Citation: Zhang Tong, Yang Zi, Li Hongliang, Zhuang Quanchao, Cui Yanhua. Electrochemical Impedance Spectroscopic Studies of All Solid State battery with Li₁₀GeP₂S₁₂ as Electrolyte[J]. Acta Chimica Sinica, ;2019, 77(6): 525-532. doi: 10.6023/A19010013 shu

Electrochemical Impedance Spectroscopic Studies of All Solid State battery with Li₁₀GeP₂S₁₂ as Electrolyte

a.
School of Materials Science and Engineering, China University of Mining and Technology, Xuzhou 221116
b.
Institute of Electronic Engineering, China Academy of Engineering Physics, Mianyang 621900

Corresponding author: Zhuang Quanchao, zhuangquanchao@126.com Cui Yanhua, cuiyanhua@netease.com
Received Date: 5 January 2019
Available Online: 9 June 2019
Fund Project: the National Natural Science Foundation of China U1730136Project supported by the National Natural Science Foundation of China (No. U1730136)

Figures(12)

All-solid-state batteries will be the main direction of lithium-ion batteries in the future. Current research mainly focuses on improving the conductivity of solid-state electrolytes, but there are few studies on the electronic and ionic transport in all solid state batteries. In this paper, we synthesized Li₁₀GeP₂S₁₂ through high temperature solid phase method. The ionic conductivity of Li₁₀GeP₂S₁₂ at room temperature is 2.02×10^-3 S/cm and it's activation energy calculated from Arrhenius plots is 29.8 kJ/mol. The all solid-state battery of LiNbO₃@LiNi_1/3Co_1/3Mn_1/3O₂/Li₁₀GeP₂S₁₂/Li was successfully fabricated and characterized by galvanostatic charge/discharge (DC), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The first discharge capacity of the all-solid-state battery is 121.2 mAh/g, the coulombic efficiency stabilize at 99.8% after 40 weeks and the capacity retention rate is 93.7% after 100 weeks. After analyzing the electrochemical impedance spectroscopy, the typical impedance spectra of the battery is composed of high frequency semicircle (HFS), middle frequency semicircle (MFS) and low frequency line (LFL). And HFS belongs to the impedance of electrolyte (R_el), MFS belongs to charge transfer impedance (R_ct) and LFL belongs to diffusion process of lithium ion in active material. The continuous increase of R_el between 3.8 V and 4.3 V is due to the decomposition of LGPS to GeS₂, S and P₂S₅ at high potential, which results in the decrease of grain conductivity. On the other hand, the voltage range of 3.8~4.3 V is near the charging and discharging plateau at which concentration polarization is large. The stress in the crystal may lead to the breakup of some grains which resulting in the generation of more grain boundaries and the increase of grain boundary impedance. According to the fitting results of R_ct, we find that R_ct decreases with the increase of potential until 4.3 V at which R_ct reaches the minimum value in the first process of charging and it is a reversible process while discharging.
