Review Article

Cite This: J. Phys. Chem. C 2017, 121, 27775−27787 [Link]/JPCC

Silicon Anode Design for Lithium-Ion Batteries: Progress and

Perspectives
Alba Franco Gonzalez,∥,†,‡ Nai-Hsuan Yang,∥,† and Ru-Shi Liu*,†,§
†
Department of Chemistry, National Taiwan University, Taipei 106, Taiwan
‡
School of Chemistry, The University of Edinburgh, King’s Buildings, Edinburgh EH9 3JJ, U.K.
§
Department of Mechanical Engineering and Graduate Institute of Manufacturing Technology, National Taipei University of
Technology, Taipei 106, Taiwan

ABSTRACT: Silicon has long been regarded as a prospective

anode material for lithium-ion batteries. However, its huge
volumetric changes during cycling are a major obstacle to its
commercialization, as these changes result in irreversible cracking
and disconnection of the active mass from the current collector,
as well as an excessive formation of a highly resistive solid
electrolyte interphase. Multiple mechanical stress relief strategies
that primarily use silicon nanostructurization have been
previously developed. However, despite the significant improve-
ments on the active material cycle life, using nanomaterials still
results in complications, such as low conductivity, reduced
volumetric energy density, and increased side reactions. This
work provides a historical context for the development of silicon
anodes and focuses on the surface chemistry and structural
integrity of the electrode, thereby highlighting the most effective strategies reported recently for their optimization.

1. INTRODUCTION ions intercalate reversibly between the graphite layers in a ratio

Improved energy storage systems are necessary to meet the of one lithium per six carbons, as represented by eq 1:
increasing global energy demand, which fluctuates daily and Li + 6C → LiC6 (1)
seasonally.1−3 Furthermore, the broadened environmental
awareness has popularized electric vehicles and expanded The opposite processes occur spontaneously during
renewable energies, which are limited by the intermittent discharge, and the stored energy is released by lithium
energy production of their sources.2 Finally, the development of deintercalation and graphite oxidation. The anode is the
portable electronic devices and the increased dependency on electrode where oxidation occurs, and the cathode is where
these gadgets have reinforced the need for improved energy reduction occurs. However, these definitions would cause the
and power densities without compromising safety and costs.2−6 electrodes to alternate names during the charge and discharge
Rechargeable lithium-ion batteries (LIBs) have been widely cycles, and thus for practical purposes, the electrodes are
used in portable electronics in the past two decades and are conventionally labeled with their role during the discharge
promising candidates for fulfilling the requirements for future cycle.
renewable energy storage grids, as well as for replacing To achieve increased energy densities, the intercalation
petroleum fuels for automotive applications.2,3,7−11 chemistry of graphite must be replaced by anode materials that
At present, the storage capacity of commercial LIBs is limited are capable of electrochemically alloying with lithium.9,19
by electrode materials.8 In particular, the maximum theoretical Among these materials, silicon has the highest gravimetric
gravimetric capacity of the conventional graphite anode is only capacity of 4200 mAh g−1, which corresponds to the formation
372 mAh g−1, which is a conservative figure compared with of the amorphous Li22Si5, as shown in eq 2.5,20 However, X-ray
3800 mAh g−1 obtained from using lithium metal as the diffraction studies by Obrovac and Christensen21 suggested that
anode.11−16 Safety concerns regarding dendrite growth over the the reaction at room temperature undergoes a lower level of
charge−discharge cycles make lithium metal anodes an lithiation, corresponding to eq 3 and to a theoretical capacity of
infeasible alternative for rechargeable batteries. Nevertheless, 3579 mAh g−1.11,22 This biphasic lithiation has since been
replacing the anode with a material of improved theoretical
capacity is still needed.8,15−17 Received: August 5, 2017
LIBs function via a “Rocking Chair” mechanism.18 During Revised: October 30, 2017
the charge cycle, the graphite electrode is reduced, and lithium Published: November 15, 2017

© 2017 American Chemical Society 27775 DOI: 10.1021/[Link].7b07793

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Figure 1. Schematic of morphological changes occurring in bulk silicon upon electrochemical cycling. Enormous volumetric changes cause high
mechanical strain, which in turn leads to cracking and disconnection from the current collector.

Figure 2. Schematic of SEI formation occurring at the surface of silicon upon electrochemical cycling. A thin SEI forms upon charging on the
expanded state of lithiated silicon. During discharge, silicon’s volume decreases, forcing the SEI to break into separate pieces and exposing the fresh
silicon surface to the electrolyte. More SEI is then formed on the following charge cycles, and this recurrent process eventually leads to an excessively
thick SEI surrounding the electrode.

