锂离子电池正极材料球形LiNi_（1/3）Mn_（1/3）Co_（1/3）O_2的制备与性能研究
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摘要
由于Co价格昂贵,且有一定毒性,人们一直试图寻找目前广泛商品化的锂离子电池正极材料LiCoO_2的替代材料。其中LiNi_xCo_(1-2x)Mn_xO_2系列材料相对于LiCoO_2材料成本更低,且有望得到更好的性能,早已成为国内外的研究热点。
本文采用碳酸盐共沉淀法成功合成了球形LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料,同时采用TG-DTA、ICP、XRD、SEM、模拟电池测试等多种测试手段对该体系的制备与结构、形貌、性能做了系统的研究。综合考察了预处理方式和高温处理方式对材料的影响,优化了合成工艺。实验表明:控制溶液pH值在7.4-7.6,沉淀剂与金属盐溶液浓度比为1.2～1.5,反应温度为50℃得到球形前体,氧化、掺Li后850℃下煅烧15h得到的材料有很好的电化学性能。2.5-4.5V,0.05C放电时,材料比容量可达191.5mAh/g;2C放电仍有169.2mAh/g;0.1C循环30圈,保持率为97.2%。
对LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2材料掺Li改性发现适量增加Li含量能显著提高材料循环性能,Li_(1.1)Ni_(1/3)Co_(1/3)Mn_(1/3)O_2材料综合性能最佳。在LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2材料的基础上,进一步降低Co含量,得到LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2和LiNi_(0.45)Co_(0.1)Mn_(0.45)O_2材料,降低了成本,循环性能也有所提高。LiNi_(0.45)Co_(0.1)Mn_(0.45)O_2材料循环性能优异,但比容量不高,倍率性能差。LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2材料具有优异的电性能:比容量可达193.3 mAh/g;2C放电比容量为170.6 mAh/g;0.1C循环30圈容量保持率为93.0%。
作为比较,用氢氧根法合成出了LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2材料,经优化比较得出该体系在前体制备时控制pH在10.5,高温处理时煅烧温度选择950℃时材料性能最好。本实验未使用氨水等络合剂,合成出的材料为块状粒子。用两种共沉淀法合成出的LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2材料均有较高的比容量和较好的循环性能,但用碳酸盐法合成出的材料倍率性能更好。
People have been trying to find the alternate materials for commercial LiCoO_2 because of the cost and toxicity of Co.The materials of LiNi_xCO_(1-2x)Mn_xO_2 series have been the hot point at home and abroad for a long time as it's cheaper than LiCoO_2 but may acquire better performance.
A series of spherical cathode material—LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 was synthesized by carbonate co-precipitation method and then examined by TG-DTA、ICP、XRD、SEM etc.in this thesis.The synthetic process was optimized after a comprehensive inspection of the effect of the pretreatment and thermal treatment.The experiment results showed that the best synthetic process was as follows:pH=7.4-7.6,the concentration ratio of the precipitator to the metal salt solution was 1.5,reaction temperature was 50℃,the calcination temperature and holding time were 850℃and 15h,respectively.For the best sample of LiNi_(1/3)CO_(1/3)Mn_(1/3)O_2,the discharge capacity could reach 191.5mAh/g in the voltage range of 2.5-4.5V and at 0.05C;the capacity of 169.2mAh/g could be retained at 2C;cycled at 0.1C for 30 cycles,the retention rate could reach 97.2%.
The results showed that increasing the Li content could improve the cycle performance significantly.Li_(1.1)Ni_(1/3)Co_(1/3)Mn_(1/3)O_2 showed the best performance.On the base of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 material,the Co content was reduced to synthesize LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2 and LiNi_(0.45)Co_(0.1)Mn_(0.45)O_2 which had lower cost but better cycle performance.The LiNi_(0.45)Co_(0.1)Mn_(0.45)O_2 had excellent cycle performance but low capacity,poor high-rate capability.The electrochemistry performance of LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2 was very well:the discharge capacity could reach 193.3mAh/g; the capacity was 170.6mAh/g when discharged at 2C;cycled at 0.1C for 30 cycles, the retention rate was 93.0%.
For comparison,LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 was synthesized by hydroxyl co-precipitation method.The materials had the best performance when controlled pH=10.5 and the calcination temperature at 950℃.The surface topography of the materials were lumpish as NH_3·H_2O and other complexing agents hadn't been used.The capacity and cycle performance of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 synthesized by the two different co-precipitation methods were both very well,but the high-rate dischargeability of the materials prepared by carbonate co-precipitation method were much better.
