CN111180718A - Hydrogen storage alloy powder of nickel-hydrogen battery for ultralow temperature environment and preparation method thereof - Google Patents
Hydrogen storage alloy powder of nickel-hydrogen battery for ultralow temperature environment and preparation method thereof Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 156
- 239000000956 alloy Substances 0.000 title claims abstract description 156
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 131
- 239000001257 hydrogen Substances 0.000 title claims abstract description 131
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 239000000843 powder Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229910052987 metal hydride Inorganic materials 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000009792 diffusion process Methods 0.000 description 9
- 229910052779 Neodymium Inorganic materials 0.000 description 7
- 230000004913 activation Effects 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910000652 nickel hydride Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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
-
- 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
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
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Abstract
The invention belongs to the technical field of nickel-metal hydride batteries, and particularly relates to hydrogen storage alloy powder of a nickel-metal hydride battery for an ultralow temperature environment, which comprises first hydrogen storage alloy powder and second hydrogen storage alloy powder, wherein the first hydrogen storage alloy powder comprises 19-24% of La, 9-12% of Ce and 0.5-2% of Nd in percentage by mass of the total hydrogen storage alloy powder, and the second hydrogen storage alloy powder comprises 57-63% of Ni, 5-7.5% of Co, 0.8-2.2% of Al and 0.5-2% of Mn in percentage by mass of the total hydrogen storage alloy powder. The hydrogen storage alloy powder prepared by the preparation method and the nickel-metal hydride battery prepared from the hydrogen storage alloy powder can be charged and discharged in an ultralow temperature environment at-40 ℃, the 0.1C discharge efficiency is more than or equal to 95 percent, the 0.2C discharge efficiency is more than or equal to 70 percent, the discharge efficiency is improved, and the use requirement of the nickel-metal hydride battery in the ultralow temperature environment is met.
Description
Technical Field
The invention belongs to the technical field of nickel-metal hydride batteries, and particularly relates to hydrogen storage alloy powder of a nickel-metal hydride battery for an ultralow temperature environment and a preparation method thereof.
Background
With the rapid development of the new energy automobile field, a series of advanced battery technologies are expected to be applied to the field, including lithium ion batteries, nickel hydride batteries, super capacitors and the like. Among them, the lithium ion battery has the advantages of high energy density, high power density, small self-discharge, etc., and becomes the most widely used energy storage device in the field of pure electric vehicles. However, the disadvantages of poor safety performance and low temperature performance, and high battery cost, etc. prevent the large-scale popularization and application of the battery in the field of electric vehicles.
As a mature secondary battery technology, a nickel-metal hydride battery has excellent safety, overcharge/overdischarge resistance, good high/low temperature performance, easy recovery, high recoverable value and the like, and is widely applied to the field of hybrid vehicles and is also an energy storage device which is applied to the field of pure electric vehicles at the earliest time.
However, the performance of nickel-metal hydride batteries at low temperature has not been sufficiently superior. The conventional nickel-metal hydride battery is generally used at a temperature of between-20 ℃ and +40 ℃, the discharge efficiency of the nickel-metal hydride battery is gradually reduced after the temperature is lower than-20 ℃, and when the temperature is only-40 ℃, the discharge efficiency of the nickel-metal hydride battery is lower than 50 percent, so that the requirement of the conventional electric automobile on the low-temperature performance of the nickel-metal hydride battery cannot be met.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the hydrogen storage alloy powder of the nickel-metal hydride battery for the ultralow temperature environment is provided, so that the prepared nickel-metal hydride battery can improve the charge and discharge performance in the ultralow temperature environment of-20 to-40 ℃ and improve the discharge efficiency.
