the bond during ure 5f). The Al-MoS2/PTh B battery with oxidant shows a higher
the reaction and achieved self-adaptive re-organization, achiev- voltage plateau, but the coulombic efficiency is low. It may be
ing a cycle life of 100 000 cycles.[53] Raju et al.[54] self-assembled due to the insertion mechanism of Al3 + and AlCl4 anion, poor
polythiophene on the multi-walled carbon nanotube (MWCNT) reversibility not conducive to a long-term cycle.
template to form composite materials as cathode materials for Given the high conductivity of polythiophene, researchers
RAIBs. Figure 5e shows that Pth is deposited and wrapped on have done a lot of research on high conductive polymer
the surface of carbon nanotubes, and the galvanostatic charge- polythiophene derivative poly(3,4-ethylenedioxythiophene) (PE-

DOT), including electropolymerization synthesis of PEDOT,[88,89] pyrene) was 100 mAh g 1, which was higher than that of pure
and its application in battery energy storage and supercapacitor polypyrene (70 mAh g 1) or crystalline pyrene (20 mAh g 1). The
energy storage.[90,91] Schoetz et al.[56] polymerized PEDOT on electrochemical test results of poly(nitropyrene-co-pyrene) were
three-dimensional reticulated vitreous carbon (RVC) electrode similar to those of polypyrene. The capacity attenuation was
and used in aluminum batteries. PEDOT shows a three-dimen- hardly observed in 1000 cycles, and the stable average
sional structure and shows multiple discharge plateaus (Fig- discharge voltage was about 1.7 V (Figure 6b). Though
ure 5g). The polymerization potential window is very important poly(nitropyrene-co-pyrene) showed much higher capacity than
for the performance of polymers in ionic liquids. It has been polypyrene, the contour of constant current charging and
proved that anion insertion/removal can occur at a high discharging curves remained almost unchanged (Figure 6c),
potential only when the polymer is synthesized at the same indicating that the introduction of NO2 group does not change
high potential (polymer “memory effect”). Due to the electro- the redox potential. Due to the better dispersion of
polymerization of PEDOT in ionic liquids and the narrow poly(nitropyrene-co-pyrene) in NMP than homopolymers, thus
potential window, the discharge plateau is low. The polymer- better contact with conductive additives, resulting in higher
ization method can be adjusted to change the potential utilization of active materials and higher capacity.
window and ensure the stability of the polymer in ionic liquids,
thus improving the battery performance. Craig et al.[92] modeled
the cathodic half-cell of PEDOT cathode in an AlCl3-1-ethyl-3- 3.1.4. Polypyrrole
methylimidazolium chloride ([EMIm]Cl) electrolyte. Density
functional theory (DFT) calculations can visualize the charge There are a few examples of polypyrrole used in aluminum ion
distribution on the electrode surface and the interaction batteries. Hudak[58] compared the three-electrode system per-
between PEDOT and active charge carrier ions. It is necessary to formance of polypyrrole and polythiophene (Figure 7a,b), and
adopt the diffuse functions and dispersion corrections when proved the feasibility of polypyrrole as a cathode material of
simulating intermolecular interactions, such as the interaction RAIBs. Polypyrrole is mostly used in lithium batteries,[93–95] for
AlCl4 and PEDOT. They demonstrated the importance of example, Wu et al.[96] prepared core-shell polypyrrole by vapor
computational chemistry to accelerate the development of deposition polymerization for lithium batteries (Figure 7c). If it
conductive polymer cathodes for next-generation batteries. can be used for reference in RAIBs, it is believed that it will have
good performance in subsequent research and can improve the
performance of aluminum-organic batteries.
3.1.3. Polypyrene Polymers have been combined with other compounds for
energy storage.[97] The combination of the two polymers can
Polypyrene is a kind of unusual conductive polymer, Walter also be used for energy storage. Khan et al.[98] combined
et al.[57] showed a novel cathode based on cheap pyrene polythiophene and polypyrrole for supercapacitors can play the
polymer during the charging process, the condensed aromatic role of the two and improve performance. Perhaps this can also
rings of these polymers were oxidized, accompanied by the be applied to the cathode of aluminum batteries. Of course,
absorption of aluminum tetrachloride (AlCl4 ) from chloroalumi- this needs to consider the respective energy storage mecha-
nate ionic liquids. In the process of electrooxidation, the nism of the two polymers.
average positive charge of each four aromatic rings of pyrene
can be obtained, thus forming a free radical cation, which can
be balanced by the embedding of AlCl4 anions in ionic liquids. 3.1.5. Polyphenylene
The electrochemical properties of polypyrene can be fine-tuned
by appropriate chemical derivation. This process was demon- Poly-(p-phenylene) (PPP) can be electrochemically doped to
strated by poly(nitropyrene-co-pyrene) (Figure 6a). Under high form n-type or p-type complexes and be employed as
discharge voltage, the storage capacity of poly(nitropyrene-co- rechargeable battery electrodes, either together as anode and

Figure 6. a) FTIR spectra of polypyrene and poly(nitropyrene-co-pyrene). b) Capacity retention upon cycling and average discharge voltages of
poly(nitropyrene-co-pyrene), c) Corresponding GCD curves for the 100th, 200th, and 500th cycles of poly(nitropyrene-co-pyrene). Reproduced with
permission.[57] Copyright 2018, Wiley-VCH.

Figure 7. a) Cyclic voltammograms at 10 mV s 1 of polypyrrole. b) Discharge capacities of polypyrrole at 20 mA g 1. Reproduced with permission.[58] Copyright
2014, American Chemical Society. c) Scheme of vapor deposition polymerization polypyrrole. Reproduced with permission.[96] Copyright 2021, Elsevier.

cathode or in conjunction with other electrodes such as lithium Other unusual p-type conductive electrode materials such
metal.[99] Li et al.[59] synthesized conjugated conducting polymer as heterocyclic compounds of anthracene also have good redox
polyphenylene by polymerizing benzene molecules, and as a properties. Yang et al.[60] grafted phenoxazine (PX) with
cathode material for RAIBs (Figure 8a). PPP exhibits bulk poly(vinylbenzyl chloride) to form poly(vinylbenzyl-N-phenoxa-
structures rich in mesopores (10–40 nm) (Figure 8b). In the zine) (PVBPX) to achieve low solubility. Moreover, the extended
electrochemical reaction, PPP was oxidized to form free radical π-conjugated structure was introduced into the PVBPX polymer,
cation [C6H4]3n +, and AlCl4 anion was intercalated to form and the π-electron of the delocalized conjugated system of the
electroneutrality and realize electrochemical energy storage. molecular main chain increased the electronic conductivity of
The discharge capacity is 92 mAh g 1 at 100 mA g < M < 1 and the the polymer. The dual active sites of N and O achieve better
discharge plateau is 1.4 V. PPP shows good rate capability. At redox performance, which ensured rapid reaction kinetics and
the ultra-high discharge current density of 5 A g 1, the dis- contributed to an amazing ultra-long lifetime of 50 000 cycles.
charge specific capacity is close to 72 mAh g 1 (Figure 8c). The Such polymers also provide a reference for the application of
reaction kinetics of the PPP cathode is almost completely aluminum-organic batteries in large-scale energy storage.
controlled by the intercalation pseudocapacitance (Figure 8d),
thus improving the rate capability. Ionic liquids are convenient
electrolytes for electrochemical synthesis poly-(p-phenylene) 3.2. Carbonyl compounds & imine polymers
(the degree of polymerization n > 10) (Figure 8e). This memory
effect may improve the stability of PPP in rechargeable Carbonyl compounds usually exhibit the characteristics of n-
aluminum-ion batteries. type cathode materials, realizing the coordination of carbonyl

Figure 8. a) Schematic diagram of the energy storage mechanism of PPP cathode in aluminum-ion batteries. b) SEM image and GCD curve of PPP. e) Rate
performance of PPP. d) Comparison of the pseudocapacitance contribution and CV curve at 1.0 mV s 1. Reproduced with permission.[59] Copyright 2022,
American Chemical Society. e) Dependence of the degree of polymerization of PPP on the concentration of benzene. Reproduced with permission.[100]
Copyright 1992, The Royal Society of Chemistry.

sites with cations. Figure 9 is the aluminum storage reaction ing (Figure 10d), so that the rechargeable aluminum metal
mechanism of COCs. battery has high power performance. The active surface area of
the 3D thin film anode is about four to eight times of metal foil,
which significantly reduces the electrochemical overpotential
3.2.1. Quinones and improves the utilization rate of materials. By distributing
the current on a larger surface area, the current density is
Bitenc et al.[33] referred to the concept of aluminum anode- effectively reduced to improve the rate capability of the anode
organic cathode battery based on anthraquinone (AQ) electro- (i. e., the speed of metal plating and stripping). The 3D film
chemical. To improve the capacity retention rate, while anode delivers a discharge capacity of 165 mAh g 1 at 0.5 C and
maintaining the rate performance and the accessibility of active a capacity retention of 81 % at 20 C (Figure 10e). However, the
substances, the cathode of AQ-based polymer increased side reactions with the increase of anode surface area
poly(anthraquinone sulfide) (PAQS) was prepared by in situ make the coulombic efficiency of 3D thin film battery slightly
polymerization in the multi-walled carbon nanotubes (MWCNT) lower than that of 2D foil anode (Figure 10f). Zhou et al.[62] used
suspension (Figure 10a). The battery with PAQS cathode organic 9,10-anthraquinone (AQ) as an aluminum storage
showed a high capacity of 190 mAh g 1 and an average cathode, showing an ideal discharge voltage of 1.1 V and
discharge voltage of 1.0 V (Figure 10b). The initial rapid capacity polarization of 0.1 V during charge-discharge (Figure 10g). AQ
decay can be ascribed to the dissolution of short-chain exhibited a reversible capacity of 215 mAh g 1 at 20 mA g 1. The
oligomers in the discharge state, while the later slower capacity capacity was 192.4 mAh g 1 after 200 cycles at 100 mA g 1, a
decay can be ascribed to the interaction of different effects: specific capacity of 166 mAh g 1 can be obtained at 500 mA g 1
cathode passivation, gradual dissolution of polymers, and (Figure 10h,i). In addition, during the discharge process, an AQ
degradation of polymers and/or electrolytes. Figure 10c shows molecule has two carbonyl groups for 2/3 Al3 + ions to form
the excellent rate performance of Al-PAQS/MWCNT battery. enol-aluminum bonds. The enol bond is converted to carbonyl
Electrochemical AQ cathode undergoes either two-step single- during charge, showing good reversibility. Due to the steric
electron reduction or one-step double-electron reduction, hindrance, each Al3 + binds to three oxygen atoms in the
depending on the electrolyte, resulting in the reduction of carbonyl of three adjacent AQ molecules. Based on the working
dianion AQ2 (Figure 10c). The Cl/Al ratio of the discharge mechanism of Al3 +, the redox curve (relatively stable long
cathode is 1.02, which indicates that the main aluminum plateau) of AQ is difficult to obtain from inorganic materials.
species coordinated with AQ is AlCl2 +. The advantage of AlCl2 + Anthraquinone organic compounds have shown good
species greatly improves the theoretical energy density electrochemical activity, anthraquinone derivatives also contain
(101 Wh kg 1) of the current aluminum-organic battery over the carbonyl sites (C=O) to achieve ion storage. Wang et al.[63]
most advanced aluminum-graphite battery (48 Wh kg < M < 1). reported a benzo[1,2-b:4,5-b’]dithiophene-4,8-dione (BDTD) or-
Lindahl et al.[61] also used PAQS/MWNTs and Al based on cation ganic cathode material with an elongated plate-like morphol-
coordination to form aluminum-organic batteries. However, the ogy (Figure 11a,b). The separator was modified by conductive
anode aluminum was improved. Aluminum 3D thin film anode carbon Super P to alleviate the accidental shuttle of soluble
fully integrated with the diaphragm was fabricated by sputter- BDTD species and improve the overall conductivity of the

Figure 9. Aluminum storage reactions of carbonyl compounds. a) AQ, b) TDK, c) PTCDA, d) BDTD, e) PQ-~, and f) TPBQ.

