CN104513916B - Zirconium and titanium-doped A2B7 type rare earth-yttrium-nickel family hydrogen storage alloy - Google Patents
Zirconium and titanium-doped A2B7 type rare earth-yttrium-nickel family hydrogen storage alloy Download PDFInfo
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- CN104513916B CN104513916B CN201410427220.2A CN201410427220A CN104513916B CN 104513916 B CN104513916 B CN 104513916B CN 201410427220 A CN201410427220 A CN 201410427220A CN 104513916 B CN104513916 B CN 104513916B
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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
Technical field
The present invention relates to a kind of A containing zirconium, titanium elements2B7Type rare earth-yttrium-nickel base hydrogen storage alloy.
Background technology
Hydrogen bearing alloy is the functional material that the class for finding at the end of the sixties in last century has high storage hydrogen density, has hydrogen storage
Alloy is broadly divided into six classes from composition：Rare Earth AB5Type such as LaNi5；Magnesium system such as Mg2Ni、MgNi、La2Mg17；Rare-earth and Mg-
Nickel system AB3-3.5Type such as La2MgNi9, La5Mg2Ni23, La3MgNi14；Titanium system AB type such as TiNi, TiFe；Zirconium, titanium system Laves phases AB2
Type such as ZrNi2；Vanadium system solid solution such as (V0.9Ti0.1)1-xFex。
Now widely used hydrogen storage material is LaNi5Type hydrogen storage alloy.The alloy is mainly used as metal hydride-nickel two
The negative material of primary cell (MH/Ni), its theoretical electrochemistry capacity is 373mAhg-1, the commodity negative material Mm of practical application
(NiCoMnAl)5The maximum capacity about 350mAhg of (wherein, Mm is norium)-1.In order to develop chemical property
The bigger hydrogen bearing alloy of higher or hydrogen storage content, the research to magnesium base alloy gives the attention of height.Mg-base hydrogen-bearing alloy material
Theoretical electrochemistry capacity it is high, especially RE-Mg-Ni system AB3Type, A2B7Type, A5B19The research of type hydrogen storage alloy achieves weight
It is in progress, and into the commercial application stage.Zirconium, titanium system and vanadium system hydrogen storage material are because activation is difficult, the too high original of cost
Because not all being widely used.
A widely studied at present2B7Mg elements are one of principal component in type RE-Mg-Ni materials base hydrogen storage alloy.
CN103326004A discloses one kind and uses for nickel-hydrogen battery A2B7Type hydrogen storage alloy and preparation method thereof.Its general structure is：
LnaMgbNixYyZz, wherein Ln is at least one element selected from rare earth element, Y be Al, Co, Nb, V, Fe, Cu, Zn, As,
At least one element that Ga, Mo, Sn, In, W, Si, P are selected, Z is at least one element for selecting in Ag, Sr, Ge, 0.5≤a ＜
The ＜ Z ＜ 1 of 2,0 ＜ b ＜, 1,5 ＜ X+Y+Z ＜, 9,0 ＜ Y ＜ 3,0.In the alloy composition must contain Mg elements, do not contain Mn, Zr,
Ti elements.Due to the vapour pressure height of active metal element magnesium so that manufacture difficulty increases, and alloying component is difficult to control to, while waving
The fine magnesium powder sent out is inflammable and explosive and there is potential safety hazard.
The content of the invention
The present invention is intended to provide a kind of lanthanon hydrogen storage alloy for not containing Mg elements, with overcome it is of the prior art not
Foot.
A kind of formula is RExYyNiz-a-b-cMnaAlbMcZrATiBNovel rare-earth base hydrogen storage alloy, wherein, RE=La, Ce,
One or more elements in Pr, Nd, Sm, Gd, x ＞ 0, y >=0.5, x+y=3；One kind in M=Cu, Fe, Co, Sn, V, W or
Several elements, 11 ＞ z >=9.5 (are stoichiometric proportion A during z=10.52B7Type；It is non-stoichiometric A during z ≠ 10.52B7
Type), 3.5 >=a+b ＞ 0,3 >=c >=0,2 >=A+B ＞ 0.
