CN108149073A - Low-temperature nickel-hydrogen battery La-Mg-Ni base hydrogen storage alloys and preparation method thereof - Google Patents
Low-temperature nickel-hydrogen battery La-Mg-Ni base hydrogen storage alloys and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 120
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 116
- 239000001257 hydrogen Substances 0.000 title claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000003860 storage Methods 0.000 title claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910020791 La—Mg—Ni Inorganic materials 0.000 title claims description 21
- 238000010791 quenching Methods 0.000 claims abstract description 25
- 238000002844 melting Methods 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000005266 casting Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000012216 screening Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 31
- 229910052746 lanthanum Inorganic materials 0.000 claims description 30
- 230000000171 quenching effect Effects 0.000 claims description 21
- 238000003723 Smelting Methods 0.000 claims description 13
- 230000006698 induction Effects 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 229910002335 LaNi5 Inorganic materials 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 229910000831 Steel Inorganic materials 0.000 claims description 10
- 239000010959 steel Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910000838 Al alloy Inorganic materials 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000005275 alloying Methods 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000007499 fusion processing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 229910000878 H alloy Inorganic materials 0.000 claims 2
- 238000007670 refining Methods 0.000 claims 1
- 238000000227 grinding Methods 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 66
- 238000012360 testing method Methods 0.000 description 23
- 239000000843 powder Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 5
- 239000006260 foam Substances 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- -1 (La Substances 0.000 description 3
- 229910018095 Ni-MH Inorganic materials 0.000 description 3
- 229910018477 Ni—MH Inorganic materials 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000002074 melt spinning Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910002640 NiOOH Inorganic materials 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 2
- 239000001996 bearing alloy Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910019566 Re—Mg—Ni Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000007578 melt-quenching technique Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
-
- B22F1/0003—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- 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
- C22C1/023—Alloys based on nickel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
- C22C2202/04—Hydrogen absorbing
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a kind of low-temperature nickel-hydrogen battery La Mg Ni base hydrogen storage alloys and preparation method thereof.The chemical composition of the alloy is La0.75‑xCexMg0.25Ni3Co0.5, wherein, the leftover bits and pieces in the chemical composition is designated as the atomic ratio of each corresponding component, and the value range of x is 0.09 0.11.The alloy preparation method includes the following steps：Raw material preparation process, melting casting step, alloy thin band preparation process and grinding screening step.Alloy prepared by this method has higher low temperature electrochemical performance, and under the conditions of 248K, quench fast 10ms‑1When its charge and discharge cycles 100 times when discharge capacity (C100) up to maximum value be 245.9mAhg‑1, the alloy material for preparing of the present invention is particularly suitable for using under 0 DEG C of the following conditions, can particularly use or even can be used under the conditions of 30 DEG C under the conditions of 25 DEG C.
Description
Technical field
The invention belongs to hydrogen storage material preparation field, more particularly to a kind of low-temperature nickel-hydrogen battery is closed with La-Mg-Ni systems hydrogen storage
Gold and preparation method thereof, the hydrogen bearing alloy is particularly suitable as the negative material of the Ni-MH battery used under cryogenic conditions.