Figure 10. a) SEM of the PAQS/MWCNTs. b) Charge-discharge voltage curves of PAQS/MWCNT cell at 0.5 C. c) Rate capability test at 0.5–10 C. (The
electrochemical mechanism of AQ, inset). Reproduced with permission.[33] Copyright 2020, Elsevier. d) SEM of an as-sputtered 3D thin film anode in cross-
section. Galvanostatic tests for full cells with 3D thin film and 2D foil anodes: e) discharge capacities at varying rates, and f) polarization voltages and CEs.
Reproduced with permission.[61] Copyright 2020, Wiley-VCH. g) Schematic illustration of the RAIBs with AQ as the cathode material and the GCD profiles of AQ
at 20 mA g 1. h) Cycling performance of AQ. (i) Rate performance of AQ. Reproduced with permission.[62] Copyright 2021, Elsevier.

battery. The initial capacity of BDTD is 143 mAh g 1, and there is provides a basis for the conversion between C=O bond and
a flat discharge voltage plateau at about 1.2 V (vs. Al/Al3 +) C O Al.
(Figure 11c). Energy dispersive X-ray (EDX) showed that the Cl/ Phenanthrenequinone is a quinone compound with a
Al atomic ratio was about 2.4, indicating that AlCl2 + was the structure similar to anthraquinone. Kim et al.[65] covalently linked
main reaction species that interacted with carbonyl (C=O) the redox-active units of phenanthrenequinone to form a
reversibly. The cyclic reaction mechanism was further studied layered superstructure of phenanthrenequinone triangles (PQ-
by time-of-flight secondary-ion mass spectroscopy (ToF-SIMS). Δ). PQ-Δ showed a specific capacity of 110 mAh g 1 at 0.1 A g 1
During the discharge process, AlCl2 + was inserted into the current rate. Due to the clear ion channels along the PQ-Δ π–π
electrode, and AlCl2 + was extracted during the charging process stacking superconjugated molecular structure, it has an extra-
(Figure 11d,e). At the same time, Wu et al.[64] used MXene@BD- ordinary rate capability (70 mAh g 1 at 10 A g 1) Fast storage
TO as the Al3 + intercalated cathode of aluminum batteries, and kinetics is due to the rapid charge transfer of AlCl2 + complex
Ti3C2 (MXene) was used as the load structure of benzo[1,2-b:4,5- ions at the interface without separate desolvation.[101] The
b’]dithiophene-4,8-dione (BDTO) (Figure 11f,g). The reversible robustness of the PQ-Δ molecular triangle allows it to remain
capacity is 229.8 mAh g 1 at 500 mA g 1 (Figure 11h). In addi- 53 mAh g 1 after 5000 cycles (Figure 12a). They also prepared
tion, the capacity of 134.9 mAh g 1 can still be maintained after PQ triangle hybrid (PQ-Δ-HY) electrode doped with graphite
500 cycles. BDTO is embedded in MXene, and this unique flakes. The flake graphite not only increases the electron
structure inhibits the dissolution of BDTO in the organic conductivity as a conductive agent but also acts as an active
electrolyte so that Al3 + can be intercalated/delaminated material with PQ-Δ in a high voltage range. This optimization
efficiently and reversibly. One Al3 + ion combined with three realized the double insertion of cationic and anionic chloroalu-
carbonyl groups on average to form an Al-enol bond (Fig- minates. The capacity contribution of PQ-Δ-HY is divided into
ure 11f). The two-dimensional structure of BDTO molecule with two parts (Figure 12b). When charged, the oxidation of (PQ-
a small deformation probability makes BDTO molecule very Δ3·)3AlCl2 shows a smooth plateau in the range of 0.75-1.75 V,
stable in Al3 + intercalation and deintercalation reactions, which and the total specific capacity is 68 mAh g 1. In addition, PQ-Δ-
HY can be embedded in AlCl4 through graphite oxide sheets.

Figure 11. a) Schematic illustration of the Al/BDTD battery employing Super P-modified membrane. b) Secondary electron (SE) image of the pristine BDTD. c)
Voltage profiles of BDTD at different discharging/charging rates. The CS , AlCl2 , and C2H6N + ToF-SIMS mappings of d) the discharged electrode, and e) the
charged electrode. Reproduced with permission.[63] Copyright 2022, Wiley-VCH. f) Adsorption energies of BDTO molecule and Al3 +. g) TEM image of
MXene@BDTO. h) Charge/discharge plateaus of MXene@BDTO and BDTO. Reproduced with permission.[64] Copyright 2022, Elsevier.

When charged to 2.35 V, the total capacity of PQ-Δ-HY is coordination and storage mechanism of AlCl2 + with 2,3,5,6-
130 mAh g 1. In the discharge process, this multi-step oxidation tetra-phthalimide-p-benzoquinone (TPBQ) as the cathode. TPBQ
process is opposite. provides multiple oxidative active carbonyl sites, and four
The dissolution of small organic molecules in liquid electro- aromatic rigid phthalimide (C8H4NO ) groups are directly
lytes is still a fundamental challenge. Kao et al.[44] studied a connected to the benzoquinone skeleton at symmetrical
series of small molecule quinone derivatives as AIB cathode positions. The high solubility and low conductivity of carbonyl
materials. To effectively eliminate the dissolution problem, 1,4- compounds in electrolytes are alleviated by introducing rigid
benzoquinone was combined with four large phthalimide groups and heteroatoms (O and N) with a pair of lone electrons.
groups to form 2,3,5,6-tetraphthalimide-1,4-benzoquinone (TPB) The basic unit structure formed by TPBQ π-π stack exposes all
as cathode material of Al/TPB batteries (Figure 12c). In the urea the active carbonyl sites, which is beneficial to the electro-
electrolyte system, the Al/TPB battery provides a capacity of up chemical redox reaction and the rapid diffusion of charge
to 178 mAh g 1 in the first cycle (Figure 12d). TPB store energy carrier ions. The first cycle discharge capacity of TPBQ is
through ion coordination. In the electrochemical reduction of 177 mAh g 1 at 20 mA g 1 and exhibits 3000 cycles stability at
carbonyl compounds, oxygen atoms with negative charge 1 A g 1 (Figure 12e,f). Part of the carbonyl group in TPBQ
coordinate with groups or atoms with positive charge, which is participates in the anchoring of AlCl2 +. Two oxygens in the
reversible in the oxidation process. AlCl2(urea)2 + cation is an trioxygen carbonyl group combine with AlCl2 + to form a
active substance, which is adsorbed on the oxygen atom O of tetrahedral structure, and one oxygen in the dioxygen carbonyl
TPB during the discharge state and desorbed during the group combines with AlCl2 +. Therefore, each TPBQ molecule
charging state. The redox reaction of organic materials was can accommodate four AlCl2 + cations in a complete discharge
mainly the coordination between the guest ions and the surface state, accompanied by a change in the discharge voltage,
redox active sites, which significantly accelerated the diffusion because the AlCl2 + bound by three oxygens has two Al O
process. Mao et al.[66] proposed the electrochemical surface bonds, which can impose higher voltage (2.13 V and 1.91 V). As

Figure 12. a) Cycling performance test of PQ-Δ (inset: GCD profile of PQ-Δ and a schematic for each ex situ state). b) GCD profile of PQ-Δ-HY and an
electrochemical redox schematic. Reproduced with permission.[65] Copyright 2019, Nature Publishing Group. c) Schematic illustration of the Al/TPB cell. d) First
discharge–charge curves of the Al/TPB cell with [EMIm]Cl and urea electrolytes. Reproduced with permission.[44] Copyright 2020, American Chemical Society.
Electrochemical performance of TPBQ Al pouch cells: (e) GCD curves for the first three cycles at 20 mA g 1 and (f) long-term cycling performance of TPBQ. (g)
Two types of AlCl2 + coordination sites: “Tri-oxygen” and “Di-oxygen” denoted as “T” and “D”, respectively. (h) Discharge voltage profile from DFT calculations
for (AlCl2)x(TPBQ) model cathodes. Reproduced with permission.[66] Copyright 2020, The Royal Society of Chemistry.

AlCl2 gradually occupies the “hydrogen peroxide” position, the consumption of the electrolyte limits the energy density. The
discharge voltage decreases to 1.08 V (Figure 12g,h). ratio of aluminum to chlorine determines the amount of
electrolyte, and the storage of AlCl2 + consumption electrolyte is
1/8 of the storage of AlCl4 consumption electrolyte.[45] By
3.2.2. Ketones simply replacing carbon black with activated carbon (AC) as a
conductive agent, TDK penetrated into the pores of AC to
Ketones are a class of compounds containing C=O groups. Yoo reduce the dissolution of active molecules in the electrolyte
et al.[67] reported a tetradiketone (TDK) macrocycle as a cathode (Figure 13b). At the current density of 0.1 A g 1, the TDK-AC
material for AIBs. The benzene rings in TDK are not coplanar, mixture maintained a high capacity of 170 mAh g 1 after 300
resulting in a larger void (Figure 13a). The reversible capacity of cycles (Figure 13c). During discharge, the four carbonyl groups
TDK is 350 mAh g 1 at 20 mA g 1, corresponding to the storage on TDK can bind to eight electrons, and the adjacent carbonyl
of 7 e per molecular unit, indicating a reversible reaction with groups on four corners can chelate with four AlCl2 + (Figure 9b).
divalent ions (AlCl2 +). It shows that the storage of divalent ions The graphite, PQ, and TDK electrodes were analyzed by X-ray
has great advantages. In AIBs, the charge carrier ions used in photoelectron spectroscopy (XPS) to study the effect of func-
the anode and cathode are different, which means that at least tional groups on the charge carrier ions. Based on the fact that
one carrier ion must be provided by the electrolyte, and the the atomic ratio of Cl to Al is 3.93, 1.75, and 0.97, the carrier
amount of electrolyte must be considered when calculating the ions stored in graphite, PQ, and TDK are AlCl4 , AlCl2 +, and
energy density. In AIBs, most cathode materials acted by storing AlCl2 +, respectively. When the elements are combined with
aluminum complex ions (such as AlCl4 ). Considering this functional groups or elements with high electronegativity, the
reaction from the perspective of energy density, it is unfavor- binding energy will move to a higher value (Figure 13d,e).
able to utilize AlCl4 ions in the electrolyte, because the large Figure 13f shows the excellent performance of TDK as a divalent

Figure 13. a) Optimized structure and electron density of TDK. b) SEM images of TDK with AC. c) Cycling performance of TDK with different carbon materials.
Comparison of cathode materials exploiting AlCl4 , AlCl2 + and AlCl2 + ions. d), e) XPS curves of graphite-AlCl4, PQ-AlCl2 and TDK-AlCl; d) Al 2p and e) Cl 2p
branches. g) Galvanostatic voltage profiles of graphite, PQ and TDK. Reproduced with permission.[67] Copyright 2021, Nature Publishing Group.

cation storage electrode material. The energy stored in 3.2.3. Imine polymers
monovalent ions is limited, so an organic electrode based on
the polyvalent ion should be designed to improve the capacity When imine polymers are used as cathode materials for RAIBs,
of the battery.[46,102] the active ion to achieve storage is usually AlCl2 +. The
aluminum storage reaction mechanism of different IPs is shown
in Figure 14.
Peng et al.[47] synthesized a heterocyclic conjugated polymer
TYPQ with C=O and C=N synergistic redox-active centers using
pyrene-4,5,9,10-tetraone (PYT) and tetraaminobenzoquinone

Figure 14. Aluminum storage reaction of imine compounds. a) H2TPP, b) PYTQ, c) PI, and d) PNA.

(TABQ). The C=N site in the polymer is not only beneficial to reported a pyrazine-based polymer electrode material for
good π conjugation but also enhances the redox reactivity of sodium, magnesium, and aluminum batteries. DFT calculation,
the C=O site. By combining PYTQ and CNT, both the XPS, Raman spectroscopy, and FTIR showed that the electron-
conductivity and the specific surface area of the electrode were deficient pyrazine site in PHATN was the redox center of the
increased. The PYTQ-CNT electrode has a high specific capacity reversible reaction with metal ions (Na + or Mg2 + or AlCl2 +). For
of 208 mAh g 1 at 0.2 A g 1 (Figure 15a). Figure 15b shows two aluminum batteries, at 50 mA g 1 current density, the first
pairs of redox peaks, which are not obvious, corresponding to discharge capacity is 145 mAh g 1, accompanied by a 0. V
its inclined charge-discharge curve. This phenomenon is similar discharge plateau (Figure 15d). The overpotential between
to PNA.[73] In the long cycle test at 1 A g 1, PYTQ-CNT can charge and discharge is 0.2–0.3 V. After 100 cycles, the Al/
maintain 85 mAh g 1 after 4000 cycles. The combination of PHATN battery maintained a capacity of 92 mAh g 1 with a CE
PYTQ and CNT established a stable ion and electron conduction of 99.7 % (Figure 15e), indicating that PHATN has good stability
network in the electrode, which was helpful for rapid electron in RAIBs.
and ion transport (Figure 15c). The synergistic C=O and C=N At present, the OEMs reported in RAIBs mainly refer to the
active sites on the PYTQ polymer are reduced to C O and C oxygen or nitrogen active center of carbonyl compounds (C=O)
N bonds after discharge, further coordinating the four positive or nitrogen-containing compounds (C=N), which are mainly
AlCl2(urea)2 + ions in the electrolyte, and each repeat unit based on coordination chemical reactions. Due to the presence
transfers four electrons (Figure 14b). Compared with the of aromatic π-conjugated plane macrocycles, porphyrins have a
previously reported OEMs with a single type of redox center small gap between the highest occupied molecular orbital
(C=O or C=N),[65,71] PYTQ-CNT shows superior performance. (HOMO) and the lowest occupied molecular orbital (LUMO),
Hexaazatrinaphthalene (HATN) containing the imine group is an thus achieving rapid charge transfer through rapid electron
electron-deficient aromatic compound (n-type). Mao et al.[69] absorption and release. The N atom containing a pair of lone

