CN104532095A - Yttrium-nickel rare earth-based hydrogen storage alloy - Google Patents

Yttrium-nickel rare earth-based hydrogen storage alloy Download PDF

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CN104532095A
CN104532095A CN201410429202.8A CN201410429202A CN104532095A CN 104532095 A CN104532095 A CN 104532095A CN 201410429202 A CN201410429202 A CN 201410429202A CN 104532095 A CN104532095 A CN 104532095A
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hydrogen storage
alloy
storage alloy
lanthanon
type
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CN104532095B (en
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闫慧忠
熊玮
王利
李宝犬
李金�
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Baotou Rare Earth Research Institute
Ruike Rare Earth Metallurgy and Functional Materials National Engineering Research Center Co Ltd
Tianjin Baogang Rare Earth Research Institute Co Ltd
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Baotou Rare Earth Research Institute
Ruike Rare Earth Metallurgy and Functional Materials National Engineering Research Center Co Ltd
Tianjin Baogang Rare Earth Research Institute Co Ltd
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Publication of CN104532095A publication Critical patent/CN104532095A/en
Priority to CN201580046681.8A priority patent/CN107075617B/en
Priority to JP2017530386A priority patent/JP6464268B2/en
Priority to US15/507,133 priority patent/US10566614B2/en
Priority to PCT/CN2015/088274 priority patent/WO2016029861A1/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to A2B7 type RExYnNiz-a-bMnaAlb hydrogen storage alloy. The alloy is good in pressure-composition-isothermality, and has a maximum hydrogen storage amount of up to more than 1.36 wt.% under usual conditions. The alloy of the invention has better electrochemical performance as a hydrogen storage electrode and better gas-phase hydrogen absorption and desorption performance as a hydrogen storage material than traditional LaNi5 type hydrogen storage alloy; the alloy contains no magnesium element in the composition, so the preparation method of the alloy is simple and safe when compared with that of traditional rare earth-magnesium-nickel-based A2B7 type hydrogen storage alloy.