Background technology
In recent years, the universal and development of fuel-engined vehicle is so that the environmental problems such as atmosphere pollution increasingly aggravate, therefore new energy
The Devoting Major Efforts To Developing of power vehicle is extremely urgent, wherein using Ni-MH batteries as the hybrid electric vehicle (HEV) of power source and pure electricity
Motor-car (EV) has obtained generation due to having many excellent characteristics such as superior performance, safe, stable structure, environmental-friendly
The extensive concern of various countries of boundary.Therefore, flourishing along with Ni/MH battery industries, the hydrogen storage as cell negative electrode material are closed
Gold also shows increasingly vast potential for future development.The current commercialized hydrogen storage applied to Ni/MH cell negative electrode materials
Alloy is AB5Type alloy, but the maximum capacity of the alloy has had reached limiting value 330mAh/g, can not gradually meet increasingly
The market performance level of raising and requirement, and La-Mg-Ni systems A2B7The theoretical capacity of type alloy reach 380-410mAh/g, into
For the strong competitor of Ni/MH cell negative electrode materials, but the greatest problem for restricting the alloy industrialization is its cycle life
It is not ideal enough.A is improved at present2B7The more universal method of type alloy comprehensive performance level is melt-quenching method, has pertinent literature
Report (such as document 1：Y.H.Zhang,D.L.Zhao,S.H.Guo,Y.Qi,Q.C.Wang,X.L.Wang,Influences of
substitution of Zr for La on structures and electrochemical performances of
A2B7-Type electrode alloys by melt-spinning,Rare Met.Mater.Eng.39(7)(2010)
1141-1146. document 2：Y.H.Zhang,T.Yang,H.W.Shang,L.C.Chen,H.P.Ren,D.L.Zhao,
Electrochemical hydrogen storage kinetics of La0.75-xZrxMg0.25Ni3.2Co0.2Al0.1
(x=0-0.2) 16 (2012) 1275-1282. of alloys prepared by melt spinning, Energy Procedia
Document 3：J.L.Gao,H.W.Shang,C.Xu,H.Yong,S.Xu,H.T.Wang,Y.H.Zhang,Electrochemical
hydrogen storage kinetics of as-cast and melt spun
La0.55M0.2Mg0.25Ni3.2C00.2Al0.1 (M=Zr, Pr) alloys, Met.Funct.Mater.21 (2) (2014) 2-
7. document 4：Y.H.Zhang,Y.Cai,T.Yang,Z.H.Hou,G.F.Zhang,D.L.Zhao,Influence of melt
spinning on the electrochemical hydrogen storage kinetics of Re-Mg-Ni-based
A2B7-type alloys, Rare Met.Mater.Eng.42 (11) (2013) 2201-2206.), the minimum of Ni/MH batteries makes
With temperature up to 248K near, and at present for La-Mg-Ni systems A2B7The research of type alloy property mostly or its at room temperature
Performance.
Invention content
The purpose of the present invention is to provide a kind of low-temperature nickel-hydrogen battery La-Mg-Ni base hydrogen storage alloys and preparation method thereof,
The hydrogen bearing alloy particularly suitable as the negative material of the Ni-MH battery used under cryogenic conditions, prepared alloy 298K,
Under tetra- temperature conditions of 268K, 258K, 248K, quench fast 10ms-1When its charge and discharge cycles 100 times when discharge capacity (C100)
It is respectively 268.3mAhg up to maximum value-1、265.1mAh·g-1、253.4mAh·g-1、245.9mAh·g-1, high power is forthright
Energy (HRD) is also preferable.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of low-temperature nickel-hydrogen battery La-Mg-Ni base hydrogen storage alloys, the chemical composition of the alloy is La0.75- xCexMg0.25Ni3Co0.5, wherein, the leftover bits and pieces in the chemical composition is designated as the atomic ratio of each corresponding component, and the value range of x is
0.09-0.11。
In the alloy of the present invention, the introducing of Ce has larger impact to the cryogenic property of alloy, in order to ensure the low of alloy
Warm nature energy, the value range of the atomic ratio x of Ce are selected as 0.09-0.11, for example, the value of x is 0.091,0.093,0.095,
0.098、0.1、0.102、0.105、0.107、0.109。
In above-mentioned low-temperature nickel-hydrogen battery La-Mg-Ni base hydrogen storage alloys, as a kind of preferred embodiment, the alloy
In include at least (La, Mg)2Ni7Phase, it is highly preferred that further including (La, Mg) Ni in the alloy3Phase and LaNi5Phase；Further
Preferably, in the alloy, (La, Mg) Ni3The abundance of phase be 0.85%-1.23%, (La, Mg)2Ni7The abundance of phase is
50.06%-69.84%, LaNi5The abundance of phase is 28.93%-49.09%；It is further preferred that in the alloy, (La,
Mg)Ni3The abundance of phase is 1.23%, (La, Mg)2Ni7The abundance of phase is 69.84%, LaNi5The abundance of phase is 28.93%.
In the alloy of the present invention, (La, Mg)2Ni7Phase abundance is bigger, and alloy discharge capacity is higher, (La, Mg) Ni3Phase abundance gets over primary alloy
Cycle life is higher.
