退火处理对新型无镁Y0.7La0.3Ni3.25Al0.1Mn0.15储氢合金结构和电化学性能的影响

doi:10.7503/cjcu20190430

高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (1): 145.doi: 10.7503/cjcu20190430

退火处理对新型无镁Y_0.7La_0.3Ni_3.25Al_0.1Mn_0.15储氢合金结构和电化学性能的影响

邓安强^1,^2,³,罗永春^1,^2,^*(),夏元华⁴,彭思慧²,马伟旗²,赵旭东²,杨洋²,侯晓东²

^1. 兰州理工大学省部共建有色金属先进加工与再利用国家重点实验室, 兰州 730050
^2. 兰州理工大学材料科学与工程学院, 兰州 730050
^3. 宁夏大学机械工程学院, 银川 750021
^4. 中国工程物理研究院核物理与化学研究所, 绵阳 621999

收稿日期:2019-07-31 出版日期:2020-01-10 发布日期:2019-11-04
通讯作者: 罗永春 E-mail:luoyc@lut.cn
基金资助:
国家自然科学基金批准号(51761026);宁夏自然科学基金批准号(2019AAC03003);省部共建有色金属先进加工与再利用国家重点实验室(兰州理工大学)开放课题资助批准号(SKLAB02019004)

Effect of Annealing Treatment on Structure and Electrochemical Properties of New Mg-free Y_0.7La_0.3Ni_3.25Al_0.1Mn_0.15Hydrogen Storage Alloys ^†

DENG Anqiang^1,^2,³,LUO Yongchun^1,^2,^*(),XIA Yuanhua⁴,PENG Sihui²,MA Weiqin²,ZHAO Xudong²,YANG Yang²,HOU Xiaodong²

^1. State Key Laboratory of Advanced Processing and Recycling of Non-ferrous Metals,Lanzhou University of Technology, Lanzhou 730050, China
^2. School of Materials Science and Engineering, Lanzhou University of Technology, Lanzhou 730050, China
^3. School of Mechanical Engineering, Ningxia University, Yinchuan 750021, China
^4. Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621999, China

Received:2019-07-31 Online:2020-01-10 Published:2019-11-04
Contact: Yongchun LUO E-mail:luoyc@lut.cn
Supported by:
? Supported by the National Natural Science Fundation of China No(51761026);the Ningxia Natural Science Fund, China No(2019AAC03003);the Open Fund of the State Key Laboratory of Advanced Processing and Recycling of Non-ferrous Metals, Lanzhou University of Technology, China No(SKLAB02019004)

摘要/Abstract

摘要：

通过电弧熔炼制备了无镁La-Y-Ni系A₂B₇型Y_0.7La_0.3Ni_3.25Al_0.1Mn_0.15合金, 并在高纯0.2 MPa Ar气氛下分别对合金进行850~1050 ℃真空24 h退火热处理. 通过X射线衍射(XRD)、中子衍射(ND)、扫描电子显微镜/能量分散谱(SEM/EDS)和电化学测试方法研究了退火温度对合金结构和性能的影响. 结构分析表明, 铸态合金由CaCu₅, Ce₅Co₁₉, Gd₂Co₇, Ce₂Ni₇多相构成, 随着退火温度升高, CaCu₅, Ce₅Co₁₉, Gd₂Co₇相逐步减少直至消失, Ce₂Ni₇主相相丰度逐步增加. 900~950 ℃退火时, 合金为单相Ce₂Ni₇结构. 退火温度继续升高, 合金中出现少量PuNi₃相. 合金电极的最大放电容量随着退火温度的升高先增加后降低. 从铸态的307.6 mA·h/g增加到900 ℃退火时的最大值393.1 mA·h/g, 后又降到1050 ℃退火时的366.4 mA·h/g. 合金电极的电化学循环稳定性随退火温度的升高而升高, 循环100次后电化学容量保持率(S₁₀₀)从铸态的66%上升到1050 ℃退火后的88.5%, 900~950 ℃退火时, 合金电极具有较好的综合电化学性能.

