稀土系过化学计量比贮氢合金Re（NiMMn）_（5+X）的组织及电化学性能
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摘要
为了提高AB_5型贮氢电极合金在市场中的竞争力，满足我国Ni／MH电池产业的发展及贮氢电极合金对更高的性能价格比的要求，本文确定以研究和优化AB_5型低成本无Co贮氢电极合金为目标，采用过化学计量比、高温长时间均匀化退火、合金成分优化的方式对合金相结构及电化学性能的影响规律进行深入的分析和讨论。力求提高合金的综合电化学性能，为开发低成本长寿命稀土系贮氢电极合金奠定基础。根据文献报道[13]，本课题拟选用LaNi_(4.75)Mn_(1.25)作研究的基础成分，在该合金成分的基础上，通过采用1273K 168h的退火处理、合金优化、降低合金计量比的办法改善合金的综合电化学性能。并对合金的组织结构的变化，合金元素对电化学性能影响规律做以分析和总结。
LaNi_(4.75)Mn_(1.25)高温退火合金及快凝合金的中子衍射及电化学行为表明，Mn元素在晶体结构中通过两种占位方式影响合金电极的循环稳定性；①形成2c哑铃占位②3g位置的占有状况，在一定范围内3g位置占有数增大时有利于合金电极的稳定性。
过化学计量比合金电极的容量主要与过化学计量比大小，3g位置上替代元素的种类和数量有关。一方面计量比增大，合金结构中2e位置哑铃结构数增加，这样会减少氢原子在6m间隙位置的占有数；另一方面，合金优化后由于原子尺寸差异、合金元素电子结构以及合金吸放氢热力及学动力学性能的变化均会对合金电极的容量产生影响。
对合金B端元素的优化结果表明，采用少量的非Co过渡族金属Cu、Fe、Cr、Sn替代LaNi_(4.75)Mn_(1.25)合金中的Ni能有效改善合金的电化学循环稳定性但个别合金的电化学容量有所降低。而使用这些元素用来替代合金中的Mn元素会明显降低合金的电化学循环稳定性。但使合金的活化性能及循环初始容量有所改善。采用Ce、Nd、Pr替代LaNi_(4.75)Mn_(1.25)合金A端的La元素有助于提高合金综合电化学性能。Ce、Nd在提高基础合金的循环稳定性方面表现突出而Pr在对合金的容量方面影响作用大。
对LaNi_(4.68)Mn_(0.93)合金电化学性能的测试表明，降低LaNi_(4.75)Mn_(1.25)合金计量比能够提高合金的电化学活化和循环容量。对LaNi_(4.48)Cu_(0.2)Mn_(0.93)合金电化学性能的测试表明，通过降低合金过化学计量比，使用少量B端Cu元素优化的方式可以得到综合电化学性能较好的合金。
To improve the competition ability of AB5 type hydrogen storage electrode alloy in the market, meet the need of the Ni/ MH battery industry's development of our nation and the need for high cost performance of Ni/MH electrode alloy, this paper will lays emphasis on investigating Co-free hydrogen storage alloys and optimizing its composition. By means of over stoichiometry, composition optimization, keeping annealing at high temperature for long time, the effects of the composition on phase structure and electrochemical properties were studied systemically so as to improve the comprehensive electrochemical properties. According to reference [13], LaNi4.75Mn1.25 was choosed to be our basic composition. Through the method of 1273K 168h annealing treatment, composition optimization and reducing stoichiometry ratio of alloys, the feasibility of improving the alloy's comprehensive electrochemical properties was investigated.
Neutron diffraction and electrochemical behavior of LaNi4.75Mn1.25 annealing and quenching alloys showed that the element Mn in the alloy may influence the electrochemical cycle stability of metal hydride electrode by occupying two atom site in the lattice: (1) dumbbells pairs of B-type atoms occupying the atom site 2e (2) occupation of atom site 3g , increase in amount of Mn at 3g site will do good to the cycle stability of metal hydride electrode in some extent.
The capacity of over stoichiometric metal hydride electrodes is in relationship with the extent of over-stoichiometry, the atom sort and its amount. On the one hand, the amount of dumbbell pairs of B-type atoms will decreases the amount of H atom occupying interstitial site 6m; on the other hand , the difference of atom size, the influence of electron structure of alloying elements, the variation in thermodynamics and kinetics of absorption and desorption processes will all affect the electrochemical capacity.