Description

A kind of yttrium-nickel lanthanon hydrogen storage alloy
Technical field
The present invention relates to a kind of A 2b 7type rare earth-yttrium-nickel base hydrogen storage alloy.
Background technology
Hydrogen storage alloy is that the class found the end of the sixties in last century has the high functional materials storing hydrogen density, and existing hydrogen storage alloy is broadly divided into six classes from composition: Rare Earth AB 5type is as LaNi 5; Magnesium system is as Mg 2ni, MgNi, La 2mg 17; RE-Mg-Ni system AB 3-4type is as La 2mgNi 9, La 5mg 2ni 23, La 3mgNi 14; Titanium system AB type is as TiNi, TiFe; Zirconium, titanium system Laves phase AB 2type is as ZrNi 2; Vanadium system solid solution is as (V 0.9ti 0.1) 1-xfe x.
Now widely used hydrogen storage material is LaNi 5type hydrogen storage alloy.This alloy is mainly used as the negative material of metal hydride-nickel secondary batteries (MH/Ni), and its theoretical electrochemistry capacity is 373mAhg -1, the commodity negative material Mm (NiCoMnAl) of practical application 5the maximum capacity of (wherein Mm is norium) is about 350mAhg -1.In order to develop the hydrogen storage alloy that chemical property is better or hydrogen-storage amount is larger, focus is become to the research of Magnuminium.The theoretical electrochemistry capacity of Mg-base hydrogen-bearing alloy material is high, especially RE-Mg-Ni system AB 3type, A 2b 7type, A 5b 19the research of type hydrogen storage alloy achieves impressive progress, and enters the commercial application stage.Zirconium, titanium system and vanadium system hydrogen storage material are not all widely used owing to activating the too high reason of difficulty, cost.
A 2b 7in type RE-Mg-Ni materials base hydrogen storage alloy, Mg element is one of principal constituent.Disclose one in CN201310228766.0 to use for nickel-hydrogen battery A 2b 7type hydrogen storage alloy and preparation method thereof.Its general structure is: Ln amg bni xy yz zwherein Ln is one or more rare earth elements, Y is one or more elements in Al, Co, Nb, V, Fe, Cu, Zn, As, Ga, Mo, Sn, In, W, Si, P, Z is one or more elements in Ag, Sr, Ge, 0.5≤a < 2,0 < b < 1,5 < X+Y+Z < 9,0 < Y < 3,0 < Z < 1.Must contain Mg element in this proprietary alloy composition, because the vapour pressure of active metal element magnesium is high, manufacture difficulty be increased, alloying constituent is difficult to control, and the fine magnesium powder simultaneously volatilized is inflammable and explosive and there is potential safety hazard.
Summary of the invention
The present invention aims to provide a kind of lanthanon hydrogen storage alloy not containing Mg element, to overcome deficiency of the prior art.
The present invention relates to a kind of general formula is RE xy yni z-a-bmn aal bnovel rare-earth base hydrogen storage alloy, wherein, one or more elements in RE=La, Ce, Pr, Nd, Sm, Gd, x > 0, y>=0.5, x+y=3; 11 > z>=9.5 (are stoichiometric ratio A during z=10.5 2b 7type; Be non-stoichiometric A during z ≠ 10.5 2b 7type); 4.5>=a+b > 0.
Further, the preferred content range of RE element is 0.5 ~ 2.0:
Further, the preferred content range of Mn element is 0.5 ~ 2.5;
Further, the preferred content range of Al element is 0.2 ~ 1.0.
Alloy of the present invention can adopt high melt-quick quenching technique to prepare, its technological process is: the equal > 99.0% of the purity of each elemental metals or master alloy raw material in composition, calculate according to chemical molecular formula proportioning and accurately take each raw material, raw material is put into Al successively 2o 3crucible, is evacuated to 3.0Pa, is filled with rare gas element Ar to 0.055MPa.Intensification melting, is incubated rapid hardening after about 6min.Rapid hardening copper roller linear velocity is 3.4m/s.Copper roller normal open water coolant, coolant water temperature 25 DEG C.Easy scaling loss raw material need increase proportioning in right amount, increases ratio as following table:
Raw material RE Y Mn Al
Increase ratio 2％ 1％ 5％ 3％
Except above-mentioned preparation method, RE of the present invention xy yni z-a-bmn aal bhydrogen storage alloy can also adopt this area other hydrogen storage alloy preparation method to be prepared, such as: high melt teeming practice, mechanical alloying (MA) method, powder sintering, high melt-gas atomization, reduction-diffusion process, displacement diffusion process, conbustion synthesis (CS) method, self-propagating high-temperature synthesis (SHS) etc.
Present invention also offers a kind of by described RE xy yni z-a-bmn aal bthe secondary cell that type hydrogen storage alloy prepares.
RE of the present invention xy yni z-a-bmn aal bhydrogen storage alloy also can press different ratios compound with other hydrogen storage material, prepares new hydrogen storage material.
RE of the present invention xy yni z-a-bmn aal btype hydrogen storage alloy can adopt heat treating method to improve its weave construction and performance, as: eliminate alloy structure stress and solute segregation, improve hydrogen platform identity or alloy electrode are inhaled/put to alloy charge/discharge platform identity, raising hydrogen－sucking amount and cycle life etc.Also various surface treatment method can be adopted to improve its performance, as: improve the suction of alloy/put hydrogen or charge/discharge dynamic performance, strengthen the resistance of oxidation of alloy, improve the electrical and thermal conductivity performance etc. of alloy.
