石榴石型固态电解质/铝锂合金界面构筑及电化学性能

doi:10.13208/j.electrochem.181001

摘要/Abstract

摘要：

本文通过在锂负极中熔入少量铝制备了一种含Al-Li合金（Al₄Li₉）的新型复合锂负极,可有效改善Garnet/金属锂界面润湿性,从而显著降低了界面阻抗. XRD研究结果表明这一复合锂负极由Al₄Li₉合金和金属锂两相复合而成. SEM研究表明,复合锂负极可以有效改善金属锂与Garnet电解质的界面接触,形成更为紧密的接触界面. 电化学测试表明,复合锂负极显著降低了金属锂与Garnet电解质的界面阻抗,界面阻抗由锂/Garnet电解质界面的740.6 Ω·cm ²降低到复合锂负极/Garnet电解质界面的75.0 Ω·cm ². 使用复合锂负极制备的对称电池在50 μA·cm ^-2和100 μA·cm ^-2电流密度锂沉积-溶出过程中表现出较低的极化和良好的循环稳定性,在50 μA·cm ^-2电流密度下,可以稳定循环超过400小时.

关键词: 石榴石型固体电解质, 电极/固态电解质界面, 铝锂合金

Abstract:

Garnet-type solid electrolyte is a newly developed Li ion conductor and promising in the application of all-solid-state batteries. However, Garnet is incompatible with Li anode, which restricts the application of Garnet-type solid batteries. In order to improve the contact between Garnet-type solid electrolyte and Li electrode, a composite anode which contains Al-Li alloy (Al₄Li₉) was prepared as an electrode. Al-Li alloy has many advantages such as easy preparation, low cost, simple post-treatment and high capacity. Garnet-type Li_6.5La₃Zr_1.75W_0.25O₁₂ (LLZWO) was synthesized via solid-state reaction. Garnet solid electrolyte has poor interfacial wettability with lithium, but has good interfacial wettability with Al-Li alloy. By using Al-Li alloy as an electrode, the contact between LLZWO and Li electrodes could be well improved. SEM images also confirmed that Al-Li alloy and Garnet had a sufficient interface contact. On the other side, the interface resistance could be dramatically reduced. Impedance spectra show that the interface resistance between Al-Li alloy and Garnet reduced from 740.6 Ω·cm ² to 75.0 Ω·cm ², which is only one-tenth of interface resistance between Li alloy and Garnet. Symmetric cell with Al-Li alloy and Garnet showed excellent and stable cycle performance with almost 0 polarization voltage when cycling at a current density between 50 μA·cm ^-2 and 100 μA·cm ^-2. At a current density of 50 μA·cm ^-2, the cell cycled 400 hours stably without formation of lithium dendrite.

Key words: Garnet-type solid electrolyte, electrode/solid electrolyte interface, Al-Li alloy

中图分类号:

O646

Support info: 支持信息

马嘉林, 王红春, 龚正良, 杨勇. 石榴石型固态电解质/铝锂合金界面构筑及电化学性能[J]. 电化学（中英文）, 2020, 26(2): 262-269.

MA Jia-lin, WANG Hong-chun, GONG Zheng-liang, YANG Yong. Construction and Electrochemical Performance of Garnet-Type Solid Electrolyte/Al-Li Alloy Interface[J]. Journal of Electrochemistry, 2020, 26(2): 262-269.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.181001