本文采用碳酸盐共沉淀法成功合成了球形LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料,同时采用TG-DTA、ICP、XRD、SEM、模拟电池测试等多种测试手段对该体系的制备与结构、形貌、性能做了系统的研究。综合考察了预处理方式和高温处理方式对材料的影响,优化了合成工艺。实验表明:控制溶液pH值在7.4-7.6,沉淀剂与金属盐溶液浓度比为1.2～1.5,反应温度为50℃得到球形前体,氧化、掺Li后850℃下煅烧15h得到的材料有很好的电化学性能。2.5-4.5V,0.05C放电时,材料比容量可达191.5mAh/g;2C放电仍有169.2mAh/g;0.1C循环30圈,保持率为97.2%。
对LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2材料掺Li改性发现适量增加Li含量能显著提高材料循环性能,Li_(1.1)Ni_(1/3)Co_(1/3)Mn_(1/3)O_2材料综合性能最佳。在LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2材料的基础上,进一步降低Co含量,得到LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2和LiNi_(0.45)Co_(0.1)Mn_(0.45)O_2材料,降低了成本,循环性能也有所提高。LiNi_(0.45)Co_(0.1)Mn_(0.45)O_2材料循环性能优异,但比容量不高,倍率性能差。LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2材料具有优异的电性能:比容量可达193.3 mAh/g;2C放电比容量为170.6 mAh/g;0.1C循环30圈容量保持率为93.0%。
作为比较,用氢氧根法合成出了LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2材料,经优化比较得出该体系在前体制备时控制pH在10.5,高温处理时煅烧温度选择950℃时材料性能最好。本实验未使用氨水等络合剂,合成出的材料为块状粒子。用两种共沉淀法合成出的LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2材料均有较高的比容量和较好的循环性能,但用碳酸盐法合成出的材料倍率性能更好。
People have been trying to find the alternate materials for commercial LiCoO_2 because of the cost and toxicity of Co.The materials of LiNi_xCO_(1-2x)Mn_xO_2 series have been the hot point at home and abroad for a long time as it's cheaper than LiCoO_2 but may acquire better performance.
A series of spherical cathode material—LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 was synthesized by carbonate co-precipitation method and then examined by TG-DTA、ICP、XRD、SEM etc.in this thesis.The synthetic process was optimized after a comprehensive inspection of the effect of the pretreatment and thermal treatment.The experiment results showed that the best synthetic process was as follows:pH=7.4-7.6,the concentration ratio of the precipitator to the metal salt solution was 1.5,reaction temperature was 50℃,the calcination temperature and holding time were 850℃and 15h,respectively.For the best sample of LiNi_(1/3)CO_(1/3)Mn_(1/3)O_2,the discharge capacity could reach 191.5mAh/g in the voltage range of 2.5-4.5V and at 0.05C;the capacity of 169.2mAh/g could be retained at 2C;cycled at 0.1C for 30 cycles,the retention rate could reach 97.2%.
The results showed that increasing the Li content could improve the cycle performance significantly.Li_(1.1)Ni_(1/3)Co_(1/3)Mn_(1/3)O_2 showed the best performance.On the base of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 material,the Co content was reduced to synthesize LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2 and LiNi_(0.45)Co_(0.1)Mn_(0.45)O_2 which had lower cost but better cycle performance.The LiNi_(0.45)Co_(0.1)Mn_(0.45)O_2 had excellent cycle performance but low capacity,poor high-rate capability.The electrochemistry performance of LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2 was very well:the discharge capacity could reach 193.3mAh/g; the capacity was 170.6mAh/g when discharged at 2C;cycled at 0.1C for 30 cycles, the retention rate was 93.0%.
For comparison,LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 was synthesized by hydroxyl co-precipitation method.The materials had the best performance when controlled pH=10.5 and the calcination temperature at 950℃.The surface topography of the materials were lumpish as NH_3·H_2O and other complexing agents hadn't been used.The capacity and cycle performance of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 synthesized by the two different co-precipitation methods were both very well,but the high-rate dischargeability of the materials prepared by carbonate co-precipitation method were much better.
引文
【1]禹筱元 层状LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2与改性尖晶石的研究—锂离子电池正极材料深度研发之一[D].中南大学2005.6
【2]吴宇平等 锂离子电池:应用与实践【M].北京:化学工业出版社2004
【3]管从胜等 高能化学电源[M].北京:化学工业出版社2002.11第1版
【4]王双才等 锂离子电池正极材料研究动态[J].中国锰业2004,22(3):32-34
[5]Mizushima K,Jones P C,Jones P J,et al.LixCoO_2(0＜x＜—1):A new cathode material for batteries of high energy density[J].Mater.Res.Bull.,1980,15(6):783-789.
[6]Yabuuchi N,Ohzuku T.[J].J Power Sources,2003,119-121:171-174.
[7]Takahashi M,Tobishima S,Takei K,et al.Reaction behavior of LiFePO_4 as a cathode material for rechargeable lithium batteries[J].Solid State Ionics,2002,148(3-4):A283-A289.
[8]MacneilD D,Zhonghu L,Zhaohui C,et al.A comparison of the electrode/elec-trolyte reaction at elevated temperatures for various L i2ion battery cathodes[J].J Power Sources,2002,108(1-2):A8-A14.
【9]毕道治 大容量高功率锂离子蓄电池研究进展【C].2007中国国际电池产业链论坛论文集193-205
[10]Kanno R,Kubo H,Kawamoto Y,et al.Phase relationship and lithium deinter-calation in lithium nickel oxides[J].J Solid State Chem,1994,110:216-225.
