CN110492086B - Preparation method of hydrogen storage alloy composite material - Google Patents
Preparation method of hydrogen storage alloy composite material Download PDFInfo
- Publication number
- CN110492086B CN110492086B CN201910846058.0A CN201910846058A CN110492086B CN 110492086 B CN110492086 B CN 110492086B CN 201910846058 A CN201910846058 A CN 201910846058A CN 110492086 B CN110492086 B CN 110492086B
- Authority
- CN
- China
- Prior art keywords
- alloy
- ball milling
- bfe
- lay
- hydrogen storage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 85
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000001257 hydrogen Substances 0.000 title claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000003860 storage Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000498 ball milling Methods 0.000 claims abstract description 55
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 230000001681 protective effect Effects 0.000 claims description 14
- 238000003723 Smelting Methods 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 150000002739 metals Chemical class 0.000 claims description 11
- 229910052573 porcelain Inorganic materials 0.000 claims description 10
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000005275 alloying Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 28
- 239000011572 manganese Substances 0.000 description 22
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000013021 overheating Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- 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
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to a preparation method of a hydrogen storage alloy composite material. The preparation method of the hydrogen storage alloy composite material comprises the following steps: mixing the BFe material and citric acid uniformly by ball milling according to a certain proportion, heating in a tube furnace to oxidize and decompose the citric acid into carbon, and coating the outside of the BFe material; mixing the obtained BFe-C material with LaY2Ni9.5Mn0.5Al0.5Ball-milling the hydrogen storage alloy according to the proportion of 1-15: 100 to obtain BFe-C/LaY2Ni9.5Mn0.5Al0.5A hydrogen storage alloy composite material. The hydrogen storage composite material obtained by the invention has the advantages of simple preparation method, good discharge capacity and good stability.
Description
Technical Field
The invention relates to the technical field of materials, and particularly relates to a preparation method of a composite hydrogen storage alloy material.
Background
Energy is indispensable for human survival and development. With the progress of human society and the improvement of living standard, the demand of energy is increasing, and people are aware that limited fossil energy such as oil, natural gas and the like is consumed in the last day, so that people are forced to try to find a renewable clean energy.
Since the first proposal of hydrogen storage alloys in 1958, hydrogen storage alloys have received wide attention worldwide due to their high energy density, good cycle stability, good performance at high rates, and their non-environmental pollution. The nickel-hydrogen battery is a high-energy green secondary battery with hydrogen storage alloy as negative electrode material. Has excellent electrochemical performance and outstanding environmental compatibility and safety performance. The rapid rise of the lithium ion battery has a certain impact on the development of the MH/Ni battery, but the MH/Ni battery is still an ideal power source of the hybrid electric vehicle. Currently, research and development of new high energy density batteries has been a hot topic in the field of MH/Ni battery research. The technical key for improving the performance of the MH/Ni battery is the negative hydrogen storage alloy material.
At present, most of electrode materials in the market have fast capacity attenuation, the discharge capacity is greatly influenced by temperature, and even some batteries have poor high-rate discharge performance.
Disclosure of Invention
The invention provides the BFe-C/LaY which has simple preparation method, good discharge capacity and can obviously improve a composite system for solving the technical problems in the prior art2Ni9.5Mn0.5Al0.5A hydrogen storage alloy composite material and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems in the prior art is as follows: a preparation method of a hydrogen storage alloy composite material comprises the following experimental steps:
the method comprises the following steps: preparation LaY2Ni9.5Mn0.5Al0.5Alloy powder
According to LaY2Ni9.5Mn0.5Al0.5Placing the pure metals into a smelting furnace for smelting according to the mass ratio of the alloy, wherein the pure metals are sequentially placed from bottom to top from the lower melting point to the higher melting point, then naturally cooling in the furnace to form an alloy ingot, mechanically crushing the alloy ingot and grinding the alloy ingot into powder of less than 200 meshes to obtain LaY2Ni9.5Mn0.5Al0.5Alloying powder;
step two: preparation of BFe-C composite
Taking 99.9% of BFe alloy and citric acid in a ball milling tank according to the proportion of 1: 1-5, then placing the mixture in a ball milling machine for ball milling, wherein the effective ball milling time is 330-390 minutes, completely taking out a sample after ball milling, placing the sample in a porcelain boat, placing the porcelain boat in a tubular furnace filled with argon atmosphere, heating to 850 ℃ and keeping constant temperature for 360 minutes to enable the citric acid to be oxidized and decomposed into carbon, coating C outside the BFe material, and then naturally cooling to room temperature in the furnace to obtain BFe-C;
step three: preparation of BFe-C/LaY2Ni9.5Mn0.5Al0.5Composite hydrogen storage alloy material
According to BFe-C and LaY2Ni9.5Mn0.5Al0.5Putting the alloy powder into a ball mill according to the mass ratio of 1-15: 100 for ball milling to prepare BFe-C/LaY2Ni9.5Mn0.5Al0.5A composite hydrogen storage alloy material.
