{"id":202900,"date":"2020-06-03T06:13:02","date_gmt":"2020-06-02T22:13:02","guid":{"rendered":"\/\/m.iemloyee.com\/?p=202900"},"modified":"2020-06-02T18:13:16","modified_gmt":"2020-06-02T10:13:16","slug":"crps-li2mno3%e5%9f%ba%e9%94%82%e7%94%b5%e6%ad%a3%e6%9e%81%e6%9d%90%e6%96%99%e9%ab%98%e4%bb%b7%e9%94%b0%e5%b1%80%e5%9f%9f%e7%94%b5%e5%ad%90%e4%ba%a4%e6%8d%a2","status":"publish","type":"post","link":"\/\/m.iemloyee.com\/?p=202900","title":{"rendered":"CRPS: Li2MnO3\u57fa\u9502\u7535\u6b63\u6781\u6750\u6599\u9ad8\u4ef7\u9530\u5c40\u57df\u7535\u5b50\u4ea4\u6362"},"content":{"rendered":"
\u3010\u7814\u7a76\u4eae\u70b9\u3011<\/b><\/strong><\/p>\n 1\u00a0\u53d1\u73b0\u4e86Li2<\/sub>MnO3<\/sub>\u4e2dMn\u5143\u7d20\u53c2\u4e0e\u7535\u5316\u5b66\u53cd\u5e94\u7684\u503e\u5411\uff0c\u8131\u9502\u540e\u7ed3\u6784\u65e0\u5e8f\u5316\u6709\u5229\u4e8e\u5f62\u6210\u542b\u6709Mn6+<\/sup>\u548cMn7+<\/sup>\u7684MnO4<\/sub>\u56db\u9762\u4f53\uff0c\u8be5\u8fc7\u7a0b\u53d7Li+<\/sup>\u542b\u91cf\u548c\u52a8\u529b\u5b66\u80fd\u5792\u63a7\u5236\u3002<\/p>\n 2 \u63ed\u793a\u4e86\u77ac\u6001\u9ad8\u4ef7\u6001Mn\u4e0e\u5468\u8fb9O\u7684\u5c40\u57df\u7535\u5b50\u4ea4\u6362\u673a\u5236\uff0c\u81f4\u4f7f\u9ad8\u4ef7\u6001\u7684Mn\u5143\u7d20\u88ab\u8fd8\u539f\uff0c\u5468\u8fb9O\u5931\u53bb\u7535\u5b50\u4ef7\u6001\u5347\u9ad8\uff0c\u6750\u6599\u6574\u4f53\u8868\u73b0\u51faO\u53c2\u4e0e\u53cd\u5e94\u7684\u73b0\u8c61\u3002<\/p>\n \u8fd1\u5e74\u6765\uff0c\u57fa\u4e8e\u5c42\u72b6Li2<\/sub>MnO3<\/sub>\u548cLiTMO2<\/sub>\u00a0(TM=Mn, Co,\u00a0Ni)\u7684\u5bcc\u9502\u9530\u57fa\u9502\u79bb\u5b50\u7535\u6c60\u6b63\u6781\u6750\u6599\uff08LLOs\uff09\u56e0\u5176\u9ad8\u80fd\u91cf\u5bc6\u5ea6\u53d7\u5230\u4e86\u5e7f\u6cdb\u5173\u6ce8\u3002\u4e0e\u5e38\u89c1\u7684\u4e09\u5143\u6b63\u6781\u6750\u6599\u76f8\u6bd4\uff0c\u5bcc\u9502\u9530\u57fa\u6750\u6599\u7684\u9ad8\u80fd\u91cf\u5bc6\u5ea6\u4e3b\u8981\u6765\u81eaLi2<\/sub>MnO3<\/sub>\u7ed3\u6784\u5355\u5143\u7684\u9ad8\u7406\u8bba\u5bb9\u91cf\u3002\u7136\u800c\uff0cLi2<\/sub>MnO3<\/sub>\u7684\u7535\u5316\u5b66\u53cd\u5e94\u8fc7\u7a0b\u975e\u5e38\u590d\u6742\uff0c\u5c24\u5176\u662f\u5b83\u57284.5 