In above-mentioned low-temperature nickel-hydrogen battery La-Mg-Ni base hydrogen storage alloys, as a kind of preferred embodiment, the low temperature
The La-Mg-Ni base hydrogen storage alloys that use for nickel-hydrogen battery are powdered, and granularity is preferably 300 mesh to 400 mesh (i.e. 38 μm -48 μm).
The above-mentioned low-temperature nickel-hydrogen battery preparation method of La-Mg-Ni base hydrogen storage alloys, includes the following steps：
Raw material preparation process weighs La, Ce, Mg, Ni, Co raw material according to above-mentioned alloying component proportioning；
Melting casting step by above-mentioned raw materials melting and is cast into cast alloy ingot；
The cast alloy ingot is prepared into thin alloy strip steel rolled stock by alloy thin band preparation process using single-roller rapid quenching with quenching；
Screening step is ground, the thin alloy sheet is crushed successively, grind, is sieved, obtains powdered La-Mg-Ni
Base hydrogen storage alloy.
In above-mentioned preparation method, as a kind of preferred embodiment, in the melting casting step, the melting is
It is carried out using high-frequency induction smelting process, the aluminium alloy after fusing is sufficiently stirred during the melting；More preferably
Ground, in the fusion process, the crucible used is alumina crucible, and the atmosphere used is helium or argon gas atmosphere, further
Preferably, raw material placement location in the crucible is：Ni, Co are in bottom, and Mg is in centre position, La and Ce most upper
Face；Further, the high-frequency induction smelting process refers to the crucible being placed in high-frequency induction smelting furnace and be evacuated to
0.1Pa is subsequently charged with helium to 0.3MPa, carry out again later high-frequency induction melting (:High frequency typically refers to power frequency 100
In the range of~500kHz).High frequency smelting process is especially suitable for the fusing of alloy of the present invention, and high-frequency induction smelting process be suitble to it is of large quantities
It produces and at low cost, high-frequency induction smelting process of the invention can be reduced as far as the segregation of alloying component；In addition, due to
Crucible centre position temperature highest, the fusing point of element is respectively Co-1495 DEG C, Ni-1453 DEG C, La-921 DEG C, Ce-799 DEG C,
Mg-648 DEG C, therefore, loading sequence according to the invention, Mg, La, the mischmetal containing Ce first melt after to the Gao Rong of bottom
Point Ni and Co plays the role of impregnating fusing, further increases the uniformity of alloying component.
In above-mentioned preparation method, as a kind of preferred embodiment, in the melting casting step, the casting is
Molten alloy liquid after melting is cast on water cooled copper mould by finger, so as to obtain cast alloy ingot.
In above-mentioned preparation method, as a kind of preferred embodiment, the single-roller rapid quenching with quenching prepares the thin alloy strip
During material, the aluminium alloy after fusing is ejected into linear velocity as 5-30m/s (such as 6m/s, 8m/s, 10m/s, 15m/s, 18m/s, 23m/
S, 25m/s, 27m/s, 29m/s) roll surface on, it is highly preferred that the linear velocity be 10m/s；It is highly preferred that the single roller rapid quenching
Method prepares the thin alloy strip steel rolled stock and refers to the cast alloy ingot being placed in single roller rapid quenching stove, is evacuated to 10-2-10-3Mpa
It is filled with the argon gas of 0.1-0.5MPa (such as 0.15MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.45MPa) afterwards, heats described in fusing
Aluminium alloy is ejected on the roll surface for the water-cooled copper roller that linear velocity is 10m/s after cast alloy ingot, is obtained after quickly solidifying
The thin alloy strip steel rolled stock.
In above-mentioned preparation method, as a kind of preferred embodiment, the powdered La-Mg-Ni base hydrogen storage alloys
Granularity is 300 mesh to 400 mesh (i.e. 38 μm -48 μm).
The beneficial effects of the present invention are：
1. raw material La, Ce, Mg, Ni, Co that the present invention uses belong to commercially produced product, raw material is easy to get.