Further, the preferred content range of RE elements is 0.5～2.0；
Further, the preferred content range of Mn elements is 0.5～2.0；
Further, the preferred content range of Al elements 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 elements is 0.1～1.0；
Further, the preferred content range of Ti elements is 0.1～1.0.
Alloy of the present invention can be prepared using high melt-quick quenching technique, and its technical process is：Each simple substance in composition
The equal ＞ 99.0% of purity of metal or intermediate alloy raw material, calculates according to chemical molecular formula proportioning and accurately weighs each raw material, will
Raw material is sequentially placed into Al2O3Crucible, is evacuated to 3.0Pa, is filled with inert gas Ar to 0.055MPa.Intensification melting, insulation is about
Rapid hardening after 6min.Rapid hardening copper roller linear velocity is 3.4m/s.Copper roller normal open cooling water, 25 DEG C of coolant water temperature.Easily scaling loss raw material need to be fitted
Amount increases proportioning, increases ratio such as following table：
| Raw material | RE | Y | Mn | Al |
| Increase ratio | 2% | 1% | 5% | 3% |
In addition to above-mentioned preparation method, RE of the present inventionxYyNiz-a-b-cMnaAlbMcZrATiBHydrogen bearing alloy can also be adopted
With this area, other hydrogen bearing alloy preparation methods are prepared, for example：High melt casting method, mechanical alloying (MA) method, powder
Last sintering process, high melt-gas atomization, reduction-diffusion process, displacement diffusion method, conbustion synthesis (CS) method, self propagating high temperature
Synthetic method (SHS) etc..
Present invention also offers a kind of by described RExYyNiz-a-b-cMnaAlbMcZrATiBWhat type hydrogen storage alloy was prepared
Secondary cell.
RE of the present inventionxYyNiz-a-b-cMnaAlbMcZrATiBHydrogen bearing alloy can also be from other hydrogen storage materials by different
Ratio is combined, and prepares new hydrogen storage material.
RE of the present inventionxYyNiz-a-b-cMnaAlbMcZrATiBType hydrogen storage alloy can improve it using heat treatment method
Institutional framework and performance, such as：Eliminate alloy structure stress and solute segregation, improve alloy inhale/put hydrogen platform identity or alloy electricity
The charge/discharge platform identity of pole, raising hydrogen-sucking amount and cycle life etc.；Various surface treatment methods can also be adopted to improve it
Performance, such as：Improve the suction of alloy/put hydrogen or charge/discharge dynamic performance, strengthen the oxidation resistance of alloy, improve alloy
Electrical and thermal conductivity performance etc..
RE of the present inventionxYyNiz-a-b-cMnaAlbMcZrATiBThe peak capacity of hydrogen-bearing alloy electrode is higher than LaNi5Type is stored up
Hydrogen alloy, manufacture method is simple and safe.Hydrogen circulation is put with good activity function, multiplying power discharging ability, discharge and recharge or suction
Stability, can use within the scope of wider temperature, and self discharge is little；Can be used for preparing the negative pole of alkaline secondary cell and
Secondary cell containing the hydrogen bearing alloy.
Description of the drawings
Fig. 1 is La1.2Y1.8Ni9.2Mn0.5Al0.3Co0.5Zr0.1Ti0.1The XRD of hydrogen bearing alloy.
Specific embodiment
RE described in embodiment 1～34 is prepared using preceding methodxYyNiz-a-b-cMnaAlbMcZrATiBHydrogen bearing alloy.
Embodiment 14 and alloy described in embodiment 15 are using identical raw material than being obtained.Alloy described in embodiment 14 is using front
State high melt-quick quenching technique to prepare, its technical process is：The equal ＞ of the purity of each elemental metals or intermediate alloy raw material in composition
99.0%, calculate according to chemical molecular formula proportioning and accurately weigh each raw material (easy scaling loss raw material need in right amount increase proportioning), by original
Material is sequentially placed into Al2O3Crucible, is evacuated to 3.0Pa, is filled with inert gas Ar to 0.055MPa.Intensification melting, is incubated about 6min
Rapid hardening afterwards.Rapid hardening copper roller linear velocity is 3.4m/s.Copper roller normal open cooling water, 25 DEG C of coolant water temperature.