V\u5de6\u53f3\u7684\u7535\u538b\u5e73\u53f0\u901a\u5e38\u88ab\u8ba4\u4e3a\u662f\u7531\u4e8eO\u7684\u5f97\u5931\u7535\u5b50\u6240\u5f15\u8d77\u7684\uff0c\u800c\u975e\u5e38\u89c1\u7684\u8fc7\u6e21\u91d1\u5c5e\u539f\u5b50\u5f97\u5931\u7535\u5b50\u3002\u76ee\u524d\uff0cO\u53c2\u4e0e\u53cd\u5e94\u7684\u673a\u7406\u5df2\u7ecf\u5f97\u5230\u4e86\u7535\u5b50\u987a\u78c1\u5171\u632f\uff08EPR\uff09\u3001\u5171\u632f\u975e\u5f39\u6027X\u5c04\u7ebf\u6563\u5c04\u5149\u8c31\uff08RIXS\uff09\u7b49\u591a\u79cd\u5b9e\u9a8c\u624b\u6bb5\u7684\u9a8c\u8bc1\uff0c\u4e5f\u88ab\u7814\u7a76\u8005\u4eec\u5e7f\u6cdb\u5730\u63a5\u53d7\uff1b\u76f8\u53cd\uff0c\u5728\u5b9e\u9a8c\u4e0a\u5374\u51e0\u4e4e\u6ca1\u6709\u4efb\u4f55\u8bc1\u636e\u652f\u6301Mn\u7684\u6c27\u5316\uff0c\u90a3\u4e48+4\u4ef7\u7684Mn\u5728\u5176\u4e2d\u6709\u6ca1\u6709\u53c2\u4e0e\u6c27\u5316\u8fd8\u539f\u53cd\u5e94\u7684\u53ef\u80fd\u6027\u5462\uff1f<\/p>\n \u56fe1. (a)\u00a0Lix<\/sub>MnO3<\/sub>\u00a0(x = 2\u30011.5\u30011\u30010.5)\u4e2dMn\u00a03d\u548cO\u00a02p\u8f68\u9053\u7684\u504f\u6001\u5bc6\u5ea6\uff08PDOS\uff09\uff0c0\u00a0eV\u5904\u4e3a\u8d39\u7c73\u80fd\u7ea7\uff08\u865a\u7ebf\uff09\u3002\u6700\u9ad8\u5360\u636e\u6001\uff08HOS\uff0c-0.5~0 eV\uff09\u7528\u9ec4\u8272\u533a\u57df\u8868\u793a\u3002(b) Lix<\/sub>MnO3<\/sub>\u4e2d\u6700\u9ad8\u5360\u636e\u6001\u7684\u7535\u8377\u5bc6\u5ea6\u3002(c) Lix<\/sub>MnO3<\/sub>\u8131Li+<\/sup>\u7684\u5dee\u5206\u7535\u8377\u5bc6\u5ea6\uff0c\u9ec4\u8272\u548c\u84dd\u8272\u5206\u522b\u4ee3\u8868\u7535\u5b50\u589e\u52a0\u548c\u51cf\u5c11\u7684\u533a\u57df\u3002<\/p>\n \u9488\u5bf9\u8fd9\u4e2a\u95ee\u9898\uff0c\u5317\u4eac\u5de5\u4e1a\u5927\u5b66\u5c09\u6d77\u519b\u6559\u6388\u8bfe\u9898\u7ec4\u57fa\u4e8e\u8fc7\u53bb10\u5e74\u5728LLOs\u65b9\u9762\u7684\u5b9e\u9a8c\u548c\u7406\u8bba\u7814\u7a76\u57fa\u7840\uff0c\u901a\u8fc7\u5bc6\u5ea6\u6cdb\u51fd\u7406\u8bba\u8ba1\u7b97\uff0c\u7cfb\u7edf\u5730\u7814\u7a76\u4e86\u4e0d\u540cLi+<\/sup>\u6d53\u5ea6\u4e0bLi2<\/sub>MnO3<\/sub>\u4e2dMn\u548cO\u5143\u7d20\u5f97\u5931\u7535\u5b50\u7684\u8d8b\u52bf\u4ee5\u53ca\u9ad8\u4ef7\u6001Mn\u5f62\u6210\u7684\u53ef\u80fd\u6027\u3002\u7814\u7a76\u53d1\u73b0\uff0c\u5c3d\u7ba1\u5728\u521d\u59cb\u72b6\u6001\u4e0bLi2<\/sub>MnO3<\/sub>\u4e2d\u53ea\u6709O\u5177\u6709\u5931\u7535\u5b50\u8d8b\u52bf\uff0c\u7136\u800c\u968f\u7740Li+<\/sup>\u7684\u6d53\u5ea6\u964d\u4f4e\uff0c\u7535\u5b50\u7ed3\u6784\u663e\u793aMn\u5143\u7d20\u4f1a\u8868\u73b0\u51fa\u8d8a\u6765\u8d8a\u5f3a\u7684\u5931\u7535\u5b50\u80fd\u529b\uff08\u56fe1\uff09\u3002<\/p>\n \u56fe2. \uff08a\uff09\u65e0\u5e8f\u5316\u7ed3\u6784\u7684Li0.5<\/sub>MnO3<\/sub>\u4e2d\u7684Mn4+<\/sup>\u3001Mn6+<\/sup>\u3001Mn7+<\/sup>\u7684\u504f\u6001\u5bc6\u5ea6\uff0c\u9ec4\u8272\u548c\u84dd\u8272\u7684\u533a\u57df\u5206\u522b\u8868\u793a\u6700\u9ad8\u5360\u636e\u6001\u548c\u6700\u4f4e\u672a\u5360\u636e\u6001\uff0c\u5176\u7535\u8377\u5bc6\u5ea6\u5206\u522b\u5728\uff08b\uff09\u548c\uff08c\uff09\u4e2d\u5c55\u793a\u3002<\/p>\n \u901a\u8fc7\u7b2c\u4e00\u6027\u539f\u7406\u5206\u5b50\u52a8\u529b\u5b66\u7814\u7a76Li0.5<\/sub>MnO3<\/sub>\u7684\u7ed3\u6784\u6f14\u5316\uff0c\u53ef\u4ee5\u5f97\u5230\u5728\u70ed\u529b\u5b66\u4e0a\u66f4\u52a0\u7a33\u5b9a\u7684\u65e0\u5e8f\u7ed3\u6784\uff0c\u540c\u65f6\u4f34\u968f\u7740MnO4<\/sub>\u56db\u9762\u4f53\u7684\u751f\u6210\u548cO2<\/sub>\u7684\u91ca\u653e\u3002\u5bf9\u8fd9\u4e9b\u56db\u9762\u4f53\u7ed3\u6784\u4e2d\u7684Mn\u7684\u4ef7\u6001\u548c\u7535\u5b50\u7ed3\u6784\u8fdb\u884c\u5206\u6790\uff0c\u53ef\u4ee5\u53d1\u73b0\u8fd9\u4e9bMn\u4e3a+6\u6216+7\u4ef7\uff0c\u5e76\u4e14\u5177\u6709\u5f88\u5f3a\u7684\u6c27\u5316\u6027\u3002\uff08\u56fe2\uff09<\/p>\n \u56fe3. \uff08a\uff09MnO4<\/sub>\u5c40\u57df\u6c27\u5316\u8fd8\u539f\u53cd\u5e94\u7684\u8fc7\u7a0b\uff0c\u4ee5\u53caMn\u7684\u78c1\u77e9\u548cMn-O\u952e\u957f\u7684\u53d8\u5316\u3002\uff08b\uff09\u88ab\u8fd8\u539f\u7684\u9ad8\u4ef7Mn\u548c\u5468\u56f4\u7684O\u539f\u5b50\u5728\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u7684\u504f\u6001\u5bc6\u5ea6\u4ee5\u53ca\u7535\u8377\u5bc6\u5ea6\uff0c\u9ec4\u8272\u548c\u84dd\u8272\u7684\u533a\u57df\u5206\u522b\u8868\u793a\u6700\u9ad8\u5360\u636e\u6001\u548c\u6700\u4f4e\u672a\u5360\u636e\u6001\u3002\uff08c\uff09\u9ad8\u4ef7\u6001Mn\u4e0e\u5468\u8fb9O\u5c40\u57df\u7535\u5b50\u4ea4\u6362\u7684\u793a\u610f\u56fe\u3002<\/p>\n \u540c\u65f6\uff0c\u5bf9\u4e8eO2<\/sub>\u5f62\u6210\u8fc7\u7a0b\u7684\u5206\u6790\u53d1\u73b0\uff0c\u90e8\u5206O2<\/sub>\u662f\u9ad8\u4ef7\u6001\u7684MnO4<\/sub>\u56db\u9762\u4f53\u6c27\u5316\u5468\u56f4O\u539f\u5b50\u7684\u4ea7\u7269\u3002\u8fd9\u4e00\u8fc7\u7a0b\u9996\u5148\u7531MnO4<\/sub>\u56db\u9762\u4f53\u7684O\u4e0e\u5468\u56f4\u7684O\u5f62\u6210O-O\u4e8c\u805a\u4f53\u5e76\u8131\u9644\uff0c\u4e4b\u540eMn\u4e0e\u5468\u56f4\u7684O\u539f\u5b50\u7ed3\u5408\u5f62\u6210MnO6<\/sub>\u7684\u516b\u9762\u4f53\u7ed3\u6784\uff0c\u88ab\u8fd8\u539f\u4e3a+4\u4ef7\u3002\u4ece\u7535\u5b50\u7ed3\u6784\u6765\u770b\uff0c\u9ad8\u4ef7\u6001Mn\u76843d\u8f68\u9053\u53ef\u4ee5\u63a5\u6536\u6765\u81ea\u5468\u56f4O\u539f\u5b50\u6700\u9ad8\u5360\u636e\u6001\u76842p\