confirmed by multiple in situ transition electron microscopy Both mechanical and chemical degradations, along with the
(TEM) studies.23,24 intrinsically low conductivity of silicon, comprise the key issues
that lead to the poor cycling performance of this anode and
22Li + 5Si → Li 22Si5 (2) hamper its commercialization as a new-generation LIB.
Subsequently, advances have been reported and follow three
15Li + 4Si → Li15Si4 (3) main strategies, namely, improving the mechanical properties of
the electrode, enhancing the chemical stability of the
Silicon possesses other desirable qualities, such as being the electrode−electrolyte interphase, and increasing its conductiv-
second most abundant element in the Earth’s crust, cost- ity. This review will illustrate the main approaches in the
effective, and environmentally benign.25 Additionally, silicon literature and bridge the gap between structural and chemical
has a low electrochemical potential between 0.37 and 0.45 V knowledge.
versus Li/Li+, which is 0.27 V higher than graphite but still
provides an ample cell voltage on coupling with a 2. STRATEGIES FOR ENHANCED PERFORMANCE
cathode.19,26,27 Despite multiple advantages, the commercializa-
tion of silicon-based anode LIBs is being hindered by its poor This section highlights the most heavily investigated methods
cycling performance, wherein the failure mechanism is largely for enhancing the performance of silicon anodes in Li-ion
attributed to the severe volumetric expansion (∼300%−400%) batteries. We grouped these strategies into six categories as
of this material that occurs during lithium insertion.4,7,8,17 As a listed in Figure 3: nanostructures, porous structures, unusual
result, the mechanical strain within the active mass increases, designs, composites, SEI formation, and binders.
thereby leading to the cracking and pulverization of silicon and 2.1. Nanostructures. The mechanical strain relief attained
disconnection from the current collector, as displayed in Figure by using nanostructures marked the largest breakthrough in the
1.1,28,29 cycle life of silicon anodes. Particles under a critical size can
In addition, the interphase between the anode and electrolyte withstand large volume variations without cracking.17,34 More
is critically affected by volume changes.7 The low working specifically, the first in situ TEM study on silicon cells
potential of the anode, which is comparable to that of lithium- conducted by Liu and Huang23 determined the critical diameter
ion reduction, lies outside the window of stability of most size for the prevention of nanoparticle fracture to be 150 nm, as
common electrolytes.30 During the first charge cycle or silicon illustrated in Figure 4. Hence, silicon nanostructures with
lithiation, the reduction of both salts and solvents of the multiple morphologies have been designed, including nano-
electrolyte at the silicon surface produces a solid layer called powders, nanotubes, nanofibers, nanorods, nanowires, and
solid electrolyte interphase (SEI).18,31 This film may enhance other nanoporous structures.11,35 However, the large surface
battery performance by passivating the anode reactivity and area of these structures increases side reactions and further
preventing further electrolyte degradation, as is the case with stimulates overgrowth of unnecessary SEI, thereby increasing
conventional graphite LIBs.30,32 However, given the volume the impedance for Li-ion transport and decreasing the capacity
variation exhibited by silicon, the SEI layer often becomes over cycling.30
deformed or breaks, exposing a fresh electrode surface where Silicon nanowires were first synthesized by Chan et al.29
more electrolyte may be reduced during the succeeding charge motivated by previous one-dimensional studies of alternative
cycle, as illustrated in Figure 2.6 This recurrent process anode materials. The nanowire anode reported by this group
consumes lithium and leads to the excessive growth of a displayed astonishing capacities above 3000 mAh g−1, yet this
thick, inhomogeneous, ionically insulating SEI, ultimately capacity was only maintained for 10 cycles at the current rate of
resulting in the battery’s capacity fading.7,30,33 210 mA g−1. There has been little improvement in the field
27776 DOI: 10.1021/[Link].7b07793
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since. In a recent study by Ramesh and Nagaraja36 nanowire

anodes were cycled at a substantially larger rate of 4200 mA
g−1, retaining a capacity of 1134 mAh g−1, but dropped to near
zero values after the 12th cycle. It is speculated that the failure
of nanowires arises from the earlier mentioned excessive SEI
formation, from internal mechanical stress, or from the facile
delamination of the small point of contact of nanowires with
the current collector.37,38
Analysis of the plausible failures of silicon nanowires lead
Quiroga-González et al.38 to optimize the wire size and
geometry, presenting wires with a controversially large diameter
of 1 μm. Until then, the upper limit for wire diameters was
deemed to be 300 nm, yet the novel microwire anode endured
a capacity of 3150 mAh g−1 for 100 cycles with a current rate of
2100 mA g−1.38 Concurrently, nanowire research inspired the
synthesis of nanotubes by Park et al.39 This first nanotube
design integrated carbon as a protective coating, which hampers
its direct correlation to the performance of nanowires. A
subsequent study by Wu et al.6 compared the performance of
double-walled silicon nanotubes (DWSiNTs) to that of
nanowires and nanotubes in the absence of coatings or
Figure 3. Summary of the six most prominent strategies investigated conductive additives. The galvanostatic cycling curves are
to enhance the performance of silicon anodes for Li-ion batteries.
presented in Figure 5, where the capacity of each nanostructure
is plotted as a function of the cycle number. The capacities
retained by these nanotubes are slightly lower than that
obtained through an independent investigation of bare silicon
nanotubes by Song et al.37 which retained a capacity of 2000 by
the 50th cycle under the same current rate. However, the graph
still effectively highlights the difference in the capacities
retained by nanowires, nanotubes, and DWSiNTs. It is worth
noting that the high performance of DWSiNTs is attributed to
the protective SiO2 outer layer, which buffers the excessive
production of the SEI.6
Thin-film anodes are reported with very stable cycling and
high capacities. Takamura et al.40 communicated the synthesis
of a vacuum deposited silicon thin-film which endured 1000
cycles with a reversible capacity above 2000 mAh g−1 at the vast
current rate of 42 000 mA g−1. However, to prevent irreversible
morphological changes such as cracking, the anode size must be
limited. The critical thickness is estimated to be between 100
Figure 4. Size-dependent fracture of Si nanoparticles during lithiation. and 200 nm for amorphous Si in a stainless steel substrate.37,41
(a) Pristine Si nanoparticles with diameters of 80 and 150 nm. (b−d) This size constraint compromises the maximum capacity of the
Lithiation process of the particles. The two phases (crystalline and
anode, so the long cycling with negligible fading of thin films
amorphous) are clearly distinct. (e) The larger particle cracked, while
the smaller remained integral upon full lithiation. Reprinted with cannot be exploited for the creation of viable batteries.37
permission from ref 23. Copyright 2011 The Royal Society of 2.2. Porous Structures. Porous structures work on the
Chemistry. same principle as nanostructures by providing space for the
volume expansion of silicon, thereby relieving mechanical
strain. Porous structures are also particularly effective in

Figure 5. Galvanostatic cycling of double-walled silicon nanotubes, silicon nanotubes, and silicon nanowires between 1 and 0.01 V under a current
rate of 840 mA g−1. Reprinted with permission from ref 6. Copyright 2012 Macmillan Publishers Limited.