The experimental result of optimizing B-type elements of the alloy indicated using less transition elements (Cu, Fe, Cr, Sn) to substitute for Ni of alloy LaNi4.75Mn1.25 improved the cycle stability of metal hydride electrode, but some of them suffer from decrease of electrochemical capacity. Meanwhile, when using these alloying elements to substitute for element Mn will reduce the cycle stability of metal hydride electrodes greatly, but increase the maximum cycle capacity of hydride electrodes. The experimental result also indicated when substituting Ce, Pr, Nd.for Ni will improve the comprehensive electrochemical performances. Ce, Nd can benefit the cycle stability of the hydride electrodes, while Pr can improve the electrochemical capacity of hydride electrodes.
The result of electrochemical measurement of LaNi4.68Mn0.93 indicated decrease in the stoichiometry of LaNi4.75Mn1.25 can increase the electrochemical capacity. The electrochemical performances of LaNi4.48Cuo.2Mn0.93 indicated that adopting lower
stoichiometry and less B-site element such as Cu substituting for Ni of LaNi4.75Mn1.25 could achieve better comprehensive electrochemical properties.
LaNi_(4.75)Mn_(1.25)高温退火合金及快凝合金的中子衍射及电化学行为表明，Mn元素在晶体结构中通过两种占位方式影响合金电极的循环稳定性；①形成2c哑铃占位②3g位置的占有状况，在一定范围内3g位置占有数增大时有利于合金电极的稳定性。
过化学计量比合金电极的容量主要与过化学计量比大小，3g位置上替代元素的种类和数量有关。一方面计量比增大，合金结构中2e位置哑铃结构数增加，这样会减少氢原子在6m间隙位置的占有数；另一方面，合金优化后由于原子尺寸差异、合金元素电子结构以及合金吸放氢热力及学动力学性能的变化均会对合金电极的容量产生影响。
对合金B端元素的优化结果表明，采用少量的非Co过渡族金属Cu、Fe、Cr、Sn替代LaNi_(4.75)Mn_(1.25)合金中的Ni能有效改善合金的电化学循环稳定性但个别合金的电化学容量有所降低。而使用这些元素用来替代合金中的Mn元素会明显降低合金的电化学循环稳定性。但使合金的活化性能及循环初始容量有所改善。采用Ce、Nd、Pr替代LaNi_(4.75)Mn_(1.25)合金A端的La元素有助于提高合金综合电化学性能。Ce、Nd在提高基础合金的循环稳定性方面表现突出而Pr在对合金的容量方面影响作用大。
对LaNi_(4.68)Mn_(0.93)合金电化学性能的测试表明，降低LaNi_(4.75)Mn_(1.25)合金计量比能够提高合金的电化学活化和循环容量。对LaNi_(4.48)Cu_(0.2)Mn_(0.93)合金电化学性能的测试表明，通过降低合金过化学计量比，使用少量B端Cu元素优化的方式可以得到综合电化学性能较好的合金。
To improve the competition ability of AB5 type hydrogen storage electrode alloy in the market, meet the need of the Ni/ MH battery industry's development of our nation and the need for high cost performance of Ni/MH electrode alloy, this paper will lays emphasis on investigating Co-free hydrogen storage alloys and optimizing its composition. By means of over stoichiometry, composition optimization, keeping annealing at high temperature for long time, the effects of the composition on phase structure and electrochemical properties were studied systemically so as to improve the comprehensive electrochemical properties. According to reference [13], LaNi4.75Mn1.25 was choosed to be our basic composition. Through the method of 1273K 168h annealing treatment, composition optimization and reducing stoichiometry ratio of alloys, the feasibility of improving the alloy's comprehensive electrochemical properties was investigated.
Neutron diffraction and electrochemical behavior of LaNi4.75Mn1.25 annealing and quenching alloys showed that the element Mn in the alloy may influence the electrochemical cycle stability of metal hydride electrode by occupying two atom site in the lattice: (1) dumbbells pairs of B-type atoms occupying the atom site 2e (2) occupation of atom site 3g , increase in amount of Mn at 3g site will do good to the cycle stability of metal hydride electrode in some extent.
The capacity of over stoichiometric metal hydride electrodes is in relationship with the extent of over-stoichiometry, the atom sort and its amount. On the one hand, the amount of dumbbell pairs of B-type atoms will decreases the amount of H atom occupying interstitial site 6m; on the other hand , the difference of atom size, the influence of electron structure of alloying elements, the variation in thermodynamics and kinetics of absorption and desorption processes will all affect the electrochemical capacity.
