CN110993932B - High temperature and high cycle negative electrode active material and preparation method thereof, and nickel-hydrogen battery - Google Patents
High temperature and high cycle negative electrode active material and preparation method thereof, and nickel-hydrogen battery Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 173
- 239000001257 hydrogen Substances 0.000 title claims abstract description 173
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 164
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 141
- 239000000956 alloy Substances 0.000 claims abstract description 141
- 239000002245 particle Substances 0.000 claims abstract description 79
- 239000000843 powder Substances 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 4
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 4
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 4
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 4
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 4
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 4
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 4
- 229910052738 indium Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000003792 electrolyte Substances 0.000 claims description 31
- 229910052987 metal hydride Inorganic materials 0.000 claims description 26
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- -1 amine compound Chemical class 0.000 claims description 17
- 238000005530 etching Methods 0.000 claims description 17
- 239000011777 magnesium Substances 0.000 claims description 16
- 239000007774 positive electrode material Substances 0.000 claims description 16
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 claims description 16
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 14
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000007514 bases Chemical class 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 8
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 8
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 7
- 238000010981 drying operation Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 239000006183 anode active material Substances 0.000 claims 1
- 230000007774 longterm Effects 0.000 abstract description 8
- 229910052779 Neodymium Inorganic materials 0.000 abstract description 3
- 229910052777 Praseodymium Inorganic materials 0.000 abstract description 3
- 229910052758 niobium Inorganic materials 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 238000005260 corrosion Methods 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 10
- 230000002035 prolonged effect Effects 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 238000002336 sorption--desorption measurement Methods 0.000 description 7
- 239000012528 membrane Substances 0.000 description 6
- 229910002335 LaNi5 Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- 238000010828 elution Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002815 nickel Chemical group 0.000 description 2
- 229910004269 CaCu5 Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/383—Hydrogen absorbing alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明涉及镍氢电池领域，公开了一种高温高循环负极活性物质及其制备方法和镍氢电池，该高温高循环负极活性物质，含有储氢合金粉末，储氢合金粉末包括多个储氢合金粒子，储氢合金粒子具有通式R1‑a‑bMgaYbNic‑d‑eAldTe所示的组成，其中，R包括La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Ca、Sr、Sc、Ti、Zr和Hf其中至少一种，T包括Mn、Co、V、Nb、Ta、Cr、Mo、Fe、Ga、Zn、Sn、In、Cu、Si、P和B其中至少一种，a满足0＜a≤0.2，b满足0＜b≤0.2，c满足3≤c≤4，d满足0＜d≤0.50，e满足0＜e≤1。如此来提高电池的容量，改善电池在55℃以上的高温环境下长期充放电性能，提高电池循环使用寿命。
The invention relates to the field of nickel-hydrogen batteries, and discloses a high-temperature and high-cycle negative electrode active material and a preparation method thereof, and a nickel-hydrogen battery. The high-temperature and high-cycle negative electrode active material contains hydrogen storage alloy powder, and the hydrogen storage alloy powder includes a plurality of hydrogen storage alloys. Alloy particles, the hydrogen storage alloy particles have a composition represented by the general formula R 1‑a‑b Mg a Y b Ni c‑d‑e Al d T e , wherein R includes La, Ce, Pr, Nd, Pm, Sm , at least one of Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ca, Sr, Sc, Ti, Zr and Hf, T includes Mn, Co, V, Nb, Ta, Cr, Mo , at least one of Fe, Ga, Zn, Sn, In, Cu, Si, P and B, a satisfies 0<a≤0.2, b satisfies 0<b≤0.2, c satisfies 3≤c≤4, d satisfies 0 <d≤0.50, e satisfies 0<e≤1. In this way, the capacity of the battery is increased, the long-term charge and discharge performance of the battery in a high temperature environment above 55°C is improved, and the cycle life of the battery is improved.
Description
Technical Field
The invention relates to the field of nickel-metal hydride batteries, in particular to a high-temperature high-cycle negative electrode active material, a preparation method thereof and a nickel-metal hydride battery.
Background
The nickel-hydrogen battery is used as a back-up power supply, is synthesized by hydrogen ions and metal nickel, has 30 percent more electric quantity reserve than a nickel-cadmium battery, is lighter than the nickel-cadmium battery, has longer service life, has no pollution to the environment, has the advantages of environmental protection, long service life, mature process and the like, and has larger and wider use amount and wider use temperature. The current high-temperature nickel-hydrogen battery has an application environment temperature of 50 ℃, and cannot meet the new increasing requirements of the market, for example, the application temperature is raised to be more than 55 ℃, and the service life needs to be kept for more than 4 years.
