CN108149073B - La-Mg-Ni series hydrogen storage alloy for low-temperature nickel-metal hydride battery and preparation method thereof - Google Patents
La-Mg-Ni series hydrogen storage alloy for low-temperature nickel-metal hydride battery and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 153
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 149
- 239000001257 hydrogen Substances 0.000 title claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910020791 La—Mg—Ni Inorganic materials 0.000 title claims abstract description 29
- 229910052987 metal hydride Inorganic materials 0.000 title claims abstract description 25
- 238000003860 storage Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000010791 quenching Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 230000000171 quenching effect Effects 0.000 claims abstract description 27
- 238000003723 Smelting Methods 0.000 claims abstract description 19
- 238000005266 casting Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000012216 screening Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 31
- 229910052749 magnesium Inorganic materials 0.000 claims description 30
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- 230000006698 induction Effects 0.000 claims description 13
- 229910002335 LaNi5 Inorganic materials 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 239000001307 helium Substances 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims 1
- 238000010309 melting process Methods 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 69
- 238000012360 testing method Methods 0.000 description 25
- 239000000843 powder Substances 0.000 description 18
- 229910019094 Mg-S Inorganic materials 0.000 description 4
- 229910019397 Mg—S Inorganic materials 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 229910002640 NiOOH Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000007712 rapid solidification Methods 0.000 description 2
- -1 La was 14.44 atomic% Inorganic materials 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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- 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
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- B22F1/0003—
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
- C22C2202/04—Hydrogen absorbing
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Abstract
The invention discloses a La-Mg-Ni series hydrogen storage alloy for a low-temperature nickel-metal hydride battery and a preparation method thereof. The chemical composition of the alloy is La0.75‑xCexMg0.25Ni3Co0.5Wherein, the subscript in the chemical composition is the atomic ratio of each corresponding component, and the numeric area of x is 0.09-0.11. The preparation method of the alloy comprises the following steps: the method comprises the steps of raw material preparation, smelting and casting, alloy thin strip preparation and grinding and screening. The alloy prepared by the method has high low-temperature electrochemical performance, and the quenching speed is 10 m.s under the condition of 248K‑1Discharge capacity at 100 times of charge-discharge cycle (C)100) The maximum value is 245.9mAh g‑1The alloy material prepared by the invention is particularly suitable for being used at the temperature below 0 ℃, particularly can be used at the temperature of-25 ℃ and even can be used at the temperature of-30 ℃.
Description
Technical Field
The invention belongs to the field of hydrogen storage material preparation, and particularly relates to La-Mg-Ni hydrogen storage alloy for a low-temperature nickel-metal hydride battery and a preparation method thereof.
Background
In recent years, the popularization and development of fuel vehicles have made environmental problems such as air pollution increasingly worse, and therefore, vigorous development of new energy vehicles has been imminent, wherein Hybrid Electric Vehicles (HEV) and pure Electric Vehicles (EV) using Ni-MH batteries as power sources have excellent characteristics such as excellent performance, high safety, stable structure, environmental friendliness and the likeSexually, the people have attracted much attention from countries all over the world. Therefore, with the vigorous development of the Ni/MH battery industry, hydrogen storage alloys as battery negative electrode materials also exhibit increasingly broad development prospects. The hydrogen storage alloy which is commercially applied to the cathode material of the Ni/MH battery at present is AB5Type alloys, but the maximum capacity of which has reached the limit of 330mAh/g, are increasingly unable to meet the ever-increasing market performance levels and requirements, while the La-Mg-Ni series A2B7The theoretical capacity of the alloy reaches 380-410mAh/g, and the alloy has become a powerful competitor for the cathode material of the Ni/MH battery, but the biggest problem for restricting the industrialization of the alloy is that the cycle life of the alloy is not ideal enough. Currently increasing A2B7A more common method for the overall performance level of Type alloys is melt rapid quenching, which is reported in related documents (e.g., document 1: Y.H.Zhang, D.L.Zhao, S.H.Guo, Y.Qi, Q.C.Wang, X.L.Wang, alloys of catalysis of Zr for La on structures and Electrochemical technologies of A2B7-Type Electrochemical by melt, ray Met.Mater.Eng.39(7) (2010)1141 and 1146. document 2: Y.H.Zhang, T.Yang, H.W.Shang, L.C.Chen, H.P.Ren, D.L.Zhao, Electrochemical storage of L.C.Cheng, H.P.J.S. J.S.S. 2. Lang, Mg-3.S.J.S.S. 2, Mg-2 H.Zhang, Mg-3, Mg-Al 2, Mg-X.Zhang, Mg-S.S.S.J.S. 2, Mg-S.S.S.S.S.S.S.S.J.S. 2, Mg-3, Mg-S.S.S.S.S.S.S. 1, M.S.S. 1, M.S.S.S.S.S. 1, Mg-3, Mg-2, Mg-S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S. 2, S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.3, S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.1, S.S.S.No. 1, 2, S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.No. 1, S.S.S.S.S.S.S.S., rare Met.Mater.Eng.42(11) (2013)2201-2206.), the lowest service temperature of the Ni/MH battery can reach about 248K, and the La-Mg-Ni series A is currently treated2B7The properties of the type alloy are mostly studied and also the properties at room temperature.