Figure 15. a) Galvanostatic discharge-charge profiles of PYTQ-CNT, PYTQ, and CNT electrodes. b) CV profiles of PYTQ-CNT. c) Rate capability of PYTQ-CNT.
Reproduced with permission.[47] Copyright 2022, Wiley-VCH. d) The discharge–charge curves of PHATN in RAIBs. e) Cycling performance and CE of PHATN in
RAIBs. Reproduced with permission.[69] Copyright 2019, Wiley-VCH. The electrochemical performances of Al j AlCl3/[EMIm]Cl j porphyrin batteries: f) CV profiles,
g) discharge-charge curves of H2TPP and H2TCPP. h) Gibbs free energy of the reaction process, i) discharge voltage profile from DFT calculations for H2TPP-
xAlCl2 model positive. Reproduced with permission.[70] Copyright 2021, Wiley-VCH.

electrons in the porphyrin ring is responsible for the ion as cathode materials for aluminum-organic batteries (Fig-
coordination chemical reaction, which is different from other ure 16a). PI/MOFs hybrid materials have customizable pore
OEMs. Han et al.[70] reported two cathode materials, 5,10,15,20- sizes, which can provide good ion transport channels, and the
tetraphenylporphyrin (H2TPP) and 5,10,15,20-tetrakis(4-carboxy- skeleton can effectively slow down the dissolution of PI in ionic
phenyl) porphyrin (H2TCPP). Both H2TPP and H2TCPP have the liquid electrolytes. At 1000 mA g 1, the capacity of the PI/MOFs
same 18π electron system. In a planar ring, there are two N hybrid electrode reached 78 mAh g 1 (Figure 16b). It also
atoms, one with covalent bonds and the other with lone pair exhibits excellent cycling performance for 1800 cycles. The
electrons. Provide sufficient active centers for chemical reac- electrochemical storage mechanism shows that the chloralumi-
tions. The delocalized π bond can be used to improve electron nate cation interacting with the reduced carbonyl bond in
transport and act as the chemical reaction center. Different polyimide during discharge is AlCl2 +. The excellent performance
from the strong coordination between metal ions and porphyr- of PI/MOFs hybrid materials comes from the synergistic effect of
in nitrogen atoms in traditional organic chemistry reactions, in PI and MOFs. MOFs can prevent the aggregation of PI, and the
AlCl3/[EMIm]Cl electrolyte, porphyrin materials show reversible customizable pore size provides favorable ion transport
coordination and dissociation of cationic chloraluminate during channels. PI with conjugated carbonyl group can provide fast
discharge and charging. Due to the large π-conjugated system charge transfer and efficient cation chloraluminate ion diffusion
of porphyrin, at 100 mA g 1, the reversible specific capacities of for a redox reaction, thereby increasing the capacity. Brunauer-
H2TPP and H2TCPP cathode materials are 101 and 23.7 mAh g 1, Emmett-Teller (BET) measurement demonstrated that PI/MOFs
respectively (Figure 15g). Compared with H2TPP, the redox peak hybrids had heterogeneous structures with mesopores and
of H2TCPP electrode material is not obvious (Figure 15f). On the macropores, which contribute to electrolyte permeation. Fan
one hand, the increase in molecular weight of H2TCPP inhibits et al.[72] prepared PI@CNT cathode material for lithium, magne-
its capacity. On the other hand, due to the influence of carboxyl sium, and aluminum batteries. The in situ formed polyimide
functional groups, the carboxyl functional groups with an was filled into the gap between carbon nanotubes to achieve a
electron-withdrawing effect will reduce the electron cloud good compaction density. These long carbon nanotubes are
density of the π-conjugated system. As a result, the Lewis randomly distributed in the composites and connect different
basicity of H2TCPP decreased and the coordination reaction regions of polyimide to form an effective conductive network
with AlCl2 + was inhibited. During the discharge process, the (Figure 16c,f). CNTs are interconnected to construct a 3D
coordination of H2TPP with AlCl2 + ions is accompanied by an electronic conductive matrix. PI@CNT reversibly stored cations
increase in Gibbs free energy (Figure 15h,i). with different valences (Li +, Mg2 +, Al3 +). An important advant-
Polyimide (PI) has been used in the study of aluminum age for Mg and Al batteries is the potential non-dendritic
batteries, but due to the relatively low potential of polyimide, it deposition because the bond energy of Mg Mg or Al Al bonds
is only used as the anode material of aluminum batteries.[103] is relatively higher than that of Li Li bonds. Li +, Mg2 +, and Al3 +
Some researchers combined PI with other materials and applied are embedded in polyimide through a stable ion coordination
them to the cathode materials of energy storage batteries. charge storage mechanism, which is the key reason for the
Zhou et al.[71] reported a one-pot synthesis of PI/MOFs hybrids excellent power density of multivalent batteries. For the Al-

Figure 16. a) TEM image of PI/MOFs. d) Charge-discharge curves of pure PI, pure MOFs and PI/MOFs hybrid at 1000 mA g 1. Reproduced with permission.[71]
Copyright 2018, Wiley-VCH. c) Illustration of PI@CNT synthesis. d) TEM image of the PI/CNT composite. e) GCD profiles of PI@CNT at a current density of 1 C
(1 C = 150 mA g 1). f) Cycling performance of PI@CNT. Reproduced with permission.[72] Copyright 2020, Elsevier.

PI@CNT battery, the reversible capacity is 110 mAh g 1 at 3.3. Polycyclic aromatic hydrocarbons
150 mA g 1, and the capacity remains 100 mAh g 1 after 100
cycles (Figure 16d,e). No aluminum dendrite was found when As a new type of electrode material, polycyclic aromatic
the discharge current increased to 3 A g 1. hydrocarbons (PAHs) have great potential. In the previous
chapter, polypyrene is also mentioned as a cathode material,[57]
and pyrene is a kind of tetracyclic aromatic hydrocarbon. The
application of PAHs in dual-ion batteries[104] has attracted
researchers to apply them to aluminum batteries. Figure 17
shows the aluminum storage reaction mechanism of
anthracene and the structure of common PAHs.
Das et al.[105] used first-principles calculations to evaluate
four light PAHs (pyrene, perylene, triphenylene, and coronene)
as potential cathode materials for aluminum-DIBs. Theoretical
calculations show that AlCl4 has a good intercalation effect
and maintains its tetrahedral geometry in a flexible lattice. The
charge transfer of the PAHs system shows its p-type redox
activity, that is, they can be oxidized to + 1 state when inserting
monovalent anions. Different cathode materials for anion
insertion have different effects on the capacity and voltage
characteristics of Al-DIB (Figure 18a). Based on the electro-
chemical properties, pyrene and coronene have been found to
deliver around 1.32 and 1.43 V, respectively, at appreciably high
specific capacity. Triphenylene can be used to meet high
Figure 17. a) Aluminum storage reaction of anthracene. b) Molecular voltage requirements. Therefore, considering the different
structures of PAHs.

Figure 18. a) Variation in voltage and storage capacity for the considered PAH systems. Reproduced with permission.[105] Copyright 2021, American Chemical
Society. b) Theoretical specific capacity of PAHs. c) Specific charge and discharge capacity of anthracene, pyrene and coronene as cathode materials for AIBs.
d) Rate capability of anthracene. e) Capacity retention and coulombic efficiency of anthracene at 100 mA g 1. f) Adsorption structure for C14H10[AlCl4]2.
Reproduced with permission.[74] Copyright 2021, Wiley-VCH.

electrochemical properties of PAHs systems, they can be 3.4. Organic frameworks

considered for battery design according to specific require-
ments. Inspired by the large conjugated π bond of graphite, 3.4.1. Covalent organic frameworks
Kong et al.[74] constructed a reversible AIBs based on novel
organic PAHs. Seven PAHs with small conjugated system Covalent organic frameworks (COFs) have become an attractive
(including benzene (C6H6), naphthalene (C10H8), anthracene research topic because of their potential applications in many
(C14H10), pyrene (C16H10), perylene (C20H12), benzo(g,h,i)perylene fields. COFs have different compositions and structures, which
(C22H12) and coronene (C24H12)) were selected as the research can be accurately prepared by carefully naming them.[106] COFs
objects. With the increase of the number of benzene rings in are a new class of crystalline porous materials with a large
PAHs, the theoretical specific capacity generally shows a number of π-conjugated frameworks, abundant pores and
negative correlation (Figure 18b). Electrochemical tests show crystalline polymer frameworks. These characteristics make this
that anthracene exhibits excellent electrochemical performance. kind of polymer a promising material for energy storage and
The discharge specific capacity of anthracene can reach electrochemical applications.[107,108] Compared with conventional
143 mAh g 1 at 100 mA g 1 (Figure 18c). At 500 mA g 1, the polymers, two-dimensional (2D) conjugated polymers such as
anthracene electrode still maintained the discharge capacity of COFs usually have high surface area and porous structure, so
82 mAh g 1. After 800 cycles, the battery capacity can still be they usually exhibit high activity in metal ion batteries and have
maintained at 130 mAh g 1 (Figure 18d,e). The theoretical been used as electrode materials for various metal ion
calculation and in situ Raman characterization results show that batteries.[109,110] Different structures of COFs also affect the
the energy storage mechanism of anthracene as RAIBs cathode performance of metal ion batteries.[111]
material is based on the plane adsorption interaction between Lu et al.[75] synthesized a highly crystalline framework
anthracene molecule and AlCl4 (Figure 18f). The main active TpBpy-COF with a typical two-dimensional hexagonal layered
sites are the conjugated π bond and γ C H bond in the network (Figure 19a). The COFs–Al battery showed an ultra-long
molecular structure of anthracene. cycle life of 13000 cycles at 2 A g 1 (Figure 19b). It also shows
excellent rate capability with a specific capacity of 113 mAh g 1
at 5 A g 1 (Figure 19c). The chemical stability of this COF

Figure 19. a) Schematic representation of the synthesis route of TpBpy-COF. b) GCD capacities of the COFs Al battery in 0.01–2.3 V. c) Rate performance of
TpBpy-COF. Reproduced with permission.[75] Copyright 2020, Wiley-VCH. d) Preparation procedure of NPC. e) Galvanostatic cycling of NPC. f) Detailed GCD
curves of NPC at different cycles (5000 mA g 1). Reproduced with permission.[76] Copyright 2019, American Chemical Society.

material makes it resistant to Lewis acid electrolyte corrosion 3.4.2. Metal–organic frameworks
and improves long-term stability. In addition, regular intercon-
nected porous channels and huge conjugated structures can Metal-organic frameworks (MOFs) are a kind of unique coordi-
promote the transfer of electrons and AlCl4 ions (Figure 20a), nation polymers composed of organic ligands and metal ions.
thus greatly accelerating the kinetics of electrochemical reac- They have the advantages of composition designability, struc-
tions. The large surface area of TpBpy-COF (1794 m2 g 1) tural diversity, high specific surface area and high porosity, and
supports the pseudo-capacitance characteristics, that is, the are widely used as electrodes in the fields of electrochemistry
material experiencing the capacitance-dominated behavior and catalysis.[113] Zeolitic imidazolate frameworks (ZIFs) are a
exhibits excellent rate performance due to the rapid capaci- kind of porous crystal material. MOF porous composites
tance response. Benefit from the unique structure of COF, commonly used in RAIBs cathode are derived from ZIF-67. ZIF-
Zhang et al.[76] used nitrogen-rich COF-JLU2 (Hydrazine-1,3,5- 67 is a Co-MOFs compound with rich carbon and a three-
triformylphloroglucinol copolymer)[112] as the precursor to dimensional topological structure. Some people call it “original
prepare COF-derived nitrogen-doped porous carbon (NPC) material” or “sacrificial material”,[114] because it is generally used
(Figure 19d) for potassium ion batteries and aluminum batteries as a self-sacrificial template to prepare inorganic compounds,
by simple carbonization. As the cathode of RAIBs, it still resulting in carbon-rich polyhedron composites.[115] Reasonable
provides 83 mAh g 1 discharge capacity even after 30000 cycles structure design, polymerization and carbon coating can
(Figure 19e), and its charge-discharge curves almost overlap significantly improve the electrochemical performance of small
during the ultralong cycle (Figure 19f). NPC is synthesized by organic molecules. Rigid and expanded MOF structures can
simple self-template carbonization, which is low cost and easy solve the problems of high solubility and poor stability of small
to be produced on a large scale. The porous structure as the organic molecules.
interconnect channel can promote high electrolyte permeabil- Guo et al.[77] believed that 2D copper-based MOF with
ity, larger interlayer spacing to promote the transfer of anion bipolar ligand was an ideal candidate for RAIBs cathode.
AlCl4 , thereby improving the electrochemical performance. The Organic ligands in 2D Cu-based MOFs are bipolar and can store
uniform distribution of N in NPC can alter the electronic anions or cations. High density active Cu sites in 2D Cu-based
structure, thereby activating electron transport, increasing MOFs can also store more aluminum-complex ions to obtain
conductivity and electrochemical reactions. higher capacity. The interlayer distance of the 2D Cu-based
MOF was calculated to be � 1.3 nm (Figure 21a), which was
sufficient to accommodate large-size chloraluminate ions. The
ultra-thin microchip structure provides a more open channel for
electrolyte permeation and ion diffusion and promotes the
effective utilization of multiple active centers (Figure 21b). Al-
MOF battery based on AlCl3/[EMIm]Cl electrolyte is constructed
with 2D copper-based MOF as cathode and aluminum foil as
anode (Figure 21d). High electron/ionic conductivity is a
necessary prerequisite for efficient and maximum utilization of
all redox active sites. The 2D copper-based MOF was optimized
by in situ coating reduction graphene oxide (rGO), and the
electronic conductivity and structural stability were improved.
The maximum reversible capacity of 2D Cu-based MOF@rGO
composites is 184 mAh g 1 at 50 mA g 1 (Figure 21e). During the
charging/discharging process, the bipolar ligand in 2D Cu-
based MOF can realize the alternating storage of AlCl4 anion
and AlCl2 + cation (Figure 21c, Figure 20b). Both the experimen-
tal results and the first-principles calculations reveal a six-
electron transfer process in the charge-discharge process,
namely, a three-step redox reaction, and two-electron transfer
in each step. In the discharge process, AlCl4 anion was first
removed from the ligand of MOF structure (from 16π to 18π
electrons), and then AlCl2 + cation was inserted into the same
ligand (from 18π to 20π electrons), and AlCl2 + cation was
adsorbed on the Cu site of Cu2(AC)4 cluster (from CuII to CuI).
Reversible reactions occur during charging.
It is desirable to construct ordered hierarchical porous
structures while maintaining their overall crystalline order, but
it is still a formidable challenge. Hong et al.[116] successfully
Figure 20. Aluminum storage reaction of a) TpBpy-COF and b) 2D Cu-based realized the growth of single crystal MOFs in the pores of three-
MOF. dimensional (3D) ordered macroporous template through the

