尿素均相沉淀法制备La掺杂Zn/Al取代α-Ni（
OH）_2电极材料的性能研究
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摘要
论文全面综述了α-Ni(OH)2电极材料作为MH-Ni电池正极活性物质的研究现状。基于稀土元素物质独特的电子组态及4f电子运动特性,并考虑到相关金属离子的电化学功能性作用,采用尿素均相沉淀法成功制备出稀土La掺杂Zn/Al取代α-Ni(OH)2粉体材料,并系统研究了其制备合成条件及行为规律,测试分析了所制备材料的物理特性及其微结构特征,研究考察了样品材料电极的电化学性能及材料的掺杂元素组成、含量对其微结构及其电极材料在电极过程中的电化学活性效应与电化学性能的影响,并讨论了其内在联系机制的电化学作用机理。
文中通过采用尿素用量、反应温度、反应时间、分散剂等单因素对电极材料性能影响的实验研究,确定出尿素均相沉淀法制备La掺杂Zn/Al取代α-Ni(OH)2稳定结构粉体材料的优化体系工艺条件为:乙醇-水溶液体系,尿素与金属盐比例为30:1、反应温度控制在90±1℃、搅拌反应3h、粉体干燥温度为60℃。
实验研究结果发现,在确定的优化工艺条件下制备出不同比例配制量的La掺杂Zn/Al取代α-Ni(OH)2样品粉体材料,形貌为无数片状微晶相互粘连且具有较多孔隙的类球状颗粒。样品材料经XRD、Raman、IR和TG-DSC测试结果表明,材料的微结构比Zn/Al取代α-Ni(OH)2具有较多的微结构缺陷和较大层间距,并含有较多结晶水,同时热稳定性明显增强。将其合成MH-Ni电池正极材料的电化学性能测试结果表明,当La掺杂摩尔用量为5%的Zn代α-Ni(OH)2的样品材料电极在0.1C放电下,其放电比容量达382.85mAh·g-1,放电中值电压较高并稳定于1.2943V,在1.0C下,放电比容量为359.85mAh·g-1,经30次充放电循环后样品电极容量保持率达到91.04%;La掺杂Al取代α-Ni(OH)2的样品材料电极在0.1C下放电,La掺杂摩尔含量为5%的样品材料电极放电比容量高达404.95mAh·g-1,放电中值电压为1.2968V,在1.0C倍率下的充放电循环测试结果表明,经30次充放电循环后电极比容量保持率为92.14%,显示了样品电极材料在较大倍率放电条件下较好的结构稳定性和充放电循环寿命。
研究La掺杂Zn/Al取代α-Ni(OH)2样品粉体材料的电化学活性效应及其作用机理发现,其电极材料在电极过程的电子转移数分别为1.247e和1.328e,均具有较好的充电接受能力和放电电子转移能力,导电能力和活化性能,比Zn/Al分别一元取代α-Ni(OH)2电极材料相比明显增强。同时,发现稀土元素物质La掺杂可以明显改善电极反应的充放电循环可逆性,并有效抑制镍电极上的析氧反应和降低电极反应的电化学极化和欧姆阻抗,提高其放电电压。
This paper summarized the present research situation of the electrode material Ni(OH)2 as positive electrode active material of the MH-Ni battery systemly. Based on the unique electron configuration of rare earth element materials and the 4f electron moving features and some electrochemical functional characteristics of the metal positive ions, through the homogeneous precipitation method with urea, this article studied the technological conditions and the behavior rule of nickel electrode active materialα-Ni(OH)2 prepared by rare earth La doped Zn/Al-substituted. Moreover, the sample material structural features, electrochemical activity and the electrochemical performance were studied. Simultaneously the electrochemical action effect mechanism of the samples as electrode materialα-Ni(OH)2 was discussed.
In this paper, we investigated the influence on the performance of electrode material by single factor with the urea content, reaction temperature, reaction time and dispersant. The results show that optimum process conditions of homogeneous precipitation method are that the molar ratio of urea: metal salt is 30:1, the reaction temperature is 90±1℃, and the time of the reaction is 3h, and the drying temperature is 60℃.
Zn/Al-substitutedα-Ni(OH)2 samples with doping different La contents were synthesized at optimum processing conditions. The research experimental result indicates that the morphology of samples is the adhesions of numerous sheet and spherical particles with more porous. The microstructure is characterized by the methods such as XRD, Raman, IR, and TG-DSC. The results show that comparing with only Zn/Al-substitutedα-Ni(OH)2, the La doped Zn/Al-substitutedα-nickel hydroxide electrode material have more structure defect and much bigger interlayer distance, and there are much more water molecular and the thermal stability becomes stronger. When the samples power of La doped Zn/Al-substituted were made as the nickel electrode active material, then assembled the MH-Ni simulation battery, the charge/discharge test shows that 5% La doped Zn-substituted sample has a relative high specific capacity (382.85mAh·g-1 at rate of 0.1C), the value of the middle discharge voltage reaches 1.2943V, while the discharge specific capacity reaches 359.85mAh/g at 1.0C and the capacity still remains 91.04% after 30 cycles. In addition, the material electrode of 5% molar ratio La doped Al-substituted sample whose middle discharge voltage 1.2968V is higher, the discharge specific capacity reaches 404.95 mAh/g at 0.1C. And the charge/discharge at the rate of 1.0C test shows that after 30 cycles the capacity still remains 92.14% and it has better structural stability and cycle life at high-rate discharge condition.
The research on the electrochemical activity and the electrochemical action effect mechanism of the La doped Zn/Al-substitutedα-nickel hydroxide samples discovery that the number of electrons transferred of the electrode materials are 1.247e and 1.328e in the electrode process, and there are much better charge acceptance and discharge capacity of electron transferred, electrical conductivity and activation performance. Furthermore, the cyclic reversibility of the electrode reaction improves after doping La and the rare earth La has good effect in inhibiting the oxygen evolution reaction of sample electrode, reducing the electrode reaction of the electrochemical polarization and ohmic resistance, and increasing the discharge voltage.