The invention has the advantages and positive effects that:
1. the invention provides a preparation method of carbon-coated BFe for the first time;
2. compared with the existing hydrogen storage alloy, the BFe-C/La-Y-Ni hydrogen storage alloy prepared by the invention has better discharge capacity and also shows excellent discharge performance at high temperature;
3. the cost is low, the preparation process is simple, and industrialization is easy to realize.
Preferably: in the first step, argon is used as protective gas in the smelting furnace, and the alloy is turned over three times in the furnace.
Preferably: and in the ball milling process in the second step, small balls are used for ball milling, the ball material ratio is 1: 10-20, argon is used as protective gas in a ball milling tank, each ball milling time is 10 minutes, and the ball mill is cooled for 5 minutes.
Preferably: and in the third step, argon is used as protective gas for ball milling, and the effective ball milling time is 30 minutes.
Drawings
FIG. 1 is a graph of the cycling stability of a BFe-C added hydrogen storage alloy;
FIG. 2 is a graph of the discharge capacity of BFe-C added hydrogen storage alloys at different temperatures.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. 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.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
First, some terms or terms appearing in the description of the embodiments of the present application are applicable to the following explanations:
the purity of lanthanum (La), yttrium (Y), nickel (Ni), manganese (Mn), aluminum (Al) and BFe alloy powder used in the experiment is 99.9%, and the purity of citric acid is 99.5%.
Example 1
Press LaY2Ni9.5Mn0.5Al0.5Preparing materials according to the stoichiometric ratio of a molecular formula, placing metals such as La, Y, Ni, Mn, Al and the like (the purity is higher than 99.9%) into a smelting furnace from bottom to top in sequence from low to high in melting point, cooling and protecting a copper crucible by using circulating water, carrying out arc smelting in an argon atmosphere, and then naturally smelting in the furnaceCooling to form alloy ingot, circularly turning the alloy in a furnace for three times to ensure the uniformity of the alloy, naturally cooling the smelted alloy, taking out, grinding and crushing the alloy by using an agate mortar, and sieving the crushed alloy by using a 200-mesh sieve to obtain LaY2Ni9.5Mn0.5Al0.5And (3) alloying powder.
Taking 99.9% of BFe alloy and citric acid according to the weight ratio of 1: placing the mixture in a ball milling tank according to the proportion of 1, then placing small balls with the ball material ratio of 1:15 in the ball milling tank, introducing protective gas argon into the ball milling tank, placing the ball milling tank in a high-energy ball mill, and setting the effective ball milling time of the ball milling process to be 360 minutes. To avoid overheating the sample, the machine was cooled for 5 minutes for 10 minutes per ball mill. And (3) completely taking out the sample after ball milling, placing the sample into a porcelain boat, placing the porcelain boat into a tube furnace filled with argon atmosphere, heating to 850 ℃, keeping the constant temperature for 360 minutes, and naturally cooling to room temperature in the furnace to obtain the C-coated BFe alloy-BFe-C.
According to BFe-C and LaY2Ni9.5Mn0.5Al0.5The alloy powder with the mass ratio of 5:100 is placed in a ball milling tank, argon is used as protective gas for ball milling, the effective ball milling time is 30 minutes, the alloy powder and the protective gas are uniformly mixed, and the prepared BFe-C/LaY2Ni9.5Mn0.5Al0.5A composite hydrogen storage alloy material.
The alloy powder is pressed into tablets to prepare a simulation battery for testing the electrochemical performance. Electrochemical properties, including fade performance, maximum capacity, were tested with a DC-5 cell tester. Wherein the maximum capacity and the activation performance are tested when the charging current density and the discharging current density are both 60 mA/g.
