Research Progress on Rare Earth Element Modified V-Based Solid Solution Hydrogen Storage Alloys

doi:10.19894/j.issn.1000-0518.230201

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (12): 1601-1612.DOI: 10.19894/j.issn.1000-0518.230201

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Research Progress on Rare Earth Element Modified V-Based Solid Solution Hydrogen Storage Alloys

Quan-Bing REN¹, Ming ZHONG¹, Bo ZHENG¹, Lan FENG¹, Nan DING²(), Dong-Ming YIN²(), Yong CHENG², Li-Min WANG²

^1.Jiangxi Jiangwu Haoyun High-tech Co. ?，Ltd. ，Nanchang 330095，China
^2.State Key Laboratory of Rare Earth Resources Utilization，Changchun Institute of Applied Chemistry，Chinese Academy of Sciences，Changchun 130022，China

Received:2023-07-12 Accepted:2023-10-23 Published:2023-12-01 Online:2024-01-03
Contact: Nan DING,Dong-Ming YIN
About author:dingnan@ciac.ac.cn
dmyin@ciac.ac.cn；
Supported by:
the National Key R&D Program of China(2021YFB4000604);the Key R&D Projects of Jilin Provincial Science and Technology Development Plan(20230201125GX)

Abstract

Abstract:

V-based solid solution hydrogen storage alloys possess BCC structures and have the weight hydrogen storage capacity of above 3.8% and the charge/discharge capacity of 1052 mA·h/g， which is superior to series alloys such as AB₂ type and AB₅ type. They exhibit high hydrogen solubility and diffusion coefficients at ambient temperature and pressure， therefore， and have a broad application prospect in the field of hydrogen storage and transport system as well as hydrogen energy supply. However， V-based solid solution alloys suffer from difficult activation， harsh hydrogen release conditions， short cycle life and oxygen sensitivity and oxidation. Studies have shown that rare earths have a positive effect on modifying various solid-state hydrogen storage materials. The inclusion of rare earth elements in V-based solid solution alloys through elemental substitution or doping produces a vigorously active second phase of rare earths or rare earth oxides， substantially enhancing the material's capacity for hydrogen absorption and desorption， cycling durability， and anti-toxicity characteristics. Simultaneously， it decreases the oxygen content and enhances the activity properties of materials. In terms of electrochemical performance， the addition of rare earth elements can significantly improve the cycle stability， corrosion resistance and high rate discharge performance of the alloy electrode. Therefore， rare earth element substitution is a well-established method for achieving practical applications of V-based solid solution hydrogen storage materials. This report presents the recent research status of rare earth-modified V-based solid solution hydrogen storage alloys， with a focus on summarizing the rare earth elements' mechanism of action and providing an outlook for future key research directions.

Key words: Vanadium-based solid solution alloys, Rare earth element, Hydrogen storage performance

CLC Number:

O614

Quan-Bing REN, Ming ZHONG, Bo ZHENG, Lan FENG, Nan DING, Dong-Ming YIN, Yong CHENG, Li-Min WANG. Research Progress on Rare Earth Element Modified V-Based Solid Solution Hydrogen Storage Alloys[J]. Chinese Journal of Applied Chemistry, 2023, 40(12): 1601-1612.

Figures/Tables 13

References 60

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VH _x	Lattice constant						Unit-cell V/μm³	Phase type
VH _x	a/nm	b/nm	c/nm	α/（°）	β/（°）	γ/（°）	Unit-cell V/μm³	Phase type
V	0.302 6	0.302 6	0.303 0	90.00	90.00	90.00	27.73	BCC
VH_0.125	0.304 5	0.304 5	0.303 2	89.99	89.99	90.04	28.11	BCC
VH_0.25	0.304 8	0.304 8	0.303 4	90.03	90.00	90.00	28.18	BCC
VH_0.50	0.306 5	0.306 6	0.311 3	89.97	90.02	90.09	29.96	BCT
VH_0.75	0.316 7	0.316 2	0.316 8	89.94	89.88	89.77	31.71	Amorphosis BCC
VH	0.317 1	0.317 0	0.315 4	90.00	89.99	89.99	31.71	BCC
VH	4.102	4.102	4.102	90.00	90.00	90.00	34.50	FCC
VH_1.25	0.412 7	0.411 0	0.411 0	90.02	89.97	89.99	34.87	FCC
VH_1.50	0.410 4	0.410 4	0.410 4	89.99	89.99	89.99	34.56	FCC
VH_1.75	0.420 0	0.420 0	0.420 0	90.28	90.09	90.15	37.05	Amorphosis FCC
VH_2.0	0.427 6	0.427 9	0.427 9	89.99	90.00	90.01	39.09	FCC

