Functional Coatings Overview

The Cathodic Electrodeposition of

Manganese Oxide Films for
Electrochemical Supercapacitors
I. Zhitomirsky, M. Cheong, and J. Wei

Electrochemical supercapacitors (ES) of power density as well as allowing tance.2–6 High-surface-area nanostruc-
are urgently needed as components in significant energy savings. Emerging tured oxides and hydroxides of Ru, Mn,
many advanced power systems. The electric vehicle technologies require ES Ni, Sn, and Fe exhibit significantly higher
development of advanced ES is expected as efficient energy storage devices, which specific capacitance (SC) compared to
to enable radical innovation in the accumulate braking energy to be reused carbon materials. The ability to achieve
area of hybrid vehicles and electronic in the next acceleration phase. Super- high specific capacitance with oxide
devices. Electrochemical supercapaci- capacitors are also attractive for other electrode materials has generated a grow-
tors become of interest in hybrid electric applications such as power sources for ing research activity in this field. There
vehicles as auxiliary power sources in lasers, biomedical and communication is increasing interest in the development
combination with fuel cells or batteries. devices, cellular phones, cameras, CD of advanced electrode materials based
Nanostructured manganese oxides have players, and other electronic devices. on MnO2. Manganese oxides in their
been found to be promising electrode Three types of materials have been various forms offer low cost, an envi-
materials for ES. This paper describes mostly used for ES: high-surface-area ronmentally friendly character, and high
new electrochemical methods for the carbon, metal oxides or hydroxides, and SC. The values of SC for thick MnO2
fabrication of nanostructured manga- conducting polymers. Energy-storage films and composites reported in the
nese oxide electrodes for ES. mechanisms of ES include double-layer literature are usually in the range of 100
capacitance arising from the charge F/g to 300 F/g. These values are far from
INTRODUCTION
separation at an electrode/electrolyte the theoretical SC of ~1,370 F/g and
Electrochemical supercapacitors (ES) interface and pseudocapacitance arising reported experimental SC for very thin
are attracting significant interest for from reversible Faradaic reactions or films.7,8
their potential role in electric and fuel from the surface adsorption of poten- Significant interest has been generated
cell vehicles.1 The incorporation of ES tial determining ions. Charge storage in the application of electrochemical
into new vehicles in a combination with on carbon electrodes is predominantly methods for the fabrication of manganese
batteries and fuel cells offers important capacitive in the electrochemical double oxide films. The research on the electro-
advantages. For example, batteries layer. synthesis of MnO2 has been mainly
and fuel cells are low power devices, Nanostructured metal oxides and focused on the anodic deposition from
and electrochemical supercapacitors hydroxides are promising materials for Mn 2+ solutions. 7–12 The interest in
improve their performance in terms ES and exhibit high pseudocapaci- cathodic electrodeposition stems from
the perspectives of modification of film
composition, conductivity, and electro-
chemical performance. The ability to
avoid the anodic oxidation and dissolu-
tion of metallic current collectors is
another advantage of the cathodic elec-
trodeposition methods.
CATHODIC
ELECTROPHORETIC
AND ELECTROLYTIC
Figure 1. X-ray diffraction patterns
DEPOSITION OF OXIDES
for the deposits obtained from the
0.02 M KMnO4 aqueous solutions:
Cathodic electrodeposition of oxides
(a) as prepared and after heat treat- can be achieved using electrophoretic
ment at (b) 200, (c) 300, (d) 400, (e) deposition (EPD) or electrolytic depo-
500, and (f) 600°C.
sition (ELD).13 Electrolytic deposition
includes electrosynthesis of inorganic
nanoparticles from the solutions of