Figure 21. a) Synthesis of 2D Cu-based MOF. b) SEM image of 2D Cu-based MOF. c) Representation of the charge-storage mechanism of 2D Cu-based MOF. d)
Schematic illustration of the Al-MOF battery. e) Charge-discharge profiles of organic monomer, 2D Cu-based MOF, and 2D Cu-based MOF@rGO electrodes.
Reproduced with permission.[77] Copyright 2022, Wiley-VCH. f) Synthesis routine of 3DOM CoSe2@C. g) Schematic of the working mechanism for rechargeable
Al/3DOM CoSe2@C Cell. Reproduced with permission.[116] Copyright 2019, American Chemical Society. h) The synthetic process of MOFs-Co3(PO4)2@C from ZIF-
67. Reproduced with permission.[113] Copyright 2019, Wiley-VCH.

dual solvent-assisted strategy based on saturated solution, and macroporous structure can not only effectively promote the
accurately controlled the nucleation process. The prepared diffusion of large-scale chloraluminate anions, but also increase
single-crystal ordered macro-microporous cobalt-based MOFs the contact area with the electrolyte (Figure 21g), and provide
(SOM ZIF-67) exhibit ordered large microporous structures with more exposed active sites, thus showing excellent reversible
solid single-crystal properties. In addition, 3D-ordered macro- rate capacity (86 mAh g 1 at 5.0 A g 1) and remarkable cycle
porous cobalt diselenide@carbon (3DOM CoSe2@C) can be performance (125 mAh g 1 after 1000 cycles at 2.0 A g 1).
obtained by simple carbonization-selenium treatment using Many researchers used the polyhedron skeleton structure of
SOM ZIF-67 as a precursor (Figure 21f). The derived 3DOM MOF to improve the conductivity of the material by carbon-
CoSe2@C can well retain the 3D ordered macroporous structure ization, and the electrode material obtained by selenization and
of the precursor. More importantly, CoSe2 nanoparticles can be tellurization showed excellent performance in aluminum
uniformly confined in the conductive ordered macroporous batteries.[114,115,117–123] The storage of aluminum in such MOF-
carbon framework, providing regular interconnected macro- derived cathode is based on the transformation-alloying
porous channels and large surface areas. Therefore, when reaction mechanism, which is significantly different from the
evaluated as the cathode material of RAIBs, the ordered previously reported transformation or intercalation energy

storage mechanism in AIBs. Co3(PO4)2@C composite with porous redistribution of aluminum complex ions. Organic functional
tunnel structure derived from ZIF-67 was carefully designed by groups as reaction centers should have high polar and
Li et al.[113] As the cathode of RAIBs, MOFs-derived Co3(PO4)2@C symmetric geometry, such as two adjacent phenanthrenequi-
composite showed increased active sites, high ion mobility and none groups.[65] Cyano group (C � N) is a typical strong polar
high Al3 + ion diffusion coefficient, resulting in enhanced structure. Figure 23a–c showed three organic compounds
discharge-charge redox reaction kinetics. The carbon shell and containing cyanide (i. e. tetracyanoethylene (TCNE), tetrakis (4-
porous structure act as armor to reduce volume change and cyanophenyl)methane (TCPM), and tetracyanoquinodimethane
maintain structural integrity of the cathode. Ultrafine (TCNQ)). TCNQ with high conductivity (1.53 × 10 3 S m 1) was
Co3(PO4)2@C nanoparticles with tunnel structure are embedded selected as the best cyanide organic cathode material by Guo
in hollow carbon capsules (Figure 21h). The designed MOFs- et al.[78] The intrinsic electron-deficient cyano group shows
derived Co3(PO4)2@C species have large pore volume greater electron affinity, which is easy to be reduced and then
(0.37 cm3 g 1) and high surface area (132 m2 g 1), which can be reversibly coordinated/dissociated with positively charged
provide enough transmission paths for Al3 + insertion and more aluminum complex cations in the electrolyte. The lower binding
active sites for electrochemical reactions. The initial capacity of energy (~E) of coordinating with AlCl2 + cations for cyano-
Co3(PO4)2@C hybrid was 171 mAh g 1 and remained at organic molecules illustrates that the cyano-organic molecule is
151 mAh g 1 after 500 cycles at 1 A g 1. prone to combine with AlCl2 + cation (Figure 23d,e). TCNQ
shows a maximum discharge capacity of 115 mAh g 1 and a
high plateau of 1.4 V at 500 mA g 1 (Figure 23f). To overcome
3.5. Other organic cathodes the dissolution problem of organic molecules, the acetylene
black modified separator (ABMS) was used to alleviate the
Other organic compounds can also realize the storage of shuttle effect of TCNQ and its intermediates during charge and
AlClx(3 x) ions, such as tetracyanoquinodimethane (TCNQ), discharge. The battery using TCNQ + ABMS showed a high
amine, and phenazine (PZ), tetrachloro-1,4-benzoquinone reversible capacity of 115 mAh g 1 after 2000 cycles (Fig-
(TCQ), 9,10-anthraquinone (AQ). Their aluminum storage reac- ure 23g). The TCNQ-based compounds can be chemically
tions are shown in Figure 22. absorbed on the ABMS, which effectively avoids the transfer of
soluble compounds from the positive region to the negative
region.
3.5.1. Cyano-based organic molecules

The electrochemical combination of aluminum complex ions 3.5.2. Copper phthalocyanine

with active groups is more difficult when compared with the
coordination of free metal ions because the charge distribution When AlCl3/[EMIm]Cl is used as the ionic liquid electrolyte, in
is uneven and the ion volume is large, which limits the charge order to achieve coulombic efficiency greater than 96 %, the

Figure 22. Aluminum storage reactions of other organic cathode materials. a) TCNQ, b) Amine, c) PZ, d) TCQ, e) AQ.

Figure 23. Chemical structures of a) TCNE, b) TCPM, and c) TCNQ. d) The binding energy (ΔE) of TCNE, TCNQ and TCPM molecules with possible ions in AlCl3/
[EMIm]Cl electrolyte. e) Simulated redox mechanism of TCNQ in the aluminum batteries using DFT. f) GCD curves for TCNE, TCNQ and TCPM. g) Cycling
performance of TCNQ in the Al batteries. Reproduced with permission.[78] Copyright 2020, Elsevier.

cut-off charging voltage of aluminum-graphite battery is recent years due to their low cost and high safety. However, the
generally set to 2.45 V, which is close to the decomposition application of organic electrodes in aqueous aluminum-ion
voltage of electrolyte. Once overcharged, the electrolyte will batteries (AABs) is rarely reported. Most of the positive materials
produce H2.[8] (some researchers said that this process produces for AABs are inorganic materials (e. g., ultrathin graphite
Cl2 (4 AlCl4 + 2 e !2 Al2Cl7 + Cl2)[12,124,125]). The generation of nanosheets,[126] AlxMnO2·n H2O,[127] Bir-MnO2,[128] α-MnO2.[129]).
these unwanted gases poses a certain safety hazard, which These materials usually realize the typical insertion/desertion
undoubtedly limits the practical application of large-scale mechanism of Al3 +. However, the strong electrostatic force
energy storage devices such as soft-package batteries. Bian between Al3 + and host materials usually leads to slow
et al.[79] prepared a new cathode material by adding the organic dynamics, poor reversibility and poor cycling stability. Com-
compound copper phthalocyanine (CuPc) to the graphite pared with the inorganic cathodes, the weak van der Waals
cathode, which effectively increased the working potential force of organic materials allows high valence ions such as Al3 +
window to 2.82 V (vs. Al/Al3 +), improved the protection of the to migrate rapidly through the lattice with low resistance.
battery during overcharge, and also slowed down the inflation. Chen et al.[81] proposed a highly rechargeable aqueous
At 320 mA g 1, the Al CuPc@Graphite battery shows a capacity aluminum-organic battery system based on phenazine (PZ)
of 110 mAh g 1, while the Al Graphite battery provides a cathode. The aluminum trifluoromethanesulfonate (Al(OTF)3)
capacity of 90 mAh g 1. Although the addition of CuPc increases electrolyte is stable without any side reactions between 0.1 and
the voltage window, the possible oxidation of CuPc in the 2.3 V vs. Al/Al3 + (Figure 24a). CV curve shows that the PZ
composite cathode will lead to a decrease in coulombic exhibits a pair of symmetrical cathode/anode peaks at 0.43/
efficiency, reduce reversibility and affect the cycle life of the 0.75 V, indicating that the electrochemical intercalation/ dein-
batteries. tercalation of carrier ions is completely reversible during one-
step ion absorption process (Figure 24b), which is also corre-
sponding to the charge-discharge curve (Figure 24c). After 300
3.5.3. Organic cathodes for aqueous electrolyte cycles, PZ electrode remained at a specific capacity of
101 mAh g 1 at 50 mA g 1 (Figure 24e). This excellent cycling
The electrolytes used in the above RAIBs are ionic liquids, and stability is attributed to the minimum structural change,
the use conditions of ionic liquids are harsh. Compared with conjugated system and inherent flexibility of PZ organic
aluminum metal batteries using ionic liquids electrolytes, molecules, which can maintain their integrity during electro-
aqueous aluminum metal batteries (AAMBs) using water-based chemical reactions. PZ exhibits high capacity and stable Al3 +
electrolytes have attracted more and more research interest in storage capacity. It is found that the C=N of PZ acts as the

Figure 24. Electrochemical characterization of PZ-based AABs. a) Electrochemical window of electrolyte. b) CV curves of PZ at 0.1 mV s < M < 1. c) GCD curves of
PZ at various current densities. d) Most possible structure of reduced product according to calculations. e) Cycling performance of PZ. Reproduced with
permission.[81] Copyright 2020, Wiley-VCH. f) Schematic illustration of fabricated aqueous Al-quinone batteries. g) GCD curves for aqueous Al C4Q battery. h)
Comparison of rate performance between reported AABs. Reproduced with permission.[82] Copyright 2021, Wiley-VCH.