The negative active material of nickel-hydrogen battery is hydrogen storage alloy powder, LaNi is used5Type of hydrogen storage alloy, said LaNi5The hydrogen storage alloy is a kind of alloy with CaCu5A rare earth-Ni intermetallic compound having a crystal structure as a main phase, and a hydrogen storage alloy containing Ti, Zr, V and Ni as constituent elements and having a Laves crystal structure as a main phase. This LaNi5The hydrogen storage alloy has small capacity, poor long-term charge and discharge performance in a high-temperature environment of more than 55 ℃ and short cycle service life.
In addition, in the process of charging and discharging the battery, the anode reaches the oxygen evolution potential due to local severe polarization or overcharge of the anode, so that oxygen is generated, the generated oxygen reaches the cathode through the diaphragm, part of the oxygen is compounded at the cathode to generate water, and part of the oxygen can not be compounded to oxidize the hydrogen storage alloy, after the surface of the hydrogen storage alloy powder is oxidized, the electrical contact property and the electrochemical activity of the powder are reduced, and the oxidation phenomenon is more severe along with the gradual rise of the temperature, which is the main reason for causing the rapid capacity attenuation of the battery in the high-temperature circulation process. In order to prevent the oxidation phenomenon of the negative electrode, metal nickel or metal copper is coated on the surface of the hydrogen storage alloy powder, however, the capacity density of the hydrogen storage alloy powder is reduced, the effective capacity of the battery is reduced, and the effect of preventing the oxidation phenomenon of the negative electrode is poor because the surface of the hydrogen storage alloy powder is not tightly combined with the metal nickel or metal copper coating layer.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a high-temperature high-cycle negative electrode active material, a preparation method thereof and a nickel-metal hydride battery, so that the capacity of the battery is improved, the long-term charge and discharge performance of the battery in a high-temperature environment of more than 55 ℃ is improved, and the cycle service life of the battery is prolonged.
The purpose of the invention is realized by the following technical scheme:
a high-temperature high-cycle negative active material comprises a hydrogen storage alloy powder including a plurality of hydrogen storage alloy particles having a general formula R1-a-bMgaYbNic-d-eAldTeThe composition is shown In the specification, wherein R comprises at least one of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ca, Sr, Sc, Ti, Zr and Hf, T comprises at least one of Mn, Co, V, Nb, Ta, Cr, Mo, Fe, Ga, Zn, Sn, In, Cu, Si, P and B, a is more than 0 and less than or equal to 0.2, B is more than 0 and less than or equal to 0.2, c is more than 3 and less than or equal to c and less than or equal to 4, d is more than 0 and less than or equal to 0.50, and e is more than 0 and less than or equal to 1.
In one embodiment, the hydrogen storage alloy particles include hydrogen storage alloy macroparticles, hydrogen storage alloy mesoparticles, and hydrogen storage alloy macroparticles, and the hydrogen storage alloy macroparticles, the hydrogen storage alloy mesoparticles, and the hydrogen storage alloy mesoparticles have a diameter ratio of 3:2: 1.
In one embodiment, the diameter of the large hydrogen storage alloy particles is 60nm to 150nm, the diameter of the hydrogen storage alloy particles is 40nm to 100nm, and the diameter of the small hydrogen storage alloy particles is 20nm to 50 nm.
A preparation method of a high-temperature high-cycle negative active material comprises the following steps:
mixing an alkaline compound and an amine compound, and uniformly stirring to obtain an alkaline etching solution;
putting the hydrogen storage alloy particles into the alkaline etching solution, and performing microwave treatment;
and sequentially carrying out filtering operation, washing operation and drying operation on the hydrogen storage alloy particles to obtain the high-temperature high-cycle negative electrode active material.
In one embodiment, the microwave frequency of the microwave treatment is 5000MHZ to 8000MHZ, the temperature of the microwave treatment is 50 ℃ to 80 ℃, and the time of the microwave treatment is 5min to 20 min.
In one embodiment, the mass ratio of the basic compound to the amine compound is 1: 3-6.
In one embodiment, the basic compound comprises at least one of sodium hydroxide, potassium hydroxide, magnesium hydroxide, hydrazine hydrate, and ammonia.
In one embodiment, the amine compound includes at least one of methylamine, diethylamine and aniline.
The nickel-metal hydride battery comprises a negative plate, wherein the negative plate comprises a negative current collector and a negative active material layer coated on the negative current collector, and the negative active material layer contains the high-temperature high-cycle negative active material prepared by the preparation method of the high-temperature high-cycle negative active material.
