CN108165829A - A kind of yttrium-magnesium-calcium-nickel system ABnType hydrogen storage alloy and preparation method thereof - Google Patents
A kind of yttrium-magnesium-calcium-nickel system ABnType hydrogen storage alloy and preparation method thereof Download PDFInfo
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- CN108165829A CN108165829A CN201611121053.4A CN201611121053A CN108165829A CN 108165829 A CN108165829 A CN 108165829A CN 201611121053 A CN201611121053 A CN 201611121053A CN 108165829 A CN108165829 A CN 108165829A
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of yttrium magnesium calcium nickel system ABnType hydrogen storage alloy and preparation method thereof.The chemical formula of the hydrogen bearing alloy is YaMgbCacNixAlyTz, wherein a, b, c, x, y, z represent the atomicity ratio between element, at least one element that T expressions are selected from Mn, Fe, Co, Zn, Sn, V, Cr, Mo, In, Cu, Si, P, Nb and B respectively；Wherein, 0 ＜ a ＜, 1,0 ＜ b ＜, 1,0 ＜ c ＜ 1, a+b+c=1；0 ＜ x≤3.8,0≤y ＜ 3.8,0≤z ＜ 3.8,3≤x+y+z≤3.8.The hydrogen bearing alloy of the present invention is prepared using induction melting.The hydrogen bearing alloy of the present invention has relatively low cost, higher electrochemical discharge capacity, good activity function and stable circulation performance, has broad application prospects in nickel-hydrogen battery negative pole material.
Description
Technical field
The present invention relates to a kind of yttrium-magnesium-calcium-nickel system AB for nickel-hydrogen battery negative pole materialnType hydrogen storage alloy and its system
Preparation Method belongs to hydrogen bearing alloy technical field.
Background technology
With the increasingly depleted of fossil energy and the getting worse of environmental problem, the alternative energy of other high-efficiency environment friendlies is found
Source has become the task of top priority of present society.Hydrogen has good application since storage capacity enriches, advantages of environment protection
Prospect has obtained the extensive concern of countries in the world government.So far, the key factor for hindering " hydrogen economy " development is the storage of hydrogen
It deposits, therefore suitable hydrogen storage material is selected just to become the emphasis that people study.
Now widely used hydrogen storage material is LaNi5Type hydrogen storage alloy, the alloy are mainly used as metal hydride-nickel
The negative material of secondary cell (MH-Ni), theoretical electrochemistry capacity are 373mAhg-1.In practical applications, the negative material
Usually Mm (NiCoMnAl)5(wherein Mm is norium) its maximum discharge capacity is about 350mAhg-1, affect
Application of the future in high-power and great-capacity power battery field.Therefore, there is bigger electrochemical discharge capacity and more excellent
The rare-earth and Mg base alloy of comprehensive hydrogen storage property has received widespread attention.
With LaNi5Type hydrogen storage alloy is compared, rare-earth and Mg base hydrogen bearing alloy have higher theoretical discharge capacity, preferably
Low self-discharge performance and less expensive price have very big researching value and application prospect, have obtained extensive concern.Mesh
Before, it studies more rare-earth and Mg base hydrogen bearing alloy and mainly includes RE-Mg-Ni system AB3Type, A287Type and A5B19The alloys such as type,
Some have come into the commercial application stage.In these hydrogen bearing alloys, rare earth is typically all to use La, Ce mischmetal,
It is substantially free of Y element or Y element content is few.In addition, being found by a large amount of literature survey, research or part are produced extensively
Ca elements are not all contained in the rare-earth and Mg base hydrogen bearing alloy ingredient of industry.
In addition, only related Y-Mg-Ca-Ni systems AB in document3In the report of type alloy, preparation method is burnt for powder
Connection, and research method is relatively simple, tested only gaseous state hydrogen storage capability, is not involved with the research of chemical property,
Influence of the content of different Ca elements to its electrochemical hydrogenation and dehydrogenation performance is not studied.
Invention content
The purpose of the present invention is to provide a kind of yttrium-magnesium-calcium-nickel system AB for nickel-hydrogen battery negative pole materialnType hydrogen storage
Alloy.The hydrogen bearing alloy has larger gaseous state hydrogen storage capability and electrochemical discharge capacity, preferable charge and discharge cycles stability
Matter and more cheap price, are with a wide range of applications.
