Electrochemical and Solid-State Letters, 12 共4兲 A91-A94 共2009兲 A91

1099-0062/2009/12共4兲/A91/4/$23.00 © The Electrochemical Society

Crystallite Size Control and Resulting Electrochemistry

of Magnetite, Fe3O4
Shali Zhu,a Amy C. Marschilok,b,* Esther S. Takeuchi,a,b,c,* and
Kenneth J. Takeuchia,z
a
Department of Chemistry, bDepartment of Electrical Engineering, and cDepartment of Chemical
and Biological Engineering, University at Buffalo (SUNY), Buffalo, New York 14260, USA

As an environmentally benign, superparamagnetic material, magnetite 共Fe3O4兲 has been a topic of interest for applications ranging
from drug delivery to data storage. We report here investigation of magnetite as a lithium-battery material. While Fe3O4 synthesis
has been widely studied, our approach afforded excellent crystallite size control without constraining media or elaborate equip-
ment. Upon electrochemical testing, a strong correlation between performance and crystallite size was observed, resulting in a
⬃30% capacity increase. To the best of our knowledge, this is the first study of electrochemical effects of Fe3O4 crystallite size
where all nanocrystalline samples were prepared using the same method.
© 2009 The Electrochemical Society. 关DOI: 10.1149/1.3078076兴 All rights reserved.

Manuscript submitted December 8, 2008; revised manuscript received January 12, 2009. Published February 9, 2009.