By combining the attached drawings 1 and 2, the maximum discharge capacity of the BFe-C composite material added with 5 wt% in the first circulation is reached, and the maximum discharge capacity is 314.5mAh/g and is 258.1mAh/g higher than that of the reference alloy; wherein, the discharge capacity of the hydrogen storage alloy added with 5 wt% of BFe-C composite material in 100 circles is 131mAh/g respectively, which is still higher than 122mAh/g of the reference alloy in 100 circles; the discharge capacity at 29.85-59.85 ℃ of the BFe-C composite material added with 5 wt% is higher than that of the reference alloy. Therefore, the maximum discharge capacity and the high-temperature discharge capacity of the BFe-C composite material added with 5 wt% are improved.
Example 2
Press LaY2Ni9.5Mn0.5Al0.5Preparing materials according to a stoichiometric ratio of a molecular formula, placing metals such as La, Y, Ni, Mn, Al and the like (the purity is higher than 99.9%) into a smelting furnace from bottom to top in sequence from low to high in melting point, cooling the metals in a protected copper crucible by circulating water, carrying out electric arc smelting in an argon atmosphere, naturally cooling the metals in the furnace to form an alloy ingot, circularly turning the alloy in the furnace for three times in order to ensure the uniformity and uniformity of the alloy, naturally cooling and taking out the smelted alloy, grinding and crushing the alloy by using an agate mortar, and sieving the alloy by using a 200-mesh sieve to obtain LaY2Ni9.5Mn0.5Al0.5And (3) alloying powder.
Taking 99.9% of BFe alloy and citric acid according to the weight ratio of 1: placing the mixture in a ball milling tank according to the proportion of 1, then placing small balls with the ball material ratio of 1:15 in the ball milling tank, introducing protective gas argon into the ball milling tank, placing the ball milling tank in a high-energy ball mill, and setting the effective ball milling time of the ball milling process to be 360 minutes. To avoid overheating the sample, the machine was cooled for 5 minutes for 10 minutes per ball mill. And (3) completely taking out the sample after ball milling, placing the sample into a porcelain boat, placing the porcelain boat into a tube furnace filled with argon atmosphere, heating to 850 ℃, keeping the constant temperature for 360 minutes, and naturally cooling to room temperature in the furnace to obtain the C-coated BFe alloy-BFe-C.
According to BFe-C and LaY2Ni9.5Mn0.5Al0.5The alloy powder with the mass ratio of 10:100 is placed in a ball milling tank, argon is used as protective gas for ball milling, the effective ball milling time is 30 minutes, the alloy powder and the protective gas are uniformly mixed, and the prepared BFe-C/LaY2Ni9.5Mn0.5Al0.5A composite hydrogen storage alloy material.
The alloy powder is pressed into tablets to prepare a simulation battery for testing the electrochemical performance. Electrochemical properties, including fade performance, maximum capacity, were tested with a DC-5 cell tester. Wherein the maximum capacity and the activation performance are tested when the charging current density and the discharging current density are both 60 mA/g.
By combining the attached drawings 1 and 2, the maximum discharge capacity of the added BFe-C composite material in the first circulation is reached, and the maximum discharge capacity of the added 10 wt% BFe-C composite material is 370.7mAh/g in turn and is 258.1mAh/g higher than that of the reference alloy; the discharge capacity of the hydrogen storage alloy added with 10 wt% of BFe-C composite material is 147mAh/g when 100 circles are formed, and is still higher than 122mAh/g when the reference alloy is formed when 100 circles are formed; the discharge capacity at 29.85-59.85 ℃ of the BFe-C composite material added with 10 wt% is higher than that of the reference alloy. Therefore, the maximum discharge capacity and the high-temperature discharge capacity of the BFe-C composite material added with 10 wt% are improved.
Example 3
Press LaY2Ni9.5Mn0.5Al0.5Preparing materials according to a stoichiometric ratio of a molecular formula, placing metals such as La, Y, Ni, Mn, Al and the like (the purity is higher than 99.9%) into a smelting furnace from bottom to top in sequence from low to high in melting point, cooling the metals in a protected copper crucible by circulating water, carrying out electric arc smelting in an argon atmosphere, naturally cooling the metals in the furnace to form an alloy ingot, circularly turning the alloy in the furnace for three times in order to ensure the uniformity and uniformity of the alloy, naturally cooling and taking out the smelted alloy, grinding and crushing the alloy by using an agate mortar, and sieving the alloy by using a 200-mesh sieve to obtain LaY2Ni9.5Mn0.5Al0.5And (3) alloying powder.