Disclosure of Invention
The invention aims to provide a La-Mg-Ni hydrogen storage alloy for a low-temperature nickel-metal hydride battery and a preparation method thereof, wherein the hydrogen storage alloy is particularly suitable for being used as nickel-metal hydride battery under low-temperature conditionsThe negative electrode material of the battery is prepared by quenching the prepared alloy at the quenching speed of 10 m.s under the four temperature conditions of 298K, 268K, 258K and 248K-1Discharge capacity at 100 times of charge-discharge cycle (C)100) The maximum values are 268.3mAh g-1、265.1mAh·g-1、253.4mAh·g-1、245.9mAh·g-1The high rate capability (HRD) is also preferable.
The purpose of the invention is realized by the following technical scheme:
La-Mg-Ni series hydrogen storage alloy for low-temperature nickel-metal hydride battery, and the chemical composition of the alloy is La0.75- xCexMg0.25Ni3Co0.5Wherein, the subscript in the chemical composition is the atomic ratio of each corresponding component, and the numeric area of x is 0.09-0.11.
In the alloy of the invention, the introduction of Ce has a great influence on the low-temperature performance of the alloy, and in order to ensure the low-temperature performance of the alloy, the value range of the atomic ratio x of Ce is selected from 0.09-0.11, for example, the values of x are 0.091, 0.093, 0.095, 0.098, 0.1, 0.102, 0.105, 0.107 and 0.109.
In the above La-Mg-Ni based hydrogen occluding alloy for low-temperature nickel-hydrogen battery, as a preferable embodiment, the alloy contains at least (La, Mg)2Ni7Phase, more preferably (La, Mg) Ni3Phase and LaNi5Phase (1); further preferably, in the alloy, (La, Mg) Ni3The abundance of the phases is 0.85% -1.23%, (La, Mg)2Ni7The abundance of the phase is 50.06% -69.84%, LaNi5The abundance of the phases is 28.93-49.09%; further preferably, in the alloy, (La, Mg) Ni3Abundance of phase 1.23%, (La, Mg)2Ni7Abundance of phase 69.84%, LaNi5The abundance of the phase was 28.93%. In the alloy of the present invention, (La, Mg)2Ni7The larger the phase abundance, the higher the alloy discharge capacity, (La, Mg) Ni3The smaller the phase abundance, the higher the cycle life of the alloy.
In a preferred embodiment of the above La-Mg-Ni-based hydrogen storage alloy for low-temperature nickel-metal hydride batteries, the La-Mg-Ni-based hydrogen storage alloy for low-temperature nickel-metal hydride batteries is in the form of powder, and the particle size is preferably 300 to 400 mesh (i.e., 38 to 48 μm).
The preparation method of the La-Mg-Ni hydrogen storage alloy for the low-temperature nickel-metal hydride battery comprises the following steps:
a raw material preparation step, namely weighing La, Ce, Mg, Ni and Co raw materials according to the alloy component ratio;
smelting and casting, namely smelting the raw materials and casting the raw materials into an as-cast alloy ingot;
preparing an alloy thin strip, namely preparing the cast alloy ingot into a thin alloy strip by adopting a single-roller rapid quenching method;
and grinding and screening, namely crushing, grinding and screening the thin alloy sheet in sequence to obtain powdery La-Mg-Ni hydrogen storage alloy.