Iron-containing electrode batteries have been studied historically talline Fe3O4 materials were synthesized using the same technique,
as anodes and, more recently, as cathodes for primary and secondary allowing a direct evaluation of crystallite-size impacts on electro-
batteries.1 Due to their low cost and environmentally friendly nature, chemistry without any complicating factors. Upon electrochemical
iron oxides are especially attractive battery-electrode materials. His- testing, a strong correlation between performance and crystallite size
torically, interest in Fe3O4-based electrodes grew out of a desire to was observed, resulting in a significant ⬃30% capacity increase
develop an alternative electrode material to FeS2 for high- across the Fe3O4 crystallite range studied.
temperature batteries.2 In the 1980s, Thackeray and co-workers
completed significant early work associated with the development
and characterization of high-temperature and room-temperature Experimental
Fe3O4-based batteries.2-4
More recently, there has been a resurgence of interest in this A coprecipitation method was used to prepare magnetite
material, with a few electrochemical studies involving nanocrystal- 共Fe3O4兲. Stoichiometric mixtures of iron共III兲 chloride hexahydrate
line Fe3O4. Thin-film nanocrystalline magnetite and magnetite- 共FeCl3·6H2O兲 and iron共II兲 chloride tetrahydrate 共FeCl2·4H2O兲 were
based composites have been investigated.5-7 The capacitance of thin dissolved in varying volumes of degassed water. The resulting solu-
film and powdered nanocrystalline magnetite has been reported.8,9 tion was added dropwise to a roundbottom flask containing a stirred
Sivakumar et al. utilized Fe2O3−x thin films grown by pulsed laser solution of degassed water and triethylamine 关N共CH2CH3兲3兴. The
deposition and commercial Fe3O4 nanoparticles with a mean size of roundbottom flask was submerged in an ice bath throughout the
65 nm vs lithium metal electrodes.10,11 Cells were discharged at cur- synthesis to control the reaction temperature. In addition, the stirring
rent densities of 2–40 ␮A/cm2. Changes in magnetic and X-ray rate and addition rate were held constant for all reactions at
characteristics on discharge were studied, where a smaller decrease 1000 rpm and 2 s/drop, respectively. Samples were isolated using a
in saturation magnetization for thin films vs nanoparticles was at- Eppendorf 5804 Centrifuge, operating at 7000 rpm, and washed
tributed to kinetic effects. Ito and co-workers prepared 20 nm Fe3O4 with deionized water. Powdered samples were dried in vacuo at
particles and tested these in lithium batteries at room temperature 60°C. Samples were ground using a ceramic mortar and pestle and
and at 60°C.12 When discharged at 0.1 mA/cm2 to a terminal volt- passed through a 230 mesh sieve prior to characterization.
age of 1 V, 400 mAh/g was delivered at room temperature, while The material was then characterized by X-ray powder diffraction
⬎500 mAh/g was delivered on 60°C testing. The addition of india 共XRD兲. A Rigaku Ultima IV X-ray powder diffractometer was used
ink or polyvinyl alcohol was found to further improve the battery for XRD analysis. Cu K␣ radiation was utilized with Bragg–
discharge characteristics. When tested as secondary batteries, cycla- Brentano focusing geometry. MDI JADE version 8.5.3 software
bility was maintained through three charge–discharge cycles. Ko- with International Centre for Diffraction Data and National Institute
maba and co-workers recently reported the first investigation of the of Standards and Technology databases was used for search-match
crystallite size effect of nanocrystalline Fe3O4 for rechargeable analysis. Peak Fit software from Seasolve Software, Inc., was used
lithium batteries.13 Fe3O4 powders with average particle sizes of to measure the full width at half-maximum of the 共311兲 peak. Crys-
400, 100, and 10 nm, and Brunauer–Emmett–Teller surface areas of tallite sizes were determined using the Scherrer equation after cor-
6.6, 50, and 155 m2 /g, respectively, were prepared using different recting for instrumental broadening using a LaB6 standard pur-
techniques and utilized as electrode materials vs lithium-metal chased from Gem Dugout.
counter and reference electrodes. Crystallite size had a significant Cyclic voltammetry 共CV兲 data was collected inside an argon-
impact on the first discharge capacity, where the 10 nm sample de- filled glove box using a CHI 604B electrochemical analyzer. The
livered 130 mAh/g to 1.5 V in Li+ electrolyte, while the 400 nm working electrode was constructed using a 2 mm diameter platinum
sample delivered only 7 mAh/g. The nanocrystalline 10 nm sample electrode coated with a thin layer Fe3O4, graphite, and polyacrylic
also showed good performance in Na+ electrolyte, delivering acid mixture. A three electrode assembly was used, with lithium
160 mAh/g to 1.5 V on the first cycle. Good capacity retention was metal reference and counter electrodes, in an electrolyte of 1 M
observed in the nanocrystalline sample over 30 charge/discharge LiAsF6 in 50/50 共v/v兲 propylene carbonate/dimethoxyethane. An
cycles. initial and final voltage of 2.5 V, a lower limit voltage of 0.9 V, and
We report here the investigation of Fe3O4 as a battery electrode scan rates of 2.00, 4.00, or 6.00 ⫻ 10−5 V/s were used.
material for lithium primary batteries. Notably, all of our nanocrys- Cathode pellets were prepared by mixing 40% Fisher 38 graph-
ite, 10% poly共tetrafluoroethane兲 powder and 50% Fe3O4. Cathode
pellets were pressed at 6 tons/cm2. Type 2325 coin cells were fab-
* Electrochemical Society Active Member. ricated within an argon-filled glove box utilizing coin-cell parts and
z
E-mail: takeuchi@buffalo.edu assembly equipment obtained from the National Research Council

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 A92 Electrochemical and Solid-State Letters, 12 共4兲 A91-A94 共2009兲

3.5
A
3.0
B
C
2.5

voltage (V)
2.0

1.5

1.0

0.5
0.0 0.5 1.0 1.5 2.0 2.5
x in LixFe3O4

Figure 3. Background voltage 共during 0.08 mA/cm2 discharge兲 of Li/Fe3O4

batteries containing 共A兲 6.2, 共B兲 8.2, and 共C兲 9.6 nm crystallite-size Fe3O4.
Figure 1. Powder XRD of Fe3O4: 共A兲 6.2, 共B兲 8.2, and 共C兲 9.6 nm crystallite
size.