In one embodiment, the nickel-metal hydride battery further includes a positive plate, an electrolyte and an isolating film, the electrolyte and the isolating film are spaced between the positive plate and the negative plate, the positive plate includes a positive current collector and a positive active material layer coated on the positive current collector, wherein the positive active material layer includes the following components in parts by mass: 1000 parts of nickel hydroxide, 5-15 parts of calcium oxide, 15-25 parts of thulium oxide, 15-25 parts of titanium oxide and 10-20 parts of cobalt oxide; the electrolyte comprises the following components in parts by mass: 100 parts of pure water, 30-50 parts of potassium hydroxide, 20-40 parts of sodium hydroxide and 1-3 parts of lithium hydroxide; the isolating film comprises a polyethylene base film, a ceramic layer and a PMMA coating which are arranged in a laminated mode.
Compared with the prior art, the invention has at least the following advantages:
the invention adjusts the equilibrium pressure of the hydrogen storage alloy powder during hydrogen absorption/desorption by adding appropriate content of R and Y in the hydrogen storage alloy powder; adjusting the equilibrium pressure of the hydrogen storage alloy powder during hydrogen adsorption/desorption by adding Mg with proper content in the hydrogen storage alloy powder, and adjusting the hydrogen storage capacity and corrosion resistance of the hydrogen storage alloy powder; adjusting the hydrogen storage capacity, discharge capacity, cycle characteristics and safety of the hydrogen storage alloy powder by adding Ni with proper content into the hydrogen storage alloy powder; adjusting the equilibrium pressure of the hydrogen storage alloy powder during hydrogen adsorption/desorption by adding Al with proper content in the hydrogen storage alloy powder, and adjusting the corrosion resistance, the cycle characteristic, the initial capacity and the hydrogen storage capacity of the hydrogen storage alloy powder; by adding a suitable content of T to the hydrogen storage alloy powder, it is possible to suppress battery burst or suppress elution of Al into the electrolyte. Thus, by properly proportioning R, Mg, Y, Ni, Al and T, the high-temperature high-cycle negative electrode active substance with moderate equilibrium pressure, larger initial capacity, larger hydrogen storage capacity, higher corrosion resistance, better cycle characteristic and higher safety can be obtained, the dissolution of the battery or the Al into the electrolyte can be inhibited, the pulverization of the hydrogen storage alloy powder in the later charging and discharging period at the high temperature of more than 55 ℃ can be effectively improved, the increase of the internal resistance of the battery is reduced, the discharge performance is improved, and the cycle service life of the battery is prolonged.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a flowchart illustrating steps of a method for preparing a high-temperature high-cycle negative active material according to an embodiment of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In one embodiment, a high temperature high cycle negative active material includes a hydrogen storage alloy powder including a plurality of hydrogen storage alloy particles having a general formula R1-a-bMgaYbNic-d-eAldTeThe composition is shown In the specification, wherein R comprises at least one of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ca, Sr, Sc, Ti, Zr and Hf, T comprises at least one of Mn, Co, V, Nb, Ta, Cr, Mo, Fe, Ga, Zn, Sn, In, Cu, Si, P and B, a is more than 0 and less than or equal to 0.2, B is more than 0 and less than or equal to 0.2, c is more than 3 and less than or equal to c and less than or equal to 4, d is more than 0 and less than or equal to 0.50, and e is more than 0 and less than or equal to 1. In the present invention, the hydrogen occluding alloy powder is addedAppropriate amounts of R and Y to adjust the equilibrium pressure of the hydrogen storage alloy powder at the time of hydrogen adsorption/desorption; adjusting the equilibrium pressure of the hydrogen storage alloy powder during hydrogen adsorption/desorption by adding Mg with proper content in the hydrogen storage alloy powder, and adjusting the hydrogen storage capacity and corrosion resistance of the hydrogen storage alloy powder; adjusting the hydrogen storage capacity, discharge capacity, cycle characteristics and safety of the hydrogen storage alloy powder by adding Ni with proper content into the hydrogen storage alloy powder; adjusting the equilibrium pressure of the hydrogen storage alloy powder during hydrogen adsorption/desorption by adding Al with proper content in the hydrogen storage alloy powder, and adjusting the corrosion resistance, the cycle characteristic, the initial capacity and the hydrogen storage capacity of the hydrogen storage alloy powder; by adding a suitable content of T to the hydrogen storage alloy powder, it is possible to suppress battery burst or suppress elution of Al into the electrolyte. Thus, by properly proportioning R, Mg, Y, Ni, Al and T, the high-temperature high-cycle negative electrode active substance with moderate equilibrium pressure, larger initial capacity, larger hydrogen storage capacity, higher corrosion resistance, better cycle characteristic and higher safety can be obtained, the dissolution of the battery or the Al into the electrolyte can be inhibited, the pulverization of the hydrogen storage alloy powder in the later charging and discharging period at the high temperature of more than 55 ℃ can be effectively improved, the increase of the internal resistance of the battery is reduced, the discharge performance is improved, and the cycle service life of the battery is prolonged.