The experimental result of optimizing B-type elements of the alloy indicated using less transition elements (Cu, Fe, Cr, Sn) to substitute for Ni of alloy LaNi4.75Mn1.25 improved the cycle stability of metal hydride electrode, but some of them suffer from decrease of electrochemical capacity. Meanwhile, when using these alloying elements to substitute for element Mn will reduce the cycle stability of metal hydride electrodes greatly, but increase the maximum cycle capacity of hydride electrodes. The experimental result also indicated when substituting Ce, Pr, Nd.for Ni will improve the comprehensive electrochemical performances. Ce, Nd can benefit the cycle stability of the hydride electrodes, while Pr can improve the electrochemical capacity of hydride electrodes.
The result of electrochemical measurement of LaNi4.68Mn0.93 indicated decrease in the stoichiometry of LaNi4.75Mn1.25 can increase the electrochemical capacity. The electrochemical performances of LaNi4.48Cuo.2Mn0.93 indicated that adopting lower
stoichiometry and less B-site element such as Cu substituting for Ni of LaNi4.75Mn1.25 could achieve better comprehensive electrochemical properties.
引文
[1] Vuncht J H N, Kuijpers FAet al. Philips Res. Rept., 1970,25:133
[2] E. W Justi, H.H.Ewe,H. Stephan, Energy Conversion 13(1973)109
[3] A. Percheron-Guegan, J. cC. Achard, J. Sarradin, et al, Geilo,Norway, Pergamon Press,New York,1978 .p.485
[4] M.H.H.Ban Rikswiek, et al,. Proceedings International Symposium On Hydrides For Energy Storage, Geilo,Norway, Pergamon Press, Now York, 1978 .p.261
[5] J.J.G.Willems, Philips J. Res. 39(Suppl.1)(1984)
[6] M.Ikowa, H. Kawano, et al,.Eur.Patent, Appl.#0271043(1987)
[7] 大角泰章，贮氢合金，[J]．国外金属加工，1995，(3)：29—37
[8] 李全安，陈云贵，等，高性能贮氢合金电极的成分设计，[J]．电源技术，200024(4)：246—249
[9] 鲁辉，高学平，宋得英等，[J]．稀土，1995，16(5)：28
[10] Kohno T, Yoshida H, Kawashima F, et al. J. Alloys Comp, 2000(311)L5～L7
[11] Kadir K, Kuriyama N, Sakai T, et al.J. Alloys Comp,1999(284):145][Kadir K, Askai T, Uehara L J. Alloys Comp,1999(287):264
[12] 王仲民，彭成红，李祖鑫，朱敏，Mg—Ni系储氢合金电极研究最新进展，[J]．电池，2000，30(6)：
[13] P.H.L.Notten, M. Latroche. et al., J. Electrochem. Soc. 1999, 146 (9) 3181-3189
[14] P.H.L.Notten, J.L.C.Damms and R.E.F.Einerhand, J.Alloys Comp, 1994, (210) 233-241
[15] T.Voigt, JJ.Rilly, J. R. Johnson, et, al. J. Electrochemical and solid-state Letter 1999,2 (3): 111-114 1999, 2(3): 111-114].
[16] 袁满雪、韩剑文、赖成明，J．南开大学学报(自然科学)，1998，31(1)
[17] Westlake D G J. Less-Common Met, 1983(91):275
[18] 王超群，靳红梅等 稀土储氢合金的相结构的研究，电源技术，1998．6，3(22)
[19] L.O. Valoen, A. Zaluska, L. Zaluski,, et al, J. Alloys comp 2000 (306): 235
[20] percher～L. O. Valocn, A. Zaluska, L. Zaluski, et al. J. Alloys Comp, 2000(306):35～40
[21] percher～D. Chartouni, E Meli, A. Zuttel, et al. J. Alloys and Comp. 1996 (241): 60
[22] Msluiter. M. Takahashi, Y. Kawazoe, J. Alloys and Comp 1997(248):90
[23] T. SaKai, K. Oguro, H. Miyamura, N. Kuriyama, et al. J. Less-Common Met. 161(1990):193
[24] J. H. N. van Vucht, F. A. Kuijpers, H. C. A. M. Bruning, Philips Res. repts. 25 (1970) 133
[25] K. H. J. Bushow, H. H. Van Mal, J. Less-common Met. 29 (1972) 203
[26] A. Percher-Guegan, C.lartigue, J. C. Achard. J. Less-common Met. 109(1985):287
[27] Uchida H, Tada M, Huang YC. J Less-Common Met 1982(88):81
[28] Osumi Y, Suzuki H, Kato A. J Chem Soc. Jpn 1981(9):1493 (in Japanese)
[29] J. Liu, E. Lee Huston, J. Less-Common Met. 90(1983):1
[30] T. SaKai, H. MiYamura, N. Kuriyama, et al. J. Electrochem. Soc. 137(1990):795
[31] 胡子龙，贮氢材料，化学工业出版社，2002，8
[32] Y. Osumi, H. Suzuki, A. Kato, K. Oguru, S. Kawai, M. Kaneko, J.Less-Common Met. 89 (1983) 287-292.
