La-Ni-Cr三元系相图600℃等温截面及LaNi_(4.7)Si_xCr_(0.3-x)合金电化学性能的研究
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摘要
通过对151个合金样品进行系统的研究，本文确定了La-Ni-Cr三元系600℃等温截面相图。
本文通过X射线衍射分析法，差热分析法和金相分析法技术测定了La-Ni-Cr三元系600℃等温截面。测定结果表明该截面由10个单相区，17个两相区，8个三相区组成。
在本实验条件下没有观察到La_3Ni，Cr_7Ni_3和Cr_3Ni_2化合物的存在，存在La_7Ni_(16)而不存在LaNi_2，未发现新的三元化合物。在600℃下，Cr在Ni，LaNi_5，La_2Ni_7，LaNi_3，La_2Ni_3，LaNi和La_7Ni_3中的最大固溶度分别约为35，20，15，8，9，9和6at．％，Ni在Cr中的最大固溶度约为3at．％。
本文对LaNi_(4.7)Si_XCr_(0.3-X)(X=0.15，0.18，0.22，0.25)型储氢电极合金的吸放氢性能进行了研究。以LaNi_(4.7)Si_XCr_(0.3-X)合金粉均匀地涂在泡沫镍上制成的电极片为负极，以烧结Ni(OH)_2为正极，以6mol／L KOH溶液为电解液，制成开口式MH-Ni二次电池，采用自动控制充放电仪——DC-5电池测试仪进行电化学性能测试。研究发现Cr加入到LaNi_(4.7)Si_(0.3)中，形成的LaNi_(4.7)Si_XCr_(0.3-X)(X=0.15，0.18，0.22，0.25)合金均为CaCu_5型结构，适量的Cr(Cr为0.08)替代LaNi_(4.7)Si_(0.3)合金中的Si所形成合金具有优良的综合性能，小电流放电时合金的性能要优于大电流放电时的性能。
By discussing the 151 alloy samples, the 600C isothermal section of La-Ni-Cr ternary system phase diagram has been confirmed .
The 600C isothermal section of the phase diagram of the La-Ni-Cr ternary system was investigated by X-ray diffraction (XRD), differential thermal analysis (DTA) and optical microscopy techniques. The result showed that the section is composed of ten single-phase regions, seventeen two-phase regions and eight three-phase regions. The La3Ni compound does not exist. At 600C, there is La7Ni16, but not LaNi2 The patterns of Cr7Ni3 and Cr3Ni2 have not been observed. Any new compound hasn't been found . At 600C, the maximum solid solubility of Cr in Ni, LaNi5, La2Ni7, LaNi3, LaNi, La2Ni3 and La7Ni3 is about 35, 20, 15, 8, 9, 9, and 6at.%Cr, respectively. The maximum solid solubility of Ni in Cr is about 3at.%Ni.
In this paper, the hydrogen absorption-desorption propery of LaNi4.7SixCr0.3-x alloys with X=0.15, 0.18, 0.22, 0.25, 0.28 has been investigated. The open recycling batteries were made with LaNi4.7SixCr0.3-x cathode evenly smeared on foam Nickel and Ni(OH)2 anode in the electrolyte of 6mol/L KOK. By analyzing the experiment results from the automatic charge-discharge-DC-5 battery testing instrument, we found that the LaNi4.7SixCr0.3-x(X=0.15, 0.18, 0.22, 0.25, 0.28) alloys were CaCu5
structure. And the LaNi4.7SixCr0.3-x alloy possessed excellent properties at Cr=0.08. The battery property is well at little current discharge than big current discharge.