A of the present invention 2b 7type RE xy yni z-a-bmn aal bhydrogen storage alloy has good pressure-composition-isothermal (P-c-T) characteristic, and maximum storage hydrogen quantity at typical condition can reach more than 1.36wt.%.The chemical property of alloy of the present invention as hydrogen-storage electrode and the gas phase hydrogen storage property as hydrogen storage material are better than traditional LaNi 5type hydrogen storage alloy; Because of in its composition not containing magnesium elements, therefore with traditional RE-Mg-Ni system A 2b 7type hydrogen storage alloy is compared, the simple and safety of manufacture method.Alloy of the present invention has good activation performance, multiplying power discharging ability, discharge and recharge or suction and puts hydrogen cyclical stability, and can use in wide temperature range, self-discharge is little.In addition, in hydrogen storage alloy of the present invention, yttrium (Y) element is one of main component, yttrium aboundresources in the rare earth mineral reserve of China, and the use of this element is conducive to the comprehensive utilization balancing China's rare earth resources.
Accompanying drawing explanation
Fig. 1 is LaCe 0.5y 1.5ni 9.7mn 0.5al 0.3the XRD figure (embodiment 23) of hydrogen storage alloy
Fig. 2 is LaY 2ni 9.5mn 0.5al 0.5the P-c-T curve (embodiment 13) of hydrogen storage alloy
Embodiment
Employing preceding method prepares the A described in embodiment 1 ~ 23 2b 7type RE xy yni z-a-bmn aal bhydrogen storage alloy.
Alloy described in embodiment 13 and embodiment 14 adopts identical raw material ratio to obtain.Alloy described in embodiment 13 adopts afore-said hot melting-quick quenching technique preparation, its technological process is: the equal > 99.0% of the purity of each elemental metals or master alloy raw material in composition, calculate according to chemical molecular formula proportioning and accurately take each raw material (easy scaling loss raw material need increase proportioning in right amount), raw material is put into Al successively 2o 3crucible, is evacuated to 3.0Pa, is filled with rare gas element Ar to 0.055MPa.Intensification melting, is incubated rapid hardening after about 6min.Rapid hardening copper roller linear velocity is 3.4m/s.Copper roller normal open water coolant, coolant water temperature 25 DEG C.
Alloy described in embodiment 14 also can adopt high melt-quick quenching technique preparation, annealing heat treatment step is increased in its technological process, be specially: the equal > 99.0% of the purity of each elemental metals or master alloy raw material in composition, calculate according to chemical molecular formula proportioning and accurately take each raw material (easy scaling loss raw material need increase proportioning in right amount), raw material is put into Al successively 2o 3crucible, is evacuated to 3.0Pa, is filled with rare gas element Ar to 0.055MPa.Intensification melting, is incubated rapid hardening after about 6min.Rapid hardening copper roller linear velocity is 3.4m/s.Copper roller normal open water coolant, coolant water temperature 25 DEG C.Rapid hardening alloy slice is under vacuum or protection of inert gas, and anneal at 750 DEG C thermal treatment 8h.
Ml in embodiment 20 is lanthanum rich norium, is wherein about 64% containing La, Ce is about 25%, Pr is about 3%, Nd is about 8%.
The preparation method of test electrode is: embodiment 1 ~ 23 alloy becomes 200-300 object powder through Mechanical Crushing, and alloy powder and carbonyl nickel powder mix with the mass ratio of 1: 4, make under 16MPa pressure mH electrode slice, this electrode slice is placed between two panels nickel foam, sandwich the nickel strap as lug simultaneously, under 16MPa pressure, again make the storage hydrogen negative pole (MH electrode) for testing, around electrode slice, ensure the close contact between electrode slice and nickel screen by spot welding.
In open type two electrode system of test chemical property, negative pole is MH electrode, and positive pole adopts the sintering Ni (OH) of capacity excess 2/ NiOOH electrode, electrolytic solution is 6molL -1kOH solution, 24h shelved by the battery assembled, application LAND cell tester measures the chemical property (activation number of times, peak capacity, high-rate discharge capacity HRD, cyclical stability etc.) of alloy electrode with galvanostatic method, and test environment temperature is 298K.Density of charging current 70mAg -1, duration of charging 6h, discharge current density 70mAg -1, electric discharge stopping potential is 1.0V, charge and discharge intermittent time 10min.
Following table 1 lists A described in embodiment 1 ~ 23 2b 7type RE xy yni z-a-bmn aal bhydrogen storage alloy and chemical property thereof.
Table 1 A 2b 7type RE xy yni z-a-bmn aal bhydrogen storage alloy and chemical property thereof
Note: a is the cycle index that electrode activation needs; B is maximum discharge capacity; C is the capability retention of circulation 100 times; D is discharge current density I dfor 350mAg -1time multiplying power discharging ability; Discharge capacitance when e is low temperature 243K; F is the capability retention (self-discharge characteristics) after depositing 72 hours.
As seen from Table 1, alloy LaY described in embodiment 13 and 14 2ni 9.5mn 0.5al 0.5chemical property compare, the electrochemistry capacitance of annealed heat treated embodiment 14 alloy electrode increases, and cycle life, multiplying power discharging ability, cryogenic discharging characteristic, self-discharge performance all make moderate progress.
X-ray diffractometer is used to analyze LaCe 0.5y 1.5ni 9.7mn 0.5al 0.3the weave construction of alloy, alloy principal phase is Ce 2ni 7phase or Y 2ni 7phase, as shown in Figure 1.
Application Sievert method measures LaY at 313K 2ni 9.5mn 0.5al 0.5pressure-composition the thermoisopleth (P-c-T curve) of alloy, maximum storage hydrogen quantity can reach 1.36wt.%, hydrogen desorption plateau pressure at about 0.05MPa, as shown in Figure 2.