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shortening the diffusion pathways for Li ions. A pioneering

process for microporous silicon synthesis involved the
magnesiothermic reduction of silica, as displayed in eq 4,
followed by acid etching for magnesia removal. This method
was first reported by Bao et al.42 and was later replicated by Liu
et al.,43 who exploited agricultural byproducts as the source of
silica.
2Mg(g) + SiO2 (s) → 2MgO(s) + Si(s) (4)

Similarly, several other synthesis methods in the literature

consist of two-step processes. In particular, Kim et al.44 used
thermal annealing of silica followed by etching; Bang et al.45
employed silver deposition on silicon, followed by metal-
assisted chemical etching; and Ge et al.46 obtained the porosity
by ball-milling metallurgical silicon (high in Fe and Al
impurities) with subsequent stain etching. Despite novel
synthesis methods that provide the possibility of tuning particle
and pore sizes, using porous silicon structures on their own Figure 7. Schematic of a pomegranate-inspired design. (a) 3D view
seemed to have reached their electrochemical performance and (b) simplified cross-section view of one pomegranate micro-
limits. To demonstrate this limitation, porous silicon obtained particle before and after electrochemical cycling. Reprinted with
from rice husks by Liu et al.43 displayed a reversible capacity of permission from ref 49. Copyright 2014 Macmillan Publishers Limited.
2650 mAh g−1 after 200 cycles at a rate of 2100 mA g−1.
Another drawback to the use of either porous or nanoma-
terials is that their density is lower than that of raw silicon; thus, in Figure 7, to enhance conductivity and protection toward the
an increased cycle life is attained on account of volumetric electrolyte. The cells retained a considerable capacity of 1160
capacity. Nonetheless, the majority of the investigations to date mAh g−1 for 1000 cycles at a rate of 635 mA g−1.
have exploited the long cycle life of a porous or nanosized The void space design is becoming common, and recent
active mass, complementing it with an experimental coating, studies still use this advantageous feature in developing
binder, or other innovative techniques.47 innovative structures, as did Zhu et al.7 for their flexible silicon
2.3. Unusual Designs. Several ingenious architectures have and graphene/carbon nanofibers. Zhu et al.7 obtained 2002
achieved exceptional results, such as the porous graphitic mAh g−1 for 1050 cycles at a current density of 700 mA g−1.
scaffold in Figure 6 designed by Zhao et al.,48 which maintained 2.4. Composites. The presence of metals may increase the
a capacity of 2656 mAh g−1 after 150 cycles at a current rate of low conductivity of silicon and provide a range of mechanical
1000 mA g−1. This particular structure showed good perform- and chemical properties.50 As a result, many studies have
ance under high current densities and retained a capacity of 600 focused on intermetallic composites involving silver, magne-
mAh g−1 at a rate of 4000 mA g−1 for the same number of sium, calcium, nickel, iron, cobalt, aluminum, copper, tin, and
cycles. titanium, as well as some oxides of these metals.8,50−53 The
Another notable framework was designed using silicon increase in electrical conductivity is most often the aim of these
nanoparticles with carbon coating. Silicon coating has been studies, as composite anodes endure high current rates with a
proposed to enhance conductivity and reduce side reactions by stable capacity retention. For instance, the tin-doped silicon
forming a stable SEI. The pomegranate-inspired example by Liu nanowires designed by Korgel et al.53 maintained a capacity
et al.49 includes a void space between the silicon nanoparticle above 1000 mAh g−1 for 100 cycles at the current rate of 2800
and carbon coating to accommodate the large volume of mA g−1. The significance of this investigation will become
lithiated silicon particles. The coated silicon particles are evident throughout this review, owing to rates above 1500 mA
clustered and coated with a thick layer of carbon, as displayed g−1 being seldom tested on silicon anodes. The combination of
silicon with carbon is also popular due to its softness, high
conductivity, and minimal volumetric change upon lithiation,
thereby demonstrating competitive performance, as illustrated
by the graphene/silicon nanosized sandwich structure designed
by our group.54 However, the individual performance of
reported composites is beyond the scope of this review. The
detailed information on silicon-based composites may be found
in the comprehensive reviews in refs 50−52 and the references
therein.
2.5. Solid Electrolyte Interphase Formation. Some
coatings are designed to recreate naturally formed SEI, albeit
tuning the composition to minimize electrolyte reduction and
Figure 6. Schematic drawing of a section of a composite electrode
enhance electrochemical performance, as illustrated in Figure 8.
material constructed with a graphenic scaffold with in-plane carbon Commonly referred to as an artificially engineered SEI, this
vacancy defects. Silicon nanoparticles (large spheres) are enclosed result is not exclusive to coatings but may also be attained by
between graphene sheets with in-plane vacancy defects, through which adding appropriate solvents, cosolvents, and electrolyte
Li ions (small spheres) may readily diffuse. Reprinted with permission additives.15,35,55 A closely related strategy that may be
from ref 48. Copyright 2011 Wiley. conducted in parallel is using prelithiation, as demonstrated
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Figure 8. Schematic of SEI formation occurring upon electrochemical cycling of silicon coated with an artificially engineered SEI. A thin and stable
SEI forms during the beginning cycles and passivates the reactivity of silicon toward electrolyte reduction.