In the above preparation method, as a preferred embodiment, in the smelting and casting step, the smelting is performed by a high-frequency induction smelting method, and the molten alloy liquid is fully stirred during the smelting; more preferably, in the smelting process, the crucible used is an alumina crucible, and the atmosphere used is helium or argon, and further preferably, the raw materials are placed in the crucible at the following positions: ni, Co are at the bottom, Mg is in the middle, La and Ce are at the top; further, the high-frequency induction melting method is that the crucible is placed in a high-frequency induction melting furnace and is vacuumized to 0.1Pa, then helium is filled to 0.3MPa, and then high-frequency induction melting is carried out (the high frequency generally means that the current frequency is within the range of 100-500 kHz). The high-frequency melting method is particularly suitable for melting the alloy, is suitable for large-scale production and has low cost, and can reduce the segregation of alloy components as much as possible; in addition, because the middle position of the crucible has the highest temperature, and the melting points of the elements are Co-1495 ℃, Ni-1453 ℃, La-921 ℃, Ce-799 ℃ and Mg-648 ℃, respectively, according to the charging sequence of the invention, Mg, La and mixed rare earth containing Ce melt first and then play a role in soaking and melting high-melting-point Ni and Co at the bottom, thereby further increasing the uniformity of alloy components.
In the above production method, as a preferred embodiment, in the smelting and casting step, the casting refers to casting the molten alloy liquid after smelting onto a water-cooled copper mold to obtain an as-cast alloy ingot.
In the above-mentioned production method, as a preferred embodiment, when the thin alloy strip is produced by the single-roll rapid quenching method, the molten alloy is sprayed onto the roll surface at a linear velocity of 5 to 30m/s (e.g., 6m/s, 8m/s, 10m/s, 15m/s, 18m/s, 23m/s, 25m/s, 27m/s, 29m/s), more preferably at a linear velocity of 10 m/s; more preferably, the single-roller rapid quenching method for preparing the thin alloy strip refers to that the cast alloy ingot is placed in a single-roller rapid quenching furnace and is vacuumized to 10 DEG C-2-10-3And (3) filling argon gas of 0.1-0.5MPa (such as 0.15MPa, 0.2MPa, 0.3MPa, 0.4MPa and 0.45MPa) after Mpa, heating and melting the cast alloy ingot, spraying alloy liquid onto the roll surface of a water-cooled copper roll with the linear velocity of 10m/s, and quickly solidifying to obtain the thin alloy strip.
In the above production method, as a preferable embodiment, the powdered La — Mg — Ni-based hydrogen storage alloy has a particle size of 300 mesh to 400 mesh (i.e., 38 μm to 48 μm).
The invention has the beneficial effects that:
1. the raw materials La, Ce, Mg, Ni and Co used in the invention belong to commercial products, and are easily obtained.
2. The preparation process is a traditional smelting method and a rapid quenching method, and has the advantages of simple process, convenient operation and the like.
3. The reaction does not need to add a surfactant, a catalyst and the like, and a high-purity product is easily obtained.
4. The product produced contains (La, Mg) Ni3Photo (La, Mg)2Ni7Phase and LaNi5Phase, (La, Mg) Ni with increasing rapid quenching speed3Harmony (La, Mg)2Ni7Reduced abundance of phases, LaNi5The abundance of the phases increases.
5. The prepared product has higher low-temperature electrochemical performance, and the quenching speed is 10 m.s under the four temperature conditions of 298K, 268K, 258K and 248K-1Discharge capacity of 100 times of charge-discharge cycleAmount (C)100) The maximum values are 268.3mAh g-1、265.1mAh·g-1、253.4mAh·g-1、245.9mAh·g-1The alloy material prepared by the invention is particularly suitable for being used at the temperature below 0 ℃, particularly can be used at the temperature of-25 ℃ and even can be used at the temperature of-30 ℃.
