绘制了25.℃时Mn-H2O与Li-Mn-H2O系的ε-pH图, 并对锂离子电池用正极材料锰酸锂的湿化学制备以及溶液中锂的回收问题从热力学上进行了分析, 指出了可能的技术途径和对策; 计算发现, LiMn2O4完全或部分地占据了各种价态锰离子化合物的稳定区域, 在水溶液中的稳定性很好. 这对湿法制备LiMn2O4十分有利; 而LiMnO2的稳定性较差, 仅在溶液中维持较高锂离子浓度时才可存在. 湿法制备LiMnO2的条件较为苛刻; 对于从溶液中回收锂, 锰的固体氧化物如MnO2无疑是极佳的吸附剂, 理论上有很高的回收率. 吸附的锂宜采用提高溶液电势的方法进行氧化性解吸.
参考文献
[1] | Bruno Scrosati .Recent advances in lithium ion battery materials[J].Electrochimica Acta,2000(15/16):2461-2466. |
[2] | Poizot P;Laruelle S;Grugeon S et al.Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries[J].NATURE,2000,407(02):496-499. |
[3] | Winter M.;Spahr ME.;Novak P.;Besenhard JO. .Insertion electrode materials for rechargeable lithium batteries [Review][J].Advanced Materials,1998(10):725-763. |
[4] | 陈立泉 .锂离子电池最新动态和进展: 第九届国际锂电池会议简介[J].电池,1998,28(06):255-257. |
[5] | Tanaka T;Ohta K;Arai N.Year 2000 R&D status of large-scale lithium ion secondary batteries in the national project of Japan[J].Journal of Power Sources,2001:97-98: 2-6. |
[6] | Siapkas D I;Mitsas C L;Samaras I et al.Synthesis and characterization of LiMn2O4 for use in Li-ion batteries[J].Journal of Power Sources,1998,72(01):22-26. |
[7] | 刘兴泉,刘培松,陈召勇,陈栋梁,张伯兰,李庆,于作龙.锂离子电池正极材料LiMn2O4的合成及其电化学性能研究[J].功能材料,2001(02):178-180. |
[8] | 周震涛,李新生.熔融浸渍法LiMn2O4的制备及性能[J].稀有金属材料与工程,2003(02):134-136. |
[9] | Yongyao Xia;Hidefumi Takeshige;Hideyuki Noguchi;Masaki Yoshio .Studies on an Li-Mn-O spinel system (obtained by melt-impregnation) as a cathode for 4 V lithium batteries Part 1. Synthesis and electrochemical behaviour of Li_xMn_2O_4[J].Journal of Power Sources,1995(1):61-67. |
[10] | 冯守华,徐如人.无机合成与制备化学研究进展[J].化学进展,2000(04):445-457. |
[11] | 康慨,戴受惠,万玉华.锂离子电池阴极材料LiMxMn2-xO4的合成方法研究[J].无机材料学报,2001(04):586-594. |
[12] | 周济 .软化学: 材料设计与剪裁之路[J].上海:科学,1995,47(03):17-2020. |
[13] | NAYOZE C;Ansart F;Laberty C et al.New synthesis method of LiM1-xM′xO2 elaborated by soft chemistry for rechargeable batteries (M and M′ = Ni, Co or Mn)[J].Journal of Power Sources,2001,99(1-2):54-59. |
[14] | Park Y J;Kim M K .Fabrication of LiMn2O4 thin films by sol-gel method for cathode materials of microbattery[J].Journal of Power Sources,1998,76(01):41-47. |
[15] | Mitsuharu T;Kazuaki A;Hironori K et al.Synthesis of LiMnO2 with α-NaMnO2-type structure by a mixed-alkaline hydrothermal reaction[J].Journal of the Electrochemical Society,1998,145(04):L49-52. |
[16] | Huang H;Peter G .A 3volt lithium manganese oxide cathode for rechargeable lithium batteries[J].Journal of the Electrochemical Society,1994,141(07):L76-77. |
[17] | Reimers J N;Fuller Eric W .Synthesis and electrochemical studies of LiMnO2 prepared at low temperature[J].Journal of the Electrochemical Society,1993,140(12):3396-3401. |
[18] | Aemstrong A R;Bruce P G .Synthesis of layered LiMnO2 as an electrode for rechargeable lithium batteries[J].Nature,1996,381(06):499-500. |
[19] | Ooi K .Technology development for extraction from sea water[J].Journal of Sea Water Society of Japan,1998,51(05):285-288. |
[20] | Kenta O;Yoshitaka M;Shunsaku K .Recovery of lithium from sea water by manganese oxide adsorbent[J].Separation Science and Technology,1986,21(08):755-766. |