Figure 9. Schematic of changes occurring in silicon anodes upon electrochemical cycling. (a) The use of nanoparticles alleviates mechanical strain, so
active mass can endure more cycles with little cracking. (b) The use of binders aids to maintain the structural integrity of the anode made of particles.

by Zhao et al.,10 who combined prelithiated silicon with 1- silicon to reduce both the volumetric change and the electrolyte
fluorodecane to produce the artificial SEI. Generally, reduction. The theoretical rationale was successful, and the
prelithiation involves the addition of either lithium or a group obtained an extraordinary cycling life of more than 2000
lithiated compound to the anode to compensate for the cycles at a current density of 600 mA g−1, though this was
irreversible lithium loss during SEI formation.10 The technique achieved by restricting the capacity to 600 mAh g−1. Even
is also valuable as it facilitates the combination of high capacity though the study provided useful information about the
anodes with lower capacity cathodes. This would otherwise chemical structure of a stable SEI, limiting the capacity or
require large quantities of cathode to be used in compensation voltage window has direct repercussions on the charge and
for their lower capacity, or a restriction in mass, and thus in the power stored. Therefore, this strategy is not as desirable as
capacity, of the anode.56 those without such a proportionate effect. Moreover, the use of
2.6. Binders. Given the popularity of nanomaterials for nanostructures, porous structures, composites, coatings, and
high-capacity anode applications, binders had to be developed binders all reduces the mass and volume percentage of the
to hold the active material and conductive particles together active content of the electrode, but this compromise on
onto the current collector, as portrayed in Figure 9.9,30,33 Their gravimetric and volumetric capacity is compensated by the
enhanced mechanical properties suppress volume expansion prolonged cycle life and increased capacity retention achieved
and produce a stable SEI.33 Other advantages include: (1) the in the long run, which are highly desirable for commercializa-
ease of synthesis of binder anodes, which require a mere tion.
physical grinding in the presence of a solvent, as opposed to the
stringent chemical methods and vacuum conditions commonly 3. SOLID ELECTROLYTE INTERPHASE
used for the synthesis of nanowires, nanotubes, and porous The SEI is produced by competing and parallel solvent and salt
structures; (2) the low cost of reagents and anode processing; reduction processes, as indicated by the deposition of both
and (3) the possibility of using biodegradable/recycled inorganic and organic products on the electrode surface. Thus,
polymers for environmentally friendly purposes. These it would be reasonable to assume that the composition of the
interests, coupled with the competitive electrochemical SEI is directly related to the composition of the electrolyte.18
performances obtained, locate binder anodes among top However, SEI formation is greatly affected by numerous
candidates for viable silicon-based LIBs. variables, such as the dependency on the anode and cathode
The focus of binder research seems to be on obtaining the materials, the electrochemical method of formation, the
best mechanical properties of the electrode as a whole, as much presence/absence of binder and/or conductive additives, and
as the investigations for the design of artificial SEIs seem to be the ambient conditions.18,30,31 These variables and incon-
limited to surface chemistry. For this reason, and to integrate sistencies among previous studies have produced results that
structural and chemical knowledge, the performances of both vary widely from one research group to another.18,31 Despite
techniques are reviewed below. the difficulties, understanding the morphology, chemical
Although unrelated to previous categories, another notable composition, and mechanism of SEI formation in relation to
strategy is the tuning of the electrochemical protocols to the variables, as well as the influence of these variables on
prevent anode deterioration. A study reported by Markevich et battery performance, is essential for rational choices in future
al.55 limited the charge or discharge capacity on amorphous investigations.30
27779 DOI: 10.1021/[Link].7b07793
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Just as with most knowledge regarding silicon anodes, primarily composed of LiF, LEDC, LixSiOy, and Li2CO3. The
research toward the attainment of a stable SEI was inherited morphological differences of the nanoparticles cycled by this
from previous investigations performed in carbon anodes. group in the presence and absence of FEC are visible in the
Electrolyte additives that aid to produce a favorable SEI have TEM images in Figures 10 and 11, respectively, accompanied
been researched since the early 1990s. Those include inorganic
additives such as CO2, N2O, CO, and CO-complexes; crown
ethers; isocyanate compounds; and vinylene groups or organic
compounds capable of polymerization.57−64 Sulfur-containing
structures such as ethylene sulfite and polysulfides became
reasonably popular, but even more so did fluorinated species,
wherein research ranged from addition of HF to the use of
surface-fluorinated graphite.59,65−68
Fluoroethylene carbonate (FEC) and vinylene carbonate
(VC) are often included in silicon anode investigations as
electrolyte additives or cosolvents, considering that their
presence enhances cycle performance and thermal stability.35,69
An early study by Etacheri et al.15 related the superior
performance of silicon nanowire anodes to the chemical
composition and morphology of the SEI formed under the
presence of those compounds. The FEC-containing cells
retained a higher capacity than the FEC-free cells after 30
cycles, attributed to a thin and highly homogeneous SEI with a
low ionic impedance and particular chemical composition. The
major component of the SEI in FEC-containing cells was a
polycarbonate that was formed from the polymerization of VC
after this was produced from FEC, as suggested in Scheme 1.
Competing reactions were observed in the presence of the
solvent ethylene carbonate (EC), where its reduction formed a Figure 10. TEM images of BF-Si electrodes cycled in 1.2 M LiPF6/
thick and less passivating SEI that is rich in oxygen species, FEC: (a) Fresh nanosilicon, (b) nanosilicon after 1st cycle, (c)
including lithium carbonate and lithium ethylene dicarbonate nanosilicon after 5th cycle, and (d) nanosilicon after 20th cycle.
(LEDC).15 The absence of highly reactive EC also accounted Reprinted with permission from ref 69. Copyright 2013 American
for a highly pronounced reduction of PF6− into fluorine- Chemical Society.
containing species, such as LiF.15
Nie et al.69 obtained similar results two years later in a study
of SEI in FEC- and EC-based electrolytes with binder-free (BF)
silicon nanoparticle anodes. The absence of a binder limited the
galvanostatic testing to 20 cycles, and although the FEC-based
samples did improve capacity and structure retention, the
electrochemical performance was not the focus of the study. A
combination of analytical techniques was used to characterize
the SEI composition and morphology. The film formed in the
presence of FEC was thin, and the predominant species in it
were insoluble polymeric species (either polyene or poly-
carbonate), LiF, and LixSiOy. The presence of EC was again
linked to the poor passivation of the electrode and electro-
chemical performance, which are attributed to the thick SEI

