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Quantifying inactive lithium in lithium metal batteries

Author

Listed:
  • Chengcheng Fang

    (University of California San Diego)

  • Jinxing Li

    (University of California San Diego)

  • Minghao Zhang

    (University of California San Diego)

  • Yihui Zhang

    (University of California San Diego)

  • Fan Yang

    (San Diego State University)

  • Jungwoo Z. Lee

    (University of California San Diego)

  • Min-Han Lee

    (University of California San Diego)

  • Judith Alvarado

    (University of California San Diego
    US Army Research Laboratory)

  • Marshall A. Schroeder

    (US Army Research Laboratory)

  • Yangyuchen Yang

    (University of California San Diego)

  • Bingyu Lu

    (University of California San Diego)

  • Nicholas Williams

    (San Diego State University)

  • Miguel Ceja

    (University of California San Diego)

  • Li Yang

    (General Motors Research and Development Center)

  • Mei Cai

    (General Motors Research and Development Center)

  • Jing Gu

    (San Diego State University)

  • Kang Xu

    (US Army Research Laboratory)

  • Xuefeng Wang

    (University of California San Diego)

  • Ying Shirley Meng

    (University of California San Diego
    University of California San Diego)

Abstract

Lithium metal anodes offer high theoretical capacities (3,860 milliampere-hours per gram)1, but rechargeable batteries built with such anodes suffer from dendrite growth and low Coulombic efficiency (the ratio of charge output to charge input), preventing their commercial adoption2,3. The formation of inactive (‘dead’) lithium— which consists of both (electro)chemically formed Li+ compounds in the solid electrolyte interphase and electrically isolated unreacted metallic Li0 (refs 4,5)—causes capacity loss and safety hazards. Quantitatively distinguishing between Li+ in components of the solid electrolyte interphase and unreacted metallic Li0 has not been possible, owing to the lack of effective diagnostic tools. Optical microscopy6, in situ environmental transmission electron microscopy7,8, X-ray microtomography9 and magnetic resonance imaging10 provide a morphological perspective with little chemical information. Nuclear magnetic resonance11, X-ray photoelectron spectroscopy12 and cryogenic transmission electron microscopy13,14 can distinguish between Li+ in the solid electrolyte interphase and metallic Li0, but their detection ranges are limited to surfaces or local regions. Here we establish the analytical method of titration gas chromatography to quantify the contribution of unreacted metallic Li0 to the total amount of inactive lithium. We identify the unreacted metallic Li0, not the (electro)chemically formed Li+ in the solid electrolyte interphase, as the dominant source of inactive lithium and capacity loss. By coupling the unreacted metallic Li0 content to observations of its local microstructure and nanostructure by cryogenic electron microscopy (both scanning and transmission), we also establish the formation mechanism of inactive lithium in different types of electrolytes and determine the underlying cause of low Coulombic efficiency in plating and stripping (the charge and discharge processes, respectively, in a full cell) of lithium metal anodes. We propose strategies for making lithium plating and stripping more efficient so that lithium metal anodes can be used for next-generation high-energy batteries.

Suggested Citation

  • Chengcheng Fang & Jinxing Li & Minghao Zhang & Yihui Zhang & Fan Yang & Jungwoo Z. Lee & Min-Han Lee & Judith Alvarado & Marshall A. Schroeder & Yangyuchen Yang & Bingyu Lu & Nicholas Williams & Migue, 2019. "Quantifying inactive lithium in lithium metal batteries," Nature, Nature, vol. 572(7770), pages 511-515, August.
  • Handle: RePEc:nat:nature:v:572:y:2019:i:7770:d:10.1038_s41586-019-1481-z
    DOI: 10.1038/s41586-019-1481-z
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    Citations

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    Cited by:

    1. Pietro Iurilli & Luigi Luppi & Claudio Brivio, 2022. "Non-Invasive Detection of Lithium-Metal Battery Degradation," Energies, MDPI, vol. 15(19), pages 1-14, September.
    2. Kai Yang & Hongchang Cai & Suran Li & Yu Wang & Xue Zhang & Zhenxuan Wu & Yilin Lai & Minella Bezha & Klara Bezha & Naoto Nagaoka & Yuejiu Zheng & Xuning Feng, 2024. "Research on Quantitative Diagnosis of Dendrites Based on Titration Gas Chromatography Technology," Energies, MDPI, vol. 17(10), pages 1-19, May.
    3. Jiaqi Cao & Yuansheng Shi & Aosong Gao & Guangyuan Du & Muhtar Dilxat & Yongfei Zhang & Mohang Cai & Guoyu Qian & Xueyi Lu & Fangyan Xie & Yang Sun & Xia Lu, 2024. "Hierarchical Li electrochemistry using alloy-type anode for high-energy-density Li metal batteries," Nature Communications, Nature, vol. 15(1), pages 1-13, December.
    4. Minglei Mao & Xiao Ji & Qiyu Wang & Zejing Lin & Meiying Li & Tao Liu & Chengliang Wang & Yong-Sheng Hu & Hong Li & Xuejie Huang & Liquan Chen & Liumin Suo, 2023. "Anion-enrichment interface enables high-voltage anode-free lithium metal batteries," Nature Communications, Nature, vol. 14(1), pages 1-13, December.
    5. Yuanjian Li & Xiang Feng & Gaoliang Yang & Wei Ying Lieu & Lin Fu & Chang Zhang & Zhenxiang Xing & Man-Fai Ng & Qianfan Zhang & Wei Liu & Jun Lu & Zhi Wei Seh, 2024. "Toward waterproof magnesium metal anodes by uncovering water-induced passivation and drawing water-tolerant interphases," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    6. Matthew Sadd & Shizhao Xiong & Jacob R. Bowen & Federica Marone & Aleksandar Matic, 2023. "Investigating microstructure evolution of lithium metal during plating and stripping via operando X-ray tomographic microscopy," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    7. Shuo Jin & Jiefu Yin & Xiaosi Gao & Arpita Sharma & Pengyu Chen & Shifeng Hong & Qing Zhao & Jingxu Zheng & Yue Deng & Yong Lak Joo & Lynden A. Archer, 2022. "Production of fast-charge Zn-based aqueous batteries via interfacial adsorption of ion-oligomer complexes," Nature Communications, Nature, vol. 13(1), pages 1-11, December.
    8. Yan Zhao & Tianhong Zhou & Timur Ashirov & Mario El Kazzi & Claudia Cancellieri & Lars P. H. Jeurgens & Jang Wook Choi & Ali Coskun, 2022. "Fluorinated ether electrolyte with controlled solvation structure for high voltage lithium metal batteries," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    9. Yuxiang Xie & Yixin Huang & Yinggan Zhang & Tairui Wu & Shishi Liu & Miaolan Sun & Bruce Lee & Zhen Lin & Hui Chen & Peng Dai & Zheng Huang & Jian Yang & Chenguang Shi & Deyin Wu & Ling Huang & Yingji, 2023. "Surface modification using heptafluorobutyric acid to produce highly stable Li metal anodes," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    10. Hyeokjin Kwon & Hyun-Ji Choi & Jung-kyu Jang & Jinhong Lee & Jinkwan Jung & Wonjun Lee & Youngil Roh & Jaewon Baek & Dong Jae Shin & Ju-Hyuk Lee & Nam-Soon Choi & Ying Shirley Meng & Hee-Tak Kim, 2023. "Weakly coordinated Li ion in single-ion-conductor-based composite enabling low electrolyte content Li-metal batteries," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    11. Suting Weng & Xiao Zhang & Gaojing Yang & Simeng Zhang & Bingyun Ma & Qiuyan Liu & Yue Liu & Chengxin Peng & Huixin Chen & Hailong Yu & Xiulin Fan & Tao Cheng & Liquan Chen & Yejing Li & Zhaoxiang Wan, 2023. "Temperature-dependent interphase formation and Li+ transport in lithium metal batteries," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    12. Ruirui Zhao & Haifeng Wang & Haoran Du & Ying Yang & Zhonghui Gao & Long Qie & Yunhui Huang, 2022. "Lanthanum nitrate as aqueous electrolyte additive for favourable zinc metal electrodeposition," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    13. Chao Chen & Jiaming Zhang & Benrui Hu & Qianwen Liang & Xunhui Xiong, 2023. "Dynamic gel as artificial interphase layer for ultrahigh-rate and large-capacity lithium metal anode," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    14. Solomon T. Oyakhire & Wenbo Zhang & Andrew Shin & Rong Xu & David T. Boyle & Zhiao Yu & Yusheng Ye & Yufei Yang & James A. Raiford & William Huang & Joel R. Schneider & Yi Cui & Stacey F. Bent, 2022. "Electrical resistance of the current collector controls lithium morphology," Nature Communications, Nature, vol. 13(1), pages 1-12, December.
    15. Yu Wang & Tairan Wang & Shuyu Bu & Jiaxiong Zhu & Yanbo Wang & Rong Zhang & Hu Hong & Wenjun Zhang & Jun Fan & Chunyi Zhi, 2023. "Sulfolane-containing aqueous electrolyte solutions for producing efficient ampere-hour-level zinc metal battery pouch cells," Nature Communications, Nature, vol. 14(1), pages 1-13, December.
    16. Li Huang & Jian Gao & Zhijie Bi & Ning Zhao & Jipeng Wu & Qiu Fang & Xuefeng Wang & Yong Wan & Xiangxin Guo, 2022. "Comparative Study of Stability against Moisture for Solid Garnet Electrolytes with Different Dopants," Energies, MDPI, vol. 15(9), pages 1-9, April.
    17. Qing Zhao & Yue Deng & Nyalaliska W. Utomo & Jingxu Zheng & Prayag Biswal & Jiefu Yin & Lynden A. Archer, 2021. "On the crystallography and reversibility of lithium electrodeposits at ultrahigh capacity," Nature Communications, Nature, vol. 12(1), pages 1-10, December.
    18. Ziteng Liang & Yuxuan Xiang & Kangjun Wang & Jianping Zhu & Yanting Jin & Hongchun Wang & Bizhu Zheng & Zirong Chen & Mingming Tao & Xiangsi Liu & Yuqi Wu & Riqiang Fu & Chunsheng Wang & Martin Winter, 2023. "Understanding the failure process of sulfide-based all-solid-state lithium batteries via operando nuclear magnetic resonance spectroscopy," Nature Communications, Nature, vol. 14(1), pages 1-15, December.
    19. Hyeokjin Kwon & Hongsin Kim & Jaemin Hwang & Wonsik Oh & Youngil Roh & Dongseok Shin & Hee-Tak Kim, 2024. "Borate–pyran lean electrolyte-based Li-metal batteries with minimal Li corrosion," Nature Energy, Nature, vol. 9(1), pages 57-69, January.
    20. Xiaozhe Zhang & Pan Xu & Jianing Duan & Xiaodong Lin & Juanjuan Sun & Wenjie Shi & Hewei Xu & Wenjie Dou & Qingyi Zheng & Ruming Yuan & Jiande Wang & Yan Zhang & Shanshan Yu & Zehan Chen & Mingsen Zhe, 2024. "A dicarbonate solvent electrolyte for high performance 5 V-Class Lithium-based batteries," Nature Communications, Nature, vol. 15(1), pages 1-18, December.
    21. Qing Li & Ao Chen & Donghong Wang & Yuwei Zhao & Xiaoqi Wang & Xu Jin & Bo Xiong & Chunyi Zhi, 2022. "Tailoring the metal electrode morphology via electrochemical protocol optimization for long-lasting aqueous zinc batteries," Nature Communications, Nature, vol. 13(1), pages 1-9, December.

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