[33] V.N. Verbetsky, R.A. Sirotina, E.A. Umerenko, Int. J. Hydrogen Energy 21 (1996) 935-938.
[34] Chiaki Iwakura, Kazuhiro Ohkawa, Hiroshi Senoh, J. Electrochimica Acta 2001 (46):4383—4388
[35] 朱光明 浙江大学博士学位论文，1997．8
[36] Kadama K K, Kirabata O Y, et al.(Matsushita Electric Industrial Co. Ltd)US5512385. 1996
[37] Yamamoto M, Kanda M. J. Allys Comp, 1997, 253～254:660～664
[38] 靳红梅等 金属学报，1998，16(4)：348～352
[39] Tokuichi H. (Japan Storage Battery Co. , Ltd). EP0451575A1. 1991]
[40] 江建军，金国冻，雷永泉等．电源技术，1997，21(2)：61
[41] 郭靖洪等 电源技术，2000，24(5)：265～266，287
[42] 王旭东，张羊换，林玉芳等 包头钢铁学院学报，2003，22(4)：318～322
[43] Adzie G D, Johnson J R, Reilly J J, etal. J. Electrochem Soe. 1995,142(10):34243428
[44] 贺维勇，高国中J．中国有色金属学报，1998，8(1)
[45] 卞永新，郭小燕，孙东升等，J．稀土，1999，20(4)：39～41
[46] Y. Osumi, H. Suzuki, A. Kato, M. Nakane, J. Loss-Common Met.84 (1982) 99-106.
[47] 靳红梅，李国勋等，J．电源技术，1998，22(1)：170
[48] 侯万良，常新春，王建强，郝云彦，胡壮麒，气体雾化MmNi_(3.55)Co_(0.75)Mn_(0.3)Al_(0.4)微晶贮氢合金的活化，[J]．技术功能材料，1998，5(3)：121-123
[49] 王秋娟，李全安，陈云贵，涂铭旌，快淬对贮氢合金组织和电化学性能的影响，[J]．洛阳工学院学报，2001，22(2)：8-11
[50] 李传健，王新林，李岫梅，快淬 ABs 型贮氢合金研究，[J]．金属功能材料，1998，5(5)：218-231
[51] SHIOW A L.KOST M E. KUZNETSOV N T. et al. The system LaNi_(5-)H_5, [J]. J Less-Common Metals,1988.144:23-30
[52] BOONSTRA A H. BERNADS N M. LIPP1TS G J M. J Less-Common Metals, 1990.159:327-336
[53] J.J. Reilly, G.D.Adzic,J.R.Johnson, et al.,. J. Alloys and Comp. 293-295,(1999):569-582
[54] Kanda M, Yammoto M, Karmo K, et al., J Alloys Comp. 1997,253-254:579-582
[55] 钱存富，杜昊，王洪祥[J]．稀有金属材料与工程，1999．28(6)：
[56] 周志刚，谭玲生，朴英子等[J]．电源技术，1997，21(4)：153-156
[57] Willems J J G, Buschow K. H. J. J. Less-Common Metals,1991,159:127
[58] Adzic G. D, Johnxon J R, et al. J. Alloy and Comp,1997(253-254):579～582
[59] T.Sakai, K.Oguro, H.Miyamura, N.Kuriyama, et al. J. Less-Common Met. 1990(161):193(1.304 )
[60] T/ Sakai, T/Hazama, H. Miyamura, N. Kuriyama, H, Ishikawa, J. Alloys Comp. 1992(180) 32
[61] Y.Q. Lei, Z.P Li, C.p. Chen, et al.J.Less-Common Met. 1991(253-254)579
[62] Tang Wei Zhong, Sun Guang Fei. J.Alloy and Comp,1994(203):195
[63] Li ChuanJian, Wang XinLin.J.Alloy and Comp,1999(286):270
[64] F.Meli, A.Zuttel and L.Schlapbach, J. Alloy and Comp,202(1993)81
[65] Kadama K K, Kirabata O Y, et al.(Matsushita Electric Industrial Co. Ltd)US5512385. 1996
[66] Lie Fengjie, Suda S. J. Aloys Comp, 1996(232):202～211
[67] Chiaki Iwakura, Kazuhiro Ohkawa, Hiroshi Senoh, J.Electrochimica Acta 2001 (46):4383-4388
[68] S. Vivet, J.-M. Joubert, B. Knosp, A. Percheron-Guegan, J. Alloys and Compounds2003 (356-357): 779-783
[69] Cocciantelli J M, Bernard P, Fernandez S, et al. J. Alloys Comp, 1997(253-254):642-647
[70] R.C.Bowman Jr., C.H. Luo, C.C. Ahn, et al. J. Alloys and Comp. 1995(217):185
