CN104513915A - Zirconium and titanium-doped AB3 type rare earth-yttrium-nickel family hydrogen storage alloy - Google Patents

Zirconium and titanium-doped AB3 type rare earth-yttrium-nickel family hydrogen storage alloy Download PDF

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CN104513915A
CN104513915A CN201410427179.9A CN201410427179A CN104513915A CN 104513915 A CN104513915 A CN 104513915A CN 201410427179 A CN201410427179 A CN 201410427179A CN 104513915 A CN104513915 A CN 104513915A
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hydrogen storage
storage alloy
alloy
rare earth
lanthanon hydrogen
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CN104513915B (en
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王利
闫慧忠
熊玮
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 CN104513915A publication Critical patent/CN104513915A/en
Priority to PCT/CN2015/088274 priority patent/WO2016029861A1/en
Priority to US15/507,133 priority patent/US10566614B2/en
Priority to JP2017530386A priority patent/JP6464268B2/en
Priority to CN201580046681.8A priority patent/CN107075617B/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

Abstract

The invention relates to a rare earth family hydrogen storage alloy with the general formula of RExYyNiz-a-b-cMnaAlbMcZrATiB. The highest capacity of the rare earth family hydrogen storage alloy which is an electrode is higher than that of LaNi5 type hydrogen storage alloy. A preparation method of the rare earth family hydrogen storage alloy is simple and safe. The rare earth family hydrogen storage alloy has good activation performance, rate discharge ability, and charge and discharge or hydrogen absorption and desorption cycle stability, can be used in a wide temperature range, has small self discharge, and can be used to produce negative electrodes of alkaline secondary batteries, and secondary batteries containing the hydrogen storage alloy disclosed in the invention.

Description

Add the AB of zirconium, titanium elements 3type rare earth-yttrium-nickel base hydrogen storage alloy
Technical field
The present invention relates to a kind of AB containing zirconium, titanium elements 3type 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 3-3.5type 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 about 350mAhg of maximum capacity of (wherein Mm is norium) -1.In order to develop the hydrogen storage alloy that chemical property is higher or hydrogen-storage amount is larger, the research of Magnuminium is given to the attention of height.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.
Existing to AB in prior art 3the report of type La-Y-Ni hydrogen storage alloy, but not containing zirconium, titanium elements in alloy, and hydrogen storage capability is the highest only has 260mAhg -1(see: " An electrochemical study of new La 1-xce xy 2ni 9(0≤x≤1) hydrogen storage alloys "; Electrochimica Acta; 46 (2001); P2385-2393 and " New ternaryintermetallic compounds belonging to the R-Y-Ni (R=La, Ce) system as negative electrodes forNi-MH batteries "; Journal of Alloys and Compounds, 330-332 (2002), P782-786).
The AB of extensively research at present 3in type RE-Mg-Ni materials base hydrogen storage alloy, Mg element is one of principal constituent.CN102660700A discloses a kind of AB 3type hydrogen storage alloy and preparation method, the chemical formula of this alloy is La 0.35pr 0.30mg xni 2.90al 0.30, wherein x=0.30 ~ 0.35.Mg element must be contained in this alloy ingredient.Because the vapour pressure of active metal element magnesium is high, manufacture difficulty is 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.
A kind of general formula is RE xy yni z-a-b-cmn aal bm czr ati blanthanon hydrogen storage alloy, wherein, one or more elements in RE=La, Ce, Pr, Nd, Sm, Gd, x > 0, y>=0.5, x+y=3; One or more elements in M=Cu, Fe, Co, Sn, V, W, 9.5 > z>=8.5 (are stoichiometric ratio AB during z=9 3type; Be non-stoichiometric AB during z ≠ 9 3type), 3>=a+b > 0,2.5>=c>=0,2>=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 ~ 2.0;
Further, the preferred content range of Al element is 0.2 ~ 1.0;
Further, the preferred content range of M element is 0.1 ~ 2.0;
Further, the preferred content range of Zr element is 0.1 ~ 1.0;
Further, the preferred content range of Ti element is 0.1 ~ 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-b-cmn aal bm czr ati 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-b-cmn aal bm czr ati bthe secondary cell that type hydrogen storage alloy prepares.
RE of the present invention xy yni z-a-b-cmn aal bm czr ati 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-b-cmn aal bm czr ati 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.
RE of the present invention xy yni z-a-b-cmn aal bm czr ati bthe peak capacity of hydrogen-bearing alloy electrode is higher than LaNi 5type hydrogen storage alloy, the simple and safety of manufacture method.Have good activation performance, multiplying power discharging ability, discharge and recharge or suction and put hydrogen cyclical stability, can use in wide temperature range, self-discharge is little; May be used for preparing the negative pole of alkaline secondary cell and the secondary cell containing this hydrogen storage alloy.
Accompanying drawing explanation
Fig. 1 is LaY 2ni 8.3mn 0.5al 0.2zr 0.1the XRD figure of hydrogen storage alloy.
Embodiment
Employing preceding method prepares the RE described in embodiment 1 ~ 34 xy yni z-a-b-cmn aal bm czr ati btype hydrogen storage alloy.
Alloy described in embodiment 15 and embodiment 16 adopts identical raw material ratio to obtain.Alloy described in embodiment 15 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 16 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 25 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 1-34 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 lists RE described in embodiment 1-34 xy yni z-a-b-cmn aal bm czr ati bhydrogen storage alloy and chemical property thereof.
Table 1 RE xy yni z-a-b-cmn aal bm czr ati 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; The multiplying power discharging ability that d is discharge current density Id when being 350mAg-1; 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 15 and 16 2ni 8mn 0.5al 0.5zr 0.5ti 0.3chemical property compare, the electrochemistry capacitance of annealed heat treated embodiment 16 alloy electrode increases, and cycle life, multiplying power discharging ability, cryogenic discharging characteristic all make moderate progress.
As shown in Figure 1, x-ray diffractometer is used to analyze LaY 2ni 8.3mn 0.5al 0.2zr 0.1the weave construction of alloy (embodiment 18), alloy principal phase is LaY 2ni 9phase.