2. preparation process is traditional smelting process and quick quenching technique, have many advantages, such as that process is simple, it is easy to operate.
3. reaction does not need to add in surfactant, catalyst etc., it is easy to get the product of high-purity.
4. product prepared by includes (La, Mg) Ni3Phase, (La, Mg)2Ni7Phase and LaNi5Phase, with the increasing of FFR'S fuel assembly
Add, (La, Mg) Ni3Phase and (La, Mg)2Ni7The abundance of phase reduces, LaNi5The abundance raising of phase.
5. product prepared by has higher low temperature electrochemical performance, tetra- temperature strips of 298K, 268K, 258K, 248K
Under part, quench fast 10ms-1When its charge and discharge cycles 100 times when discharge capacity (C100) up to maximum value be respectively 268.3mAh
g-1、265.1mAh·g-1、253.4mAh·g-1、245.9mAh·g-1, the alloy material for preparing of the present invention is particularly suitable at 0 DEG C
It is used under the following conditions, particularly can use or even can be used under the conditions of -30 DEG C under the conditions of -25 DEG C.
Description of the drawings
Fig. 1 is quenched state La in the embodiment of the present invention 10.65Ce0.1Mg0.25Ni3Co0.5The XRD spectrum of alloy；
Fig. 2 is 10m/s quenched states La in the embodiment of the present invention 10.65Ce0.1Mg0.25Ni3Co0.5The discharge capacity of alloy declines
Subtract curve graph, wherein, the test temperature of (a) is 298K, and the test temperature of (b) is 268K, and the test temperature of (c) is 258K, (d)
Test temperature be 248K；
Fig. 3 is 10m/s quenched states La in the embodiment of the present invention 10.65Ce0.1Mg0.25Ni3Co0.5The high rate capability of alloy
Curve graph, wherein, the test temperature of (a) is 298K, and the test temperature of (b) is 268K, and the test temperature of (c) is 258K, (d's)
Test temperature is 248K；
Fig. 4 is 20m/s, 30m/s quenched state La in the embodiment of the present invention 20.65Ce0.1Mg0.25Ni3Co0.5The electric discharge of alloy
Capacity attenuation curve graph, wherein, the test temperature of (a) is 298K, and the test temperature of (b) is 268K, and the test temperature of (c) is
258K, the test temperature of (d) is 248K；
Fig. 5 is 20m/s, 30m/s quenched state La in the embodiment of the present invention 20.65Ce0.1Mg0.25Ni3Co0.5The high power of alloy
Rate performance chart, wherein, the test temperature of (a) is 298K, and the test temperature of (b) is 268K, and the test temperature of (c) is
258K, the test temperature of (d) is 248K.
Specific embodiment
With reference to specific embodiment, the present invention is further explained.It should be understood that these embodiments be only used for the present invention without
For limiting the scope of the invention.Externally it should be understood that after present disclosure has been read, those skilled in the art are to this hair
Bright to make various changes or modifications, these equivalent forms also fall within the scope of the appended claims of the present application.
The main La of following embodiment0.65Ce0.1Mg0.25Ni3Co0.5For the preparation of alloy powder, essentially according to following step
It realizes：
(1) by La, Ce, Mg, Ni, Co raw material according to La0.65Ce0.1Mg0.25Ni3Co0.5Component atoms ratio is put into oxygen after weighing
Change in aluminium crucible, it is generally considered that the volatility of Mg, the dosage of the raw material Mg of addition is equivalent to match according to alloying component and calculate
The 110% of Mg amounts gone out；
(2) it using high-frequency induction smelting process, is protected with helium, prepares La0.65Ce0.1Mg0.25Ni3Co0.5Alloy pig；
(3) La is prepared with three kinds of rapid quenching techniques of 10m/s, 20m/s, 30m/s0.65Ce0.1Mg0.25Ni3Co0.5Alloy strip
Material；
(4) for the material prepared after broken, grinding, screening obtains alloy powder and collection of 300 mesh to 400 mesh.