https://electrochem.xmu.edu.cn/CN/Y2020/V26/I2/262

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参考文献 29

[1]	Ni J E, Case E D, Sakamoto J S , et al. Room temperature elastic moduli and Vickers hardness of hot-pressed LLZO cubic garnet[J]. Journal of Materials Science, 2012,47(23):7978-7985.
[2]	Li H( 李泓), Lü Y C( 吕迎春 ). A review on electrochemical energy storage[J]. Journal of Electrochemistry( 电化学), 2015,21(5):412-424.
[3]	Hong H P . Crystal structure and ionic conductivity of Li₁₄Zn(GeO₄)₄ and other new Li + superionic conductors [J]. Materials Research Bulletin, 1978,13(2):117-124.
[4]	Thokchom J S, Kumar B . Composite effect in superionically conducting lithium aluminium germanium phosphate based glass-ceramic[J]. Journal of Power Sources, 2008,185(1):480-485.
[5]	Bohnke O . The fast lithium-ion conducting oxides Li₃_xLa_2/3-_xTiO₂ from fundamentals to application[J]. Solid State Ionics, 2008,179(1):9-15.
[6]	Kato Y, Hori S, Saito T , et al. High-power all-solid-state batteries using sulfide superionic conductors[J]. Nature Energy, 2016,1(4):16030.
[7]	Zheng B Z, Zhu J P, Wang H C , et al. Stabilizing Li₁₀SnP₂S₁₂/Li interface via an in situ formed solid electrolyte interphase layer[J]. ACS Applied Materials & Interfaces, 2018,10(30):25473-25482.
[8]	Murugan R, Thangadurai V, Weppner W . Fast lithium ion conduction in garnet-type Li₇La₃Zr₂O₁₂[J]. Angewandte Chemie International Edition, 2007,46(41):7778-7781.
[9]	Liu T, Ren Y Y, Shen Y , et al. Achieving high capacity in bulk-type solid-state lithium ion battery based on Li_6.75La₃Zr_1.75Ta_0.25O₁₂ electrolyte: Interfacial resistance[J]. Journal of Power Sources, 2016,324:349-357.
[10]	Dhivya L, Janani N, Palanivel B , et al. Li + transport properties of W substituted Li₇La₃Zr₂O₁₂ cubic lithium garnets [J]. AIP Advances, 2013,3(8):082115.
[11]	Deviannapoorani C, Dhivya L, Ramakumar S , et al. Lithium ion transport properties of high conductive tellurium substituted Li₇La₃Zr₂O₁₂ cubic lithium garnets[J]. Journal of Power Sources, 2013,240:18-25.
[12]	Liu K, Wang C A . Garnet-type Li_6.4La₃Zr_1.4Ta_0.6O₁₂ thin sheet: Fabrication and application in lithium-hydrogen peroxide semi-fuel cell[J]. Electrochemistry Communications, 2014,48:147-150.
[13]	Thangadurai V, Narayanan S, Pinzaru D . Garnet-type solid-state fast Li ion conductors for Li batteries: critical review[J]. Chemical Society Reviews, 2014,43(13):4714-4727.
[14]	Ren Y Y, Shen Y, Lin Y H , et al. Direct observation of lithium dendrites inside garnet-type lithium-ion solid electrolyte[J]. Electrochemistry Communications, 2015,57:27-30.
[15]	Sudo R, Nakata Y, Ishiguro K , et al. Interface behavior between garnet-type lithium-conducting solid electrolyte and lithium metal[J]. Solid State Ionics, 2014,262:151-154.
[16]	Tsai C L, Roddatis V, Chandran C V , et al. Li₇La₃Zr₂O₁₂ interface modification for Li dendrite prevention[J]. ACS Applied Materials & Interfaces, 2016,8(16):10617-10626.
[17]	Luo W, Gong Y H, Zhu Y Z , et al. Transition from superlithiophobicity to superlithiophilicity of garnet solid-state electrolyte[J]. Journal of the American Chemical Society, 2016,138(37):12258-12262.
[18]	Matsuyama T, Takano R, Tadanaga K , et al. Fabrication of all-solid-state lithium secondary batteries with amorphous TiS₄ positive electrodes and Li₇La₃Zr₂O₁₂ solid electrolytes[J]. Solid State Ionics, 2015,285(1):332-335.
[19]	Shao Y J, Wang H C, Gong Z L , et al. Drawing a soft interface: An effective interfacial modification strategy for garnet-type solid-state Li batteries[J]. ACS Energy Letters, 2018,3(6):1212-1218.
[20]	Wang D, Zhong G, Pang W K , et al. Toward understanding the lithium transport mechanism in garnet-type solid electrolytes: Li + ion exchanges and their mobility at octahedral/tetrahedral sites [J]. Chemistry of Materials, 2015,27(19):6650-6659.
[21]	Tang R Z( 唐仁政), Tian R Z( 田荣璋 ). Binary alloy phase diagram and crystal structure of mesophase[M]. Changsha: Central South University Press( 中南大学出版社), 2009.
[22]	Li Y, Wang Z, Cao Y , et al. W-doped Li₇La₃Zr₂O₁₂ ceramic electrolytes for solid state Li-ion batteries[J]. Electrochim-ica Acta, 2015,180:37-42.
[23]	Thangadurai V, Weppner W . Li₆ALa₂Ta₂O₁₂ (A = Sr, Ba): Novel garnet-like oxides for fast lithium ion conduction[J]. Advanced Functional Materials, 2005,15(1):107-112.
[24]	Han X G, Gong Y H, Fu K , et al. Negating interfacial impedance in garnet-based solid-state Li metal batteries[J]. Nature Materials, 2016,16(5):572-579.
[25]	Ishiguro K, Nakata Y, Matsui M , et al. Stability of Nb-doped cubic Li₇La₃Zr₂O₁₂ with lithium metal[J]. Journal of The Electrochemical Society, 2013,160(10):A1690-A1693.
[26]	Jin Y, Mcginn P J . Li₇La₃Zr₂O₁₂ electrolyte stability in air and fabrication of a Li/Li₇La₃Zr₂O₁₂/Cu_0.1V₂O₅ solid-state battery[J]. Journal of Power Sources, 2013,239:326-331.
[27]	Sharafi A, Meyer H M, Nanda J , et al. Characterizing the Li-Li₇La₃Zr₂O₁₂ interface stability and kinetics as a function of temperature and current density[J]. Journal of Power Sources, 2016,302:135-139.
[28]	Ohta S, Kobayashi T, Seki J , et al. Electrochemical performance of an all-solid-state lithium ion battery with garnet-type oxide electrolyte[J]. Journal of Power Sources, 2012,202:332-335.
[29]	Wang C W, Gong Y H, Liu B Y , et al. Conformal, nano-scale ZnO surface modification of Garnet-based solid-state electrolyte for lithium metal anodes[J]. Nano Letters, 2017,17(1):565-571.