English

Nanocomposite Current Collectors for Anode-Free All-Solid-State Lithium Batteries

• Zeyu Liu ^{1, 2,} ,
• Wenze Huang ^1, ,
• Yang Xiao ^{1, 2,} ,
• Jundong Zhang ^{1, 3,} ,
• Weijin Kong ^1, ,
• Peng Wu ^4, ,
• Chenzi Zhao ^{1, ,} ,
• Aibing Chen ^5, ,
• Qiang Zhang ^{1, ,}

• 1.

  Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

• 2.

  Zhili College, Tsinghua University, Beijing 100084, China

• 3.

  Tanwei College, Tsinghua University, Beijing 100084, China

• 4.

  BMW China Services Ltd., Beijing 101318, China

• 5.

  College of Chemical and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, China

Corresponding author: Email: zcz@tsinghua.edu.cn (C.Z.); Email: zhang-qiang@mails.tsinghua.edu.cn (Q.Z.)

• Received Date: 22 May 2023
  Accepted Date: 27 June 2023
  Revised Date: 24 June 2023
  Available Online: 15 March 2024
• Fund Project:

  the National Key Research and Development Program of China 

  the National Natural Science Foundation of China 

  the S&T Program of Hebei Province 

  the International Postdoctoral Exchange Fellowship Program 

Abstract: The anode-free solid-state lithium battery (AFSSLB) is a type of lithium battery that utilizes an initial charging process to generate lithium metal as the anode. With a 1 : 1 anode-to-cathode capacity ratio, it enables any lithiated cathode system to achieve a maximal energy density. Furthermore, the incorporation of inorganic solid electrolytes in the AFSSLB greatly enhances its intrinsic safety. However, the AFSSLB faces challenges related to interfacial issues between the electrolyte and collector. During the cycling process, uneven lithium-ion flux can result in contact loss and dendrite growth, ultimately leading to rapid battery failure. Addressing these interfacial problems is crucial for the successful implementation and performance of AFSSLBs. The absence of initial lithium metal material prevents the battery system from accommodating additional lithium through a modified anode. Instead, it relies on high Coulomb efficiency during cycling. Consequently, ensuring continuous and uniform contact at the anode interface is crucial for maintaining the reversibility of lithium deposition. Herein, a nanocomposite current collector is introduced to enhance the interface between the collector and electrolyte in AFSSLB. In this approach, silver nanoparticles are dispersed within the carbon materials to construct a composite current collector. The incorporation of the silver-carbon nanocomposite layer results in a low interfacial impedance of 10 Ω∙cm⁻², indicating that the electrolyte-collector interface maintains contact throughout the charging and discharging processes. The focused ion beam (FIB) technology and electron microscopy were employed to analyze the battery cross sections, revealing that lithium metal could be deposited in a thickness of more than 25 μm without short-circuiting using this silver-carbon nanocomposite current collector. The solid-state batteries equipped with nanocomposite current collectors exhibited an enhanced dissolution of silver in the lithium metal, leading to the formation of abundant lithiophilic sites. The nanocomposites facilitate the rapid transfer of Li atoms within the anodes, thus achieving uniform lithium metal deposition. Theoretical analysis using the nucleation equation demonstrates that using nano-silver as a current collector can reduce the nucleation work required for deposition by at least four orders of magnitude. The smaller nucleation force contributes to the uniform and stable deposition of lithium metal during continuous cycling. The solid-state batteries demonstrated improved interfacial contact, resulting in the uniform and stable lithium metal deposition of over 7.0 mAh∙cm⁻² for more than 200 cycles at 0.25 mA∙cm⁻². The cycling performances of all-solid-state batteries can be significantly improved through the design of nanocomposite collectors. This presents an effective strategy for advancing the practical implementation of all-solid-state lithium metal batteries, particularly those utilizing an anode-free configuration.