u8f68\u9053\u7684\u7535\u5b50\uff0c\u5bfc\u81f4\u9ad8\u4ef7\u6001Mn\u7684\u8fd8\u539f\u548cO\u88ab\u6c27\u5316\uff0c\u5e76\u53ef\u80fd\u4f34\u968fO-O\u4e8c\u805a\u6216O2<\/sub>\u7684\u91ca\u653e\u3002\u8fd9\u5728\u4e00\u5b9a\u7a0b\u5ea6\u4e0a\u89e3\u91ca\u4e86\u5c3d\u7ba1\u9ad8\u4ef7Mn\u6709\u5f62\u6210\u7684\u53ef\u80fd\uff0c\u4f46\u5728\u5b9e\u9a8c\u4e0a\u96be\u4ee5\u89c2\u6d4b\u5230Mn\u7684\u6c27\u5316\u3002\u5728\u5c40\u57df\u6c27\u5316\u8fd8\u539f\u4e4b\u540e\uff0c\u6574\u4f53\u7684\u8131Li+<\/sup>\u8fc7\u7a0b\u4ecd\u7136\u8868\u73b0\u4e3aO\u5931\u53bb\u7535\u5b50\u3002<\/p>\n \u56fe4. Li2<\/sub>MnO3<\/sub>\u8131Li\u8fc7\u7a0b\u7684\u7ed3\u6784\u53d8\u5316\uff0c\u7535\u5b50\u8f6c\u79fb\u548cMn-O\u5c40\u57df\u7535\u5b50\u4ea4\u6362\u793a\u610f\u56fe\u3002<\/p>\n \u3010\u5c0f\u7ed3\u3011<\/b><\/strong><\/p>\n \u4f5c\u8005\u7814\u7a76\u4e86Lix<\/sub>MnO3<\/sub>\u5728\u8131Li+<\/sup>\u8fc7\u7a0b\u4e2d\u53d1\u751f\u7684\u7ed3\u6784\u53d8\u5316\u548c\u7535\u5b50\u8f6c\u79fb\u8d8b\u52bf\uff08\u56fe4\uff09\uff1a\u5f53Li+<\/sup>\u542b\u91cf\u8f83\u9ad8\u65f6\uff0c\u8131Li+<\/sup>\u8fc7\u7a0b\u4e3b\u8981\u7531O\u63d0\u4f9b\u7535\u5b50\uff1b\u800cMn\u63d0\u4f9b\u7535\u5b50\u7684\u8d8b\u52bf\u4f1a\u968f\u7740Li+<\/sup>\u542b\u91cf\u4e0b\u964d\u800c\u9010\u6e10\u4e0a\u5347\u3002\u5f53Li\u6d53\u5ea6\u8f83\u4f4e\uff08x<1\uff09\u65f6\uff0c\u6750\u6599\u7684\u7ed3\u6784\u5728\u70ed\u529b\u5b66\u4e0a\u4f1a\u503e\u5411\u4e8e\u65e0\u5e8f\u5316\uff0c\u5e76\u53ef\u80fd\u4ea7\u751f\u542b\u6709Mn6+<\/sup>\u6216Mn7+<\/sup>\u7684MnO4<\/sub>\u56db\u9762\u4f53\uff0c\u4f46\u8fd9\u4e5f\u9700\u8981\u514b\u670d\u4e00\u5b9a\u7684\u80fd\u5792\u3002MnO4<\/sub>\u56db\u9762\u4f53\u4e2d\u7684\u9ad8\u4ef7Mn\u53ef\u4ee5\u901a\u8fc7\u5c40\u57df\u7684\u7535\u5b50\u4ea4\u6362\u88ab\u8fd8\u539f\u4e3a+4\u4ef7\u7684MnO6<\/sub>\u6784\u578b\uff0c\u540c\u65f6\u5c06\u5468\u56f4\u7684O\u539f\u5b50\u6c27\u5316\u4e3aO2<\/sub>\uff0c\u6240\u4ee5\u5728\u5b9e\u9a8c\u4e0a\u5f88\u96be\u89c2\u6d4b\u5230\u9ad8\u4ef7\u6001\u7684Mn\u3002<\/p>\n \u3010\u53c2\u8003\u6587\u732e\u3011<\/b><\/strong><\/p>\n Zihe Zhang\uff0cShu Zhao, Boya Wang, Haijun Yu. Local Redox Reaction of High Valence Manganese in Li2<\/sub>MnO3<\/sub>-Based Lithium Battery Cathodes.<\/p>\n Cell Reports Physical Science 1, 100061, May 20, 2020<\/p>\n Doi: 10.1016\/j.xcrp.2020.100061<\/p>\n<\/p>\n
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