[11]Prosini P P,Lisi M,Zane D,et al.Determination of the chemical diffusion coefficience of lithium in LiFePO4[J].Solid S rate Ionics,2002,148(1-2):A45-A51.
[12]Arai H,Okada S,Sakurai Y,et al.Reversibility of LiNiO_2 cathode[J].Solid State Ion.,1997,95(3-4):275-282.
[13]Ceder G,Mishra S K.The stability of orthorhombic and monoclinic-layered LiMnO_2[J].Electrochem.Solid-State Lett.,1999,2(11):550-552.
[14]Chen Y,Wang G X,Konstantinov K et al.Synthesis and characterization of LiCo_xMn_yNi_(1-x-y)O_2 as a cathode material for secondary lithium batteries[J].J.Power Sources,2003,119-121:184-188.
[15]Ohzuku T,Makimura Y.Layered lithium insertion material of LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2 for lithium-ion batteries[J].Chemistry Letters,2001,7:642-643.
[16]Liao P Y,Duh J G,Sheen S R.Effect of Mn content on the microstructure and electrochemical performance of LiNi_(0.75-x)Co_(0.25)Mn_xO_2 cathode materials[J].J.Electrochem.Soc.,2005,152(9):A1695-A1700.
[17]Hwang B J,Tsai Y W,Chen C H,et al.Influence of Mn content on the morp-Hology and electrochemical performance of LiNi_(1-x-y)Co_xMn_yO_2 cathode mate rials[J].J.Mater.Chem.,2003,13(8):1962-1968.
[18]Park K S,Cho M H,Jin S J,et al.Structural and electrochemical properties of nanosize layered Li[Li_(1/5)Ni_(1/10)CO_(1/5)Mn_(1/2)]O_2[J].Electrochem.Solid-State Lett.,2004,7(8):A239-A241.
[19]Ngala J K,Chernova N A,Ma M,et al.The synthesis,characterization and electrochemical behavior of the layeredLiNi_(0.4)Mn_(0.4)Co_(0.2)O_2 compound[J]:J.Mater.Chem.,2004,14(2):214-220
[20]Koyama Y,Yabuuchi N,Tanaka I,et al.Solid-state chemistry and electro-chemistry of LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2 for advanced Lithium-ionbatteries[J].J.Electrochem.Soc.,2004,151(10):A1545-A1551.
[21]易雯雯,肖汉宁,胡鹏飞LiNi_xMn_xCo_(1-2x)O_2的高温固相合成与电化学性能[J].电源技术2007,31(4):266-269
【22]汪亮,陈玉红,焦延峰合成方法对LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2材料结构与性能的影响【J].化工中间体2006,3:20-22
【23]张明,李新海等Li:(Ni+Co+Mn)对Li_xNi_(1/3)Co_(1/3)Mn_(1/3)O_性能的影响【J].电源技术2007,131(1):15-18
【24]李娟,史鹏飞,郭瑞 锂离子电池正极材料LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2的合成及性能研究【J].化工新型材料2007,35(8):75-77
[25]Cho T H,Park S M,Yoshio M,et al.Effect of synthesis condition on the structural and electrochemical properties of Li[Ni_(1/3)Mn_(1/3)Co_(1/3)]O_2 prepared by carbonate co-precipitation method[J].J.Power Sources,2005,142(1-2):306-312.
【26]禹筱元等 层状LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2正极材料合成及电化学性能【J].电源技术2005,29(10):641-644
[27]Cho TH,Shiosaki Y,Noguchi H.Preparation and characterization of layered LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2 as a cathode material by an oxalate co-precipitation method[J].J. Power Sources,2006,159(2):1322-1327.
[28]Zhang X,Wen Z,Yang X,et al.Synthesis and electrochemical behavior of a new layered cathode material LiCo_(1/2)Mn_(1/3)Ni_(1/6)O_2[J].Mater.Res.Bull.,2006,41(3):662-666.
[29]Zhang S,Qiu X,He Z,et al.Nanoparticled Li(Ni_(1/3)Co_(1/3)Mn_(1/3))O_2 as cathode material for high-rate lithium-ion batteries[J].J.Power Sources,2006,153(2):350-353.
