{"id":238987,"date":"2022-06-30T06:47:43","date_gmt":"2022-06-29T22:47:43","guid":{"rendered":"http:\/\/www.cailiaoniu.com\/?p=238987"},"modified":"2022-06-29T15:48:02","modified_gmt":"2022-06-29T07:48:02","slug":"%e9%94%82%e7%94%b5%e6%9c%80%e6%96%b0nat-mater-%e5%af%8c%e9%94%82%e6%ad%a3%e6%9e%81%e9%85%8d%e4%bd%93-%e7%94%b5%e8%8d%b7%e8%bd%ac%e7%a7%bb%e8%bf%87%e7%a8%8b%e7%9a%84%e5%8a%a8%e6%80%81%e6%8d%95","status":"publish","type":"post","link":"http:\/\/www.cailiaoniu.com\/?p=238987","title":{"rendered":"\u9502\u7535\u6700\u65b0Nat. Mater.: \u5bcc\u9502\u6b63\u6781\u914d\u4f53-\u7535\u8377\u8f6c\u79fb\u8fc7\u7a0b\u7684\u52a8\u6001\u6355\u83b7"},"content":{"rendered":"

1.<\/strong>\u3010\u5bfc\u8bfb\u3011<\/strong><\/p>\n

\u76f8\u6bd4\u4e8e\u4f20\u7edf\u7684\u9502\u79bb\u5b50\u6b63\u6781\u6750\u6599\uff0c\u5bcc\u9502\u6b63\u6781\uff08Li1+x<\/sub>M1\u2212x<\/sub>O2<\/sub>, 0<x<1\uff09\u5355\u4f4d\u8d28\u91cf\u5185\u542b\u6709\u66f4\u591a\u9502\u79bb\u5b50\uff0c\u5e76\u4e14\u5728\u6d3b\u6027\u9633\u79bb\u5b50\u7684\u57fa\u7840\u4e0a\uff0c\u9634\u79bb\u5b50\u53c2\u4e0e\u7684\u6c27\u5316\u8fd8\u539f\u8fc7\u7a0b\u53ef\u4ee5\u8d21\u732e\u989d\u5916\u5bb9\u91cf\uff0c\u63d0\u4f9b\u66f4\u9ad8\u7684\u7535\u6c60\u80fd\u91cf\u5bc6\u5ea6\u3002\u4f46\u662f\uff0c\u9634\u79bb\u5b50\u6c27\u5316\u8fd8\u539f\u53cd\u5e94\u4f1a\u5bfc\u81f4\u7f13\u6162\u7684\u52a8\u529b\u5b66\u548c\u7535\u538b\u8fdf\u6ede\u73b0\u8c61\uff0c\u8fd9\u4e3a\u5bcc\u9502\u6b63\u6781\u7684\u5b9e\u9645\u5e94\u7528\u5e26\u6765\u6311\u6218\u3002\u6df1\u5165\u7814\u7a76\u9634\u79bb\u5b50\u7684\u6c27\u5316\u8fd8\u539f\u8fc7\u7a0b\uff0c\u4e86\u89e3\u5176\u6fc0\u6d3b\u673a\u5236\u5bf9\u4e8e\u8bbe\u8ba1\u9ad8\u5bb9\u91cf\u6b63\u6781\u6750\u6599\u5177\u6709\u91cd\u8981\u610f\u4e49<\/strong>\u3002\u5176\u4e2d\uff0c\u914d\u4f53-\u91d1\u5c5e\u7535\u8377\u8f6c\u79fb\uff08LMCT\uff09\u7406\u8bba\u662f\u76ee\u524d\u4e3a\u6b62\u6700\u4e3a\u5408\u7406\u7684\u5047\u8bbe\uff1a\u91d1\u5c5e\u9633\u79bb\u5b50\u9996\u5148\u88ab\u8fc7\u6c27\u5316\u6210\u6fc0\u53d1\u6001\uff0c\u540e\u7eed\u88ab\u8fd8\u539f\u7684\u540c\u65f6\u6c27\u5316\u90e8\u5206\u9634\u79bb\u5b50\uff0c\u5b9e\u73b0\u7535\u8377\u4ece\u914d\u4f53\u5230\u91d1\u5c5e\u7684\u8f6c\u79fb\u3002\u7136\u800c\uff0c\u7531\u4e8e\u4e2d\u95f4\u6001\u9633\u79bb\u5b50\u7684\u5bff\u547d\u592a\u77ed\uff0c\u96be\u4ee5\u5bf9<\/strong>LMCT<\/strong>\u8fc7\u7a0b\u8fdb\u884c\u6709\u6548\u89c2\u5bdf<\/strong>\u3002<\/p>\n