[71] B.V. Ratnakumar, C. Witham, B.Fultz, G. Halpert, J. Electrochem, Soc. 217(8)(1994)L89
[72] Lin Qin, Song Bo, Zhao Shuang, et al. J. The ChineseSociety of Rare Earths.Beijing:2001. Metallurgicallndustry Press,2001.154
[73] 赵爽，林勤，朱大键等，J．中国有色金属学报2000(10)：73～76
[74] S.W. Lambert, K. Chandra, W.N. Cathey/etal.J.Alloys Comp. 1992(187):113
[75] Ping Li, Xin-Lin Wang, Yang-Huan Zhang J. Journal of Alloys and Compounds 354(2003) 310-314
[76] K.H.J.buschow et al,J.Less-Common Met.1972.29.203
[77] D.Chandra et al., Jr. J. Alloys Comp.1993,1993,93
[78] S.Tanaka et al.,J.Phys Chem. 1977,81,1684
[79] G.G.Zhou et al.,Z Phys.Chem.1989,164,1249
[80] 李全安，桑革等，非化学计量比贮氢合金及其电极特性，[J]．功能材料，2001，32(2)：156-157
[81] 李全安，桑革，李建文，陈云贵，涂铭旌，，中国有色金属学报，2000，10(5)：659-662
[82] 陈卫祥，唐致远等，[J]．金属学报，1998，34(2)：184-188
[83] 周志刚，谭玲生等．电源技术，1997，21(4)：153
[84] Züttel A, Chartouni D, Kross K, et.al.J.Alloys Comp,1997,253～254:642～647
[85] Hu Wei-Kang.J.Alloys Comp, 1998,279:295～300
[86] 李全安，桑革，李建文等．稀土，2000，21(4)：30～33
[87] Yasada K.J.Alloys Comp,1997,253～254:621～625
[88] Kadma K K, Kirakata O Y, et al.(Matsushita Electric Industrial Co.,Ltd).U S
5512385．1996
[89] 郭靖洪，王宝光，黄伯洋等．电池，1999，29(6)：256～258
[90] W.K.Hu,D.M.Kim,S.W. Jeon,J.Y.Lee,J.Alloys Comp., 1998,270:285
[91] 马志鸿，浙江大学硕士学位论文，2000．
[92] W.K.Hu,H.Lee,D.M.Kim,S.W.Jeon,J.Y.Lee, J.Alloys Comp., 1998,268:261
[93] T.Sakai,H.Miyamura, N.Kuriyama,etal.,Z.Phs.Chem., 1994,183:1373
[94] C.J. Li, X.L Wang, J. Alloys Comp., 1999,284:274
[95] 舒康颖，浙江大学博士学位论文，1999．
[96] Zaluski L, Hosatte S, et al,. Z Phys. Chem. 1994,183:45
[97] Zaluski L, Zaluski A, et al,. J Alloys and Comp.1995,217:295
[98] S.Orimo, H. Fujii, Ikeda, [J]. Acta Mater, 1997,45(1): 331-341
[99] Zhang Yunshi,Chen Yiuxiao,Chen Jun, et al,.Accumulation of rare earthmetal on the surface of the microeneapsulated hydrogen storage alloy,[J].J alloys and Comp. 1993,190:L37-L38
[100] 孙俊才，雷永，吴京，等．微型包覆处理稀土贮氢合金电极的循环稳定性，[J]．材料科学和工艺，1995，3(1)：49—52
[101] Yandy, Sandrockg, Sudas. Activation of Zr_(0.5)Ti_(0.5)Ni_(1025) alloy electrodes by hotal kaline solutions,[J].J Alloys and Comp.,1994, 216:237-242
[102] 马建新，潘洪革，朱云峰，李寿权，陈长聘，一种改善贮氢电极合金电化学性能的新方法，[J]．金属学报，2001，37(1)：57-60
[103] Li chuanjian, Wang xinlin, li youmei, et al. Acta metall sin (金属学季), 1998, 34(3):288-292
[104] Pin Li, xin-lin Wang, Yang-huan zhang, et, al. J. Alloys Comp, 2003, 353:178-282
[105] H. Inuc, T.Yamamoto, and Z.Di.M, J. Alloys Comp, 1998,269:294-298
[106] M. Latroche, J.-M. Joubert, A. Percheron-GueH gan, Journal of Solid State Chemistry 146, 313～321 (1999)
[107] V. Paul-Boncour, A. Percheron-GueH gan, M. Gupta, J.-M. Joubert,and E Lecoester, "LURE", Experimental Report, C,S 025～98,1998.