【30]韦旎妮 层状LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料的合成及电化学性能研究【J].无机化学学报2005,21(7):999-1003
【31]钟辉,许惠层状LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料的合成与电化学性能研究[J].化学学报2007,65(2):147-151
[32]田华,叶乃清锂离子电池正极材料LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2的低温燃烧合成【J].化学通报,2007,11:857-860
【33]吴青端等 从电解NiCoMn合金出发制备锂离子电池正极材料LiNi_(1/3)Co_(1/3) Mn_(1/3) O_2[J].南开大学学报2005,38(5):48-51
[34]Park S H,Yoon C S,Kang S G,et al.Synthesis and structural characterization of layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 cathode materials by ultrasonic spray pyrolysis method[J].Electrochim.Acta,2004,49(4):557-563
[35]Tong D G,Lai Q Y,Wei N N,et al.Synthesis of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 as a cathode material for lithium ion battery by water-in-oil emulsion method[J].Mater.Chem.and Phy.,2005,94(2-3):423-428
[36]李春霞等 掺杂Zr对LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2性能的影响【J].电池2007,37(3):223-225
【37]檀柏杉,韩恩山,李鹏LiNi_(1/3)Co_(1/4)Mn_(1/3)M_(1/12)O_2(M=Al,Ti)的性能研究[J].电池2005,35(4):259-260
【38]廖力等Li(Ni_(1/3)Co_(1/3)Mn_(1/3))_(1-2x)Mg_xAl_xO_2的合成与电化学性能[J].电源技术2007,31(1):26-29
【39]黄原君等LiNi_(1/3)Ci_(1/3)Mn_(1/3)O_2的Si/F复合掺杂及电化学性能[J].无机化学学报2007,23(3):466-452
[40]Chick L A,Pederson L R,Maupin,et al.Glycine-nitrate combustion synthesis of oxide ceramic powders[J].Mater.Lett.,1990,10(1-2):6-12.
【41]王丽琴等Li【Ni_(1/3)Mn_(1/3)Co_(1/3)]O_2掺杂Mo研究【J].化学学报2006,64(17):1854-1858
[42]Liu Z L,Yu A S,Lee J Y Synthesis and characterization of LiNi_(1-x-y)Co_xMn_y O_2 as the cathode materials of secondary lithium batteries[J].J.Power Sources.1999,81:416-419
【43]李鹏等 正极材料LiNi_(0.45)Co_(0.1)Mn_(0.45)O_2的制备与性能【J].应用化学2005,22(3):304-307
[44]蒲俊红,陈猛,韩文伟层状Li(NiMn)_(0.5-y)Co_(2y)O_2的结构和电化学性能【J].电源技术2007,31(2):126-127
【45]韩恩山等 锂离子蓄电池LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2正极材料的合成及性能[J].电源技术2006,130(7):543-545
【46]何雨石等 合成方法对LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2电化学性能的影响【J].稀有金属材料与工程2007,36(10):1831-1834
【47]代克化等 高密度LiMn_(0.4) Ni_(0.4)Co_(0.2)O_2正极材料的合成与研究【J].北京大学学报2006,48:34-38
[48]李劼等 锂离子电池正极材料LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2的合成、表征及电化学性能【J].高等学校化学学报2006,27(7):1311-1314
【49]吴英华,任凤莲 层状锂离子正极材料Li_(1+x)(Co_(0.2)Ni_(0.4)Mn_(0.4))O_2的结构和电化学性能的研究[J].化学世界2008,1:5-9
【50]朱勇军等 球形Li Ni_(0.5-x)Co_(2x)Mn_(0.5-x)O_2的合成及其电化学性能【J].无机化学学报2007,22(5):873-878
【51]杨箫等 氧化钛包覆对LiCo_(0.2)Ni_(0.4)Mn_(0.4)O_2结构和性能的影响【J].无机化学学报2007,27(5):753-758
【52]许惠层状LiNi_(1/2-x)Co_(2x)Mn_(1/2-x)O_2正极材料的合成与电化学性能研究【J].化工新型材料2008,36(6):68-71
[53]苏继桃等 锂离子电池正极材料LiNi_(0.3)Co_(0.4)Mn_(0.3)O_2的制备及性能[J].中南大学学报2008,39(1):18-21
[54]T.Ohzuku and Y.Makimura,,Layered lithium insertion material of LiNi_(1/2)Mn_(1/2)O_2:A possible alternative to LiCoO2 for advanced lithium-ion batteries[J].Chem.Lett.,2001,30(7):744-745
[55]Z.Lu,D.D.MacNeil and J.R.Dahn,Layered Li[Ni_xCo_(1-2x)Mn_x]O_2 cathode materials for lithium-ion batteries[J].Electrochem.Solid-State Lett.,2001,4(12):A200-203
[56]Z.Lu,D.D.MacNeil and J.R.Dahn,Layered cathode materials Li[Ni_xLi_((1/3-2x/3))Mn_((2/3-x/3))]O_2 for lithium-ion batteries[J].Electrochem.Solid-State Lett.,2001,4(11):A191-194
[57]K.M.Shaju,G.V.Subba Rao and B.Chowdari,Performance of layered Li(Ni_(1/3)Co_(1/3)Mn_(1/3))O_2 as cathode for Li-ion batteries[J].Electrochimica Acta,2002,48(2):145-151
[58]N.Yabuuchi and T.Ohzuku,Novel lithium insertion material of LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2 for advanced lithium-ion batteries[J].J.Power Sources,2003,171:119-121