active center to allow the reversible intercalation/deintercala- groups. In the discharge process, Al(OTF)2 + cations can
tion of large-sized Al(OTF)2 + ions during charge and discharge. coordinate with the carbonyl group of C4Q to reduce the
Al3 + and (OTF) were combined to form Al(OTF)2 +, and desolvation penalty. Compared with other AABs, Al C4Q
Al(OTF)2 + residues bridged a pair of nitrogen atoms from two batteries have a good rate capability among other AABs
ligands in the whole cage structure to form a relatively stable (Figure 24h).
structure of the reduction product (Figure 24d). The C=N of Tetrachloro-1,4-benzoquinone (TCQ) contains two carbonyl
PZ undergoes a reversible redox reaction with Al(OTF)2 + groups and four chlorine groups. He et al.[83] reported that TCQ
intercalation transfer. Li et al.[82] selected six polyoxoquinone is an excellent cathode for organic AAMBs for the first time.
compounds (1,4-naphthoquinone (1,4-NQ), 1,2-naphthoquinone Due to the strong electron attraction of chlorine groups, TCQ
(1,2-NQ), 9,10-anthraquinone (9,10-AQ), phenanthrenequinone will reduce the electron density of carbon atomic rings and
(9,10-PQ), pyrene-4,5,9,10-tetraone (PTO), and ensure the high electrochemical activity of carbonyl groups.
calix[4]quinone(C4Q)) as cathode materials (Figure 24f). Among TCQ was reduced to tetrachlorohydroquinone by accepting two
these compounds, large ring cup quinone (C4Q) has large holes electrons during discharge. The coordinated Al3 + replaced the
and multiple adjacent carbonyl structures, showing the highest hydroxyl hydrogen atom. In the charging process, the cathode
capacity of 400 mAh g 1 and lower polarization (42 mV) at will release the inserted Al3 +, and the tetrachlorohydroquinone
100 mA g 1 (Figure 24g). Compared with 9,10-AQ and 1,4-NQ, will be oxidized back to TCQ due to the loss of two electrons
compounds with adjacent carbonyl groups (9,10-PQ, 1,2-NQ, (Figure 25a,b). The CV curves of Al/TCQ battery at different
PTO, and C4Q) exhibit higher voltage and lower overpotential scanning rates are symmetrical indicating that the charge and
due to the intramolecular chelation of adjacent carbonyl groups discharge process of Al/TCQ battery corresponds to a reversible
with polyvalent cations. The large ring C4Q can bind ions or electrochemical reaction. The GCD curve of TCQ showed a high
molecules to its large cavity and is easier to coordinate with capacity of 147.7 mAh g 1 at 0.2 A g 1. After 200 cycles at
multivalent ions, thus improving the utilization rate of carbonyl 2 A g 1, the capacity retention rate was 70.7 % and the

Figure 25. a) Structure illustration of TCQ. b) Schematic diagram of the structure transformation of TCQ in the electrochemical process. c) GCD curves of TCQ
at various current densities. d) Cycling performance of the Al//TCQ battery. Reproduced with permission.[83] Copyright 2021, The Royal Society of Chemistry. e)
CV curves of AQ and K2CuFe(CN)6 and electrochemical windows of 1 m Al2(SO4)3. f) Schematic drawing of the reversible work mechanism in the novel rocking-
chair aqueous aluminum-ion battery. g) Cycling performance of AQ-K2CuFe(CN)6. h) Charge–discharge curves of AQ-K2CuFe(CN)6. Reproduced with
permission.[84] Copyright 2021, American Chemical Society.

coulombic efficiency was close to 100 % (Figure 25c,d). Yan K2CuFe(CN)6, resulting in a low discharge capacity of
et al.[84] reported an innovative AAIB system for all AQ/ 53.2 mAh g 1 (Figure 25g). The low coulombic efficiency in the
K2CuFe(CN)6 batteries. In the first two half-cell reactions of the first cycle is due to the removal of K + in K2CuFe(CN)6 during
three-electrode system, using 1 M Al2(SO4)3 as the electrolyte, charging (Figure 25h).
two kinds of active materials showed different performances
(Figure 25e). The discharge capacity of AQ at 1000 mA g 1 was
167.7 mAh g 1, and that of K2CuFe(CN)6 at 500 mA g 1 was 4. Summary and Outlook
44.1 mAh g 1. In the AQ/K2CuFe(CN)6 full-cell, due to the
hydrolysis of Al3 + in the electrolyte, the solution is acidic, so the As a new type of energy storage system in the post-lithium era,
protons in the solution will affect the electrochemical behavior rechargeable aluminum-ion batteries (RAIBs) have attracted
of AQ: when charged, protons assist the complex decomposi- extensive research. At present, in the research of many cathode
tion reaction between AQ and Al3 + to make AQ combine with materials for RAIBs, organic electrode materials (OEMs) have
Al3 +, and the large space between AQ molecules in the lattice is attracted more and more attention due to their rich source of
conducive to the diffusion of protons and Al3 +; during elements and flexible structural design. In this work, the
discharge, Al3 + is inserted into K2CuFe(CN)6. The three-dimen- research progress of organic cathodes in RAIBs is introduced.
sional open skeleton and secondary structure of K2CuFe(CN)6 The aluminum storage mechanisms of organic cathode materi-
are conducive to the diffusion of Al3 + (Figure 25f), which makes als for RAIBs are reviewed, including conducting polymers (CPs),
the rocking-chair Al3 + battery possible. The open framework carbonyl compounds (COCs), imine polymers (IPs), polycyclic
structure of K2CuFe(CN)6 Prussian white and the unique aromatic hydrocarbons (PAHs), covalent organic frameworks
coordination charge storage mechanism of AQ ensure the rapid (COFs), or metal-organic frameworks (MOFs). The p-type
reaction kinetics. However, due to the sufficient capacity of AQ, cathode materials such as CPs usually exhibit high working
the capacity of the whole battery depends on the cathode potential, and AlCl4 anions are combined to store ions in

RAIBs. The working potential of n-type cathode materials such and separator modification. The strong corrosion effect of ionic
as COCs or IPs is low, which is coordinated with AlCl2 + or AlCl2 + liquids on organic materials may also be improved by adding
in the electrolyte. As a new type of organic electrode, PAHs also certain additives to ionic liquids, or developing low-corrosivity
show ideal potential. Organic frameworks such as COFs and electrolytes.[19,130,131] The development of solid electrolytes can
MOFs can also store ions due to their porous structures; the also alleviate the dissolution problem of OEMs and improve
application of organic electrodes in aqueous aluminum bat- cycle stability.
teries also illustrates the universal application of organic A new type of organic electrode needs to be developed.
electrodes, so OEMs have great potential in energy storage. Through the evaluation of OEMs, some organic compounds
However, battery systems are usually evaluated by three containing specific atoms (C, H, O, N, P, S, etc.) can be
main parameters: energy density, power density, and cycle life. theoretically calculated to assess the feasibility of storing ions in
In order to meet the superior performance of the battery organic materials. Polymerize organic compounds and combine
system, there is still a lot of work to be done: (1) Improve them with other materials to improve the stability of organic
energy density: The energy density of the battery depends on electrodes. Looking for suitable organic cathode materials and
its output voltage and capacity. Increasing the output voltage assembling Al-organic batteries is expected to improve the
will help to achieve high energy density. In order to achieve energy density and power density of RAIBs, prolong their life,
high output voltage, cathode materials with high working promote the development of the electric vehicle industry, save
potential and anode materials with low working potential are fossil energy and contribute to environmental protection.
expected. p-Type organic materials such as conductive poly-
mers usually show high working potential; in contrast, n-type
organic materials such as carbonyl compounds and imine Acknowledgements
polymers usually exhibit lower working potential. The introduc-
tion of electron-withdrawing groups and electron-donating This work was financially supported by the National Natural
groups is a common method to regulate the working potential Science Foundation of China (Granted No. 51777152) and the
of organic materials because these groups can regulate the Natural Science Foundation of Shaanxi Province (Granted No.
energy level of the lowest unoccupied molecular orbital 2021JZ-01, 2021JQ-019).
(LUMO). A low LUMO level means high electron affinity,
resulting in high working potential.[29] In general, a flat
discharge plateau is conducive to achieving stable voltage Conflict of Interest
output. OEMs are generally composed of light elements and
therefore have a low tap density, which reduces the volumetric The authors declare no conflict of interest.
energy density of the battery. Higher theoretical capacity can
be obtained by designing organic materials with more redox Keywords: batteries · cathodes · energy storage mechanisms ·
active sites and lower molecular weight. In general, small organic electrode materials · rechargeable aluminum-ion
organic materials help to improve their practical capabilities. batteries
However, as the size of active materials decreases, the
dissolution problem may become more serious, so self-polymer-
ization or graft polymerization of small organic molecules will
reduce the dissolution problem to a certain extent. In addition, [1] G. A. Elia, K. V. Kravchyk, M. V. Kovalenko, J. Chacon, A. Holland, R. G. A.
due to the low electronic conductivity of most organic Wills, J. Power Sources 2021, 481, 228870.
materials, more carbon additives with excellent conductivity [2] F. Fu, X. Liu, X. Fu, H. Chen, L. Huang, J. Fan, J. Le, Q. Wang, W. Yang, Y.
Ren, K. Amine, S. G. Sun, G. L. Xu, Nat. Commun. 2022, 13, 2826.
will help to release higher actual capacity. However, a high [3] F. Yuan, W. Zhang, D. Zhang, Q. Wang, Z. Li, W. Li, H. Sun, Y. Wu, B.
proportion of carbon additives will inevitably reduce the energy Wang, Nanoscale 2021, 13, 5965.
density of the entire battery. Therefore, it is possible to find [4] M. Wang, W. Lu, H. Zhang, X. Li, Trans. Tianjin Univ. 2020, 27, 1.
[5] M. M. Huie, D. C. Bock, E. S. Takeuchi, A. C. Marschilok, K. J. Takeuchi,
highly conductive organic materials to reduce the ratio of Coord. Chem. Rev. 2015, 287, 15.
conductive additives. (2) Improve power density: Output [6] N. Kuperman, P. Padigi, G. Goncher, D. Evans, J. Thiebes, R. Solanki, J.
voltage and rate capability determine the power density of the Power Sources 2017, 342, 414.
[7] K. Ghanbari, M. F. Mousavi, M. Sharnsipur, H. Karami, J. Power Sources
battery. The high conjugation degree of organic molecules can 2007, 170, 513.
promote electron transfer and achieve good rate performance. [8] M. C. Lin, M. Gong, B. Lu, Y. Wu, D. Y. Wang, M. Guan, M. Angell, C.
In addition to the structure of organic molecules, their specific Chen, J. Yang, B. J. Hwang, H. Dai, Nature 2015, 520, 325.
[9] X. Y. Zhao, S. H. Ren, M. Bruns, M. Fichtner, J. Power Sources 2014, 245,
surface area and the addition of conductive substrate also have 706.
a great influence on the rate performance. High surface area [10] M. A. Nowroozi, I. Mohammad, P. Molaiyan, K. Wissel, A. R. Munnangi,
contributes to sufficient electrolyte penetration and rapid O. Clemens, J. Mater. Chem. A. 2021, 9, 5980.
[11] Y. Q. Du, B. Y. Zhang, W. Y. Zhang, H. X. Jin, J. Y. Qin, J. Q. Wan, J. X.
electron and ion diffusion, resulting in high rate capability. (3) Zhang, G. W. Chen, Energy Storage Mater. 2021, 38, 231.
Improve cycle life: The cycle life of the battery depends largely [12] J. Y. Shi, J. Zhang, J. Guo, ACS Energy Lett. 2019, 4, 2124.
on the stability of the electrode material in the electrolyte. The [13] Y. Song, S. Q. Jiao, J. G. Tu, J. X. Wang, Y. J. Liu, H. D. Jiao, X. H. Mao,
Z. C. Guo, D. J. Fray, J. Mater. Chem. A. 2017, 5, 1282.
solubility of OEMs in electrolyte can be reduced by organic [14] G. A. Elia, J. B. Ducros, D. Sotta, V. Delhorbe, A. Brun, K. Marquardt, R.
small molecule polymerization, positive electrode adsorption Hahn, ACS Appl. Mater. Interfaces 2017, 9, 38381.

