CN107523737B - A kind of vehicle-mounted energy storage hydrogen bearing alloy - Google Patents
A kind of vehicle-mounted energy storage hydrogen bearing alloy Download PDFInfo
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- CN107523737B CN107523737B CN201710782764.4A CN201710782764A CN107523737B CN 107523737 B CN107523737 B CN 107523737B CN 201710782764 A CN201710782764 A CN 201710782764A CN 107523737 B CN107523737 B CN 107523737B
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 121
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 121
- 239000001996 bearing alloy Substances 0.000 title claims abstract description 60
- 125000004435 hydrogen atom Chemical group [H]* 0.000 title claims abstract description 60
- 238000004146 energy storage Methods 0.000 title claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000956 alloy Substances 0.000 claims abstract description 37
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 36
- 238000003860 storage Methods 0.000 claims abstract description 21
- 230000014759 maintenance of location Effects 0.000 claims abstract description 9
- 230000005415 magnetization Effects 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000005266 casting Methods 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 238000010791 quenching Methods 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 230000004087 circulation Effects 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000013589 supplement Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000005496 tempering Methods 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 239000011777 magnesium Substances 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 239000011232 storage material Substances 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 230000003137 locomotive effect Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Fuel Cell (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The present invention makes the crystalline texture of alloy change by composition adjustment and heat treatment process to hydrogen bearing alloy, and the finished product of acquisition has AB2Structure and A5B19The characteristic that the sum of component ratio of structure is 40% or more, due to AB2And A5B19Type hydrogen storage alloy have the characteristics that discharge capacity is high, have extended cycle life with it is easily-activated, to ensure that this patent hydrogen bearing alloy finished product can possess the discharge capacity and hydrogen storage content bigger than prior art products, and inhale/hydrogen release capacity retention ratio and remanent magnetization performance it is also very excellent.
Description
Technical field
This patent is related to field of alloy material, in particular to a kind of vehicle-mounted energy storage hydrogen bearing alloy.
Background technique
Currently, China Auto Market is undergoing a change from traditional power automobile to new-energy automobile.Mainstream
New-energy automobile technology be based on electric vehicle engineering, electric car can be divided into hybrid vehicle, pure electric automobile and
Fuel cell car.Wherein hybrid vehicle is optimized and is reformed on the basis of traditional diesel locomotive, internal combustion
Machine technology and motor technology are organically combined together, and automobile is made to meet requirement of the people to oil consumption and environment.Hybrid power vapour
Vehicle is big to the dependence that advanced internal combustion engine is power technology.Pure electric vehicle gets rid of first to traditional power device-diesel locomotive
Into the dependence of technology, it is only necessary to battery, electric control gear and motor.In comparison, the change of fuel cell technology is most
Greatly, it includes the fuel system of fuel battery engines technology, the battery of pure electric automobile, motor technology and alternative fuel vehicle
System technology.Pure electric automobile will completely abolish engine, gearbox and vehicle sedan-chair system, be the revolution of vehicle structure；Plug-in
Formula hybrid vehicle is then that will increase electric system on the basis of orthodox car.
Existing vehicle-mounted energy storage technology is there is also many defects, and the performance of new-energy automobile is also far from reaching the pre- of people
Phase.It is short to be mainly reflected in course continuation mileage, poor safety performance, reliability deficiency, the sides such as high production cost and use region are limited
Face.In new energy car battery, Mg base hydrogen bearing alloy is since light, safety is good, hydrogen storage capability is big and price is relatively low
The advantages that be known as the hydrogen bearing alloy of the great competitiveness of a new generation.But there are electrochemistry circulations for existing Mg base hydrogen bearing alloy
Stability is bad, and kinetics performance is poor, and suction/hydrogen discharging speed is slow and hydrogen discharging temperature is higher, limits Mg base hydrogen bearing alloy
Commercialization process, there is an urgent need to be modified to existing Mg base hydrogen bearing alloy.