Taking 99.9% of BFe alloy and citric acid according to the weight ratio of 1: placing the mixture in a ball milling tank according to the proportion of 1, then placing small balls with the ball material ratio of 1:15 in the ball milling tank, introducing protective gas argon into the ball milling tank, placing the ball milling tank in a high-energy ball mill, and setting the effective ball milling time of the ball milling process to be 360 minutes. To avoid overheating the sample, the machine was cooled for 5 minutes for 10 minutes per ball mill. And (3) completely taking out the sample after ball milling, placing the sample into a porcelain boat, placing the porcelain boat into a tube furnace filled with argon atmosphere, heating to 850 ℃, keeping the constant temperature for 360 minutes, and naturally cooling to room temperature in the furnace to obtain the C-coated BFe alloy-BFe-C.
And putting the BFe-C and LaY2Ni9.5Mn0.5Al0.5 alloy powder into a ball milling tank according to the mass ratio of 15:100, and carrying out ball milling for 30 minutes by using argon as a protective gas to uniformly mix the powder to prepare the BFe-C/LaY2Ni9.5Mn0.5Al0.5 composite hydrogen storage alloy material.
The alloy powder is pressed into tablets to prepare a simulation battery for testing the electrochemical performance. Electrochemical properties, including fade performance, maximum capacity, were tested with a DC-5 cell tester. Wherein the maximum capacity and the activation performance are tested when the charging current density and the discharging current density are both 60 mA/g.
As can be seen by combining the attached figure 1 of the invention, the maximum discharge capacity of the BFe-C composite material added with 15 wt% in the first circulation is achieved, the maximum discharge capacity is 405.9mAh/g and is higher than 258.1mAh/g of the maximum discharge capacity of the reference alloy; however, after 100 cycles, the discharge capacity of the base alloy and the BFe-C composite material added with 15 wt% decayed to 122.4mAh/g and 109.8mAh/g, respectively.
As can be seen from FIG. 2, the discharge capacity at 29.85 deg.C to 59.85 deg.C was higher with the addition of 15 wt% BFe-C composite than the reference alloy. Therefore, the maximum discharge capacity and the high-temperature discharge capacity of the BFe-C composite material added with 15 wt% are improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (4)
1. The preparation method of the hydrogen storage alloy composite material is characterized by comprising the following experimental steps of:
the method comprises the following steps: preparation LaY2Ni9.5Mn0.5Al0.5Alloy powder
According to LaY2Ni9.5Mn0.5Al0.5Placing the pure metals into a smelting furnace for smelting according to the mass ratio of the alloy, wherein the pure metals are sequentially placed from bottom to top from the lower melting point to the higher melting point, then naturally cooling in the furnace to form an alloy ingot, mechanically crushing the alloy ingot and grinding the alloy ingot into powder of less than 200 meshes to obtain LaY2Ni9.5Mn0.5Al0.5Alloying powder;
step two: preparation of BFe-C composite
Putting 99.9% of BFe alloy and citric acid in a ball milling tank according to the mass ratio of 1: 1-5, then placing the mixture in a ball milling machine for ball milling, wherein the effective ball milling time is 330-390 minutes, completely taking out a sample after ball milling, placing the sample in a porcelain boat, placing the porcelain boat in a tubular furnace filled with argon atmosphere, heating to 850 ℃ and keeping constant temperature for 360 minutes to oxidize and decompose the citric acid into carbon, coating C outside the BFe material, and then naturally cooling to room temperature in the furnace to obtain BFe-C;
step three: preparation of BFe-C/LaY2Ni9.5Mn0.5Al0.5Composite hydrogen storage alloy material
According to BFe-C and LaY2Ni9.5Mn0.5Al0.5Putting the alloy powder into a ball mill according to the mass ratio of 1-15: 100 for ball milling to prepare BFe-C/LaY2Ni9.5Mn0.5Al0.5A composite hydrogen storage alloy material.
