KMS Shanghai Institute of Ceramics，Chinese Academy of Sciences
| Vacancy-induced anion and cation redox chemistry in cation-deficient F-doped anatase TiO2 | |
| Li, HX; Li, YN; Zhao, XL; Wang, YW; Huang, KX; Qiu, WJ; Wang, JF; Liu, JJ | |
| 2020-10-21 | |
| Source Publication | JOURNAL OF MATERIALS CHEMISTRY A
 |
| ISSN | 2050-7488 |
| Issue | 39Pages:20393 |
| Subtype | Article |
| Abstract | The incorporation of point defects such as cationic vacancies into electrode materials has been considered as an effective strategy to improve the charge-transfer and ion-diffusion kinetics and allow insertion and migration of multivalent ions. However, they suffer from low specific capacity and electrochemical irreversibility. To elucidate the origin of these issues, we investigated the F-doped and cation-deficient anatase TiO(2)through Mg(2+)insertion for understanding the redox activity of vacancy structure. Our first-principles calculations showed that charge transfer inductively occurs from anion O2-/F(-)to cation Ti(4+)near vacancies, forming oxidized anions F(1-x)-/O((2-y)-)and reduced cations Ti(4-z)+. We further found that cooperative cationic and anionic redox reactions, Ti3.83++ 0.19e(-)-> Ti3.64+, O1.94-+ 0.06e(-)-> O(2-)and F0.93-+ 0.07e(-)-> F-, take place during Mg(2+)insertion. The peculiar anionic redox reaction of oxidized F 2p states is attributed to low-coordination fluorine ions, which was demonstrated by the previous NMR characterization. Our calculations showed that the fluorine redox reaction contributes 26.5% of the total redox capacity. The present results provided chemical clues to use the vacancy structure design to develop efficient cationic and anionic redox materials for improving the energy density and cyclic stability of battery materials. |
| DOI | 10.1039/d0ta07578g |
| WOS Keyword | GENERALIZED GRADIENT APPROXIMATION ; TOTAL-ENERGY CALCULATIONS ; HYDROXYFLUORINATED ANATASE ; CATHODE MATERIAL ; LITHIUM ; OXIDES ; INTERCALATION ; MONOLAYER ; EXCHANGE ; INSIGHTS |
| Language | 英语 |
| WOS Research Area | Chemistry ; Energy & Fuels ; Materials Science |
| Publisher | ROYAL SOC CHEMISTRY |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.sic.ac.cn/handle/331005/27674 |
| Collection | 中国科学院上海硅酸盐研究所 |
| Recommended Citation GB/T 7714 | Li, HX,Li, YN,Zhao, XL,et al. Vacancy-induced anion and cation redox chemistry in cation-deficient F-doped anatase TiO2[J]. JOURNAL OF MATERIALS CHEMISTRY A,2020(39):20393. |
| APA | Li, HX.,Li, YN.,Zhao, XL.,Wang, YW.,Huang, KX.,...&Liu, JJ.(2020).Vacancy-induced anion and cation redox chemistry in cation-deficient F-doped anatase TiO2.JOURNAL OF MATERIALS CHEMISTRY A(39),20393. |
| MLA | Li, HX,et al."Vacancy-induced anion and cation redox chemistry in cation-deficient F-doped anatase TiO2".JOURNAL OF MATERIALS CHEMISTRY A .39(2020):20393. |
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