- all solid state batteries,
- Li₁₀GeP₂S₁₂,
- electrochemical impedance spectroscopy,
- charge transfer resistance
1. [1]
  Goodenough, J. B.; Kim, Y. Chem. Mater. 2010, 22, 587. doi: 10.1021/cm901452z
2. [2]
  Jin, Z. Q.; Xie, K.; Hong, X. B. Acta Chim. Sinica 2014, 72, 11(in Chinese).
3. [3]
  Liu, J.; Xu, J. Y.; Lin, Y.; Li, J.; Lai, Y. Q.; Yuan, C. F.; Zhang, J.; Zhu, K. Acta Chim. Sinica 2013, 71, 869(in Chinese).
4. [4]
  Bachman, J. C.; Muy, S.; Grimaud, A.; Chang, H. H.; Pour, N.; Lux, S. F.; Paschos, O.; Maglia, F.; Lupart, S.; Lamp, P. Chem. Rev. 2016, 47, 140.
5. [5]
  Lin, D.; Liu, Y.; Cui, Y. Nat. Nanotechnol. 2017, 12, 194. doi: 10.1038/nnano.2017.16
6. [6]
  Qiu, Z.; Zhang, Y.; Xia, S.; Dong, P. Acta Chim. Sinica 2015, 73, 992(in Chinese).
7. [7]
  Liu, W. Y.; Fu, Z. W.; Qin, Q. Z. Acta Chim. Sinica 2004, 62, 2223(in Chinese). doi: 10.3321/j.issn:0567-7351.2004.22.004
8. [8]
  Deng, Z.; Mo, Y.; Ong, S. P. NPG Asia Mater. 2016, 8, e254. doi: 10.1038/am.2016.7
9. [9]
  Manthiram, A.; Yu, X.; Wang, S. Nat. Rev. Mater. 2017, 2, 16103. doi: 10.1038/natrevmats.2016.103
10. [10]
  Ramakumar, S.; Deviannapoorani, C.; Dhivya, L.; Shankar, L. S.; Murugan, R. Prog. Mater. Sci. 2017, 88, 325. doi: 10.1016/j.pmatsci.2017.04.007
11. [11]
  Xu, H. H.; Wang, S. F.; Wilson, H.; Zhao, F.; Manthiram, A. Chem. Mater. 2017, 29, 7206. doi: 10.1021/acs.chemmater.7b01463
12. [12]
  Zhang, B.; Rui, T.; Yang, L.; Zheng, J.; Zhang, K.; Mo, S.; Zhan, L.; Feng, P. Energy Storage Mater. 2018, 10, 139. doi: 10.1016/j.ensm.2017.08.015
13. [13]
  He, X.; Zhu, Y.; Mo, Y. Nat. Commun. 2017, 8, 15893. doi: 10.1038/ncomms15893
14. [14]
  Fergus, J. W. J. Power Sources 2010, 195, 4554. doi: 10.1016/j.jpowsour.2010.01.076
15. [15]
  Minami, T.; Hayashi, A.; Tatsumisago, M. Solid State Ion. 2006, 177, 2715. doi: 10.1016/j.ssi.2006.07.017
16. [16]
  Luo, W.; Gong, Y.; Zhu, Y.; Li, Y.; Yao, Y.; Zhang, Y.; Fu, K. K.; Pastel, G.; Lin, C. F.; Mo, Y. Adv. Mater. 2017, 29, 1606042. doi: 10.1002/adma.201606042
17. [17]
  Zhu, Y.; He, X.; Mo, Y. J. Mater. Chem. A 2016, 4, 3253. doi: 10.1039/C5TA08574H
18. [18]
  Wang, Q.; Wen, Z.; Jin, J.; Guo, J.; Huang, X.; Yang, J.; Chen, C. Chem. Commun (Camb). 2016, 52, 1637. doi: 10.1039/C5CC08279J
19. [19]
  Li, Y.; Zhou, W.; Chen, X.; Lü, X.; Cui, Z.; Xin, S.; Xue, L.; Jia, Q.; Goodenough, J. B. Proc. Natl. Acad. Sci. U. S. A. 2016, 113, 13313. doi: 10.1073/pnas.1615912113
20. [20]
  Kato, A.; Hayashi, A.; Tatsumisago, M. J. Power Sources 2016, 309, 27. doi: 10.1016/j.jpowsour.2016.01.068
21. [21]
  Zhu, Y.; He, X.; Mo, Y. ACS Appl. Mater. Interfaces 2015, 7, 23685. doi: 10.1021/acsami.5b07517
22. [22]
  Sharafi, A.; Kazyak, E.; Davis, A. L.; Yu, S.; Thompson, T.; Siegel, D. J.; Dasgupta, N. P.; Sakamoto, J. Chem. Mater. 2017, 29, 7961. doi: 10.1021/acs.chemmater.7b03002
23. [23]
