物理化学学报 >> 2022, Vol. 38 >> Issue (6): 2105024.doi: 10.3866/PKU.WHXB202105024

所属专题： 面向电化学储能与转化的表界面工程

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三维大孔/介孔碳-碳化钛复合材料用于无枝晶锂金属负极

张威1,2, 梁海琛1, 朱科润1, 田泳1, 刘瑶1, 陈佳音1, 李伟1,*()   

  1. 1 复旦大学化学系，上海 200433
    2 珠海复旦创新研究院，横琴新区，广东 珠海 519000
  • 收稿日期:2021-05-13 录用日期:2021-06-22 发布日期:2021-07-01
  • 通讯作者: 李伟 E-mail:weilichem@fudan.edu.cn
  • 基金资助:
    国家重点研发计划(2018YFE0201701);国家重点研发计划(2018YFA0209401);国家自然科学基金(21733003);国家自然科学基金(22088101);国家自然科学基金(21975050);中国博士后科学基金(2020TQ0064);中国博士后科学基金(2020M680051);上海市科学技术委员会(19JC1410700);广东省基础与应用基础研究基金(2021A1515010108)

Three-Dimensional Macro-/Mesoporous C-TiC Nanocomposites for Dendrite-Free Lithium Metal Anode

Wei Zhang1,2, Haichen Liang1, Kerun Zhu1, Yong Tian1, Yao Liu1, Jiayin Chen1, Wei Li1,*()   

  1. 1 Department of Chemistry, Fudan University, Shanghai 200433, China.
    2 Zhuhai-Fudan Innovation Institute, Hengqin New District, Zhuhai 519000, Guangdong Province, China
  • Received:2021-05-13 Accepted:2021-06-22 Published:2021-07-01
  • Contact: Wei Li E-mail:weilichem@fudan.edu.cn
  • About author:Wei Li, Email: weilichem@fudan.edu.cn; Tel.: +86-21-31249998
  • Supported by:
    the National Key R & D Program of China(2018YFE0201701);the National Key R & D Program of China(2018YFA0209401);the National Natural Science Foundation of China(21733003);the National Natural Science Foundation of China(22088101);the National Natural Science Foundation of China(21975050);the China Postdoctoral Science Foundation(2020TQ0064);the China Postdoctoral Science Foundation(2020M680051);the Science and Technology Commission of Shanghai Municipality(19JC1410700);the Guangdong Basic and Applied Basic Research Foundation(2021A1515010108)

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摘要：

金属锂具有超高的理论容量(3860 mAh·g-1)和低氧化还原电位(-3.04 V vs.标准氢电极)，是极具吸引力的下一代高能量密度电池的负极材料。然而，循环过程中的体积膨胀、锂枝晶生长和“死锂”等问题严重的限制了其实际应用。合理设计三维骨架调控金属锂的成核行为是抑制锂枝晶生长的有效策略。本文中，我们发展了一种“软硬双模板”的方法合成了兼具大孔和介孔的三维碳-碳化钛(Three-dimensional macro-/mesoporous C-TiC，表示为3DMM-C-TiC)复合材料。多级孔道为金属锂的沉积提供了足够的空间，缓冲充放电中巨大的体积变化。此外，TiC的引入显著增强多孔骨架的导电性，改善锂金属的成核行为，促进金属锂的均匀成核和沉积，抑制锂枝晶生长。3DMM-C-TiC||Li电池测试表明，在循环300圈以后，库伦效率仍保持在98%以上。此外，所得材料与LiFePO4 (LFP)组成的全电池也表现出优异的倍率和循环性能。本工作为无枝晶锂金属负极的设计提供了新的思路。

关键词: 锂金属负极, 大孔/介孔复合结构, 碳化钛, 锂枝晶

Abstract:

In previous decades, lithium-ion batteries (LIBs) were the most commonly used energy storage systems for powering portable electronic devices because LIBs exhibit reliable cyclability. However, owing to the low specific capacity of graphite used in the anode, further increase in the energy density of LIBs was limited. The Li metal anode is promising for the construction of next-generation high-energy-density batteries because of its ultrahigh theoretical capacity (3860 mAh·g-1) and low redox potential (-3.04 V vs. standard hydrogen electrode). However, the high activity of Li causes dendritic growth during cycling, which leads to cracking of the solid-electrolyte interphase (SEI), increase in side reactions, and formation of dead Li. Several strategies have been proposed to address these issues, including use of electrolyte additives, high-concentration electrolytes, protection of the Li metal surface with various coatings, use of solid-state electrolytes, and design of a three-dimensional (3D) "Li host" for regulating the nucleation and deposition of Li metal. Among them, the design of a 3D "Li host" has proven to be a simple and effective strategy. However, the commonly used 3D "Li hosts" include nanostructured carbons, which are lithiophobic and, thus, provide limited interaction sites with Li+ ions, leading to the deposition of Li metal on the "Li host" surface. Therefore, it is necessary to design a 3D "Li host" with enhanced interaction with Li+ ions to achieve uniform deposition. Herein, we develop a soft-hard templating route to synthesize 3D macro-/mesoporous C-TiC (denoted as 3DMM C-TiC) nanocomposites, which has been used in Li metal batteries. The as-synthesized materials possess high surface areas (~510 m2·g-1), ordered structures, large pore volumes, and excellent conductivity. The continuous plating and stripping of Li metal and the formation of the hierarchically porous structure with sufficient volume to allow uniform Li deposition result in the alleviation of the volume change. The high specific surface area significantly decreases the local current density and suppresses dendrite growth. Consequently, ultrasmall TiC nanoparticles are uniformly distributed in the 3D macro-/mesoporous framework, which improves conductivity, enhances their interaction with Li+ ions, and promotes the uniform deposition of Li metal. Therefore, the fabricated 3DMM C-TiC||Li battery displays stable cycling performance with improved Coulombic efficiency (98%) over 300 cycles. Moreover, when the 3DMM C-TiC based Li metal anode is assembled with a LiFePO4 (LFP) cathode, the resultant full cells exhibit high specific capacity and excellent cycling stability. This study provides insight for the effective design of a 3D "Li host" for dendrite-free Li metal anodes.

Key words: Lithium metal anode, Macro-/mesoporous structure, TiC, Lithium dendrites