2.<\/strong>\u3010\u6210\u679c\u63a0\u5f71\u3011<\/strong><\/p>\n

\u8fd1\u65e5\uff0c\u6cd5\u5170\u897f\u516c\u5b66\u9662<\/strong>Jean-Marie Tarascon\u6559\u6388<\/strong>\uff08\u901a\u8baf\u4f5c\u8005\uff09\u7b49\u4eba\uff0c\u5229\u7528\u957f\u5bff\u547d\u4e2d\u95f4\u6001\u9633\u79bb\u5b50\uff08Ni3+<\/sup>\/4+<\/sup>\uff09\uff0c\u9996\u6b21\u6210\u529f\u89c2\u6d4b\u5230\u5bcc\u9502\u6b63\u6781\u6750\u6599Li1.17<\/sub>Ti0.58<\/sub>Ni0.25<\/sub>O2<\/sub>\u4e2d\u52a8\u6001\u7684\u914d\u4f53\u5230\u91d1\u5c5e\u7684\u7535\u8377\u8f6c\u79fb\uff08LMCT\uff09\uff0c\u660e\u786e\u4e86\u6fc0\u53d1\u6001\u9633\u79bb\u5b50\u5bf9\u9634\u79bb\u5b50\u6c27\u5316\u8fd8\u539f\u7684\u6fc0\u6d3b\u4f5c\u7528\uff0c\u4e3aLMCT\u7406\u8bba\u63d0\u4f9b\u4e86\u5b9e\u9a8c\u9a8c\u8bc1\u3002\u76f8\u5173\u7814\u7a76\u6210\u679c\u4ee5\u201cCapturing dynamic ligand-to-metal charge transfer with a long-lived cationic intermediate for anionic redox\u201d\u4e3a\u9898\u53d1\u8868\u5728Nature Materials<\/em><\/strong>\u671f\u520a\u4e0a\u3002<\/p>\n

\u00a0\"\"<\/strong><\/p>\n

3.<\/strong>\u3010\u6838\u5fc3\u521b\u65b0\u70b9\u3011<\/strong><\/p>\n

    \n
  1. \u53d1\u73b0\u4e86\u5bcc\u9502\u6b63\u6781Li1.17<\/sub>Ti0.58<\/sub>Ni0.25<\/sub>O2<\/sub>\u9634\u79bb\u5b50\u6c27\u5316\u8fd8\u539f\u8fc7\u7a0b\u4e2d\uff0c\u5b58\u5728\u4e00\u79cd\u957f\u5bff\u547d\u4e2d\u95f4\u6001\u9633\u79bb\u5b50Ni3+<\/sup>\/4+<\/sup>\uff0c\u5f1b\u8c6b\u8fc7\u7a0b\u4e2d\u53ef\u4ee5\u6f14\u53d8\u4e3aNi2+<\/sup>\u3002<\/li>\n
  2. \u7ed3\u5408\u5149\u8c31\u8868\u5f81\u4e0e\u7535\u5316\u5b66\u5206\u6790\uff0c\u5b9a\u91cf\u786e\u5b9a\u4e86Ni3+<\/sup>\/4+<\/sup>\u4e2d\u95f4\u6001\u7684\u8fd8\u539f\u8fc7\u7a0b\u662f\u4e00\u4e2a\u52a8\u6001\u7684LMCT\u8fc7\u7a0b\u3002<\/li>\n
  3. \u4e3a\u5bcc\u9502\u6b63\u6781\u6750\u6599\u4e2d\u9634\u9633\u79bb\u5b50\u6c27\u5316\u8fd8\u539f\u53cd\u8f6c\u548c\u7535\u538b\u8fdf\u6ede\u63d0\u4f9b\u4e86\u5408\u7406\u89e3\u91ca\uff0c\u4e3a\u9ad8\u5bb9\u91cf\u6b63\u6781\u6750\u6599\u7684\u8bbe\u8ba1\u63d0\u4f9b\u4e86\u6307\u5bfc\u3002<\/li>\n<\/ol>\n