Embodiment 1：
La0.65Ce0.1Mg0.25Ni3Co0.5The preparation of alloy powder, including：
(1) according to La0.65Ce0.1Mg0.25Ni3Co0.5Component atoms ratio is (i.e.：In the alloy, the atomic percentage content of La is
The atomic percentage content that the atomic percentage content that the atomic percentage content of 14.44%, Ce are 2.22%, Mg is 5.56%, Ni is
The atomic percentage content of 66.67%, Co is are put into alumina crucible after 11.11%) weighing.
(2) high-frequency induction smelting process is protected to carry out melting to alloy, and ensure molten metal in fusion process using helium
Body is adequately stirred, and alloy casting obtains cast alloy ingot to water cooled copper mould rapid cooling after the completion.
(3) cast alloy ingot is placed in single roller rapid quenching stove, is evacuated to 10-2-10-3The high-purity argon of 0.3MPa is filled with after Mpa
After high frequency electric source sensing heating melts ingot casting, the height that roll surface speed is 10m/s is ejected into 1500 DEG C of conditions by gas for aluminium alloy
In the water-cooled copper roller of speed rotation, thin alloy strip steel rolled stock is obtained after quickly solidifying.
(4) for alloy strip steel rolled stock after broken, grinding, screening obtains alloy powder and collection of 300 mesh to 400 mesh.
Alloy powder performance test：
Alloyed powder 0.1g, the carbonyl nickel powder 0.3g prepared with the electronic balance weighing above method, by the two after mixing
It is placed in the Belt-type tools of diameter 10mm, alloy anode piece obtained is wrapped in nickel foam after five minutes for die pressure 15Mpa holdings
In, after with spot welding, negative plate compacting is fixed, the nickel bar polished by the use of sand paper is also fixed on foam as lug with the mode of spot welding
On nickel.Exoergic power is overcharged in order to ensure that negative plate has, certain size is chosen by way of theoretical calculation negative plate capacity
It is sintered Ni (OH)2/ NiOOH is as positive plate, so that positive plate capacity is much larger than negative plate.By the positive plate prepared, cathode
Piece and Hg-HgO reference electrodes (KOH solution concentration 6mol/L in electrode) are placed in three-way pipe, inject the KOH solution of 6mol/L
Impregnated 24 hours after about 300mL, ensure electrode slice be impregnated with completely after start to test, specific test temperature for 298K, 268K,
258K, 248K, test temperature are controlled by high/low temperature experimental box.
It is forthright using the activation of LAND CT2001A type measuring instrument beta alloy electrodes, discharge capacity, cycle performance, high power
Energy.
1. activation and discharge capacity test：
Step 1：Stand 10min；
Step 2：10mA chargings 4.5h；
Step 3：Stand 10min；
Step 4：10mA is discharged to current potential 0.6V (vs.Hg-HgO reference electrodes)；
Step 5：Step 1-4 is repeated until alloy electrode discharge capacity reaches maximum value (Cmax), corresponding number is known as living
Change number (Na).
2. cycle performance is tested：
Step 1：Stand 10min；
Step 2：10mA chargings 4.5h；
Step 3：Stand 10min；
Step 4：10mA is discharged to current potential 0.6V (vs.Hg-HgO reference electrodes)；
Step 5：Step 1-4 is repeated until charge and discharge cycles are up to 100 times.
100 charge and discharge cycles stability active volume conservation rate (S100) characterize：
In formula, C100Represent the discharge capacity of the 100th cycle.
3. high rate capability is tested：
Step 1：Stand 10min；
Step 2：10mA chargings 4.5h；
Step 3：Stand 10min；
Step 4：30mA is discharged to current potential 0.6V (vs.Hg-HgO reference electrodes)；
Step 5：10mA is discharged to current potential 0.6V (vs.Hg-HgO reference electrodes)；
Step 6：Heavy-current discharge current strength is adjusted to 60 by 30mA respectively, 90,120,150mA, and repeat step 1-5
Step.High rate capability can be characterized with HRD：
In formula, CiRepresent the discharge capacity being large current discharge respectively with 30,60,90,120,150mA, C10Represent high current
The discharge capacity discharged again with 10mA after electric discharge.