Another object of the present invention is to provide a kind of preparation method of the hydrogen bearing alloy.
To achieve the above object, the present invention uses following technical scheme：
A kind of yttrium-magnesium-calcium-nickel system ABnType hydrogen storage alloy, wherein, 3≤n≤3.8, the chemical formula of the hydrogen bearing alloy is
YaMgbCacNixAlyTz, wherein a, b, c, x, y, z represent the atomicity ratio between element respectively, T represent from Mn, Fe, Co, Zn,
At least one element selected in Sn, V, Cr, Mo, In, Cu, Si, P, Nb and B；Wherein, 0 ＜ a ＜, 1,0 ＜ b ＜, 1,0 ＜ c ＜ 1,
A+b+c=1；0 ＜ x≤3.8,0≤y ＜ 3.8,0≤z ＜ 3.8,3≤x+y+z≤3.8.
Preferably, it is Y in the chemical formula of the hydrogen bearing alloyaMgbCacNixAlyTzIn, 0 ＜ a≤0.20, b=0.20-
0.35, c=0.30-0.60, x=2.50-3.80, y=0.05-0.35, z=0.05-0.50.
Prepared by the common preparation method of other hydrogen bearing alloys that this field may be used in the hydrogen bearing alloy of the present invention, such as
High-temp combustion casting method, mechanical alloying method, powder sintering, combustion synthesis method and self-propagating high-temperature synthesis etc..
Preferably, hydrogen bearing alloy of the invention is prepared using induction melting, which includes the following steps：
(1) raw material is weighed according to chemical formula proportioning, the difficult volatilized metal in addition to Mg, Ca element is first put into copper crucible
In, it vacuumizes → being filled with helium to 0.1MPa → and vacuumizes → be filled with helium to 0.1MPa, so operation gas washing 3 times repeatedly；
(2) power supply to be opened, heating power is adjusted to 4~5kW, then helium pressure is fixed as 0.1MPa by baking material 1min,
It gradually rises heating power and carries out melting to 5~20kW, treat the complete postcooling of all metal meltings to 20 DEG C：
(3) volatile Mg, Ca metal is put into crucible, the gas washing 3 times in the way of step (1), according to step (2)
Mode baking material 1min, the melting under 0.1MPa helium pressures.
Wherein, the equal ＞ 99.0% of the purity of raw metal or intermediate alloy raw material used.Ingredient to ensure melting is uniform,
By gained ingot casting melt back, melting number >=3 time in the step (2), (3).
In the preparation process of the present invention, easy scaling loss raw material used need to increase proportioning in right amount, be increased relative to theoretical amount
The ratio added is as follows：
| Raw material | Y | Mg | Ca |
| Increase ratio | 2% | 80% | 25% |
Heat treatment method may be used to improve its institutional framework and hydrogen storage property, such as in the hydrogen bearing alloy of the present invention：Disappear
Except alloy structure stress and component segregation, improve alloy hydrogen absorption and desorption platform property, hydrogen cyclical stability etc. is put in the suction for improving alloy.
Heat treatment should carry out under inert gas argon gas shielded, to prevent alloy oxidation.Heat treatment temperature is 800-1000 DEG C, preferably
900℃.Heat treatment time is 10-24h, preferably 20h.
The beneficial effects of the invention are as follows：
In the hydrogen bearing alloy of the present invention, rare earth is added to Ca elements only with Y element in alloying component.With list
Pure Y-Mg-Ni alloys are compared, which there are very high gaseous state hydrogen storage capability and electrochemical discharge capacity, charge and discharge to follow
Ring is had excellent performance.
The present invention hydrogen bearing alloy have relatively low cost, higher electrochemical discharge capacity, good activity function and
Stable circulation performance can be used widely in the negative material of Ni-MH battery.
Description of the drawings
Fig. 1 is the discharge curve of comparative example (1#) and (4#) hydrogen bearing alloy of embodiment 1 under 0.2C.
Fig. 2 is comparative example (1#), embodiment 1 (4#), embodiment 2 (3#) and embodiment 3 (2#) hydrogen bearing alloy discharge capacity
With the relation curve of cycle-index.