Summary of the invention
In order to solve the above-mentioned technical problem, this patent provides a kind of vehicle-mounted energy storage hydrogen bearing alloy, the hydrogen bearing alloy
It being capable of maximum discharge capacity, hydrogen storage content and suction with higher/hydrogen release capacity retention ratio.It is specific as follows:
A kind of vehicle-mounted energy storage hydrogen bearing alloy, which is characterized in that in the crystalline texture of the hydrogen bearing alloy finished product, AB2Knot
Structure and A5B19The sum of component ratio of structure is 40% or more, and preparation step is as follows:
(1) mid-frequency melting furnace is vacuumized, argon gas is passed through when vacuum degree reaches 0.1 ~ 1Pa；
(2) La is pressedaCebTicMgdNieCod-cIngredient is carried out, wherein a, b, c, d, e respectively indicate the atomicity between element
Than, 0 < a≤0.5,0 <b≤2,0 < c, 0 < e < d, 5 < c+d+e≤8, by the furnace body of alloy raw material investment step (1) with honest material
It is interior；
(3) after the alloy raw material of step (2) in furnace is powered fusing, supplement argon gas is passed through into furnace again, reaches pressure
Stablize to 400 ~ 800Pa, and by the temperature of melt at 1000 DEG C ~ 1400 DEG C；
(4) melt of step (3) is poured into the casting holding furnace of the air pressure full of nitrogen and is kept the temperature, then will be in holding furnace
Melt cast into water cooling Copper casting mould, mold is preheated to 300~400 DEG C before casting, obtains hydrogen bearing alloy；
(5) under an inert atmosphere, the hydrogen bearing alloy that step (4) obtains is quenched twice in succession, then is tempered at 650 DEG C
1 ~ 2h is air-cooled to room temperature, obtains hydrogen bearing alloy finished product.
Preferably, the hydrogen bearing alloy that step (4) obtains is quenched twice in succession, hardening heat is 900 DEG C ~ 1000
DEG C, and after keeping the temperature 4 ~ 6h water quenching to 200 ~ 250 DEG C, wherein when starting every time the water temperature that quenches lower than 20 DEG C, at the end of water
Temperature is lower than 50 DEG C, again in 650 DEG C of 1 ~ 2h of tempering after quenching twice, is air-cooled to room temperature, obtains hydrogen bearing alloy finished product.
Preferably, after the alloy raw material of step (2) in furnace is powered fusing, supplement argon gas is passed through into furnace again, makes to press
Power reaches 500 ~ 600Pa, and the temperature of melt is stablized at 1300 DEG C ~ 1350 DEG C.
The maximum discharge capacity of the hydrogen bearing alloy finished product is 480mAh/g, and hydrogen storage content is up to 4.5%, after 500 circulations
Hydrogen absorption capacity conservation rate is 88%, and hydrogen release capacity retention ratio is 85%.
The remanent magnetization of the hydrogen bearing alloy finished product is less than 0.01 emu/g.
The advantages of this patent is: this patent makes the knot of alloy by composition adjustment and heat treatment process to hydrogen bearing alloy
Crystal structure changes, and the finished product of acquisition has AB2Structure and A5B19The characteristic that the sum of component ratio of structure is 40% or more,
Due to AB2And A5B19Type hydrogen storage alloy have the characteristics that discharge capacity is high, have extended cycle life with it is easily-activated, to ensure that this specially
Sharp hydrogen bearing alloy finished product can possess the discharge capacity and hydrogen storage content bigger than prior art products, and inhale/hydrogen release capacity guarantor
Holdup and remanent magnetization performance are also very excellent.
Specific embodiment
Most metals element can be with hydrogenation symphysis at metal hydride, according to can be substantially the characteristics of reacting with hydrogen
Be divided into two kinds: one kind is easy to react with hydrogen and can largely inhale hydrogen, forms stable hydride, and releases a large amount of heat (Δ H
< 0), this kind of metal is primarily present in IA ~ VB race, such as Ti, Zr, Ca, Mg, V, Nb, RE(rare earth element)；Another gold
Belong to poor with the affinity of hydrogen, but hydrogen be easy to it is movable within, hydrogen these elements solubility very little, under usual conditions not
Generate hydride.These elements are mainly the transition metal (except Pd) of VIB ~ VIIIB race, such as Fe, Co, Ni, Cr, Cu, Al
Dissolving in these metals Deng, hydrogen is the endothermic reaction (Δ H > 0).In general, the former is known as stabilized hydrogen element by researcher, the latter is known as
Hydrogen unstability element.Stabilized hydrogen element determine alloy hydrogen storage content, hydrogen unstability element determine alloy hydrogen absorption and desorption can
Inverse property plays a part of to adjust generation heat and decomposition pressure.The hydrogen bearing alloy developed at present is the combination of above two metal,
Have preferable reversible hydrogen adsorption and desorption ability and thermodynamic property.