[15] S. Wang, K. V. Kravchyk, A. N. Filippin, U. Muller, A. N. Tiwari, S. [52] D. Kong, H. Fan, X. Ding, D. Wang, S. Tian, H. Hu, D. Du, Y. Li, X. Gao, H.
Buecheler, M. I. Bodnarchuk, M. V. Kovalenko, Adv. Sci. 2018, 5, Hu, Q. Xue, Z. Yan, H. Ren, W. Xing, ACS Appl. Mater. Interfaces 2020,
1700712. 12, 46065.
[16] L. L. Chen, W. L. Song, N. Li, H. Jiao, X. Han, Y. Luo, M. Wang, H. Chen, [53] J. Zhang, Y. Wu, M. Liu, L. Huang, Y. Li, Y. Wu, Angew. Chem. Int. Ed.
S. Jiao, D. Fang, Adv. Mater. 2020, 32, 2001212. 2022, e202215408; Angew. Chem. 2022, e202215408.
[17] B. Craig, T. Schoetz, A. Cruden, C. P. de Leon, Renew. Sust. Energ Rev. [54] V. Raju, J. V. Rani, P. Basak, Electrochim. Acta 2020, 361, 137097.
2020, 133, 110100. [55] V. Raju, Y. V. N. Kumar, V. R. Jetti, P. Basak, ACS Appl. Energ. Mater.
[18] T. Mandai, P. Johansson, J. Mater. Chem. A. 2015, 3, 12230. 2021, 4, 9227.
[19] H. Wang, S. Gu, Y. Bai, S. Chen, F. Wu, C. Wu, ACS Appl. Mater. Interfaces [56] T. Schoetz, B. Craig, C. P. de Leon, A. Bund, M. Ueda, C. T. J. Low, J.
2016, 8, 27444. Energy Storage 2020, 28, 101176.
[20] Z. J. Yu, S. Q. Jiao, J. G. Tu, W. L. Song, H. P. Lei, H. D. Jiao, H. S. Chen, [57] M. Walter, K. V. Kravchyk, C. Bofer, R. Widmer, M. V. Kovalenko, Adv.
D. N. Fang, J. Mater. Chem. A. 2019, 7, 20348. Mater. 2018, 30, 1705644.
[21] J. V. Rani, V. Kanakaiah, T. Dadmal, M. S. Rao, S. Bhavanarushi, J. [58] N. S. Hudak, J. Phys. Chem. C 2014, 118, 5203.
Electrochem. Soc. 2013, 160, A1781. [59] T. Li, H. Hu, T. Cai, X. Liu, Y. Zhang, L. Zhao, W. Xing, Z. Yan, ACS Appl.
[22] D. Y. Wang, C. Y. Wei, M. C. Lin, C. J. Pan, H. L. Chou, H. A. Chen, M. Mater. Interfaces 2022, 14, 30927.
Gong, Y. Wu, C. Yuan, M. Angell, Y. J. Hsieh, Y. H. Chen, C. Y. Wen, C. W. [60] Z. Yang, X. Huang, P. Meng, M. Jiang, Y. Wang, Z. Yao, J. Zhang, B. Sun,
Chen, B. J. Hwang, C. C. Chen, H. Dai, Nat. Commun. 2017, 8, 14283. C. Fu, Angew. Chem. Int. Ed. 2022, e202216797; Angew. Chem. 2022,
[23] W. Wang, B. Jiang, W. Xiong, H. Sun, Z. Lin, L. Hu, J. Tu, J. Hou, H. Zhu, e202216797.
S. Jiao, Sci. Rep. 2013, 3, 3383. [61] N. Lindahl, J. Bitenc, R. Dominko, P. Johansson, Adv. Funct. Mater. 2020,
[24] Y. Hu, B. Luo, D. Ye, X. Zhu, M. Lyu, L. Wang, Adv. Mater. 2017, 29, 30, 2004573.
1006132. [62] L. M. Zhou, Z. H. Zhang, L. M. Cui, F. Y. Xiong, Q. Y. An, Z. Zhou, X. F.
[25] G. Cohn, L. Ma, L. A. Archer, J. Power Sources 2015, 283, 416. Yu, P. K. Chu, K. Zhang, Cell Rep. Phys. Sci. 2021, 2, 100354.
[26] L. H. Shen, X. F. Du, M. B. Ma, S. X. Wang, S. Huang, L. L. Xiong, Adv. [63] Y. J. Wang, K. L. Ng, G. Azimi, Batteries & Supercaps 2022, 5,
Sustainable Syst. 2022, 6, 2100418. e202200182.
[27] T. Gao, X. Li, X. Wang, J. Hu, F. Han, X. Fan, L. Suo, A. J. Pearse, S. B. Lee, [64] G. Wu, C. Lv, W. Lv, X. Li, W. Zhang, Z. Li, J. Energy Chem. 2022, 74, 174.
G. W. Rubloff, K. J. Gaskell, M. Noked, C. Wang, Angew. Chem. Int. Ed. [65] D. J. Kim, D.-J. Yoo, M. T. Otley, A. Prokofjevs, C. Pezzato, M. Owczarek,
2016, 55, 9898; Angew. Chem. 2016, 128, 10052. S. J. Lee, J. W. Choi, J. F. Stoddart, Nat. Energy 2018, 4, 51.
[28] J. J. Shea, C. Luo, ACS Appl. Mater. Interfaces 2020, 12, 5361. [66] M. L. Mao, Z. Yu, Z. J. Lin, Y. S. Hu, H. Li, X. J. Huang, L. Q. Chen, M. Liu,
[29] Y. Lu, Q. Zhang, L. Li, Z. Q. Niu, J. Chen, Chem 2018, 4, 2786. L. M. Suo, J. Mater. Chem. A. 2020, 8, 23834.
[30] M. E. Bhosale, S. Chae, J. M. Kim, J. Y. Choi, J. Mater. Chem. A. 2018, 6, [67] D. J. Yoo, M. Heeney, F. Glocklhofer, J. W. Choi, Nat. Commun. 2021, 12,
19885. 2386.
[31] Q. Zhao, Y. Lu, J. Chen, Adv. Energy Mater. 2017, 7, 1601792. [68] L. Fang, L. M. Zhou, L. M. Cui, P. X. Jiao, Q. Y. An, K. Zhang, J. Energy
[32] S. Lee, G. Kwon, K. Ku, K. Yoon, S. K. Jung, H. D. Lim, K. Kang, Adv. Chem. 2021, 63, 320.
Mater. 2018, 30, 1704682. [69] M. Mao, C. Luo, T. P. Pollard, S. Hou, T. Gao, X. Fan, C. Cui, J. Yue, Y.
[33] J. Bitenc, N. Lindahl, A. Vizintin, M. E. Abdelhamid, R. Dominko, P. Tong, G. Yang, T. Deng, M. Zhang, J. Ma, L. Suo, O. Borodin, C. Wang,
Johansson, Energy Storage Mater. 2020, 24, 379. Angew. Chem. Int. Ed. 2019, 58, 17820; Angew. Chem. 2019, 131, 17984.
[34] J. Xie, Q. Zhang, Small 2019, 15, 1805061. [70] X. Han, S. J. Li, W. L. Song, N. Chen, H. S. Chen, S. Y. Huang, S. Q. Jiao,
[35] W. R. Du, X. F. Du, M. B. Ma, S. Huang, X. F. Sun, L. L. Xiong, Adv. Funct. Adv. Energy Mater. 2021, 11, 2101446.
Mater. 2022, 32, 2110871. [71] J. W. Zhou, X. Z. Yu, J. Zhou, B. G. Lu, Energy Storage Mater. 2020, 31,
[36] Y. N. Chen, W. Luo, M. Carter, L. H. Zhou, J. Q. Dai, K. Fu, S. Lacey, T. Li, 58.
J. Y. Wan, X. G. Han, Y. P. Bao, L. B. Hu, Nano Energy 2015, 18, 205. [72] X. Fan, F. Wang, X. Ji, R. Wang, T. Gao, S. Hou, J. Chen, T. Deng, X. Li, L.
[37] B. F. Pan, J. H. Huang, Z. X. Feng, L. Zeng, M. N. He, L. Zhang, J. T. Chen, C. Luo, L. Wang, C. Wang, Angew. Chem. Int. Ed. 2018, 57, 7146;
Vaughey, M. J. Bedzyk, P. Fenter, Z. C. Zhang, A. K. Burrell, C. Liao, Adv. Angew. Chem. 2018, 130, 7264.
Energy Mater. 2016, 6, 1600140. [73] K. Q. Qin, S. Tan, M. Mohammadiroudbari, Z. Z. Yang, X. Q. Yang, E. Y.
[38] H. Cui, L. Ma, Z. Huang, Z. Chen, C. Zhi, SmartMat 2022, 1. Hu, C. Luo, Nano Energy 2022, 101, 107554.
[39] P. He, Q. Chen, M. Y. Yan, X. Xu, L. Zhou, L. Q. Mai, C. W. Nan, [74] D. Kong, T. Cai, H. Fan, H. Hu, X. Wang, Y. Cui, D. Wang, Y. Wang, H. Hu,
EnergyChem 2019, 1, 100022. M. Wu, Q. Xue, Z. Yan, X. Li, L. Zhao, W. Xing, Angew. Chem. Int. Ed.
[40] X. Wang, G. Li, Y. Han, F. Wang, J. Chu, T. Cai, B. Wang, Z. Song, 2022, 61, e202114681; Angew. Chem. 2022, 134, e202114681.
ChemSusChem 2021, 14, 3174. [75] H. Lu, F. Ning, R. Jin, C. Teng, Y. Wang, K. Xi, D. Zhou, G. Xue,
[41] Z. H. Yang, F. Wang, P. Y. Meng, J. Y. Luo, C. P. Fu, Energy Storage ChemSusChem 2020, 13, 3447.
Mater. 2022, 51, 63. [76] Q. Zhang, H. Wei, L. Wang, J. Wang, L. Fan, H. Ding, J. Lei, X. Yu, B. Lu,
[42] A. Morag, M. H. Yu, J. Mater. Chem. A. 2021, 9, 19317. ACS Appl. Mater. Interfaces 2019, 11, 44352.
[43] C. J. Pan, C. Yuan, G. Zhu, Q. Zhang, C. J. Huang, M. C. Lin, M. Angell, [77] Y. Guo, W. Wang, H. Lei, M. Wang, S. Jiao, Adv. Mater. 2022, 34,
B. J. Hwang, P. Kaghazchi, H. Dai, Proc. Natl. Acad. Sci. USA 2018, 115, e2110109.
5670. [78] F. Guo, Z. Huang, M. Y. Wang, W. L. Song, A. J. Lv, X. Han, J. G. Tu, S. Q.
[44] Y. T. Kao, S. B. Patil, C. Y. An, S. K. Huang, J. C. Lin, T. S. Lee, Y. C. Lee, Jiao, Energy Storage Mater. 2020, 33, 250.
H. L. Chou, C. W. Chen, Y. J. Chang, Y. H. Lai, D. Y. Wang, ACS Appl. [79] Y. H. Bian, L. Su, Z. C. Yu, Z. C. Lv, H. Chen, Y. Zhou, C. Meng, H. P. Du,
Mater. Interfaces 2020, 12, 25853. M. Cai, H. N. Cao, M. C. Lin, Electrochim. Acta 2020, 332, 135188.
[45] J. S. Meng, L. J. Zhu, A. B. Haruna, K. I. Ozoemena, Q. Q. Pang, Sci. China [80] G. Wang, E. Dmitrieva, B. Kohn, U. Scheler, Y. Liu, V. Tkachova, L. Yang,
Chem. 2021, 64, 1888. Y. Fu, J. Ma, P. Zhang, F. Wang, J. Ge, X. Feng, Angew. Chem. Int. Ed.
[46] L. M. Zheng, H. Y. Yang, Y. Bai, C. A. Wu, J. Energy Chem. 2021, 60, 229. 2022, 61, e202116194; Angew. Chem. 2022, 134, e202116194.
[47] X. Peng, Y. Xie, A. Baktash, J. Tang, T. Lin, X. Huang, Y. Hu, Z. Jia, D. J. [81] J. Chen, Q. Zhu, L. Jiang, R. Liu, Y. Yang, M. Tang, J. Wang, H. Wang, L.
Searles, Y. Yamauchi, L. Wang, B. Luo, Angew. Chem. Int. Ed. 2022, 61, Guo, Angew. Chem. Int. Ed. 2021, 60, 5794; Angew. Chem. 2021, 133,
e202203646; Angew. Chem. 2022, 134, e202203646. 5858.
[48] S. Wang, S. Huang, M. Yao, Y. Zhang, Z. Niu, Angew. Chem. Int. Ed. [82] Y. X. Li, L. J. Liu, Y. Lu, R. J. Shi, Y. L. Ma, Z. H. Yan, K. Zhang, J. Chen,
2020, 59, 11800; Angew. Chem. 2020, 132, 11898. Adv. Funct. Mater. 2021, 31, 2102063.
[49] Y. F. Liao, D. D. Wang, X. J. Li, S. Tian, H. Y. Hu, D. Q. Kong, T. H. Cai, [83] J. He, X. Shi, C. Wang, H. Zhang, X. Liu, Z. Yang, X. Lu, Chem. Commun.
P. C. Dai, H. Ren, H. Hu, Y. P. Li, Q. Z. Xue, Z. F. Yan, X. L. Gao, W. Xing, J. 2021, 57, 6931.
Power Sources 2020, 477, 228702. [84] L. Yan, X. Zeng, S. Zhao, W. Jiang, Z. Li, X. Gao, T. Liu, Z. Ji, T. Ma, M.
[50] D. D. Wang, H. Y. Hu, Y. F. Liao, D. Q. Kong, T. H. Cai, X. L. Gao, H. Hu, Ling, C. Liang, ACS Appl. Mater. Interfaces 2021, 13, 8353.
M. B. Wu, Q. Z. Xue, Z. F. Yan, H. Ren, W. Xing, Sci. China Mater. 2021, [85] S. Sariyer, A. Ghosh, S. N. Dambasan, E. M. Halim, M. El Rhazi, H. Perrot,
64, 318. O. Sel, R. Demir-Cakan, ACS Appl. Mater. Interfaces 2022, 14, 8508.
[51] S. M. Zhao, H. X. Chen, J. L. Li, J. X. Zhang, New J. Chem. 2019, 43, [86] P. Meng, J. Huang, Z. Yang, F. Wang, T. Lv, J. Zhang, C. Fu, W. Xiao,
15014. Adv. Mater. 2022, 34, e2106511.