Scherrer equation15,16 to the 共311兲 peak of the XRD data. A strong

of Canada. Electrolyte of 1 M LiAsF6 in 50/50 共v/v兲 propylene correlation among Fe3O4 crystallite size and concentration was ob-
carbonate/dimethoxyethane was used along with a lithium-metal an- served, as shown in Fig. 2, where more concentrated solutions re-
ode. sulted in larger Fe3O4 crystallite sizes. Multiple Fe3O4 samples were
Coin cells were discharged using a Bitrode SCN Cycle Life prepared at each concentration, and the data shown are the average
Tester battery testing unit. A constant temperature of 20°C was crystallite sizes for each concentration studied. Reactant solution
maintained during discharge. Cells were discharged under a concentration of other Fe2+ and Fe3+-containing reagents has been
constant-current test protocol which involved intermittent higher previously shown to impact Fe3O4 crystallite size.17-19
current pulses. Multiple current densities and intermittent pulsing Electrochemical evaluation.— Magnetite samples with small
were used in this test to understand the behavior of the Li/Fe3O4 共6.2 nm兲, intermediate 共8.2 nm兲, and large 共9.6 nm兲 crystallite sizes
cells under multiple usage regimes. Because 0.08 mA/cm2 was the were selected for further electrochemical evaluation and utilized for
lowest current density utilized, and it was used for the majority of cathode-pellet fabrication and coin-cell assembly as described
the test, all voltage measurements made during steps 1 and 3 were above. On discharge at room temperature, the voltage shows a
termed background voltage measurements. For step 1, the cells were gradual decrease from an initial potential of 3.3 V, as shown in Fig.
discharged for 2 h at a 0.08 mA/cm2 current density. During step 2, 3. Cells made using the two larger crystallite-size Fe3O4 samples
a 2 mA/cm2 current, 5 s pulse was applied. During step 3, the cells showed similar voltage profiles, with well-defined transitions, while
were discharged for 2 h at a 0.08 mA/cm2 current density. During the smallest crystallite-size Fe3O4 resulted in a significantly
step 4, a 5 mA/cm2 current, 5 s pulse was applied. This four-step smoother discharge curve. Inflection points in the discharge curve
sequence was repeated to fully discharge the cells. Testing was sus- were probed further by constructing a differential capacity analysis
pended when the background voltage dropped below 1.0 V. as shown in Fig. 4, where the discharge curve was differentiated
Results and Discussion with respect to voltage. One large inflection was evident at 1.65 V.
In addition, a second transition was observed in the region of
Material characterization.— XRD patterns were recorded of the 1.1–1.3 V, although this transition was less well-defined.
magnetite 共Fe3O4兲 samples prepared in our laboratories, as shown in Consistent with the smoother shape of the discharge curve, the
Fig. 1. The patterns showed excellent correspondence to a literature smallest crystallite-size sample showed a much broader peak on
pattern of Fe3O4, with no extra peaks observed in our data.14 Crys- differential-capacity analysis than the two larger crystallite-size
tallite sizes of the Fe3O4 powders were determined by applying the
differential capacity (dmAh/dmV)

10

9
A
crystallite size (nm)

8 B

C
7

6
y = 55.76x + 6.31
R2 = 0.86
2.45 2.05 1.65 1.25 0.85
5
0 0.01 0.02 0.03 0.04 0.05 0.06 voltage (V)
Fe2+ concentration (M)
Figure 4. Differential capacity of Li/Fe3O4 batteries as a function of voltage:
Figure 2. Average Fe3O4 crystallite size vs Fe2+ concentration. 共A兲 containing 6.2, 共B兲 8.2, and 共C兲 9.6 nm crystallite-size Fe3O4.

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 Electrochemical and Solid-State Letters, 12 共4兲 A91-A94 共2009兲 A93

100
2.0E-06
2 mA/cm2, 1.50 V

current (A)
5 mA/cm2, 1.50 V
1.2E-06
2 mA/cm2, 1.75 V
A
capacity (mAh/g)

5 mA/cm2, 1.75 V
4.0E-07
75 0
-4.0E-07
y = -5.92x + 126.34 2.45 2.25 2.05 1.85 1.65 1.45 1.25 1.05 0.85
2.0E-06
R2 = 0.86 voltage (V)

current (A)
1.2E-06
B
50 y = -5.85x + 110.27 4.0E-07
R2 = 0.85 0
-4.0E-07
2.45 2.25 2.05 1.85 1.65 1.45 1.25 1.05 0.85
y = -7.03x + 111.63 2.0E-06

current (A)
voltage (V)
R2 = 0.95 1.2E-06
25
C
6 7 8 9 10 y = -5.77x + 91.95 4.0E-07
0
R2 = 0.85 -4.0E-07
crystallite size (nm)
2.45 2.25 2.05 1.85 1.65 1.45 1.25 1.05 0.85
voltage (V)
Figure 5. Capacity of Li/Fe3O4 batteries at different voltages 共during pulse
discharge at 2 and 5 mA/cm2兲 as a function of Fe3O4 crystallite size.
Figure 6. CV of Fe3O4 as a function of scan rate: 共A兲 6.00, 共B兲 4.00, and 共C兲
2.00 ⫻ 10−5 V/s.