66 JOM • July 2007

metals salts and the formation of deposits are defined as complexes composed of a
on the electrode surface. Electrolytic polymer ligand and metal ions in which
deposition enables rigid control of the metal ions are attached to the polymer
film thickness, uniformity, and deposi- ligand by a coordinate bond. A polymer
tion rate. Electrophoretic deposition chelate is formed when a metal ion is
is another method, based on the use added to a solution of an electrically
of suspensions containing inorganic neutral polymer such as polyethyleni-
particles or polymers. Electrophoretic mine (PEI). A soluble polymer-metal ion
deposition is essentially a two-step complex behaves as a polyelectrolyte in
process that includes the electrophoretic aqueous solutions. The electrodeposi-
motion of charged inorganic particles or tion from basic solutions, containing
Figure 3. Cyclic voltammetry data for the
polymers in a liquid toward the electrode PEI-Mn2+ complexes, resulted in the 0.1 mg/cm2 deposit prepared by ELD
and deposit formation. Various oxide formation of cathodic deposits contain- and tested in the 0.1 M Na2SO4 aqueous
materials can be deposited by EPD, ing nanoparticles of Mn3O4 and PEI.15 solution at a scan rate of 50 mV/s.
including individual oxides, complex In another strategy, acidic solutions
oxide compounds, and solid solutions.13 of protonated chitosan were used. The

300

Specific Capacitance (F/g)

The composition of the electrophoretic charged macromolecules of protonated



deposits is controlled by the stoichiom- chitosan were deposited by EPD.16 The

250


etry of the powders used for deposition. deposition mechanism was proposed,



Uniform deposits can be obtained as which included independent deposition




200

monolayers, laminates, or coatings of of the polymer and electrosynthesis of

c


graded composition on substrates of manganese species.

b
150
complex shape. Important advantages The electrosynthesis of manganese
a
gained in using EPD have stimulated species in a polymer matrix resulted 40 60 80 100
0 20
accelerated growth in the development in the formation of crystalline Mn3O4 Scan Rate (mV/s)
and application of this method.13 nanoparticles. It was shown that PEI and Figure 4. The specific capacitance versus
chitosan promote the room-temperature scan rate for 0.1 mg/cm2 deposits prepared
ELD OF MnO2 FROM at current densities of (a) 2, (b) 5, and (c)
crystallization of Mn3O4. The polymers 10 mA/cm2 and tested in the 0.1 M Na2SO4
SOLUTIONS OF Mn2+ SALTS
prevent particle agglomeration. The aqueous solutions.
It is known that cathodic ELD from size of nanoparticles can be varied on
solutions of Mn2+ salts results in the the nanometric scale in the range of
formation of manganese hydroxide 2–10 nm by the variation of polymer in SC during 1,000 cycles. In contrast,
(Mn(OH)2)deposits.14 In recent inves- concentration in the solutions used for the films prepared by chitosan-mediated
tigations a new method was developed deposition. The high surface area and electrosynthesis exhibited excellent
based on polymer mediated electrosyn- small particle size of the Mn3O4 enabled cycling stability. Further experiments
thesis.15,16 This approach enabled the further electrochemical oxidation of the showed that other polyelectrolytes such
formation of nanocrystalline Mn3O4 deposits in the 0.1 Na2SO4 solutions and as polyallylamine hydrochloride can be
deposits, which were converted elec- the formation of electrochemically active used for the polymer-mediated electro-
trochemically to MnO2 films. Obtained MnO2 films. The films exhibited SC in the synthesis of manganese oxide films.
nanostructured films showed high SC. range of up to 445 F/g. The SC decreased
ELD OF MnO2 FROM
Electrically neutral polymers can with increasing film thickness and scan
SOLUTIONS OF Mn7+ SALTS
be deposited using polymer-metal ion rate. The films prepared from solutions
complexes. Polymer-metal complexes containing PEI showed a 20% reduction Manganese oxide films were cath-
odically deposited on various substrates,
such as nickel, stainless steel, and graph-
ite, by reduction of KMnO4.17 It is sug-
gested that in neutral aqueous solutions
the following reaction can result in the
reduction of MnO4– species:

MnO4– + 2H2O + 3e– m

MnO2 + 4OH– (1)

Figure 2. An SEM image X-ray diffraction (XRD) studies showed

of a deposit prepared from that as-prepared deposits were poorly
0.02 M KMnO4 solution
at a current density of 2
crystallized and exhibited very small
mA/cm2. peaks (Figure 1). The XRD spectra taken
100 nm
from the sample annealed at 200°C for
1 h displayed broad reflexes, which can

