合金化–氧化法制备 (Mn, Ni)₃O₄固溶体及LiMn_2–xNi_xO₄正极性能

Preparation of (Mn, Ni)₃O₄ Solid Solution by Alloying–Oxidation Method and Cathode Performance of LiMn_2–xNi_xO₄

摘要

为满足锂离子电池锰基正极材料对高性能锰源的需求，本文采用合金化与氧化相结合的两步固溶法，制备了不同 Ni 掺杂量的 (Mn, Ni)₃O₄ 固溶体，并以其为锰源进一步合成了尖晶石型 LiMn_2–xNi_xO₄(x = 0.20，0.40，0.66) 正极材料，考察 Ni 掺杂量对 (Mn, Ni)₃O₄ 固溶体锰源及 LiMn_2–xNi_xO₄ 正极材料的相结构、微观形貌和电化学性能的影响。结果表明：随 Ni 掺杂质量分数从 10% 增至 33%，固溶体锰源中立方尖晶石型 (Mn, Ni)₃O₄ 相 (空间群 Fd–3m) 的占比逐渐增加，晶格常数相应减小，颗粒的截角八面体形貌也日趋规整。在所制备的正极材料中，LiMn_1.80Ni_0.20O₄ 表现出最优的综合电化学性能：在 100 mA/g 电流密度下，其首次放电比容量达 120.1 mA•h•g^–1，经 500 次循环后容量保持率仍达 78.1%，同时兼具较低的电荷转移阻抗和优良的倍率性能。适量 Ni 掺杂不仅能有效增强材料的结构稳定性，还可保留充足的 Mn³⁺/Mn⁴⁺氧化还原反应以保障容量输出，二者协同作用是电化学性能显著提升的关键。本研究为开发高性能锂离子电池正极材料用锰源提供了可行的技术思路。

Abstract

To address the demand of high-performance manganese sources for Mn-based cathode materials in lithium-ion batteries, (Mn, Ni)₃O₄ solid solutions with varying Ni doping levels were prepared via a two-step solid-state method combining alloying and oxidation. The spinel-type LiMn_2–xNi_xO₄ (x = 0.20, 0.40, 0.66) cathode materials were subsequently synthesized using (Mn, Ni)₃O₄ solid solutions as manganese sources. The influence of Ni doping content on the phase structure, morphology, and electrochemical properties of (Mn, Ni)₃O₄ solid solution precursors and the resulting LiMn_2–xNi_xO₄ cathode materials was systematically investigated. The results indicate that as the Ni doping mass fraction increases from 10% to 33%, the proportion of the cubic spinel (Mn, Ni)₃O₄ phase (space group Fd–3m) in the solid solution precursor increases, accompanied by a decrease in lattice constant and a more pronounced truncated octahedral morphology. Among the obtained cathode materials, LiMn_1.80Ni_0.20O₄ exhibits the best overall electrochemical performance, delivering an initial specific discharge capacity of 120.1 mA•h•g^–1 at a current density of 100 mA/g, retaining 78.1% of its initial capacity after 500 cycles, and showing low charge transfer resistance as well as favorable rate capability. Appropriate Ni doping not only enhances structural stability but also preserves sufficient capacity contribution from Mn³⁺/Mn⁴⁺ redox, which is the primary reason for its superior electrochemical performance. This study provides a feasible technical approach for developing manganese sources used in high-performance cathode materials for lithium-ion batteries.

关键词

锂离子电池 / 正极材料 / Ni 掺杂 / LiMn_2−xNi_xO₄ / 电化学性能 / (Mn, Ni)₃O₄ 固溶体 / 合金化 / 氧化法

Key words

lithium-ion battery / cathode materials / Ni doping / LiMn_2−xNi_xO₄ / electrochemical performance / (Mn, Ni)₃O₄ solid solution / alloying / oxidation method

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基金资助

国家自然科学基金项目(52104291)