Key words:
• All-solid-state battery
•  /  Anode-free rechargeable battery
•  /  Nanocomposite current collector
•  /  Interfacial contact
•  /  Li metal battery

• 1. [1]

     Cheng, X. B.; Zhao, C. Z.; Yao, Y. X.; Liu, H.; Zhang, Q. Chem 2019, 5, 74. doi: 10.1016/j.chempr.2018.12.002

  2. [2]

     Li, B. Q.; Kong, L.; Zhao, C. X.; Jin, Q.; Chen, X.; Peng, H. J.; Qin, J. L.; Chen, J. X.; Yuan, H.; Zhang, Q.; et al. InfoMat 2019, 1, 533. doi: 10.1002/inf2.12056

  3. [3]

     Shen, X.; Cheng, X.; Shi, P.; Huang, J.; Zhang, X.; Yan, C.; Li, T.; Zhang, Q. J. Energy Chem. 2019, 37, 29. doi: 10.1016/j.jechem.2018.11.016

  4. [4]

     Chen, J. X.; Zhang, X. Q.; Li, B. Q.; Wang, X. M.; Shi, P.; Zhu, W.; Chen, A.; Jin, Z.; Xiang, R.; Huang, J. Q. J. Energy Chem. 2020, 47, 128. doi: 10.1016/j.jechem.2019.11.024

  5. [5]

     Ding, J.; Xu, R.; Yan, C.; Xiao, Y.; Liang, Y.; Yuan, H.; Huang, J. Chin. Chem. Lett. 2020, 31, 2339. doi: 10.1016/j.cclet.2020.03.015

  6. [6]

     Peng, H. J.; Huang, J. Q.; Cheng, X. B.; Zhang, Q. Adv. Energy Mater. 2017, 7, 1700260. doi: 10.1002/aenm.201700260

  7. [7]

     Yan, C.; Yuan, H.; Park, H. S.; Huang, J. Q. J. Energy Chem. 2020, 47, 217. doi: 10.1016/j.jechem.2019.09.034

  8. [8]

     郭峰, 陈鹏, 康拓, 王亚龙, 刘承浩, 沈炎宾, 卢威, 陈立桅. 物理化学学报, 2019, 35, 1365. doi: 10.3866/PKU.WHXB201903008Guo, F.; Chen, P.; Kang, T.; Wang, Y. L.; Liu, C. H.; Shen, Y. B.; Lu, W.; Chen, L. W. Acta Phys. -Chim. Sin. 2019, 35, 1365. doi: 10.3866/PKU.WHXB201903008

  9. [9]

     Zhang, X. Q.; Zhao, C. Z.; Huang, J. Q.; Zhang, Q. Engineering 2018, 4, 831. doi: 10.1016/j.eng.2018.10.008

  10. [10]

      Zhao, C. Z.; Duan, H.; Huang, J. Q.; Zhang, J.; Zhang, Q.; Guo, Y. G.; Wan, L. J. Sci. China Chem. 2019, 62, 1286. doi: 10.1007/s11426-019-9519-9

  11. [11]

      Ates, T.; Keller, M.; Kulisch, J.; Adermann, T.; Passerini, S. Energy Storage Mater. 2019, 17, 204. doi: 10.1016/j.ensm.2018.11.011

  12. [12]

      Busche, M. R.; Drossel, T.; Leichtweiss, T.; Weber, D. A.; Falk, M.; Schneider, M.; Reich, M. L.; Sommer, H.; Adelhelm, P.; Janek, J. Nat. Chem. 2016, 8, 426. doi: 10.1038/nchem.2470

  13. [13]

      Yu, Q.; Jiang, K.; Yu, C.; Chen, X.; Zhang, C.; Yao, Y.; Jiang, B.; Long, H. Chin. Chem. Lett. 2021, 32, 2659. doi: 10.1016/j.cclet.2021.03.032

  14. [14]

      Shen, Y. Q.; Zeng, F. L.; Zhou, X. Y.; Wang, A. B.; Wang, W. K.; Yuan, N. Y.; Ding, J. N. J. Energy Chem. 2020, 48, 267. doi: 10.1016/j.jechem.2020.01.016

  15. [15]

      Wu, J. Y.; Ling, S. G.; Yang, Q.; Li, H.; Xu, X. X.; Chen, L. Q. Chin. Phys. B 2016, 25, 078204. doi: 10.1088/1674-1056/25/7/078204

  16. [16]

      朱高龙, 赵辰孜, 袁洪, 南皓雄, 赵铂琛, 侯立鹏, 何传新, 刘全兵, 黄佳琦. 物理化学学报 2021, 37, 2005003. doi: 10.3866/PKU.WHXB202005003Zhu, G. L.; Zhao, C. Z.; Yuan, H.; Nan, H. X.; Zhao, B. C.; Hou, L. P.; He, C. X.; Liu, Q. B.; Huang, J. Q. Acta Phys. -Chim. Sin. 2021, 37, 2005003. doi: 10.3866/PKU.WHXB202005003