Magnesium-base hydrogen storage material has 3 major class of composite hydrogen storage material, simple substance hydrogen storage material and alloy hydrogen storage material.Elemental magnesium hydrogen storage
Material is seldom used to storage hydrogen, mainly due to the suction of magnesium simple substance/hydrogen discharging temperature height and suction/hydrogen discharge reaction dynamic performance
Difference.Therefore, it is necessary to composite material is made in magnesium simple substance or carries out alloying to improve the hydrogen storage property of magnesium.Control the phase group of alloy
At and relative amount be the important means for changing alloy property, phase structure is many kinds of in RE-Ti-Mg system, and part is mutually also deposited
In ppolymorphism structure.
Composition adjustment is to have carried out most work in alloy modification research, can be convenient by alloying and changes alloy suction
Hydrogen release thermodynamics, to obtain different chemical properties.Existing research shows that the substitution of single-element is difficult to obtain alloy
Obtain satisfied performance, the multi-element alloyed acquisition that would be even more beneficial to comprehensive performance.It can not be ignored, the addition of extraneous element is to alloy
Phase composition equally will cause influence, and distribution of the alloying element in different phases and its may also on the influence of out of phase performance
It has differences.These factors can all influence the final chemical property of alloy, but its precise mechanism needs to further clarify.
Often there is an optimum value in alloy adding, however optimum content can change with alloy entirety composition transfer.
Heat treatment process has close relationship to hydrogen storage property, the chemical property of alloy.Even if it is identical chemistry at
Point, under different heat treatment process conditions, the different performance of superiority and inferiority is also presented in the various performances of alloy.By being quenched twice this patent
Burning hot treatment process is handled, and the chemical property of hydrogen bearing alloy can be effectively improved.
This patent is further described below with reference to embodiment and comparative example.
Embodiment 1:
A kind of vehicle-mounted energy storage hydrogen bearing alloy, which is characterized in that in the crystalline texture of the hydrogen bearing alloy finished product, AB2Knot
Structure and A5B19The sum of component ratio of structure is 40%, and preparation step is as follows: (1) vacuumizing to mid-frequency melting furnace, work as vacuum degree
Argon gas is passed through when reaching 0.1 ~ 1Pa；(2) La is pressed0.2Ce0.5Ti1.5Mg3.7Ni0.2Co2.2Ingredient is carried out, the alloy with honest material is former
In the furnace body of material investment step (1)；(3) after the alloy raw material of step (2) in furnace is powered fusing, supplement is passed through into furnace again
Argon gas makes pressure reach 500Pa, and the temperature of melt is stablized at 1200 DEG C；(4) melt of step (3) is poured into full of nitrogen
It is kept the temperature in the air pressure casting holding furnace of gas, then by the melt cast in holding furnace into water cooling Copper casting mould, it will before casting
Mold is preheated to 300 DEG C, obtains hydrogen bearing alloy；(5) under an inert atmosphere, hydrogen bearing alloy step (4) obtained carries out continuous
Quench twice, hardening heat is 1000 DEG C, and after keeping the temperature 4h water quenching to 250 DEG C, wherein the water temperature that quenches when starting every time
Lower than 20 DEG C, at the end of water temperature be lower than 50 DEG C, twice quench after again in 650 DEG C of tempering 1h, be air-cooled to room temperature, obtain hydrogen storage close
Golden finished product.The maximum discharge capacity of the hydrogen bearing alloy finished product is 480mAh/g, and hydrogen storage content is up to 4.5%, after 500 circulations
Hydrogen absorption capacity conservation rate is 88%, and hydrogen release capacity retention ratio is 85%.The remanent magnetization of the hydrogen bearing alloy finished product is less than 0.01
emu/g。
Embodiment 2:
A kind of vehicle-mounted energy storage hydrogen bearing alloy, which is characterized in that in the crystalline texture of the hydrogen bearing alloy finished product, AB2Knot
Structure and A5B19The sum of component ratio of structure is 60%, and preparation step is as follows: (1) vacuumizing to mid-frequency melting furnace, work as vacuum
Degree is passed through argon gas when reaching 0.1 ~ 1Pa；(2) La is pressed0.5Ce1.5Ti2.1Mg3.5Ni1.1Co1.4Ingredient is carried out, the alloy of honest material will be matched
Raw material is put into the furnace body of step (1)；(3) after the alloy raw material of step (2) in furnace is powered fusing, benefit is passed through into furnace again
Applying argon gas makes pressure reach 600Pa, and the temperature of melt is stablized at 1300 DEG C；(4) melt of step (3) is poured into and is full of