    4.<\/strong>\u3010\u6570\u636e\u6982\u89c8\u3011<\/strong><\/p>\n

    \u56fe<\/strong>1. xLi2<\/sub>TiO3<\/sub>\u00b7(1-x)LiTi0.5<\/sub>Ni0.5<\/sub>O2<\/sub> (0\u2009<\u2009x\u2009<\u20091)<\/strong>\u7684\u7ed3\u6784\u4e0e\u7535\u5316\u5b66\u6027\u8d28<\/strong><\/p>\n

    \"\"<\/p>\n

    \uff08a\uff09X\u5c04\u7ebf\u884d\u5c04\u56fe\u8c31\u3002<\/p>\n

    \uff08b\uff092.0-4.8 V\u7535\u538b\u8303\u56f4\u5185\uff0c\u7535\u6d41\u5bc6\u5ea6\u4e3a20 mA g\u22121<\/sup>\u65f6\u524d\u4e24\u4e2a\u5faa\u73af\u7684\u6052\u6d41\u5145\u653e\u7535\u66f2\u7ebf\u3002<\/p>\n

    \uff08c\uff09x=4\u65f6\uff080.4Li2<\/sub>TiO3<\/sub>\u00b70.6Li1.17<\/sub>Ti0.58<\/sub>Ni0.25<\/sub>O2<\/sub>\uff09\u7684\u7cbe\u4fee\u540c\u6b65X\u5c04\u7ebf\u884d\u5c04\u56fe\u8c31\u3002<\/p>\n

    \uff08d\uff09\u539f\u59cb0.4LTO-0.6LTNO\u6837\u54c1\u7684[001] HAADF-STEM\u56fe\u50cf\u3002<\/p>\n

    \u56fe<\/strong>2. <\/strong>\u901a\u8fc7<\/strong>X<\/strong>\u5c04\u7ebf\u5438\u6536\u5149\u8c31<\/strong>\u548c<\/strong>DFT<\/strong>\u8ba1\u7b97\u7814\u7a76<\/strong>0.4LTO-0.6LTNO<\/strong>\u7684\u6c27\u5316\u8fd8\u539f\u673a\u7406<\/strong><\/p>\n

    \"\"<\/p>\n

    \uff08a\uff090.4LTO-0.6LTNO\u7684\u5faa\u73af\u66f2\u7ebf\uff0c\u6807\u8bb0\u4e86\u975e\u539f\u4f4dX\u5c04\u7ebf\u5438\u6536\u5149\u8c31\uff08XAS\uff09\u7814\u7a76\u7684\u7279\u5b9a\u70b9\u3002<\/p>\n

    \uff08b\uff09Ni\u7684L\u8fb9iPFY-XAS\u8868\u5f81\u7ed3\u679c\u3002\u5149\u8c31\u4e24\u533a\u57df\u5206\u522b\u5bf9\u5e94L3<\/sub>\u548cL2<\/sub>\u8fb9\uff0c\u6bcf\u4e2a\u533a\u57df\u8fdb\u4e00\u6b65\u88c2\u5206\u6210\u4e24\u4e2a\u5cf0\uff08Ni 2p<\/em>\u2009\u2192\u2009Ni 3d<\/em>–t<\/em>2g<\/sub>\u548c3d<\/em>-eg<\/sub><\/em>\u7684\u7535\u5b50\u8dc3\u8fc1\uff09\u3002<\/p>\n