Alloy described in embodiment 15 may also be employed high melt-quick quenching technique and prepare, and increase in its technical process at annealing heat
Reason step, specially：The equal ＞ 99.0% of the purity of each elemental metals or intermediate alloy raw material, matches somebody with somebody according to chemical molecular formula in composition
Than calculate and accurately weigh each raw material (easy scaling loss raw material need in right amount increase proportioning), raw material is sequentially placed into into Al2O3Crucible, takes out true
Sky is filled with inert gas Ar to 0.055MPa to 3.0Pa.Intensification melting, rapid hardening after insulation about 6min.Rapid hardening copper roller linear velocity is
3.4m/s.Copper roller normal open cooling water, 25 DEG C of coolant water temperature.Rapid hardening alloy is annealed under vacuum or inert gas shielding at 750 DEG C
Heat treatment 8h.
M1 in embodiment 28 is lanthanum rich norium, is about wherein being about 64%, Ce containing La and being about 25%, Pr
3%th, Nd is about 8%.
The preparation method of test electrode is：The alloy Jing Mechanical Crushings of embodiment 1～34 into 200-300 mesh powder, alloy
Powder is mixed with carbonyl nickel powder with 1: 4 mass ratio, is made under 16MPa pressureMH electrode slices, the electrode slice is put
Between two panels nickel foam, while sandwiching the nickel strap as lug, make under 16MPa pressure again negative for the hydrogen storage of test
Pole (MH electrodes), the close contact between electrode slice and nickel screen is ensured around electrode slice by spot welding.
In the electrode system of open type two of test chemical property, negative pole is MH electrodes, and positive pole adopts the burning of capacity excess
Knot Ni (OH)2/ NiOOH electrodes, electrolyte is 6molL-1KOH solution, the battery for assembling shelves 24h, using LAND batteries
Tester with galvanostatic method determine alloy electrode chemical property (activation number of times, peak capacity, high-rate discharge capacity HRD,
Cyclical stability etc.), test environment temperature is 298K.Density of charging current 70mAg-1, charging interval 6h, discharge current density
70mA·g-1, electric discharge stopping potential is 1.0V, charge and discharge intermittent time 10min.
Following table lists RE described in embodiment 1～34xYyNiz-a-b-cMnaAlbMcZrATiBHydrogen bearing alloy and its electrochemistry
Energy.
Table 1RExYyNiz-a-b-cMnaAlbMcZrATiBHydrogen bearing alloy and its chemical property
Note：A is the cycle-index that electrode activation needs；B is maximum discharge capacity；C be circulate 100 times capacity keep
Rate；D be discharge current density Id be 350mAg-1 when multiplying power discharging ability；Discharge capacity when e is low temperature 243K keeps
Rate；F is the capability retention (self-discharge characteristics) after depositing 72 hours.
As seen from Table 1, alloy LaY described in embodiment 14 and 152Ni9.5Mn0.5Al0.5Zr0.5Ti0.3Chemical property phase
Than, increase through the electrochemistry capacitance of the alloy electrode of embodiment 15 of annealing heat-treats, cycle life, multiplying power discharging energy
Power, cryogenic discharging characteristic, self-discharge performance make moderate progress.
As shown in figure 1, analyzing La using x-ray diffractometer1.2Y1.8Ni9.2Mn0.5Al0.3Co0.5Zr0.1Ti0.1Alloy is (real
Apply example 18) institutional framework, alloy principal phase be Ce2Ni7Phase or Y2Ni7Phase.
Claims (10)
1. a kind of lanthanon hydrogen storage alloy, it is characterised in that：Composition formula is RExYyNiz-a-b-cMnaAlbMcZrATiB, wherein RE
For 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>1.5, x+y=3；11 ＞ z >=9.5；3.5 >=a+b ＞ 0,3 >=c >=0,2 >=A+B ＞ 0.
