Study on Li₃BO₃ Interface Modification of Garnet Solid Electrolyte

Authors

Gui-Wei Chen, College of Energy, Xiamen University, Xiamen 361005, Fujian, China;
Zheng-Liang Gong, College of Energy, Xiamen University, Xiamen 361005, Fujian, China;Follow

Corresponding Author

Zheng-Liang Gong(zlgong@xmu.edu.cn)

Abstract

Garnet solid-state electrolytes have become the research hotspot due to their high ionic conductivity, wide electrochemical stability window and good air stability. However, there are still a series of problems to be solved. The poor contact between the lithium (Li) metal and garnet pellet make it difficult to build stable ion diffusion channels, resulting in large interfacial resistance. The continuous growth of lithium dendrites can penetrate the electrolyte pellet and cause a short circuit in the solid-state battery. Herein, a novel strategy is proposed to improve the wettability of LLZTO electrolyte with Li metal, via interfacial modification of LLZTO electrolyte with tri-lithium borate (Li₃BO₃). Li₃BO₃ is chemically stable with Li metal and effective to improve the wettability between Li and LLZTO pellet. A stable and even Li₃BO₃ interfacial layer was constructed on the LLZTO electrolyte surface by liquid-phase deposition combing with high temperature sintering. The low melting point (700℃) of Li₃BO₃ facilitated the formation of a dense and uniform coating layer. SEM images show that the Li₃BO₃ layer was about 2.5 μm thick and completely covered the pellet surface. Intimate contact between Li metal and LLZTO electrolyte could be realized after the Li₃BO₃ interfacial modification, which was confirmed by SEM analysis and wettability experiment. Benefiting from the significantly improved interfacial contact, the interfacial impedance was dramatically reduced from 1780 Ω·cm2 of Li/LLZTO interface to 58 Ω·cm2 of Li/LBO-LLZTO interface. The Li|LBO-LLZTO|Li symmetric cell could produce a low overpotential and work stably at the current density of 0.1 mA·cm-2 for more than 700 h. By contrast, the Li|LLZTO|Li symmetric cell displayed high overpotential and was short circuited after 20 min of lithium plating/stripping at the current density of 0.05 mA·cm-2. Our results show that Li₃BO₃ interfacial modification is an effective approach to improve the wettability and interfacial stability between Li metal and garnet electrolyte, which is a key to the successful use of solid-state battery.

Graphical Abstract

Keywords

Garnet electrolyte, Li3BO3 layer, interfacial modification, Li anode, interfacial wettability

DOI Link

https://doi.org/10.13208/j.electrochem.200516

Publication Date

2021-02-28

Online Available Date

2020-06-28

Revised Date

2020-06-22

Received Date

2020-05-15

Recommended Citation

Gui-Wei Chen, Zheng-Liang Gong. Study on Li₃BO₃ Interface Modification of Garnet Solid Electrolyte[J]. Journal of Electrochemistry, 2021 , 27(1): 76-82.
DOI: 10.13208/j.electrochem.200516
Available at: https://jelectrochem.xmu.edu.cn/journal/vol27/iss1/9

References

[1] Tarascon J M, Armand M. Issues and challenges facing rechargeable lithium batteries[J]. Nature, 2001,414(6861):359-367.
doi: 10.1038/35104644 URL pmid: 11713543

[2] Goodenough J B, Kim Y. Challenges for rechargeable Li batteries[J]. Chem. Mat., 2010,22(3):587-603.
doi: 10.1021/cm901452z URL

[3] Whittingham M S. Lithium batteries and cathode materials[J]. Chem. Rev., 2004,104(10):4271-4301.
doi: 10.1021/cr020731c URL pmid: 15669156

[4] Kang K S, Meng Y S, Breger J, Grey C P, Ceder G. Electrodes with high power and high capacity for rechargeable lithium batteries[J]. Science, 2006,311(5763):977-980.
URL pmid: 16484487

[5] Cheng X B, Zhang R, Zhao C Z, Zhang Q. Toward safe lithium metal anode in rechargeable batteries: A review[J]. Chem. Rev., 2017,117(15):10403-10473.
doi: 10.1021/acs.chemrev.7b00115 URL pmid: 28753298

[6] Yao X Y(姚霞银), Huang B X(黄冰心), Yin J Y(尹景云), Peng G(彭刚), Huang Z(黄祯), Gao C(高超), Liu D(刘登), Xu X X(许晓雄). All-solid-state lithium batteries with inorganic solid electrolytes: Review of fundamental science[J]. Chin. Phys. B (中国物理B), 2016,25(1):018802.

[7] Kim J G, Son B, Mukherjee S, Schuppert N, Bates A, Kwon O, Choi M J, Chung H Y, Park S. A review of lithium and non-lithium based solid state batteries[J]. J. Power Sources, 2015,282:299-322.
doi: 10.1016/j.jpowsour.2015.02.054 URL

[8] Lü F, Wang Z Y, Shi L Y, Zhu J F, Edstrom K, Mindemark J, Yuan S. Challenges and development of composite solid-state electrolytes for high-performance lithium ion batteries[J]. J. Power Sources, 2019,441:227175.
doi: 10.1016/j.jpowsour.2019.227175 URL

[9] Zhao N, Khokhar W, Bi Z J, Shi C, Guo X X, Fan L Z, Nan C W. Solid garnet batteries[J]. Joule, 2019,3(5):1190-1199.
doi: 10.1016/j.joule.2019.03.019 URL

[10] Samson A J, Hofstetter K, Bag S, Thangadurai V. A bird's-eye view of Li-stuffed garnet-type Li₇La₃Zr₂O₁₂ ceramic electrolytes for advanced all-solid-state Li batteries[J]. Energy Environ. Sci., 2019,12(10):2957-2975.
doi: 10.1039/C9EE01548E URL

[11] Peng F F(彭峰峰), Li S Y(李世友), Geng T T(耿彤彤), Li C L(李春雷), Zeng S W(曾双威). Syntheses and properties of Ta⁵+ doped Li₇La₃Zr₂O₁₂[J]. J. Electrochem. (电化学), 2020,26(2):308-314.