[87] C. Zhang, X. Kong, W. Liu, J. Yang, H. Zhao, Polym. Test. 2021, 101, [114] K. Zhang, T. H. Lee, J. H. Cha, H. W. Jang, J. W. Choi, M. Mahmoudi, M.
107299. Shokouhimehr, Sci. Rep. 2019, 9, 13739.
[88] T. Schoetz, C. P. de Leon, A. Bund, M. Ueda, Electrochem. Commun. [115] L. J. Kong, M. Liu, H. Huang, Y. H. Xu, X. H. Bu, Adv. Energy Mater. 2022,
2018, 89, 52. 12, 2100172.
[89] T. Schoetz, C. P. de Leon, A. Bund, M. Ueda, Electrochim. Acta 2018, [116] H. Hong, J. Liu, H. Huang, C. Atangana Etogo, X. Yang, B. Guan, L.
263, 176. Zhang, J. Am. Chem. Soc. 2019, 141, 14764.
[90] T. Schoetz, M. Ueda, A. Bund, C. P. de Leon, J. Solid State Electrochem. [117] W. Xing, D. F. Du, T. H. Cai, X. C. Li, J. Zhou, Y. M. Chai, Q. Z. Xue, Z. F.
2017, 21, 3237. Yan, J. Power Sources 2018, 401, 6.
[91] R. Liu, S. B. Lee, J. Am. Chem. Soc. 2008, 130, 2942. [118] T. H. Cai, L. M. Zhao, H. Y. Hu, T. G. Li, X. C. Li, S. Guo, Y. P. Li, Q. Z. Xue,
[92] B. Craig, C. K. Skylaris, T. Schoetz, C. P. de Leon, Energy Rep. 2020, 6, W. Xing, Z. F. Yan, L. Z. Wang, Energy Environ. Sci. 2018, 11, 2341.
198. [119] X. Xiao, M. Y. Wang, J. G. Tu, Y. W. Luo, S. Q. Jiao, ACS Sustainable
[93] J. T. Sun, C. Liu, H. L. Wang, Y. Cao, X. P. Han, S. J. Zhang, H. P. Wang, Chem. Eng. 2019, 7, 16200.
Y. M. Zhang, A. B. Chen, Z. X. Yang, J. Sun, ACS Appl. Energ. Mater. [120] C. X. Li, S. H. Dong, R. Tang, X. L. Ge, Z. W. Zhang, C. X. Wang, Y. P. Lu,
2021, 4, 4112. L. W. Yin, Energy Environ. Sci. 2018, 11, 3201.
[94] J. John, M. Manoj, A. Abhilash, S. Jayalekshmi, Ionics 2021, 27, 1733. [121] B. Zhang, Y. Zhang, J. L. Li, J. Liu, X. G. Huo, F. Y. Kang, J. Mater. Chem.
[95] O. Folorunso, Y. Hamam, R. Sadiku, S. S. Ray, G. J. Adekoya, Mater. A. 2020, 8, 5535.
Today: Proc. 2021, 38, 635. [122] J. J. Li, W. M. Liu, Z. Z. Yu, J. Q. Deng, S. K. Zhong, Q. Xiao, F. M. Chen,
[96] C. Y. Wu, P. H. Kuo, J. G. Duh, Surf. Coat. Technol. 2021, 421, 127418. D. L. Yan, Electrochim. Acta 2021, 370, 137790.
[97] Q. F. Meng, K. F. Cai, Y. X. Chen, L. D. Chen, Nano Energy 2017, 36, 268. [123] Z. Li, W. Lv, G. Wu, X. Li, X. Wang, W. Zhang, Chem. Eng. J. 2022, 430,
[98] S. Khan, A. Majid, R. Raza, J. Mater. Sci. Mater. Electron. 2020, 31, 13597. 133135.
[99] L. W. Shacklette, R. L. Elsenbaumer, R. R. Chance, J. M. Sowa, D. M. [124] P. K. Lai, M. Skyllas-Kazacos, J. Electroanal. Chem. Interfacial Electro-
Ivory, G. G. Miller, R. H. Baughman, J. Chem. Soc. Chem. Commun. 1982, chem. 1988, 248, 431.
361. [125] T. Jiang, M. J. Chollier Brym, G. Dubé, A. Lasia, G. M. Brisard, Surf. Coat.
[100] V. M. Kobryanskii, S. A. Arnautov, J. Chem. Soc. Chem. Commun. 1992, Technol. 2006, 201, 1.
727. [126] F. Wang, F. Yu, X. Wang, Z. Chang, L. Fu, Y. Zhu, Z. Wen, Y. Wu, W.
[101] D. J. Yoo, J. W. Choi, J. Phys. Chem. Lett. 2020, 11, 2384. Huang, ACS Appl. Mater. Interfaces 2016, 8, 9022.
[102] F. Wu, H. Yang, Y. Bai, C. Wu, Adv. Mater. 2019, 31, 1806510. [127] C. Wu, S. Gu, Q. Zhang, Y. Bai, M. Li, Y. Yuan, H. Wang, X. Liu, Y. Yuan,
[103] R. B. Cang, Y. P. Song, K. Ye, K. Zhu, J. Yan, J. L. Yin, G. L. Wang, D. X. N. Zhu, F. Wu, H. Li, L. Gu, J. Lu, Nat. Commun. 2019, 10, 73.
Cao, J. Electroanal. Chem. 2020, 861, 113967. [128] S. M. He, J. Wang, X. Zhang, J. Z. Chen, Z. C. Wang, T. T. Yang, Z. W. Liu,
[104] I. A. Rodriguez-Perez, C. Bommier, D. D. Fuller, D. P. Leonard, A. G. Y. Liang, B. Y. Wang, S. Q. Liu, L. Q. Zhang, J. Y. Huang, J. Huang, L. A.
Williams, X. Ji, ACS Appl. Mater. Interfaces 2018, 10, 43311. O’Dell, H. J. Yu, Adv. Funct. Mater. 2019, 29, 1905228.
[105] S. Das, P. Bhauriyal, B. Pathak, J. Phys. Chem. C 2020, 125, 49. [129] Q. Zhao, M. J. Zachman, W. I. Al Sadat, J. Zheng, L. F. Kourkoutis, L.
[106] S. B. Alahakoon, C. M. Thompson, G. Occhialini, R. A. Smaldone, Archer, Sci. Adv. 2018, 4, eaau8131.
ChemSusChem 2017, 10, 2116. [130] C. Li, J. Patra, J. Li, P. C. Rath, M. H. Lin, J. K. Chang, Adv. Funct. Mater.
[107] D. G. Wang, T. J. Qiu, W. H. Guo, Z. B. Liang, H. Tabassum, D. G. Xia, 2020, 30, 1909565.
R. Q. Zou, Energy Environ. Sci. 2021, 14, 688. [131] S. Das, S. S. Manna, B. Pathak, ACS Omega 2021, 6, 1043.
[108] K. Zhang, K. O. Kirlikovali, R. S. Varma, Z. Jin, H. W. Jang, O. K. Farha, M.
Shokouhimehr, ACS Appl. Mater. Interfaces 2020, 12, 27821.
[109] Z. Wang, W. Jin, X. Huang, G. Lu, Y. Li, Chem. Rec. 2020, 20, 1198.
[110] X. D. Chen, W. W. Sun, Y. Wang, ChemElectroChem 2020, 7, 3905.
[111] Y. Lu, Y. Cai, Q. Zhang, J. Chen, J. Phys. Chem. Lett. 2021, 12, 8061.
[112] Z. Li, Y. Zhi, X. Feng, X. Ding, Y. Zou, X. Liu, Y. Mu, Chem. Eur. J. 2015, Manuscript received: December 19, 2022
21, 12079. Revised manuscript received: January 21, 2023
[113] C. Li, S. Dong, P. Wang, C. Wang, L. Yin, Adv. Energy Mater. 2019, 9, Accepted manuscript online: February 2, 2023
1902352. Version of record online: March 21, 2023