[2] E. W Justi, H.H.Ewe,H. Stephan, Energy Conversion 13(1973)109
[3] A. Percheron-Guegan, J. cC. Achard, J. Sarradin, et al, Geilo,Norway, Pergamon Press,New York,1978 .p.485
[4] M.H.H.Ban Rikswiek, et al,. Proceedings International Symposium On Hydrides For Energy Storage, Geilo,Norway, Pergamon Press, Now York, 1978 .p.261
[5] J.J.G.Willems, Philips J. Res. 39(Suppl.1)(1984)
[6] M.Ikowa, H. Kawano, et al,.Eur.Patent, Appl.#0271043(1987)
[7] 大角泰章，贮氢合金，[J]．国外金属加工，1995，(3)：29—37
[8] 李全安，陈云贵，等，高性能贮氢合金电极的成分设计，[J]．电源技术，200024(4)：246—249
[9] 鲁辉，高学平，宋得英等，[J]．稀土，1995，16(5)：28
[10] Kohno T, Yoshida H, Kawashima F, et al. J. Alloys Comp, 2000(311)L5～L7
[11] Kadir K, Kuriyama N, Sakai T, et al.J. Alloys Comp,1999(284):145][Kadir K, Askai T, Uehara L J. Alloys Comp,1999(287):264
[12] 王仲民，彭成红，李祖鑫，朱敏，Mg—Ni系储氢合金电极研究最新进展，[J]．电池，2000，30(6)：
[13] P.H.L.Notten, M. Latroche. et al., J. Electrochem. Soc. 1999, 146 (9) 3181-3189
[14] P.H.L.Notten, J.L.C.Damms and R.E.F.Einerhand, J.Alloys Comp, 1994, (210) 233-241
[15] T.Voigt, JJ.Rilly, J. R. Johnson, et, al. J. Electrochemical and solid-state Letter 1999,2 (3): 111-114 1999, 2(3): 111-114].
[16] 袁满雪、韩剑文、赖成明，J．南开大学学报(自然科学)，1998，31(1)
[17] Westlake D G J. Less-Common Met, 1983(91):275
[18] 王超群，靳红梅等 稀土储氢合金的相结构的研究，电源技术，1998．6，3(22)
[19] L.O. Valoen, A. Zaluska, L. Zaluski,, et al, J. Alloys comp 2000 (306): 235
[20] percher～L. O. Valocn, A. Zaluska, L. Zaluski, et al. J. Alloys Comp, 2000(306):35～40
[21] percher～D. Chartouni, E Meli, A. Zuttel, et al. J. Alloys and Comp. 1996 (241): 60
[22] Msluiter. M. Takahashi, Y. Kawazoe, J. Alloys and Comp 1997(248):90
[23] T. SaKai, K. Oguro, H. Miyamura, N. Kuriyama, et al. J. Less-Common Met. 161(1990):193
[24] J. H. N. van Vucht, F. A. Kuijpers, H. C. A. M. Bruning, Philips Res. repts. 25 (1970) 133
[25] K. H. J. Bushow, H. H. Van Mal, J. Less-common Met. 29 (1972) 203
[26] A. Percher-Guegan, C.lartigue, J. C. Achard. J. Less-common Met. 109(1985):287
[27] Uchida H, Tada M, Huang YC. J Less-Common Met 1982(88):81
[28] Osumi Y, Suzuki H, Kato A. J Chem Soc. Jpn 1981(9):1493 (in Japanese)
[29] J. Liu, E. Lee Huston, J. Less-Common Met. 90(1983):1
[30] T. SaKai, H. MiYamura, N. Kuriyama, et al. J. Electrochem. Soc. 137(1990):795
[31] 胡子龙，贮氢材料，化学工业出版社，2002，8
[32] Y. Osumi, H. Suzuki, A. Kato, K. Oguru, S. Kawai, M. Kaneko, J.Less-Common Met. 89 (1983) 287-292.
[33] V.N. Verbetsky, R.A. Sirotina, E.A. Umerenko, Int. J. Hydrogen Energy 21 (1996) 935-938.