In order to achieve the purpose, the invention adopts the following technical scheme:
the hydrogen storage alloy powder of the nickel-metal hydride battery for the ultralow temperature environment comprises a first hydrogen storage alloy powder and a second hydrogen storage alloy powder, wherein the first hydrogen storage alloy powder comprises, by mass, 19-24% of La, 9-12% of Ce and 0.5-2% of Nd respectively, and the second hydrogen storage alloy powder comprises, by mass, 57-63% of Ni, 5-7.5% of Co, 0.8-2.2% of Al and 0.5-2% of Mn respectively. The proper addition of Nd can reduce the balanced hydrogen pressure, so that the nickel-metal hydride battery can discharge at low temperature, but the excessive Nd is unfavorable for the stability of the cycle performance, and the atomic radius of Ce is smaller than that of La, so that the volume of an alloy crystal cell is reduced, namely, the number of hydrogen atoms entering and exiting the alloy crystal lattice in the charging and discharging process is reduced, the damage effect of the hydrogen atoms on the alloy crystal lattice structure is weakened, and the cycle stability of the alloy is improved. The atomic radius of Co is larger than that of Ni, the volume of alloy unit cells is increased, hydrogen atoms which participate in charging and discharging are increased correspondingly in the unit cells, and the alloy discharge capacity is increased. Al can reduce the equilibrium hydrogen pressure, improve the corrosion resistance of the alloy in alkali liquor, reduce the hydrogen absorption expansion and pulverization rate of the alloy, and improve the cycle life of the alloy. Mn can adjust the pressure of the alloy hydrogen absorption and desorption platform, improve the dynamic performance of the alloy, improve the discharge capacity and high-rate discharge performance of the alloy, but reduce the cycle life. Therefore, the discharge performance of the nickel-metal hydride battery at the low temperature of minus 40 ℃ is met through the synergistic effect of the first hydrogen storage alloy powder and the second hydrogen storage alloy powder.
As an improvement of the hydrogen storage alloy powder of the nickel-hydrogen battery for the ultralow temperature environment, the first hydrogen storage alloy powder also comprises 0-0.5% of Pr by mass percentage of the total mass of the hydrogen storage alloy powder. The Pr element can improve the discharge capacity of the nickel-metal hydride battery and improve the cycle stability of the battery, but too much Pr element can also adversely affect donor ties.
As an improvement of the hydrogen storage alloy powder of the nickel-hydrogen battery for the ultralow temperature environment, the first hydrogen storage alloy powder also comprises a metal A accounting for 0-0.5% of the total mass of the hydrogen storage alloy powder, and the metal A is at least one of Zr, Y and Mg. The electronegativity of Y is high, and the corrosion resistance of the alloy can be improved by adding a proper amount of Y. Mg is used as a hydrogen absorption element with low atomic weight, and the metal and the alloy thereof have high hydrogen storage capacity and discharge capacity. The electronegativity of Mg element is closer to La, the atomic radius is closer to Ni, therefore, the content of Mg is in a proper range, and the excessive content of Mg can replace a part of Ni, so that a large amount of surface dangling bonds appear in the alloy, the energy of the system is increased, and the thermodynamic instability is caused.
As an improvement of the hydrogen storage alloy powder of the nickel-hydrogen battery for the ultralow temperature environment, the second hydrogen storage alloy powder also comprises metal B accounting for 0.01-0.5% of the total mass of the hydrogen storage alloy powder, and the metal B is Cu and/or Si. Cu reduces hydrogen diffusion activation energy of an electrode prepared from alloy powder, the smaller the hydrogen diffusion activation energy is, the smaller the driving force required by hydrogen atoms to fully diffuse in the alloy is, and the hydrogen diffusion activation energy in the alloy is related to an energy barrier required by the hydrogen atoms to migrate to adjacent hydrogen atom sites and the diffusion of the hydrogen inside to the surface. The diffusion of hydrogen from the inside to the surface is related to the surface concentration of hydrogen atoms, the better the electrocatalytic activity of the alloy surface is, the higher the surface reaction rate is, the thickness of the diffusion layer on the alloy surface is reduced, the hydrogen atom concentration is reduced, the migration of the hydrogen atoms in the alloy to the surface is accelerated, the hydrogen diffusion activation energy of the alloy is reduced, and the better the low-temperature performance of the alloy is. Si element can improve the activation performance of the alloy, improve the cycle life of the battery and reduce the high-power discharge performance of the battery.
As an improvement of the hydrogen storage alloy powder of the nickel-hydrogen battery for the ultra-low temperature environment, the first hydrogen storage alloy powder comprises, by mass, 22% of La, 10% of Ce, 2% of Nd, 0.5% of Pr and 0.5% of metal A respectively, the metal A comprises Zr, Y and Mg, the second hydrogen storage alloy powder comprises, by mass, 57% of Ni, 5% of Co, 1% of Al, 1.5% of Mn and 0.5% of metal B respectively, and the metal B comprises Cu and Si.