In order to make the equilibrium pressure of the high-temperature high-cycle negative active material more moderate, the initial capacity is larger, the hydrogen storage capacity is larger, the corrosion resistance is higher, the cycle characteristics are better and the safety is higher, in another embodiment, a high-temperature high-cycle negative active material comprises a hydrogen storage alloy powder comprising a plurality of hydrogen storage alloy particles having a general formula of La0.8Mg0.1Y0.1Ni2.8Al0.2B0.5The composition shown. Therefore, the balance pressure of the high-temperature high-cycle negative active material is more moderate, the initial capacity is larger, the hydrogen storage capacity is larger, the corrosion resistance is higher, the cycle characteristic is better, and the safety is higher.
In order to make the balance pressure of the high-temperature high-cycle negative active material more moderate, the initial capacity is larger, the hydrogen storage capacity is larger, the corrosion resistance is higher, and the cycle characteristic is moreGood and more safe, and in yet another embodiment, a high-temperature high-cycle negative active material comprising a hydrogen storage alloy powder including a plurality of hydrogen storage alloy particles having a general formula Sc0.8Mg0.1Y0.1Ni2.7Al0.3Cu0.5The composition shown. Therefore, the balance pressure of the high-temperature high-cycle negative active material is more moderate, the initial capacity is larger, the hydrogen storage capacity is larger, the corrosion resistance is higher, the cycle characteristic is better, and the safety is higher.
In one embodiment, the hydrogen storage alloy particles include hydrogen storage alloy large particles, hydrogen storage alloy medium particles, and hydrogen storage alloy small particles, and the hydrogen storage alloy large particles, the hydrogen storage alloy medium particles, and the hydrogen storage alloy small particles have a diameter ratio of 3:2: 1. By the collection of hydrogen storage alloy particles with different particle sizes, the density of the high-temperature high-cycle negative electrode active material can be improved, and the initial capacity of the battery can be further improved; the battery can be improved in that, after the battery is used after being left for a long period of time, the capacity remaining rate of the battery can be kept high while suppressing self-discharge and a decrease in operating voltage even after the battery is recharged, and the capacity of the battery can be fully utilized.
In order to further increase the initial capacity of the battery, further improve the long-term charge and discharge performance of the battery in a high-temperature environment of 55 ℃ or higher, and further improve the cycle life of the battery, in one embodiment, the hydrogen storage alloy large particles have a diameter of 60nm to 150nm, for example, the hydrogen storage alloy large particles have a diameter of 60nm, 75nm, 90nm, 105nm, 120nm, 135nm, or 150 nm. As another example, the diameter of the particles in the hydrogen storage alloy is 40nm to 100nm, for example, the diameter of the hydrogen storage alloy large particles is 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, or 100 nm. As another example, the hydrogen storage alloy small particles have a diameter of 20nm to 50nm, and the hydrogen storage alloy large particles have a diameter of 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, or 50nm, for example. The concentration of the nano-scale hydrogen storage alloy particles with different particle sizes is selected, so that the density of the high-temperature high-cycle negative electrode active material can be further improved, the initial capacity of the battery is further improved, the long-term charge and discharge performance of the battery in a high-temperature environment of more than 55 ℃ is further improved, and the cycle service life of the battery is further prolonged.
In one embodiment, referring to fig. 1, a method for preparing a high-temperature high-cycle negative active material includes the following steps: s110, mixing an alkaline compound and an amine compound, and uniformly stirring to obtain an alkaline etching solution; s120, putting the hydrogen storage alloy particles into the alkaline etching solution, and performing microwave treatment; and S130, sequentially carrying out filtering operation, washing operation and drying operation on the hydrogen storage alloy particles to obtain the high-temperature high-cycle negative electrode active material. It should be noted that, in the alkaline condition, the invention is assisted by microwave, so the inner depth of the hydrogen storage alloy particle is heated, and in the alkaline condition, the water molecule shows extremely strong polarity, can absorb microwave well, overcomes the heat conduction process of conventional heating, and the transmission performance of microwave heats the inner and outer media of the material at the same time, so the nickel atom contained in the hydrogen storage alloy particle can be enriched to the surface of each particle uniformly by the microwave treatment, and at the same time, the roughness of the surface of the hydrogen storage alloy particle can be increased by the micro-corrosivity of amine compound, and the combination tightness and combination strength of the nickel atom and the particle are further improved, so the conductivity of the cathode can be improved better, the pulverization and oxidation of the high-temperature high-cycle cathode active material can be reduced better, the stability of the high-temperature high-cycle cathode active material can be increased better, and the long-term charge and discharge performance of the battery in the high-temperature environment above 55 ℃ can be improved better, the cycle service life of the battery can be better prolonged.
