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

doi:10.6023/A19010013

Acta Chim. Sinica ›› 2019, Vol. 77 ›› Issue (6): 525-532.DOI: 10.6023/A19010013 Previous Articles Next Articles

Article

Li₁₀GeP₂S₁₂固态电解质电极界面特性研究

张桐^a, 杨梓^a, 李红亮^a, 庄全超^a, 崔艳华^b

a 中国矿业大学材料科学与工程学院徐州 221116;
b 中国工程物理研究院电子工程研究所绵阳 621900

投稿日期:2019-01-05 发布日期:2019-05-10
通讯作者: 庄全超, 崔艳华 E-mail:zhuangquanchao@126.com;cuiyanhua@netease.com
基金资助:
项目受国家自然科学基金（No.U1730136）资助.

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

Zhang Tong^a, Yang Zi^a, Li Hongliang^a, Zhuang Quanchao^a, Cui Yanhua^b

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

Received:2019-01-05 Published:2019-05-10
Supported by:
Project supported by the National Natural Science Foundation of China (No. U1730136).

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.

Key words: all solid state batteries, Li₁₀GeP₂S₁₂, electrochemical impedance spectroscopy, charge transfer resistance

Cite this article

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 Chim. Sinica, 2019, 77(6): 525-532.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[1] Goodenough, J. B.; Kim, Y. Chem. Mater. 2010, 22, 587.
[2] Jin, Z. Q.; Xie, K.; Hong, X. B. Acta Chim. Sinica 2014, 72, 11(in Chinese). (金朝庆, 谢凯, 洪晓斌, 化学学报, 2014, 72, 11.)
[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). (刘晋, 徐俊毅, 林月, 李劼, 赖延清, 袁长福, 张锦, 朱凯, 化学学报, 2013, 71, 869.)
[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] Lin, D.; Liu, Y.; Cui, Y. Nat. Nanotechnol. 2017, 12, 194.
[6] Qiu, Z.; Zhang, Y.; Xia, S.; Dong, P. Acta Chim. Sinica 2015, 73, 992(in Chinese). (邱振平, 张英杰, 夏书标, 董鹏, 化学学报, 2015, 73, 992.)
[7] Liu, W. Y.; Fu, Z. W.; Qin, Q. Z. Acta Chim. Sinica 2004, 62, 2223(in Chinese). (刘文元, 傅正文, 秦启宗, 化学学报, 2004, 62, 2223.)
[8] Deng, Z.; Mo, Y.; Ong, S. P. NPG Asia Mater. 2016, 8, e254.
[9] Manthiram, A.; Yu, X.; Wang, S. Nat. Rev. Mater. 2017, 2, 16103.
[10] Ramakumar, S.; Deviannapoorani, C.; Dhivya, L.; Shankar, L. S.; Murugan, R. Prog. Mater. Sci. 2017, 88, 325.
[11] Xu, H. H.; Wang, S. F.; Wilson, H.; Zhao, F.; Manthiram, A. Chem. Mater. 2017, 29, 7206.
[12] Zhang, B.; Rui, T.; Yang, L.; Zheng, J.; Zhang, K.; Mo, S.; Zhan, L.; Feng, P. Energy Storage Mater. 2018, 10, 139.
[13] He, X.; Zhu, Y.; Mo, Y. Nat. Commun. 2017, 8, 15893.
[14] Fergus, J. W. J. Power Sources 2010, 195, 4554.
