石榴石基半固态电池负极Li3N@Li21Si5复合界面相的研究
收稿日期: 2025-01-31
网络出版日期: 2025-05-21
Study on anode Li3N@Li21Si5 composited interface phase for garnet based hybrid solid-state batteries
Received date: 2025-01-31
Online published: 2025-05-21
石榴石型固体电解质具有离子电导率高、电压窗口宽的优点，但其面临的最大问题是与金属锂负极之间的高界面阻抗，因此制约着石榴石基固体电解质的发展。目前改进手段主要是采用合金修饰层加强界面浸润，但易导致锂枝晶生长。采用磁控溅射手段沉积氮化硅修饰层，极大增强石榴石电解质与金属锂的界面浸润，并将界面阻抗值由2 101 Ω降低至181 Ω。同时，对比纯Li3N修饰层与Li3N@Li21Si5修饰层电化学性能的差异。通过金属锂对称电池直流极化与NCM/Li半固态电池循环测试表明，Li3N尽管具有一定的离子电导率，但由于其缺乏对锂的亲和性，导致其界面阻抗较高（1 123 Ω）；而Si的存在增强对锂的亲和性，因此所组装的金属锂对称电池直流循环可持续500 h以上。以镍钴锰622作为正极材料，首次放电比容量达到188.6 mA·h/g，石榴石基NCM/Li半固态电池循环300次后容量保持率可达85.3%。
张计军 , 郭魏源 , 代宣军 . 石榴石基半固态电池负极Li3N@Li21Si5复合界面相的研究[J]. 无机盐工业, 2026 , 58(3) : 25 -31 . DOI: 10.19964/j.issn.1006-4990.2025-0057
Garnet type solid electrolyte has the advantages of high ionic conductivity and wide voltage window，but the biggest problem it faced is the high interfacial resistance with lithium metal anode，which restricts the development of the garnet based solid-state batteries.At present，the main improvement method is to use alloy modification layer to strengthen the interfacial contact，but easily to lead to lithium dendrite growth.In this work，different from the conventional alloy interfacial modification layers，the application of magnetron sputtered silicon nitride modification layer could greatly increase the interfacial affinity between garnet electrolyte and lithium metal，and reduce the interfacial resistance from 2 101 Ω to 181 Ω.At the same time，the electrochemical properties of pure Li3N modified layer and Li3N@Li21Si5 modification layers were compared.The direct current（DC） polarization of Li symmetric cells and NCM/Li hybrid solid-state batteries cycling tests showed that although Li3N was ionic conductive，it had a high interface impedance（1 123 Ω） due to its lack of affinity for lithium.The existence of Si enhanced the lithium affinity，so the assembled Li symmetric battery lasted more than 500 h DC cycle.Using nickel cobalt manganese 622 as the cathode material，the specific capacity of the initial discharge was 188.6 mA·h/g.and the capacity retention rate of garnet based NCM/Li hybrid solid-state battery was 85.3% after 300 cycles.