Scheme 1. Suggested Mechanism of Formation of

Polycarbonate From FEC (Adapted with Permission from
Ref 15. Copyright 2011 American Chemical Society)

Figure 11. TEM images of BF-Si electrodes cycled in 1.2 M LiPF6/

EC: (a) Fresh nanosilicon, (b) nanosilicon after 1st cycle, (c)
nanosilicon after 5th cycle, and (d) nanosilicon after 20th cycle.
Reprinted with permission from ref 69. Copyright 2013 American
Chemical Society.

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Scheme 2. Suggested Mechanism of Formation of Lithium Scheme 4. Suggested Mechanism of Formation of Polyene
Alkoxide and Alkyllithium from DEC (Adapted with from FEC (Adapted with Permission from Ref 55. Copyright
Permission from Ref 30. Copyright 2012 American 2013 The Electrochemical Society)
Chemical Society)

by the elemental concentrations at the surface determined by

EDX. The thinner SEI of the FEC containing sample is
apparent from the first cycle, and following 20 cycles, the
nanoparticles remain more evidently discrete units than those
in the EC-based electrolyte. Table 1. Compounds Present in the SEI as Reported in the
Schroder et al.30 established a dependency between electro- Literature with Relation to the Solvent Used and Remarks
chemical conditions and the formation of SEI, thereby on the Electrochemical Performance (*if Provided)
obtaining high atomic percentages of alkyl species, ethers,
and alkoxides by linear sweep voltammetry and cyclic remarks on
voltammetry, as well as a high percentage of carbonates by compound solvent ref performance
chronoamperometry. Furthermore, this group proposed the polycarbonate FEC-DMC 15* *enhancing
mechanisms in Schemes 2 and 3 for the reduction of EC and polyene FEC-based 55* *enhancing
diethyl carbonate (DEC) into LEDC, lithium alkyls, and polymer FEC 31, 69* *enhancing
alkoxides. This paper does not associate the battery perform- LiF EC, FEC, PC, EC- 15,*30−32, 55,* *enhancing
DEC 69*
ance to the SEI composition formed with different electro-
organic PC 32 -
chemical protocols.
alkyl EC-DEC 30, 31 -
A link of this sort was only provided by Markevich et al.,55
LiOR EC, DMC, FEC, 15, 30, 31, 55* *deteriorating
who investigated the charge/discharge-restricted cycling EC-DEC
mentioned in Section 2. The aim of the capacity restriction −RO2R, EC-DEC 30, 31 -
was to reduce volume variation and electrode degradation. −RO2−
However, SEIs that formed at different potentials had different LixSiOy EC or FEC 69* *both
compositions and passivation abilities. Moreover, the test Li2CO3 EC-DMC, PC 15,* 32, *deteriorating
involved the presence and absence of FEC and concluded that LEDC EC, EC-DMC 15,* 69,* *deteriorating
performance is dependent on both electrolyte composition and carbonates EC-DEC, PC 30, 32, 55* *deteriorating
cycling protocol. The FEC-containing charge-limited cells were
the only ones to retain the restricted capacity of 600 mAh g−1 changes occurring with solvent rinse or reactions of the highly
for 2000 cycles. This SEI was thin and had polyenes and LiF as sensitive SEI with contamination, air, and humidity. Further-
its major components. The discharge-limited cells and more, the researchers suggested plausible components of the
particularly those cells without FEC had the worst electro- SEI, formed in a propylene carbonate (PC) solvent. These
chemical performance, and their SEI had increased oxygen- components are summarized in Table 1, together with the main
containing species. The presence of a polyene rather than a compounds reported by various investigations and, if provided,
polycarbonate in this investigation was suggested to have an association to the influence of the presence of each
resulted via two possible four-step mechanisms displayed in compound on the passivating ability of the SEI.
Scheme 4. 3.1. Artificial SEI. Inspired by the reported SEI
Liu et al.32 attributed the disparities in the results to the compositions that yielded superior performance, recent
analytical procedures used. The in situ study discredited other investigations have explored the use of coatings, such as LiF,
ex situ approaches due to the risk of mechanical or chemical long-chain organocarbonates, and even an unexpected yet