In order to further increase the efficiency of the microwave treatment, in an embodiment, the microwave frequency of the microwave treatment is 5000MHZ to 8000MHZ, for example 5000MHZ, 5500MHZ, 6000MHZ, 6500MHZ, 7000MHZ, 7500MHZ or 8000 MHZ. For another example, the temperature of the microwave treatment is 50 ℃ to 80 ℃, for example, the temperature of the microwave treatment is 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃. For another example, the microwave treatment time is 5min to 20min, for example, the microwave treatment time is 5min, 7min, 10n, 12min, 15min, 18min or 20 min. This can further improve the efficiency of the microwave treatment.
In order to make the corrosiveness of the alkaline etching solution more moderate, in one embodiment, the mass ratio of the alkaline compound to the amine compound is 1: 3-6, for example, the mass ratio of the alkaline compound to the amine compound is 1:3, 1:4, 1:5, or 1: 6. This makes the alkaline etching solution more moderately corrosive. As another example, the basic compound includes at least one of sodium hydroxide, potassium hydroxide, magnesium hydroxide, hydrazine hydrate, and aqueous ammonia, for example, the basic compound includes sodium hydroxide, potassium hydroxide, magnesium hydroxide, hydrazine hydrate, and aqueous ammonia. For example, the basic compound includes hydrazine hydrate and ammonia water. For example, the basic compound includes sodium hydroxide, potassium hydroxide, magnesium hydroxide, hydrazine hydrate, or ammonia water. As another example, the amine compound includes at least one of methylamine, diethylamine and aniline. For example, the amine-based compounds include methylamine, diethylamine and aniline. For example, the amine compound includes methylamine, diethylamine or aniline. For example, the amine compound includes methylamine. Therefore, the corrosivity of the alkaline etching solution is more moderate, and the over-corrosion of the hydrogen storage alloy particles is avoided.
In one embodiment, the nickel-metal hydride battery comprises a negative plate, wherein the negative plate comprises a negative current collector and a negative active material layer coated on the negative current collector, and the negative active material layer contains the high-temperature high-cycle negative active material prepared by the preparation method of the high-temperature high-cycle negative active material. Thus, by properly proportioning R, Mg, Y, Ni, Al and T, the high-temperature high-cycle negative electrode active substance with moderate equilibrium pressure, larger initial capacity, larger hydrogen storage capacity, higher corrosion resistance, better cycle characteristic and higher safety can be obtained, the dissolution of the battery or the Al into the electrolyte can be inhibited, the pulverization of the hydrogen storage alloy powder in the later charging and discharging period at the high temperature of more than 55 ℃ can be effectively improved, the increase of the internal resistance of the battery is reduced, the discharge performance is improved, and the cycle service life of the battery is prolonged.
In one embodiment, the nickel-metal hydride battery further includes a positive plate, an electrolyte and an isolating film, the electrolyte and the isolating film are spaced between the positive plate and the negative plate, the positive plate includes a positive current collector and a positive active material layer coated on the positive current collector, wherein the positive active material layer includes the following components in parts by mass: 1000 parts of nickel hydroxide, 5-15 parts of calcium oxide, 15-25 parts of thulium oxide, 15-25 parts of titanium oxide and 10-20 parts of cobalt oxide; the electrolyte comprises the following components in parts by mass: 100 parts of pure water, 30-50 parts of potassium hydroxide, 20-40 parts of sodium hydroxide and 1-3 parts of lithium hydroxide; the isolating film comprises a polyethylene base film, a ceramic layer and a PMMA coating which are arranged in a laminated mode. Thus, the charging efficiency of the battery in a high-temperature environment of more than 55 ℃ can be further improved, the long-term charging and discharging performance of the battery in the high-temperature environment of more than 55 ℃ can be further improved, and the cycle service life of the battery can be further prolonged.
In another embodiment, the nickel-metal hydride battery further includes a positive plate, an electrolyte and a separator, the electrolyte and the separator are spaced between the positive plate and the negative plate, the positive plate includes a positive current collector and a positive active material layer coated on the positive current collector, wherein the positive active material layer includes the following components in parts by mass: 1000 parts of nickel hydroxide, 10 parts of calcium oxide, 20 parts of thulium oxide, 20 parts of titanium oxide and 15 parts of cobalt oxide; the electrolyte comprises the following components in parts by mass: 100 parts of pure water, 40 parts of potassium hydroxide, 30 parts of sodium hydroxide and 2 parts of lithium hydroxide. Thus, the charging efficiency of the battery in a high-temperature environment of more than 55 ℃ can be further improved, the long-term charging and discharging performance of the battery in the high-temperature environment of more than 55 ℃ can be further improved, and the cycle service life of the battery can be further prolonged.
