Average and local structure analysis of Na/Li ion-exchanged Lix(Mn,Ni,Ti)O2 using synchrotron X-ray and neutron sources

Average and local structure analysis of Na/Li ion-exchanged Lix(Mn,Ni,Ti)O2 using synchrotron X-ray and neutron sources
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使用同步加速器 X 射线和中子源对 Na/Li 离子交换 Lix(Mn,Ni,Ti)O2 进行平均和局部结构分析

DOI:
10.1007/s10008-021-04909-x
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发表时间:
2021
影响因子:
2.5
通讯作者:
Yasushi Idemoto
Yasushi Idemoto
中科院分区:
工程技术4区
文献类型:
--
作者:
Naoya Ishida;Kotaro Kawagoe;Naoto Kitamura;Junji Akimoto;Yasushi Idemoto

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以P3-Na0.7(Mn,Ni,Ti)O2为前驱体,通过Na/Li离子交换合成了富Mn层状Lix(Mn,Ni,Ti)O2。 ICP-AES、滴定技术和 XANES 的组合化学分析表明,过渡金属 (TM) 的一些空位满足电中性。使用同步加速器 X 射线和中子粉末衍射图分析的平均结构证实了 TM 位点上存在大量空位,并进一步揭示了层状岩盐类型 Lix(Mn,Ni,Ti)O2 中存在小四面体 Li。 Li0.6Na0.02Mn0.71Ni0.13Ti0.12□0.04O2的电化学性能表现出较高的首次放电容量。 250 mAh g−1 和第 50 次循环超过 200 mAh g−1 的高循环性能。 PDF 分析对同步加速器 X 射线和中子的总散射以及额外的四面体 Li 和一些 TM 空位实现了良好的拟合。计算细化局部结构中的每个 (Mn,Ni,Co)O6 八面体并将其表示为 3D 分布,其中 NiO6 和主体 MnO6 八面体在视觉上分别被表征为明显较少扭曲和高度扭曲的八面体。 Ni2+和Ti4+的共取代起到了稳定整体结构和保留过渡金属空位的作用,从而在循环过程中保持高容量。
Mn-rich layered Lix(Mn,Ni,Ti)O2was synthesized by Na/Li ion exchange of a P3-Na0.7(Mn,Ni,Ti)O2precursor. The combined chemical analysis with the ICP-AES, titration technique, and XANES indicated that their electroneutralities were satisfied in some vacancies of the transition metals (TMs). Average structure analyzed using synchrotron X-ray and neutron powder diffraction patterns confirmed a significant amount of vacancies at TM sites and further revealed the existence of a minor tetrahedral Li in the layered rock-salt type Lix(Mn,Ni,Ti)O2. Electrochemical properties of Li0.6Na0.02Mn0.71Ni0.13Ti0.12□0.04O2exhibited high first discharge capacity of ca. 250 mAh g−1and high cyclability of exceeding 200 mAh g−1at the 50th cycle. PDF analysis achieved good fittings for the both total scatterings of synchrotron X-ray and neutron with additional tetrahedral Li and some TM vacancies. Each (Mn,Ni,Co)O6octahedron in the refined local structure was calculated and expressed as 3D distributions, where the NiO6and the host MnO6octahedra were visually characterized as significantly less distorted and highly distorted octahedra, respectively. The co-substitution of Ni2+ant Ti4+played the role of stabilizing whole structure and preserving the transition metal vacancy to maintain the high capacity during cycles.
具有高锂嵌入/脱嵌能力的非化学计量层状 LixMnyO2。
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