[21] | Yang SH.;Middaugh RL. .Redox reactions of cobalt, aluminum and titanium substituted lithium manganese spinel compounds in lithium cells[J].Solid state ionics,2001(1/2):13-25. |
[22] | 雷家珩,尚建华,陈永熙,弓巧侠,李英霞.锰系离子筛材料的合成及性能研究[J].化工新型材料,2001(06):28-30. |
[23] | 林传仙.矿物及有关化合物热力学数据手册[M].北京:北京科学技术出版社,1985 |
[24] | Yokokawa H.;Yamaji K.;Horita T.;Ishikawa M.;Sakai N. .Thermodynamic determining factors of the positive electrode potential of lithium batteries[J].Solid state ionics,1998(Special Issue SI):1-9. |
[25] | Zhang YC.;Wang H.;Xu HY.;Wang B.;Yan H.;Ahniyaz A.;Yoshimura M. .Low-temperature hydrothermal synthesis of spinel-type lithium manganese oxide nanocrystallites[J].Solid state ionics,2003(1/2):113-117. |
[26] | Kim J;Manthiram A .Low temperature synthesis and electrode properties of Li4Mn5O12[J].Journal of the Electrochemical Society,1998,145(04):L53-55. |
[27] | 刘兴泉;于作龙 .一种合成锂(离子)电池中正极材料的新方法[P].CN 99115147.X,1999. |
[28] | 刘兴泉,李庆,于作龙.锂离子电池阴极材料Li1+xMn2O4的水热合成及表征[J].合成化学,1999(04):382-388. |
[29] | 古映莹,邓永达,贾莉英,孟晓虎,桑商斌,钟世安,唐爱东,刘占明.隐钾锰型水合MnO2的合成及其离子交换选择性[J].中国有色金属学报,2001(05):915-919. |
[30] | 李运姣;李洪桂;赵中伟 .一种锂离子电池正极材料的湿化学合成方法[P].CN 02114391.9,2002. |
[31] | 李运姣;李洪桂;孙培梅 .一种锂锰氧化物的湿化学合成方法[P].CN 00113534.1,2000. |
[32] | Yoshimura M.;Tsurimoto S.;Han KS. .Direct fabrication of thin-film LiNiO2 electrodes in LiOH solution by electrochemical-hydrothermal method[J].Solid state ionics,1998(1/2):39-44. |
[33] | Song SW.;Sasagawa I.;Watanabe T.;Yoshimura M.;Han KS. .Effect of LiOH concentration change on simultaneous preparation of LiCoO2 film and powder by hydrothermal method[J].Solid state ionics,2000(1/4):277-281. |
[34] | Song S W;Han K S;Yoshimura M .Effect of 20.℃-200.℃ fabrication temperature on microstructure of hydrothermally prepared LiCoO2 films[J].Journal of the American Ceramic Society,2000,83(11):2839-2844. |
[35] | Tsang C.;Manthiram A. .A NEW ROUTE FOR THE SYNTHESIS OF LIMN2O4 CATHODE - VARIATION OF COMPOSITION, MICROSTRUCTURE, AND ELECTROCHEMICAL BEHAVIOR WITH SYNTHESIS TEMPERATURE[J].Solid state ionics,1996(3/4):305-312. |
[36] | 詹晖,周运鸿.以不同二氧化锰为原料制备的锂锰氧化物的性能研究[J].高等学校化学学报,2002(06):1100-1104. |
[37] | Mengqiang Wu;Ai Chen;Rongqing Xu;Yue Li .Low temperature hydrothermally synthesized nanocrystalline orthorhombic LiMnO_2 cathode material for lithium-ion cells[J].Microelectronic engineering,2003(1/4):180-185. |
[38] | 许名飞,李新海,张云河,吴显明.层状锰酸锂的制备及改性[J].电源技术,2003(04):366-369. |
[39] | 雷家珩,尚建华,郭丽萍,袁启华.锂锰氧化物离子筛及其研究进展[J].无机盐工业,2002(06):15-16,42. |
[40] | 蔡邦肖.日本的海水化学资源提取技术研究[J].东海海洋,2000(04):52. |
[41] | 宋彭生,姚燕.盐湖卤水体系的热力学模型及其应用Ⅰ:在Li+,Na+,K+,Mg2+/Cl-,SO42--H2O体系物理化学方面的应用[J].盐湖研究,2003(03):1-8. |
[42] | HIDEKI OGINO,TAKAO OI,袁复怀,肖应凯,祁海萍.过二硫酸铵法从LiMn2O4中萃取锂及所获得的吸附剂对锂同位素的选择性[J].过滤与分离,2000(01):41-45. |
[43] | JOHNSON P J;Picciotto L;Bruce P G et al.Electrochemical extraction of lithium from LiMn2O4[J].Materials Research Bulletin,1984,19(02):179-187. |
上一张
下一张
上一张
下一张
计量
- 下载量()
- 访问量()
文章评分
- 您的评分:
-
10%
-
20%
-
30%
-
40%
-
50%