摘要
本文在绪论中综述了储氢合金的应用原理、研究发展与现状等,以储氢量较高的AB_(3.0-3.5)(新型RE-Mg-Ni系)储氢合金作为研究对象,较为系统地研究了A/B比和退火热处理对材料的结构特征、电化学性能以及自放电性能的影响。
通过中频感应熔炼制备了La_(0.65)Mg_(0.35)Ni_x(x=3.0-3.5)系列储氢电极合金。研究了合金的结构、电化学性能以及自放电性能。XRD研究表明,该系列合金主要由三相组成:LaNi_5相、(La,Mg)Ni_3相和(La,Mg)_2Ni_4相,随着x值的增大,LaNi_5相的丰度逐渐增加,(La,Mg)Ni_3相的丰度逐渐减少;最大放电容量从350.6mAh·g~(-1)(x=3.0)增加到351.2mAh·g_(-1)(x=3.1),然后逐渐减小到244.1mAh·g~(-1)(x=3.5);合金电极72h的荷电保持率从77.7%(x=3.0)增加到79.5%(x=3.1)然后逐渐减小到63.5%(x=3.5)。x=3.1的合金的荷电保持率最高,表明AB_(3-3.5)型La-Mg-Ni系储氢合金的A/B比对合金电极的自放电性能有较大的影响。
另一方面,研究了1173K热处理对该系储氢合金结构和性能的影响,并且对该系列合金电极的热处理前后进行对比。结果表明,热处理后的合金电极最大放电容量、循环稳定性、高倍率放电性能(HRD)、电极的自放电都有明显改善。
The application status,research and development of hydrogen storage alloy were comprehensively introduced in the first part of this paper.The new series of RE-Mg-Ni based AB_(3.0-3.5)-type alloys with PuNi_3-type structure had higher capacity than that of the AB_5-type alloys and thus were regarded as promising candidates for reversible hydrogen storage.In this work,the effect of the A/B ratio and annealing treatment on the structural,electrochemical properties and self-discharge property of the AB_(3.0-3.5)-type hydrogen storage alloys has been studied systematically.
The La_(0.65)Mg_(0.35)Ni_x(X=3.0-3.5) hydrogen storage alloys is prepared by induction melting.The structure,electrochemical properties and self-discharge property of as-cast alloys have been studied systematically by X-ray diffraction(XRD),scanning electron microscope(SEM) and electrochemical experiments.It is found by XRD analysis that all these alloys mainly consist of three phases:the LaNi_5 phase, (La,Mg)Ni_3 phase and(La,Mg)_2Ni_4 phase.The abundance of the LaNi_5 phase increases and that of La(La,Mg)Ni_3 phase decreases with increasing x.The electrochemical studies show that as x increases the maximum discharge capacity of the alloy electrodes first increases from 350.6mAh·g~(-1)(x=3.0)to 351.2mAh·g~(-1)(x=3.1)and then decreases to 244.1mAh·g~(-1)(x=3.5).Moreover,the capacity retention rate of 72h self-discharge increases from 77.7%(x=3.0)to 79.5%(x=3.1),and then decreases to 63.5%(x=3.5).When x=3.1,the capacity retention rate of alloy electrode is the maximum.
Besides,lectrochemical experiments show that the discharge capacity,high rate discharge performance,cycle stability and self-discharge property of the La_(0.35)Mg_(0.65)Ni_x(X=3.0-3.5) alloy electrodes were improved after annealing treatment at 1173K.
