硅酸盐学报

全浓度梯度富锂材料双功能基元序构与性能优化

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黄少娟 ¹^,²^,³ , 李诚瀚 ¹^,²^,³ , 刘世奇 ¹^,²^,³ , 李小强 ¹ , 李玉强 ¹^,²^,³ , 王博亚 ⁵ , 王群 ¹ , 谷林 ⁵ , 王国庆 ¹^,⁴ , 白珍辉 ⁴ , 张旭 ¹^,²^,³ , 郭现伟 ¹^,⁴ , 尉海军 ¹^,²^,³

硅酸盐学报 | 研究论文 2026,54(7): 2173-2183

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硅酸盐学报 |研究论文 2026 , 54 (7) : 2173 -2183

全浓度梯度富锂材料双功能基元序构与性能优化

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黄少娟¹^,²^,³, 李诚瀚¹^,²^,³, 刘世奇¹^,²^,³, 李小强¹, 李玉强¹^,²^,³, 王博亚⁵, 王群¹, 谷林⁵, 王国庆¹^,⁴, 白珍辉⁴, 张旭¹^,²^,³, 郭现伟¹^,⁴, 尉海军¹^,²^,³

作者信息

^1．北京工业大学材料科学与工程学院，北京 100124

^2．工大国创先进电池材料与器件研究院，北京 100176

^3．北京工业大学材料循环低碳再生全国重点实验室，北京 100124

^4．北京创能惠通科技有限公司，北京，100176

^5．清华大学材料学院，北京 100084

通讯作者:

尉海军（1980—），男，博士，教授。

作者简介:

黄少娟（2000—），女，硕士研究生。

Bifunctional Unit Sequential Structure and Performance Optimization of Full-Concentration Gradient Lithium-Rich Manganese-Based Layered Oxide

Shaojuan HUANG¹^,²^,³, Chenghan LI¹^,²^,³, Shiqi LIU¹^,²^,³, Xiaoqiang LI¹, Yuqiang LI¹^,²^,³, Boya WANG⁵, Qun WANG¹, Lin GU⁵, Guoqing WANG¹^,⁴, Zhenhui BAI⁴, Xu ZHANG¹^,²^,³, Xianwei GUO¹^,⁴, Haijun YU¹^,²^,³

Affiliations

^1.College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, China

^2.Institute of Gongda-Guochuang, Advanced Battery Materials and Devices, Beijing 100176, China

^3.State Key Laboratory of Materials Low-Carbon Recycling, Beijing University of Technology, Beijing 100124, China

^4.Create Energy & Benefit Future Co. Ltd., Beijing 100176, China

^5.School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China

Corresponding Author:

{YU} Haijun (1980-), male, Ph.D., Professor. E-mail: hj-yu@bjut.edu.cn

HUANG Shaojuan (2000-), female, Master candidate. E-mail: huangsj@emails.bjut.edu.cn

出版时间: 2026-06-04 doi: 10.14062/j.issn.0454-5648.20260109

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摘要

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富锂锰基层状氧化物凭借阴阳离子氧化还原反应赋予的超高放电比容量，成为下一代高比能电池的核心正极材料。然而，其在高电压下存在的晶格氧不可逆析出及界面副反应严重等问题制约其实际应用。通过室温氨气等离子体技术对体相全浓度梯度设计的双晶畴富锂锰基层状氧化物进行表界面功能基元序构设计，该策略仅需数分钟即可实现高效表界面重构与温和氮化，克服传统气相热处理动力学迟缓、易引发表面晶体结构过度转变的局限。氨气室温等离子体改性在正极晶粒表面构建出稳定的尖晶石-无定形包覆的纳米复合双功能基元序构界面。内层尖晶石相作为快速离子通道显著提升Li⁺传输动力学，外层含N无定形层通过化学键合抑制晶格氧流失与电解液腐蚀，短时处理有效避免了材料表面Mn的过度还原和向岩盐相结构的过度转变。得益于体相全浓度梯度双晶畴设计与表面纳米复合双功能基元序构的协同作用，材料的电化学性能显著提升，1 C倍率下循环900圈容量保持率为81.5%，平均电压衰减仅为0.21 mV/cycle。建立体相和表面功能基元序构协同设计理念，可以为开发高能量密度电池提供普适性的改性路径新思路。

关键词

功能基元序构 / 氨气 / 等离子体 / 富锂锰基层状氧化物正极材料 / 全浓度梯度 / 锂离子电池

Abstract

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Introduction

With the ever-increasing industrial demand for high energy density lithium-ion batteries, lithium-rich manganese-based layered oxide cathodes have attracted much attention due to their high specific capacity and low cost. However, their practical application is hindered by critical drawbacks including low initial Coulombic efficiency, irreversible oxygen release, and severe voltage fade. In this paper, bulk-engineered lithium-rich manganese-based layered oxides with a full concentration gradient were prepared by a room-temperature ammonia plasma interfacial modification strategy. In contrast to direct ammonia sintering, ammonia plasma modification could construct a stable spinel-amorphous composite nano-bifunctional motif ordered interface on the cathode surface that endowed fast Li⁺ transport kinetics. This bulk-surface functional motif ordering design concept could provide a novel and effective strategy for improving the overall electrochemical performance of lithium-rich oxide cathodes.