samples. Delville and co-workers have invoked band theory to con-

ceptualize the smoother voltage profiles of nanocrystalline materials
relative to their well-crystallized homologues.20 Due to their higher faces between unoccupied octahedral sites and two adjacent tetrahe-
numbers of surface defects 共i.e., distorted coordination polyhedra dral sites provide a migration pathway for the A cations. Lithium
and dangling bonds兲, more nanocrystalline materials possess more ions are mobile in a close-packed anion array with interconnected
sub-bandgap states, effectively decreasing the energy gap between edge-sharing octahedra. During lithium insertion, the lithium cations
their conduction and valance bands. During discharge, Li+ insertion occupy the vacant octahedral sites and the adjacent tetrahedral Fe3+
fills these localized sub-bandgap states, allowing an incremental ions are displaced into adjacent empty octahedral sites, resulting in a
change in the electrode Fermi energy without any substantial struc- shift from an inverse spinel to a defect-containing rock salt structure
tural change. Assuming cubic crystallite shape, our Fe3O4 crystallite at x 艋 1. 共1兲 The discharge mechanism at higher values of x is more
sizes of 6.2, 8.2, and 9.6 nm would have corresponding surface area/ complex, where some authors have proposed that extrusion of me-
volume ratios of 0.96, 0.73, and 0.62, respectively, so the 6.2 nm tallic iron can occur, 共2兲 while others have found no room tempera-
sample could be anticipated to have ⬃20% more defects per unit ture extrusion of iron up to x = 2.0.21,22
volume than the 8.2 nm sample, based solely on surface area differ- CV was conducted on Fe3O4 vs lithium counter and reference
ences. electrodes. While there has been extensive collection and discussion
Fe3O4 has mixed iron valence, with 2 FeIII and 1 FeII. Assuming of voltammetry data associated with Fe3O4 and related iron oxides
complete reduction of Fe3+ to Fe2+, the Fe3O4 would transfer two in acidic aqueous solutions,26-40 to our knowledge, ours is the first
electrons per formula unit, translating to a 232 mAh/g theoretical report of slow-scan voltammetry of Fe3O4 in organic electrolyte.
gravimetric capacity. The background voltage data 共collected during Scan-rate dependence data for a sample of intermediate crystallite
0.08 mA/cm2 discharge兲 was utilized to analyze the overall capacity size 共8.2 nm兲 is shown in Fig. 6. The Fe3O4 showed well-resolved
of our Fe3O4 batteries. Our Fe3O4 batteries delivered over peaks collected at scan rates of 2, 4, and 6 ⫻ 10−5 V/s.
230 mAh/g at 1.3 V background, exhibiting good correspondence to Consistent with the differential capacity data shown in Fig. 4,
a two electron per formula unit assumption. At 1.5 V background, one large cathodic peak was present near 1.65 V at all scan rates,
our batteries delivered over 110 mAh/g. This shows reasonable cor- with a second cathodic peak visible at the higher scan rates near
respondence to previous data, where Komaba and co-workers re- 1.10 V. Because the higher potential peak 共⬃1.65 V兲 was visible at
ported a 130 mAh/g capacity to 1.5 V from discharge at room all scan rates, we attribute this peak to Fe3+ reduction within the
temperature.13 The small differences in observed capacity are likely solid state. Because one Fe3+ is in an octahedral position while the
due to differences in cell construction and discharge current utilized other is in a tetrahedral position in Fe3O4, it has been noted that they
for the tests. should be electrochemically inequivalent, where each ion may be
The pulse power capability of the coin cells was evaluated by reduced and solubilized at a different potential;37,41 therefore, it is
applying higher rate 5 s constant current pulses every 2 h. Alternat- possible that reduction of only one type of Fe3+ is represented by
ing current densities of 2 and 5 mA/cm2 were utilized, where these this peak. Thus, we propose that the displacement and reduction of
higher current densities were selected to apply additional demand to tetrahedral Fe3+ to octahedral Fe2+ is the most probable assignment
the batteries over a shorter time period. The capacities delivered to for our 1.65 V cathodic peak. Because the 1.65 and 1.10 V peaks
pulse voltages of 1.50 and 1.75 V are shown in Fig. 5. Delivered have similar areas, each should represent a one-electron process,
capacity increased linearly with decreasing Fe3O4 crystallite size, based on our capacity calculation discussed above. We propose that
where ⬃30% capacity increases were achieved with 6.2 vs 9.6 nm reduction of octahedral Fe3+ to octahedral Fe2+ is the most likely
crystallites. Because the crystallite size effects were different for the assignment for the 1.10 V peak. For all crystallite sizes, our CV data
pulse discharge data 共Fig. 5兲 than for the background discharge data were not reversible. This is consistent with the previous statement of
共Fig. 3兲, this suggests that these are kinetically driven phenomena. Thackeray and co-workers that lithium-insertion reactions for x
The structural changes accompanying lithiation of Fe3O4 have 艋 1 in LixFe3O4 were irreversible by CV, although their data were
been investigated by XRD studies2,3,21-24 as well as theoretical en- not reported.4
ergy simulation studies.25 In the A关B2兴O4 inverse spinel structure, A
cations occupy 1/8 of the tetrahedral sites and B cations occupy 1/2 Conclusion
of the octahedral sites. Magnetite 共Fe3O4兲 is an inverse spinel, These results demonstrate the successful use of nanosized Fe3O4
where Fe3+ cations 共A, B⬘兲 occupy tetrahedral and octahedral sites, as a lithium-battery cathode material. Crystallite size control of the
while Fe2+ cations occupy other octahedral sites 共B⬙兲. Common Fe3O4 provided the ability to significantly impact its electrochemical