| [1] | JANEK J， ZEIER W G.A solid future for battery development［J］.Nature Energy，2016，1：16141. |
| [2] | FAMPRIKIS T， CANEPA P， DAWSON J A，et al.Fundamentals of inorganic solid-state electrolytes for batteries［J］.Nature Materials，2019，18（12）：1278-1291. |
| [3] | SCHLEM R， BANIK A， OHNO S，et al.Insights into the lithium sub-structure of superionic conductors Li3YCl6 and Li3YBr6 ［J］.Chemistry of Materials，2021，33（1）：327-337. |
| [4] | ZHANG Zhizhen， SHAO Yuanjun， LOTSCH B，et al.New horizons for inorganic solid state ion conductors［J］.Energy & Environmental Science，2018，11（8）：1945-1976. |
| [5] | PARK K H， KAUP K， ASSOUD A，et al.High-voltage superionic halide solid electrolytes for all-solid-state Li-ion batteries［J］.ACS Energy Letters，2020，5（2）：533-539. |
| [6] | KIM S Y， KAUP K， PARK K H，et al.Lithium ytterbium-based halide solid electrolytes for high voltage all-solid-state batteries［J］.ACS Materials Letters，2021，3（7）：930-938. |
| [7] | HELM B， SCHLEM R， WANKMILLER B，et al.Exploring aliovalent substitutions in the lithium halide superionic conductor Li3- x In1- x Zr x Cl6（0≤x≤0.5）［J］.Chemistry of Materials，2021，33（12）：4773-4782. |
| [8] | XING Chunxian， Haoran DA， YANG Peng，et al.Aluminum impurity from current collectors reactivates degraded NCM cathode materials toward superior electrochemical performance［J］.ACS Nano，2023，17（3）：3194-3203. |
| [9] | LIU Xiaoming， GARCIA-MENDEZ R， LUPINI A R，et al.Local electronic structure variation resulting in Li‘filament’formation within solid electrolytes［J］.Nature Materials，2021，20（11）：1485-1490. |
| [10] | CHEN Shaojie， NIE Zhiwei， TIAN Feifei，et al.The influence of surface chemistry on critical current density for garnet electroly-te［J］.Advanced Functional Materials，2022，32（23）：2113318. |
| [11] | WANG Shuhua， YUE Junpei， DONG Wei，et al.Tuning wettability of molten lithium via a chemical strategy for lithium metal anodes［J］.Nature Communications，2019，10：4930. |
| [12] | KRAVCHYK K V， OKUR F， KOVALENKO M V.Break-even analysis of all-solid-state batteries with Li-garnet solid electrolytes［J］.ACS Energy Letters，2021，6（6）：2202-2207. |
| [13] | 白小洁，曹德富，王君慧，等.半固态储能电池的研究进展［J］.无机盐工业，2022，54（2）：6-15. |
| BAI Xiaojie， CAO Defu， WANG Junhui，et al.Research progress on semi-solid energy storage batteries［J］.Inorganic Chemicals Industry，2022，54（2）：6-15. | |
| [14] | SHAO Yuanjun， WANG Hongchun， GONG Zhengliang，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. |
| [15] | HARTWIG P， WEPPNER W， WICHELHAUS W.Fast ionic lithium conduction in solid lithium nitride chloride［J］.Materials Research Bulletin，1979，14（4）：493-498. |
| [16] | MIZUSAKI J I， FUEKI K， MUKAIBO T.An investigation of the hebb-Wagner′s d-c polarization technique I.steady-state chemical potential profiles in solid electrolytes［J］.Bulletin of the Che- mical Society of Japan，1975，48（2）：428-431. |
| [17] | MAITI S， SCLAR H， SHARMA R，et al.Understanding the role of alumina（Al2O3），pentalithium aluminate（Li5AlO4），and pentasodium aluminate（Na5AlO4） coatings on the Li and Mn‐rich NCM cathode material for enhanced electrochemical performance［J］.Advanced Functional Materials，2021，31（8）：202008083. |
| [18] | YU Yuran， WANG Zhuo， SHAO Guosheng.Formulation of Li-metal-halide（LMX） solid state electrolytes through extensive first principles modelling［J］.Journal of Materials Chemistry A，2021，9（45）：25585-25594. |
| [19] | 况新亮，刘垂祥，熊朋.锂离子电池产业分析及市场展望［J］.无机盐工业，2022，54（8）：12-19，32. |
| KUANG Xinliang， LIU Chuixiang， XIONG Peng.Industry analysis and market prospect of lithium ion battery［J］.Inorganic Chemicals Industry，2022，54（8）：12-19，32. | |
| [20] | 闫雅婧.锂离子电池用固态电解质的研究现状与展望［J］.无机盐工业，2020，52（7）：22-25. |
| YAN Yajing.Research status and prospect of solid electrolyte for lithium ion batteries［J］.Inorganic Chemicals Industry，2020，52（7）：22-25. | |
| [21] | XU Kang.Interfaces and interphases in batteries［J］.Journal of Power Sources，2023，559：232652. |
| [22] | ZHOU Laidong， ZUO Tongtong， HAN Dong，et al.High areal capacity，long cycle life 4 V ceramic all-solid-state Li-ion batteries enabled by chloride solid electrolytes［J］.Nature Energy，2022，7：83-93. |
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