Specific embodiment
The present invention is described in further detail, but embodiments of the present invention not only limit below in conjunction with drawings and examples
In this.
Embodiment 1-5
The hydrogen bearing alloy formed shown in table 1 is prepared using induction melting, technical process is：Each elemental gold in composition
The equal ＞ 99.0% of purity of category or intermediate alloy raw material is matched according to chemical molecular formula and is calculated and accurately weigh each raw material, first will
Difficult volatilized metal in addition to Mg, Ca element is put into copper crucible, vacuumizes → be filled with inert gas helium to 0.1MPa → pumping
Vacuum → be filled with inert gas helium to 0.1MPa.So operation gas washing 3 times repeatedly.Power supply is opened, under vacuum baking material
Then helium atmospheric pressure is fixed as 0.1MPa by 1min, heat up melting, treats the complete postcooling of all metal meltings, cooling water water
Temperature is 20 DEG C.Ingredient to ensure melting is uniform, by ingot casting melting 3 times.Next volatile Mg, Ca metal is put into earthenware
Crucible, gas washing 3 times, under vacuum baking material 1min, the melting under 0.1MPa helium pressures are adjusted according to Mg, Ca degree of volatility
The power and number of whole melting.In embodiment 1-5, the monitor system of alloy is 15kW, and melting number is 3 times, Y element
Excessive ratio of quality be 2%, the excessive ratio of quality of Mg elements is 80%, and the quality excess ratio of Ca elements is 25%.
Obtained hydrogen bearing alloy is heat-treated under inert gas argon gas shielded, the heat treatment in embodiment 1-3
Temperature is 900 DEG C, heat treatment time 20h.Heat treatment temperature in embodiment 4-5 is 1000 DEG C, heat treatment time 20h.
Y as shown in Table 1 is prepared using preceding methodaMgbCacNixAlyTzHydrogen bearing alloy.
The charge discharge performance of the hydrogen bearing alloy of testing example 1-5, test method are：0.20g granularities are weighed to exist
Hydrogen storing alloy powder between the mesh of 160 mesh~200, weighs 0.80g carbonyl nickel powders, and the two is mixed grinding 10 minutes,
The pressure of 14MPa depresses to the small pieces of a diameter of 16mm.Then sample pieces are wrapped up using nickel foam and be compacted, spot welding conductive nickel
Band is put into three electric grade test systems and carries out electrochemical property test.Test temperature is 30 DEG C, and electrolyte is 6M KOH solutions,
The just extremely sintering Ni (OH) of capacity excess2/ NiOOH electrodes, reference electrode are Hg/HgO electrodes.Activation process uses 12mA
The current density of (0.2C) carries out charge-discharge test, and stable circulation performance carries out charge and discharge electrical measurement using the current density of 60mA (1C)
Examination, blanking voltage 0.6V.Capacity retention ratio S after 100 cycles100=C100/Cmax。
The Y of comparative example and embodiment 1-5 are listed in table 1aMgbCacNixAlyTzHydrogen bearing alloy and its electrochemical hydrogen storage
Energy.
As it can be seen from table 1 and YMg2Ni9Alloy is compared, and is added to the activity function of alloy and electric discharge appearance after Ca elements
Amount is improved largely, and wherein Ca contents are higher, and the activity function of alloy is better, and maximum discharge capacity is higher, but recycles
Stability decreases.
By Fig. 1 it can be seen that, compared with comparative example, 1 (Y of embodiment0.35Mg0.85Ca1.80Ni9) discharge curve it is more flat
Smooth, discharge capacity significantly increases.Fig. 2 is comparative example, 1 (Y of embodiment0.35Mg0.85Ca1.80Ni9), embodiment 2
(Y0.50Mg1.00Ca1.50Ni9) and 3 (Y of embodiment0.65Mg1.32Ca1.03Ni9) discharge capacity with the relation curve of cycle-index, can be with
See, compared with comparative example, the electrochemical hydrogen storage performance of embodiment is all significantly improved.It can be seen with reference to the data that table 1 is summarized
Go out：With the increase of Ca constituent contents, YaMgbCacNixAlyTzThe activation number of hydrogen bearing alloy is reduced, and discharge capacity increases, and is held
Measuring conservation rate slightly reduces, and after adding appropriate Al elements, the capacity of alloy decreases, but stable circulation performance is changed
It is kind.