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 A94 Electrochemical and Solid-State Letters, 12 共4兲 A91-A94 共2009兲

properties in primary batteries. On electrochemical test, a strong 15. P. Scherrer, Nachr. Ges. Wiss. Goettingen, Math.-Phys. Kl., 1918, 96.
16. A. L. Patterson, Phys. Rev., 56, 978 共1939兲.
correlation between performance and crystallite size was observed, 17. H. Iida, K. Takayanagi, T. Nakanishi, and T. Osaka, J. Colloid Interface Sci., 314,
resulting in a ⬃30% capacity increase across our Fe3O4 crystallite 274 共2007兲.
size range studied. To our knowledge, this is the first study of elec- 18. I. Martinez-Mera, M. E. Espinosa-Pesqueira, R. Perez-Hernandez, and J. Arenas-
trochemical effects of Fe3O4 crystallite size, where all nanocrystal- Alatorre, Mater. Lett., 61, 4447 共2007兲.
19. W.-G. Yu, T.-L. Zhang, X.-J. Qiao, J.-G. Zhang, and L. Yang, Mater. Sci. Eng., B,
line samples were prepared using the same synthetic method. Along 136, 101 共2007兲.
with good battery performance, the environmentally friendly nature 20. C. W. Kwon, M. Quintin, S. Mornet, C. Barbieri, O. Devos, G. Campet, and M. H.
and low cost of this material make it deserving of further electro- Delville, J. Electrochem. Soc., 151, A1445 共2004兲.
chemical study. 21. J. Rodriguez and J. Fontcuberta, J. Mater. Sci., 22, 1001 共1987兲.
22. J. Fontcuberta, J. Rodriguez, M. Pernet, G. Longworth, and J. B. Goodenough, J.
University at Buffalo assisted in meeting the publication costs of this Appl. Phys., 59, 1918 共1986兲.
article. 23. M. Pernet and P. Strobel, Defect Diffus. Forum, 127–128, 73 共1995兲.
24. J. M. Neto, E. Nunez, and P. H. Domingues, Mater. Res. Bull., 25, 509 共1990兲.
25. M. S. Islam and C. R. A. Catlow, J. Solid State Chem., 77, 180 共1988兲.
References 26. P. Encinas Bachiller, M. L. Tascon Garcia, M. D. Vazquez Barbado, and P. Sanchez
1. J. F. Jackovitz and G. A. Bayles, in Handbook of Batteries, 3rd ed., D. Linden and Batanero, J. Electroanal. Chem., 424, 217 共1997兲.
T. B. Reddy, Editors, p. 25.1, Mc-Graw Hill, New York 共2002兲. 27. P. D. Allen, N. A. Hampson, and G. J. Bignold, J. Electroanal. Chem. Interfacial
2. M. M. Thackeray, J. Am. Ceram. Soc., 82, 3347 共1999兲. Electrochem., 111, 223 共1980兲.
3. M. M. Thackeray, W. I. F. David, and J. B. Goodenough, Mater. Res. Bull., 17, 785 28. P. D. Allen, N. A. Hampson, and G. J. Bignold, J. Electroanal. Chem. Interfacial