  Takada, K. Langmuir 2013, 29, 7538. doi: 10.1021/la3045253
24. [24]
  Yokokawa, H. Solid State Ion. 2016, 285, 126. doi: 10.1016/j.ssi.2015.05.010
25. [25]
  Long, P.; Xu, Q.; Peng, G.; Yao, X.; Xu, X. ChemElectroChem 2016, 3, 764. doi: 10.1002/celc.201500570
26. [26]
  Wan, H.; Gang, P.; Yao, X.; Jing, Y.; Ping, C.; Xu, X. Energy Storage Mater. 2016, 4, 59. doi: 10.1016/j.ensm.2016.02.004
27. [27]
  Nagao, M.; Kitaura, H.; Hayashi, A.; Tatsumisago, M. J. Power Sources 2009, 189, 672. doi: 10.1016/j.jpowsour.2008.09.025
28. [28]
  Gao, J.; Zhao, Y. S.; Shi, S. Q.; Li, H. Chinese Phys. B 2016, 25, 35.
29. [29]
  Haruyama, J.; Sodeyama, K.; Tateyama, Y. ACS Appl. Mater. Interfaces 2017, 9, 286. doi: 10.1021/acsami.6b08435
30. [30]
  Tatsumisago, M.; Nagao, M.; Hayashi, A. J. Asian Ceram. Soc. 2013, 1, 17. doi: 10.1016/j.jascer.2013.03.005
31. [31]
  Noriaki, K.; Kenji, H.; Yuichiro, Y.; Masaaki, H.; Ryoji, K.; Masao, Y.; Takashi, K.; Yuki, K.; Shigenori, H.; Koji, K. Nat. Mater. 2011, 10, 682. doi: 10.1038/nmat3066
32. [32]
  Amani, J. A.; Koppe, T.; Hofsäss, H.; Vetter, U. Phys. Rev. Appl. 2015, 4, 044007. doi: 10.1103/PhysRevApplied.4.044007
33. [33]
  Zhuang, Q. C.; Xu, S. D.; Qiu, X. Y.; Cui, Y. L.; Fang, L.; Sun, S. G. Prog. Chem. 2010, 22, 1044(in Chinese).
34. [34]
  Siroma, Z.; Sato, T.; Takeuchi, T.; Nagai, R.; Ota, A.; Ioroi, T. J. Power Sources 2016, 316, 215. doi: 10.1016/j.jpowsour.2016.03.059
35. [35]
  Boulineau, S.; Courty, M.; Tarascon, J. M.; Viallet, V. Solid State Ion. 2012, 221, 1. doi: 10.1016/j.ssi.2012.06.008
36. [36]
  Han, F.; Gao, T.; Zhu, Y.; Gaskell, K. J.; Wang, C. Adv. Mater. 2015, 27, 3473. doi: 10.1002/adma.v27.23
37. [37]
  Qiu, X. Y.; Zhuan, Q. C.; Zhang, Q. Q.; Cao, R.; Qiang, Y. H.; Ying, P. Z.; Sun, S. G. J. Electroanal. Chem. 2013, 688, 392. doi: 10.1016/j.jelechem.2013.02.019
38. [38]
  Liu, W.; Sun, D.; Feng, T.; Xia, J.; Wang, Q.; Jiang, D. J. Ceram. 2013, 34, 555(in Chinese). doi: 10.3969/j.issn.1000-2278.2013.04.032
39. [39]
  Verkerk, M.; Middelhuis, B.; Burggraaf, A. Solid State Ion. 1982, 6, 159. doi: 10.1016/0167-2738(82)90083-2
40. [40]
  Näfe, H. Solid State Ion. 1984, 13, 255. doi: 10.1016/0167-2738(84)90040-7
41. [41]
  Mo, Y.; Ong, S. P.; Ceder, G. Chem. Mater. 2012, 24, 15. doi: 10.1021/cm203303y
42. [42]
  Levi, M. D.; Gamolsky, K.; Aurbach, D.; Heider, U.; Oesten, R. Electrochim. Acta 2000, 45, 1781. doi: 10.1016/S0013-4686(99)00402-8
43. [43]
  Ohta, N.; Takada, K.; Sakaguchi, I.; Zhang, L. Q.; Ma, R. Z.; Fukuda, K.; Osada, M.; Sasaki, T. Electrochem. Commun. 2007, 9, 1486. doi: 10.1016/j.elecom.2007.02.008
1. [1]
  Lingbang Qiu , Jiangmin Jiang , Libo Wang , Lang Bai , Fei Zhou , Gaoyu Zhou , Quanchao Zhuang , Yanhua Cui . In Situ Electrochemical Impedance Spectroscopy Monitoring of the High-Temperature Double-Discharge Mechanism of Nb₁₂WO₃₃ Cathode Material for Long-Life Thermal Batteries. Acta Physico-Chimica Sinica, 2025, 41(5): 100040-0. doi: 10.1016/j.actphy.2024.100040