Claims (10)

1. a lanthanon hydrogen storage alloy, is characterized in that: composition general formula is RE xy yni z-a-b-cmn aal bm czr ati b, wherein RE is one or more elements in La, Ce, Pr, Nd, Sm, Gd; M is one or more elements in Cu, Fe, Co, Sn, V, W; X > 0, y>=0.5, x+y=3; 9.5 > z>=8.5; 3>=a+b > 0,2.5>=c>=0,2>=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: 2.0 >=a >=0.5,1.0 >=b >=0.2.
4. a kind of lanthanon hydrogen storage alloy as claimed in claim 1 or 2, is characterized in that: 2.0 >=c >=0.1.
5. a kind of lanthanon hydrogen storage alloy as claimed in claim 1 or 2, is characterized in that: 1.0 >=A >=0.1,1.0 >=B >=0.1.
6. a kind of lanthanon hydrogen storage alloy as claimed in claim 1 or 2, is characterized in that: z=9.
7. a kind of lanthanon hydrogen storage alloy as claimed in claim 1, is characterized in that: 2.0 >=x >=0.5,2.0 >=a >=0.5,1.0 >=b >=0.2,2.0 >=c >=0.1,1.0 >=A >=0.1,1.0 >=B >=0.1, z=9.
8. 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.
9. the preparation method of a kind of lanthanon hydrogen storage alloy as claimed in claim 8, 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.
10. a secondary cell, is characterized in that containing the electrode of the lanthanon hydrogen storage alloy according to any one of claim 1-6 as hydrogen storage media.
CN201410427179.9A 2014-08-28 2014-08-28 Zirconium and titanium-doped AB3 type rare earth-yttrium-nickel family hydrogen storage alloy Active CN104513915B (en)

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CN201410427179.9A CN104513915B (en) 2014-08-28 2014-08-28 Zirconium and titanium-doped AB3 type rare earth-yttrium-nickel family hydrogen storage alloy
PCT/CN2015/088274 WO2016029861A1 (en) 2014-08-28 2015-08-27 Rare-earth based hydrogen storage alloy and application thereof
US15/507,133 US10566614B2 (en) 2014-08-28 2015-08-27 Rare earth based hydrogen storage alloy and application thereof
JP2017530386A JP6464268B2 (en) 2014-08-28 2015-08-27 Rare earth hydrogen storage alloy and its use
CN201580046681.8A CN107075617B (en) 2014-08-28 2015-08-27 A kind of lanthanon hydrogen storage alloy and application thereof

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Cited By (7)

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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
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
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
CN111224092A (en) * 2019-12-05 2020-06-02 包头稀土研究院 Zirconium or titanium doped samarium-containing hydrogen storage alloy, negative electrode, battery and preparation method
CN111471912A (en) * 2020-04-14 2020-07-31 包头稀土研究院 Doped AB3 type hydrogen storage alloy, negative electrode, battery and preparation method
CN114686772A (en) * 2022-03-31 2022-07-01 包头稀土研究院 Rare earth-iron-based alloy material and preparation method and application thereof
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

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
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
CN111224092A (en) * 2019-12-05 2020-06-02 包头稀土研究院 Zirconium or titanium doped samarium-containing 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
CN111224092B (en) * 2019-12-05 2022-08-30 包头稀土研究院 Zirconium or titanium doped samarium-containing hydrogen storage alloy, negative electrode, battery and preparation method
CN111471912A (en) * 2020-04-14 2020-07-31 包头稀土研究院 Doped AB3 type hydrogen storage alloy, negative electrode, battery and preparation method
CN111471912B (en) * 2020-04-14 2022-01-11 包头稀土研究院 Doped AB3Hydrogen storage alloy, negative electrode, battery and preparation method
CN114686772A (en) * 2022-03-31 2022-07-01 包头稀土研究院 Rare earth-iron-based alloy material and preparation method and application thereof
CN114686772B (en) * 2022-03-31 2023-08-15 包头稀土研究院 Rare earth-iron-based alloy material, and preparation method and application thereof
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

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