CN111471913B - AB3 type rare earth-samarium-nickel hydrogen storage alloy, negative electrode, battery and preparation method - Google Patents

AB3 type rare earth-samarium-nickel hydrogen storage alloy, negative electrode, battery and preparation method Download PDF

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CN111471913B
CN111471913B CN202010292004.7A CN202010292004A CN111471913B CN 111471913 B CN111471913 B CN 111471913B CN 202010292004 A CN202010292004 A CN 202010292004A CN 111471913 B CN111471913 B CN 111471913B
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hydrogen storage
storage alloy
rare earth
negative electrode
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CN111471913A (en
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徐津
李金�
周淑娟
李宝犬
闫慧忠
王利
熊玮
赵玉园
郑天仓
张旭
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Baotou Rare Earth Research Institute
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    • 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
    • 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
    • C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
    • 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
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/383—Hydrogen absorbing alloys
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses an AB3A rare earth-samarium-nickel hydrogen storage alloy, a negative electrode, a battery and a preparation method. The hydrogen storage alloy has the composition of RExSmyNizMnaAlbMc(ii) a RE is one or more selected from rare earth metal elements except Sm; m is selected from one or more of Cu, Fe, Co, Sn, V, W, Cr, Zn, Mo and Si elements; x, y, z, a, b and c represent mole fractions of RE, Sm, Ni, Mn, Al and M, respectively; x is the number of>0，y≥0.1，x+y＝3；4≥a+b>0; c is more than or equal to 0, and a + b + c + z is more than 9.5 and more than or equal to 7.8. The invention simultaneously improves the maximum discharge capacity, the electrochemical activation performance and the capacity retention rate of the hydrogen storage alloy after 100 times of circulation.