文中通过采用尿素用量、反应温度、反应时间、分散剂等单因素对电极材料性能影响的实验研究,确定出尿素均相沉淀法制备La掺杂Zn/Al取代α-Ni(OH)2稳定结构粉体材料的优化体系工艺条件为:乙醇-水溶液体系,尿素与金属盐比例为30:1、反应温度控制在90±1℃、搅拌反应3h、粉体干燥温度为60℃。
实验研究结果发现,在确定的优化工艺条件下制备出不同比例配制量的La掺杂Zn/Al取代α-Ni(OH)2样品粉体材料,形貌为无数片状微晶相互粘连且具有较多孔隙的类球状颗粒。样品材料经XRD、Raman、IR和TG-DSC测试结果表明,材料的微结构比Zn/Al取代α-Ni(OH)2具有较多的微结构缺陷和较大层间距,并含有较多结晶水,同时热稳定性明显增强。将其合成MH-Ni电池正极材料的电化学性能测试结果表明,当La掺杂摩尔用量为5%的Zn代α-Ni(OH)2的样品材料电极在0.1C放电下,其放电比容量达382.85mAh·g-1,放电中值电压较高并稳定于1.2943V,在1.0C下,放电比容量为359.85mAh·g-1,经30次充放电循环后样品电极容量保持率达到91.04%;La掺杂Al取代α-Ni(OH)2的样品材料电极在0.1C下放电,La掺杂摩尔含量为5%的样品材料电极放电比容量高达404.95mAh·g-1,放电中值电压为1.2968V,在1.0C倍率下的充放电循环测试结果表明,经30次充放电循环后电极比容量保持率为92.14%,显示了样品电极材料在较大倍率放电条件下较好的结构稳定性和充放电循环寿命。
研究La掺杂Zn/Al取代α-Ni(OH)2样品粉体材料的电化学活性效应及其作用机理发现,其电极材料在电极过程的电子转移数分别为1.247e和1.328e,均具有较好的充电接受能力和放电电子转移能力,导电能力和活化性能,比Zn/Al分别一元取代α-Ni(OH)2电极材料相比明显增强。同时,发现稀土元素物质La掺杂可以明显改善电极反应的充放电循环可逆性,并有效抑制镍电极上的析氧反应和降低电极反应的电化学极化和欧姆阻抗,提高其放电电压。
This paper summarized the present research situation of the electrode material Ni(OH)2 as positive electrode active material of the MH-Ni battery systemly. Based on the unique electron configuration of rare earth element materials and the 4f electron moving features and some electrochemical functional characteristics of the metal positive ions, through the homogeneous precipitation method with urea, this article studied the technological conditions and the behavior rule of nickel electrode active materialα-Ni(OH)2 prepared by rare earth La doped Zn/Al-substituted. Moreover, the sample material structural features, electrochemical activity and the electrochemical performance were studied. Simultaneously the electrochemical action effect mechanism of the samples as electrode materialα-Ni(OH)2 was discussed.
In this paper, we investigated the influence on the performance of electrode material by single factor with the urea content, reaction temperature, reaction time and dispersant. The results show that optimum process conditions of homogeneous precipitation method are that the molar ratio of urea: metal salt is 30:1, the reaction temperature is 90±1℃, and the time of the reaction is 3h, and the drying temperature is 60℃.
Zn/Al-substitutedα-Ni(OH)2 samples with doping different La contents were synthesized at optimum processing conditions. The research experimental result indicates that the morphology of samples is the adhesions of numerous sheet and spherical particles with more porous. The microstructure is characterized by the methods such as XRD, Raman, IR, and TG-DSC. The results show that comparing with only Zn/Al-substitutedα-Ni(OH)2, the La doped Zn/Al-substitutedα-nickel hydroxide electrode material have more structure defect and much bigger interlayer distance, and there are much more water molecular and the thermal stability becomes stronger. When the samples power of La doped Zn/Al-substituted were made as the nickel electrode active material, then assembled the MH-Ni simulation battery, the charge/discharge test shows that 5% La doped Zn-substituted sample has a relative high specific capacity (382.85mAh·g-1 at rate of 0.1C), the value of the middle discharge voltage reaches 1.2943V, while the discharge specific capacity reaches 359.85mAh/g at 1.0C and the capacity still remains 91.04% after 30 cycles. In addition, the material electrode of 5% molar ratio La doped Al-substituted sample whose middle discharge voltage 1.2968V is higher, the discharge specific capacity reaches 404.95 mAh/g at 0.1C. And the charge/discharge at the rate of 1.0C test shows that after 30 cycles the capacity still remains 92.14% and it has better structural stability and cycle life at high-rate discharge condition.
The research on the electrochemical activity and the electrochemical action effect mechanism of the La doped Zn/Al-substitutedα-nickel hydroxide samples discovery that the number of electrons transferred of the electrode materials are 1.247e and 1.328e in the electrode process, and there are much better charge acceptance and discharge capacity of electron transferred, electrical conductivity and activation performance. Furthermore, the cyclic reversibility of the electrode reaction improves after doping La and the rare earth La has good effect in inhibiting the oxygen evolution reaction of sample electrode, reducing the electrode reaction of the electrochemical polarization and ohmic resistance, and increasing the discharge voltage.
引文
[1]郭炳馄,李新海,杨松青.化学电源[M].中南工业大学出版社, 2000年
[2]杨书廷,尹艳红,丁玉珍,等. MH/Ni电池正负极材料研究进展(I)—正极材料[J].河南师范大学学报(自然科学版), 2000, 28(1): 206-210.
[3]袁安保,张鉴清,曹楚南.镍电极研究进展[J].电源技术, 2001, 25(1): 53-57.
[4]王殿龙,刘颖,戴长松,等.影响MH/Ni电池正极放电容量的因素[J].电池, 2004, 34(1): 64-66.
[5] Ramesh T N, Kamath P V. The effect of stacking faults on the electrochemical performance of nickel hydroxide electrodes [J]. Mater. Res. Bull., 2008, 43(11): 2827-2832.
[6] Bernard M C, Cortes R, Keddam M, et al. Structural defects and electrochemical reactivity ofβ-Ni(OH)2[J]. J. Power Sources, 1996, 63(2): 247-254.
[7] Liu C J, Li Y W. Synthesis and characterization of amorphousα-nickel hydroxide[J]. J. Alloys Compd., 2009, 478(1-2): 315-418.
[8]雷永泉,万群,石永康.新能源材料[M].天津大学出版社, 2000, 19-27.
[9]原鲜霞,王荫东,詹锋. MH-Ni电池镍电极膨胀抑制剂的研究[J].电源技术, 2000, 24(4): 192-196.
[10] Van der Ven A, Morgan D, Meng Y S, et al. Phase Stability of Nickel Hydroxides and Oxyhydroxides[J]. J. Electrochem. Soc., 2006, 53(2): A210-215.