关键词: 退火处理, 储氢合金, 结构, 电化学性能

Abstract:

Mg-free A₂B₇ type Y_0.7La_0.3Ni_3.25Al_0.1Mn_0.15 alloy of La-Y-Ni system was prepared by arc melting and annealed for 24 h in high purity Ar atmosphere at 800—1050 ℃. X-ray diffraction(XRD), neutron diffraction(ND), scanning electron microscopy and energy dispersive spectroscopy(SEM/EDS) and electrochemical test methods were used to research the influence of annealing temperature on the structure and properties of the alloys. Structural analysis shows that as-cast alloy consists of CaCu₅, Ce₅Co₁₉, Gd₂Co₇ and Ce₂Ni₇. As the annealing temperature increases, CaCu₅, Ce₅Co₁₉ and Gd₂Co₇ gradually decrease to disappear, while the phase abundance of Ce₂Ni₇ main phase increases gradually. When annealing at 900—950 ℃, the alloy is single-phase Ce₂Ni₇ structure. When annealing temperature continues to rise, a small amount of PuNi₃ phase appears in the alloy. The maximum discharge capacity of the alloy electrodes increases first and then decreases as the annealing temperature increases. It increases from 307.6 mA·h/g for the as-cast alloy to 393.1 mA·h/g at the nnealing temperature of 900 ℃, and then decreases to 366.4 mA·h/g at the nnealing temperature of 1050 ℃. The electrochemical cycle stability of alloy electrodes increase with the increase of annealing temperature. After 100 cycles, the electrochemical capacity retention rate(S₁₀₀) increases from 66% for the as-cast alloys to 88.5% at the nnealing temperature of 1050 ℃. When annealing at 900—950 ℃, the alloy electrodes have better comprehensive electrochemical properties.

Key words: Annealing treatment, Hydrogen storage alloy, Structure, Electrochemical property

中图分类号:

O646
TG139.7

TrendMD:

邓安强,罗永春,夏元华,彭思慧,马伟旗,赵旭东,杨洋,侯晓东. 退火处理对新型无镁Y_0.7La_0.3Ni_3.25Al_0.1Mn_0.15储氢合金结构和电化学性能的影响. 高等学校化学学报, 2020, 41(1): 145.

DENG Anqiang,LUO Yongchun,XIA Yuanhua,PENG Sihui,MA Weiqin,ZHAO Xudong,YANG Yang,HOU Xiaodong. Effect of Annealing Treatment on Structure and Electrochemical Properties of New Mg-free Y_0.7La_0.3Ni_3.25Al_0.1Mn_0.15Hydrogen Storage Alloys ^†. Chem. J. Chinese Universities, 2020, 41(1): 145.

图/表 15

Fig.1 Backscattered SEM images of the as-cast(A) and annealed(B—G) alloys Y0.7La0.3Ni3.25Al0.1Mn0.15 Annealing temperature/℃: (B) 800; (C) 850; (D) 900; (E) 950; (F) 1000; (G) 1050.

Table 1 Chemical composition of the alloys determined by ICP and micro-area composition by EDS analysis

Sample	Phase	Atomic fraction(%)					Stoichiometric B/A
Sample	Phase	La	Y	Ni	Al	Mn	Stoichiometric B/A
As-cast		0.3106	0.6894	3.2298	0.1021	0.1560	3.49
As-cast	A₂B₇	0.2806	0.7194	3.2273	0.0711	0.1302	3.43
	Ce₅Co₁₉	0.2525	0.7475	3.5112	0.1121	0.1595	3.78
	CaCu₅	0.2147	0.7853	4.6011	0.1791	0.1638	4.94
Annealed at 800 ℃	A₂B₇	0.3359	0.6641	3.1878	0.0804	0.1329	3.40
	CaCu₅	0.2021	0.7979	4.3549	0.2176	0.1536	4.73
Annealed at 850 ℃	A₂B₇	0.3020	0.6980	3.2045	0.0943	0.1388	3.44
	CaCu₅	0.2090	0.7910	4.3423	0.2736	0.1642	4.78
Annealed at 900 ℃	Ce₂Ni₇	0.2596	0.7404	3.1830	0.1106	0.1617	3.46
Annealed at 950 ℃	Ce₂Ni₇	0.3075	0.6925	3.1879	0.0961	0.1423	3.43
Annealed at 1000 ℃	Ce₂Ni₇	0.2958	0.7042	3.1633	0.1175	0.1317	3.41
	PuNi₃	0.3704	0.6296	2.7189	0.1099	0.1164	2.95
Annealed at 1050 ℃	Ce₂Ni₇	0.2600	0.7400	3.1340	0.1080	0.1280	3.37
	PuNi₃	0.3312	0.6688	2.7239	0.0942	0.1051	2.92

Fig.2 XRD patterns of as-cast and annealed alloys(A) and its partial magnification(B) a. As-cast; b. 800 ℃; c. 850 ℃; d. 900 ℃; e. 950 ℃; f. 1000 ℃; g. 1050 ℃.