Methods

A precursor of cobalt-free full-concentration gradient twin-domain lithium-rich manganese-based layered oxide cathode material was synthesized by a co-precipitation method. After washing for impurity removal and vacuum drying, the precursor was uniformly mixed with 3% (in mole fraction) excess Li₂CO₃ for lithium supplementation and sintered to prepare the cobalt-free gradient lithium-rich manganese-based layered oxide cathode material (GLLOs). To investigate the modification effects of different treatment methods under ammonia atmosphere, the equal mass of GLLOs was subjected to direct ammonia sintering and ammonia plasma modification, respectively. The crystal structure, micro-morphology, electrochemical performance, ion transport kinetics, and transition metal valence state evolution of the materials before and after modification were determined by systematic characterizations including X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, electrochemical measurements, and kinetic analysis, respectively. Furthermore, the regulatory differences of ammonia treatment in different states on the performance of GLLOs and their intrinsic action mechanisms were revealed.

Results and discussion

Two distinct ammonia-based treatments (i.e., direct ammonia sintering and ammonia plasma technology) have different impacts on the GLLOs' surface structure, valence variation, electrochemical performance, and stability. Direct ammonia sintering forms a rock salt-amorphous interface with more significant Mn valence reduction, improving initial efficiency and rate capability, while degrading cycling stability. Ammonia plasma constructs a stable spinel-amorphous interface facilitating Li⁺transport, with a milder Mn valence change, effectively stabilizing interfacial reactions and structure to remarkably enhance long-cycle performance and mitigate voltage decay.

The formation of rock salt and spinel phase functional units on GLLOs surface stems from ammonia-induced TM valence reduction, triggering Li leaching, oxygen vacancy formation, and TM migration to Li layers that drive layered-to-spinel/rock salt transformation. Direct ammonia sintering requires prolonged heating with limited ammonia decomposition, most nitrogen intermediates adsorb on the material surface, causing excessive TM migration and a rock salt-N-rich amorphous interface. Ammonia plasma enables a rapid ammonia decomposition into nitrogen intermediates for quick modification, forming a spinel-amorphous interface that enhances Li⁺ transport, inhibits oxygen loss, electrolyte corrosion, and stabilizes cycling via short-time treatment.

Conclusion

In this work, twin-domain lithium-rich manganese-based layered oxide cathodes with bulk full-concentration gradient were interface-modified via direct ammonia sintering and ammonia plasma treatment. The effect of interface modification method on the surface structure, electrochemical performance, TMs valence, kinetics, and stability was investigated. Ammonia nitridation could form a 2-3 nm N-containing amorphous interface, alleviating oxygen vacancies and enhancing oxygen redox reversibility. Ammonia plasma, operating at room temperature for minutes, could decompose into nitrogen active species under high electric field, constructing a spinel-amorphous composite interface favorable for Li⁺ transport. It could avoid Mn over-reduction and spinel-to-rock salt transformation, maintaining TMs reversibility. A robust bulk-surface synergistic stabilization system was established via integrating the bulk full concentration gradient twin-domain design with the surface composite nano-bifunctional motif ordering construction, remarkably boosting the electrochemical performance of the cathodes (i.e., the capacity retention of 81.5% after 900 cycles at 1 C, accompanied by a low voltage decay of only 0.21 mV/cycle). Controllable ammonia decomposition could facilitate a stable interface formation, offering a novel pathway to boost the comprehensive performance of LLOs.

Key words

functional unit sequential structure / ammonia / plasma / lithium-rich manganese-based layered oxide cathodes / full-concentration gradient / lithium-ion battery

引用本文

黄少娟, 李诚瀚, 刘世奇, 李小强, 李玉强, 王博亚, 王群, 谷林, 王国庆, 白珍辉, 张旭, 郭现伟, 尉海军. 全浓度梯度富锂材料双功能基元序构与性能优化. 硅酸盐学报, 2026 , 54 (7) : 2173 -2183 . DOI: 10.14062/j.issn.0454-5648.20260109

Shaojuan HUANG, Chenghan LI, Shiqi LIU, Xiaoqiang LI, Yuqiang LI, Boya WANG, Qun WANG, Lin GU, Guoqing WANG, Zhenhui BAI, Xu ZHANG, Xianwei GUO, Haijun YU. Bifunctional Unit Sequential Structure and Performance Optimization of Full-Concentration Gradient Lithium-Rich Manganese-Based Layered Oxide[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (7) : 2173 -2183 . DOI: 10.14062/j.issn.0454-5648.20260109

基金

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国家自然科学基金项目(92263206; 92572203; U23A20577; 52372168)
国家重点研发计划(2022YFB2404401)

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排序方式：

2026年第54卷第7期

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文章信息

doi: 10.14062/j.issn.0454-5648.20260109

接收时间：2026-02-28
首发时间：2026-10-22
出版时间：2026-06-04

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出版历史

收稿日期：2026-02-28
修回日期：2026-03-26

基金

国家自然科学基金项目(92263206; 92572203; U23A20577; 52372168)

国家重点研发计划(2022YFB2404401)

作者信息

^1．北京工业大学材料科学与工程学院，北京 100124

^2．工大国创先进电池材料与器件研究院，北京 100176

^3．北京工业大学材料循环低碳再生全国重点实验室，北京 100124

^4．北京创能惠通科技有限公司，北京，100176

^5．清华大学材料学院，北京 100084

通讯作者:

尉海军（1980—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20260109

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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