[11]陈飞彪,蒋文全,安伟峰.新型氢氧化镍正极材料的制备和表征[J].分析科学学报, 2009, 25(2): 148-152.
[12]徐艳辉,陈长聘,吴俊,等.α-Ni(OH)2活性物质的初步探索[J].电源技术, 1999,23(4): 209-211.
[13]倪佩,覃奇贤,郭鹤桐. NiOOH/Ni(OH)2电极的发展历程及前景[J].电池, 1994, 24: 35-40.
[14]刘寿长,王兰典,董全锋,等.氢氧化镍活性、堆积密度、形貌与结构研究[J].电源技术, 1995, 19: 28-33.
[15]朱文化,张登君,柯家骏.氢氧化镍电极反应机理的研究[J].电源技术, 1996, 20: 235-240.
[16] Conway B E, Bourgault P L. Analytical relations between reaction order and tafel slope derivatives for electrocatalytic reactions involving chemisorbed intermediates[J]. J Electrochemica Acta, 1992, 37(1): 51-63.
[17] Conway B E, Gileadi E. Specificity of hydration of individual ions in relation to their adsorption at electrodes[J]. Inorganica Chemica Acta, 1980, 40:1933-1943.
[18] Barnard R, Randell C F, Tye F L. Studies concerning charged nickel hydroxide electrodes: Part III. Reversible potentials at low states of charge[J]. J Electroanalytical Chemistry, 1981, 119(1): 17-24.
[19] Barnard R, Randell C F, Tye F L. Migration of soluble cadmium species in nickel-cadmium cells[J]. J Power Sources, 1978, 13(2) :175-181.
[20] Barnard R, Randell C F, Tye F L. Thermal decomposition of managanese oxyhydroxide[J]. J Solid State Chemistry, 1980, 91(1): 81-93.
[21] Zimmerman A H , Effa P K. Zinc deposition during charging nickel/zinc batteries[J]. J Electrochemical Soc, 1984, 131(4): 709-713.
[22]肖慧明,王建明,陈惠,等. Al取代α-Ni(OH)2的有机溶剂法合成及其电化学性能[J].功能材料, 2003,34(5):553-555.
[23] Barnard R, Randell C F, Tye F L. The electrochemical reduction of manganese dioxide in acidic solutions: Part III. voltammetric peak 3 [J]. J Electroanalytical Chemistry, 1980, 110(1-3):145-158.
[24]张倩,徐艳辉,王晓琳.均相沉淀法制备α-Ni(OH)2及其电化学性能研究[J].稀有金属材料与工程, 2004, 33(12): 1291-1294.
[25]张秀英,胡志国,赵春霞.离子交换树脂法制备氢氧化镍和氧化镍超细微粒[J].功能材料, 2000, 31(1): 109-110.
[26] Delmas C, Braconnier J J, Borthomieu Y, et al. New families of cobalt substituted nickel oxyhydroxides and hydroxides obtained by soft chemistry [J]. Materials Research Bulletin, 1987, 22(6): 741-751.
[27] Demourgues-Guerlou L, Braconnier J J, Delmas C. Iron-Substituted Nickel Oxyhydroxides and Hydroxides Obtained by Chimie Douce [J]. J Solid State Chem., 1993, 104(2): 359-367.
[28]赵卫民,刘长久,宋莎,等.掺杂钇和铝的α-Ni(OH)2的结构及电化学性能[J].稀有金属, 2009, 33(3): 366-370.
[29] Zhang W, Jiang W, Yu L, et al. Effect of Nickel Hydroxide Composition on the Electrochemical Performance of Spherical Ni(OH)2 Positive Materials for Ni–MH Batteries[J]. Int. J. Hydrogen Energy, 2009, 34(1): 473-480.
[30]周震,阎杰,林进,等.纳米Ni(OH)2的质子扩散行为研究[J].电源技术, 1999, 23(6): 319-321.
[31] Dixit M, Kamath P V, Gopalakrishnan J. Zinc-substitutedα-nickel hydroxide as an electrode material for alkaline secondary cells [J]. Journal of the Electrochemical Society, 1999, 146(1): 79-82.
[32] Tessier C, Faure C, Guerlou-Demourgues L, et al. Electrochemical study of zinc-substituted nickel hydroxide [J]. Journal of the Electrochemical Society, 2002, 149(9): 1136-1145.
[33] Jeevanandam P, Koltypin Y, Gedanken A. Synthesis of nanosizedα-nickel hydroxide by a sonochemical method [J]. Nano Letters, 2001, 1(5): 263-266.
[34]曹晓燕,毛立彩,周作祥.氢氧化镍电极及其添加剂电池[J]. 1994, 24(5): 236-239.
[35]许娟,周益明,唐亚文,等.掺锰的氢氧化镍的制备、结构及充放电性能[J].南京师范大学学报, 2002, 2(4): 21-22.
[36] Doniat D, Bugnet B. Structure of nickel hydroxide-based electrode doped with cobalt foran electrochemical generator[P]. US5100748.1992.3.31.
[37] Zhang X Z, Gong Z X, Zhao S M. High-temperature characteristics of advanced Ni-MH batteries using nickel electrodes containing CaF2[J]. Journal of Power Sources, 2008, 175: 630-634.
[38] Faure C, Delmas C, Fouasier M. Preparation and characterization of cobalt-substitutedα-Ni(OH)2 stable in KOH medium Part I.α-Hydroxide with an ordered packing[J]. Journal of Power Sources, 1991, 35: 249-261.
[39] Mi X, Gao X P, Jiang C Y. High temperature performances of yttrium-doped spherical nickel hydroxide[J]. J Electrochemica Acta, 2004, 49: 3361-3366.
[40]杨书廷,陈改荣,尹艳红,等.掺杂稀土元素Ni(OH)2晶格的影响[J].电源技术, 2002, 26(4): 278~280.
[41]杨幼平,张平民,张友标,等.掺杂La的α-Ni(OH)2的制备及电化学性能[J].中南学学报, 2005, 36(6): 988-992.
[42] Oshitani M, Watada M, Shodai K. Effect of lanthanide oxide additives on the high-temperature charge acceptance characteristics of pasted nickel electrodes[J]. Electro chemical Soc, 2001, 148(1): 67-73.