Compared with the prior art, the invention has at least the following advantages:
the invention adjusts the equilibrium pressure of the hydrogen storage alloy powder during hydrogen absorption/desorption by adding appropriate content of R and Y in the hydrogen storage alloy powder; adjusting the equilibrium pressure of the hydrogen storage alloy powder during hydrogen adsorption/desorption by adding Mg with proper content in the hydrogen storage alloy powder, and adjusting the hydrogen storage capacity and corrosion resistance of the hydrogen storage alloy powder; adjusting the hydrogen storage capacity, discharge capacity, cycle characteristics and safety of the hydrogen storage alloy powder by adding Ni with proper content into the hydrogen storage alloy powder; adjusting the equilibrium pressure of the hydrogen storage alloy powder during hydrogen adsorption/desorption by adding Al with proper content in the hydrogen storage alloy powder, and adjusting the corrosion resistance, the cycle characteristic, the initial capacity and the hydrogen storage capacity of the hydrogen storage alloy powder; by adding a suitable content of T to the hydrogen storage alloy powder, it is possible to suppress battery burst or suppress elution of Al into the electrolyte. Thus, by properly proportioning R, Mg, Y, Ni, Al and T, the high-temperature high-cycle negative electrode active substance with moderate equilibrium pressure, larger initial capacity, larger hydrogen storage capacity, higher corrosion resistance, better cycle characteristic and higher safety can be obtained, the dissolution of the battery or the Al into the electrolyte can be inhibited, the pulverization of the hydrogen storage alloy powder in the later charging and discharging period at the high temperature of more than 55 ℃ can be effectively improved, the increase of the internal resistance of the battery is reduced, the discharge performance is improved, and the cycle service life of the battery is prolonged.
The following are detailed description of the embodiments
Example 1
S111, mixing 100g of sodium hydroxide and 300g of methylamine, and uniformly stirring to obtain an alkaline etching solution;
s121, putting hydrogen storage alloy particles into the alkaline etching solution, and introducing microwaves with the frequency of 8000MHZ at the temperature of 50 ℃ for microwave treatment for 5 min; wherein the hydrogen storage alloy particles comprise 10g of large hydrogen storage alloy particles with the diameter of 60nm, 10g of medium hydrogen storage alloy particles with the diameter of 40nm and 10g of small hydrogen storage alloy particles with the diameter of 20nm, and the large hydrogen storage alloy particles and the small hydrogen storage alloy particles have the general formula Pr0.9Mg0.05Y0.05Ni3.8Al0.1Mn0.1The composition shown.
S131, sequentially carrying out filtering operation, washing operation and drying operation on the hydrogen storage alloy particles to obtain the high-temperature high-cycle negative electrode active material.
S141, preparing a nickel-metal hydride battery by using the high-temperature high-cycle negative electrode active material, wherein the prepared nickel-metal hydride battery comprises a positive plate, a negative plate, electrolyte and an isolating membrane, the electrolyte and the isolating membrane are arranged between the positive plate and the negative plate, the positive plate comprises a positive current collector and a positive active material layer coated on the positive current collector, the negative plate comprises a negative current collector and a negative active material layer coated on the negative current collector, and the negative active material layer contains the high-temperature high-cycle negative electrode active material; the positive active material layer comprises the following components in parts by mass: 100g of nickel hydroxide, 0.5 g of calcium oxide, 1.5g of thulium oxide, 1.5g of titanium oxide and 2g of cobalt oxide; the electrolyte comprises the following components in parts by mass: 10g of pure water, 3g of potassium hydroxide, 2g of sodium hydroxide and 0.3g of lithium hydroxide.
Example 2
S112, mixing 100g of ammonia water and 600g of diethylamine, and uniformly stirring to obtain an alkaline etching solution;
s122, putting the hydrogen storage alloy particles into the alkaline etching solution, and introducing microwaves with the frequency of 5000MHZ at the temperature of 80 ℃ for microwave treatment for 20 min; wherein the hydrogen storage alloy particles comprise 10g of large hydrogen storage alloy particles with the diameter of 150nm, 10g of medium hydrogen storage alloy particles with the diameter of 100nm and 10g of small hydrogen storage alloy particles with the diameter of 50nm, and the hydrogen storage alloy particles have the general formula Ce0.6Mg0.2Y0.2Ni1.5Al0.5Sn1The composition shown.
