Electrochemical impedance spectroscopy analysis with a symmetric cell for LiCoO<sub>2</sub> cathode degradation correlated with Co dissolution

Hiroki Nara; Keisuke Morita; Tokihiko Yokoshima; Daikichi Mukoyama; Toshiyuki Momma; Tetsuya Osaka; Hiroki Nara; Keisuke Morita; Tokihiko Yokoshima; Daikichi Mukoyama; Toshiyuki Momma; Tetsuya Osaka

doi:10.3934/matersci.2016.2.448

AIMS Materials Science

2016, Volume 3, Issue 2: 448-459. doi: 10.3934/matersci.2016.2.448

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Electrochemical impedance spectroscopy analysis with a symmetric cell for LiCoO₂ cathode degradation correlated with Co dissolution

1.
Research Institute for Science and Engineering, Waseda University, 3-4-1, Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
2.
Graduate School of Science and Engineering, Waseda University, 3-4-1, Okubo, Shinjuku-ku, Tokyo 169-8555, Japan

Received: 18 January 2016 Accepted: 28 March 2016 Published: 05 April 2016

Static degradation of LiCoO₂ cathodes is a problem that hinders accurate analysis using our developed separable symmetric cell. Therefore, in this study we investigate the static degradation of LiCoO₂ cathodes in separable symmetric cells by electrochemical impedance spectroscopy (EIS) and inductively coupled plasma analyses. EIS measurements of LiCoO₂ cathodes are conducted in various electrolytes, with different anions and with or without HF and/or H₂O. This allows us to determine the static degradation of LiCoO₂ cathodes relative to their increase of charge transfer resistance. The increase of the charge transfer resistance of the LiCoO₂ cathodes is attributed to cobalt dissolution from the active material of LiCoO₂. Cobalt dissolution from LiCoO₂ is revealed to occur even at low potential in the presence of HF, which is generated from LiPF₆ and H₂O. The results indicate that avoidance of HF generation is important for the analysis of lithium-ion battery electrodes by using the separable cell. These findings reveal the condition to achieve accurate analysis by EIS using the separable cell.
- electrochemical impedance spectroscopy (EIS),
- Lithium-ion Battery (LIB),
- LiCoO₂ cathode,
- degradation,
- Co dissolution,
- LiPF₆,
- LiClO₄,
- HF
Citation: Hiroki Nara, Keisuke Morita, Tokihiko Yokoshima, Daikichi Mukoyama, Toshiyuki Momma, Tetsuya Osaka. Electrochemical impedance spectroscopy analysis with a symmetric cell for LiCoO2 cathode degradation correlated with Co dissolution[J]. AIMS Materials Science, 2016, 3(2): 448-459. doi: 10.3934/matersci.2016.2.448

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Abstract

Static degradation of LiCoO₂ cathodes is a problem that hinders accurate analysis using our developed separable symmetric cell. Therefore, in this study we investigate the static degradation of LiCoO₂ cathodes in separable symmetric cells by electrochemical impedance spectroscopy (EIS) and inductively coupled plasma analyses. EIS measurements of LiCoO₂ cathodes are conducted in various electrolytes, with different anions and with or without HF and/or H₂O. This allows us to determine the static degradation of LiCoO₂ cathodes relative to their increase of charge transfer resistance. The increase of the charge transfer resistance of the LiCoO₂ cathodes is attributed to cobalt dissolution from the active material of LiCoO₂. Cobalt dissolution from LiCoO₂ is revealed to occur even at low potential in the presence of HF, which is generated from LiPF₆ and H₂O. The results indicate that avoidance of HF generation is important for the analysis of lithium-ion battery electrodes by using the separable cell. These findings reveal the condition to achieve accurate analysis by EIS using the separable cell.