Fig. 1 is quenched state La in embodiment 10.65Ce0.1Mg0.25Ni3Co0.5The XRD spectrum of alloy.It will be seen from figure 1 that
Prepared product includes (La, Mg) Ni3Phase, (La, Mg)2Ni7Phase and LaNi5Phase, wherein, (La, Mg) Ni3The abundance of phase is
1.23%, (La, Mg)2Ni7The abundance of phase is 69.84%, LaNi5The abundance of phase is 28.93%.
Fig. 2 is quenched state La in the embodiment of the present invention 10.65Ce0.1Mg0.25Ni3Co0.5Alloy is under four kinds of temperature conditions
Discharge capacity attenuation curve figure.Figure it is seen that under tetra- temperature conditions of 298K, 268K, 258K, 248K, speed of quenching
10m·s-1When its charge and discharge cycles 100 times when discharge capacity (C100) up to maximum value be respectively 268.3mAhg-1、
265.1mAh·g-1、253.4mAh·g-1、245.9mAh·g-1, the maximum discharge capacity under four temperature conditions is respectively
311.5mAh·g-1、305.6mAh·g-1、285.8mAh·g-1、271.2mAh·g-1。
Fig. 3 is quenched state La in the embodiment of the present invention 10.65Ce0.1Mg0.25Ni3Co0.5Alloy is under four kinds of temperature conditions
High rate capability curve graph.From figure 3, it can be seen that under tetra- temperature conditions of 298K, 268K, 258K, 248K, speed of quenching
10ms-1When its high rate capability (HRD) it is as shown in table 1 up to maximum value.
1 La of table0.65Ce0.1Mg0.25Ni3Co0.5The high rate capability of alloy
Embodiment 2：
La0.65Ce0.1Mg0.25Ni3Co0.5The preparation of alloy powder, including：
(1) according to La0.65Ce0.1Mg0.25Ni3Co0.5Component atoms ratio is put into after weighing in alumina crucible；
(2) high-frequency induction smelting process is protected to carry out melting to alloy, and ensure molten metal in fusion process using helium
Body is adequately stirred, and alloy casting obtains cast alloy ingot to water cooled copper mould rapid cooling after the completion.
(3) cast alloy ingot is placed in single roller rapid quenching stove, is evacuated to 10-2-10-3The high-purity argon of 0.3MPa is filled with after Mpa
Gas after high frequency electric source sensing heating melts ingot casting, is ejected into roll surface speed as 20m/s, 30m/s under the conditions of 1500 DEG C respectively
High-speed rotating water-cooled copper roller on, thin alloy strip steel rolled stock is obtained after quickly solidifying；
(4) for thin alloy strip steel rolled stock after broken, grinding, screening obtains alloy powder and collection of 300 mesh to 400 mesh.
The quenched state La from embodiment 20.65Ce0.1Mg0.25Ni3Co0.5The XRD spectrum of alloy can be seen that FFR'S fuel assembly
In the alloy powder obtained during 20m/s, (La, Mg) Ni3The abundance of phase is 1.04%, (La, Mg)2Ni7The abundance of phase is
58.67%, LaNi5The abundance of phase is 40.29%；In the alloy powder that FFR'S fuel assembly obtains when being 30m/s, (La, Mg) Ni3Phase
Abundance for 0.85%, (La, Mg)2Ni7The abundance of phase is 50.06%, LaNi5The abundance of phase is 49.09%.
Alloy powder performance test：
First, with electronic balance weighing alloyed powder 0.1g manufactured in the present embodiment, carbonyl nickel powder 0.3g, the two is uniformly mixed
It is placed in the Belt-type tools of diameter 10mm, alloy anode piece obtained is wrapped in foam after five minutes for die pressure 15Mpa holdings
In nickel, after with spot welding, negative plate compacting is fixed, the nickel bar polished by the use of sand paper is also fixed on bubble as lug with the mode of spot welding
On foam nickel.Exoergic power is overcharged in order to ensure that negative plate has, certain size is chosen by way of theoretical calculation negative plate capacity
Sintering Ni (OH)2/ NiOOH is as positive plate, so that positive plate capacity is much larger than negative plate.By the positive plate prepared, bear
Pole piece and Hg-HgO reference electrodes (6 mol/L of KOH solution concentration in electrode) are placed in three-way pipe, inject the KOH of 6 mol/L
Impregnated 24 hours after solution about 300mL, ensure electrode slice be impregnated with completely after start to test, specific test temperature for 298K,
268K, 258K, 248K, test temperature are controlled by high/low temperature experimental box.The activation of alloy electrode, discharge capacity, cycle performance, height
The test method of high rate performance is the same as embodiment 1.