  17. [17]

      刘凡凡, 张志文, 叶淑芬, 姚雨, 余彦. 物理化学学报, 2021, 37, 2006021. doi: 10.3866/PKU.WHXB202006021Liu, F. F.; Zhang, Z. W.; Ye, S. F.; Yao, Y.; Yu, Y. Acta Phys. -Chim. Sin. 2021, 37, 2006021. doi: 10.3866/PKU.WHXB202006021

  18. [18]

      赵雨萌, 任凌霄, 王澳轩, 罗加严. 物理化学学报, 2021, 37, 2008090. doi: 10.3866/PKU.WHXB202008090Zhao, Y. M.; Ren, L. X.; Wang, A. X.; Luo, J. Y. Acta Phys. -Chim. Sin. 2021, 37, 2008090. doi: 10.3866/PKU.WHXB202008090

  19. [19]

      Huang, W.-Z.; Zhao, C.-Z.; Wu, P.; Yuan, H.; Feng, W.-E.; Liu, Z.-Y.; Lu, Y.; Sun, S.; Fu, Z.-H.; Hu, J.-K.; et al. Adv. Energy Mater. 2022, 12, 2201044. doi: 10.1002/aenm.202201044

  20. [20]

      Suzuki, N.; Yashiro, N.; Fujiki, S.; Omoda, R.; Shiratsuchi, T.; Watanabe, T.; Aihara, Y. Adv. Energy Sustain. Res. 2021, 2, 2100066. doi: 10.1002/aesr.202100066

  21. [21]

      Neudecker, B. J.; Dudney, N. J.; Bates, J. B. J. Electrochem. Soc. 2000, 147, 517. doi: 10.1149/1.1393226

  22. [22]

      Huang, W.-Z.; Liu, Z.-Y.; Xu, P.; Kong, W.-J.; Huang, X.-Y.; Shi, P.; Wu, P.; Zhao, C.-Z.; Yuan, H.; Huang, J.-Q.; et al. J. Mater. Chem. A 2023. 11, 12713. doi: 10.1039/D3TA00121K

  23. [23]

      Ikhe, A. B.; Park, W. B.; Han, S. C.; Seo, J. Y.; Han, S.; Sohn, K.-S.; Pyo, M. J. Mater. Chem. A 2022, 10, 21456. doi: 10.1039/D2TA06379D

  24. [24]

      Heubner, C.; Maletti, S.; Auer, H.; Hüttl, J.; Voigt, K.; Lohrberg, O. Adv. Funct. Mater. 2021, 31, 2106608. doi: 10.1002/adfm.202106608

  25. [25]

      Lin, Y.; Chen, J.; Zhang, H.; Wang, J. J. Energy Chem. 2023, 80, 207. doi: 10.1016/j.jechem.2023.02.005

  26. [26]

      Shen, X.; Zhang, R.; Shi, P.; Chen, X.; Zhang, Q. Adv. Energy Mater. 2021, 11, 2003416. doi: 10.1002/aenm.202003416

  27. [27]

      Jiang, F.-N.; Yang, S.-J.; Liu, H.; Cheng, X.-B.; Liu, L.; Xiang, R.; Zhang, Q.; Kaskel, S.; Huang, J.-Q. SusMat 2021, 1, 506. doi: 10.1002/sus2.37

  28. [28]

      Kasemchainan, J.; Zekoll, S.; Spencer Jolly, D.; Ning, Z.; Hartley, G. O.; Marrow, J.; Bruce, P. G. Nat. Mater. 2019, 18, 1105. doi: 10.1038/s41563-019-0438-

  29. [29]

      Zhang, X.; Huang, L.; Xie, B.; Zhang, S.; Jiang, Z.; Xu, G.; Li, J.; Cui, G. Adv. Energy Mater. 2023, 13, 2203648. doi: 10.1002/aenm.202203648

  30. [30]

      Jo, C.-H.; Sohn, K.-S.; Myung, S.-T. Energy Storage Mater. 2023, 57, 471. doi: 10.1016/j.ensm.2023.02.040

  31. [31]

      Raj, V.; Venturi, V.; Kankanallu, V. R.; Kuiri, B.; Viswanathan, V.; Aetukuri, N. P. B. Nat. Mater. 2022, 21, 1050. doi: 10.1038/s41563-022-01264-8