Scheme 3. Suggested Mechanism of Formation of LEDC from EC (Adapted with Permission from Ref 30. Copyright 2012
American Chemical Society)

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Table 2. Reported Electrochemical Performance Data for Various Artificial SEIs in Silicon anodes
capacity retention current density ICE rate capability
coating solvent silicon and binder cycles (mAh g−1) (A g−1) (%) (mAh g−1 at A g−1) ref
LiPON EC/DEC 3:7 thin-film 50 nm, no 100 1600 N/A N/A N/A 75
binder
1-fluorodecane EC/DEC 1:1 NPs 50 nm, PVDF 70 ∼1500 2.2 96.8 N/A 10
titanium oxide EC/EMC 1:1 NPs N/A, alginate 100 1200 0.2 52.2 ∼900 at 20 72
LiF−Li2CO3 EC/DMC 1:2 thin-film ∼100 nm, no 50 ∼3500 N/A 88.78 N/A 70
binder
nitrogen-doped EC/EMC 3:7 porous, PAA 100 1933 0.8 84 1904 at 20 74
carbon
nitrogen-doped EC/EMC/DEC/FEC NPs < 50 nm, no 100 1145 0.2 62 810 at 3 73
carbon 27:18:45:10 binder
silicon nitride EC/EMC 1:1 thin-film 1−2 μm, no 200 1121 N/A 80 N/A 13
binder
LiF EC/DMC/EMC 1:1:1 NPs ∼ 30 nm, LA-132 30 607 N/A 78.5 N/A 71

promising combination of LiF with Li2CO3, considering that mAh g−1. However, the test was only performed for 50 cycles,
the last is usually associated with a poorly passivating which is far from practical applications, which require at least
SEI.10,15,70,71 Carbon, metal oxides, and doped silicon are 300 cycles with fast charge/discharge.19
other popular types of coatings designed to produce stable In fact, only silicon nitride coating was reported with a cycle
SEIs. Materials that are commonly used as electrolytes in solid- test over 100. Overall, the performances of the different
state lithium-ion batteries have been tested, as exemplified by coatings are not particularly distinctive, with an average capacity
lithium phosphorus oxynitride (LiPON).12−14,72−74 retention of 1580 mAh g−1 and average cycle life test of 94. The
However, all investigations of artificial SEI lack stand- credibility of any further comparison would be questionable,
ardization. As shown in Table 1, the use of different considering the number of unstandardized variables across the
combinations of the common solvents FEC, EC, DEC, PC, investigations, which are known to influence the electro-
dimethyl carbonate (DMC), and ethyl methyl carbonate chemical performance, and the lack of clarity with respect to the
(EMC), drastically affected SEI composition. Moreover, current rates used.
different silicon nanostructures are often used, and in the
case of nanoparticles (NPs), they are accompanied by different 4. USE OF BINDERS
binders, which are discussed in the following section to have To date, the use of binders in combination with nanoparticles
extremely disparate performances. The rate of the current used comprises a major part of silicon anode research and provides
in charge and discharge has a nonlinear effect on the capacity some of the most promising results.49 Polyvinylidene fluoride
stored, and most investigations are performed under different (PVDF) was one of the former compounds to be used as a
current rates, thereby making their specific capacities binder, even in conventional graphite anode LIBs.20 However,
incomparable to each other. Capacity retention is the specific the weak van der Waals forces of attraction and the linear chain
capacity that the electrode is able to discharge after a specific nature of PVDF are insufficient to maintain the structure in
number of cycles at a specific current rate. This current rate place during prolonged cycling, so the silicon particles are
may be measured as a C rate, where 1C is a rate at which the susceptible to sliding and irreversibly deforming the electrode,
electrode is completely discharged in 1 h. Some groups which eventually leads to capacity fading.20
considered the 1C rate to be 4.0−4.2 A g−1, which is close to Under ambient conditions, the silicon surface possesses an
the theoretical capacity of silicon, whereas others considered oxide layer that can be exploited by the formation of polar,
1C to be 3.5−3.58 A g−1 for the maximum metastable alloying hydrogen, covalent, or ionic bonding interactions with
composition of Li15Si4 at room temperature.11,35,55,69,71 There- binders.19,20,25,33 The dynamic reassociation of hydrogen
fore, it is more equitable to compare the performances in A g−1, bonds at room temperature is particularly advantageous by
but researchers often avoid disclosing what their 1C rate providing a self-healing behavior.20,25 Carboxymethyl cellulose
corresponds to. (CMC) is a prime example utilizing this chemistry, and in 2010,
Despite the inconsistencies, various coatings for artificial SEI poly(acrylic acid) (PAA) was reported by Magasinski et al.20
formation and their electrochemical performance values are with an improved electrochemical performance attributed to a
summarized in Table 2 to gain perspective on the galvanostatic higher functional group density. After a year, Kovalenko et al.25
cycling quantitative limitations to date. The Coulombic communicated the use of alginate, a natural polysaccharide
efficiency (CE) describes the stability of the anode capacity binder that can tolerate 1300 cycles at a capacity limited to
over cycling. CE is given as a percentage and calculated by 1200 mAh g−1. Alginate also performs well at high rates of 4200
dividing the charge exiting the anode during the delithiation of mA g−1, thereby maintaining a capacity over 1700 mAh g−1 for
silicon over the charge entering during the lithiation process. 100 cycles. Alginate differs from CMC and PAA, in that the
The initial Coulombic efficiency (ICE) is merely the CE for the polymer chain comprises two monomer units, namely, (1,4)-
first cycle, in which SEI formation accounts for the largest linked β-D-mannuronic acid and α-L-guluronic acid, making it a
capacity loss. The rate capability is the capacity retained under copolymer rather than a homopolymer. Furthermore, alginate is
high current densities, which is essential for commercial environmentally friendly and easily integrated into an anode,
applications. making it an attractive candidate.25
With the exception of LiF and LiF−Li2CO3, most artificial In 2012, a major breakthrough in the field of binder research
coatings achieve capacities between 1000 and 2000 mAh g−1. occurred with the synthesis of the first cross-linked binder
The latter retained an outstanding capacity higher than 3000 network by Koo et al.26 The particular 3D design of this
27782 DOI: 10.1021/[Link].7b07793
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The Journal of Physical Chemistry C Review Article