2. [2]
  Zeyu Liu , Wenze Huang , Yang Xiao , Jundong Zhang , Weijin Kong , Peng Wu , Chenzi Zhao , Aibing Chen , Qiang Zhang . Nanocomposite Current Collectors for Anode-Free All-Solid-State Lithium Batteries. Acta Physico-Chimica Sinica, 2024, 40(3): 2305040-0. doi: 10.3866/PKU.WHXB202305040
3. [3]
  Mingyang Men , Jinghua Wu , Gaozhan Liu , Jing Zhang , Nini Zhang , Xiayin Yao . Sulfide Solid Electrolyte Synthesized by Liquid Phase Approach and Application in All-Solid-State Lithium Batteries. Acta Physico-Chimica Sinica, 2025, 41(1): 100004-0. doi: 10.3866/PKU.WHXB202309019
4. [4]
  Da Wang , Xiaobin Yin , Jianfang Wu , Yaqiao Luo , Siqi Shi . All-Solid-State Lithium Cathode/Electrolyte Interfacial Resistance: From Space-Charge Layer Model to Characterization and Simulation. Acta Physico-Chimica Sinica, 2024, 40(7): 2307029-0. doi: 10.3866/PKU.WHXB202307029
5. [5]
  Xuechen Hu , Qiuying Xia , Fan Yue , Xinyi He , Zhenghao Mei , Jinshi Wang , Hui Xia , Xiaodong Huang . Electrochemical Characteristics of LiNbO₃ Anode Film and Its Applications in All-Solid-State Thin-Film Lithium-Ion Battery. Acta Physico-Chimica Sinica, 2024, 40(2): 2309046-0. doi: 10.3866/PKU.WHXB202309046
6. [6]
  Tao Jiang , Yuting Wang , Lüjin Gao , Yi Zou , Bowen Zhu , Li Chen , Xianzeng Li . Experimental Design for the Preparation of Composite Solid Electrolytes for Application in All-Solid-State Batteries: Exploration of Comprehensive Chemistry Laboratory Teaching. University Chemistry, 2024, 39(2): 371-378. doi: 10.3866/PKU.DXHX202308057
7. [7]
  Ping Ye , Lingshuang Qin , Mengyao He , Fangfang Wu , Zengye Chen , Mingxing Liang , Libo Deng . Potential of Zero Charge-Mediated Electrochemical Capture of Cadmium Ions from Wastewater by Lotus Leaf-Derived Porous Carbons. Acta Physico-Chimica Sinica, 2025, 41(3): 2311032-0. doi: 10.3866/PKU.WHXB202311032
8. [8]
  Yong Zhou , Jia Guo , Yun Xiong , Luying He , Hui Li . Comprehensive Teaching Experiment on Electrochemical Corrosion in Galvanic Cell for Chemical Safety and Environmental Protection Course. University Chemistry, 2024, 39(7): 330-336. doi: 10.3866/PKU.DXHX202310109
9. [9]
  Yue-Zhou Zhu , Kun Wang , Shi-Sheng Zheng , Hong-Jia Wang , Jin-Chao Dong , Jian-Feng Li . Application and Development of Electrochemical Spectroscopy Methods. Acta Physico-Chimica Sinica, 2024, 40(3): 2304040-0. doi: 10.3866/PKU.WHXB202304040
10. [10]
  Dong Xiang , Kunzhen Li , Kanghua Miao , Ran Long , Yujie Xiong , Xiongwu Kang . Amine-Functionalized Copper Catalysts: Hydrogen Bonding Mediated Electrochemical CO₂ Reduction to C₂ Products and Superior Rechargeable Zn-CO₂ Battery Performance. Acta Physico-Chimica Sinica, 2024, 40(8): 2308027-0. doi: 10.3866/PKU.WHXB202308027
11. [11]