本文通过X射线衍射分析法，差热分析法和金相分析法技术测定了La-Ni-Cr三元系600℃等温截面。测定结果表明该截面由10个单相区，17个两相区，8个三相区组成。
在本实验条件下没有观察到La_3Ni，Cr_7Ni_3和Cr_3Ni_2化合物的存在，存在La_7Ni_(16)而不存在LaNi_2，未发现新的三元化合物。在600℃下，Cr在Ni，LaNi_5，La_2Ni_7，LaNi_3，La_2Ni_3，LaNi和La_7Ni_3中的最大固溶度分别约为35，20，15，8，9，9和6at．％，Ni在Cr中的最大固溶度约为3at．％。
本文对LaNi_(4.7)Si_XCr_(0.3-X)(X=0.15，0.18，0.22，0.25)型储氢电极合金的吸放氢性能进行了研究。以LaNi_(4.7)Si_XCr_(0.3-X)合金粉均匀地涂在泡沫镍上制成的电极片为负极，以烧结Ni(OH)_2为正极，以6mol／L KOH溶液为电解液，制成开口式MH-Ni二次电池，采用自动控制充放电仪——DC-5电池测试仪进行电化学性能测试。研究发现Cr加入到LaNi_(4.7)Si_(0.3)中，形成的LaNi_(4.7)Si_XCr_(0.3-X)(X=0.15，0.18，0.22，0.25)合金均为CaCu_5型结构，适量的Cr(Cr为0.08)替代LaNi_(4.7)Si_(0.3)合金中的Si所形成合金具有优良的综合性能，小电流放电时合金的性能要优于大电流放电时的性能。
By discussing the 151 alloy samples, the 600C isothermal section of La-Ni-Cr ternary system phase diagram has been confirmed .
The 600C isothermal section of the phase diagram of the La-Ni-Cr ternary system was investigated by X-ray diffraction (XRD), differential thermal analysis (DTA) and optical microscopy techniques. The result showed that the section is composed of ten single-phase regions, seventeen two-phase regions and eight three-phase regions. The La3Ni compound does not exist. At 600C, there is La7Ni16, but not LaNi2 The patterns of Cr7Ni3 and Cr3Ni2 have not been observed. Any new compound hasn't been found . At 600C, the maximum solid solubility of Cr in Ni, LaNi5, La2Ni7, LaNi3, LaNi, La2Ni3 and La7Ni3 is about 35, 20, 15, 8, 9, 9, and 6at.%Cr, respectively. The maximum solid solubility of Ni in Cr is about 3at.%Ni.
In this paper, the hydrogen absorption-desorption propery of LaNi4.7SixCr0.3-x alloys with X=0.15, 0.18, 0.22, 0.25, 0.28 has been investigated. The open recycling batteries were made with LaNi4.7SixCr0.3-x cathode evenly smeared on foam Nickel and Ni(OH)2 anode in the electrolyte of 6mol/L KOK. By analyzing the experiment results from the automatic charge-discharge-DC-5 battery testing instrument, we found that the LaNi4.7SixCr0.3-x(X=0.15, 0.18, 0.22, 0.25, 0.28) alloys were CaCu5
structure. And the LaNi4.7SixCr0.3-x alloy possessed excellent properties at Cr=0.08. The battery property is well at little current discharge than big current discharge.
引文
[1]．崔忠圻，金属学与热处理，高等教育出版社，1993年。
[2]．胡忠鲠，金继红，李盛华，现代化学基础，高等教育出版社，2000年。
[3]. Editor, Binary Alloy Phase Diagrams, pp.2424-2426,1997
[4]. K.A.Gschneidner, Jr., in Rare Earth Alloy, Van Nostrand, Prunceton, 187-188(1961)
[5]. Y.Y.Pan, P.Nash, in:T.B.Massalski,, P.R.Subramanian, H.Okamoto, L.Kacprzak(Eds.), Binary Alloy Phase Diagrams, 2nd Edition, ASM International,Materials Park, OH, 1991, pp.2406-2408
[6]. A.V.Klimyenko, J.Seuntjens, L.L.Miller, B.J.Beaudry, R.A.Jacoson and K.A.Gschneidner, Jr. Journal of the Less-Common Metals, 144 (1988) 133-141