[59]T.Cho,S.Park,and M.Yoshio,Preparation of layered Li[Ni_(1/3)Mn_(1/3)Co_(1/3)]O_2 as a cathode for lithium secondary battery by carbonate coprecipitation method[J].Chem.Lett.,2004,33(6):704-705
[60]S.Park,T.Cho and M.Yoshio,Novel synthesis method for preparing layered Li[Mn_(1/2)Ni_(1/2)]O_2 as a cathode material for lithium ion secondary battery[J].Chem.Lett.,2004,33(6):748-74
[61]H.Park,H.Shin,S.Myung,et al.Synthesis of nanostructured Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O_2 via a modified carbonate process[J].Chem.Mater.,2005,17(1):6-8
[62]P.He,H.Wang,L.Qi and T.Osaka,Electrochemical characteristics of layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 and with different synthesis conditions[J].J.Power Sources,2006,160(1):627-632
[63]Y.-K.Sun,C.S.Yoon,Y S.Lee,Electrochemical properties and structural characterization of layered Li[Ni_(0.5)Mn_(0.5)]O_2 cathode materials[J].Electrochimica Acta,2003,48(18):2589-2592
[64]D.Li,T.Muta,L.Zhang,et al,Effect of synthesis method on the electrochemical performance of LiNi_(1/3)Mn_(1/3)Co_(1/3)O_2[J].J.Power Sources,2004,132(1-2):150-155
[65]J.Kim,C.Park,Y.-K.Sun,Electrical sensitive behavior of a polyelectrolyte complex composed of chitosan/hyaluronic acid[J].Solid State Ionics,2003,164(3-4):199-204
[66]K.M.Shaju,P.Bruce,Macroporous Li(Ni_(1/3)Co_(1/3)Mn_(1/3))O_2:A high-power and high-energy cathode for rechargeable lithium batteries[J].Adv.Mater.,2006,18(17):2330-2334,
[67]S.Myung,S.Komaba,N.Kumagai,Effect of excess lithium on LiNi0.5Mn0.5O2+delta and its electrochemistry as lithium insertion material [J].Solid State Ionics,2004,170(1-2):139-144
[68]Y.He,Z.Ma,X.Liao,Y Jiang,Synthesis and characterization of submicron-sized LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 by a simple self-propagating solid-state metathesis method[J]J.Power Sources,2007,163:1053
[69]Ohzuku T,Ueda A,Nagayama M,et al.Electrochimica Acta,1993,38:1159-1167
【70]叶茂,周震,阎杰,溶胶凝胶法制备钇掺杂锂离子电池正极材料LiCo1/3Ni1/3Mn1/3O2[J].中国稀土学报2006,24(6):759-763
[71]Ngala J K,Chernova N A,Ma M,et al.J.Mater.Chem.,2004,14(2):214-220
【72]王成刚等 碳酸锰热解过程的动力学[J].中国有色金属学报2000,10(1):113-116
【73]王海燕等LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料的制备与倍率性能研究【J].,无机化学学报,2008.4,24(4):593-599
【74]苏继桃等LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料的制备及其表征【J].中南大学学报2008,39(2):221-227
【75]常照荣等LiOH-LiNO_3低共熔混合锂盐体系合成LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2【J].物理化学学报2008,24(3):513-519
【76]宋梅等 层状结构LiNi_+(1/3)Co_(1/3)Mn_(1/3)O_2正极材料制备过程与电化学性能【J].化工时刊2007,21(12):1-4
【77]王丽琴等 煅烧温度对锂离子正极材料Li【Ni_(0.475)Mn_(0.475)Co_(0.05)]O_2结构和电化学性能的影响[J].电化学2006,12(3):275-278
【78]曹四海等固相法制备层状LiNi_(0.5)Mn_(0.5)O_2的研究[J].电池工业2006,11(3):178-181
【79]李丹等 锂离子蓄电池材料LiNi_(0.7)Co_(0.2)Mn_(0.1)O_2的制备与性能[J].电源技术2007,31(4):263-265
【80]王瑞忠,樊勇利烧结温度对锂离子蓄电池Li_(1+x)Ni_(1/3)Co_(1/3)Mn_(1/3)O_2性能的影响【J].电源技术2007,31(12):971-973
【81]周震涛,黄鲲微粒溶胶-凝胶法制备Li(Ni_(1/3)Co_(1/3)Mn_(1/3))O_2及其性能【J].电源技术2006,30(8):649-652
【82]彭庆文,刘兴江,唐致远Li与Ni+Co+Mn摩尔比对LixNi_(1/3)Co_(1/3)Mn_(1/3)O_2结构和性能的影响【J].电源技术2008,32(7):456-460
【83]王志兴等 初始Li/(Mn+Ni)摩尔比对LiNi_(0.5)Mn_(0.5)O_2电化学性能的影响[J].中国有色金属学报2006,16(8):1434-1438
【2]吴宇平等 锂离子电池:应用与实践【M].北京:化学工业出版社2004
【3]管从胜等 高能化学电源[M].北京:化学工业出版社2002.11第1版
【4]王双才等 锂离子电池正极材料研究动态[J].中国锰业2004,22(3):32-34
[5]Mizushima K,Jones P C,Jones P J,et al.LixCoO_2(0＜x＜—1):A new cathode material for batteries of high energy density[J].Mater.Res.Bull.,1980,15(6):783-789.
[6]Yabuuchi N,Ohzuku T.[J].J Power Sources,2003,119-121:171-174.