2007 July • JOM 67

 of various oxides and modification of
composition and properties of the depos-
its. The deposit composition can be
varied by the use of polychelates.19 The
co-deposition of manganese oxide and
other materials from KMnO4 solutions
presents difficulties related to the reduc-
tion of MnO4– species in the presence of
other cations and organic materials.
Figure 5. An SEM image EPD OF MnO2 FILMS
of the deposit prepared
by EPD from 2 g/L MnO2 Electrophoretic deposition requires
suspension in ethanol. the use of stable suspensions of charged
100 nm particles. The deposition rate in the EPD
process is proportional to the particle
concentration in the suspensions.13 How-
be attributed to rancieite structure charge storage mechanism. The experi- ever, stable suspensions with a high
(JCPDS file 22-0718). The peak broad- mental results presented in Figure 3 concentration of MnO2 nanoparticles are
ening could be related to the small indicate that within the potential range difficult to prepare because of the strong
particle size. More distinct and sharp of 0–1.0 V versus a saturated calomel tendency of manganese oxides to
rancieite peaks were observed at higher electrode, the manganese oxide elec- coagulate and precipitate. It was observed
temperatures in the range of up to trodes exhibit capacitive-like current- that any increase in the MnO2 concentra-
600°C. potential responses and that there are no tion above 10–3 M invariably leads to the
Energy-dispersive spectroscopy, redox peaks in that potential range. A destabilization of the colloidal suspen-
chemical analysis, and thermogravimet- quasi-rectangular shape of the cyclic sion.20 Another difficulty involves the
ric studies have further supported the voltammetry curves indicates ideal fabrication of suspensions containing
results of the x-ray analysis. The rancie- pseudocapacitive behavior. The films positively charged MnO2 nanoparticles
ite structure has the near-MnO2 compo- prepared in the galvanostatic mode for cathodic EPD. This is attributed to
sition with a general formula of showed higher porosity and higher SC the low zero point of charge of MnO2.21,22
AxMnO2+y(H2O)z where A = K, Li, Ca, compared to the films prepared by poten- The charging of oxide particles can be
or other cations.18 Energy dispersive tiostatic and potentiodynamic deposi- achieved by the addition of metal ions
spectroscopy studies showed that the tion. The increase in current density to the suspension. However, manganese
deposits contained K and Mn with a resulted in higher microporosity and dioxide shows a strong tendency to
K/Mn atomic ratio of x=0.35±0.04. higher SC (Figure 4). The reduction in coagulate and precipitate in the presence
Thermogravimetric data showed weight the SC with increasing scan rate can be of metal ions.23
loss of ~14 wt.% in the temperature range attributed to the diffusion limitations in Cathodic EPD has been developed for
of up to 600°C, which can be mainly pores. the fabrication of manganese oxide films
attributed to the deposit dehydration. Heat treatment resulted in a 10–15% for ES. Manganese oxide nanoparticles
The results of chemical analysis indicate increase in SC in the range of 20–300°C. with particle size of ~30 nm were pre-
that mean oxidation state (MS) of man- The results of electrochemical investiga- pared using the reduction reaction:
ganese increased from 3.51 to 3.74 with tions coupled with the thermogravimetry
4MnO4– + 3CH3CH2OH + 4H+
the increasing temperature in the range data indicate that this increase in SC can
m 4MnO2 + 3CH3COOH + 5H2O (2)
of 20–500°C. The MS values are in be attributed to deposit dehydration and
agreement with the literature data for the an increase in the concentration of elec-
rancieite-type manganese oxide.18 trochemically active manganese oxide
The deposits were obtained by galva- in the films. Obtained films exhibited
nostatic, potentiostatic, or potentiody- excellent cycling stability during the
namic deposition. The thickness of the 1,000 cycles and no change in film
films was in the range of up to 2 Mm. morphology after cycling.
Figure 2 shows a scanning-electron Compared to the polymer-mediated
microscopy (SEM) image of a deposit electrosynthesis, this approach offers the
prepared galvanostatically at a current advantage of direct formation of elec-
density of 2 mA/cm2 from 0.02M KMnO4 trochemically active MnO2 by the reduc-
solution. The SEM investigations tion of MnO4– species. In contrast,
revealed the porous microstructure of polymer-mediated electrosynthesis
the films with typical pore size of about requires burning out of polymers and Figure 6. Cyclic voltammetry data for the
0.1 mg/cm2 deposit prepared by EPD
100–200 nm. Such porous microstruc- electrochemical oxidation of the Mn3O4 and tested in the 0.1 M Na2SO4 aqueous
tures are beneficial to ion transport and phase. However, polymer-mediated solutions at a scan rate 50 mV/s.
redox reactions, which underlie the electrosynthesis enables co-deposition

