Stable structure and pair distribution function analysis of 0.4Li2MnO3–0.6Li(Mn1/3Ni1/3Co1/3)O2 as cathode materials lithium ion secondary batteries during charge-discharge process using first-principle calculation and quantum beam

IF 3 4区 材料科学 Q3 CHEMISTRY, PHYSICAL
Chiaki Ishibashi , Ryohei Kosasa , Yuiko Koitabashi , Naoto Kitamura , Yasushi Idemoto
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Abstract

In this study, first-principles calculations were conducted to identify a local structure model that replicates both the pristine state and the state of the electrode after five charge and discharge cycles at 25 and 60 °C. The material studied was 0.4Li2MnO3–0.6Li(Mn1/3Ni1/3Co1/3)O2, which is used as a Li-ion battery positive electrode. The stable structures obtained were compared with the pair distribution function G(r) derived from synchrotron X-ray total scattering measurements. Our calculated G(r) models are in good agreement with the observed G(r) values from these measurements. In the model that reproduces the stable structure during the fifth cycle charging at 25 and 60 °C, Li atoms in the transition metal (TM) layer, surrounded by Mn and not adjacent to Co, move toward the Li layer due to weak LiO bonding, partially creating vacancies. The coordination number of Mn near these vacancies in the TM layer changed during charging. During discharging, the model in which Li ions were locally coordinated away from the vacancies in the TM layer was stable. In the 25 °C-charging model, compared to the pristine model, less changes were observed in MnO bonds within the MnO6 octahedra, which are most abundant in the TM layer. Furthermore, less distortion in the Mn-O₆ octahedra was observed, resulting in minimal changes to the host structure during charging and discharging. Therefore, compared to 60 °C, the cycle characteristics were evidently improved when charging and discharging at 25 °C.

Abstract Image

用第一性原理计算和量子束分析正极材料锂离子二次电池充放电过程中的稳定结构和对分布函数
在本研究中,通过第一性原理计算确定了一个局部结构模型,该模型可以复制电极在25°C和60°C下经过五次充放电循环后的原始状态和状态。所研究的材料为0.4Li2MnO3-0.6Li (Mn1/3Ni1/3Co1/3)O2,用于锂离子电池正极。将得到的稳定结构与同步加速器x射线全散射测量得到的对分布函数G(r)进行了比较。我们计算的G(r)模型与从这些测量中观察到的G(r)值吻合得很好。在25°C和60°C第五次循环充电时的稳定结构模型中,过渡金属(TM)层中的Li原子被Mn包围而不与Co相邻,由于LiO键合弱而向Li层移动,部分产生空位。在充电过程中,TM层中空位附近Mn的配位数发生了变化。在放电过程中,Li离子局部协调远离TM层空位的模型是稳定的。在25°c充电模型中,与原始模型相比,MnO6八面体中MnO键的变化较小,而MnO6八面体中的MnO键在TM层中最为丰富。此外,Mn-O货号八面体的变形较小,在装料和出料过程中对主体结构的变化最小。因此,与60°C相比,25°C充放电时的循环特性有明显改善。
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来源期刊
Solid State Ionics
Solid State Ionics 物理-物理:凝聚态物理
CiteScore
6.10
自引率
3.10%
发文量
152
审稿时长
58 days
期刊介绍: This interdisciplinary journal is devoted to the physics, chemistry and materials science of diffusion, mass transport, and reactivity of solids. The major part of each issue is devoted to articles on: (i) physics and chemistry of defects in solids; (ii) reactions in and on solids, e.g. intercalation, corrosion, oxidation, sintering; (iii) ion transport measurements, mechanisms and theory; (iv) solid state electrochemistry; (v) ionically-electronically mixed conducting solids. Related technological applications are also included, provided their characteristics are interpreted in terms of the basic solid state properties. Review papers and relevant symposium proceedings are welcome.
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