Engineering the diphasic Li-rich Mn-based composite with alleviated Jahn–Teller effect for high-energy Li-ion batteries

IF 9.6 1区 材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY
Feng Li, Jia-Cheng Li, Mao-Sheng Gong, Ze-Zhou Lin, Xuan-Ming Chang, Mo-Han Dong, Pei-Yu Hou
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Abstract

The unique oxygen stacking sequence of O2-type structures restricts the irreversible transition metal movement into Li vacancies for the delithiated Li-rich layered oxides (LLOs) and maintains outstanding voltage stability. However, the ion-exchange synthesis promotes the Mn-ion valence reduction and aggravates the Jahn–Teller (J–T) distortion alongside disproportionation. Since the main oxidation state of the Mn ions is +4 in the traditional O3-type LLOs, synergistic effects of the O2-type and O3-type structures are expected in the O2/O3 diphasic Li-rich material. Herein, O2/O3 biphasic intergrowth LLOs were rationally designed, and the synergic optimization of the biphasic structure was planned to retard the J–T effect. The O2/O3 intergrowth nature was confirmed, and the percentages of the O2 and O3 phases were 56% and 44%, respectively. Density functional theory calculations demonstrated that the Mn2+(EC) sheath had a remarkably lower energy barrier than the Li+(EC) sheath. This finding suggests that Mn2+ ions that are dissolved into the electrolyte accelerate the electrolyte oxidization, so the deposition of the cathode electrolyte interface for pristine O2-LLOs causes a high electrochemical impedance. The designed O2/O3 biphasic LLOs boost the capacity stability and suppress the voltage drop upon repeated Li+ de-intercalation. The phase regulation strategy offers great potential for developing low-cost LLOs with enhanced structural stability for advanced Li-ion batteries.

Graphical abstract

高能量锂离子电池的富锂双相锰基复合材料的设计与改善
o2型结构独特的氧层序限制了贫锂富锂层状氧化物(LLOs)不可逆的过渡金属向Li空位的移动,并保持了出色的电压稳定性。然而,离子交换合成促进了mn离子价态的还原,并加剧了歧化和jhn - teller (J-T)畸变。由于传统的O3型LLOs中Mn离子的主要氧化态为+4,因此在O2/O3双相富锂材料中,O2型和O3型结构的协同效应有望实现。本文合理设计了O2/O3两相互生LLOs,并对两相结构进行了协同优化,以延缓J-T效应。证实了O2/O3共生的性质,O2和O3相的比例分别为56%和44%。密度泛函理论计算表明,Mn2+(EC)鞘层的能垒明显低于Li+(EC)鞘层。这一发现表明,溶解在电解质中的Mn2+离子加速了电解质的氧化,因此原始O2-LLOs阴极电解质界面的沉积导致了高电化学阻抗。所设计的O2/O3双相LLOs提高了容量稳定性,抑制了反复Li+脱插时的电压下降。相位调节策略为开发低成本LLOs提供了巨大的潜力,并增强了先进锂离子电池的结构稳定性。图形抽象
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Rare Metals
Rare Metals 工程技术-材料科学:综合
CiteScore
12.10
自引率
12.50%
发文量
2919
审稿时长
2.7 months
期刊介绍: Rare Metals is a monthly peer-reviewed journal published by the Nonferrous Metals Society of China. It serves as a platform for engineers and scientists to communicate and disseminate original research articles in the field of rare metals. The journal focuses on a wide range of topics including metallurgy, processing, and determination of rare metals. Additionally, it showcases the application of rare metals in advanced materials such as superconductors, semiconductors, composites, and ceramics.
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