References

[1]	Nishi Y (2001) Lithium ion secondary batteries; past 10 years and the future. J Power Sources 100: 101–106.
[2]	Etacheri V, Marom R, Elazari R, et al. (2011) Challenges in the development of advanced Li-ion batteries: a review. Energy Environ Sci 4: 3243–3262. doi: 10.1039/c1ee01598b
[3]	Dunn B, Kamath H, Tarascon J-M (2011) Electrical energy storage for the grid: a battery of choices. Science 334: 928–935. doi: 10.1126/science.1212741
[4]	Yang Z, Zhang J, Kintner-Meyer MCW, et al. (2011) Electrochemical Energy Storage for Green Grid. Chem Rev 111: 3577–3613. doi: 10.1021/cr100290v
[5]	Broussely M, Biensan P, Bonhomme F, et al. (2005) Main aging mechanisms in Li ion batteries. J Power Sources 146: 90–96. doi: 10.1016/j.jpowsour.2005.03.172
[6]	Vetter J, Novák P, Wagner MR, et al. (2005) Ageing mechanisms in lithium-ion batteries. J Power Sources 147: 269–281.
[7]	Smart MC, Ratnakumar BV (2011) Effects of Electrolyte Composition on Lithium Plating in Lithium-Ion Cells. J Electrochem Soc 158: A379–A389. doi: 10.1149/1.3544439
[8]	Aurbach D, Markovsky B, Salitra G, et al. (2007) Talyossef, M. Koltypin, et al., Review on electrode–electrolyte solution interactions, related to cathode materials for Li-ion batteries. J Power Sources 165: 491–499.
[9]	Aurbach D, Markovsky B, Rodkin A, et al. (2002) On the capacity fading of LiCoO2 intercalation electrodes. Electrochimica Acta 47: 4291–4306. doi: 10.1016/S0013-4686(02)00417-6
[10]	Takami N, Satoh A, Hara M, et al. (1995) Structural and Kinetic Characterization of Lithium Intercalation into Carbon Anodes for Secondary Lithium Batteries. J Electrochem Soc 142: 371–379. doi: 10.1149/1.2044017
[11]	Aurbach D, Levi MD, Levi E, et al. (1998) Common Electroanalytical Behavior of Li Intercalation Processes into Graphite and Transition Metal Oxides. J Electrochem Soc 145: 3024–3034. doi: 10.1149/1.1838758
[12]	Markovsky B, Levi MD, Aurbach D (1998) The basic electroanalytical behavior of practical graphite–lithium intercalation electrodes. Electrochimica Acta 43: 2287–2304. doi: 10.1016/S0013-4686(97)10172-4
[13]	Barsoukov E, Kim JH, Yoon CO, et al. (1999) Kinetics of lithium intercalation into carbon anodes: in situ impedance investigation of thickness and potential dependence. Solid State Ionics.
[14]	Zhang D, Haran BS, Durairajan A, et al. (2000) Studies on capacity fade of lithium-ion batteries. J Power Sources 91: 122–129. doi: 10.1016/S0378-7753(00)00469-9
[15]	Nagasubramanian G (2000) Two- and three-electrode impedance studies on 18650 Li-ion cells. J Power Sources 87: 226–229. doi: 10.1016/S0378-7753(99)00469-3
[16]	Li J, Murphy E, Winnick J, et al. (2001) Studies on the cycle life of commercial lithium ion batteries during rapid charge–discharge cycling. J Power Sources 102: 294–301. doi: 10.1016/S0378-7753(01)00821-7
[17]	Seki S, Kihira N, Mita Y, et al. (2011) AC Impedance Study of High-Power Lithium-Ion Secondary Batteries—Effect of Battery Size. J Electrochem Soc 158: A163–A166. doi: 10.1149/1.3525277
[18]	Mukoyama D, Momma T, Nara H, et al. (2012) Electrochemical Impedance Analysis on Degradation of Commercially Available Lithium Ion Battery during Charge–Discharge Cycling. Chem Lett 41: 444–446. doi: 10.1246/cl.2012.444
[19]	Osaka T, Momma T, Mukoyama D, et al. (2012) Proposal of novel equivalent circuit for electrochemical impedance analysis of commercially available lithium ion battery. J Power Sources 205: 483–486.
[20]	Hang T, Mukoyama D, Nara H, et al. (2013) Electrochemical impedance spectroscopy analysis for lithium-ion battery using Li4Ti5O12 anode. J Power Sources 222: 442–447. doi: 10.1016/j.jpowsour.2012.09.010
[21]	Illig J, Ender M, Weber A, et al. (2015) Modeling graphite anodes with serial and transmission line models. J Power Sources 282: 335–347. doi: 10.1016/j.jpowsour.2015.02.038
