Li Jianlong * Liu Wenbo Zhang Zhichao.Multi-element doping inhibits the accumulation of internal stress in cathode material[J].Plating & Finishing,2024,(11):49-57.
多元素掺杂抑制正极材料的内应力积累
- Title:
- Multi-element doping inhibits the accumulation of internal stress in cathode material
- Keywords:
- high nickel layer oxide ; energy density ; synergistic doping strategy ; phase change ; internal stress
- 分类号:
- TM 911
- 文献标志码:
- A
- 摘要:
- 高镍层状氧化物 LiNi x Mn y Co 1 - x - y O 2 （ NCM ， x ≥ 0.8 ）由于其高的能量密度和低廉的成本是锂离子电池（ LIBs ）最有前途的正极材料之一。提高 NCM 镍含量和截止电压可以提升正极材料的实际放电比容量，然而，高镍含量导致其表面残留大量的锂化合物，影响界面处锂离子的传输；同时长循环过程中产生的 HF 会溶解层状晶体结构中的过渡金属离子，使其电化学性能变差，严重阻碍了 NCM 大规模的实际应用。改善 NCM 的结构不稳定性可以通过掺杂来实现，在此，提出了一种协同掺杂改性策略，在 NCM 晶体内部同时掺杂 Ta 、 Ti 和 Mg 元素， 3 种元素的协同作用抑制了不可逆相变的发生，缓解了晶体内应力的积累。 Ta@Ti@Mg 改性的 NCM 在 2.75 ～ 4.60 V ， 0.5 C 循环 100 次后放电比容量为 175.5 mAh/g ，该协同掺杂策略为其它正极材料的改性提供了借鉴作用。
- Abstract:
- ： High-nickel layered oxide LiNi x Mn y Co 1 - x - y O 2 （ NCM ， x ≥ 0.8 ） is one of the most promising cathode materials for lithium-ion batteries （ LIBs ） due to its high energy density and low cost. Increasing nickel content and cut-off voltage of NCM can improve the actual specific discharge capacity of cathode materials. However ， high nickel content leads to a large number of lithium compounds remaining on the surface ， which affects the transmission of lithium ions at the interface. At the same time ， HF produced in the long cycle process will dissolve the transition metal ions in the layered crystal structure ， making its electrochemical performance worse ， which seriously hinders the practical application of NCM on a large scale. The structural instability of NCM can be improved by doping. Here ， we report a synergistic doping modification strategy ， in which Ta ， Ti and Mg are doped inside NCM crystals at the same time. The synergistic effect of the three elements inhibits the occurrence of irreversible phase transition and alleviates the accumulation of internal stress in the crystals. The specific discharge capacity of Ta@Ti@Mg modified NCM is 175.5 mAh/g after 100 cycles of 2.75?4.60 V and 0.5 C . This collaborative doping strategy provides a reference for the modification of other cathode electrode materials.
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备注/Memo
基金项目： 国家自然科学基金资助项目（ 52175123 ）中文 收稿日期： 2024-07-02 修回日期： 2024-07-16 作者简介： 李建龙 （ 1982 ─ ）男，硕士，高级工程师，研究方向为轨道交通新能源材料， email ： lijianlong@zzrvtc.edu.cn
作者简介:；河南省科技攻关课题（ 242102210171 ） 多元素掺杂抑制正极材料的内应力积累 李建龙 * ，刘文博， 张志超