2. The method for producing a hydrogen occluding alloy composite material as recited in claim 1, wherein: in the first step, argon is used as protective gas in the smelting furnace, and the alloy is turned over three times in the furnace.
3. The method for producing a hydrogen occluding alloy composite material as recited in claim 1, wherein: and in the ball milling process in the second step, small balls are used for ball milling, the ball material ratio is 1: 10-20, argon is used as protective gas in a ball milling tank, each ball milling time is 10 minutes, and the ball mill is cooled for 5 minutes.
4. The method for producing a hydrogen occluding alloy composite material as recited in claim 1, wherein: and in the third step, argon is used as protective gas for ball milling, and the effective ball milling time is 30 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910846058.0A CN110492086B (en) | 2019-09-09 | 2019-09-09 | Preparation method of hydrogen storage alloy composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910846058.0A CN110492086B (en) | 2019-09-09 | 2019-09-09 | Preparation method of hydrogen storage alloy composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110492086A CN110492086A (en) | 2019-11-22 |
| CN110492086B true CN110492086B (en) | 2021-01-26 |
Family
ID=68556959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910846058.0A Active CN110492086B (en) | 2019-09-09 | 2019-09-09 | Preparation method of hydrogen storage alloy composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110492086B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113540427B (en) * | 2021-03-31 | 2022-08-23 | 有研工程技术研究院有限公司 | Preparation method of carbon-coated hydrogen storage alloy |
| CN115312738A (en) * | 2022-09-01 | 2022-11-08 | 燕山大学 | Pr-doped metal oxide/La-Y-Ni composite material and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7404842B1 (en) * | 2003-01-23 | 2008-07-29 | Jesse Wainright | Microfabricated hydrogen storage device and metal hydride fuel cell/battery |
| CN101554992A (en) * | 2009-05-22 | 2009-10-14 | 南开大学 | Method for preparing light metal complex hydrides by catalyzing boride and applications thereof |
| CN102674245A (en) * | 2011-11-01 | 2012-09-19 | 南开大学 | MgH2/Mg transition metal boride composite hydrogen storage material and preparation method thereof |
| CN105779822A (en) * | 2016-04-06 | 2016-07-20 | 广州有色金属研究院 | Hydrogen storage alloy for nickel-hydrogen power battery |
| CN106001543A (en) * | 2016-06-09 | 2016-10-12 | 桂林理工大学 | Method for modifying La-Mg-Ni based hydrogen storage alloy by utilizing Ni-B-C alloy |
| EP2945171B1 (en) * | 2014-05-14 | 2017-08-16 | TDK Corporation | Soft magnetic metal powder and soft magnetic metal powder core using the same |
| CN107164657A (en) * | 2017-06-15 | 2017-09-15 | 燕山大学 | A kind of preparation method of graphene/La Fe B systems low temperature hydrogen storage composite |
| CN108467956A (en) * | 2018-03-22 | 2018-08-31 | 燕山大学 | A kind of Si/La15Fe2Ni72Mn7B2Mo2The preparation method of composite hydrogen occluding alloy material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160322136A1 (en) * | 2015-04-30 | 2016-11-03 | Jozef Stefan Institute | METAL-BONDED RE-Fe-B MAGNETS |
-
2019
- 2019-09-09 CN CN201910846058.0A patent/CN110492086B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7404842B1 (en) * | 2003-01-23 | 2008-07-29 | Jesse Wainright | Microfabricated hydrogen storage device and metal hydride fuel cell/battery |
| CN101554992A (en) * | 2009-05-22 | 2009-10-14 | 南开大学 | Method for preparing light metal complex hydrides by catalyzing boride and applications thereof |
| CN102674245A (en) * | 2011-11-01 | 2012-09-19 | 南开大学 | MgH2/Mg transition metal boride composite hydrogen storage material and preparation method thereof |
| EP2945171B1 (en) * | 2014-05-14 | 2017-08-16 | TDK Corporation | Soft magnetic metal powder and soft magnetic metal powder core using the same |
| CN105779822A (en) * | 2016-04-06 | 2016-07-20 | 广州有色金属研究院 | Hydrogen storage alloy for nickel-hydrogen power battery |
| CN106001543A (en) * | 2016-06-09 | 2016-10-12 | 桂林理工大学 | Method for modifying La-Mg-Ni based hydrogen storage alloy by utilizing Ni-B-C alloy |
