Anionic redox reaction in Na-deficient layered oxide cathodes: Role of Sn/Zr substituents and in-depth local structural transformation revealed by solid-state NMR
文献类型：期刊论文
| 作者 | Zhao, Chong3; Li, Chao3; Yang, Qi3; Qiu, Qing3; Tong, Wei2 ; Zheng, Shun1; Ma, Jingyuan1; Shen, Ming3; Hu, Bingwen3
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| 刊名 | ENERGY STORAGE MATERIALS
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| 出版日期 | 2021-08-01 |
| 卷号 | 39 |
| 关键词 | Oxygen redox Layered oxides Sn/Zr metal substituents Solid-state NMR Li/Mn migrations |
| ISSN号 | 2405-8297 |
| DOI | 10.1016/j.ensm.2021.04.007 |
| 通讯作者 | Li, Chao(lchao@phy.ecnu.edu) ; Hu, Bingwen(bw.hu@phy.ecnu.edu) |
| 英文摘要 | Anionic redox reaction (ARR) offers a complementary electron reservoir that affords the egress/ingress of additional Na beyond the conventional cation redox reaction. However, oxygen-related ARR in sodium-ion batteries is universally confronted with several roadblocks such as insufficient reversibility and poor understanding on the functioning mechanisms. We herein attempt to improve the reversibility of oxygen-related ARR in a Na-deficient Li/Mn(IV)-based layered oxide cathode by Sn and Zr substitutions. The as-designed P2-Na0.66Li0.22Mn0.775Sn0.005O2 and P2-Na0.66Li0.22Mn0.775Zr0.005O2 demonstrate much enhanced cycle stability and rate capability (72% capacity retention at 10 mA g(-1) after 100 cycles and 92 mAh g(-1) reversible capacity at 1 A g(-1) for the former). The role of Sn/Zr substituents was meticulously studied, manifesting the effective inhibition of the anisotropic O2-alpha-Mn4+ coupling (0 < alpha < 2) and the irreversible lattice oxygen loss. More impressively, the local structural transformations studied via Na-23/Li-7 solid-state NMR substantiate that (i) Li-ions migrate from TM (transition metal) layer to AM (alkali metal) layer upon charge, and do not return to the original sites in TM layer upon discharge; (H) the egress/ingress of Na follows a solid-solution reaction within 4.5-1.5 V, but the local structural transition is not fully reversible; (Hi) Li/Mn migrations continue beyond the initial cycle, bringing about irreversible Li/Mn losses and Na-site local disorder upon prolonged cycling. Altogether, this study provides deep insights into the ARR mechanism of Na-deficient layered oxide cathodes and will pave a new avenue to fully address the intrinsic shortcomings of oxygen-related ARR. |
| WOS关键词 | HIGH-PERFORMANCE CATHODE ; SODIUM-ION BATTERIES ; OXYGEN-REDOX ; VOLTAGE HYSTERESIS ; TI SUBSTITUTION ; LOW-COST ; CAPACITY ; METAL ; CHEMISTRY ; OXIDATION |
| 资助项目 | National Natural Science Foundation of China[21902049] ; National Natural Science Foundation of China[21872055] ; National Natural Science Foundation of China[21703068] ; Shanghai Sailing Program[19YF1413000] ; Fundamental Research Funds for the Central Universities ; Shanghai Synchrotron Radiation Facility[BL02B02] ; Shanghai Synchrotron Radiation Facility[BL14W] ; Shanghai Synchrotron Radiation Facility[BL14B] |
| WOS研究方向 | Chemistry ; Science & Technology - Other Topics ; Materials Science |
| 语种 | 英语 |
| WOS记录号 | WOS:000658385000006 |
| 出版者 | ELSEVIER |
| 资助机构 | National Natural Science Foundation of China ; Shanghai Sailing Program ; Fundamental Research Funds for the Central Universities ; Shanghai Synchrotron Radiation Facility |
| 源URL | [http://ir.hfcas.ac.cn:8080/handle/334002/123726]  |
| 专题 | 中国科学院合肥物质科学研究院 |
| 通讯作者 | Li, Chao; Hu, Bingwen |
| 作者单位 | 1.Shanghai Synchrotron Radiat Facil SSRF, Shanghai 201204, Peoples R China 2.Chinese Acad Sci, High Field Magnet Lab, Anhui Key Lab Condensed Matter Phys Extreme Condi, Hefei 230031, Peoples R China 3.East China Normal Univ, Sch Phys & Elect Sci, Shanghai Key Lab Magnet Resonance, Shanghai 200241, Peoples R China |
| 推荐引用方式 GB/T 7714 | Zhao, Chong,Li, Chao,Yang, Qi,et al. Anionic redox reaction in Na-deficient layered oxide cathodes: Role of Sn/Zr substituents and in-depth local structural transformation revealed by solid-state NMR[J]. ENERGY STORAGE MATERIALS,2021,39. |
| APA | Zhao, Chong.,Li, Chao.,Yang, Qi.,Qiu, Qing.,Tong, Wei.,...&Hu, Bingwen.(2021).Anionic redox reaction in Na-deficient layered oxide cathodes: Role of Sn/Zr substituents and in-depth local structural transformation revealed by solid-state NMR.ENERGY STORAGE MATERIALS,39. |
| MLA | Zhao, Chong,et al."Anionic redox reaction in Na-deficient layered oxide cathodes: Role of Sn/Zr substituents and in-depth local structural transformation revealed by solid-state NMR".ENERGY STORAGE MATERIALS 39(2021). |
入库方式： OAI收割
来源：合肥物质科学研究院
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