It is kept the temperature in the air pressure casting holding furnace of nitrogen, then the melt cast in holding furnace is wanted before casting into water cooling Copper casting mould
Mold is preheated to 400 DEG C, obtains hydrogen bearing alloy；(5) under an inert atmosphere, the hydrogen bearing alloy that step (4) obtains is connected
Continuous to quench twice, hardening heat is 1000 DEG C, and after keeping the temperature 5h water quenching to 250 DEG C, wherein the water quenched when starting every time
Temperature be lower than 20 DEG C, at the end of water temperature be lower than 50 DEG C, twice quench after again in 650 DEG C of tempering 1h, be air-cooled to room temperature, obtain hydrogen storage
Alloy finished product.The maximum discharge capacity of the hydrogen bearing alloy finished product is 480mAh/g, and hydrogen storage content is up to 4.5%, after 500 circulations
Hydrogen absorption capacity conservation rate be 88%, hydrogen release capacity retention ratio be 85%.The remanent magnetization of the hydrogen bearing alloy finished product is less than 0.01
emu/g。
Embodiment 3:
A kind of vehicle-mounted energy storage hydrogen bearing alloy, which is characterized in that in the crystalline texture of the hydrogen bearing alloy finished product, AB2Knot
Structure and A5B19The sum of component ratio of structure is 45%, and preparation step is as follows: (1) vacuumizing to mid-frequency melting furnace, work as vacuum
Degree is passed through argon gas when reaching 0.1 ~ 1Pa；(2) La is pressed0.2Ce0.2Ti0.5Mg2.7Ni2Co2.2Ingredient is carried out, the alloy with honest material is former
In the furnace body of material investment step (1)；(3) after the alloy raw material of step (2) in furnace is powered fusing, supplement is passed through into furnace again
Argon gas makes pressure reach 500Pa, and the temperature of melt is stablized at 1350 DEG C；(4) melt of step (3) is poured into full of nitrogen
It is kept the temperature in the air pressure casting holding furnace of gas, then by the melt cast in holding furnace into water cooling Copper casting mould, it will before casting
Mold is preheated to 400 DEG C, obtains hydrogen bearing alloy；(5) under an inert atmosphere, hydrogen bearing alloy step (4) obtained carries out continuous
Quench twice, hardening heat is 900 DEG C DEG C, and after keeping the temperature 6h water quenching to 250 DEG C, wherein the water that quenches when starting every time
Temperature be lower than 20 DEG C, at the end of water temperature be lower than 50 DEG C, twice quench after again in 650 DEG C of tempering 2h, be air-cooled to room temperature, obtain hydrogen storage
Alloy finished product.The maximum discharge capacity of the hydrogen bearing alloy finished product is 480mAh/g, and hydrogen storage content is up to 4.5%, after 500 circulations
Hydrogen absorption capacity conservation rate be 88%, hydrogen release capacity retention ratio be 85%.The remanent magnetization of the hydrogen bearing alloy finished product is less than 0.01
emu/g。
Comparative example 1:
The ingredient of this patent hydrogen bearing alloy be will differ from as raw material, the ratio of especially Ti, Mg and Ni element is unsatisfactory for 5
When < c+d+e≤8, due to the change of element ratio, the rare earth alloy crystal structure formed after melting is caused to change, AB2Knot
Structure and A5B19The component ratio of structure is significantly lower than 45%, even if after same heat treatment process processing, obtained hydrogen bearing alloy
The maximum discharge capacity of finished product is only 350mAh/g, and hydrogen storage content is only 2.5%.
Comparative example 2:
By elemental composition and ratio hydrogen bearing alloy identical with the art of this patent scheme, without the heat treatment quenched twice
When, only with heat treatment mode in the prior art, obtained hydrogen bearing alloy can not obtain the electrification that this patent is improved
Performance is learned, there are lattice defect or alloy structure are uneven, therefore its maximum discharge capacity is only 300mAh/g, 500 circulations
Hydrogen absorption capacity conservation rate afterwards is 70%, and hydrogen release capacity retention ratio is 65%.
This patent passes through the composition adjustment and Re Chu to hydrogen bearing alloy it can be seen from embodiment 1-3 and comparative example 1 and 2
Science and engineering skill makes the crystalline texture of alloy change, and the finished product of acquisition has AB2Structure and A5B19The sum of component ratio of structure
For 40% or more characteristic, due to AB2And A5B19Type hydrogen storage alloy have discharge capacity is high, have extended cycle life with it is easily-activated etc. special
Point, so that the maximum discharge capacity that ensure that this patent hydrogen bearing alloy finished product is 480mAh/g, hydrogen storage content is up to 4.5%, at 500 times
Hydrogen absorption capacity conservation rate after circulation is 88%, and hydrogen release capacity retention ratio is 85%.Remanent magnetization is less than 0.01 emu/g.