    \uff08c\uff09O\u7684K\u8fb9TFY-XAS\u8868\u5f81\u7ed3\u679c\u3002525-536 eV\u8303\u56f4\u7684\u5cf0\u5bf9\u5e94\u4eceO (1s<\/em>)\u5230O (2p<\/em>) -Ni \/Ti (3d<\/em>)\u6742\u5316\u6001\u7684\u7535\u5b50\u8dc3\u8fc1\u3002<\/p>\n

    \uff08d\uff090.4LTO-0.6LTNO\u8131\u9502\u8fc7\u7a0b\u4e2dDFT\u8ba1\u7b97\u7684\u6001\u5bc6\u5ea6\uff08DOS\uff09\uff0c\u865a\u7ebf\u6807\u6ce8\u7684\u4e3a\u8d39\u7c73\u80fd\u7ea7\u3002<\/p>\n

    \uff08e\uff090.4LTO-0.6LTNO\u8131\u9502\u8fc7\u7a0b\u4e2dNi\u4e0eO\u7684\u7535\u8377\u8f6c\u79fb\u3002<\/p>\n

    \u56fe<\/strong>3. 0.4LTO-0.6LTNO<\/strong>\u7684\u539f\u4f4d<\/strong>X<\/strong>\u5c04\u7ebf\u884d\u5c04\u56fe\u8c31<\/strong><\/p>\n

    \"\"<\/p>\n

    \uff08a\uff090.4LTO-0.6LTNO\u57284.8-2 V\u7535\u538b\u8303\u56f4\u5185\u7684\u524d\u4e24\u4e2a\u7535\u5316\u5b66\u5faa\u73af\u3002<\/p>\n

    \uff08b\uff09\u4ece\u539f\u4f4dX\u5c04\u7ebf\u884d\u5c04\u56fe\u8c31\u4e2d\u63d0\u53d6\u7684a<\/em>\u6676\u683c\u53c2\u6570\u3002<\/p>\n

    \uff08c\uff09\u524d\u4e24\u4e2a\u5faa\u73af\u7684\u539f\u4f4dX\u5c04\u7ebf\u884d\u5c04\u56fe\u8c31\u3002<\/p>\n

    \uff08d\uff09\u6676\u683c\u53c2\u6570\u968fLi\u542b\u91cf\u7684\u53d8\u5316\u3002<\/p>\n

    \uff08e\uff09\u7535\u6781\u6750\u6599\u5feb\u901f\u5145\u7535\u81f34.8 V\u540e\uff0c\u6e05\u6d17\u5e72\u71e5\u5f1b\u8c6b\u6062\u590d\u8fc7\u7a0b\u4e2d\u7684\u539f\u4f4dX\u5c04\u7ebf\u884d\u5c04\u56fe\u8c31\u3002<\/p>\n

    \uff08f\uff09\u5168\u56fa\u6001\u7535\u6c60\u4e2d\u7684\u7535\u6781\u539f\u4f4dX\u5c04\u7ebf\u884d\u5c04\u56fe\u8c31\uff0c\u6db2\u6001\u7535\u89e3\u6db2\u4e2d\u7684\u81ea\u653e\u7535\u73b0\u8c61\u5f97\u4ee5\u6d88\u9664\u3002<\/p>\n

    \u56fe<\/strong>4. LMCT<\/strong>\u8fc7\u7a0b\u7684\u7535\u5316\u5b66\u6ef4\u5b9a<\/strong><\/p>\n

    \"\"<\/p>\n

    \uff08a\uff09\u6837\u54c1\u5728\u4e0d\u540c\u6e29\u5ea6\u4e0b\u52a0\u70ed24 h\u540e\u7684\u653e\u7535\u66f2\u7ebf\u3002<\/p>\n