[7]Takahashi M,Tobishima S,Takei K,et al.Reaction behavior of LiFePO_4 as a cathode material for rechargeable lithium batteries[J].Solid State Ionics,2002,148(3-4):A283-A289.
[8]MacneilD D,Zhonghu L,Zhaohui C,et al.A comparison of the electrode/elec-trolyte reaction at elevated temperatures for various L i2ion battery cathodes[J].J Power Sources,2002,108(1-2):A8-A14.
【9]毕道治 大容量高功率锂离子蓄电池研究进展【C].2007中国国际电池产业链论坛论文集193-205
[10]Kanno R,Kubo H,Kawamoto Y,et al.Phase relationship and lithium deinter-calation in lithium nickel oxides[J].J Solid State Chem,1994,110:216-225.
[11]Prosini P P,Lisi M,Zane D,et al.Determination of the chemical diffusion coefficience of lithium in LiFePO4[J].Solid S rate Ionics,2002,148(1-2):A45-A51.
[12]Arai H,Okada S,Sakurai Y,et al.Reversibility of LiNiO_2 cathode[J].Solid State Ion.,1997,95(3-4):275-282.
[13]Ceder G,Mishra S K.The stability of orthorhombic and monoclinic-layered LiMnO_2[J].Electrochem.Solid-State Lett.,1999,2(11):550-552.
[14]Chen Y,Wang G X,Konstantinov K et al.Synthesis and characterization of LiCo_xMn_yNi_(1-x-y)O_2 as a cathode material for secondary lithium batteries[J].J.Power Sources,2003,119-121:184-188.
[15]Ohzuku T,Makimura Y.Layered lithium insertion material of LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2 for lithium-ion batteries[J].Chemistry Letters,2001,7:642-643.
[16]Liao P Y,Duh J G,Sheen S R.Effect of Mn content on the microstructure and electrochemical performance of LiNi_(0.75-x)Co_(0.25)Mn_xO_2 cathode materials[J].J.Electrochem.Soc.,2005,152(9):A1695-A1700.
[17]Hwang B J,Tsai Y W,Chen C H,et al.Influence of Mn content on the morp-Hology and electrochemical performance of LiNi_(1-x-y)Co_xMn_yO_2 cathode mate rials[J].J.Mater.Chem.,2003,13(8):1962-1968.
[18]Park K S,Cho M H,Jin S J,et al.Structural and electrochemical properties of nanosize layered Li[Li_(1/5)Ni_(1/10)CO_(1/5)Mn_(1/2)]O_2[J].Electrochem.Solid-State Lett.,2004,7(8):A239-A241.
[19]Ngala J K,Chernova N A,Ma M,et al.The synthesis,characterization and electrochemical behavior of the layeredLiNi_(0.4)Mn_(0.4)Co_(0.2)O_2 compound[J]:J.Mater.Chem.,2004,14(2):214-220
[20]Koyama Y,Yabuuchi N,Tanaka I,et al.Solid-state chemistry and electro-chemistry of LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2 for advanced Lithium-ionbatteries[J].J.Electrochem.Soc.,2004,151(10):A1545-A1551.
[21]易雯雯,肖汉宁,胡鹏飞LiNi_xMn_xCo_(1-2x)O_2的高温固相合成与电化学性能[J].电源技术2007,31(4):266-269
【22]汪亮,陈玉红,焦延峰合成方法对LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2材料结构与性能的影响【J].化工中间体2006,3:20-22
【23]张明,李新海等Li:(Ni+Co+Mn)对Li_xNi_(1/3)Co_(1/3)Mn_(1/3)O_性能的影响【J].电源技术2007,131(1):15-18
【24]李娟,史鹏飞,郭瑞 锂离子电池正极材料LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2的合成及性能研究【J].化工新型材料2007,35(8):75-77
[25]Cho T H,Park S M,Yoshio M,et al.Effect of synthesis condition on the structural and electrochemical properties of Li[Ni_(1/3)Mn_(1/3)Co_(1/3)]O_2 prepared by carbonate co-precipitation method[J].J.Power Sources,2005,142(1-2):306-312.
【26]禹筱元等 层状LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2正极材料合成及电化学性能【J].电源技术2005,29(10):641-644
[27]Cho TH,Shiosaki Y,Noguchi H.Preparation and characterization of layered LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2 as a cathode material by an oxalate co-precipitation method[J].J. Power Sources,2006,159(2):1322-1327.
[28]Zhang X,Wen Z,Yang X,et al.Synthesis and electrochemical behavior of a new layered cathode material LiCo_(1/2)Mn_(1/3)Ni_(1/6)O_2[J].Mater.Res.Bull.,2006,41(3):662-666.
[29]Zhang S,Qiu X,He Z,et al.Nanoparticled Li(Ni_(1/3)Co_(1/3)Mn_(1/3))O_2 as cathode material for high-rate lithium-ion batteries[J].J.Power Sources,2006,153(2):350-353.