Table 3. Structural Classification of Polymer Binders for Silicon Anodes

network could retain superior structural integrity upon cycling. For instance, the self-healing chemistry earlier mentioned has
This network was produced via a condensation reaction of the been further developed by groups, such as Wang et al.77 and
alcohol groups in CMC and carboxylic acid groups in PAA, Wu et al.,33 who reported about silicon anodes with synthetic
which could also covalently bond with the intrinsic oxide layer self-healing polymers (SHPs) and a combination of alginate
on the silicon surface.26 Since then, multiple binder network with carboxymethyl chitosan (CMCS), respectively. These
combinations have been investigated. In chronological order of structures display dynamic balance between chain reorganiza-
publication, these combinations include PAA with poly(vinyl tion and melt flow behavior due to the supramolecular
alcohol) (PVA); PAA with pullulan; chitosan (CS), another interactions (i.e., ionic or hydrogen bonds) between polymer
natural polysaccharide, cross-linked by glutaraldehyde (GA); chains and silicon particles, and between the polymer chains
PAA cross-linked by 3-amino-propyltriethoxysilane (APTES); themselves.33,77,78
and PVA with poly(ethylene imine) (PEI).5,9,19,28,76 The Branched-type binders have been reported, such as the
combinations of CS-GA and PAA-APTES may be considered karaya gum by Bie et al.,79 and recently, polymer coatings or
a distinctive subcategory of cross-linked structures, owing to the matrices have also earned a category of their own.11,80,81 The
long-chain polymer and a short-chain polymer or coupling use of polymer coatings or matrices combines strategies that are
agent that comprises both binder networks, instead of being individually beneficial to silicon anodes. Most binders stabilize
formed by the condensation of two long polymer chains. the SEI by suppressing volume change, whereas the uniform
Table 3 summarizes the binder types described above, as well encapsulation of the polymer coatings aims to maintain the
as some novel ones, exemplified with corresponding references. beneficial mechanical properties, as well as serve as artificial
27783 DOI: 10.1021/[Link].7b07793
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Table 4. Reported Electrochemical Performance Data for Binder-Based Silicon Anodes

silicon size (nm), content ICE capacity retention current density rate capability (mAh g−1 at
binders (wt %) (%) (mAh g−1) cycles (A g−1) A g−1) ref
PAA−CMC <100, 60 88.2 2000 100 0.3 1500 at 30 26
CMCS 150, 62 89 950 50 0.5 651 at 1.5 84
SHP 3000, 50 ∼80 2093 90 0.4 ∼1400 at 2.0 77
PAA−PVA 30−100, 60 83.9 2283 100 0.4 2660 at 4.0 19
PAA−pullulan 100, 60 84 1464 200 N/A N/A 76
CS−GA ∼100, 60 89 1969 100 0.5 2704 at 2.0 28
PEDOT:PSS ∼60, 80 ∼78 1950 100 1 ∼1500 at 10 11
PAN ∼50, 80 86.2 1639.6 50 0.1 N/A 82
PAA−APTES 50−200, 80 76.6 1871.8, fixed 1000 200, 1200 1.54 1000 at 4 5
alginate−CMC ∼100, 50 74.5 750 100 0.1 N/A 33
PVA−PEI ∼100, 60 83.8 1063.1 300 1 1590 at 10 9
lignin (600 °C) 30−50, 50 81.6 2378 100 1 ∼1600 at 3.6 80
nPAA 30−50, 75 74.76 1370 100 0.42 N/A 83
karaya gum 50−200, 60 N/A 2421 150 1.5 1336 at 4 79
PAA (ATRP) <100, 60 N/A 2000 300 0.34 ∼800 at 17 81