[34] Chiaki Iwakura, Kazuhiro Ohkawa, Hiroshi Senoh, J. Electrochimica Acta 2001 (46):4383—4388
[35] 朱光明 浙江大学博士学位论文，1997．8
[36] Kadama K K, Kirabata O Y, et al.(Matsushita Electric Industrial Co. Ltd)US5512385. 1996
[37] Yamamoto M, Kanda M. J. Allys Comp, 1997, 253～254:660～664
[38] 靳红梅等 金属学报，1998，16(4)：348～352
[39] Tokuichi H. (Japan Storage Battery Co. , Ltd). EP0451575A1. 1991]
[40] 江建军，金国冻，雷永泉等．电源技术，1997，21(2)：61
[41] 郭靖洪等 电源技术，2000，24(5)：265～266，287
[42] 王旭东，张羊换，林玉芳等 包头钢铁学院学报，2003，22(4)：318～322
[43] Adzie G D, Johnson J R, Reilly J J, etal. J. Electrochem Soe. 1995,142(10):34243428
[44] 贺维勇，高国中J．中国有色金属学报，1998，8(1)
[45] 卞永新，郭小燕，孙东升等，J．稀土，1999，20(4)：39～41
[46] Y. Osumi, H. Suzuki, A. Kato, M. Nakane, J. Loss-Common Met.84 (1982) 99-106.
[47] 靳红梅，李国勋等，J．电源技术，1998，22(1)：170
[48] 侯万良，常新春，王建强，郝云彦，胡壮麒，气体雾化MmNi_(3.55)Co_(0.75)Mn_(0.3)Al_(0.4)微晶贮氢合金的活化，[J]．技术功能材料，1998，5(3)：121-123
[49] 王秋娟，李全安，陈云贵，涂铭旌，快淬对贮氢合金组织和电化学性能的影响，[J]．洛阳工学院学报，2001，22(2)：8-11
[50] 李传健，王新林，李岫梅，快淬 ABs 型贮氢合金研究，[J]．金属功能材料，1998，5(5)：218-231
[51] SHIOW A L.KOST M E. KUZNETSOV N T. et al. The system LaNi_(5-)H_5, [J]. J Less-Common Metals,1988.144:23-30
[52] BOONSTRA A H. BERNADS N M. LIPP1TS G J M. J Less-Common Metals, 1990.159:327-336
[53] J.J. Reilly, G.D.Adzic,J.R.Johnson, et al.,. J. Alloys and Comp. 293-295,(1999):569-582
[54] Kanda M, Yammoto M, Karmo K, et al., J Alloys Comp. 1997,253-254:579-582
[55] 钱存富，杜昊，王洪祥[J]．稀有金属材料与工程，1999．28(6)：
[56] 周志刚，谭玲生，朴英子等[J]．电源技术，1997，21(4)：153-156
[57] Willems J J G, Buschow K. H. J. J. Less-Common Metals,1991,159:127
[58] Adzic G. D, Johnxon J R, et al. J. Alloy and Comp,1997(253-254):579～582
[59] T.Sakai, K.Oguro, H.Miyamura, N.Kuriyama, et al. J. Less-Common Met. 1990(161):193(1.304 )
[60] T/ Sakai, T/Hazama, H. Miyamura, N. Kuriyama, H, Ishikawa, J. Alloys Comp. 1992(180) 32
[61] Y.Q. Lei, Z.P Li, C.p. Chen, et al.J.Less-Common Met. 1991(253-254)579
[62] Tang Wei Zhong, Sun Guang Fei. J.Alloy and Comp,1994(203):195
[63] Li ChuanJian, Wang XinLin.J.Alloy and Comp,1999(286):270
[64] F.Meli, A.Zuttel and L.Schlapbach, J. Alloy and Comp,202(1993)81
[65] Kadama K K, Kirabata O Y, et al.(Matsushita Electric Industrial Co. Ltd)US5512385. 1996
[66] Lie Fengjie, Suda S. J. Aloys Comp, 1996(232):202～211
[67] Chiaki Iwakura, Kazuhiro Ohkawa, Hiroshi Senoh, J.Electrochimica Acta 2001 (46):4383-4388
[68] S. Vivet, J.-M. Joubert, B. Knosp, A. Percheron-Guegan, J. Alloys and Compounds2003 (356-357): 779-783
[69] Cocciantelli J M, Bernard P, Fernandez S, et al. J. Alloys Comp, 1997(253-254):642-647
[70] R.C.Bowman Jr., C.H. Luo, C.C. Ahn, et al. J. Alloys and Comp. 1995(217):185