68 JOM • July 2007

X-ray diffraction studies showed that as- fabrication of MnO2 nanoparticles and 12. J-K. Chang and W-T. Tsai, “Effects of Temperature
precipitated powders were amorphous. optimization of microstructure of EPD and Concentration on the Structure and Specific
Capacitance of Manganese Oxide Deposited in
Stable suspensions of manganese dioxide films. Manganese Acetate Solution,” J. Appl. Electrochem.,
nanoparticles in ethanol were used for 34 (2004), p. 953.
ACKNOWLEDGEMENT 13. I. Zhitomirsky, “Cathodic Electrodeposition of
EPD. The concentration of nanoparticles
Ceramic and Organoceramic Materials. Fundamental
in the suspensions was in the range of The authors acknowledge financial Aspects,” Adv. Colloid Interface Sci., 97 (2002) p. 279.
up to 3 g/L. support of Natural Sciences and Engi- 14. W.H. Ho and S.K. Yen, “Characterization of
Manganese oxide particles were posi- neering Research Council of Canada. Electrolytic Manganese Oxide Coating on Pt for
Lithium Battery Applications,” J. Electrochem. Soc.,
tively charged in the ethanol suspensions References 152 (2005), p. A506.
and deposited on a cathode under an 15. N. Nagarajan, H. Humadi, and I. Zhitomirsky,
applied electric field. The particle-charg- 1. C. Ashtiani, R. Wright, and G. Hunt, “Ultracapacitors “Cathodic Electrodeposition of MnOx Films for
for Automotive Applications,” J. Power Sources, 154 Electrochemical Supercapacitors,” Electrochim. Acta.,
ing mechanism can be attributed to the (2006), p. 561. 51 (2006), p. 3039.
adsorption of ethanol, which ionizes into 2. T. Cottineau et al., “Nanostructured Transition 16. N. Nagarajan, M. Cheong, and I. Zhitomirsky,
a protonated alcohol and an alkoxide ion. Metal Oxides for Aqueous Hybrid Electrochemical “Electrochemical Capacitance of MnOx Films,” Mater.
Supercapacitors,” Appl. Phys. A., 82 (2006), p. 599. Chem. Phys., in press.
The dissociated alcohol and alkoxide 3. N. Nagarajan and I. Zhitomirsky, “Cathodic 17. [Link], N. Nagarajan, and I. Zhitomirsky, “Manganese
ion desorb into the solution, leaving the Electrosynthesis of Iron Oxide Films for Electrochemical Oxide Films for Electrochemical Supercapacitors,” J.
particle positively charged in the suspen- Supercapacitors,” J. Appl. Electrochem., 36 (2006), p. Mater. Process Tech., in press.
1399. 18. F. Leroux, D. Guyomard, and Y. Piffard, “The 2D
sion.24 4. J.H. Jang et al., “Supercapacitor Performance of Rancieite-Type Manganic Acid and its Alkali-Exchanged
Figure 5 shows an SEM image of a Hydrous Ruthenium Oxide Electrodes Prepared by Derivatives: Part 1–Chemical Characterization and
deposit prepared by EPD on a nickel Electrophoretic Deposition,” J. Electrochem. Soc., 153 Thermal Behavior,” Solid State Ionics., 80 (1995), p.
(2006), p. A321. 299.
substrate. The deposits contained MnO2 5. K-W. Nam et al., “Synthesis and Electrochemical 19. I. Zhitomirsky, “Electrophoretic Deposition of
nanoparticles and exhibited porosity. Investigations of Ni1–xO Thin Films and Ni1–xO on Three- Organic-Inorganic Nanocomposites,” J. Mater. Sci., 41