The second purpose of the invention is: the hydrogen storage alloy powder of the nickel-hydrogen battery for the ultra-low temperature environment is prepared by the method, so that the prepared nickel-hydrogen battery can improve the charge and discharge performance in the ultra-low temperature environment of-20 to-40 ℃ and improve the discharge efficiency, and the preparation method comprises the following steps:
step one, preparing and melting each component in the first hydrogen storage alloy powder and the second hydrogen storage alloy powder according to mass percentage to prepare hydrogen storage alloy sheets;
step two, carrying out heat treatment on the hydrogen storage alloy sheet;
and step three, mechanically crushing the hydrogen storage alloy sheet into hydrogen storage alloy powder to obtain the hydrogen storage alloy powder of the nickel-hydrogen battery for the ultralow temperature environment.
In the first step, the thickness of the hydrogen storage alloy sheet is 70 um-160 um.
In the first step, the thickness of the hydrogen storage alloy sheet is 80-150 um. The first hydrogen storage alloy powder and the second hydrogen storage alloy powder are prepared into a required internal structure according to the design requirement by preparing hydrogen storage alloy sheets with proper thickness.
In the second step, the heat treatment temperature is 800-1100 ℃, and the heat treatment time is 2-6 hours.
In the second step, the heat treatment temperature is 860 to 1010 ℃, and the heat treatment time is 3 to 5 hours. The proper heat treatment temperature leads the unit cell volume of the alloy to be increased, the crystal grains to grow gradually, the alloy to be refined gradually and the uniformity of the alloy structure to be improved. The proper heat treatment temperature can improve the low-temperature discharge efficiency and the low-temperature capacity of the alloy.
The beneficial effects of the invention include but are not limited to: the hydrogen storage alloy powder prepared by the preparation method and the nickel-metal hydride battery prepared from the hydrogen storage alloy powder can be charged and discharged in an ultralow temperature environment at-40 ℃, the 0.1C discharge efficiency is more than or equal to 95 percent, the 0.2C discharge efficiency is more than or equal to 70 percent, the discharge efficiency is improved, and the use requirement of the nickel-metal hydride battery in the ultralow temperature environment is met.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The implementation provides a preparation method of hydrogen storage alloy powder of a nickel-metal hydride battery for an ultralow temperature environment, which comprises the following steps:
step one, preparing and melting each component in the first hydrogen storage alloy powder and the second hydrogen storage alloy powder according to mass percentage to prepare hydrogen storage alloy sheets; the thickness of the hydrogen storage alloy sheet is 80 um-150 um.
Step two, carrying out heat treatment on the hydrogen storage alloy sheet; the heat treatment temperature is 860 to 1010 ℃, and the heat treatment time is 3 to 5 hours.
And step three, mechanically crushing the hydrogen storage alloy sheet into hydrogen storage alloy powder to obtain the hydrogen storage alloy powder of the nickel-hydrogen battery for the ultralow temperature environment.
Wherein the first hydrogen storage alloy powder comprises 22 percent of La, 10 percent of Ce and 2 percent of Nd respectively based on the total mass percent of the hydrogen storage alloy powder, and the second hydrogen storage alloy powder comprises 59 percent of Ni, 5 percent of Co, 1 percent of Al and 1 percent of Mn respectively based on the total mass percent of the hydrogen storage alloy powder.
Coating hydrogen storage alloy powder on a negative electrode substrate, respectively preparing a positive electrode, a negative electrode, a diaphragm and electrolyte, and assembling the positive electrode, the negative electrode, the diaphragm and the electrolyte into the nickel-hydrogen battery for the D8000 ultralow temperature environment.
The battery number is recorded as No. 1.
Example 2
Different from the embodiment 1, the hydrogen storage alloy powder comprises the following components in percentage by weight: the first hydrogen storage alloy powder comprises, by mass, 22% of La, 10% of Ce, 2% of Nd, 0.5% of Pr and 0.5% of Zr, Y and Mg in a mass ratio of 1:1:1, respectively, and the second hydrogen storage alloy powder comprises, by mass, 57% of Ni, 5% of Co, 1% of Al, 1.5% of Mn and 0.5% of Cu and Si in a mass ratio of 1:1, respectively.
The rest is the same as embodiment 1, and the description is omitted here.
The battery number is recorded as No. 2.
Example 3
Different from the embodiment 1, the hydrogen storage alloy powder comprises the following components in percentage by weight: the first hydrogen storage alloy powder comprises, by mass, 22.4% of La, 10% of Ce, 2% of Nd, 0.3% of Pr and 0.3% of Zr, Y and Mg in a ratio of 1:1:1, respectively, and the second hydrogen storage alloy powder comprises, by mass, 57% of Ni, 5% of Co, 1% of Al and 2% of Mn, respectively.
