热处理对Nd-Mg-Ni储氢合金结构和性能的影响
|
摘要
采用磁悬浮感应熔炼法制备了Nd-Mg-Ni系储氢合金,重点研究了热处理工艺对合金相组成和电化学性能的影响。采用X射线衍射、扫描电镜和电化学测试系统研究了合金的相结构、显微结构及电化学性能。研究结果表明,Nd0.75Mg0.25Ni2.75Al0.25合金经1173,1273,1373 K退火处理后,随着退火温度的升高,不同相间元素分布更加均匀,Mg元素的浓度差减小,主相Nd2Ni7六方相逐渐增加。电化学P-C-T曲线平台变平缓、平台压降低,电化学容量,倍率性能和荷电保持率有较大提升。对于Nd0.75Mg0.25Ni3.2Al0.1合金,经1373 K,5 h热处理后慢冷较快冷更利于Nd2Ni7相的形成,慢冷试样中Nd2Ni7相可达92.31%,电化学性能更加优异,最大电化学容量为330.1 mA.g-1,循环100周容量保持率为92.2%。
The as-cast Nd-Mg-Ni-system hydrogen storage electrode alloy was prepared by vacuum induction levitation melting method.The influence of heat treatment on the phase components and the electrochemical properties was investigated.The XRD,SEM,and electrochemical tests were used to study the phase structure,microscopic structure,and the electrochemcial properties of the alloys.After heat treatment at 1173,1273,and 1373 K,it was found that the element distribution became uniform and the concentration difference of Mg element in different phases decreased with the increase of the heat treatment temperature.The hexagonal Nd2Ni7-type main-phase content increased.The P-C-T curves became smoothly and the plateau pressure descended.The electrochemical capacity,high rate dischargeability,and the charge retention were improved with the increase of the heat treatment temperature.For Nd0.75Mg0.25Ni3.2Al0.1 hydrogen storage electrode alloy,the slow cooling method after heat treatment at 1373 K for 5 h was in favor of the formation of Nd2Ni7 phase,better than the fast cooling method.The Nd2Ni7 phase content could reach to 92.31%,the maximum discharge capacity was 330.1 mA · g-1,and the charge retainion after 100 cycles was 92.2%.
The as-cast Nd-Mg-Ni-system hydrogen storage electrode alloy was prepared by vacuum induction levitation melting method.The influence of heat treatment on the phase components and the electrochemical properties was investigated.The XRD,SEM,and electrochemical tests were used to study the phase structure,microscopic structure,and the electrochemcial properties of the alloys.After heat treatment at 1173,1273,and 1373 K,it was found that the element distribution became uniform and the concentration difference of Mg element in different phases decreased with the increase of the heat treatment temperature.The hexagonal Nd2Ni7-type main-phase content increased.The P-C-T curves became smoothly and the plateau pressure descended.The electrochemical capacity,high rate dischargeability,and the charge retention were improved with the increase of the heat treatment temperature.For Nd0.75Mg0.25Ni3.2Al0.1 hydrogen storage electrode alloy,the slow cooling method after heat treatment at 1373 K for 5 h was in favor of the formation of Nd2Ni7 phase,better than the fast cooling method.The Nd2Ni7 phase content could reach to 92.31%,the maximum discharge capacity was 330.1 mA · g-1,and the charge retainion after 100 cycles was 92.2%.
引文
[1]Zhang P L,Zhu Y G,Luo G P,Ge J,Hao G J,Lin JP.Research status in high rate dischargeability of rareearth-Mg-Ni-based hydrogen storage alloys[J].ChineseJournal of Rare Metals,2012,36(4):636.(张沛龙,朱永国,罗桂平,葛静,郝国建,林均品.RE-Mg-Ni系储氢合金高倍率放电性能研究现状[J].稀有金属,2012,36(4):636.)