【30]韦旎妮 层状LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料的合成及电化学性能研究【J].无机化学学报2005,21(7):999-1003
【31]钟辉,许惠层状LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料的合成与电化学性能研究[J].化学学报2007,65(2):147-151
[32]田华,叶乃清锂离子电池正极材料LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2的低温燃烧合成【J].化学通报,2007,11:857-860
【33]吴青端等 从电解NiCoMn合金出发制备锂离子电池正极材料LiNi_(1/3)Co_(1/3) Mn_(1/3) O_2[J].南开大学学报2005,38(5):48-51
[34]Park S H,Yoon C S,Kang S G,et al.Synthesis and structural characterization of layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 cathode materials by ultrasonic spray pyrolysis method[J].Electrochim.Acta,2004,49(4):557-563
[35]Tong D G,Lai Q Y,Wei N N,et al.Synthesis of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 as a cathode material for lithium ion battery by water-in-oil emulsion method[J].Mater.Chem.and Phy.,2005,94(2-3):423-428
[36]李春霞等 掺杂Zr对LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2性能的影响【J].电池2007,37(3):223-225
【37]檀柏杉,韩恩山,李鹏LiNi_(1/3)Co_(1/4)Mn_(1/3)M_(1/12)O_2(M=Al,Ti)的性能研究[J].电池2005,35(4):259-260
【38]廖力等Li(Ni_(1/3)Co_(1/3)Mn_(1/3))_(1-2x)Mg_xAl_xO_2的合成与电化学性能[J].电源技术2007,31(1):26-29
【39]黄原君等LiNi_(1/3)Ci_(1/3)Mn_(1/3)O_2的Si/F复合掺杂及电化学性能[J].无机化学学报2007,23(3):466-452
[40]Chick L A,Pederson L R,Maupin,et al.Glycine-nitrate combustion synthesis of oxide ceramic powders[J].Mater.Lett.,1990,10(1-2):6-12.
【41]王丽琴等Li【Ni_(1/3)Mn_(1/3)Co_(1/3)]O_2掺杂Mo研究【J].化学学报2006,64(17):1854-1858
[42]Liu Z L,Yu A S,Lee J Y Synthesis and characterization of LiNi_(1-x-y)Co_xMn_y O_2 as the cathode materials of secondary lithium batteries[J].J.Power Sources.1999,81:416-419
【43]李鹏等 正极材料LiNi_(0.45)Co_(0.1)Mn_(0.45)O_2的制备与性能【J].应用化学2005,22(3):304-307
[44]蒲俊红,陈猛,韩文伟层状Li(NiMn)_(0.5-y)Co_(2y)O_2的结构和电化学性能【J].电源技术2007,31(2):126-127
【45]韩恩山等 锂离子蓄电池LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2正极材料的合成及性能[J].电源技术2006,130(7):543-545
【46]何雨石等 合成方法对LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2电化学性能的影响【J].稀有金属材料与工程2007,36(10):1831-1834
【47]代克化等 高密度LiMn_(0.4) Ni_(0.4)Co_(0.2)O_2正极材料的合成与研究【J].北京大学学报2006,48:34-38
[48]李劼等 锂离子电池正极材料LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2的合成、表征及电化学性能【J].高等学校化学学报2006,27(7):1311-1314
【49]吴英华,任凤莲 层状锂离子正极材料Li_(1+x)(Co_(0.2)Ni_(0.4)Mn_(0.4))O_2的结构和电化学性能的研究[J].化学世界2008,1:5-9
【50]朱勇军等 球形Li Ni_(0.5-x)Co_(2x)Mn_(0.5-x)O_2的合成及其电化学性能【J].无机化学学报2007,22(5):873-878
【51]杨箫等 氧化钛包覆对LiCo_(0.2)Ni_(0.4)Mn_(0.4)O_2结构和性能的影响【J].无机化学学报2007,27(5):753-758
【52]许惠层状LiNi_(1/2-x)Co_(2x)Mn_(1/2-x)O_2正极材料的合成与电化学性能研究【J].化工新型材料2008,36(6):68-71
[53]苏继桃等 锂离子电池正极材料LiNi_(0.3)Co_(0.4)Mn_(0.3)O_2的制备及性能[J].中南大学学报2008,39(1):18-21
[54]T.Ohzuku and Y.Makimura,,Layered lithium insertion material of LiNi_(1/2)Mn_(1/2)O_2:A possible alternative to LiCoO2 for advanced lithium-ion batteries[J].Chem.Lett.,2001,30(7):744-745
[55]Z.Lu,D.D.MacNeil and J.R.Dahn,Layered Li[Ni_xCo_(1-2x)Mn_x]O_2 cathode materials for lithium-ion batteries[J].Electrochem.Solid-State Lett.,2001,4(12):A200-203
[56]Z.Lu,D.D.MacNeil and J.R.Dahn,Layered cathode materials Li[Ni_xLi_((1/3-2x/3))Mn_((2/3-x/3))]O_2 for lithium-ion batteries[J].Electrochem.Solid-State Lett.,2001,4(11):A191-194
[57]K.M.Shaju,G.V.Subba Rao and B.Chowdari,Performance of layered Li(Ni_(1/3)Co_(1/3)Mn_(1/3))O_2 as cathode for Li-ion batteries[J].Electrochimica Acta,2002,48(2):145-151