Fig.3 Rietveld refinement patterns of XRD(A) and neutron diffraction(B) for the alloy annealed at 900 ℃

Table 2 Structure parameters of various phases for different annealed alloys*

Condition	Phase	Space group(No.)	Phase abundance(%)	Lattice constant		V/nm³	Strain(%)	$d A B 2$ / $d A B 5$ Ce₂Ni₇
Condition	Phase	Space group(No.)	Phase abundance(%)	a/nm	c/nm	V/nm³	Strain(%)	$d A B 2$ / $d A B 5$ Ce₂Ni₇
As-cast	Ce₂Ni₇	P6₃/mmc(194)	65.78	0.50173	2.43745	0.53138	1.29	1.674
	Gd₂Co₇	R $3 ˉ$ m(166)	15.80	0.44902	3.93293	0.68672
	Ce₅Co₁₉	R $3 ˉ$ m(166)	8.37	0.50579	4.80588	1.06470
	CaCu₅	P6/mmm(191)	10.05	0.49621	0.40003	0.08530
Annealed at 800 ℃	Ce₂Ni₇	P6₃/mmc(194)	82.03	0.50191	2.43675	0.53161	0.80	1.247
	Gd₂Co₇	R $3 ˉ$ m(166)	9.01	0.44832	3.96713	0.69054
	CaCu₅	P6/mmm(191)	8.96	0.50048	0.40145	0.08708
Annealed at 850 ℃	Ce₂Ni₇	P6₃/mmc(194)	89.16	0.50172	2.44092	0.53211	0.55	1.116
	Gd₂Co₇	R $3 ˉ$ m(166)	6.45	0.44669	4.04017	0.69813
	CaCu₅	P6/mmm(191)	4.39	0.49996	0.40513	0.08770
Annealed at 900 ℃	Ce₂Ni₇	P6₃/mmc(194)	100.00	0.50281	2.44133	0.53451	0.17	1.030
Annealed at 950 ℃	Ce₂Ni₇	P6₃/mmc(194)	100.00	0.50202	2.43837	0.53219	0.20	1.030
Annealed at 1000 ℃	Ce₂Ni₇	P6₃/mmc(194)	89.92	0.50161	2.43729	0.53108	0.22	1.028
	PuNi₃	R $3 ˉ$ m(166)	10.08	0.49521	2.43776	0.51772
Annealed at 1050 ℃	Ce₂Ni₇	P63/mmc(194)	84.68	0.50158	2.43659	0.53087	0.24	1.020
	PuNi₃	R $3 ˉ$ m(166)	15.32	0.49448	2.43004	0.51456

Table 2 Structure parameters of various phases for different annealed alloys*

Condition	Phase	Space group(No.)	Phase abundance(%)	Lattice constant		V/nm³	Strain(%)	$d A B 2$ / $d A B 5$ Ce₂Ni₇
Condition	Phase	Space group(No.)	Phase abundance(%)	a/nm	c/nm	V/nm³	Strain(%)	$d A B 2$ / $d A B 5$ Ce₂Ni₇
As-cast	Ce₂Ni₇	P6₃/mmc(194)	65.78	0.50173	2.43745	0.53138	1.29	1.674
	Gd₂Co₇	R $3 ˉ$ m(166)	15.80	0.44902	3.93293	0.68672
	Ce₅Co₁₉	R $3 ˉ$ m(166)	8.37	0.50579	4.80588	1.06470
	CaCu₅	P6/mmm(191)	10.05	0.49621	0.40003	0.08530
Annealed at 800 ℃	Ce₂Ni₇	P6₃/mmc(194)	82.03	0.50191	2.43675	0.53161	0.80	1.247
	Gd₂Co₇	R $3 ˉ$ m(166)	9.01	0.44832	3.96713	0.69054
	CaCu₅	P6/mmm(191)	8.96	0.50048	0.40145	0.08708
Annealed at 850 ℃	Ce₂Ni₇	P6₃/mmc(194)	89.16	0.50172	2.44092	0.53211	0.55	1.116
	Gd₂Co₇	R $3 ˉ$ m(166)	6.45	0.44669	4.04017	0.69813
	CaCu₅	P6/mmm(191)	4.39	0.49996	0.40513	0.08770
Annealed at 900 ℃	Ce₂Ni₇	P6₃/mmc(194)	100.00	0.50281	2.44133	0.53451	0.17	1.030
Annealed at 950 ℃	Ce₂Ni₇	P6₃/mmc(194)	100.00	0.50202	2.43837	0.53219	0.20	1.030
Annealed at 1000 ℃	Ce₂Ni₇	P6₃/mmc(194)	89.92	0.50161	2.43729	0.53108	0.22	1.028
	PuNi₃	R $3 ˉ$ m(166)	10.08	0.49521	2.43776	0.51772
Annealed at 1050 ℃	Ce₂Ni₇	P63/mmc(194)	84.68	0.50158	2.43659	0.53087	0.24	1.020
	PuNi₃	R $3 ˉ$ m(166)	15.32	0.49448	2.43004	0.51456