| CN107164657A (en) * | 2017-06-15 | 2017-09-15 | 燕山大学 | A kind of preparation method of graphene/La Fe B systems low temperature hydrogen storage composite |
| CN108467956A (en) * | 2018-03-22 | 2018-08-31 | 燕山大学 | A kind of Si/La15Fe2Ni72Mn7B2Mo2The preparation method of composite hydrogen occluding alloy material |
Non-Patent Citations (1)
| Title |
|---|
| Investigations on AB3-, A2B7- and A5B19-type Lae;Huizhong Yan etal.;《Hydrogen Energy》;20170126;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110492086A (en) | 2019-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102226243B (en) | Magnesium-containing superlattice hydrogen storage alloy and preparation method thereof | |
| CN104513925B (en) | Yttrium-nickel rare earth family hydrogen storage alloy, and secondary battery containing hydrogen storage alloy | |
| CN104532095A (en) | Yttrium-nickel rare earth-based hydrogen storage alloy | |
| CN107302083A (en) | A kind of solid reaction process preparation method of nickel lithium manganate cathode material | |
| CN104532062A (en) | Yttrium-nickel rare earth-based hydrogen storage alloy | |
| CN110492086B (en) | Preparation method of hydrogen storage alloy composite material | |
| CN108893656B (en) | La-Mg-Ni system A2B7Hydrogen storage alloy and preparation method thereof | |
| CN110116992A (en) | A kind of preparation method and application of two selenizing niobium of sodium ion battery electrode material | |
| CN101643864B (en) | Multielement silicon alloy/carbon composite material and preparation method and application thereof | |
| CN103456927B (en) | Containing vanadyl titanio hydrogen-storing alloy as electrode and preparation method thereof | |
| CN103531776B (en) | The lithium ion battery and its positive electrode and chemical synthesizing method of high security extra long life | |
| CN101552337A (en) | Superlattice hydrogen storage alloy and preparation method thereof | |
| CN108149073A (en) | Low-temperature nickel-hydrogen battery La-Mg-Ni base hydrogen storage alloys and preparation method thereof | |
| CN100453454C (en) | Preparation method of lithium ferrous phosphate positive electrode material | |
| CN104451219B (en) | A kind of containing A2b7the A of phase5b19the preparation method of type RE-Mg-Ni series hydrogen storage alloy | |
| CN101899591B (en) | Superlattice hydrogen storage alloy material for nickel hydrogen battery and preparation method thereof | |
| CN103199236A (en) | Doped lithium manganate precursor, modified lithium manganate positive electrode material and preparation method thereof | |
| CN102888545B (en) | A kind of preparation method of Mg base hydrogen bearing alloy | |
| CN106544535B (en) | Preparation method of hydrogen storage alloy containing yttrium and nickel elements | |
| CN107075617A (en) | A kind of lanthanon hydrogen storage alloy and application thereof | |
| CN100467640C (en) | AB3.5 type hydrogen-storing negative pole material and its prepn process and use | |
| CN107201457B (en) | A kind of preparation method of Gd2Co7 type Nd-Mg-Ni system single-phase alloy | |
| CN102054982A (en) | La-Mg-Ni type negative-pole hydrogen storage material for low-temperature nickel-hydrogen battery | |
| CN109390580A (en) | A kind of V-Based Hydrogen Storage Alloy and its preparation method and application | |
| CN108467956B (en) | A kind of Si/La15Fe2Ni72Mn7B2Mo2The preparation method of composite hydrogen occluding alloy material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230330 Address after: 201800 room 4, 1 story E, 4 358_368, 4 Fu Fu Road, Shanghai. Patentee after: SHANGHAI YINGZHI INFORMATION TECHNOLOGY Co.,Ltd. Address before: 066004 No. 438 west section of Hebei Avenue, seaport District, Hebei, Qinhuangdao Patentee before: Yanshan University Effective date of registration: 20230330 Address after: Room 6241, Building 16, No. 741 Hangzhou Road, Yangpu District, Shanghai 200082 Patentee after: Shanghai Zhonghailong High and New Technology Research Institute Address before: 201800 room 4, 1 story E, 4 358_368, 4 Fu Fu Road, Shanghai. Patentee before: SHANGHAI YINGZHI INFORMATION TECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right |