SEIs.81 Furthermore, conductive additives are often not used in ing to the highest mass loading is pursued for materials to
these investigations, as is the case for the combination of become promising prospective anodes.
poly(3,4-ethylenedioxythiopene)/poly(styrene-4-sulfonate)
(PEDOT:PSS) reported by Higgins et al.;11 thus, the coating 5. CONCLUSION AND OUTLOOK
polymers require a good balance between conductivity and
passivation toward side reactions. Linear-type binders are still Progress in silicon anode performance has been gradual. Since
an active field of research, as demonstrated by the the discovery of its high theoretical capacity for lithium alloying,
polyacrylonitriles (PANs) synthesized by Luo et al.82 or the the nanostructurization, coatings, development of binders, and
other improvements have incremented its cycle life and
neutralized PAA (nPAA) by Yuca and Ç olak,83 both obtaining
capacity retention to values above 1500 mAh g−1, generally
highly competitive electrochemical results.
tested for 100 cycles. This capacity is about four times larger
As for artificial SEI studies, binders are reported at different
than the maximum theoretical of graphite. However, conven-
current rates and for different numbers of cycles, with varying
tional batteries generally have a cycle life of over 300, which
sizes of nanosilicon and different compositions of solvent and
results in having no advantage on the production of the present
additives, which significantly challenge their comparison. Small
high capacity/short cycle life silicon anodes.
particles have improved mechanical strain endurance but have a Thus far, structural approaches, such as the use of cross-
proportionally larger surface area for chemical deterioration.17 linked or branched style binders, have achieved the highest
The two effects influence electrochemical performance to cycling stabilities and current rate capabilities. This result can
different extents, thereby making unstandardized studies be attributed to the superior mechanical properties and strong
incomparable. Likewise, the weight percentage of silicon in bonding within the binder networks and the oxide surface of
the electrode is an important variable. The whole anode silicon particles. Reforming bonds, such as the self-healing
capacity is commonly normalized to the weight of silicon, and types, is a prominent field of research. However, the
this can be especially misleading in the case of a low silicon electrochemical performances of the most novel polymeric
weight percentage, given that the capacity corresponding to the binders have plateaued, in the same manner as the use of
lithiation of other electrode components (i.e., carbon coating) nanostructures and porous structures, which are limited
would be falsely attributed to silicon, thereby resulting in a without further treatment.
misrepresentative high gravimetric capacity. Previous studies on coatings and/or electrolyte components
Table 4 summarizes the electrochemical performance of the have repeatedly demonstrated that the presence of an artificially
most notable binders recently reported for silicon anodes engineered SEI may enhance electrochemical performance to
alongside silicon particle size and content per weight that as prominent as the use of binders. Therefore, a reasonable
percentage of electrode. Although the average gravimetric evolution on silicon anode design would involve addressing
capacity of 1750 mAh g−1 is only slightly higher than that for chemical and physical degradation simultaneously. In particular,
the reported artificial SEI retention capacities, the average the advantageous mechanical properties of the polymeric
current density appears substantially larger (average of 0.65 A binders should be used in combination with the knowledge
g−1), and none of the binders were tested for less than 50 cycles of surface chemistry to attain a satisfactory mechanical stability
and had a considerably higher average of 136. and an ideal SEI.
Finally, being aware of the concept of mass loading is Perhaps this convergent approach is already being pursued
essential, although this parameter is rarely reported and, by the above-reported investigations using silicon coatings with
therefore, not included in Table 4. Mass loading defines the binders, porous structures with coatings, or coatings with
mass per area of electrode. Capacity is directly proportional to enhanced mechanical properties. Nevertheless, little is known
the mass of active material; thus, large-scale battery applications about the interaction of binders with the electrolyte and how
require high amounts of electrode (high mass loadings), which the formation of the SEI is affected by their presence. This area
often correlate to increased impedance and poor performance. of research could lay the foundation for designing the next
Hence, the greatest electrochemical performance correspond- generation of silicon anodes that benefit from the long cycle life
27784 DOI: 10.1021/[Link].7b07793
J. Phys. Chem. C 2017, 121, 27775−27787
The Journal of Physical Chemistry C Review Article

of nanostructures and from enhanced mechanical and chemical Alba Franco Gonzalez is an undergraduate Master’s (MChem Hons)
properties of binder/coating combinations which synergistically student from The University of Edinburgh, currently undergoing a
enhanced the anode performance. research project under the supervision of Prof. Ru-Shi Liu at National

■
Taiwan University. She is working on the synthesis of novel silicon-
AUTHOR INFORMATION based anode materials for lithium-ion batteries.

Corresponding Author
*E-mail: rsliu@[Link].
ORCID
Ru-Shi Liu: 0000-0002-1291-9052
Author Contributions
∥
A.F.G. and N.H.Y. contributed equally to this work. The
manuscript was written through contributions of all authors. All
authors have given approval to the final version of the
manuscript.
Notes
The authors declare no competing financial interest.
Biographies
Dr. Nai-Hsuan Yang is a postdoctoral researcher and leader of the
Energy Storage Group from Materials Chemistry Laboratory at
National Taiwan University. She received her Bachelor’s and Master’s
degrees in Chemical Engineering from Chung Yuan University in 2005
and 2007, respectively. In 2015 she completed her PhD at National
Taiwan University, having also experience as a lecturer and teaching
assistant at both universities. She has published 5 papers, including
some of international recognition. Her research interest is that of
anodes for LIBs, having worked with silicon carbon composites,
amorphous carbon, silicon with inorganic coatings, and most recently
silicon anodes with polymeric binders.

■ ACKNOWLEDGMENTS
This work was supported by the Ministry of Science and
Professor Ru-Shi Liu is currently a professor at the Department of Technology of Taiwan with Contract No. MOST 104-2113-M-
Chemistry, National Taiwan University. He received his Bachelor’s 002-012-MY3 and Economic Affair of Taiwan with Contract
degree in Chemistry from Shoochow University (Taiwan) in 1981. He No. 106-EC-17-A-22-0497. A.F.G. would like to acknowledge
received his Master’s degree in nuclear science from the National the support and guidance of Prof. Neil Robertson and the
Tsing Hua University (Taiwan) in 1983. He obtained two PhD School of Chemistry from The University of Edinburgh.

■
degrees in chemistry - one from National Tsing Hua University in
1990 and one from the University of Cambridge in 1992. He worked
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27787 DOI: 10.1021/[Link].7b07793

J. Phys. Chem. C 2017, 121, 27775−27787