Table 3 Crystallographic parameters for the alloy annealed at 900 ℃*

Subunit	Atom	Site	x	y	z	10²Biso/nm²	Occ
Laves	Y	4f	0.33333	0.66667	0.02776	1.24	1.00
CaCu₅	Y	4f	0.33333	0.66667	0.16953	0.78	0.40
	La	4f	0.33333	0.66667	0.16953	0.78	0.60
Laves	Ni	2a	0	0	0	0.66	0.92
	Al	2a	0	0	0	0.66	0.02
	Mn	2a	0	0	0	0.66	0.06
CaCu₅	Ni	4e	0	0	0.17051	1.60	0.83
	Al	4e	0	0	0.17051	1.60	0.08
	Mn	4e	0	0	0.17051	1.60	0.09
CaCu₅	Ni	4f	0.66667	0.33333	0.1681	0.39	0.90
	Al	4f	0.66667	0.33333	0.1681	0.39	0.05
	Mn	4f	0.66667	0.33333	0.1681	0.39	0.06
CaCu₅	Ni	6h	0.1692	0.33838	0.75	0.35	0.77
	Al	6h	0.1692	0.33838	0.75	0.35	0.10
	Mn	6h	0.1692	0.33838	0.75	0.35	0.13
Laves/CaCu₅	Ni	12k	0.167	0.33406	0.91513	0.21	0.81
	Al	12k	0.167	0.33406	0.91513	0.21	0.06
	Mn	12k	0.167	0.33406	0.91513	0.21	0.12

Fig.4 Phase abundance variation curves for different annealed alloys

Fig.5 Phase abundance and cell volume variation curves for Ce2Ni7 main phase

Fig.6 Model representation of Ce2Ni7-type(2H) structures for the alloy annealed at 900 ℃

Fig.7 Activation curves of different annealed alloy electrodes The inset shows the discharge capacity for different annealed alloys.

Fig.8 Discharge curve of different annealed alloy electrodes

Fig.9 Electrochemical desorption P-C isotherms(A) and its partial magnification(B) for different annealed alloy electrodes

Fig.10 Cyclic stability curves of different annealed alloy electrodes

Fig.11 Tafel curves of different annealed alloy electrodes(A) and its partial magnification(B)

Table 4 Electrochemical properties for different annealed alloy electrodes*

Alloy	N^a	C_max/(mA·h·g^-1)	S₁₀₀(%)	E_corr/V	i_corr/(mA·cm^-2)
As-cast	2	307.6	66.0	-0.933	21.34
Annealed at 800 ℃	5	347.3	68.1	-0.925	18.56
Annealed at 850 ℃	3	372.8	79.2	-0.921	18.25
Annealed at 900 ℃	2	393.1	80.0	-0.906	14.06
Annealed at 950 ℃	3	371.8	88.0	-0.913	14.71
Annealed at 1000 ℃	3	366.4	87.5	-0.917	14.71
Annealed at 1050 ℃	6	366.4	88.5	-0.92	14.84