[7]. V.Paul-Boncour, A.Percheron-Guegan, M.Diaf and J.C.Achard, Journal of the Less-Common Metals, 131 (1987) 201-208
[8]．朱延果，La-Ni-Fe三元系合金相图400℃和550℃等温截面，广西大学硕士学位论，2002
[9]. P.Villars,Pearson's Handbook, Desk Edition, Crystallographic Data for Intermetallic Phases, ASM, Materials Park, Ohio, 1997
[10]. P.Nash, Binary Alloy Phase diagrams, 2nd Edition, ASM International,Materials Park, OH, 1991, pp. 1298-1302
[11]. Powder Diffraction File, International Center for Diffraction Data, 1999
[12]. Alphabetical Indexes Powder Diffraction File, International Center for Diffraction Data Sets 1-46, 1996, p. 180
[13]. R.P.Elliott, Constitution of Binary Alloys, First Supplement, Me Graw-Hill, New York, 1965, p.349. Company, 1965,349
[14]. Svechnikov V. N., Ivanchenko V. G., Kobzenko G. F. Diagramm' Sostoyaniya Metallicheskikh Sistem, 27 (1981) 60-62. (in Russian)
[15]．张圣弼，李道子，相图—原理、计算及在冶金中的应用，冶金工业出版社，1986。
[16]．李树棠，晶体X射线衍射学基础，冶金工业出版社，1990。
[17]．陆学善，相图与相变，中国科技大学出版社，1990。
[18]．梁敬魁，相图与相结构，中国科学技术出版社，1983。
[19]．梁敬魁，粉末衍射法测定晶体结构，科学出版社，2003。
[20]．肖特·裴卓，金相浸蚀手册，科学普及出版社，1982。
[21]．马世良，金属X射线衍射学，西北工业大学出版社，1987。
[22]. Materials Data JADE Release 5, XRD Pattern Processing, Materials Data Inc.(MDI)
[23]．常铁军，祁欣，材料近代分析测试方法，哈尔滨工业大学出版社，2000。
[24]．E．B．潘钦科等，金相实验室，冶金工业出版社，1956。
[25]．韩德伟，金属学实验指导书，中南工业大学出版社，1990。
[26]．魏全金，金属电子显微分析，冶金工业出版社，1990。
[27]．任怀亮，金相实验技术，冶金工业出版社，1986。
[28]. H.Okamoto Joural of Phase Equilibria Vol. 12 No5 1991
[29]．邓海霞，La-Ni-Sn三元系合金相图及LaNi_(5-x)Sn_x，广西大学硕士学位论文，2003
[30]．姚青荣，La-Ni-Si三元系合金相图400℃等温截面，广西大学硕士学位论文，2003
[31]. Powder Diffraction File, International Center for Diffraction Data, Pennsylvania, 1993 p. 180
[32]. SAKAI T, YOSHINGA H, MIYAMURA H, et al. Rechargeable hydrogen batteries using rare-earth-based hydrogen storage alloys J.Less-Common. Met., 1992, 180:37-54.
[33]. SAKAI T, HAZAMA T, MIYAMURA H, et al. Rare-earth-based electrodes for a nickel-metal hydride battery J.Less-Common. Met. 1991, 172-174:1175-1184.
[34]．郭生武，张勇，张中平，柳永宁，掺硅MlNi_5系稀土贮氢合金电化学性能，中国稀土学报，18(2000)325-328)
[35]. Willems J J G. Philips. J. Res., 1984,39(Suppl. 1):1
[36]．王国元，潘洪革，陈长聘，贮氢电极合金研究概况，电源技术，25(2001)118-123。
[37]. LEE H H, LEE K Y, LEE J. Degradation mechanism of Ti-Zr-V-Mn-Ni metal hydride electrodes [J]. J. Alloys Comic., 1997, 260:201-207.
[38]．胡子龙，储氢材料，化学工业出版社，2002
[39]．雷永泉，新能源材料，天津大学出版社，2002
[40]. Sumita Srivastava, S.S. Sai Raman, B.K. Singh, O.N. Srivastava. On the synthesis and characterization of some new AB_5 type MmNi_(4.3)Al_(0.3)Mn_(0.4), LaNi_(5-x)Si_x(x=0.1, 0.3, 0.5) and Mg-x wt.% CFMmNi_5-y) wt.% Si hydrogen storage materials, International Journal of Hydrogen Energy, 25 (2000) 431-440.