Claims (10)

1. a lanthanon hydrogen storage alloy, is characterized in that: composition general formula is RE xy yni z-a-bmn aal b, wherein RE is one or more elements in La, Ce, Pr, Nd, Sm, Gd; X > 0, y>=0.5, x+y=3; 11 > z>=9.5; 4.5>=a+b > 0.
2. a kind of lanthanon hydrogen storage alloy as claimed in claim 1, is characterized in that: 2.0 >=x >=0.5.
3. a kind of lanthanon hydrogen storage alloy as claimed in claim 1 or 2, is characterized in that: 2.5 >=a >=0.5.
4. a kind of lanthanon hydrogen storage alloy as claimed in claim 1 or 2, is characterized in that: 1.0 >=b >=0.2.
5. a kind of lanthanon hydrogen storage alloy as claimed in claim 1 or 2, is characterized in that: z=10.5.
6. a kind of lanthanon hydrogen storage alloy as claimed in claim 1, is characterized in that: 2.0 >=x >=0.5,2.5 >=a >=0.5,1.0 >=b >=0.2, z=10.5.
7. a preparation method for lanthanon hydrogen storage alloy, is characterized in that: calculate according to chemical molecular formula proportioning and accurately take each elemental metals raw material, material purity is all greater than 99.0%; Raw material is put into Al 2o 3crucible, is evacuated to 3.0Pa, is filled with rare gas element Ar to 0.055MPa; Intensification melting, be incubated rapid hardening after about 6min, rapid hardening copper roller linear velocity is 3.4m/s, copper roller normal open water coolant, coolant water temperature 25 DEG C.
8. the preparation method of a kind of lanthanon hydrogen storage alloy as claimed in claim 7, is characterized in that: after rapid hardening step terminates, and alloy is under vacuum or protection of inert gas, and anneal at 750 DEG C thermal treatment 8h.
9. a hydrogen-bearing alloy electrode, is characterized in that using the lanthanon hydrogen storage alloy according to any one of claim 1-6 as hydrogen storage media.
10. a secondary cell, is characterized in that containing hydrogen-bearing alloy electrode according to claim 9.
CN201410429202.8A 2014-08-28 2014-08-28 Yttrium-nickel rare earth-based hydrogen storage alloy Active CN104532095B (en)

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Application Number Priority Date Filing Date Title
CN201410429202.8A CN104532095B (en) 2014-08-28 2014-08-28 Yttrium-nickel rare earth-based hydrogen storage alloy
CN201580046681.8A CN107075617B (en) 2014-08-28 2015-08-27 A kind of lanthanon hydrogen storage alloy and application thereof
JP2017530386A JP6464268B2 (en) 2014-08-28 2015-08-27 Rare earth hydrogen storage alloy and its use
US15/507,133 US10566614B2 (en) 2014-08-28 2015-08-27 Rare earth based hydrogen storage alloy and application thereof
PCT/CN2015/088274 WO2016029861A1 (en) 2014-08-28 2015-08-27 Rare-earth based hydrogen storage alloy and application thereof

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Cited By (12)

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WO2016029861A1 (en) * 2014-08-28 2016-03-03 包头稀土研究院 Rare-earth based hydrogen storage alloy and application thereof
CN106757169A (en) * 2016-12-10 2017-05-31 包头稀土研究院 A kind of hydrogen bearing alloy rare earth intermediate alloy and preparation method thereof
CN109868390A (en) * 2017-12-04 2019-06-11 北京有色金属研究总院 A kind of rare-earth-nickel-base AB2Type hydrogen storage alloy material and preparation method
CN110157951A (en) * 2019-06-06 2019-08-23 宜宾天原集团股份有限公司 The preparation method of alloy material storing hydrogen
CN110714139A (en) * 2018-07-13 2020-01-21 有研工程技术研究院有限公司 Rare earth-nickel-based hydrogen storage alloy material and preparation method thereof
CN111082037A (en) * 2019-12-31 2020-04-28 有研工程技术研究院有限公司 Nickel-hydrogen secondary battery
CN111118346A (en) * 2019-12-05 2020-05-08 包头稀土研究院 Zirconium or titanium containing A2B7 type hydrogen storage alloy, negative electrode, battery and preparation method
CN111118343A (en) * 2019-10-23 2020-05-08 包头稀土研究院 A2B7 type gadolinium-nickel-containing hydrogen storage alloy, negative electrode, battery and preparation method
CN111118344A (en) * 2019-11-15 2020-05-08 包头稀土研究院 Multi-element gadolinium-containing rare earth hydrogen storage material, cathode, battery and preparation method
WO2020224589A1 (en) * 2019-05-06 2020-11-12 中国石油化工股份有限公司 Organic hydrogen storage raw material dehydrogenation catalyst, carrier of catalyst, hydrogen storage alloy, and method for providing high-purity hydrogen gas
CN114703400A (en) * 2022-04-24 2022-07-05 包头稀土研究院 A5B19Rare earth-yttrium-nickel hydrogen storage alloy, battery and preparation method
CN114955988A (en) * 2022-05-30 2022-08-30 赣州有色冶金研究所有限公司 Rare earth yttrium-nickel hydrogen storage alloy and preparation method and application thereof