[71] B.V. Ratnakumar, C. Witham, B.Fultz, G. Halpert, J. Electrochem, Soc. 217(8)(1994)L89
[72] Lin Qin, Song Bo, Zhao Shuang, et al. J. The ChineseSociety of Rare Earths.Beijing:2001. Metallurgicallndustry Press,2001.154
[73] 赵爽，林勤，朱大键等，J．中国有色金属学报2000(10)：73～76
[74] S.W. Lambert, K. Chandra, W.N. Cathey/etal.J.Alloys Comp. 1992(187):113
[75] Ping Li, Xin-Lin Wang, Yang-Huan Zhang J. Journal of Alloys and Compounds 354(2003) 310-314
[76] K.H.J.buschow et al,J.Less-Common Met.1972.29.203
[77] D.Chandra et al., Jr. J. Alloys Comp.1993,1993,93
[78] S.Tanaka et al.,J.Phys Chem. 1977,81,1684
[79] G.G.Zhou et al.,Z Phys.Chem.1989,164,1249
[80] 李全安，桑革等，非化学计量比贮氢合金及其电极特性，[J]．功能材料，2001，32(2)：156-157
[81] 李全安，桑革，李建文，陈云贵，涂铭旌，，中国有色金属学报，2000，10(5)：659-662
[82] 陈卫祥，唐致远等，[J]．金属学报，1998，34(2)：184-188
[83] 周志刚，谭玲生等．电源技术，1997，21(4)：153
[84] Züttel A, Chartouni D, Kross K, et.al.J.Alloys Comp,1997,253～254:642～647
[85] Hu Wei-Kang.J.Alloys Comp, 1998,279:295～300
[86] 李全安，桑革，李建文等．稀土，2000，21(4)：30～33
[87] Yasada K.J.Alloys Comp,1997,253～254:621～625
[88] Kadma K K, Kirakata O Y, et al.(Matsushita Electric Industrial Co.,Ltd).U S
5512385．1996
[89] 郭靖洪，王宝光，黄伯洋等．电池，1999，29(6)：256～258
[90] W.K.Hu,D.M.Kim,S.W. Jeon,J.Y.Lee,J.Alloys Comp., 1998,270:285
[91] 马志鸿，浙江大学硕士学位论文，2000．
[92] W.K.Hu,H.Lee,D.M.Kim,S.W.Jeon,J.Y.Lee, J.Alloys Comp., 1998,268:261
[93] T.Sakai,H.Miyamura, N.Kuriyama,etal.,Z.Phs.Chem., 1994,183:1373
[94] C.J. Li, X.L Wang, J. Alloys Comp., 1999,284:274
[95] 舒康颖，浙江大学博士学位论文，1999．
[96] Zaluski L, Hosatte S, et al,. Z Phys. Chem. 1994,183:45
[97] Zaluski L, Zaluski A, et al,. J Alloys and Comp.1995,217:295
[98] S.Orimo, H. Fujii, Ikeda, [J]. Acta Mater, 1997,45(1): 331-341
[99] Zhang Yunshi,Chen Yiuxiao,Chen Jun, et al,.Accumulation of rare earthmetal on the surface of the microeneapsulated hydrogen storage alloy,[J].J alloys and Comp. 1993,190:L37-L38
[100] 孙俊才，雷永，吴京，等．微型包覆处理稀土贮氢合金电极的循环稳定性，[J]．材料科学和工艺，1995，3(1)：49—52
[101] Yandy, Sandrockg, Sudas. Activation of Zr_(0.5)Ti_(0.5)Ni_(1025) alloy electrodes by hotal kaline solutions,[J].J Alloys and Comp.,1994, 216:237-242
[102] 马建新，潘洪革，朱云峰，李寿权，陈长聘，一种改善贮氢电极合金电化学性能的新方法，[J]．金属学报，2001，37(1)：57-60
[103] Li chuanjian, Wang xinlin, li youmei, et al. Acta metall sin (金属学季), 1998, 34(3):288-292
[104] Pin Li, xin-lin Wang, Yang-huan zhang, et, al. J. Alloys Comp, 2003, 353:178-282
[105] H. Inuc, T.Yamamoto, and Z.Di.M, J. Alloys Comp, 1998,269:294-298
[106] M. Latroche, J.-M. Joubert, A. Percheron-GueH gan, Journal of Solid State Chemistry 146, 313～321 (1999)
[107] V. Paul-Boncour, A. Percheron-GueH gan, M. Gupta, J.-M. Joubert,and E Lecoester, "LURE", Experimental Report, C,S 025～98,1998.