The rest is the same as embodiment 1, and the description is omitted here.
The battery number is recorded as No. 3.
Example 4
Different from the embodiment 1, the hydrogen storage alloy powder comprises the following components in percentage by weight: the first hydrogen storage alloy powder comprises 24 percent of La, 10 percent of Ce, 0.3 percent of Nd and 0.5 percent of Pr by mass percentage of the total hydrogen storage alloy powder, and the second hydrogen storage alloy powder comprises 57 percent of Ni, 5 percent of Co, 1 percent of Al, 1.5 percent of Mn and 0.5 percent of Cu and Si by mass percentage of 1: 1.
The rest is the same as embodiment 1, and the description is omitted here.
The battery number is recorded as No. 4.
Comparative example 1
Different from the embodiment 1, the hydrogen storage alloy powder comprises the following components in percentage by weight: the first hydrogen storage alloy powder comprises 25 percent of La and 10 percent of Ce respectively in percentage by mass of the total hydrogen storage alloy powder, and the second hydrogen storage alloy powder comprises 57.5 percent of Ni, 5 percent of Co, 1 percent of Al and 1.5 percent of Mn respectively in percentage by mass of the total hydrogen storage alloy powder.
The rest is the same as embodiment 1, and the description is omitted here.
The battery number is recorded as No. 5.
Comparative example 2
Different from the embodiment 1, the hydrogen storage alloy powder comprises the following components in percentage by weight: the first hydrogen storage alloy powder comprises 22 percent of La, 10 percent of Ce and 3 percent of Nd respectively according to the total mass percent of the hydrogen storage alloy powder, and the second hydrogen storage alloy powder comprises 58.5 percent of Ni, 5 percent of Co, 1 percent of Al and 1.5 percent of Mn respectively according to the total mass percent of the hydrogen storage alloy powder.
The rest is the same as embodiment 1, and the description is omitted here.
The battery number is recorded as No. 6.
The No. 1-6 batteries are marked as a first group; no. 1-6 batteries were prepared in the same manner and were marked as the second group.
The specific capacity of the batteries 1 to 6 is tested, and the specific capacity of the batteries 1 to 4 is more than or equal to 305 mAh/g.
And (3) performing a low-temperature performance experiment on the battery No. 1-6: discharging the first group of No. 1-6 batteries at a temperature of-40 ℃ with a current of 0.2C, and discharging the second group of No. 1-6 batteries with a current of 0.1C.
And (5) carrying out cycle performance test on No. 1-6 batteries.
The experimental results obtained are shown in table 1.
TABLE 1
As can be seen from the examples 1-2 and 3, the Cu element is added into the alloy powder, which is beneficial to improving the low-temperature performance. The reason is that the Cu element reduces the hydrogen diffusion activation energy of the electrode prepared from the alloy powder, the hydrogen atom concentration is reduced, the migration of the hydrogen atoms in the alloy to the surface is accelerated, the hydrogen diffusion activation energy of the alloy is reduced, and the low-temperature performance of the alloy is better.
It can be seen from examples 1 to 2 and 4 that the content of neodymium element is too small, and the cycle performance of the nickel-metal hydride battery is slightly improved, but the low-temperature discharge efficiency cannot meet the requirement. This is because the appropriate addition of the neodymium element can lower the equilibrium hydrogen pressure, enabling the nickel-metal hydride battery to discharge at low temperature.
As can be seen from example 1 and comparative examples 1 to 2, when the first hydrogen storage alloy powder does not contain neodymium metal, the nickel-metal hydride battery does not substantially operate at low temperature. When the content of the neodymium metal in the first hydrogen storage alloy powder is excessive, the low-temperature discharge efficiency of the nickel-metal hydride battery is improved, but the cycle performance of the battery is influenced. And the atomic radius of Ce is smaller than that of La, so that the volume of an alloy crystal cell is reduced, namely, the number of hydrogen atoms entering and exiting the alloy crystal lattice in the charging and discharging process is reduced, the damage effect of the hydrogen atoms on the alloy crystal lattice structure is weakened, the circulation stability of the alloy is improved, and the Nd element and the Ce element are required to be cooperatively used.