参考文献 22

[1]	Kadir K., Sakai T., Uehara I ., J. Alloys Compd., 1997,257(1/2), 115— 121 doi: 10.1016/S0925-8388(96)03132-5 URL
[2]	Zhao Y. M ., Wang W. F.,Han S. M.,Guo W.,Li Y.,Zhang L.,Xu G. C., J. Alloys Compd., 2019,775, 259— 269 doi: 10.1016/j.jallcom.2018.10.079 URL
[3]	Denys R. V ., Riabov A. B.,Yartys V. A.,Sato M.,Delaplane R. G., J. Solid State Chem., 2008,181(4), 812— 821 doi: 10.1016/j.jssc.2007.12.041 URL
[4]	Gal L., Charbonnier V., Zhang J., Goubault L., Int. J. Hydrogen Energy, 2015,40(47), 17017— 17020 doi: 10.1016/j.ijhydene.2015.06.068 URL
[5]	Deng A. Q., Fan J. B.,Qian K. N.,Luo Y. C., Acta Phys. Chim. Sin., 2011,27(1), 103— 107 doi: 10.3866/PKU.WHXB20110133 URL
	( 邓安强, 樊静波, 钱克农, 罗永春. 物理化学学报, 2011,27(1), 103— 107) doi: 10.3866/PKU.WHXB20110133 URL
[6]	Baddour-Hadjean R., Meyer L., Pereira-Ramos J. P ., Latroche M.,Percheron-Guegan A., Electrochim. Acta, 2001,46(15), 2385— 2393 doi: 10.1016/S0013-4686(01)00440-6 URL
[7]	Aoki K., Masumoto T ., J. Alloys Compd., 1995,231(1/2), 20— 28 doi: 10.1016/0925-8388(95)01832-8 URL
[8]	Charbonnier V., Zhang J., Monnier J., Goubault L., Bernard P., Magén C., Serin V., Latroche M ., J. Phys. Chem. C, 2015,119(22), 12218— 12225 doi: 10.1021/acs.jpcc.5b03096 URL
[9]	Berezovets’ V. V ., Denys R. V.,Ryabov O. B.,Zavalii I. Y., Mater. Sci., 2007,43(4), 499— 507 doi: 10.1007/s11003-007-0058-4 URL
[10]	Lartigue C., Percheron-Guégan A., Achard J. C ., Tasset F., J. Less. Common. Met., 1980,75(11), 23— 29 doi: 10.1016/0022-5088(80)90365-3 URL
[11]	Takeshita T., Gschneidner K. A ., Lakner J. F., J. Less. Common. Met., 1981,78(1), 43— 47 doi: 10.1016/0022-5088(81)90142-9 URL
[12]	Subramanian P. R ., Smith J. F., Metall. Trans. B, 1985,16(3), 577— 584 doi: 10.1007/BF02654856 URL
[13]	Roisnel T., Rodríquez-Carvajal J., Mater. Sci. Forum., 2001, 378—381(1), 118— 123
[14]	Will G ., Powder Diffraction: the Rietveld Method and the Two-stage Method to Determine and Refine Crystal Structures from Powder Diffraction Data, Springer,. Berlin, 2006
[15]	Latroche M., Baddour-Hadjean R., Percheron-Guégan A ., J. Solid State Chem., 2003,173(1), 236— 243 doi: 10.1016/S0022-4596(03)00038-0 URL
[16]	Yasuoka S., Ishida J. Kai T., Kajiwara T., Doi S.,Yamazaki T.,Kishida K.,Inui H., Int. J. Hydrogen Energy, 2017, 42(16), 11574—11583 doi: 10.1016/j.ijhydene.2017.02.150 URL
[17]	Denys R. V., Riabov B., Yartys V. A., Delaplane R. .,Sato M., J. Alloys Compd., 2007,446/447(1), 166— 172 doi: 10.1016/j.jallcom.2006.12.137 URL
[18]	Liu J. J ., Li Y.,Han D.,Yang S. Q.,Chen X. C.,Zhang L.,Han S. M., J. Power Sources, 2015,300(12), 77— 86 doi: 10.1016/j.jpowsour.2015.09.058 URL
[19]	Senoh H., Takeichi N., Takeshita H. T ., Tanaka H.,Kiyobayashi T.,Kuriyama N.,. Materials Science and Engineering: B, 2004,108(1/2), 96— 99 doi: 10.1016/j.mseb.2003.10.055 URL
[20]	Iwase K., Mori K., Hoshikawa A., Ishigaki T., Int. J. Hydrogen Energy, 2012,37(6), 5122— 5127 doi: 10.1016/j.ijhydene.2011.12.108 URL
[21]	Liu Y. R ., Yuan H. P.,Guo M.,Jiang L. J., Int.J. Hydrogen Energy, 2019,44(39), 22064— 22073
[22]	Fang F., Chen Z. L ., Wu D. Y.,Liu H.,Dong C. K.,Song Y.,Sun D. L., J. Power Sources, 2019,427(7), 145— 153 doi: 10.1016/j.jpowsour.2019.04.072 URL

退火处理对新型无镁Y_0.7La_0.3Ni_3.25Al_0.1Mn_0.15储氢合金结构和电化学性能的影响

Effect of Annealing Treatment on Structure and Electrochemical Properties of New Mg-free Y_0.7La_0.3Ni_3.25Al_0.1Mn_0.15Hydrogen Storage Alloys ^†

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