    \uff08b\uff09\u76f8\u5173dQ\/dV\u66f2\u7ebf\u8868\u73b0\u4e86Ni\u3001O\u6c27\u5316\u8fd8\u539f\u8fc7\u7a0b\u4e2d\u7684\u5bb9\u91cf\u53d8\u5316\u3002<\/p>\n

    \uff08c\uff0cd\uff09140\u2103\u52a0\u70ed\u4e0d\u540c\u65f6\u95f4\u540e\u6837\u54c1\u7684\u653e\u7535\u66f2\u7ebf\uff08c\uff09\u4e0e\u76f8\u5173dQ\/dV\u66f2\u7ebf\uff08d\uff09\u3002<\/p>\n

    \u56fe<\/strong>5. <\/strong>\u786c<\/strong>X<\/strong>\u5c04\u7ebf\u5149\u7535\u5b50\u80fd\u8c31\uff08<\/strong>HAXPES<\/strong>\uff09\u548c\u7ed3\u6784\u5206\u6790\u7814\u7a76<\/strong>LMCT<\/strong>\u8fc7\u7a0b\u3002<\/strong><\/p>\n

    \"\"<\/p>\n

    \uff08a\uff0cb\uff09\u6837\u54c1\u5145\u7535\u81f34.5 V\u548c\u5728120\u2103\u52a0\u70ed\u4e0d\u540c\u65f6\u95f4\u5f1b\u8c6b\u540e\u7684Ni 2p<\/em>\uff08a\uff09\u548cO 1s<\/em>\uff08b\uff09\u8c31\u3002<\/p>\n

    \uff08c\uff09\u539f\u59cb0.4LTO-0.6LTNO\u6837\u54c1\u7684Ni 2p<\/em>\u8c31\u663e\u793a\u51fa\u7eaf\u7684Ni2+<\/sup>\u4fe1\u53f7\u3002<\/p>\n

    \uff08d\uff09\u5145\u7535\u81f34.8 V\u7684\u5bcc\u9502NMC\u5bf9\u6bd4\u6837\u54c1O 1s<\/em>\u8c31\u3002<\/p>\n

    \uff08e\uff0cf\uff090.4LTO-0.6LTNO\u5728\u5f1b\u8c6b\u524d\uff08e\uff09\u548c\u5f1b\u8c6b\u540e\uff08140\u00b0C 24 h\uff09\uff08f\uff09\u5145\u7535\u52304.5 V\u7684[001] HAADF-STEM\u56fe\u50cf\u53ca\u76f8\u5e94\u7684[001]\u7535\u5b50\u884d\u5c04\u56fe\u50cf\u3002<\/p>\n

    \u56fe<\/strong>6. <\/strong>\u5bf9\u6c27\u5316\u8fd8\u539f\u53cd\u8f6c\u548c\u7535\u538b\u8fdf\u6ede\u73b0\u8c61\u7684\u63a2\u7a76<\/strong><\/p>\n

    \"\"<\/p>\n

    \uff08a\uff0cb\uff09\u7b2c2\u6b21\u5faa\u73af\u4e2d\uff0c0.4LTO-0.6LTNO\u5316\u5408\u7269\u91c7\u7528\u4e0d\u540c\u622a\u6b62\u7535\u538b\uff08a\uff09\u548c\u76f8\u5e94\u7684dQ<\/em>\/dV<\/em>\u66f2\u7ebf\uff08b\uff09\uff0cb\u56fe\u4e2d\u53ef\u89c2\u5bdf\u5230\u660e\u663e\u7684Ni-O\u6c27\u5316\u8fd8\u539f\u53cd\u8f6c\u3002<\/p>\n

    \uff08c\uff0cd\uff09\u7b2c2\u6b21\u5faa\u73af\u4e2d\uff0c\u5bcc\u9502\u7684NMC\u5316\u5408\u7269\u91c7\u7528\u4e0d\u540c\u622a\u6b62\u7535\u538b\uff08c\uff09\u548c\u76f8\u5e94\u7684dQ<\/em>\/dV<\/em>\u66f2\u7ebf\uff08d\uff09\uff0cd\u56fe\u4e2d\u53ef\u89c2\u5bdf\u5230\u4e0e0.4LTO-0.6LTNO\u5316\u5408\u7269\u76f8\u4f3c\u7684\u9634\u9633\u79bb\u5b50\u6c27\u5316\u8fd8\u539f\u53cd\u8f6c\u3002<\/p>\n