[43]于涛,翟玉春,闫永恒.稀土在Ni/MH电池中应用研究[J].稀土, 2006, 27(4): 83-86.
[44] Liu C J, Song S, Li Y W, et al. Investigations on structure and proton diffusioncoefficient of rare earth ion (Y3+/Nd3+) and aluminum codopedα-Ni(OH)2[J]. Journal of Rare Earths, 2009, 478(1-2): 415-418.
[45]马丁F,查凯A1.用于电化学电池的氢氧化镍活性材料[P]. CN:1287693A,2001-03-141.
[46] Chen H, Wang J M, Pan T. Effects of coprecipitated zinc on the structure and electrochemical performance of Ni/Al-layered double hydroxide[J]. International Journal of Hydrogen Energy, 2002, 27(5): 489-496.
[47] Sugimoto A, Ishida S, Hanawa K. Nickel distribution in (Ni, Mg)/Al-layered double hydroxides[J]. J Electrochem Soc, 1999, 146(2): 251-255.
[48] Wang C Y, Zhong S, Bradhurst D H. Ni/Al/Co-substitutedα-Ni(OH)2 as electrode material in the nickel metal hydride cell[J]. Journal of Alloys and Compounds, 2002, 330-332: 802-805.
[49] Mufit A, Nathalie J, Jacques L. Effect of crystallinity on the electrochemical performance of nanometer Al-stabilizedα-nickel hydroxide [J]. Journal of the European Ceramic Society, 1998, 18(2): 1559-1564.
[50] Liu B, Yuan H, Zhang Y. Impedance of Al-substitutedα-nickel Hydroxide Electrode[J]. Int. J. Hydrogen Energy, 2004, 29: 453-458.
[51] Ramesh T N, Kamath P V, Shivakumara C. Correlation of structural disorder with the reversible discharge capacity of nickel hydroxide electrode[J]. J.Electrochem.Soc., 2005, (152): A806-A810.
[52]杨书廷,尹艳红,陈红军,等.不同镍盐合成的球形β-Ni(OH)2的充放电特性与结构变化规律[J].电化学, 2001, 7(3):310-315.
[53]吉特克内特W,瑞曼D,奥尔布里希A,等.制备金属氢氧化物的方法[J]. CNI 107440A, (BJ)1456, 1995:12.
[54] Jayshree R S, Vishnukamath P, Subbanna G N. The Effeet of Crystallinity on the Reversible Diseharge Capaeity of Nikel Hydroxide[J]. J.Eletroehem. Soc.2000, 147(6): 2029-2032.
[55]张倩,徐艳辉,王晓琳. Al取代α-Ni(OH)2的结构与电化学性能[J].稀有金属材料与工程, 2003, 32(10): 825-828.
[56]张玉敏,刘桂华,尹周澜.表面活性剂在干燥中控制粒子团聚的机理[J].矿冶工程, 2006, 26(6): 65-67.
[57]赵培正,成庆堂,赵林治,等.掺杂α-Ni(OH)2的制备、结构和电化学性能[J].电源技术, 1999, 23(5): 260-263.
[58]陈惠,王建明,潘淘. Al与Zn复合取代α-Ni(OH)2的结构和电化学性能[J].中国有色金属学报, 2003, 13(1): 85-90.
[59] Avena M J, Vasquez M V, Carbonio R E. Influence of MII/MIII ratio in surface-charging behavior of Zn-Al layered double hydroxides[J]. J Appl.Electrochem, 1994, 24(15): 256-260.
[60] Mavis B, Akinc M. Three-component Layer Double Hydroxides by Urea Precipitation: Structural Stability and Electrochemistry [J]. J. Power Sources, 2004, 134(2): 308-312.
[61]许娟,周益明,王青,等.掺铝的α型氢氧化镍的合成及其电化学性能[J].南京师范大学学报(工程技术版), 2003, 2(64): 79-81.
[62]吕文广,郑景宜.掺锰球形氢氧化镍微结构表征[J].稀有金属快报, 2005, 2(46): 37-39.
[63] Acharya R, Subbaiah T, Anand S, et al. Effect of precipitating agents on the physicochemical and electrolytic characteristics of nickel hydroxide[J]. Materials Letters, 2003, 57(20): 3089-3095.
[64] Acharya R, Subbaiah T, Anand S. Effect of preparation parameters on electrolytic behaviour of turbostratic nickel hydroxide [J]. Materials Chemistry and Physics, 2003, 81(1): 45-49.
[65] Acharya R, Subbaiah T, Anand S, et al. Effect of precipitating agents on the physicochemical and electrolytic characteristics of nickel hydroxide[J]. Materials Letters, 2003, 57(20): 3089-3095.
[66] Zhao Y L, Wang J M, Chen H. Different additives-substitutedα-nickel hydroxide prepar-ed by urea decomposition[J]. Electrochemica Acta, 2004, 50(1): 91-98.
[67] Zhao Y L, Wang J M, Chen H. Al-substitutedα-nickel hydroxide prepared by homogeneous precipitation method with urea[J]. International Journal of Hydrogen Energy, 2004, 29(8): 889-896.
[68] Zhang O, Xu Y H, Wang X L. Effect of preparation conditions on propertie of Al-substitutedα-Ni(OH)2 prepared by homogeneous precipitation[J]. Trans.Nonferrous Met.Soc China, 2005, 15(3): 653-658.
[69] Liu B, Wang X Y, Yuan H T, et al. Study of the effects of nanometerβ-Ni(OH)2 in nickel hydroxide electrodes[J].J Electrochemica Acta, 2005, 50(14): 2763-2769.
[70]刘元刚,唐致远,徐强,等. Al代α-Ni(OH)2的高温电化学性能[J].无机材料学报, 2008, 23(2): 291-294.
[71] Deabate S, Foergeot F, Henn F. X-ray diffraction and micro-Raman spectroscopy analysis of new nickel hydroxide obtained by electrodialysis[J]. J.Power Source, 2000, (87):125-136.
[72] Nathira Begum S, Muralidharan VS, Ahmed Basha C. The Influences of Some additives on Electrochemical Behaviour of Nickel Electrodes[J]. Int. J. Hydrogen Energy, 2009, 34(3): 1548-1555.
[73]刘寿长,王文祥,张元珍,等.制备条件对正极Ni(OH)2活性和堆积密度的影响[J].电源技术, 1994, 18: 1-5.
[74]葛华才,袁高清,范祥清,等.影响Ni(OH)2性能因素的研究[J].电池, 1999, 29: 150-153.