While there has been shown and described that the embodiment of this patent, it will be understood by those skilled in the art that: not
A variety of change, modification, replacement and modification can be carried out to these embodiments in the case where being detached from the principle and objective of this patent, this
The range of patent is defined by the claims and their equivalents.
Claims (5)
1. a kind of vehicle-mounted energy storage hydrogen bearing alloy, which is characterized in that in the crystalline texture of the hydrogen bearing alloy finished product, AB2Structure and
A5B19The sum of component ratio of structure is 40% or more, and preparation step is as follows: (1) vacuumizing to mid-frequency melting furnace, work as vacuum
Degree is passed through argon gas when reaching 0.1 ~ 1Pa；(2) La is pressedaCebTicMgdNieCod-cIngredient is carried out, wherein a, b, c, d, e are respectively indicated
The alloy raw material with honest material is thrown in atomicity ratio between element, 0 < a≤0.5,0 <b≤2,0 < c, 0 < e < d, 5 < c+d+e≤8
In the furnace body for entering step (1)；(3) after the alloy raw material of step (2) in furnace is powered fusing, supplement argon is passed through into furnace again
Gas makes pressure reach 400 ~ 800Pa, and the temperature of melt is stablized at 1000 DEG C ~ 1400 DEG C；(4) by the melt of step (3)
It pours into the air pressure casting holding furnace full of nitrogen and is kept the temperature, then by the melt cast in holding furnace into water cooling Copper casting mould,
Mold is preheated to 300~400 DEG C before casting, obtains hydrogen bearing alloy；(5) under an inert atmosphere, step (4) is obtained
Hydrogen bearing alloy is quenched twice in succession, then in 650 DEG C of 1 ~ 2h of tempering, is air-cooled to room temperature, is obtained hydrogen bearing alloy finished product.
2. vehicle-mounted energy storage hydrogen bearing alloy according to claim 1, it is characterised in that: the hydrogen storage for obtaining step (4) is closed
Gold quenched twice in succession, hardening heat is 900 DEG C ~ 1000 DEG C, and heat preservation 4 ~ 6h after water quenching to 200 ~ 250 DEG C,
In, when starting every time the water temperature that quenches lower than 20 DEG C, at the end of water temperature be lower than 50 DEG C, be tempered 1 at 650 DEG C again after quenching twice
~ 2h, is air-cooled to room temperature, obtains hydrogen bearing alloy finished product.
3. alloy according to claim 1, it is characterised in that: after the alloy raw material of step (2) in furnace is powered fusing, then
It is secondary that supplement argon gas is passed through into furnace, so that pressure is reached 500 ~ 600Pa, and the temperature of melt is stablized at 1300 DEG C ~ 1350 DEG C.
4. vehicle-mounted energy storage hydrogen bearing alloy according to claim 3, it is characterised in that: the maximum of the hydrogen bearing alloy finished product
Discharge capacity is 480mAh/g, and the hydrogen absorption capacity conservation rate after 500 circulations is 88%, and hydrogen release capacity retention ratio is 85%.
5. according to claim 1 to vehicle-mounted energy storage hydrogen bearing alloy described in one of 4, it is characterised in that: the hydrogen bearing alloy at
The remanent magnetization of product is less than 0.01 emu/g.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1235301C (en) * | 2003-03-24 | 2006-01-04 | 浙江大学 | New type hydrogen storage alloy as well as method of its preparation and quench treatment method |
| CN1563453A (en) * | 2004-04-01 | 2005-01-12 | 桂林电子工业学院 | rEXmGYnI4-zAz alloy of storing hydrogen and uncrystallized preparation method |
| CN101626076A (en) * | 2008-07-07 | 2010-01-13 | 北京有色金属研究总院 | High-capacity long-life low-cost rare earth and magnesium-based hydrogen storage alloy |
| CN101871060B (en) * | 2010-06-21 | 2012-05-23 | 桂林电子科技大学 | Nickel-hydrogen battery negative electrode hydrogen storage material capable of being used at low temperature and matched electrolytic solution thereof |
| WO2012011946A2 (en) * | 2010-07-20 | 2012-01-26 | Iowa State University Research Foundation, Inc. | Method for producing la/ce/mm/y base alloys, resulting alloys, and battery electrodes |
| JP2013147753A (en) * | 2013-04-11 | 2013-08-01 | Toshiba Corp | Method for manufacturing hydrogen storing alloy for battery |
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