[15] Minami, T.; Hayashi, A.; Tatsumisago, M. Solid State Ion. 2006, 177, 2715.
[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.
[17] Zhu, Y.; He, X.; Mo, Y. J. Mater. Chem. A 2016, 4, 3253.
[18] Wang, Q.; Wen, Z.; Jin, J.; Guo, J.; Huang, X.; Yang, J.; Chen, C. Chem. Commun (Camb). 2016, 52, 1637.
[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.
[20] Kato, A.; Hayashi, A.; Tatsumisago, M. J. Power Sources 2016, 309, 27.
[21] Zhu, Y.; He, X.; Mo, Y. ACS Appl. Mater. Interfaces 2015, 7, 23685.
[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.
[23] Takada, K. Langmuir 2013, 29, 7538.
[24] Yokokawa, H. Solid State Ion. 2016, 285, 126.
[25] Long, P.; Xu, Q.; Peng, G.; Yao, X.; Xu, X. ChemElectroChem 2016, 3, 764.
[26] Wan, H.; Gang, P.; Yao, X.; Jing, Y.; Ping, C.; Xu, X. Energy Storage Mater. 2016, 4, 59.
[27] Nagao, M.; Kitaura, H.; Hayashi, A.; Tatsumisago, M. J. Power Sources 2009, 189, 672.
[28] Gao, J.; Zhao, Y. S.; Shi, S. Q.; Li, H. Chinese Phys. B 2016, 25, 35.
[29] Haruyama, J.; Sodeyama, K.; Tateyama, Y. ACS Appl. Mater. Interfaces 2017, 9, 286.
[30] Tatsumisago, M.; Nagao, M.; Hayashi, A. J. Asian Ceram. Soc. 2013, 1, 17.
[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.
[32] Amani, J. A.; Koppe, T.; Hofsäss, H.; Vetter, U. Phys. Rev. Appl. 2015, 4, 044007.
[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). (庄全超, 徐守冬, 邱祥云, 崔永丽, 方亮, 孙世刚, 化学进展, 2010, 22, 1044.)
[34] Siroma, Z.; Sato, T.; Takeuchi, T.; Nagai, R.; Ota, A.; Ioroi, T. J. Power Sources 2016, 316, 215.
[35] Boulineau, S.; Courty, M.; Tarascon, J. M.; Viallet, V. Solid State Ion. 2012, 221, 1.
[36] Han, F.; Gao, T.; Zhu, Y.; Gaskell, K. J.; Wang, C. Adv. Mater. 2015, 27, 3473.
[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.
[38] Liu, W.; Sun, D.; Feng, T.; Xia, J.; Wang, Q.; Jiang, D. J. Ceram. 2013, 34, 555(in Chinese). (刘薇, 孙大志, 冯涛, 夏金峰, 王琪, 蒋丹宇, 陶瓷学报, 2013, 34, 555.)
[39] Verkerk, M.; Middelhuis, B.; Burggraaf, A. Solid State Ion. 1982, 6, 159.
[40] Näfe, H. Solid State Ion. 1984, 13, 255.
[41] Mo, Y.; Ong, S. P.; Ceder, G. Chem. Mater. 2012, 24, 15.
[42] Levi, M. D.; Gamolsky, K.; Aurbach, D.; Heider, U.; Oesten, R. Electrochim. Acta 2000, 45, 1781.
[43] Ohta, N.; Takada, K.; Sakaguchi, I.; Zhang, L. Q.; Ma, R. Z.; Fukuda, K.; Osada, M.; Sasaki, T. Electrochem. Commun. 2007, 9, 1486.