[2]Young K,Huang B,Regmi R K,Lawes G,Liu Y.Comparisons of metallic clusters imbedded in the surfaceoxide of AB2,AB5,and A2B7 alloys[J].Journal of Al-loys and Compounds,2010,506(2):831.
[3]Cheng L F,Wang R B,Pu Z H,Li Z L,He D N,XiaB J.Study on microstructure and electrochemical per-formance of La0.7Mg0.3(Ni0.9Co0.1)x hydrogen storage al-loys[J].Journal of Power Sources,2008,1854(2):1519.
[4]Zhou Z L,Song Y Q,Cui S,Lin C G,Guo Z M,Qu XH.Effects of heat treatment on the hydrogen storageproperties of La-Mg-Ni-system electrode alloys-micro-structure and phase analysis[J].Rare Metal MaterialsAnd Engineering,2008,37(7):1188.(周增林,宋月清,崔舜,林晨光,郭志猛,曲选辉.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.)
[5]Zhou Z L,Song Y Q,Cui S,Lin C G,Guo Z M,Qu XH.Effects of heat treatment on the hydrogen storageproperties of La-Mg-Ni-system electrode slloys(Ⅱ)hy-drogen storage and electrochemical properties[J].RareMetal Materials and Engineering,2008,37(6):964.(周增林,宋月清,崔舜,林晨光,郭志猛,曲选辉.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].稀有金属材料与工程,2008,37(6):964.)
[6]Wang B P,Chen Y Z,Wang L,Liu Y N.Effect ofannealing time on the structure and electrochemical prop-erties of La0.72Nd0.08Mg0.2Ni3.4Al0.1 hydrogen storage al-loys[J].Journal of Alloys and Compounds,2012,541(15):305.
[7]Gao J,Yan X L,Zhao Z Y,Chai Y J,Hou D L.Effect of annealed treatment on microstructure and cyclicstability for La-Mg-Ni hydrogen storage alloys[J].Jour-nal of Power Sources,2012,209(1):257.
[8]Zhou Z L,Song Y Q,Cui S,Huang C G,Qian W L,Lin C G,Zhang Y J,Lin Y L.Effect of annealingtreatment on structure and electrochemical performance ofquenched MmNi4.2Co0.3Mn0.4Al0.3Mg0.03 hydrogen stor-age alloy[J].Journal of Alloys and Compounds,2010,501(1):47.
[9]Tan M,Zhu R R,Ding Y,Liu S H,Xiong K,Guo J.Effects of rare-earth content on electrochemical propertiesof La0.7(Pr0.75Nd0.25)xMg0.3Ni3.3(Co0.7Al0.3)0.3(x=0.0,0.1,0.2,0.3)alloy electrodes[J].Chinese Jour-nal of Rare Metals,2012,36(5):732.(覃铭,祝蓉蓉,丁杨,刘淑辉,熊凯,郭进.稀土含量对La0.7(Pr0.75Nd0.25)xMg0.3Ni3.3(Co0.7Al0.3)0.3(x=0.0～0.3)合金电极电化学性能影响[J].稀有金属,2012,36(5):732.)
[10]Li F,Young K,Ouchi T,Fetcenko M A.Annealingeffects on structural and electrochemical properties of(LaPrNdZr)0.83Mg0.17(NiCoAlMn)3.3 alloy[J].Journalof Alloys and Compounds,2009,471(1-2):371.
[11]Yang X F,Luo Y C,Kang L.Electrochemical proper-ties of the La-Mg-Ni system A2B7-type and A5B19-typehydrogen storage alloys[J].China Foundry Machinery&Technology,2009,(4):5.(杨晓峰,罗永春,康龙.La-Mg-Ni系A2B7与A5B19型相结构储氢合金的电化学性能[J].中国铸造装备与技术,2009,(4):5.)
[12]Deng A Q,Fan J B,Qian K N,Luo Y C.Effect ofheat treatment on the structure and properties ofLa4MgNi19 hydrogen storage electrode alloys[J].ActaPhysico-China Sinica,2011,27(1):103.(邓安强,樊静波,钱克农,罗永春.热处理对La4MgNi19储氢电极合金结构和性能的影响[J].物理化学学报,2011,27(1):103.)