[12] Guo Y, Li H, Zhai T. Reviving lithium-metal anodes for next-generation high-energy batteries[J]. Adv. Mater., 2017,29(29):1700007.
doi: 10.1002/adma.201700007 URL

[13] Dai J Q, Yang C P, Wang C W, Pastel G, Hu L B. Interface engineering for garnet-based solid-state lithium-metal batteries: materials, structures, and characterization[J]. Adv. Mater., 2018,30(48):1802068.
doi: 10.1002/adma.v30.48 URL

[14] Krauskopf T, Dippel R, Hartmann H, Peppler K, Mogwitz B, Richter F H, Zeier W G, Janek J. Lithium-metal growth kinetics on LLZO Garnet-type solid electrolytes[J]. Joule, 2019,3(8):2030-2049.
doi: 10.1016/j.joule.2019.06.013 URL

[15] Krauskopf T, Hartmann H, Zeier W G, Janek J. Toward a fundamental understanding of the lithium metal anode in solid-state batteries-an electrochemo-mechanical study on the Garnet-type solid electrolyte Li_6.25Al_0.25La₃Zr₂O₁₂[J]. ACS Appl. Mater. Interfaces, 2019,11(15):14463-14477.
doi: 10.1021/acsami.9b02537 URL pmid: 30892861

[16] Kasemchainan J, Zekoll S, Spencer Jolly D, Ning Z Y, Hartley G O, Marrow J, Bruce P G. Critical stripping current leads to dendrite formation on plating in lithium anode solid electrolyte cells[J]. Nat. Mater., 2019,18(10):1105-1111.
doi: 10.1038/s41563-019-0438-9 URL pmid: 31358941

[17] Han X G, Gong Y H, Fu K, He X F, Hitz G T, Dai J Q, Pearse A, Liu B Y, Wang H, Rublo G, Mo Y F, Thangadurai V, Wachsman E D, Hu L B. Negating interfacial impedance in garnet-based solid-state Li metal batteries[J]. Nat. Mater., 2017,16(5):572-579.
doi: 10.1038/nmat4821 URL pmid: 27992420

[18] Wang C W, Gong Y H, Liu B Y, Fu K, Yao Y G, Hitz E, Li Y J, Dai J Q, Xu S M, Luo W, Wachsman E D, Hu L B. Conformal, nanoscale ZnO surface modification of Garnet-based solid-state electrolyte for lithium metal anodes[J]. Nano Lett., 2017,17(1):565-571.
doi: 10.1021/acs.nanolett.6b04695 URL pmid: 27936780

[19] Shao Y J, Wang H C, Gong Z L, Wang D W, Zheng B Z, Zhu J P, Lu Y X, Hu Y S, Guo X X, Li H, Huang X J, Yang Y, Nan C W, Chen L Q. Drawing a soft interface: An effective interfacial modification strategy for Garnet-type solid-state Li batteries[J]. ACS Energy Lett., 2018,3(6):1212-1218.
doi: 10.1021/acsenergylett.8b00453 URL

[20] He M H, Cui Z H, Chen C, Li Y Q, Guo X X. Formation of self-limited, stable and conductive interfaces between Garnet electrolytes and lithium anodes for reversible lithium cycling in solid-state batteries[J]. J. Mater. Chem. A, 2018,6(24):11463-11470.
doi: 10.1039/C8TA02276C URL

[21] Ma J L(马嘉林), Wang H C(王红春), Gong Z L(龚正良), Yang Y(杨勇). Construction and electrochemical performance of Garnet-type solid electrolyte/Al-Li alloy interface[J]. J. Electrochem. (电化学), 2020,26(2):262-269.

[22] Huo H Y, Chen Y, Zhao N, Lin X T, Luo J, Yang X F, Liu Y L, Guo X X, Sun X L. In-situ formed Li₂CO₃-free garnet/Li interface by rapid acid treatment for dendrite-free solid-state batteries[J]. Nano Energy, 2019,61:119-125.
doi: 10.1016/j.nanoen.2019.04.058 URL

[23] Kokal I, Somer M, Notten P H L, Hitzen H T. Sol-gel synjournal and lithium ion conductivity of Li₇La₃Zr₂O₁₂ with garnet-related type structure[J]. Solid State Ion., 2011,185(1):42-46.
doi: 10.1016/j.ssi.2011.01.002 URL

[24] Zhang X Q, Chen X, Hou L P, Li B Q, Cheng X B, Huang J Q, Zhang Q. Regulating anions in the solvation sheath of lithium ions for stable lithium metal batteries[J]. ACS Energy Lett., 2019,4(2):411-416.
doi: 10.1021/acsenergylett.8b02376 URL

[25] Cai M L, Lu Y, Su J M, Ruan Y D, Chen C H, Chowdari B V R, Wen Z Y. In situ lithiophilic layer from H⁺/Li⁺ exchange on garnet surface for the stable lithium-solid electrolyte interface[J]. ACS Appl. Mater. Interfaces, 2019,11(38):35030-35038.
doi: 10.1021/acsami.9b13190 URL pmid: 31487146