  Qingtang ZHANG , Xiaoyu WU , Zheng WANG , Xiaomei WANG . Performance of nano Li₂FeSiO₄/C cathode material co-doped by potassium and chlorine ions. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1689-1696. doi: 10.11862/CJIC.20240115
12. [12]
  Xinpeng LIU , Liuyang ZHAO , Hongyi LI , Yatu CHEN , Aimin WU , Aikui LI , Hao HUANG . Ga₂O₃ coated modification and electrochemical performance of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ cathode material. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1105-1113. doi: 10.11862/CJIC.20230488
13. [13]
  Jiahong ZHENG , Jingyun YANG . Preparation and electrochemical properties of hollow dodecahedral CoNi₂S₄ supported by MnO₂ nanowires. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1881-1891. doi: 10.11862/CJIC.20240170
14. [14]
  Qianwen Han , Tenglong Zhu , Qiuqiu Lü , Mahong Yu , Qin Zhong . Performance and Electrochemical Asymmetry Optimization of Hydrogen Electrode Supported Reversible Solid Oxide Cell. Acta Physico-Chimica Sinica, 2025, 41(1): 100005-0. doi: 10.3866/PKU.WHXB202309037
15. [15]
  Hongyi LI , Aimin WU , Liuyang ZHAO , Xinpeng LIU , Fengqin CHEN , Aikui LI , Hao HUANG . Effect of Y(PO₃)₃ double-coating modification on the electrochemical properties of Li[Ni_0.8Co_0.15Al_0.05]O₂. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1320-1328. doi: 10.11862/CJIC.20230480
16. [16]
  Xue Dong , Xiaofu Sun , Shuaiqiang Jia , Shitao Han , Dawei Zhou , Ting Yao , Min Wang , Minghui Fang , Haihong Wu , Buxing Han . Electrochemical CO₂ Reduction to C₂₊ Products with Ampere-Level Current on Carbon-Modified Copper Catalysts. Acta Physico-Chimica Sinica, 2025, 41(3): 2404012-0. doi: 10.3866/PKU.WHXB202404012
17. [17]
  Shuhui Li , Rongxiuyuan Huang , Yingming Pan . Electrochemical Synthesis of 2,5-Diphenyl-1,3,4-Oxadiazole: A Recommended Comprehensive Organic Chemistry Experiment. University Chemistry, 2025, 40(5): 357-365. doi: 10.12461/PKU.DXHX202407028
18. [18]
  Weilai Yu , Chuanbiao Bie . Unveiling S-Scheme Charge Transfer Mechanism. Acta Physico-Chimica Sinica, 2024, 40(4): 2307022-0. doi: 10.3866/PKU.WHXB202307022
19. [19]
  Hong Yan , Wenfeng Wang , Keyin Ye , Yaofeng Yuan . Organic Electrochemistry and Its Integration into Chemistry Teaching. University Chemistry, 2025, 40(5): 301-310. doi: 10.12461/PKU.DXHX202407027
20. [20]
  Wenqi Gao , Xiaoyan Fan , Feixiang Wang , Zhuojun Fu , Jing Zhang , Enlai Hu , Peijun Gong . Exploring Nernst Equation Factors and Applications of Solid Zinc-Air Battery. University Chemistry, 2024, 39(5): 98-107. doi: 10.3866/PKU.DXHX202310026

Get Citation

PDF

XML

Metrics

PDF Downloads(43)
Abstract views(2816)
HTML views(838)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Electrochemical Impedance Spectroscopic Studies of All Solid State battery with Li10GeP2S12 as Electrolyte

Metrics

通讯作者: 陈斌, bchen63@163.com

Electrochemical Impedance Spectroscopic Studies of All Solid State battery with Li₁₀GeP₂S₁₂ as Electrolyte