VH _x	Lattice constant						Unit-cell V/μm³	Phase type
VH _x	a/nm	b/nm	c/nm	α/（°）	β/（°）	γ/（°）	Unit-cell V/μm³	Phase type
V	0.302 6	0.302 6	0.303 0	90.00	90.00	90.00	27.73	BCC
VH_0.125	0.304 5	0.304 5	0.303 2	89.99	89.99	90.04	28.11	BCC
VH_0.25	0.304 8	0.304 8	0.303 4	90.03	90.00	90.00	28.18	BCC
VH_0.50	0.306 5	0.306 6	0.311 3	89.97	90.02	90.09	29.96	BCT
VH_0.75	0.316 7	0.316 2	0.316 8	89.94	89.88	89.77	31.71	Amorphosis BCC
VH	0.317 1	0.317 0	0.315 4	90.00	89.99	89.99	31.71	BCC
VH	4.102	4.102	4.102	90.00	90.00	90.00	34.50	FCC
VH_1.25	0.412 7	0.411 0	0.411 0	90.02	89.97	89.99	34.87	FCC
VH_1.50	0.410 4	0.410 4	0.410 4	89.99	89.99	89.99	34.56	FCC
VH_1.75	0.420 0	0.420 0	0.420 0	90.28	90.09	90.15	37.05	Amorphosis FCC
VH_2.0	0.427 6	0.427 9	0.427 9	89.99	90.00	90.01	39.09	FCC

RE	Phase	Lattice parameters/nm		Cell volume/nm³
RE	Phase	a	c	Cell volume/nm³
—	BCC	0.293 4	0.798 0	0.025 26
—	C14 Laves	0.487 3	0.798 0	0.164 1
La	BCC	0.296 0	0.803 0	0.025 93
La	C14 Laves	0.490 1	0.803 0	0.167 0
Ce	BCC	0.298 0	0.801 4	0.026 46
Ce	C14 Laves	0.487 7	0.801 4	0.165 1
Pr	BCC	0.298 4	0.804 6	0.026 58
Pr	C14 Laves	0.493 7	0.804 6	0.169 8
Nd	BCC	0.299 0	0.803 6	0.026 73
Nd	C14 Laves	0.490 1	0.803 6	0.167 2
Gd	BCC	0.299 0	0.798 4	0.026 73
Gd	C14 Laves	0.492 5	0.798 4	0.167 8

RE	Phase	Lattice parameters/nm		Cell volume/nm³
RE	Phase	a	c	Cell volume/nm³
—	BCC	0.293 4	0.798 0	0.025 26
—	C14 Laves	0.487 3	0.798 0	0.164 1
La	BCC	0.296 0	0.803 0	0.025 93
La	C14 Laves	0.490 1	0.803 0	0.167 0
Ce	BCC	0.298 0	0.801 4	0.026 46
Ce	C14 Laves	0.487 7	0.801 4	0.165 1
Pr	BCC	0.298 4	0.804 6	0.026 58
Pr	C14 Laves	0.493 7	0.804 6	0.169 8
Nd	BCC	0.299 0	0.803 6	0.026 73
Nd	C14 Laves	0.490 1	0.803 6	0.167 2
Gd	BCC	0.299 0	0.798 4	0.026 73
Gd	C14 Laves	0.492 5	0.798 4	0.167 8

Products	ΔH/（kJ·mol^-1）	ΔS/（J·K·mol^-1）	ΔG/（kJ·mol^-1） at 298 K
VH₂	-40.2	-142.3	2.2
LaH₂	-207.9	148.5	-252.2
PrH₂	-200.0	146.4	-243.6
CeH₂	-141.8	148.1	-186.0
CeH_2.69	-176.8	148.1	-221.0

Research Progress on Rare Earth Element Modified V-Based Solid Solution Hydrogen Storage Alloys

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Cycles	Capacity/%		Capacity retention rate（R）/%
Cycles	TiV_1.1Cr_0.3Mn_0.6	Ti_0.9Y_0.1V_1.1Mn_0.7Cr_0.2	TiV_1.1Cr_0.3Mn_0.6	Ti_0.9Y_0.1V_1.1Mn_0.7Cr_0.2
1^st	3.345	3.084	100	100
25^th	3.283	2.97	98.15	96.30
50^th	3.177	2.95	94.98	95.65
75^th	3.068	2.889	91.72	93.68
100^th	2.852	2.851	85.23	92.44

Samples	R_ct /Ω	I₀/（mA·g^-1）
Norm	0.154	169.5
Gd	0.453	57.6
Ho	0.125	208.8
Er	0.155	178.4
Yb	0.152	171.7
Y	0.143	182.6

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