共1982兲. Electrochem., 99, 299 共1979兲.
4. M. M. Thackeray, L. A. De Picciotto, A. De Kock, P. J. Johnson, V. A. Nicholas, 29. P. D. Allen, G. J. Bignold, and N. A. Hampson, J. Electroanal. Chem. Interfacial
and K. T. Adendorff, J. Power Sources, 21, 1 共1987兲. Electrochem., 112, 239 共1980兲.
5. P. L. Taberna, S. Mitra, P. Poizot, P. Simon, and J. M. Tarascon, Nature Mater., 5, 30. J. M. Lecuire and O. Evrard, J. Electroanal. Chem. Interfacial Electrochem., 78,
567 共2006兲. 331 共1977兲.
6. S. Mitra, P. Poizot, A. Finke, and J.-M. Tarascon, Adv. Funct. Mater., 16, 2281 31. J. M. Lecuire, J. Electroanal. Chem. Interfacial Electrochem., 66, 195 共1975兲.
共2006兲. 32. J. M. Lecuire, Analusis, 2, 495 共1973兲.
7. C.-L. Teng and M. P. Ryan, Electrochem. Solid-State Lett., 10, D108 共2007兲. 33. J. M. Lecuire, Analusis, 2, 489 共1973兲.
8. N.-L. Wu, S.-Y. Wang, C.-Y. Han, D.-S. Wu, and L.-R. Shiue, J. Power Sources, 34. V. B. Fetisov, A. N. Ermakov, G. M. Belysheva, A. V. Fetisov, V. M. Kamyshov,
113, 173 共2003兲. and K. Z. Brainina, J. Solid State Electrochem., 8, 565 共2004兲.
9. S.-Y. Wang, K.-C. Ho, S.-L. Kuo, and N.-L. Wu, J. Electrochem. Soc., 153, A75 35. F. J. Santos, L. C. Varanda, L. C. Ferracin, and M. Jafelicci, Jr., J. Phys. Chem. C,
共2006兲. 112, 5301 共2008兲.
10. V. Sivakumar, S. Kumar, C. A. Ross, and Y. Shao-Horn, ECS Trans., 2共8兲, 1 36. P. Encinas, L. Lorenzo, M. L. Tascon, M. D. Vazquez, and P. Sanchez-Batanero, J.
共2007兲. Electroanal. Chem., 371, 161 共1994兲.
11. V. Sivakumar, S. Kumar, C. A. Ross, and Y. Shao-Horn, IEEE Trans. Magn., 43, 37. E. Barrado, J. I. Montequi, J. Medina, R. Pardo, and F. Prieto, J. Electroanal.
3121 共2007兲. Chem., 441, 227 共1998兲.
12. S. Ito, K. Nakaoka, M. Kawamura, K. Ui, K. Fujimoto, and N. Koura, J. Power 38. A. F. White, M. L. Peterson, and M. F. Hochella, Jr., Geochim. Cosmochim. Acta,
Sources, 146, 319 共2005兲. 58, 1859 共1994兲.
13. S. Komaba, T. Mikumo, and A. Ogata, Electrochem. Commun., 10, 1276 共2008兲. 39. Z. Z. Sharara, O. Vittori, and B. Durand, Electrochim. Acta, 29, 1685 共1984兲.
14. National Bureau of Standards, U.S. Monograph, PDF no. 00-019-0629, p. 31 40. C. M. Das and M. Sudersanan, J. Appl. Electrochem., 33, 333 共2003兲.
共1967兲. 41. M. Laffitte, Cours de Chimie Minerale, Gauthiers-Villars, Paris 共1967兲.

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