[75]陈滨,李小斌,冯岗涛.均匀沉淀法制备单分散颗粒研究进展[J].无机盐工业, 2006, 38(3): 9-12.
[76]张倩,徐艳辉,王晓琳.均相沉淀法制备α-Ni(OH)2及其电化学性能研究[J].稀有金属材料与工程, 2004, 33(12): 1291-1294.
[77]郭学益,黄凯,张多墨.尿素均相沉淀法制备均分散氧化亚镍粉末(I)——前驱体的制备研究[J].中南工业大学学报, 1999, 30(3): 255-259.
[78] Hu W K, Noreus D. Alpha Nickel Hydroxides as Lightweight Nickel Electrode Materials for Alkaline Rechargeable cells[J]. J Chem. Mater., 2003, 15: 974-978.
[79] Guerlou-Demourgues L, Delmas C. New manganese-substituted nickel hydroxides : Part 1. Crystal chemistry and physical characterization [J]. J Power Sources, 1994, 52(2): 269-274.
[80]郭学益,黄凯,张多墨.尿素均相沉淀法制备均分散氧化亚镍粉末(Ⅱ)——前驱体的热分解研究[J].中南工业大学学报, 1999, 30(4): 378-381.
[81] Delmas C, Borthomieu Y. Chimie Douce reaction: A new route to obtain well crystallized layer double hydroxides[J]. Solid State Chem, 1993, 104: 345-352.
[82] Watanabe K, Kikuoka T. Physical and Electrochemical Characteristics of Nickel Hydroxide as a Positive Material for Rechargeable Alkaline Batteries[J]. J. Appl. Electrochem., 1995, 25: 219-222.
[83]刘元刚,唐致远,徐强,等.α-Ni(OH)2的研究进展[J].电源技术, 2006, 18(7/8): 883-888.
[84]王占良,唐致远,雷荣.稳定的α-Ni(OH)2研究进展[J].辽宁化工, 2001, 30(2): 57-61.
[85]苏凌浩,范少华. Ni(OH)2电化学性能改进研究的现状和展望[J].化工学报, 2005, 26(1): 100-104.
[86] Ying T K, Gao X P, Hu W K. Studies on rechargeable Ni/MH batteries[J]. International Journal of Hydroxide Energy, 2006, 31(4): 525-530.
[87] Liu Y G, Tang Z Y, Xu Q. Effects of Doped Elements on Electrochemical Performanceof Ni(OH)2 material[J]. Chemical Research in Chinese Universities, 2007, 23(4): 452-455.
[88] Fetcenko M A, Ovshinsky S R, Reichman B. Recent advances in Ni/MH battery technology[J]. Journal of Power Sources, 2007, 33(4): 442-460.
[89]邓超,史鹏飞,曾佳. MH-Ni蓄电池正负极阻抗分布的电化学研究[J].电源技术, 2005, 29(4): 204-205.
[90] MU D, HATANO Y, ABE T, et al. Degradation kinetics of discharge capacity for amorphous Mg-Ni electrode[J]. J Alloys Comp, 2002, 334:232-237.
[91]翟大程,工建平,江志裕,等.镍在碱性溶液中阳极氧化膜的拉曼光谱[J].复旦学报(自然科学版), 1994, 6: 685-691.
[92] Delmas C, Borthomieu Y. Chimie Douce reaction: A new route to obtain well crystallized layer double hydroxides[J]. J Solid State Chem, 1993, 104: 345-352.
[93] Kamath P V, Dixit M, Indira L, Electrosynthesis of layered double hydroxides of nickel with trivalent cations [J] J Power Sources,1994,52(1): 93-97.
[94] Kamath P V, Dixit M, Indira L.Stabilizedα-Ni(OH)2 as electrode material for alkaline secondary cells[J]. J Electrochem Soc, 1994, 141(11): 2956-2959.
[95]周环波,周震涛.高Al含量Ni/Al双氢氧化物的结构及循环伏安特性[J].化学通报, 2006, 1: 31-35.
[96]周环波,周震涛. Al掺杂纳米Ni(OH)2的结构及电性能[J].电池, 2005, 35(3): 180-182.
[97]王丽坤,宋彩霞,刘章勇,等.层次结构α-Ni(OH)_2微球的制备和表征[J].稀有金属材料与工程, 2007, (S2): 56-60.
[98]王兴威,沙永香,唐琛明,等.掺杂α-Ni(OH)2制备及其电化学性能研究[J].电池工业, 2006, (05): 47-51.
[99] Oliva P, Leonardi J, Laurent J F, et al. Review of the structure and the electrochemistry of nickel hydroxides and oxy-hydroxides.J Power Sources 1982, 8: 229–255.
[100] Singh D. Characteristies and effects ofγ-NiOOH on cell performace and a method to quantify it in nickel electrodes [J]. Journal of the Electrochemical Society, 1998, 145(l):116-121.
[101] Shinyama K, Nakamura H, Nohma T. Improvement of high-and low temperature characteristics of nickel-metal hydride secondary battery using rare-earth compounds[J]. Journal of Alloys and Compounds, 2006, 408-412(9): 288-293.
[102] Wu J B, Tu J P,Wang X L,Zhang W K. Synthesis of nanoscale CoO particles and their effect on the positive electrodes of nickel-metal hydride batteries[J]. Int J Hydrogen Energy, 2007: 32(5):606–610.
[103] Nethravathi C, Ravishankar N, Shivakumara C, et al. Nanocomposites ofα-hydroxides of nickel and cobalt by delamination and co-stacking:enhanced stability of a-motifs in alkaline medium and electrochemical behaviour[J]. J Power Sources 2007, 172(2): 970–974.
[2]杨书廷,尹艳红,丁玉珍,等. MH/Ni电池正负极材料研究进展(I)—正极材料[J].河南师范大学学报(自然科学版), 2000, 28(1): 206-210.
[3]袁安保,张鉴清,曹楚南.镍电极研究进展[J].电源技术, 2001, 25(1): 53-57.
[4]王殿龙,刘颖,戴长松,等.影响MH/Ni电池正极放电容量的因素[J].电池, 2004, 34(1): 64-66.
[5] Ramesh T N, Kamath P V. The effect of stacking faults on the electrochemical performance of nickel hydroxide electrodes [J]. Mater. Res. Bull., 2008, 43(11): 2827-2832.