Drawings
FIG. 1 shows La in a rapidly quenched state in example 1 of the present invention0.65Ce0.1Mg0.25Ni3Co0.5XRD pattern of the alloy;
FIG. 2 is 10m/s rapidly quenched La according to example 1 of the present invention0.65Ce0.1Mg0.25Ni3Co0.5The discharge capacity decay curve of the alloy, wherein the test temperature of (a) is 298K, the test temperature of (b) is 268K, the test temperature of (c) is 258K, and the test temperature of (d) is 248K;
FIG. 3 shows 10m/s rapidly quenched La of example 1 of the present invention0.65Ce0.1Mg0.25Ni3Co0.5Graph of high rate performance of the alloy, wherein the test temperature of (a) is 298K, the test temperature of (b) is 268K, the test temperature of (c) is 258K, and the test temperature of (d) is 248K;
FIG. 4 shows 20m/s and 30m/s rapidly quenched La in example 2 of the present invention0.65Ce0.1Mg0.25Ni3Co0.5The discharge capacity decay curve of the alloy, wherein the test temperature of (a) is 298K, the test temperature of (b) is 268K, the test temperature of (c) is 258K, and the test temperature of (d) is 248K;
FIG. 5 shows 20m/s and 30m/s rapidly quenched La in example 2 of the present invention0.65Ce0.1Mg0.25Ni3Co0.5Graph of high rate performance for an alloy wherein the test temperature of (a) is 298K, the test temperature of (b) is 268K, the test temperature of (c) is 258K, and the test temperature of (d) is 248K.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for the purpose of the present invention and are not intended to limit the scope of the present invention. It should be understood that various changes and modifications can be made by those skilled in the art after reading the disclosure of the present invention, and equivalents fall within the scope of the appended claims.
Examples the following examples predominantly La0.65Ce0.1Mg0.25Ni3Co0.5The preparation of the alloy powder is taken as an example and is mainly realized according to the following steps:
(1) la, Ce, Mg, Ni and Co are used as raw materials according to the La0.65Ce0.1Mg0.25Ni3Co0.5Weighing the component atomic ratio, and putting the weighed component atomic ratio into an alumina crucible, wherein the volatility of Mg is generally considered, and the amount of the added raw material Mg is equal to 110% of the amount of Mg calculated according to the component proportion of the alloy;
(2) preparing La by adopting a high-frequency induction melting method and using helium for protection0.65Ce0.1Mg0.25Ni3Co0.5An alloy ingot;
(3) la is prepared by three rapid quenching processes of 10m/s, 20m/s and 30m/s0.65Ce0.1Mg0.25Ni3Co0.5An alloy strip;
(4) the prepared material is crushed, ground and sieved to obtain alloy powder of 300-400 meshes and the alloy powder is collected.
Example 1:
La0.65Ce0.1Mg0.25Ni3Co0.5preparation of an alloy powder comprising:
(1) according to La0.65Ce0.1Mg0.25Ni3Co0.5The components were weighed in atomic ratio (i.e., in the alloy, La was 14.44 atomic%, Ce was 2.22 atomic%, Mg was 5.56 atomic%, Ni was 66.67 atomic%, and Co was 11.11 atomic%) and placed in an alumina crucible.
(2) And smelting the alloy by adopting a helium protection high-frequency induction smelting method, ensuring that the metal liquid is fully stirred in the smelting process, and casting the alloy into a water-cooled copper mold to be rapidly cooled to obtain an as-cast alloy ingot.
(3) Placing the as-cast alloy ingot in a single-roller rapid quenching furnace, and vacuumizing to 10 DEG-2-10-3And (3) introducing high-purity argon of 0.3MPa after Mpa, injecting alloy liquid onto a water-cooled copper roller rotating at a high speed with the roller surface linear speed of 10m/s at 1500 ℃ after melting the cast ingot by high-frequency power supply induction heating, and obtaining the thin alloy strip after rapid solidification.
(4) After crushing and grinding the alloy strip, screening to obtain alloy powder of 300 meshes to 400 meshes and collecting the alloy powder.
Testing the performance of the alloy powder:
0.1g of the alloy powder prepared by the method and 0.3g of carbonyl nickel powder are weighed by an electronic balance, the alloy powder and the carbonyl nickel powder are uniformly mixed and then placed in a high-pressure die with the diameter of 10mm, the alloy negative plate prepared after the die pressure is kept at 15Mpa for 5 minutes is wrapped in foamed nickel, the negative plate is compacted and fixed by spot welding, and then a nickel strip polished by abrasive paper is used as a tab and is also fixed on the foamed nickel in a spot welding mode. In order to ensure that the negative plate has over-charge and discharge capacity, sintered Ni (OH) with a certain size is selected in a mode of theoretically estimating the capacity of the negative plate2and/NiOOH is used as the positive plate, so that the capacity of the positive plate is far larger than that of the negative plate. Placing the prepared positive plate, the prepared negative plate and the Hg-HgO reference electrode (the concentration of KOH solution in the electrode is 6mol/L) in a three-way pipe, injecting about 300mL of 6mol/L KOH solution, soaking for 24 hours, ensuring that the electrode plate starts to be tested after being completely soaked, and controlling the testing temperatures to be 298K, 268K, 258K and 248K by a high-low temperature experiment box.