From the above experimental results, it can be seen that the elements added in example 2 are more favorable for the low-temperature discharge performance of the nickel-metal hydride battery, and do not affect the cycle performance of the battery, because the elements interact with each other in a proper ratio, the advantages of each element are ensured, and the disadvantages of each element are compensated. The hydrogen storage alloy powder prepared by the preparation method and the nickel-metal hydride battery prepared from the hydrogen storage alloy powder can be charged and discharged in an ultralow temperature environment at-40 ℃, the 0.1C discharge efficiency is more than or equal to 95 percent, the 0.2C discharge efficiency is more than or equal to 70 percent, the discharge efficiency is improved, and the use requirement of the nickel-metal hydride battery in the ultralow temperature environment is met.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. The hydrogen storage alloy powder of the nickel-metal hydride battery for the ultralow temperature environment is characterized by comprising a first hydrogen storage alloy powder and a second hydrogen storage alloy powder, wherein the first hydrogen storage alloy powder comprises 19-24% of La, 9-12% of Ce and 0.5-2% of Nd in percentage by mass of the total hydrogen storage alloy powder, and the second hydrogen storage alloy powder comprises 57-63% of Ni, 5-7.5% of Co, 0.8-2.2% of Al and 0.5-2% of Mn in percentage by mass of the total hydrogen storage alloy powder.
2. The hydrogen-storing alloy powder for the nickel-metal hydride battery used in the ultra-low temperature environment as claimed in claim 1, wherein the first hydrogen-storing alloy powder further comprises 0 to 0.5% by mass of Pr.
3. The hydrogen-storing alloy powder for a nickel-metal hydride battery for an ultra-low temperature environment as set forth in claim 2, wherein the first hydrogen-storing alloy powder further comprises a metal A in an amount of 0 to 0.5% by mass based on the total mass of the hydrogen-storing alloy powder, and the metal A is at least one of Zr, Y and Mg.
4. The hydrogen-storing alloy powder for the nickel-metal hydride battery used in the ultra-low temperature environment as claimed in claim 3, wherein the second hydrogen-storing alloy powder further comprises a metal B in an amount of 0.01 to 0.5% by mass based on the total mass of the hydrogen-storing alloy powder, and the metal B is Cu and/or Si.
5. The hydrogen storage alloy powder for a nickel-metal hydride battery for an ultra-low temperature environment as set forth in claim 4, wherein said first hydrogen storage alloy powder comprises, in total mass percent of said hydrogen storage alloy powder, 22% of La, 10% of Ce, 2% of Nd, 0.5% of Pr and 0.5% of metal A, said metal A comprising Zr, Y and Mg, said second hydrogen storage alloy powder comprises, in total mass percent of said hydrogen storage alloy powder, 57% of Ni, 5% of Co, 1% of Al, 1.5% of Mn and 0.5% of metal B, said metal B comprising Cu and Si.
6. A method for producing a hydrogen-absorbing alloy powder for a nickel-metal hydride battery used in an ultra-low temperature environment according to any one of claims 1 to 5, comprising the steps of:
step one, preparing and melting each component in the first hydrogen storage alloy powder and the second hydrogen storage alloy powder according to mass percentage to prepare hydrogen storage alloy sheets;
step two, carrying out heat treatment on the hydrogen storage alloy sheet;
and step three, mechanically crushing the hydrogen storage alloy sheet into hydrogen storage alloy powder to obtain the hydrogen storage alloy powder of the nickel-hydrogen battery for the ultralow temperature environment.
7. The method for preparing a hydrogen-storing alloy powder for a nickel-metal hydride battery used in an ultra-low temperature environment as claimed in claim 6, wherein in the first step, the thickness of the hydrogen-storing alloy sheet is 70 to 160 um.
8. The method for preparing a hydrogen-absorbing alloy powder for a nickel-metal hydride battery used in an ultra-low temperature environment as claimed in claim 7, wherein in the first step, the thickness of the hydrogen-absorbing alloy sheet is 80 to 150 um.
9. The method for producing a hydrogen-storing alloy powder for a nickel-metal hydride battery used in an ultra-low temperature environment as claimed in claim 6, wherein the heat treatment temperature is 800 to 1100 ℃ and the heat treatment time is 2 to 6 hours in the second step.
10. The method for producing a hydrogen-storing alloy powder for a nickel-metal hydride battery used in an ultra-low temperature environment as claimed in claim 9, wherein the heat treatment temperature is 860 to 1010 ℃ and the heat treatment time is 3 to 5 hours in the second step.
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