[13]Young K,Ouchi T,Huang B.Effects of annealing andstoichiometry to(Nd,Mg)(Ni,Al)3.5 metal hydride al-loys[J].Journal of Power Sources,2012,215(1):152.
[14]Pan C C,Yang B,Javed I,Yu R H.Effects of annea-ling treatment on microstructure and properties of Nd0.75Mg0.25(Ni0.8Co0.2)3.5 hydrogen storage alloys[J].RareMetal Materials And Engineering,2011,40(2):367.(潘崇超,杨白,Javed Iqbal,于荣海.退火热处理对Nd0.75Mg0.25(Ni0.8Co0.2)3.5储氢合金结构和性能的影响[J].稀有金属材料与工程,2011,40(2):367.)
[15]Pan C C,Yang S L,Yu R H,Shi J,Nakamura Y.Mechanism of the enhancement of discharge rate propertyfor Nd0.8Mg0.2(Ni0.8Co0.2)3.8 hydrogen storage alloy bymagnetic annealing[J].Journal of Rare Earths,2010,28(2):286.
[16]Pan C C,Cai W P,Iqbal J,Wang Z,Geng C Q,Yu RH.Microstructure and electrochemical properties ofmelt-spun Nd0.8Mg0.2(Ni0.8Co0.2)3.8 hydrogen storage al-loy[J].Journal of Rare Earths,2010,28(1):100.
[17]Shang G Y,Han S M,Hao J S,Liu Y,Zhu X L,Li Y,Xie D Y.Study on self-discharge property of Nd0.88Mg0.12Ni3.10+xAl0.20(x=0.00,0.10,0.20,0.30)hy-drogen storage alloys[J].Journal of Alloys and Com-pounds,2010,493(1-2):573.
[2]Young K,Huang B,Regmi R K,Lawes G,Liu Y.Comparisons of metallic clusters imbedded in the surfaceoxide of AB2,AB5,and A2B7 alloys[J].Journal of Al-loys and Compounds,2010,506(2):831.
[3]Cheng L F,Wang R B,Pu Z H,Li Z L,He D N,XiaB J.Study on microstructure and electrochemical per-formance of La0.7Mg0.3(Ni0.9Co0.1)x hydrogen storage al-loys[J].Journal of Power Sources,2008,1854(2):1519.
[4]Zhou Z L,Song Y Q,Cui S,Lin C G,Guo Z M,Qu XH.Effects of heat treatment on the hydrogen storageproperties of La-Mg-Ni-system electrode alloys-micro-structure and phase analysis[J].Rare Metal MaterialsAnd Engineering,2008,37(7):1188.(周增林,宋月清,崔舜,林晨光,郭志猛,曲选辉.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.)
[5]Zhou Z L,Song Y Q,Cui S,Lin C G,Guo Z M,Qu XH.Effects of heat treatment on the hydrogen storageproperties of La-Mg-Ni-system electrode slloys(Ⅱ)hy-drogen storage and electrochemical properties[J].RareMetal Materials and Engineering,2008,37(6):964.(周增林,宋月清,崔舜,林晨光,郭志猛,曲选辉.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].稀有金属材料与工程,2008,37(6):964.)
[6]Wang B P,Chen Y Z,Wang L,Liu Y N.Effect ofannealing time on the structure and electrochemical prop-erties of La0.72Nd0.08Mg0.2Ni3.4Al0.1 hydrogen storage al-loys[J].Journal of Alloys and Compounds,2012,541(15):305.
[7]Gao J,Yan X L,Zhao Z Y,Chai Y J,Hou D L.Effect of annealed treatment on microstructure and cyclicstability for La-Mg-Ni hydrogen storage alloys[J].Jour-nal of Power Sources,2012,209(1):257.