And the activation, discharge capacity, cycle performance and high rate performance of the alloy electrode are tested by adopting a LAND CT2001A type measuring instrument.
1. Activation and discharge capacity test:
step 1: standing for 10 min;
step 2: charging for 4.5h at 10 mA;
and step 3: standing for 10 min;
and 4, step 4: 10mA was discharged to a potential of 0.6V (vs. Hg-HgO reference electrode);
and 5: repeating the steps 1-4 until the discharge capacity of the alloy electrode reaches the maximum value (C)max) Corresponding time scaleThe number of activation times (Na) was used.
2. And (3) testing the cycle performance:
step 1: standing for 10 min;
step 2: charging for 4.5h at 10 mA;
and step 3: standing for 10 min;
and 4, step 4: 10mA was discharged to a potential of 0.6V (vs. Hg-HgO reference electrode);
and 5: repeating the steps 1-4 until the charge-discharge cycle reaches 100 times.
Capacity retention ratio (S) for 100 charge-discharge cycle stability100) To characterize:
in the formula, C100The discharge capacity at the 100 th cycle is shown.
3. High rate performance testing:
step 1: standing for 10 min;
step 2: charging for 4.5h at 10 mA;
and step 3: standing for 10 min;
and 4, step 4: 30mA was discharged to a potential of 0.6V (vs. Hg-HgO reference electrode);
and 5: 10mA was discharged to a potential of 0.6V (vs. Hg-HgO reference electrode);
step 6: the intensity of the large-current discharge current is respectively adjusted to 60 mA, 90 mA, 120 mA and 150mA from 30mA, and the steps 1 to 5 are repeated. High rate performance can be characterized by HRD:
in the formula, CiThe discharge capacities discharged at large currents of 30, 60, 90, 120 and 150mA, respectively, are shown as C10The discharge capacity after discharging at a large current and then discharging at 10mA is shown.
FIG. 1 shows La in the fast-quenched state in example 10.65Ce0.1Mg0.25Ni3Co0.5XRD pattern of the alloy. As can be seen from FIG. 1, the product produced contains (La, Mg) Ni3Photo (La, Mg)2Ni7Phase and LaNi5Phase of which (La, Mg) Ni3Abundance of phase 1.23%, (La, Mg)2Ni7Abundance of phase 69.84%, LaNi5The abundance of the phase was 28.93%.
FIG. 2 shows La in a rapidly quenched state in example 1 of the present invention0.65Ce0.1Mg0.25Ni3Co0.5The discharge capacity decay curve of the alloy under four temperature conditions. As can be seen from FIG. 2, the quenching speed is 10 m.s under the four temperature conditions of 298K, 268K, 258K and 248K-1Discharge capacity at 100 times of charge-discharge cycle (C)100) The maximum values are 268.3mAh g-1、265.1mAh·g-1、253.4mAh·g-1、245.9mAh·g-1The maximum discharge capacities at four temperatures were 311.5mAh · g, respectively-1、305.6mAh·g-1、285.8mAh·g-1、271.2mAh·g-1。
FIG. 3 shows La in a rapidly quenched state in example 1 of the present invention0.65Ce0.1Mg0.25Ni3Co0.5High rate performance curves of the alloy under four temperature conditions. As can be seen from FIG. 3, the quenching speed is 10ms under the four temperature conditions of 298K, 268K, 258K and 248K-1The maximum high rate performance (HRD) is shown in table 1.
TABLE 1 La0.65Ce0.1Mg0.25Ni3Co0.5High rate capability of alloy
Example 2:
La0.65Ce0.1Mg0.25Ni3Co0.5preparation of an alloy powder comprising:
(1) according to La0.65Ce0.1Mg0.25Ni3Co0.5Weighing the components according to the atomic ratio, and then putting the components into an alumina crucible;
(2) and smelting the alloy by adopting a helium protection high-frequency induction smelting method, ensuring that the metal liquid is fully stirred in the smelting process, and casting the alloy into a water-cooled copper mold to be rapidly cooled to obtain an as-cast alloy ingot.