Main Challenges Faced by Anode Materials of SIBs
No ratings yet
Main Challenges Faced by Anode Materials of SIBs
22 pages
1 s2.0 S2590049821000199 Main
No ratings yet
1 s2.0 S2590049821000199 Main
19 pages
Innovations in Beyond Lithium-Ion Batteries
No ratings yet
Innovations in Beyond Lithium-Ion Batteries
3 pages
Advances and Challenges in Metal Sulfides Selenides For Next Generation Rechargeable
No ratings yet
Advances and Challenges in Metal Sulfides Selenides For Next Generation Rechargeable
24 pages
ChemistrySelect - 2023 - Verma
No ratings yet
ChemistrySelect - 2023 - Verma
11 pages
Metal Sulfides in Sodium Ion Batteries
No ratings yet
Metal Sulfides in Sodium Ion Batteries
20 pages
Advanced Anode Materials for SIBs
100% (1)
Advanced Anode Materials for SIBs
33 pages
Nonaqueous Aluminum-Ion Batteries Review
No ratings yet
Nonaqueous Aluminum-Ion Batteries Review
2 pages
Critical Insights on Aluminum-Ion Batteries
No ratings yet
Critical Insights on Aluminum-Ion Batteries
6 pages
Carbon Materials for Zinc Anodes in AZIBs
No ratings yet
Carbon Materials for Zinc Anodes in AZIBs
19 pages
Sodium-Ion Batteries: Materials & Mechanisms
No ratings yet
Sodium-Ion Batteries: Materials & Mechanisms
50 pages
Ca (PF6) 2 at RT
No ratings yet
Ca (PF6) 2 at RT
6 pages
Re-Aluminum Batteries Unique Potentials and Addressing Key Challenges in Energy Storage
No ratings yet
Re-Aluminum Batteries Unique Potentials and Addressing Key Challenges in Energy Storage
16 pages
Re-Aluminum Batteries Unique Potentials and Addressing Key Challenges in Energy Storage
No ratings yet
Re-Aluminum Batteries Unique Potentials and Addressing Key Challenges in Energy Storage
16 pages
Advancements in Aluminium-Ion Batteries
No ratings yet
Advancements in Aluminium-Ion Batteries
27 pages
Advances in Mn-based Sodium Ion Cathodes
No ratings yet
Advances in Mn-based Sodium Ion Cathodes
12 pages
Calcium Ion Battery Anode Chemistry Review
No ratings yet
Calcium Ion Battery Anode Chemistry Review
15 pages
JCU 54399 Gummow Et Al 2018 Accepted
No ratings yet
JCU 54399 Gummow Et Al 2018 Accepted
39 pages
Organic Electrode Materials for SIBs
No ratings yet
Organic Electrode Materials for SIBs
22 pages
Advances in Aqueous Zinc-Ion Batteries
No ratings yet
Advances in Aqueous Zinc-Ion Batteries
22 pages
Advances in Aluminum-Sulfur Batteries
No ratings yet
Advances in Aluminum-Sulfur Batteries
22 pages
High-Performance 2D Anodes for Batteries
No ratings yet
High-Performance 2D Anodes for Batteries
12 pages
High-Capacity Bi@C Anode for Batteries
No ratings yet
High-Capacity Bi@C Anode for Batteries
8 pages
Electrochemical Performance of MgNiO2 Supercapacitors
No ratings yet
Electrochemical Performance of MgNiO2 Supercapacitors
10 pages
Sn-based Anodes for Sodium-ion Batteries
No ratings yet
Sn-based Anodes for Sodium-ion Batteries
24 pages
Si2BN Nanosheets for Mg-Ion Battery Anodes
No ratings yet
Si2BN Nanosheets for Mg-Ion Battery Anodes
9 pages
Aluminium-Ion Battery - Wikipedia
No ratings yet
Aluminium-Ion Battery - Wikipedia
62 pages
Sodium-Ion Battery Electrode Materials
No ratings yet
Sodium-Ion Battery Electrode Materials
9 pages
Sodium-Ion Battery Innovations 2024
No ratings yet
Sodium-Ion Battery Innovations 2024
6 pages
Small - 2019 - Liu - Recent Progress of Layered Transition Metal Oxide Cathodes For Sodium Ion Batteries
No ratings yet
Small - 2019 - Liu - Recent Progress of Layered Transition Metal Oxide Cathodes For Sodium Ion Batteries
24 pages
Recent Advances in NASICON Type Oxide Electrolytes For Solid State Sodium Ion Rechargeable Batteries
No ratings yet
Recent Advances in NASICON Type Oxide Electrolytes For Solid State Sodium Ion Rechargeable Batteries
31 pages
Zheng Et Al 2017 Crystal Structures and Electrochemical Performance of Air Stable Na2 3ni1 3 Xcuxmn2 3o2 in Sodium Cells
No ratings yet
Zheng Et Al 2017 Crystal Structures and Electrochemical Performance of Air Stable Na2 3ni1 3 Xcuxmn2 3o2 in Sodium Cells
9 pages
Anie 202011144
No ratings yet
Anie 202011144
7 pages
Practical Assessment of The Performance of Aluminium Battery Technologies
No ratings yet
Practical Assessment of The Performance of Aluminium Battery Technologies
9 pages
Reliable Cathode Materials for Aluminum-Ion Batteries
No ratings yet
Reliable Cathode Materials for Aluminum-Ion Batteries
18 pages
High-Performance Na-Based Dual-Ion Battery
No ratings yet
High-Performance Na-Based Dual-Ion Battery
9 pages
Materials Chemistry A: Journal of
No ratings yet
Materials Chemistry A: Journal of
9 pages
1 s2.0 S0079642524001622 Main
No ratings yet
1 s2.0 S0079642524001622 Main
53 pages
Metal Phosphide Anodes in Sodium Ion Batteries Latest Applications and Progress
No ratings yet
Metal Phosphide Anodes in Sodium Ion Batteries Latest Applications and Progress
26 pages
Advanced Energy Materials - 2024 - Yao - Prussian Blue Analogues For Aqueous Sodium Ion Batteries Progress and
No ratings yet
Advanced Energy Materials - 2024 - Yao - Prussian Blue Analogues For Aqueous Sodium Ion Batteries Progress and
21 pages
Aluminum Anodes in Energy Storage Batteries
No ratings yet
Aluminum Anodes in Energy Storage Batteries
10 pages
Aluminum Anodes in Energy Storage
No ratings yet
Aluminum Anodes in Energy Storage
10 pages
Adv Funct Materials - 2023 - Li - Developing Cathode Materials For Aqueous Zinc Ion Batteries Challenges and Practical
No ratings yet
Adv Funct Materials - 2023 - Li - Developing Cathode Materials For Aqueous Zinc Ion Batteries Challenges and Practical
26 pages
High Efficiency Aluminum-Ion Battery
No ratings yet
High Efficiency Aluminum-Ion Battery
6 pages
Review-Practical Issues and Future Perspective For Na-Ion Batteries
No ratings yet
Review-Practical Issues and Future Perspective For Na-Ion Batteries
13 pages
E9419 IranArze
No ratings yet
E9419 IranArze
68 pages
Nanotechnology Engineering of Polyanionic
No ratings yet
Nanotechnology Engineering of Polyanionic
35 pages
Na-Rich Oxyfluoride for Sodium Batteries
No ratings yet
Na-Rich Oxyfluoride for Sodium Batteries
8 pages
Zinc-Ion Battery Electrolyte Strategies
No ratings yet
Zinc-Ion Battery Electrolyte Strategies
19 pages
Acs Jpclett 0c00324
No ratings yet
Acs Jpclett 0c00324
9 pages
Zinc/Sodium Battery with Na2SO4 Additive
No ratings yet
Zinc/Sodium Battery with Na2SO4 Additive
10 pages
Batteries 11 00061
No ratings yet
Batteries 11 00061
25 pages
Aqueous Rechargeable Lithium Batteries
No ratings yet
Aqueous Rechargeable Lithium Batteries
9 pages
Materials: Chemistry
No ratings yet
Materials: Chemistry
30 pages
Novel Aluminum-Ion Battery Design
No ratings yet
Novel Aluminum-Ion Battery Design
3 pages
Novel Na-Ion Battery Cathode Design
No ratings yet
Novel Na-Ion Battery Cathode Design
11 pages
Manganese P2-Type Oxides for Na-Ion Batteries
No ratings yet
Manganese P2-Type Oxides for Na-Ion Batteries
16 pages
Astm A923 PDF
No ratings yet
Astm A923 PDF
10 pages
Blinking LED with Raspberry Pi Guide
No ratings yet
Blinking LED with Raspberry Pi Guide
7 pages
Understanding Electrolysis: Key Concepts
No ratings yet
Understanding Electrolysis: Key Concepts
32 pages
Corrosion in Pharmaceutical Engineering
No ratings yet
Corrosion in Pharmaceutical Engineering
11 pages
Measuring Tungsten Work Function
50% (2)
Measuring Tungsten Work Function
3 pages
Power Diodes and Thyristors Overview
No ratings yet
Power Diodes and Thyristors Overview
7 pages
Home Automation with Arduino Nano
No ratings yet
Home Automation with Arduino Nano
38 pages
Chemical Effects of Electric Current Notes
No ratings yet
Chemical Effects of Electric Current Notes
8 pages
Electrochemical Series in Reactions
No ratings yet
Electrochemical Series in Reactions
47 pages
Nernst Equation for Daniel Cell Explained
No ratings yet
Nernst Equation for Daniel Cell Explained
2 pages
Rainwater Conductivity and Electrolysis
No ratings yet
Rainwater Conductivity and Electrolysis
2 pages
Sensors and Energy Systems Overview
No ratings yet
Sensors and Energy Systems Overview
15 pages
IGCSE Chemistry ATP Study Guide
No ratings yet
IGCSE Chemistry ATP Study Guide
25 pages
Engineering Materials Question Paper 2022
No ratings yet
Engineering Materials Question Paper 2022
18 pages
NEET Electrochemistry Study Notes
No ratings yet
NEET Electrochemistry Study Notes
8 pages
Intruder Detector Design Project
No ratings yet
Intruder Detector Design Project
49 pages
Types and Applications of Electrodes
No ratings yet
Types and Applications of Electrodes
16 pages
Acsami 1c17341
No ratings yet
Acsami 1c17341
11 pages
J. Phys. D-Appl. Phys.-Coexistence of Bipolar and Threshold Resistive Switching in TiO2 Based Structure With Embedded Hafnium Nanoparticles
No ratings yet
J. Phys. D-Appl. Phys.-Coexistence of Bipolar and Threshold Resistive Switching in TiO2 Based Structure With Embedded Hafnium Nanoparticles
11 pages
Electrochemistry MCQs for 12th Grade
No ratings yet
Electrochemistry MCQs for 12th Grade
7 pages
Understanding Electrical Circuits and Components
No ratings yet
Understanding Electrical Circuits and Components
7 pages
NCERT Solutions For Class 12 Chemistry Part 1 Chapter 3
No ratings yet
NCERT Solutions For Class 12 Chemistry Part 1 Chapter 3
23 pages
Thomson's Cathode Ray Experiments
No ratings yet
Thomson's Cathode Ray Experiments
17 pages
Understanding Standard Electrode Potential
No ratings yet
Understanding Standard Electrode Potential
12 pages
NEET Electrochemistry Class 12 Notes
No ratings yet
NEET Electrochemistry Class 12 Notes
17 pages
Vimal Jyothi Engineering College: Micro-Nano Manufacturing Syllabus
No ratings yet
Vimal Jyothi Engineering College: Micro-Nano Manufacturing Syllabus
59 pages
LTC4015-Based Li-ion Charger Design
No ratings yet
LTC4015-Based Li-ion Charger Design
50 pages
X-ray Tube Components and Functions
No ratings yet
X-ray Tube Components and Functions
8 pages
Li-ion vs NiCd Battery Comparison
No ratings yet
Li-ion vs NiCd Battery Comparison
19 pages
Corrosion Resistant Distributor Training
No ratings yet
Corrosion Resistant Distributor Training
43 pages

Organic Cathodes for Aluminum-Ion Batteries

Uploaded by

Organic Cathodes for Aluminum-Ion Batteries

Uploaded by

Review

ChemSusChem 2023, 16, e202202358 (1 of 33) © 2023 Wiley-VCH GmbH

1. Introduction is generally ionic liquid. Although ionic liquid electrolyte is

ChemSusChem 2023, 16, e202202358 (2 of 33) © 2023 Wiley-VCH GmbH

Table 1. A comparison of different metal anodes.

Li 1 6.941 0.534 3861 2062 0.002 3.05

Xianfeng Du is a professor of the School of

ChemSusChem 2023, 16, e202202358 (3 of 33) © 2023 Wiley-VCH GmbH

through functional groups (Figure 1). PAHs and COFs usually

3. Research Progress of Aluminum-Organic

3.1. Conductive polymers

The most notable p-type organic cathode material is CPs, so it

ChemSusChem 2023, 16, e202202358 (4 of 33) © 2023 Wiley-VCH GmbH

8 : 1 : 1 (AM/car- Whatman Swagelok- 140/100

glass fiber 200/1000

ChemSusChem 2023, 16, e202202358 (5 of 33)

bon black/PVDF) 934-AH cells 75.5/500/5000

5 : 4 : 1 (AM/CB/ Whatman Custom-

Poly(nitropyrene-co- 5 : 4 : 1 (AM/CB/ Whatman custom- ~ 85/1000/200

© 2023 Wiley-VCH GmbH

ChemSusChem 2023, 16, e202202358 (6 of 33)

6 : 3 : 1 (AM/CB/ Whatman Swagelok- 165/0.5 C

© 2023 Wiley-VCH GmbH

[EMIm][AlCl4]/ 3 : 5 : 2 (AM/Denka Whatman Swagelok- 110/100 82/200/200

ChemSusChem 2023, 16, e202202358 (7 of 33)

© 2023 Wiley-VCH GmbH

ChemSusChem 2023, 16, e202202358 (8 of 33)

© 2023 Wiley-VCH GmbH

ChemSusChem 2023, 16, e202202358 (9 of 33)

© 2023 Wiley-VCH GmbH

ChemSusChem 2023, 16, e202202358 (10 of 33)

8 : 1 : 1 (AM/ W or car- 136/50

7 : 2 : 1 (AM/car- glass fiber CR2032 coin 132/50

© 2023 Wiley-VCH GmbH

grew orderly on the surface of mesoporous carbon (Figure 4a),

120 mAh g 1 can be obtained at 1000 mA g 1. The synergistic

increase the conductivity. The self-regulation of the polyaniline

capacity of 121 mAh g 1, long cycle life of 5000 cycles (Fig-

ure 4b). PANI with special morphology increases the interface

between PANI and electrolyte, resulting in the effective

utilization of active sites of PANI and good rate performance.

The combination of PANI and OMC effectively improves the

dedoped with anions (e. g. AlCl4 ), thus obtaining excellent

cyclic stability. Protonated PANI(H +)@SWCNT composite mem-

arranged in a cross shape, showing a porous network structure

(Figure 4c). Because of protonation, more NH + active sites

can be obtained, thus PANI(H +)@SWCNT electrode shows a

stronger redox peak than PANI@SWCNT cathode (Figure 4d).

Therefore, the discharge capacity of Al/PANI(H +) battery is twice

that of the initial composite film. PANI(H +)@SWCNT electrode

(Figure 4e). The structure of PANI(H +)@SWCNT not only facili-

ion diffusion. With the increase of protonation time, the

quinone rings were further converted into benzene rings, and

the crystallinity of PANI was improved due to the structural

trode materials exhibits reversible AlCl2 + intercalation/deinter-

show that AlCl4 prefers to combine with the hydrogen atom of

rather than forming chemical bonds. Wang et al.[50] in situ

3.1.2. Polythiophene and derivatives

Polythiophene (PTh) is a common long chain polymer con-

materials and CPs have good electrical/electrochemical proper-

ties and dimensional stability. Zhao et al.[51] synthesized poly-

ChemSusChem 2023, 16, e202202358 (11 of 33) © 2023 Wiley-VCH GmbH

ChemSusChem 2023, 16, e202202358 (12 of 33) © 2023 Wiley-VCH GmbH

ChemSusChem 2023, 16, e202202358 (13 of 33) © 2023 Wiley-VCH GmbH

ChemSusChem 2023, 16, e202202358 (14 of 33) © 2023 Wiley-VCH GmbH

ChemSusChem 2023, 16, e202202358 (15 of 33) © 2023 Wiley-VCH GmbH

ChemSusChem 2023, 16, e202202358 (16 of 33) © 2023 Wiley-VCH GmbH

ChemSusChem 2023, 16, e202202358 (17 of 33) © 2023 Wiley-VCH GmbH

ChemSusChem 2023, 16, e202202358 (18 of 33) © 2023 Wiley-VCH GmbH

ChemSusChem 2023, 16, e202202358 (19 of 33) © 2023 Wiley-VCH GmbH

ChemSusChem 2023, 16, e202202358 (20 of 33) © 2023 Wiley-VCH GmbH

ChemSusChem 2023, 16, e202202358 (21 of 33) © 2023 Wiley-VCH GmbH

ChemSusChem 2023, 16, e202202358 (22 of 33) © 2023 Wiley-VCH GmbH

ChemSusChem 2023, 16, e202202358 (23 of 33) © 2023 Wiley-VCH GmbH

electrochemical properties of PAHs systems, they can be 3.4. Organic frameworks

ChemSusChem 2023, 16, e202202358 (24 of 33) © 2023 Wiley-VCH GmbH