Fig. 4 is quenched state La in the embodiment of the present invention 20.65Ce0.1Mg0.25Ni3Co0.5Alloy is under four kinds of temperature conditions
Discharge capacity attenuation curve figure.From fig. 4, it can be seen that under tetra- temperature conditions of 298K, 268K, 258K, 248K, speed 20 of quenching
m·s-1With 30 ms-1Alloy charge and discharge cycles 100 times when discharge capacity (C100) and discharge capacity such as 2 institute of table for the first time
Show.Illustrate 10 ms of speed that quench-1When the C of alloy for preparing100Most preferably.
2 as cast condition of table, quench fast 20ms-1And 30ms-1Shi Hejin C100
Fig. 5 is quenched state La in the embodiment of the present invention 20.65Ce0.1Mg0.25Ni3Co0.5Alloy is under four kinds of temperature conditions
High rate capability curve graph.From fig. 5, it can be seen that under tetra- temperature conditions of 298K, 268K, 258K, 248K, speed 20 of quenching
m·s-1With 30 ms-1When its high rate capability (HRD) it is as shown in table 3.Illustrate 10 ms of speed that quench-1When the alloy prepared
High rate capability is best.
3 as cast condition of table, 20 ms of speed of quenching-1With 30 ms-1The high rate capability of Shi Hejin
Claims (10)
1. a kind of low-temperature nickel-hydrogen battery La-Mg-Ni base hydrogen storage alloys, which is characterized in that the chemical composition of the alloy is
La0.75-xCexMg0.25Ni3Co0.5, wherein, the leftover bits and pieces in the chemical composition is designated as the atomic ratio of each corresponding component, the value of x
Ranging from 0.09-0.11.
2. low-temperature nickel-hydrogen battery according to claim 1 La-Mg-Ni base hydrogen storage alloys, which is characterized in that the alloy
In include at least (La, Mg)2Ni7Phase, it is preferable that (La, Mg) Ni is further included in the alloy3Phase and LaNi5Phase.
3. low-temperature nickel-hydrogen battery according to claim 2 La-Mg-Ni base hydrogen storage alloys, which is characterized in that in the conjunction
Jin Zhong, (La, Mg) Ni3The abundance of phase be 0.85%-1.23%, (La, Mg)2Ni7The abundance of phase is 50.06%-69.84%,
LaNi5The abundance of phase is 28.93%-49.09%；Preferably, in the alloy, (La, Mg) Ni3The abundance of phase is 1.23%,
(La,Mg)2Ni7The abundance of phase is 69.84%, LaNi5The abundance of phase is 28.93%.
4. low-temperature nickel-hydrogen battery according to claim 1 La-Mg-Ni base hydrogen storage alloys, which is characterized in that the low temperature
The La-Mg-Ni base hydrogen storage alloys that use for nickel-hydrogen battery are powdered, and granularity is preferably 300 mesh to 400 mesh.
5. the preparation method of claim 1-3 any one of them low-temperature nickel-hydrogen battery La-Mg-Ni base hydrogen storage alloys, special
Sign is, includes the following steps：
Raw material preparation process weighs La, Ce, Mg, Ni, Co original according to claim 1-3 any one of them alloying component proportioning
Material；
Melting casting step by above-mentioned raw materials melting and is cast into cast alloy ingot；
The cast alloy ingot is prepared into thin alloy strip steel rolled stock by alloy thin band preparation process using single-roller rapid quenching with quenching；
Screening step is ground, the thin alloy sheet is crushed successively, grind, is sieved, obtains powdered La-Mg-Ni systems storage
Hydrogen alloy.