Table 1
Claims (10)
1. a kind of yttrium-magnesium-calcium-nickel system ABnType hydrogen storage alloy, wherein, 3≤n≤3.8, which is characterized in that the change of the hydrogen bearing alloy
Formula is YaMgbCacNixAlyTz, wherein a, b, c, x, y, z represent the atomicity ratio between element respectively, T represent from Mn, Fe,
At least one element selected in Co, Zn, Sn, V, Cr, Mo, In, Cu, Si, P, Nb and B；Wherein, 0 ＜ a ＜, 1,0 ＜ b ＜ 1,0
＜ c ＜ 1, a+b+c=1；0 ＜ x≤3.8,0≤y ＜ 3.8,0≤z ＜ 3.8,3≤x+y+z≤3.8.
2. hydrogen bearing alloy according to claim 1, which is characterized in that 0 ＜ a≤0.20.
3. hydrogen bearing alloy according to claim 1, which is characterized in that b=0.20-0.35.
4. hydrogen bearing alloy according to claim 1, which is characterized in that c=0.30-0.60.
5. hydrogen bearing alloy according to claim 1, which is characterized in that x=2.50-3.80.
6. hydrogen bearing alloy according to claim 1, which is characterized in that y=0.05-0.35.
7. hydrogen bearing alloy according to claim 1, which is characterized in that z=0.05-0.50.
8. the preparation method of the hydrogen bearing alloy described in a kind of any one of claim 1-7, which is characterized in that including following step
Suddenly：
(1) raw material is weighed according to chemical formula proportioning, first the difficult volatilized metal in addition to Mg, Ca element is put into copper crucible, taken out
Vacuum → being filled with helium to 0.1MPa → vacuumizes → is filled with helium to 0.1MPa, so operation gas washing 3 times repeatedly；
(2) power supply is opened, heating power is adjusted to 4~5kW, then helium pressure is fixed as 0.1MPa, gradually by baking material 1min
It increases heating power and carries out melting to 5~20kW, treat the complete postcooling of all metal meltings to 20 DEG C；
(3) volatile Mg, Ca metal is put into crucible, the gas washing 3 times in the way of step (1), in the way of step (2)
Baking material 1min, the melting under 0.1MPa helium pressures.
9. the preparation method of hydrogen bearing alloy according to claim 8, which is characterized in that will in the step (2), (3)
Gained ingot casting melt back, melting number >=3 time.
10. the preparation method of hydrogen bearing alloy according to claim 8, which is characterized in that easy scaling loss raw material used is opposite
It is as follows in the increased ratio of theoretical amount institute：
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114107739A (en) * | 2021-11-10 | 2022-03-01 | 浙江大学 | Solid rare earth hydrogen storage alloy with low hysteresis and high pulverization resistance and preparation and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906545A (en) * | 2010-07-13 | 2010-12-08 | 北京科技大学 | Preparation method of Mg-contained hydrogen storage alloy |
| CN103579591A (en) * | 2012-07-27 | 2014-02-12 | Fdktwicell株式会社 | Nickel-metal hydride secondary cell and negative electrode therefor |
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- 2016-12-07 CN CN201611121053.4A patent/CN108165829A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906545A (en) * | 2010-07-13 | 2010-12-08 | 北京科技大学 | Preparation method of Mg-contained hydrogen storage alloy |
| CN103579591A (en) * | 2012-07-27 | 2014-02-12 | Fdktwicell株式会社 | Nickel-metal hydride secondary cell and negative electrode therefor |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114107739A (en) * | 2021-11-10 | 2022-03-01 | 浙江大学 | Solid rare earth hydrogen storage alloy with low hysteresis and high pulverization resistance and preparation and application thereof |
| CN114107739B (en) * | 2021-11-10 | 2022-05-10 | 浙江大学 | Solid rare earth hydrogen storage alloy with low hysteresis and high pulverization resistance and preparation and application thereof |
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Application publication date: 20180615 |