[8]Zhou Z L,Song Y Q,Cui S,Huang C G,Qian W L,Lin C G,Zhang Y J,Lin Y L.Effect of annealingtreatment on structure and electrochemical performance ofquenched MmNi4.2Co0.3Mn0.4Al0.3Mg0.03 hydrogen stor-age alloy[J].Journal of Alloys and Compounds,2010,501(1):47.
[9]Tan M,Zhu R R,Ding Y,Liu S H,Xiong K,Guo J.Effects of rare-earth content on electrochemical propertiesof La0.7(Pr0.75Nd0.25)xMg0.3Ni3.3(Co0.7Al0.3)0.3(x=0.0,0.1,0.2,0.3)alloy electrodes[J].Chinese Jour-nal of Rare Metals,2012,36(5):732.(覃铭,祝蓉蓉,丁杨,刘淑辉,熊凯,郭进.稀土含量对La0.7(Pr0.75Nd0.25)xMg0.3Ni3.3(Co0.7Al0.3)0.3(x=0.0～0.3)合金电极电化学性能影响[J].稀有金属,2012,36(5):732.)
[10]Li F,Young K,Ouchi T,Fetcenko M A.Annealingeffects on structural and electrochemical properties of(LaPrNdZr)0.83Mg0.17(NiCoAlMn)3.3 alloy[J].Journalof Alloys and Compounds,2009,471(1-2):371.
[11]Yang X F,Luo Y C,Kang L.Electrochemical proper-ties of the La-Mg-Ni system A2B7-type and A5B19-typehydrogen storage alloys[J].China Foundry Machinery&Technology,2009,(4):5.(杨晓峰,罗永春,康龙.La-Mg-Ni系A2B7与A5B19型相结构储氢合金的电化学性能[J].中国铸造装备与技术,2009,(4):5.)
[12]Deng A Q,Fan J B,Qian K N,Luo Y C.Effect ofheat treatment on the structure and properties ofLa4MgNi19 hydrogen storage electrode alloys[J].ActaPhysico-China Sinica,2011,27(1):103.(邓安强,樊静波,钱克农,罗永春.热处理对La4MgNi19储氢电极合金结构和性能的影响[J].物理化学学报,2011,27(1):103.)
[13]Young K,Ouchi T,Huang B.Effects of annealing andstoichiometry to(Nd,Mg)(Ni,Al)3.5 metal hydride al-loys[J].Journal of Power Sources,2012,215(1):152.
[14]Pan C C,Yang B,Javed I,Yu R H.Effects of annea-ling treatment on microstructure and properties of Nd0.75Mg0.25(Ni0.8Co0.2)3.5 hydrogen storage alloys[J].RareMetal Materials And Engineering,2011,40(2):367.(潘崇超,杨白,Javed Iqbal,于荣海.退火热处理对Nd0.75Mg0.25(Ni0.8Co0.2)3.5储氢合金结构和性能的影响[J].稀有金属材料与工程,2011,40(2):367.)
[15]Pan C C,Yang S L,Yu R H,Shi J,Nakamura Y.Mechanism of the enhancement of discharge rate propertyfor Nd0.8Mg0.2(Ni0.8Co0.2)3.8 hydrogen storage alloy bymagnetic annealing[J].Journal of Rare Earths,2010,28(2):286.
[16]Pan C C,Cai W P,Iqbal J,Wang Z,Geng C Q,Yu RH.Microstructure and electrochemical properties ofmelt-spun Nd0.8Mg0.2(Ni0.8Co0.2)3.8 hydrogen storage al-loy[J].Journal of Rare Earths,2010,28(1):100.
[17]Shang G Y,Han S M,Hao J S,Liu Y,Zhu X L,Li Y,Xie D Y.Study on self-discharge property of Nd0.88Mg0.12Ni3.10+xAl0.20(x=0.00,0.10,0.20,0.30)hy-drogen storage alloys[J].Journal of Alloys and Com-pounds,2010,493(1-2):573.