[22]	Hoshi Y, Narita Y, Honda K, et al. (2015) Optimization of reference electrode position in a three-electrode cell for impedance measurements in lithium-ion rechargeable battery by finite element method. J Power Sources 288: 168–175. doi: 10.1016/j.jpowsour.2015.04.065
[23]	Osaka T, Mukoyama D, Nara H (2015) Review—Development of Diagnostic Process for Commercially Available Batteries, Especially Lithium Ion Battery, by Electrochemical Impedance Spectroscopy. J Electrochem Soc 162: A2529–A2537.
[24]	Osaka T, Nara H, Mukoyama D, et al. (2013) New Analysis of Electrochemical Impedance Spectroscopy for Lithium-ion Batteries. J Electrochem Sci Tech 4: 157–162. doi: 10.5229/JECST.2013.4.4.157
[25]	Mendoza-Hernandez OS, Ishikawa H, Nishikawa Y, et al. (2014) State of Charge Dependency of Graphitized-Carbon-Based Reactions in a Lithium-ion Secondary Cell Studied by Electrochemical Impedance Spectroscopy. Electrochimica Acta 131: 168–173. doi: 10.1016/j.electacta.2014.01.057
[26]	Bünzli C, Kaiser H, Novák P (2015) Important Aspects for Reliable Electrochemical Impedance Spectroscopy Measurements of Li-Ion Battery Electrodes. J Electrochem Soc 162: A218–A222.
[27]	Yokoshima T, Nara H, Mukoyama D, et al. (2011) Performance of Fine Reference Electrode in Thin Laminated Li-Ion Cell, in: Meet. Abstr, The Electrochemical Society, pp. 1451–1451.
[28]	Jansen AN, Dees DW, Abraham DP, et al. ((2007)) Low-temperature study of lithium-ion cells using a LiySn micro-reference electrode. J Power Sources 174: 373–379.
[29]	La Mantia F, Wessells CD, Deshazer HD, et al. (2013) Reliable reference electrodes for lithium-ion batteries. Electrochem Commun 31: 141–144.
[30]	Gómez-Cámer JL, Novák P (2013) Electrochemical impedance spectroscopy: Understanding the role of the reference electrode. Electrochem Commun 34: 208–210. doi: 10.1016/j.elecom.2013.06.016
[31]	Adler SB (2002) Reference Electrode Placement in Thin Solid Electrolytes. J Electrochem Soc 149: E166–E172. doi: 10.1149/1.1467368
[32]	Klink S, Höche D, La Mantia F, et al. (2013) FEM modelling of a coaxial three-electrode test cell for electrochemical impedance spectroscopy in lithium ion batteries. J Power Sources 240: 273–280. doi: 10.1016/j.jpowsour.2013.03.186
[33]	Momma T, Yokoshima T, Nara H, et al. (2014) Distinction of impedance responses of Li-ion batteries for individual electrodes using symmetric cells. Electrochimica Acta 131: 195–201. doi: 10.1016/j.electacta.2014.01.091
[34]	Chen CH, Liu J, Amine K (2001) Symmetric cell approach and impedance spectroscopy of high power lithium-ion batteries. J Power Sources 96: 321–328.
[35]	Levi MD, Dargel V, Shilina Y, et al. (2014) Impedance Spectra of Energy-Storage Electrodes Obtained with Commercial Three-Electrode Cells: Some Sources of Measurement Artefacts. Electrochimica Acta 149: 126–135. doi: 10.1016/j.electacta.2014.10.083
[36]	Amatucci G (1996) Cobalt dissolution in LiCoO2-based non-aqueous rechargeable batteries. Solid State Ionics 83: 167–173.
[37]	Levi MD, Salitra G, Markovsky B, et al. (1999) Solid‐State Electrochemical Kinetics of Li‐Ion Intercalation into Li1 − x CoO2: Simultaneous Application of Electroanalytical Techniques SSCV, PITT, and EIS. J Electrochem Soc 146: 1279–1289.
[38]	Momma T, Matsunaga M, Mukoyama D, et al. (2012) Ac impedance analysis of lithium ion battery under temperature control. J Power Sources 216: 304–307. doi: 10.1016/j.jpowsour.2012.05.095
[39]	Nara H, Mukoyama D, Yokoshima T, et al. (2016) Impedance Analysis with Transmission Line Model for Reaction Distribution in a Pouch Type Lithium-Ion Battery by Using Micro Reference Electrode. J Electrochem Soc 163: A434–A441.

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