[6] Bernard M C, Cortes R, Keddam M, et al. Structural defects and electrochemical reactivity ofβ-Ni(OH)2[J]. J. Power Sources, 1996, 63(2): 247-254.
[7] Liu C J, Li Y W. Synthesis and characterization of amorphousα-nickel hydroxide[J]. J. Alloys Compd., 2009, 478(1-2): 315-418.
[8]雷永泉,万群,石永康.新能源材料[M].天津大学出版社, 2000, 19-27.
[9]原鲜霞,王荫东,詹锋. MH-Ni电池镍电极膨胀抑制剂的研究[J].电源技术, 2000, 24(4): 192-196.
[10] Van der Ven A, Morgan D, Meng Y S, et al. Phase Stability of Nickel Hydroxides and Oxyhydroxides[J]. J. Electrochem. Soc., 2006, 53(2): A210-215.
[11]陈飞彪,蒋文全,安伟峰.新型氢氧化镍正极材料的制备和表征[J].分析科学学报, 2009, 25(2): 148-152.
[12]徐艳辉,陈长聘,吴俊,等.α-Ni(OH)2活性物质的初步探索[J].电源技术, 1999,23(4): 209-211.
[13]倪佩,覃奇贤,郭鹤桐. NiOOH/Ni(OH)2电极的发展历程及前景[J].电池, 1994, 24: 35-40.
[14]刘寿长,王兰典,董全锋,等.氢氧化镍活性、堆积密度、形貌与结构研究[J].电源技术, 1995, 19: 28-33.
[15]朱文化,张登君,柯家骏.氢氧化镍电极反应机理的研究[J].电源技术, 1996, 20: 235-240.
[16] Conway B E, Bourgault P L. Analytical relations between reaction order and tafel slope derivatives for electrocatalytic reactions involving chemisorbed intermediates[J]. J Electrochemica Acta, 1992, 37(1): 51-63.
[17] Conway B E, Gileadi E. Specificity of hydration of individual ions in relation to their adsorption at electrodes[J]. Inorganica Chemica Acta, 1980, 40:1933-1943.
[18] Barnard R, Randell C F, Tye F L. Studies concerning charged nickel hydroxide electrodes: Part III. Reversible potentials at low states of charge[J]. J Electroanalytical Chemistry, 1981, 119(1): 17-24.
[19] Barnard R, Randell C F, Tye F L. Migration of soluble cadmium species in nickel-cadmium cells[J]. J Power Sources, 1978, 13(2) :175-181.
[20] Barnard R, Randell C F, Tye F L. Thermal decomposition of managanese oxyhydroxide[J]. J Solid State Chemistry, 1980, 91(1): 81-93.
[21] Zimmerman A H , Effa P K. Zinc deposition during charging nickel/zinc batteries[J]. J Electrochemical Soc, 1984, 131(4): 709-713.
[22]肖慧明,王建明,陈惠,等. Al取代α-Ni(OH)2的有机溶剂法合成及其电化学性能[J].功能材料, 2003,34(5):553-555.
[23] Barnard R, Randell C F, Tye F L. The electrochemical reduction of manganese dioxide in acidic solutions: Part III. voltammetric peak 3 [J]. J Electroanalytical Chemistry, 1980, 110(1-3):145-158.
[24]张倩,徐艳辉,王晓琳.均相沉淀法制备α-Ni(OH)2及其电化学性能研究[J].稀有金属材料与工程, 2004, 33(12): 1291-1294.
[25]张秀英,胡志国,赵春霞.离子交换树脂法制备氢氧化镍和氧化镍超细微粒[J].功能材料, 2000, 31(1): 109-110.
[26] Delmas C, Braconnier J J, Borthomieu Y, et al. New families of cobalt substituted nickel oxyhydroxides and hydroxides obtained by soft chemistry [J]. Materials Research Bulletin, 1987, 22(6): 741-751.
[27] Demourgues-Guerlou L, Braconnier J J, Delmas C. Iron-Substituted Nickel Oxyhydroxides and Hydroxides Obtained by Chimie Douce [J]. J Solid State Chem., 1993, 104(2): 359-367.
[28]赵卫民,刘长久,宋莎,等.掺杂钇和铝的α-Ni(OH)2的结构及电化学性能[J].稀有金属, 2009, 33(3): 366-370.
[29] Zhang W, Jiang W, Yu L, et al. Effect of Nickel Hydroxide Composition on the Electrochemical Performance of Spherical Ni(OH)2 Positive Materials for Ni–MH Batteries[J]. Int. J. Hydrogen Energy, 2009, 34(1): 473-480.
[30]周震,阎杰,林进,等.纳米Ni(OH)2的质子扩散行为研究[J].电源技术, 1999, 23(6): 319-321.
[31] Dixit M, Kamath P V, Gopalakrishnan J. Zinc-substitutedα-nickel hydroxide as an electrode material for alkaline secondary cells [J]. Journal of the Electrochemical Society, 1999, 146(1): 79-82.
[32] Tessier C, Faure C, Guerlou-Demourgues L, et al. Electrochemical study of zinc-substituted nickel hydroxide [J]. Journal of the Electrochemical Society, 2002, 149(9): 1136-1145.
[33] Jeevanandam P, Koltypin Y, Gedanken A. Synthesis of nanosizedα-nickel hydroxide by a sonochemical method [J]. Nano Letters, 2001, 1(5): 263-266.
[34]曹晓燕,毛立彩,周作祥.氢氧化镍电极及其添加剂电池[J]. 1994, 24(5): 236-239.
[35]许娟,周益明,唐亚文,等.掺锰的氢氧化镍的制备、结构及充放电性能[J].南京师范大学学报, 2002, 2(4): 21-22.
[36] Doniat D, Bugnet B. Structure of nickel hydroxide-based electrode doped with cobalt foran electrochemical generator[P]. US5100748.1992.3.31.
[37] Zhang X Z, Gong Z X, Zhao S M. High-temperature characteristics of advanced Ni-MH batteries using nickel electrodes containing CaF2[J]. Journal of Power Sources, 2008, 175: 630-634.
[38] Faure C, Delmas C, Fouasier M. Preparation and characterization of cobalt-substitutedα-Ni(OH)2 stable in KOH medium Part I.α-Hydroxide with an ordered packing[J]. Journal of Power Sources, 1991, 35: 249-261.
[39] Mi X, Gao X P, Jiang C Y. High temperature performances of yttrium-doped spherical nickel hydroxide[J]. J Electrochemica Acta, 2004, 49: 3361-3366.
