Corresponding Author

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


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


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

Publication Date


Online Available Date


Revised Date


Received Date



[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 Li6.25Al0.25La3Zr2O12[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



To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.