引文
[1]大角泰章,敖建平.贮氢合金[J].国外金属加工,1995,(3):29-37
[2]李全安,陈云贵,王立华等,贮氢合金的开发与应用[J].材料开发与应用,1999,14(3):33-36
[3]胡子龙.贮氢材料[M].北京:化学工业出版社,2002:1-321
[4]郑雪萍,曲选辉,李平.稀土系储氢合金性能影响因素的研究现状[J].金属功能材料,2006,13(6).32-36
[5]J.J.Reilly,G.D.Adzic,J.R.Johnson,etc.The correlation between composition and electrochemical properties of metal hydride electrodes[J].Journal of Alloys and Compounds,1999,295(293):569-582
[6]许炜,陶占良,陈军.储氢研究进展[J].化学进展,2006,18(2/3):200-210
[7]J.Chena,H.T.Takeshitaa,H.Tanakaa,etc.Hydriding properties of LaNi_3 and CaNi_3 and their substitutes with PuNi_3 type structure[J].Journal of Alloys and Compounds,302(2000):304-313
[8]肖玲玲,王一菁,刘毅等.储氢合金La_(0.7-x)Ce_xMg_(0.3)Ni_(2.4)Co_(0.6)(x=0-0.4)电化学性能研究[J].电化学,2007,13(1):40-43
[9]罗永春,陈江平,邓安强等.La_(0.8-x)Pr_xMg_(0.2)Ni_(3.2)Co_(0.4)Al_(0.2)(x=0-0.4)储氢合金的相结构与电化学性能[J].中国稀土学报,2007,25(4):454-460
[10]周增林,宋月清,崔舜等.Nd替代La对La-Mg-Ni系A_2B_7贮氢电极合金性能的影响[J].中国有色金属学报,2007,17(1):45-52
[11]周增林,宋月清等.替代元素铝和钕对La-Mg-Ni系AB_(3.5)型贮氢合金性能的影响[J].中国稀土学报,2007,25(6):713-719
[12]柳东明,王常春,斯庭智等.La_2Mg_(4-x)Ca_xNi_(13)贮氢合金的相结构与电化学性能[J].功能材料,2007,38:1619-1621
[13]王大辉,吴彦军,闫汝煦等.Al替代Mg对La_2MgNi_(7.5)Co_(1.5)贮氢合金电化学循环稳定性的影响[J].稀有金属材料与工程,2008,37(1):40-44
[14]张羊换,任慧平,李保卫等.La_(0.7)Mg_(0.3)Ni_(2.55-x)Co_(0.45)Al_x(x=0-0.4)贮氢合金的循环稳定性[J].中国有色金属学报,2006,16(8):1320-1325
[15]宋月清,周增林,崔舜.铝在新型稀土镁基AB_3型贮氢电极合金中的作用研究[J].稀有 金属,2006,,30(1):114-117
[16]许剑轶,闫汝煦,王大辉等.A_2B_7型La_(0.75)Mg_(0.25)Ni_(3.5-x)Al_x(x=0-0.3)合金相结构及电化学性能[J].稀有金属材料与工程,2007,36(2):349-353
[17]刘永锋,潘洪革,金勤伟等.La_(0.7)Mg_(0.3)Ni_(3.4-x)Co_(0.6)Mn_x(x=0.0-0.5)贮氢电极合金的结构、储氢特性及电化学性能[J].稀有金属材料与程,2005,34(6):867-871
[18]X.B.Zhang,D.Z.Sun,W.Y.Yin.Effect of Mn content on the structure and electroch emical characteristics of La_(0.7)Mg_(0.3)Ni_(2.975-x)Co_(0.525)Mn_x(X=0-0.4) hydrogen storage alloys[J].Electrochimica Acta,2005,50(14):2911-2918
[19]许妮君,韩选利,侯雪燕.Cu替代Ni对La-Mg-Ni系储氢合金电化学性能的影响[J].应用化工,2007,36(1):54-60
[20]杜青春,魏伟,阎汝煦等.La_(1.5)Mg_(0.5)Ni_(7-x)Cu_x(x=0.1-1.2)贮氢合金电化学性能的研究[J].功能材料与器件学报,2005,11(4):476-480
[21]张羊换,董小平,王国清等.铸态及快淬态La_2Mg(Ni_(0.85)Co_(0.15)_9Cr_x(x=0-0.2)电极合金的微观结构及电化学性能[J].稀有金属材料与工程,2006,35(6):876-879
[22]唐睿,刘丽琴,柳永宁等.(MlMg)Ni_(4-x)Co_(0.7)Zn_x合金的储氢性能[J].中国有色金属学报,2003,13(2):428-431
[23]张海昌,墨伟,申元等.La_(0.7)Mg_(0.3)(Ni_(1-x)Co_x)_(3.5)(0<x<0.5)储氢合金电化学性能[J].中国稀土学报,2004,22(5):712-714
[24]张法亮,罗永春,孙凯.La_(1.5)Mg_(0.5)Ni_(7-x)Co_x(x=O-1.8)贮氢合金结构和电化学性能研究[J].功能材料,2006,37(2):265-269
[25]魏学东,唐春,朱杰武等.低钴储氢合金Ml_(0.9)Mg_(0.1)Ni_(3.4)Co_(0.3)Al_(0.3)电化学性能研究[J].稀有金属材料与工程,2005,34(12):1866-1870
[26]刘永锋,金勤伟,高明霞等.热处理对La_(0.7)Mg_(0.3)Ni_(2.8)Co_(0.5)贮氢合金电化学性能的影响[J].稀有金属材料与工程,2003,32(11):942-945