[58]N.Yabuuchi and T.Ohzuku,Novel lithium insertion material of LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2 for advanced lithium-ion batteries[J].J.Power Sources,2003,171:119-121
[59]T.Cho,S.Park,and M.Yoshio,Preparation of layered Li[Ni_(1/3)Mn_(1/3)Co_(1/3)]O_2 as a cathode for lithium secondary battery by carbonate coprecipitation method[J].Chem.Lett.,2004,33(6):704-705
[60]S.Park,T.Cho and M.Yoshio,Novel synthesis method for preparing layered Li[Mn_(1/2)Ni_(1/2)]O_2 as a cathode material for lithium ion secondary battery[J].Chem.Lett.,2004,33(6):748-74
[61]H.Park,H.Shin,S.Myung,et al.Synthesis of nanostructured Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O_2 via a modified carbonate process[J].Chem.Mater.,2005,17(1):6-8
[62]P.He,H.Wang,L.Qi and T.Osaka,Electrochemical characteristics of layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 and with different synthesis conditions[J].J.Power Sources,2006,160(1):627-632
[63]Y.-K.Sun,C.S.Yoon,Y S.Lee,Electrochemical properties and structural characterization of layered Li[Ni_(0.5)Mn_(0.5)]O_2 cathode materials[J].Electrochimica Acta,2003,48(18):2589-2592
[64]D.Li,T.Muta,L.Zhang,et al,Effect of synthesis method on the electrochemical performance of LiNi_(1/3)Mn_(1/3)Co_(1/3)O_2[J].J.Power Sources,2004,132(1-2):150-155
[65]J.Kim,C.Park,Y.-K.Sun,Electrical sensitive behavior of a polyelectrolyte complex composed of chitosan/hyaluronic acid[J].Solid State Ionics,2003,164(3-4):199-204
[66]K.M.Shaju,P.Bruce,Macroporous Li(Ni_(1/3)Co_(1/3)Mn_(1/3))O_2:A high-power and high-energy cathode for rechargeable lithium batteries[J].Adv.Mater.,2006,18(17):2330-2334,
[67]S.Myung,S.Komaba,N.Kumagai,Effect of excess lithium on LiNi0.5Mn0.5O2+delta and its electrochemistry as lithium insertion material [J].Solid State Ionics,2004,170(1-2):139-144
[68]Y.He,Z.Ma,X.Liao,Y Jiang,Synthesis and characterization of submicron-sized LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 by a simple self-propagating solid-state metathesis method[J]J.Power Sources,2007,163:1053
[69]Ohzuku T,Ueda A,Nagayama M,et al.Electrochimica Acta,1993,38:1159-1167
【70]叶茂,周震,阎杰,溶胶凝胶法制备钇掺杂锂离子电池正极材料LiCo1/3Ni1/3Mn1/3O2[J].中国稀土学报2006,24(6):759-763
[71]Ngala J K,Chernova N A,Ma M,et al.J.Mater.Chem.,2004,14(2):214-220
【72]王成刚等 碳酸锰热解过程的动力学[J].中国有色金属学报2000,10(1):113-116
【73]王海燕等LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料的制备与倍率性能研究【J].,无机化学学报,2008.4,24(4):593-599
【74]苏继桃等LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料的制备及其表征【J].中南大学学报2008,39(2):221-227
【75]常照荣等LiOH-LiNO_3低共熔混合锂盐体系合成LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2【J].物理化学学报2008,24(3):513-519
【76]宋梅等 层状结构LiNi_+(1/3)Co_(1/3)Mn_(1/3)O_2正极材料制备过程与电化学性能【J].化工时刊2007,21(12):1-4
【77]王丽琴等 煅烧温度对锂离子正极材料Li【Ni_(0.475)Mn_(0.475)Co_(0.05)]O_2结构和电化学性能的影响[J].电化学2006,12(3):275-278
【78]曹四海等固相法制备层状LiNi_(0.5)Mn_(0.5)O_2的研究[J].电池工业2006,11(3):178-181
【79]李丹等 锂离子蓄电池材料LiNi_(0.7)Co_(0.2)Mn_(0.1)O_2的制备与性能[J].电源技术2007,31(4):263-265
【80]王瑞忠,樊勇利烧结温度对锂离子蓄电池Li_(1+x)Ni_(1/3)Co_(1/3)Mn_(1/3)O_2性能的影响【J].电源技术2007,31(12):971-973
【81]周震涛,黄鲲微粒溶胶-凝胶法制备Li(Ni_(1/3)Co_(1/3)Mn_(1/3))O_2及其性能【J].电源技术2006,30(8):649-652
【82]彭庆文,刘兴江,唐致远Li与Ni+Co+Mn摩尔比对LixNi_(1/3)Co_(1/3)Mn_(1/3)O_2结构和性能的影响【J].电源技术2008,32(7):456-460
【83]王志兴等 初始Li/(Mn+Ni)摩尔比对LiNi_(0.5)Mn_(0.5)O_2电化学性能的影响[J].中国有色金属学报2006,16(8):1434-1438