    \uff08e\uff09\u6837\u54c1\u5f1b\u8c6b\u5230\u4e0d\u540c\u72b6\u6001\u7684\u653e\u7535\u66f2\u7ebf\u3002\u6837\u54c1\u5145\u7535\u52304.5 V\u540e\u56de\u6536\uff0c\u7136\u540e\u5728140\u00b0C\u52a0\u70ed\u4e0d\u540c\u65f6\u95f4\uff08\u4ece0 s\u523024 h\uff09\u3002<\/p>\n

    \uff08f\uff09 \u7528\u6700\u5c0f\u4e8c\u4e58\u65b9\u6cd5\u62df\u5408\u5f00\u8def\u7535\u538b\uff08OCV\uff09\u4e0eNi\u4e2d\u95f4\u4f53\u7ec4\u5206\u542b\u91cf\u7684\u5173\u7cfb\u3002<\/p>\n

    5.<\/strong>\u3010\u6210\u679c\u542f\u793a\u3011<\/strong><\/p>\n

    \u672c\u5de5\u4f5c\u4e2d\uff0c\u901a\u8fc7\u957f\u5bff\u547d\u7684\u9633\u79bb\u5b50\u4e2d\u95f4\u4f53\u7684\u53d1\u73b0\uff0c\u9996\u5148\u5b9e\u73b0\u4e86\u5bf9\u5bcc\u9502\u6b63\u6781\u4e2d\u52a8\u6001LMCT\u8fc7\u7a0b\u7684\u5b9e\u9a8c\u89c2\u5bdf\uff0c\u5bf9\u9634\u79bb\u5b50\u6c27\u5316\u8fd8\u539f\u7684\u6fc0\u53d1\u63d0\u4f9b\u4e86\u5408\u7406\u89e3\u91ca\u3002\u5728\u6b64\u57fa\u7840\u4e0a\uff0c\u901a\u8fc7\u7b5b\u9009\u5408\u9002\u7684\u957f\u5bff\u547d\u9633\u79bb\u5b50\u4e2d\u95f4\u4f53\uff0c\u53ef\u4ee5\u8fdb\u4e00\u6b65\u8bbe\u8ba1\u57fa\u4e8e\u9634\u79bb\u5b50\u6c27\u5316\u8fd8\u539f\u7684\u9ad8\u5bb9\u91cf\u6b63\u6781\u6750\u6599<\/strong>\u3002\u540c\u65f6\uff0cLMCT\u5728\u53d1\u5149\u3001\u5149\u654f\u548c\u5149\u50ac\u5316\u7b49\u7814\u7a76\u9886\u57df\u4e5f\u662f\u4e00\u79cd\u5e38\u89c1\u8fc7\u7a0b\uff0c\u5229\u7528\u957f\u5bff\u547d\u4e2d\u95f4\u4f53\u7684\u7814\u7a76\u601d\u8def\u4e5f\u5177\u6709\u6f5c\u5728\u9002\u7528\u6027\u3002\u6b64\u5916\uff0c\u672c\u5de5\u4f5c\u4e2d\u5bf9<\/strong>LMCT<\/strong>\u8fc7\u7a0b\u7684\u5b9e\u9a8c\u9a8c\u8bc1\uff0c\u4e3a\u5316\u5b66\u3001\u7269\u7406\u66f4\u5e7f\u6cdb\u9886\u57df\u4e2d\u7c7b\u4f3c\u7684\u7535\u5b50\u8f6c\u79fb\u73b0\u8c61\u63d0\u4f9b\u4e86\u5f88\u597d\u7684\u7814\u7a76\u501f\u9274<\/strong>\u3002<\/p>\n

     <\/p>\n

     <\/p>\n

     <\/p>\n

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