And S130, sequentially carrying out filtering operation, washing operation and drying operation on the hydrogen storage alloy particles to obtain the high-temperature high-cycle negative electrode active material.
S140, preparing the nickel-metal hydride battery by using the high-temperature high-cycle negative electrode active material, wherein the prepared nickel-metal hydride battery comprises a positive plate, a negative plate, electrolyte and an isolating membrane, the electrolyte and the isolating membrane are arranged between the positive plate and the negative plate, the positive plate comprises a positive current collector and a positive active material layer coated on the positive current collector, the negative plate comprises a negative current collector and a negative active material layer coated on the negative current collector, and the negative active material layer contains the high-temperature high-cycle negative electrode active material; the positive active material layer comprises the following components in parts by mass: 100g of nickel hydroxide, 1.5g of calcium oxide, 2.5g of thulium oxide, 2.5g of titanium oxide and 1g of cobalt oxide; the electrolyte comprises the following components in parts by mass: 10g of pure water, 5g of potassium hydroxide, 4g of sodium hydroxide and 0.1g of lithium hydroxide.
Example 3
S113, mixing 100g of hydrazine hydrate and 450g of aniline, and uniformly stirring to obtain an alkaline etching solution;
s123, putting the hydrogen storage alloy particles into the alkaline etching solution, and introducing microwaves with the frequency of 6500MHZ at the temperature of 65 ℃ for microwave treatment for 12 min; wherein the hydrogen storage alloy particles comprise 10g of large hydrogen storage alloy particles with the diameter of 135nm, 10g of medium hydrogen storage alloy particles with the diameter of 90nm and 10g of small hydrogen storage alloy particles with the diameter of 45nm, and the hydrogen storage alloy particles have the general formula Sc0.8Mg0.1Y0.1Ni2.8Al0.2B0.5The composition shown.
And S133, sequentially carrying out filtering operation, washing operation and drying operation on the hydrogen storage alloy particles to obtain the high-temperature high-cycle negative electrode active material.
S143, preparing the nickel-metal hydride battery by using the high-temperature high-cycle negative electrode active material, wherein the prepared nickel-metal hydride battery comprises a positive plate, a negative plate, electrolyte and an isolating film, the electrolyte and the isolating film are arranged between the positive plate and the negative plate, the positive plate comprises a positive current collector and a positive active material layer coated on the positive current collector, the negative plate comprises a negative current collector and a negative active material layer coated on the negative current collector, and the negative active material layer contains the high-temperature high-cycle negative electrode active material; the positive active material layer comprises the following components in parts by mass: 100g of nickel hydroxide, 1g of calcium oxide, 2g of thulium oxide, 2g of titanium oxide and 1.5g of cobalt oxide; the electrolyte comprises the following components in parts by mass: 10g of pure water, 4g of potassium hydroxide, 3g of sodium hydroxide and 0.2g of lithium hydroxide.
Example 4
S114, mixing 100g of potassium hydroxide and 400g of diethylamine, and uniformly stirring to obtain an alkaline etching solution;
s124, putting the hydrogen storage alloy particles into the alkaline etching solutionIntroducing microwave with frequency of 7000MHz at 70 deg.C for microwave treatment for 10 min; wherein the hydrogen storage alloy particles comprise 10g of large hydrogen storage alloy particles with the diameter of 120nm, 10g of medium hydrogen storage alloy particles with the diameter of 80nm and 10g of small hydrogen storage alloy particles with the diameter of 40nm, and the hydrogen storage alloy particles have the general formula La0.7Mg0.1Y0.2Ni2.2Al0.3Cu0.5The composition shown.
And S134, sequentially carrying out filtering operation, washing operation and drying operation on the hydrogen storage alloy particles to obtain the high-temperature high-cycle negative electrode active material.
S144, preparing the nickel-metal hydride battery by using the high-temperature high-cycle negative electrode active material, wherein the prepared nickel-metal hydride battery comprises a positive plate, a negative plate, electrolyte and an isolating membrane, the electrolyte and the isolating membrane are arranged between the positive plate and the negative plate, the positive plate comprises a positive current collector and a positive active material layer coated on the positive current collector, the negative plate comprises a negative current collector and a negative active material layer coated on the negative current collector, and the negative active material layer contains the high-temperature high-cycle negative electrode active material; the positive active material layer comprises the following components in parts by mass: 100g of nickel hydroxide, 1g of calcium oxide, 2g of thulium oxide, 2g of titanium oxide and 1.5g of cobalt oxide; the electrolyte comprises the following components in parts by mass: 10g of pure water, 4g of potassium hydroxide, 3g of sodium hydroxide and 0.2g of lithium hydroxide.