Li₁₀GeP₂S₁₂固态电解质电极界面特性研究

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

PDF

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Zewei Lyu, Minfang Han, Zaihong Sun, Kaihua Sun. Evolution of Electrochemical Characteristics of Solid Oxide Fuel Cells During Initial-Stage Operation [J]. Acta Chimica Sinica, 2021, 79(6): 763-770.
[2]	Tang Xiao, Wang Yuxun. Charge Recombination in Dye-sensitized Solar Cells with Low Adsorbed Concentration of Dye [J]. Acta Chimica Sinica, 2013, 71(02): 193-198.
[3]	Lin Qinghan, Qiu Liqin, Cheng Xuan, Zhou Jian. Electrochemical Impedance Spectroscopic Study of Electrodeposited Bi₂Te₃-based Thin Films [J]. Acta Chimica Sinica, 2012, 70(10): 1173-1178.
[4]	DU Li-Li, ZHUANG Quan-Chao, WEI Tao, SHI Yue-Li, QIANG Ying-Huai, SUN Shi-Gang. Electrochemical Impedance Spectroscopic Studies of the First Lithiation of Si/C Composite Electrode [J]. Acta Chimica Sinica, 2011, 69(22): 2641-2647.
[5]	SHI Juan-Lan, WANG Qing-Xiang, CHEN Jian-Ping, ZHENG Mei-Xia, GAO Fei. Electrochemical DNA Biosensor Based on the Immobilization of Probe DNA on a Fulleropyrrolidine Derivative Modified Glassy Carbon Electrode [J]. Acta Chimica Sinica, 2011, 69(17): 2015-2020.
[6]	PANG Xue-Hui, ZHANG Yu-Xuan, ZHANG Jie, JIE Jian-Dong, HOU Bao-Rong. Corrosion Inhibition and Mechanisms Study on Pipemidic Acid, Levofloxacin and Ciprofloxacin for Mild Steel in 0.5 mol/L H₂SO₄ [J]. Acta Chimica Sinica, 2011, 69(04): 483-491.
[7]	DENG Meng, WANG Mang, CHEN Hong-Zheng. Electrochemically Synthesized Polypyrrole Coatings and Their Effect on Electrical Properties of Neural Microelectrode [J]. Acta Chimica Sinica, 2011, 69(04): 477-482.
[8]	ZHOU Qiong-Yu, SHENG Min-Qi, ZHONG Qing-Dong, LIN Hai, NIU Xiao-Bo, WANG Yi. Electrochemical Study for Magnesium Alloy Passivating Behavior in the NaOH Solution with F^－ [J]. Acta Chimica Sinica, 2010, 68(15): 1487-1493.
[9]	LIN Hai, SHENG Min-Qi, ZHONG Qing-Dong, ZHOU Qiong-Yu, WANG Yi, NIU Xiao-Bo. Effect of Nd^3＋ on Corrosion Electrochemical Behavior of Copper in 3.5% NaCl Solution by Using Microelectrode Array [J]. Acta Chimica Sinica, 2010, 68(12): 1153-1160.
[10]	LI Song-Mei, ZHANG Yuan-Yuan, DU Juan, LIU Jian-Hua, XU Mei. Influence of streptomyces on the Corrosion Behavior of Steel A3 in Thiobacillus ferrooxidans Media [J]. Acta Chimica Sinica, 2010, 68(01): 67-74.
[11]	PENG Quan-Chao, WEI Chao, WEI Guo-Zhen, DONG Quan-Feng, SUN Shi-Gang. Electrochemical Impedance Spectroscopic Studies of Insertion and Deinsertion of Lithium Ion in Spinel LiMn2O4 [J]. Acta Chimica Sinica, 2009, 67(19): 2184-2192.
[12]	. The Electrochemical Behavior of ZnO-Bi2O3 Ceramic Powders [J]. Acta Chimica Sinica, 2009, 67(15): 1743-1748.
[13]	Fan Xiao-Yong. Electrochemical Impedance Spectroscopy Study on Phase Transformation of Cu6Sn5 Alloy Anode [J]. Acta Chimica Sinica, 2009, 67(14): 1547-1552.
[14]	LI Dang-Guo*; ZHOU Gen-Shu. Influence of Temperature on the Electrochemical Property of Anodic Film Formed on Lead [J]. Acta Chimica Sinica, 2008, 66(6): 617-620.
[15]	WANG, Gui-Ling ^a ZHAO, Hui ^*,b HUO, Li-Hua ^b GAO, Shan^b. Synthesis and Conducting Properties of La10(SiO4)6－x(GaO4)xO3－0.5x [J]. Acta Chimica Sinica, 2008, 66(12): 1411-1416.

Li10GeP2S12固态电解质电极界面特性研究