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WO2016029861A1 (en) * 2014-08-28 2016-03-03 包头稀土研究院 Rare-earth based hydrogen storage alloy and application thereof
US10566614B2 (en) 2014-08-28 2020-02-18 Baotou Research Institute of Rare Earths Rare earth based hydrogen storage alloy and application thereof
CN106757169A (en) * 2016-12-10 2017-05-31 包头稀土研究院 A kind of hydrogen bearing alloy rare earth intermediate alloy and preparation method thereof
CN109868390A (en) * 2017-12-04 2019-06-11 北京有色金属研究总院 A kind of rare-earth-nickel-base AB2Type hydrogen storage alloy material and preparation method
CN109868390B (en) * 2017-12-04 2020-12-18 有研工程技术研究院有限公司 Rare earth-nickel base AB2Hydrogen storage alloy material and preparation method thereof
CN110714139A (en) * 2018-07-13 2020-01-21 有研工程技术研究院有限公司 Rare earth-nickel-based hydrogen storage alloy material and preparation method thereof
WO2020224586A1 (en) * 2019-05-06 2020-11-12 中国石油化工股份有限公司 Organic hydrogen storage raw material dehydrogenation catalyst, carrier of the catalyst, hydrogen storage alloy, and method for providing high-purity hydrogen
WO2020224589A1 (en) * 2019-05-06 2020-11-12 中国石油化工股份有限公司 Organic hydrogen storage raw material dehydrogenation catalyst, carrier of catalyst, hydrogen storage alloy, and method for providing high-purity hydrogen gas
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CN110157951A (en) * 2019-06-06 2019-08-23 宜宾天原集团股份有限公司 The preparation method of alloy material storing hydrogen
CN111118343A (en) * 2019-10-23 2020-05-08 包头稀土研究院 A2B7 type gadolinium-nickel-containing hydrogen storage alloy, negative electrode, battery and preparation method
CN111118343B (en) * 2019-10-23 2021-06-11 包头稀土研究院 A2B7 type gadolinium-nickel-containing hydrogen storage alloy, negative electrode, battery and preparation method
CN111118344A (en) * 2019-11-15 2020-05-08 包头稀土研究院 Multi-element gadolinium-containing rare earth hydrogen storage material, cathode, battery and preparation method
CN111118344B (en) * 2019-11-15 2021-07-27 包头稀土研究院 Multi-element gadolinium-containing rare earth hydrogen storage material, cathode, battery and preparation method
CN111118346A (en) * 2019-12-05 2020-05-08 包头稀土研究院 Zirconium or titanium containing A2B7 type hydrogen storage alloy, negative electrode, battery and preparation method
CN111118346B (en) * 2019-12-05 2021-07-13 包头稀土研究院 Zirconium or titanium containing A2B7 type hydrogen storage alloy, negative electrode, battery and preparation method
CN111082037A (en) * 2019-12-31 2020-04-28 有研工程技术研究院有限公司 Nickel-hydrogen secondary battery
CN114703400A (en) * 2022-04-24 2022-07-05 包头稀土研究院 A5B19Rare earth-yttrium-nickel hydrogen storage alloy, battery and preparation method
CN114955988A (en) * 2022-05-30 2022-08-30 赣州有色冶金研究所有限公司 Rare earth yttrium-nickel hydrogen storage alloy and preparation method and application thereof

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