[27]Hongge Pan,Yongfeng Liu,Mingxia Gao.A study on the effect of annealing treatment on the electrochemical properties of La_(0.6)7Mg_(0.33)Ni_(2.5)Co_(0.5) alloy electrodes[J].International Journal of Hydrogen Energy,2003,28:113-117
[28]Hongge Pan,Ni Chen,Mingxia Gao.Effects of annealing temperature on structure and the electrochemical properties of La_(0.7)Mg_(0.3)Ni_(2.45)Co_(0.75)Mn0_(.1)Al_(0.2) hydrogen storage alloy[J]. Journal of Alloys and Compounds,2005,397:306-312
[29]屠德周,雷永泉,陈立新等.退火处理对La-Mg-Ni-Co合金电化学性能的影响[J].浙江大学学报(工学版),2007,41(3):519-523
[30]苗鹤,林燕,李锐等.热处理对贮氢电极合金Lao_(0.7)Mgo_(0.3)Ni_(2.45)Co_(0.75)Mn_(0.1)Al_(0.2)的微结构与电化学性能的影响[J].中山大学学报(自然科学版),2007,46:310-311
[31]周增林,宋月清,崔舜等.热处理对La-Mg-Ni系贮氢电极合金性能的影响(Ⅱ)贮氢及电化学性能[J].稀有会属材料与工程,2008,37(6):964-969
[32]周增林,宋月清,崔舜等.热处理对La-Mg-Ni系贮氢电极合金性能的影响-显微组织及相分析[J].稀有金属材料与工程,2008,37(7):1188-1192
[33]储爱,杨丽颖,刘厚才等.退火对La_(0.75)Mg_(0.25)Ni_(3.5)Co_(0.4)贮氢合金电化学性能的影响[J].材料热处理学报,2008,29(1):16-19
[34]董小平,张羊换,吕反修等.退火对La_(0.75)Mg_(0.25)Ni_(3.5)Co_x(x=0,0.6)合金结构与电化学性能影响[J].功能材料,2008,39(2):238-241
[35]钱晓静,黄国强,林波.Mg-Ni系贮氢合金的改性[J].稀有金属,2008,32(1):107-114
[36]杨化滨,张海昌,孙华等.CH_3OH-H_2O体系化学镀铜Mg_(1.85)Mm_(0.15)Ni合金的抗腐蚀性能研究[J].电化学,2003,9(2):196-202
[37]H.C.Lina,K.M.Lina,H.T.Choua,M.T.Effects of annealing and NaOH pretreatment on an LmNi_(3.65)Al_(0.34)Mn0_(.27)Co_(0.74)hydrogen storage alloy[J].Journal of Alloys and Compounds,2003,358:281-287
[38]Mao-Sung Wu,Hong-Rong Wu,Yung-Yun Wang.Surface treatment for hydrogen storage alloy of nickel/metal hydride battery[J].Journal of Alloys and Compounds 302(2000):248-257
[39]张继文,陈长聘,高林辉等.氟处理对La_(1.8)Ca_(0.2)Mg_(14)Ni_3合金吸放氢性能的影响[J].化工学报,2004,55:159-162
[40]Chang-Pin Chen,Xin-HuaWang,Guan-Ming Cai.Surface structure of F-treated La_(1.8)Ca_(0.2)Mg_(14)Ni_3 alloy and hydrogenation properties of solid-liquid system composed of the alloy and benzene[J].International Journal of Hydrogen Energy,2006,31:1261-1265
[41]Junmin Nana,b,Yong Yanga,Zugeng Lina.The effects of surface treatment on metal hydride electrodes using a weak acid solution containing Ni(Ⅱ)[J].Journal of Alloys and Compounds,2001,316:131-136
[42]Xi Shan a,Joe H.Payer a,Jesse S.Improved durability of hydrogen storage alloys[J].Journal of Alloys and Compounds,2007,430:262-268
[43]Ke Yang,Demin Chen,Lian Chen.Modification of a rapidly solidified hydrogen storage electrode alloy by ball-milling with Co_3Mo[J].Journal of Alloys and Compounds,1999,293-295:670-674