The particle size was larger (Figure 5), Dimensional Carbon Substrates for Electrochemical (2006), p. 8186.
Capacitors,” J. Electrochem. Soc., 152 (2005) p. 20. S-F. Chin, S-C. Pang, and M.A. Anderson,
compared to that for the films prepared A2123. “Material and Electrochemical Characterization of
by electrolytic deposition (Figure 2). 6. H.Y. Lee and J.B. Goodenough, “Brief Tetrapropylammonium Manganese Oxide Thin Films
Moreover, the electrolytically deposited Communication—Supercapacitor Behavior with KCl as Novel Electrode Materials for Electrochemical
Electrolyte,” J. Solid State Chem., 144 (1999), p. 220. Capacitors,” J. Electrochem. Soc., 149 (2002), p.
films showed higher porosity. The thick- 7. S. Devaraj and N. Munichandraiah, “High A379.
ness of the films prepared by EPD was Capacitance of Electrodeposited MnO2 by the Effect 21. S.S. Tripathy, S.B. Kanungo, and S.K. Mishra,
in the range of up to 3 mm. of a Surface-Active Agent,” Electrochem. Solid-State “The Electrical Double Layer at Hydrous Manganese
Lett., 8 (2005), p. A373. Dioxide/Electrolyte Interface,” J. Colloid Interface Sci.,
The films prepared by EPD exhibited a 8. S-C. Pang, M.A. Anderson, and T.W. Chapman, “Novel 241 (2001), p. 112.
capacitive behavior in the potential range Electrode Materials for Thin-Film Ultracapacitors: 22. J.W. Murray, “The Surface Chemistry of Hydrous
of 0–1.0 V versus SCE (Figure 6). The Comparison of Electrochemical Properties of Sol-Gel- Manganese Dioxide,” J. Colloid Interface Sci., 46
Derived and Electrodeposited Manganese Dioxide,” J. (1974), p. 357.
SC of the films was in the range of up Electrochem. Soc., 147 (2000), p. 444. 23. J.F. Perez-Benito, “Coagulation of Colloidal
to 240 F/g. The films prepared by EPD 9. C-C. Hu and T-W. Tsou, “Capacitive and Textural Manganese Dioxide by Divalent Cations,” Colloids
showed lower capacitance compared to Characteristics of Hydrous Manganese Oxide Surf., A., 225 (2003), p. 145.
Prepared by Anodic Deposition,” Electrochim. Acta., 24. R. Damodaran and B.M. Moudgil, “Electrophoretic
the films of the same mass prepared by 47 (2002) p. 3523. Deposition of Calcium Phosphates from Non-Aqueous
electrolytic deposition. The differences 10. M-S. Wu and P-C.J. Chiang, “Fabrication of Media,” Colloids Surf., A., 80 (1993), p. 191.
can be related to the diffusion limitations Nanostructured Manganese Oxide Electrodes for
Electrochemical Capacitors,” Electrochem. Solid-State
in the EPD films, which exhibited larger Lett., 7 (2004), p. A123. I. Zhitomirsky, M. Cheong, and J. Wei are with the
particle size, particle agglomeration, 11. J-K. Chang and W-T. Tsai, “Material Department of Materials Science and Engineering,
and lower porosity. Current research is Characterization and Electrochemical Performance McMaster University, 1280 Main Street West,
of Hydrous Manganese Oxide Electrodes for Use in Hamilton, Ontario, Canada, L8S 4L7. Dr. Zhitomirsky
focused on the further development of Electrochemical Pseudocapacitors,” J. Electrochem. can be reached at fax: (905) 528-9295; e-mail:
chemical precipitation methods for the Soc., 150 (2003), p. A1333. zhitom@[Link].

2007 July • JOM 69