  32. [32]

      Fang, C.; Lu, B.; Pawar, G.; Zhang, M.; Cheng, D.; Chen, S.; Ceja, M.; Doux, J.-M.; Musrock, H.; Cai, M.; et al. Nat. Energy 2021, 6, 987. doi: 10.1038/s41560-021-00917-3

  33. [33]

      Lin, L.; Qin, K.; Li, M.; Hu, Y.-S.; Li, H.; Huang, X.; Chen, L.; Suo, L. Energy Storage Mater. 2022, 45, 821. doi: 10.1016/j.ensm.2021.12.036

  34. [34]

      Shin, W.; Manthiram, A. Angew. Chem. Int. Ed. 2022, 61, e202115909. doi: 10.1002/anie.202115909

  35. [35]

      Lee, Y.-G.; Fujiki, S.; Jung, C.; Suzuki, N.; Yashiro, N.; Omoda, R.; Ko, D.-S.; Shiratsuchi, T.; Sugimoto, T.; Ryu, S.; et al. Nat. Energy 2020, 5, 299. doi: 10.1038/s41560-020-0575-z

  36. [36]

      Liang, P.; Sun, H.; Huang, C. L.; Zhu, G.; Tai, H. C.; Li, J.; Wang, F.; Wang, Y.; Huang, C. J.; Jiang, S. K.; et al. Adv. Mater. 2022, 34, 2207361. doi: 10.1002/adma.202207361

  37. [37]

      Lin, L.; Qin, K.; Zhang, Q.; Gu, L.; Suo, L.; Hu, Y. S.; Li, H.; Huang, X.; Chen, L. Angew. Chem. Int. Ed. 2021, 60, 8289. doi: 10.1002/anie.202017063

  38. [38]

      Yan, K.; Lu, Z.; Lee, H.-W.; Xiong, F.; Hsu, P.-C.; Li, Y.; Zhao, J.; Chu, S.; Cui, Y. Nat. Energy 2016, 1, 16010. doi: 10.1038/nenergy.2016.10

  39. [39]

      Garcia-Calvo, O.; Gutiérrez-Pardo, A.; Combarro, I.; Orue, A.; Lopez-Aranguren, P.; Urdampilleta, I.; Kvasha, A. Front. Chem. 2022, 10, 934365. doi: 10.3389/fchem.2022.934365

  40. [40]

      Chen, X.-R.; Chen, X.; Yan, C.; Zhang, X.-Q.; Zhang, Q.; Huang, J.-Q. Energy Fuels 2021, 35, 12746. doi: 10.1021/acs.energyfuels.1c01602

  41. [41]

      Lu, Y.; Zhao, C.-Z.; Hu, J.-K.; Sun, S.; Yuan, H.; Fu, Z.-H. Sci. Adv. 2022, 8, eadd0510. doi: 10.1126/sciadv.add0510

  42. [42]

      Lewis, J. A.; Cavallaro, K. A.; Liu, Y.; McDowell, M. T. Joule 2022, 6, 1418. doi: 10.1016/j.joule.2022.05.016

  43. [43]

      Han, S. Y.; Lee, C.; Lewis, J. A.; Yeh, D.; Liu, Y.; Lee, H.-W.; McDowell, M. T. Joule 2021, 5, 2450. doi: 10.1016/j.joule.2021.07.002

  44. [44]

      Zhang, R.; Chen, X.; Shen, X.; Zhang, X.-Q.; Chen, X.-R.; Cheng, X.-B.; Yan, C.; Zhao, C.-Z.; Zhang, Q. Joule 2018, 2, 764. doi: 10.1016/j.joule.2018.02.001

  45. [45]

      Wang, C.; Wang, H.; Tao, L.; Wang, X.; Cao, P.; Lin, F. ACS Energy Lett. 2023, 8, 1929. doi: 10.1021/acsenergylett.3c00180

  46. [46]

      Zhang, W.-J. J. Power Sources 2011, 196, 877. doi: 10.1016/j.jpowsour.2010.08.114

  47. [47]

      Jin, S.; Ye, Y.; Niu, Y.; Xu, Y.; Jin, H.; Wang, J.; Sun, Z.; Cao, A.; Wu, X.; Luo, Y.; et al. J. Am. Chem. Soc. 2020, 142, 8818. doi: 10.1021/jacs.0c01811

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