Corresponding Author

Yong YANG(yyang@xmu.edu.cn)


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 Li6.5La3Zr1.75W0.25O12 (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.

Graphical Abstract


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

Publication Date


Online Available Date


Revised Date


Received Date



[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 Li3xLa2/3-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 Li6.75La3Zr1.75Ta0.25O12 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 Li6.4La3Zr1.4Ta0.6O12 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/Cu0.1V2O5 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.

20200702153851.pdf (7439 kB)



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.