The nickel-metal hydride battery prepared in the above example contains LaNi at 60 deg.C5The initial capacity of the common nickel-metal hydride battery of the hydrogen storage alloy is 1.2-1.4 times. At 60 ℃ contains LaNi5The charging efficiency of the common nickel-metal hydride battery of the hydrogen storage alloy is only 80%, and the charging efficiency of the nickel-metal hydride battery prepared in the embodiment is 98-100%. Containing LaNi5The reduction of the working voltage of the common nickel-metal hydride battery of the hydrogen storage alloy after charging is 30, and the reduction of the working voltage of the nickel-metal hydride battery prepared in the embodiment after charging is 6-13. Charging and discharging at 60 deg.C under 1C according to related national standard, and contains LaNi5The cycle life of the common nickel-hydrogen battery of the hydrogen storage alloy reaches 1000 times, andthe cycle life of the nickel-metal hydride battery prepared in the embodiment reaches 2000-3000 times.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A high-temperature high-cycle negative active material comprising a hydrogen storage alloy powder including a plurality of hydrogen storage alloy particles having a general formula R1-a-bMgaYbNic-d-eAldTeThe composition is shown In the specification, wherein R comprises at least one of La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ca, Sr, Sc, Ti, Zr and Hf, T comprises at least one of Mn, V, Ta, Cr, Mo, Fe, Ga, Zn, Sn, In, Cu, Si, P and B, a is more than or equal to 0.05 and less than or equal to 0.2, B is more than or equal to 0.05 and less than or equal to 0.2, c is more than or equal to 3 and less than or equal to 4, d is more than or equal to 0.1 and less than or equal to 0.50, and e is more than or equal to 0.1 and less than or equal to 1;
the hydrogen storage alloy particles comprise hydrogen storage alloy large particles, hydrogen storage alloy medium particles and hydrogen storage alloy small particles, and the diameter ratio of the hydrogen storage alloy large particles, the hydrogen storage alloy medium particles and the hydrogen storage alloy small particles is 3:2: 1; the diameter of the large hydrogen storage alloy particles is 60 nm-150 nm, the diameter of the particles in the hydrogen storage alloy is 40 nm-100 nm, and the diameter of the small hydrogen storage alloy particles is 20 nm-50 nm.
2. A preparation method of a high-temperature high-cycle negative electrode active material is characterized by comprising the following steps:
mixing an alkaline compound and an amine compound, and uniformly stirring to obtain an alkaline etching solution;
placing the hydrogen absorbing alloy particles according to claim 1 in the alkaline etching solution, and performing microwave treatment;
and sequentially carrying out filtering operation, washing operation and drying operation on the hydrogen storage alloy particles to obtain the high-temperature high-cycle negative electrode active material.
3. The method for preparing a high-temperature high-cycle negative active material according to claim 2, wherein the microwave frequency of the microwave treatment is 5000MHZ to 8000MHZ, the temperature of the microwave treatment is 50 ℃ to 80 ℃, and the time of the microwave treatment is 5min to 20 min.
4. The method for preparing a high-temperature high-cycle negative electrode active material as claimed in claim 2, wherein the mass ratio of the basic compound to the amine compound is 1: 3-6.
5. The method for preparing a high-temperature high-cycle anode active material according to claim 4, wherein the basic compound comprises at least one of sodium hydroxide, potassium hydroxide, magnesium hydroxide, hydrazine hydrate, and ammonia water.
6. The method of claim 4, wherein the amine compound comprises at least one of methylamine, diethylamine and aniline.
7. A nickel-metal hydride battery, comprising a negative electrode sheet, wherein the negative electrode sheet comprises a negative electrode current collector and a negative electrode active material layer coated on the negative electrode current collector, and the negative electrode active material layer contains the high-temperature high-cycle negative electrode active material prepared by the method for preparing a high-temperature high-cycle negative electrode active material according to claim 2.
8. The nickel-metal hydride battery of claim 7, further comprising a positive plate, an electrolyte and a separator, wherein the electrolyte and the separator are spaced between the positive plate and the negative plate, the positive plate comprises a positive current collector and a positive active material layer coated on the positive current collector, and the positive active material layer comprises the following components in parts by mass: 1000 parts of nickel hydroxide, 5-15 parts of calcium oxide, 15-25 parts of thulium oxide, 15-25 parts of titanium oxide and 10-20 parts of cobalt oxide; the electrolyte comprises the following components in parts by mass: 100 parts of pure water, 30-50 parts of potassium hydroxide, 20-40 parts of sodium hydroxide and 1-3 parts of lithium hydroxide; the isolating film comprises a polyethylene base film, a ceramic layer and a PMMA coating which are arranged in a laminated mode.
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