[2]．胡忠鲠，金继红，李盛华，现代化学基础，高等教育出版社，2000年。
[3]. Editor, Binary Alloy Phase Diagrams, pp.2424-2426,1997
[4]. K.A.Gschneidner, Jr., in Rare Earth Alloy, Van Nostrand, Prunceton, 187-188(1961)
[5]. Y.Y.Pan, P.Nash, in:T.B.Massalski,, P.R.Subramanian, H.Okamoto, L.Kacprzak(Eds.), Binary Alloy Phase Diagrams, 2nd Edition, ASM International,Materials Park, OH, 1991, pp.2406-2408
[6]. A.V.Klimyenko, J.Seuntjens, L.L.Miller, B.J.Beaudry, R.A.Jacoson and K.A.Gschneidner, Jr. Journal of the Less-Common Metals, 144 (1988) 133-141
[7]. V.Paul-Boncour, A.Percheron-Guegan, M.Diaf and J.C.Achard, Journal of the Less-Common Metals, 131 (1987) 201-208
[8]．朱延果，La-Ni-Fe三元系合金相图400℃和550℃等温截面，广西大学硕士学位论，2002
[9]. P.Villars,Pearson's Handbook, Desk Edition, Crystallographic Data for Intermetallic Phases, ASM, Materials Park, Ohio, 1997
[10]. P.Nash, Binary Alloy Phase diagrams, 2nd Edition, ASM International,Materials Park, OH, 1991, pp. 1298-1302
[11]. Powder Diffraction File, International Center for Diffraction Data, 1999
[12]. Alphabetical Indexes Powder Diffraction File, International Center for Diffraction Data Sets 1-46, 1996, p. 180
[13]. R.P.Elliott, Constitution of Binary Alloys, First Supplement, Me Graw-Hill, New York, 1965, p.349. Company, 1965,349
[14]. Svechnikov V. N., Ivanchenko V. G., Kobzenko G. F. Diagramm' Sostoyaniya Metallicheskikh Sistem, 27 (1981) 60-62. (in Russian)
[15]．张圣弼，李道子，相图—原理、计算及在冶金中的应用，冶金工业出版社，1986。
[16]．李树棠，晶体X射线衍射学基础，冶金工业出版社，1990。
[17]．陆学善，相图与相变，中国科技大学出版社，1990。
[18]．梁敬魁，相图与相结构，中国科学技术出版社，1983。
[19]．梁敬魁，粉末衍射法测定晶体结构，科学出版社，2003。
[20]．肖特·裴卓，金相浸蚀手册，科学普及出版社，1982。
[21]．马世良，金属X射线衍射学，西北工业大学出版社，1987。
[22]. Materials Data JADE Release 5, XRD Pattern Processing, Materials Data Inc.(MDI)
[23]．常铁军，祁欣，材料近代分析测试方法，哈尔滨工业大学出版社，2000。
[24]．E．B．潘钦科等，金相实验室，冶金工业出版社，1956。
[25]．韩德伟，金属学实验指导书，中南工业大学出版社，1990。
[26]．魏全金，金属电子显微分析，冶金工业出版社，1990。
[27]．任怀亮，金相实验技术，冶金工业出版社，1986。
[28]. H.Okamoto Joural of Phase Equilibria Vol. 12 No5 1991
[29]．邓海霞，La-Ni-Sn三元系合金相图及LaNi_(5-x)Sn_x，广西大学硕士学位论文，2003
[30]．姚青荣，La-Ni-Si三元系合金相图400℃等温截面，广西大学硕士学位论文，2003
[31]. Powder Diffraction File, International Center for Diffraction Data, Pennsylvania, 1993 p. 180
[32]. SAKAI T, YOSHINGA H, MIYAMURA H, et al. Rechargeable hydrogen batteries using rare-earth-based hydrogen storage alloys J.Less-Common. Met., 1992, 180:37-54.
[33]. SAKAI T, HAZAMA T, MIYAMURA H, et al. Rare-earth-based electrodes for a nickel-metal hydride battery J.Less-Common. Met. 1991, 172-174:1175-1184.
[34]．郭生武，张勇，张中平，柳永宁，掺硅MlNi_5系稀土贮氢合金电化学性能，中国稀土学报，18(2000)325-328)
[35]. Willems J J G. Philips. J. Res., 1984,39(Suppl. 1):1
[36]．王国元，潘洪革，陈长聘，贮氢电极合金研究概况，电源技术，25(2001)118-123。
[37]. LEE H H, LEE K Y, LEE J. Degradation mechanism of Ti-Zr-V-Mn-Ni metal hydride electrodes [J]. J. Alloys Comic., 1997, 260:201-207.
[38]．胡子龙，储氢材料，化学工业出版社，2002
[39]．雷永泉，新能源材料，天津大学出版社，2002
[40]. Sumita Srivastava, S.S. Sai Raman, B.K. Singh, O.N. Srivastava. On the synthesis and characterization of some new AB_5 type MmNi_(4.3)Al_(0.3)Mn_(0.4), LaNi_(5-x)Si_x(x=0.1, 0.3, 0.5) and Mg-x wt.% CFMmNi_5-y) wt.% Si hydrogen storage materials, International Journal of Hydrogen Energy, 25 (2000) 431-440.