(3) Placing the as-cast alloy ingot in a single-roller rapid quenching furnace, and vacuumizing to 10 DEG-2-10-3Introducing high-purity argon gas of 0.3MPa after Mpa, injecting the molten cast ingot on a water-cooled copper roller rotating at high speed with the roller surface linear speed of 20m/s and 30m/s respectively at 1500 ℃ after the cast ingot is melted by induction heating of a high-frequency power supply, and obtaining a thin alloy strip after rapid solidification;
(4) after crushing and grinding the thin alloy strip, screening to obtain alloy powder of 300 meshes to 400 meshes and collecting the alloy powder.
La rapidly quenched from example 20.65Ce0.1Mg0.25Ni3Co0.5The XRD pattern of the alloy shows that (La, Mg) Ni in the alloy powder obtained at the rapid quenching speed of 20m/s3The abundance of the phases was 1.04%, (La, Mg)2Ni7Abundance of phase 58.67%, LaNi5The abundance of the phases was 40.29%; in the alloy powder obtained at the rapid quenching speed of 30m/s, (La, Mg) Ni3Abundance of phase 0.85%, (La, Mg)2Ni7Abundance of phase 50.06%, LaNi5The abundance of the phase was 49.09%.
Testing the performance of the alloy powder:
firstly, 0.1g of alloy powder and 0.3g of carbonyl nickel powder prepared in the embodiment are weighed by an electronic balance, the alloy powder and the carbonyl nickel powder are uniformly mixed and then placed in a high-pressure die with the diameter of 10mm, an alloy negative plate prepared after the die pressure is kept at 15Mpa for 5 minutes is wrapped in foamed nickel, the negative plate is compacted and fixed by spot welding, and then a nickel strip polished by abrasive paper is used as a tab and is also fixed on the foamed nickel in a spot welding mode. In order to ensure that the negative plate has over-charge and discharge capacity, sintered Ni (OH) with a certain size is selected in a mode of theoretically estimating the capacity of the negative plate2and/NiOOH is used as the positive plate, so that the capacity of the positive plate is far larger than that of the negative plate. Placing the prepared positive plate, negative plate and Hg-HgO reference electrode (the concentration of KOH solution in the electrode is 6mol/L) in a three-way pipe, injecting about 300mL of 6mol/L KOH solution, soaking for 24 hours to ensure that the electrode plate begins to be tested after being completely soaked, and concretely, the method comprises the steps ofThe test temperature is 298K, 268K, 258K and 248K, and the test temperature is controlled by a high-low temperature experiment box. The methods for testing the activation, discharge capacity, cycle performance and high rate performance of the alloy electrode are the same as those in example 1.
FIG. 4 shows La in a rapidly quenched state in example 2 of the present invention0.65Ce0.1Mg0.25Ni3Co0.5The discharge capacity decay curve of the alloy under four temperature conditions. As can be seen from FIG. 4, the quenching speed is 20 m.s under the four temperature conditions of 298K, 268K, 258K and 248K-1And 30 m.s-1The discharge capacity (C) of the alloy (2) at 100 cycles of charge and discharge100) And the first discharge capacity is shown in table 2. The quenching speed is 10 m.s-1C of the alloy thus prepared100Most preferred.
TABLE 2 as-cast condition, quench rate 20ms-1And 30ms-1Time alloy C100
FIG. 5 shows La in a rapidly quenched state in example 2 of the present invention0.65Ce0.1Mg0.25Ni3Co0.5High rate performance curves of the alloy under four temperature conditions. As can be seen from FIG. 5, the quenching speed is 20 m.s under the four temperature conditions of 298K, 268K, 258K and 248K-1And 30 m.s-1The high rate performance (HRD) is shown in table 3. The quenching speed is 10 m.s-1The high rate performance of the prepared alloy is optimal.
TABLE 3 as-cast condition, quenching speed 20 m.s-1And 30 m.s-1High rate capability of time alloy
Claims (14)
1. La-Mg-N for low-temperature nickel-metal hydride batteryi-type hydrogen storage alloy, characterized in that the alloy has a chemical composition of La0.75-xCexMg0.25Ni3Co0.5Wherein, the subscript in the chemical composition is the atomic ratio of each corresponding component, and the numeric range of x is 0.09-0.11;
the preparation method of the La-Mg-Ni hydrogen storage alloy for the low-temperature nickel-metal hydride battery comprises the following steps:
a raw material preparation step, namely weighing La, Ce, Mg, Ni and Co raw materials according to the alloy component ratio;
smelting and casting, namely smelting the raw materials and casting the raw materials into an as-cast alloy ingot;
preparing an alloy thin strip, namely preparing the cast alloy ingot into a thin alloy strip by adopting a single-roller rapid quenching method;
and grinding and screening, namely crushing, grinding and screening the thin alloy sheet in sequence to obtain powdery La-Mg-Ni hydrogen storage alloy.