2. a kind of lanthanon hydrogen storage alloy as claimed in claim 1, it is characterised in that：1.5>x≥0.5.
3. a kind of lanthanon hydrogen storage alloy as claimed in claim 1 or 2, it is characterised 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, it is characterised in that：2.0≥c≥0.1.
5. a kind of lanthanon hydrogen storage alloy as claimed in claim 1 or 2, it is characterised 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, it is characterised in that：Z=10.5.
7. a kind of lanthanon hydrogen storage alloy as claimed in claim 1, it is characterised in that：1.2 >=x >=0.5, y >=1.8,2.0 >=
A >=0.5,1.0 >=b >=0.2,2.0 >=c >=0.1,1.0 >=A >=0.1,1.0 >=B >=0.1, z=10.5.
8. a kind of preparation method of lanthanon hydrogen storage alloy as claimed in claim 1, it is characterised in that：According to chemical molecular formula
Proportioning is calculated and accurately weighs each elemental metals raw material, and material purity is all higher than 99.0%；Raw material is put into into Al2O3Crucible, takes out true
Sky is filled with inert gas Ar to 0.055MPa to 3.0Pa；Intensification melting, is incubated rapid hardening after 6min, and rapid hardening copper roller linear velocity is
3.4m/s, copper roller normal open cooling water, 25 DEG C of coolant water temperature.
9. a kind of preparation method of lanthanon hydrogen storage alloy as claimed in claim 8, it is characterised in that：Terminate in rapid hardening step
Afterwards, alloy is under vacuum or inert gas shielding, annealing heat-treats 8h at 750 DEG C.
10. a kind of secondary cell, it is characterised in that containing the lanthanon hydrogen storage alloy conduct any one of claim 1-7
The electrode of hydrogen storage media.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410427220.2A CN104513916B (en) | 2014-08-28 | 2014-08-28 | Zirconium and titanium-doped A2B7 type rare earth-yttrium-nickel family hydrogen storage alloy |
| JP2017530386A JP6464268B2 (en) | 2014-08-28 | 2015-08-27 | Rare earth hydrogen storage alloy and its use |
| PCT/CN2015/088274 WO2016029861A1 (en) | 2014-08-28 | 2015-08-27 | Rare-earth based hydrogen storage alloy and application thereof |
| CN201580046681.8A CN107075617B (en) | 2014-08-28 | 2015-08-27 | A kind of lanthanon 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 |
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| CN201410427220.2A CN104513916B (en) | 2014-08-28 | 2014-08-28 | Zirconium and titanium-doped A2B7 type rare earth-yttrium-nickel family hydrogen storage alloy |
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| CN104513916B true CN104513916B (en) | 2017-05-03 |
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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 |
| 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 |
| 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 |
| CN111471911B (en) * | 2020-04-14 | 2021-07-16 | 包头稀土研究院 | Doped AB3 type rare earth-samarium-nickel hydrogen storage alloy, battery and preparation method |
| CN115466879B (en) * | 2022-08-11 | 2023-12-26 | 甘肃稀土新材料股份有限公司 | Cobalt-free yttrium-containing long-life hydrogen storage alloy powder and preparation method thereof |
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| CN101355155A (en) * | 2007-07-27 | 2009-01-28 | 比亚迪股份有限公司 | Hydrogen storage alloy and preparation method thereof as well as cathode and battery using the alloy |
| CN102828069A (en) * | 2012-09-26 | 2012-12-19 | 鞍山鑫普电池材料有限公司 | Praseodymium-neodymium-free low-cost superlong life type hydrogen storage alloy and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101355155A (en) * | 2007-07-27 | 2009-01-28 | 比亚迪股份有限公司 | Hydrogen storage alloy and preparation method thereof as well as cathode and battery using the alloy |
| CN102828069A (en) * | 2012-09-26 | 2012-12-19 | 鞍山鑫普电池材料有限公司 | Praseodymium-neodymium-free low-cost superlong life type hydrogen storage alloy and preparation method thereof |
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