6. preparation method according to claim 5, which is characterized in that in the melting casting step, the melting is
It is carried out using high-frequency induction smelting process, the aluminium alloy after fusing is sufficiently stirred during the melting；Preferably,
In the fusion process, the crucible used is alumina crucible, and the atmosphere used is helium or argon gas atmosphere, further preferably
Ground, raw material placement location in the crucible are：Ni, Co are in bottom, and Mg is in centre position, La and Ce topmost.
7. preparation method according to claim 6, which is characterized in that the high-frequency induction smelting process refers to the crucible
It is placed in high-frequency induction smelting furnace and is evacuated to 0.1Pa, be subsequently charged with helium to 0.3MPa, carry out high-frequency induction again later and melt
Refining.
8. according to claim 4-7 any one of them preparation methods, which is characterized in that in the melting casting step, institute
It states casting to refer to the molten alloy liquid after melting being cast on water cooled copper mould, so as to obtain cast alloy ingot.
9. according to claim 4-7 any one of them preparation methods, which is characterized in that the single-roller rapid quenching with quenching prepares described thin
During alloy strip steel rolled stock, the aluminium alloy after fusing is ejected on the roll surface that linear velocity is 5-30m/s, it is preferable that the linear velocity is
10m/s；Refer to the cast alloy ingot being placed in list it is further preferred that the single-roller rapid quenching with quenching prepares the thin alloy strip steel rolled stock
In roller quick quenching furnace, it is evacuated to 10-2-10-3The argon gas of 0.1-0.5MPa is filled with after Mpa, after the cast alloy ingot is melted in heating
Aluminium alloy is ejected on the roll surface for the water-cooled copper roller that linear velocity is 10m/s, the thin alloy strip is obtained after quickly solidifying
Material.
10. according to claim 4-7 any one of them preparation methods, which is characterized in that the powdered La-Mg-Ni systems storage
The granularity of hydrogen alloy is 300 mesh to 400 mesh.
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| CN108893656A (en) * | 2018-05-30 | 2018-11-27 | 安泰科技股份有限公司 | La-Mg-Ni system A2B7Type hydrogen storage alloy and preparation method thereof |
| CN109830676A (en) * | 2019-01-21 | 2019-05-31 | 江苏集萃安泰创明先进能源材料研究院有限公司 | Rechargeable uses for nickel-hydrogen battery high capacity and long-life La-Mg-Ni type cathode hydrogen storage material and preparation method thereof |
| WO2020006843A1 (en) * | 2018-07-04 | 2020-01-09 | 黄倩 | Rear earth doped mg-based hydrogen storage alloy |
| US20200185710A1 (en) * | 2018-12-06 | 2020-06-11 | Toyota Jidosha Kabushiki Kaisha | Negative electrode active material, negative electrode, alkaline storage battery, and method of producing negative electrode active material |
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| CN106119652A (en) * | 2016-06-21 | 2016-11-16 | 安泰科技股份有限公司 | Use for nickel-hydrogen battery La Mg Ni base hydrogen storage alloy and preparation method thereof |
| CN107338380A (en) * | 2017-07-04 | 2017-11-10 | 内蒙古科技大学 | Fuel cell high capacity hydrogen storage alloy and preparation method thereof |
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| CN108893656A (en) * | 2018-05-30 | 2018-11-27 | 安泰科技股份有限公司 | La-Mg-Ni system A2B7Type hydrogen storage alloy and preparation method thereof |
| WO2020006843A1 (en) * | 2018-07-04 | 2020-01-09 | 黄倩 | Rear earth doped mg-based hydrogen storage alloy |
| US20200185710A1 (en) * | 2018-12-06 | 2020-06-11 | Toyota Jidosha Kabushiki Kaisha | Negative electrode active material, negative electrode, alkaline storage battery, and method of producing negative electrode active material |
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| CN109830676A (en) * | 2019-01-21 | 2019-05-31 | 江苏集萃安泰创明先进能源材料研究院有限公司 | Rechargeable uses for nickel-hydrogen battery high capacity and long-life La-Mg-Ni type cathode hydrogen storage material and preparation method thereof |
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