2. The La-Mg-Ni based hydrogen occluding alloy for low-temperature nickel-metal hydride batteries as claimed in claim 1, wherein the alloy contains at least (La, Mg)2Ni7And (4) phase(s).
3. The La-Mg-Ni based hydrogen storage alloy for low-temperature nickel-metal hydride batteries according to claim 2, wherein the alloy further comprises (La, Mg) Ni3Phase and LaNi5And (4) phase(s).
4. The La-Mg-Ni based hydrogen occluding alloy for low-temperature nickel-metal hydride batteries according to claim 3, wherein (La, Mg) Ni is contained in the alloy3The abundance of the phases is 0.85% -1.23%, (La, Mg)2Ni7The abundance of the phase is 50.06% -69.84%, LaNi5The abundance of the phases was 28.93-49.09%.
5. The La-Mg-Ni based hydrogen occluding alloy for low-temperature nickel-metal hydride batteries according to claim 4, wherein (La, Mg) Ni is contained in the alloy3Abundance of phase 1.23%, (La, Mg)2Ni7Abundance of phase 69.84%, LaNi5The abundance of the phase was 28.93%.
6. The La-Mg-Ni based hydrogen occluding alloy for a low-temperature nickel-metal hydride battery as claimed in claim 1, wherein in the melting and casting step, the melting is performed by a high-frequency induction melting method, and the molten alloy liquid is sufficiently stirred during the melting.
7. The La-Mg-Ni based hydrogen occluding alloy for a low-temperature nickel-metal hydride battery as claimed in claim 6, wherein a crucible used in the melting process is an alumina crucible and an atmosphere used is a helium or argon atmosphere.
8. The La-Mg-Ni based hydrogen storage alloy for low-temperature nickel-metal hydride batteries according to claim 7, wherein the raw materials are placed in the crucible at positions: ni, Co at the bottom, Mg in the middle, La and Ce at the top.
9. The La-Mg-Ni based hydrogen occluding alloy for low-temperature nickel-metal hydride batteries as claimed in claim 6, wherein the high-frequency induction melting method is characterized in that the crucible is placed in a high-frequency induction melting furnace and is vacuumized to 0.1Pa, and then helium gas is charged to 0.3MPa, and then the high-frequency induction melting is carried out.
10. The La-Mg-Ni based hydrogen occluding alloy for low-temperature nickel-metal hydride batteries according to any one of claims 1 to 9, wherein in the melting and casting step, the casting is performed by casting the molten alloy liquid after melting onto a water-cooled copper mold to obtain an as-cast alloy ingot.
11. The La-Mg-Ni based hydrogen occluding alloy for low-temperature nickel-metal hydride batteries according to any one of claims 1 to 9, wherein when the thin alloy strip is produced by the single-roll rapid quenching method, the molten alloy is sprayed onto the roll surface at a linear velocity of 5 to 30 m/s.
12. The La-Mg-Ni based hydrogen occluding alloy for low-temperature nickel-metal hydride batteries according to claim 11, wherein the linear velocity is 10 m/s.
13. The La-Mg-Ni based hydrogen occluding alloy for low-temperature nickel-metal hydride batteries as claimed in claim 12, wherein the preparation of the thin alloy strip by the single-roll rapid quenching method means that the as-cast alloy ingot is placed in a single-roll rapid quenching furnace and is vacuumized to 10 degrees-2-10-3And (3) introducing argon gas of 0.1-0.5MPa after Mpa, heating and melting the as-cast alloy ingot, spraying alloy liquid onto the surface of a water-cooled copper roller with the linear velocity of 10m/s, and quickly solidifying to obtain the thin alloy strip.
14. The La-Mg-Ni based hydrogen storage alloy for low-temperature nickel-metal hydride batteries according to any one of claims 1 to 9, wherein the powdery La-Mg-Ni based hydrogen storage alloy has a particle size of 300 to 400 mesh.
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