[40]杨书廷,陈改荣,尹艳红,等.掺杂稀土元素Ni(OH)2晶格的影响[J].电源技术, 2002, 26(4): 278~280.
[41]杨幼平,张平民,张友标,等.掺杂La的α-Ni(OH)2的制备及电化学性能[J].中南学学报, 2005, 36(6): 988-992.
[42] Oshitani M, Watada M, Shodai K. Effect of lanthanide oxide additives on the high-temperature charge acceptance characteristics of pasted nickel electrodes[J]. Electro chemical Soc, 2001, 148(1): 67-73.
[43]于涛,翟玉春,闫永恒.稀土在Ni/MH电池中应用研究[J].稀土, 2006, 27(4): 83-86.
[44] Liu C J, Song S, Li Y W, et al. Investigations on structure and proton diffusioncoefficient of rare earth ion (Y3+/Nd3+) and aluminum codopedα-Ni(OH)2[J]. Journal of Rare Earths, 2009, 478(1-2): 415-418.
[45]马丁F,查凯A1.用于电化学电池的氢氧化镍活性材料[P]. CN:1287693A,2001-03-141.
[46] Chen H, Wang J M, Pan T. Effects of coprecipitated zinc on the structure and electrochemical performance of Ni/Al-layered double hydroxide[J]. International Journal of Hydrogen Energy, 2002, 27(5): 489-496.
[47] Sugimoto A, Ishida S, Hanawa K. Nickel distribution in (Ni, Mg)/Al-layered double hydroxides[J]. J Electrochem Soc, 1999, 146(2): 251-255.
[48] Wang C Y, Zhong S, Bradhurst D H. Ni/Al/Co-substitutedα-Ni(OH)2 as electrode material in the nickel metal hydride cell[J]. Journal of Alloys and Compounds, 2002, 330-332: 802-805.
[49] Mufit A, Nathalie J, Jacques L. Effect of crystallinity on the electrochemical performance of nanometer Al-stabilizedα-nickel hydroxide [J]. Journal of the European Ceramic Society, 1998, 18(2): 1559-1564.
[50] Liu B, Yuan H, Zhang Y. Impedance of Al-substitutedα-nickel Hydroxide Electrode[J]. Int. J. Hydrogen Energy, 2004, 29: 453-458.
[51] Ramesh T N, Kamath P V, Shivakumara C. Correlation of structural disorder with the reversible discharge capacity of nickel hydroxide electrode[J]. J.Electrochem.Soc., 2005, (152): A806-A810.
[52]杨书廷,尹艳红,陈红军,等.不同镍盐合成的球形β-Ni(OH)2的充放电特性与结构变化规律[J].电化学, 2001, 7(3):310-315.
[53]吉特克内特W,瑞曼D,奥尔布里希A,等.制备金属氢氧化物的方法[J]. CNI 107440A, (BJ)1456, 1995:12.
[54] Jayshree R S, Vishnukamath P, Subbanna G N. The Effeet of Crystallinity on the Reversible Diseharge Capaeity of Nikel Hydroxide[J]. J.Eletroehem. Soc.2000, 147(6): 2029-2032.
[55]张倩,徐艳辉,王晓琳. Al取代α-Ni(OH)2的结构与电化学性能[J].稀有金属材料与工程, 2003, 32(10): 825-828.
[56]张玉敏,刘桂华,尹周澜.表面活性剂在干燥中控制粒子团聚的机理[J].矿冶工程, 2006, 26(6): 65-67.
[57]赵培正,成庆堂,赵林治,等.掺杂α-Ni(OH)2的制备、结构和电化学性能[J].电源技术, 1999, 23(5): 260-263.
[58]陈惠,王建明,潘淘. Al与Zn复合取代α-Ni(OH)2的结构和电化学性能[J].中国有色金属学报, 2003, 13(1): 85-90.
[59] Avena M J, Vasquez M V, Carbonio R E. Influence of MII/MIII ratio in surface-charging behavior of Zn-Al layered double hydroxides[J]. J Appl.Electrochem, 1994, 24(15): 256-260.
[60] Mavis B, Akinc M. Three-component Layer Double Hydroxides by Urea Precipitation: Structural Stability and Electrochemistry [J]. J. Power Sources, 2004, 134(2): 308-312.
[61]许娟,周益明,王青,等.掺铝的α型氢氧化镍的合成及其电化学性能[J].南京师范大学学报(工程技术版), 2003, 2(64): 79-81.
[62]吕文广,郑景宜.掺锰球形氢氧化镍微结构表征[J].稀有金属快报, 2005, 2(46): 37-39.
[63] Acharya R, Subbaiah T, Anand S, et al. Effect of precipitating agents on the physicochemical and electrolytic characteristics of nickel hydroxide[J]. Materials Letters, 2003, 57(20): 3089-3095.
[64] Acharya R, Subbaiah T, Anand S. Effect of preparation parameters on electrolytic behaviour of turbostratic nickel hydroxide [J]. Materials Chemistry and Physics, 2003, 81(1): 45-49.
[65] Acharya R, Subbaiah T, Anand S, et al. Effect of precipitating agents on the physicochemical and electrolytic characteristics of nickel hydroxide[J]. Materials Letters, 2003, 57(20): 3089-3095.
[66] Zhao Y L, Wang J M, Chen H. Different additives-substitutedα-nickel hydroxide prepar-ed by urea decomposition[J]. Electrochemica Acta, 2004, 50(1): 91-98.
[67] Zhao Y L, Wang J M, Chen H. Al-substitutedα-nickel hydroxide prepared by homogeneous precipitation method with urea[J]. International Journal of Hydrogen Energy, 2004, 29(8): 889-896.
[68] Zhang O, Xu Y H, Wang X L. Effect of preparation conditions on propertie of Al-substitutedα-Ni(OH)2 prepared by homogeneous precipitation[J]. Trans.Nonferrous Met.Soc China, 2005, 15(3): 653-658.
[69] Liu B, Wang X Y, Yuan H T, et al. Study of the effects of nanometerβ-Ni(OH)2 in nickel hydroxide electrodes[J].J Electrochemica Acta, 2005, 50(14): 2763-2769.
[70]刘元刚,唐致远,徐强,等. Al代α-Ni(OH)2的高温电化学性能[J].无机材料学报, 2008, 23(2): 291-294.