[44]Y.Chen,J.S.Williams.Formation of metal hydrides by mechanical alloying[J].Journal of Alloys and Compounds,1995,217:181-184
[45]叶小球,桑革.Pd含量对Mg-Ni合金相形成及贮氢性能的影响研究[J].材料导报,2006,(10):132-134
[46]任国新,陈长聘,应窕等.在四氢呋喃中球磨改性处理的LaMg_(11)Ni合金吸放氢特性研究[J].稀有金属材料与工程,2004,33(9):988-991
[47]蒙冕武,刘心宇,成钧.机械合金化LaNi_5-X%(质量)Mg(X=20,30)相组成及性能研究[J].金属功能材料2004,11(2):11-15
[48]蒙冕武,刘心宇,成钧等.高能球磨LaNi_5-X%(质量分数)Mg的相组成与热稳定性能[J].功能材料,2004,34(2):177-182
[49]Dunlap B.D.,Viccaro P.J.,Shenoy G.K.Structural relationships in rare earth-transition metal hydrides[J].J.Less-Common Met.,1980,74:75-79
[50]Chen J.,Takeshita H.T.,Tanaka H.,etc.Hydriding properties of LaNi_3 and CaNi_3 and their substitutes with PuNi_3-type structure[J].Journal of Alloys and Compounds,2000,302:304-313
[51]刘奕新,陈秋萍,刘淑辉等.La-Mg-Ni基合金储氢性能的研究[J].广西科学,2007,14(4):393-396
[52]张晶,方方,郑时有等.AB_3型贮氢合金材料的研究进展[J].稀有金属材料与工程,稀有金属材料与工程,2008,37(5):926-930
[53]张文保.金属氢化物镍电池的自放电因素分析[J].电池,2001,31(2):86-87
[54]夏洋,杨毅夫.MH/Ni电池自放电性能的研究进展[J].电池,2005,35(4):319-321
[55]郭炳馄,李新海,杨松青.化学电源-电池原理及制造技术[M].长沙:中南大学出版社,2003.5-320
[56]Feng F,Northwood,D.O.Self-discharge characteristics of a metal hydride electrode for Ni-MH rechargeable batteries[J].International Journal of Hydrogen Energy,2005,30(12):1367-1370.
[57]李志尊,雷永泉,韩凤起.添加元素对贮氢电极材料MlNi_(3.8)(CoMn)_(1.2)电化学及高温性能的影响[J].稀有金属,2002,26(1):47-48
[58]李志尊,雷永泉,韩凤起.添加Al对稀上系贮氢电极合金高温性能的影响[J].材料研究学报,2002,16(1):105-108
[59]Barnard R,Randell C R,Tye F L.Studies of concerning charged nickel hydroxide electrodes[J].J Appl Electrochem,1980,10:109-125
[60]Ovshinsky S R,Fetcenko M A,Ross J.A nickel metal hydride battery for electric vehicles[J].Science,1993,260:176-181
[61]Reilly J J,Adzic G D,Johnson J R,etc.The correlation between composition and electro chemical properties of metal hydride electrodes[J].Journal of Alloys and Compounds,1999,293-295:569-582
[62]Kohno T,Yoshida H,Kawashima F,etc.Hydrogen storage properties of new ternary system alloys:La_2MgNi_9,La_5Mg_2Ni_(23),La_3MgNi_(14)[J].Journal of Alloys and Compounds,2000,311:L5-L7
[63]Lee J H,Lee K Y,Lee J Y.Self-discharge behavior of sealed Ni-MH batteries using MmNi_(3.3+x)Co_(0.7)Al_(1.0-x) anodes[J].Journal of Alloys and Compounds,1996,232(1-2):197-203
[64]Peng C.H.,Zhu M.Microstructure and hydrogen storage properties of a multi-phase Ml_(0.7)Mg_(0.3)Ni_(3.2) hydrogen storage alloy[J].Journal of Alloys and Compounds,2004,375:324-329
[65]李志尊,韩凤起等.军用Ni/MH电池电极材料的研究[J].兵器材料科学与工程,2002,25(2):18-22
[66]曹楚南.腐蚀电化学[M].北京:化学工业出版社,1994.44-45
[67]盛丹,春林,孔繁清等.La_(0.65)Mg_(0.35)Ni_x(x=3.0-3.5)储氢合金电极的自放电性能研究[J].稀有金属材料与工程,已收录,待发表