[71] Deabate S, Foergeot F, Henn F. X-ray diffraction and micro-Raman spectroscopy analysis of new nickel hydroxide obtained by electrodialysis[J]. J.Power Source, 2000, (87):125-136.
[72] Nathira Begum S, Muralidharan VS, Ahmed Basha C. The Influences of Some additives on Electrochemical Behaviour of Nickel Electrodes[J]. Int. J. Hydrogen Energy, 2009, 34(3): 1548-1555.
[73]刘寿长,王文祥,张元珍,等.制备条件对正极Ni(OH)2活性和堆积密度的影响[J].电源技术, 1994, 18: 1-5.
[74]葛华才,袁高清,范祥清,等.影响Ni(OH)2性能因素的研究[J].电池, 1999, 29: 150-153.
[75]陈滨,李小斌,冯岗涛.均匀沉淀法制备单分散颗粒研究进展[J].无机盐工业, 2006, 38(3): 9-12.
[76]张倩,徐艳辉,王晓琳.均相沉淀法制备α-Ni(OH)2及其电化学性能研究[J].稀有金属材料与工程, 2004, 33(12): 1291-1294.
[77]郭学益,黄凯,张多墨.尿素均相沉淀法制备均分散氧化亚镍粉末(I)——前驱体的制备研究[J].中南工业大学学报, 1999, 30(3): 255-259.
[78] Hu W K, Noreus D. Alpha Nickel Hydroxides as Lightweight Nickel Electrode Materials for Alkaline Rechargeable cells[J]. J Chem. Mater., 2003, 15: 974-978.
[79] Guerlou-Demourgues L, Delmas C. New manganese-substituted nickel hydroxides : Part 1. Crystal chemistry and physical characterization [J]. J Power Sources, 1994, 52(2): 269-274.
[80]郭学益,黄凯,张多墨.尿素均相沉淀法制备均分散氧化亚镍粉末(Ⅱ)——前驱体的热分解研究[J].中南工业大学学报, 1999, 30(4): 378-381.
[81] Delmas C, Borthomieu Y. Chimie Douce reaction: A new route to obtain well crystallized layer double hydroxides[J]. Solid State Chem, 1993, 104: 345-352.
[82] Watanabe K, Kikuoka T. Physical and Electrochemical Characteristics of Nickel Hydroxide as a Positive Material for Rechargeable Alkaline Batteries[J]. J. Appl. Electrochem., 1995, 25: 219-222.
[83]刘元刚,唐致远,徐强,等.α-Ni(OH)2的研究进展[J].电源技术, 2006, 18(7/8): 883-888.
[84]王占良,唐致远,雷荣.稳定的α-Ni(OH)2研究进展[J].辽宁化工, 2001, 30(2): 57-61.
[85]苏凌浩,范少华. Ni(OH)2电化学性能改进研究的现状和展望[J].化工学报, 2005, 26(1): 100-104.
[86] Ying T K, Gao X P, Hu W K. Studies on rechargeable Ni/MH batteries[J]. International Journal of Hydroxide Energy, 2006, 31(4): 525-530.
[87] Liu Y G, Tang Z Y, Xu Q. Effects of Doped Elements on Electrochemical Performanceof Ni(OH)2 material[J]. Chemical Research in Chinese Universities, 2007, 23(4): 452-455.
[88] Fetcenko M A, Ovshinsky S R, Reichman B. Recent advances in Ni/MH battery technology[J]. Journal of Power Sources, 2007, 33(4): 442-460.
[89]邓超,史鹏飞,曾佳. MH-Ni蓄电池正负极阻抗分布的电化学研究[J].电源技术, 2005, 29(4): 204-205.
[90] MU D, HATANO Y, ABE T, et al. Degradation kinetics of discharge capacity for amorphous Mg-Ni electrode[J]. J Alloys Comp, 2002, 334:232-237.
[91]翟大程,工建平,江志裕,等.镍在碱性溶液中阳极氧化膜的拉曼光谱[J].复旦学报(自然科学版), 1994, 6: 685-691.
[92] Delmas C, Borthomieu Y. Chimie Douce reaction: A new route to obtain well crystallized layer double hydroxides[J]. J Solid State Chem, 1993, 104: 345-352.
[93] Kamath P V, Dixit M, Indira L, Electrosynthesis of layered double hydroxides of nickel with trivalent cations [J] J Power Sources,1994,52(1): 93-97.
[94] Kamath P V, Dixit M, Indira L.Stabilizedα-Ni(OH)2 as electrode material for alkaline secondary cells[J]. J Electrochem Soc, 1994, 141(11): 2956-2959.
[95]周环波,周震涛.高Al含量Ni/Al双氢氧化物的结构及循环伏安特性[J].化学通报, 2006, 1: 31-35.
[96]周环波,周震涛. Al掺杂纳米Ni(OH)2的结构及电性能[J].电池, 2005, 35(3): 180-182.
[97]王丽坤,宋彩霞,刘章勇,等.层次结构α-Ni(OH)_2微球的制备和表征[J].稀有金属材料与工程, 2007, (S2): 56-60.
[98]王兴威,沙永香,唐琛明,等.掺杂α-Ni(OH)2制备及其电化学性能研究[J].电池工业, 2006, (05): 47-51.
[99] Oliva P, Leonardi J, Laurent J F, et al. Review of the structure and the electrochemistry of nickel hydroxides and oxy-hydroxides.J Power Sources 1982, 8: 229–255.
[100] Singh D. Characteristies and effects ofγ-NiOOH on cell performace and a method to quantify it in nickel electrodes [J]. Journal of the Electrochemical Society, 1998, 145(l):116-121.
[101] Shinyama K, Nakamura H, Nohma T. Improvement of high-and low temperature characteristics of nickel-metal hydride secondary battery using rare-earth compounds[J]. Journal of Alloys and Compounds, 2006, 408-412(9): 288-293.
[102] Wu J B, Tu J P,Wang X L,Zhang W K. Synthesis of nanoscale CoO particles and their effect on the positive electrodes of nickel-metal hydride batteries[J]. Int J Hydrogen Energy, 2007: 32(5):606–610.
[103] Nethravathi C, Ravishankar N, Shivakumara C, et al. Nanocomposites ofα-hydroxides of nickel and cobalt by delamination and co-stacking:enhanced stability of a-motifs in alkaline medium and electrochemical behaviour[J]. J Power Sources 2007, 172(2): 970–974.