Description

AB3 type rare earth-samarium-nickel hydrogen storage alloy, negative electrode, battery and preparation method
Technical Field
The invention relates to an AB3A rare earth-samarium-nickel hydrogen storage alloy, a negative electrode, a battery and a preparation method.
Background
AB3Electrode materials prepared from the hydrogen storage alloy have the advantages of high capacity, low price and the like, so that the hydrogen storage alloy is more and more widely concerned. In recent years, AB3The research of the hydrogen storage alloy continuously makes new progress, and how to improve AB3The electrochemical comprehensive performance of the hydrogen storage alloy has important significance for further improving the independent innovation capability of China in the technical field of hydrogen energy and providing technical reserve for the development of hydrogen energy in China.
CN104518204B discloses a rare earth-yttrium-nickel series hydrogen storage alloy RExYyNiz-a-bMnaAlbMc(ii) a x >0, y > 1.5, x + y is 3; z is more than or equal to 12.5 and more than or equal to 8.5, a + b is more than 0 and more than or equal to 3.5, and c is more than or equal to 3.0 and more than or equal to 0. The electrochemical performance of the hydrogen storage alloy can be improved by increasing the content of yttrium, but the good improvement of each performance is difficult to ensure.
CN101376941B discloses a hydrogen storage alloy with formula LaaM(1-a)NixCuyFezCouMnvAlwThe composition expressed by a is more than or equal to 0.5 and less than or equal to 0.8, x is more than or equal to 2.6 and less than or equal to 3.2, y is more than or equal to 0.5 and less than or equal to 0.9, z is more than or equal to 0.1 and less than or equal to 0.2, u is more than or equal to 0.05 and less than or equal to 0.1, v is more than or equal to 0.4 and less than or equal to 0.6, w is more than or equal to 0.2 and less than or equal to 0.4, and. The hydrogen storage alloy has the defects of low maximum discharge capacity (below 326 mAh/g), long activation period and the like.
CN104513925B discloses a rare earth series hydrogen storage alloy RExYyNiz-a-bMnaAlbX is more than 0, y is more than or equal to 2, and x + y is 3; z is more than 9.5 and more than or equal to 8.5; 3.5 is more than or equal to a + b and more than 0. The hydrogen storage alloy battery is difficult to simultaneously improve various performances in electrochemical performances.
Disclosure of Invention
The inventors of the present application have conducted intensive studies in order to overcome the drawbacks of the prior art. An object of the present invention is to provide an AB3Rare earth-samarium-nickel hydrogen storage alloys of the type having improved maximum discharge capacity, electrochemical activation propertiesAnd capacity retention for 100 cycles. Another object of the present invention is to provide a method for producing the above hydrogen occluding alloy. It is still another object of the present invention to provide a hydrogen storage alloy negative electrode. It is yet another object of the present invention to provide a battery. The invention adopts the following technical scheme to achieve the purpose.
In one aspect, the present invention provides an AB3A rare earth-samarium-nickel hydrogen storage alloy of the type having a composition represented by formula (1):
RExSmyNizMnaAlbMc (1)
wherein RE is selected from one or more of rare earth metal elements except Sm; m is selected from one or more of Cu, Fe, Co, Sn, V, W, Cr, Zn, Mo and Si elements;
wherein x, y, z, a, b and c represent mole fractions of RE, Sm, Ni, Mn, Al and M, respectively;
wherein x is more than 0, y is more than or equal to 0.1, and x + y is 3; 4 is more than or equal to a + b and is more than 0; c is more than or equal to 0, and 9.5 is more than or equal to 7.8 of a + b + c + z.
AB according to the invention3The rare earth-samarium-nickel hydrogen storage alloy is preferably that y/x is more than or equal to 1.35.
AB according to the invention3The rare earth-samarium-nickel hydrogen storage alloy is preferably 1.5 to more than a plus b to more than 0.5, and 1 to more than c to more than 0.
AB according to the invention3The rare earth-samarium-nickel hydrogen storage alloy is preferably 2.5 or more and y/x or more and 1.6 or more; z is more than or equal to 9 and more than or equal to 8.
AB according to the invention3The rare earth-samarium-nickel hydrogen storage alloy is preferably prepared by selecting RE from one or more of La, Ce, Pr, Nd, Y, Gd and Sc rare earth metal elements.
AB according to the invention3Preferably, RE contains La, and the La accounts for 50-100 mol% of the total mole number of RE.
AB according to the invention3A rare earth-samarium-nickel hydrogen storage alloy of the type preferably having a composition represented by one of the following formulae:
LaSm2Ni8.2Mn0.5Al0.3，
LaSm2Ni8.5Mn0.5，
LaSm2Ni8.5Al0.5，
La0.8Ce0.2Sm2Ni8Mn0.5Al0.5，
LaSm2Ni8Mn0.5Al0.3Cu0.2。
on the other hand, the invention also provides an AB3The preparation method of the rare earth-samarium-nickel hydrogen storage alloy comprises the following steps:
1) placing the raw material as the formula (1) in a smelting device, vacuumizing the smelting device until the absolute vacuum degree is below 10Pa, then filling inert gas until the relative vacuum degree is-0.01 to-0.1 MPa, and smelting at 1300-1500 ℃ to obtain a smelting product; forming an alloy sheet from the smelted product through a quick quenching melt-spun strip or casting to obtain an alloy ingot;
2) placing the alloy sheet or the alloy ingot in a heat treatment device with the relative vacuum degree of-0.1 to-0.005 MPa, and carrying out heat treatment for 10-48 h at 800-1050 ℃ to obtain AB3The rare earth-samarium-nickel hydrogen storage alloy.
In still another aspect, the present invention also provides a hydrogen storage alloy negative electrode comprising a negative electrode material, the negative electrode material comprising a negative electrode active material and a conductive agent; wherein the mass ratio of the negative active material to the conductive agent is 1: 3-8, and the negative active material comprises the AB3The rare earth-samarium-nickel hydrogen storage alloy.
In yet another aspect, the present invention also provides a battery comprising a battery case, wherein an electrode group and an alkaline electrolyte are hermetically disposed in the battery case; the electrode group comprises a positive electrode, a negative electrode and a diaphragm; wherein the negative electrode is the hydrogen storage alloy negative electrode.
The hydrogen occluding alloy of the present invention contains Sm rare earth metal element and at least one other rare earth metal element. The invention controls the proportion of each rare earth metal element and the types of other metal elements, and improves the maximum discharge capacity, the electrochemical activation performance and the capacity retention rate of 100 cycles of the hydrogen storage alloy.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
In the present invention, the absolute vacuum degree indicates the actual pressure in the container. The relative vacuum represents the difference between the vessel pressure and 1 standard atmosphere. The inert gas includes nitrogen or argon, etc.
< Hydrogen occluding alloy >
AB of the invention3The type rare earth-samarium-nickel hydrogen storage alloy has a composition represented by formula (1):
RExSmyNizMnaAlbMc (1)。
in the present invention, the hydrogen storage alloy does not contain a metal element Mg. Preferably, the hydrogen occluding alloy of the present invention does not contain additional components other than some inevitable impurities. When a + b + c + z is 9, the hydrogen storage alloy is a hydrogen storage alloy AB3 type; when a + b + c + z is not equal to 9, the hydrogen storage alloy is in a non-stoichiometric ratio AB3And (4) molding.
The RE of the present invention is selected from one or more of rare earth metal elements other than Sm. Specifically, RE is selected from one or more of La, Ce, Pr, Nd, Pm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Gd, Y, Lu and Sc elements. Preferably, RE is selected from one or more elements of La, Ce, Pr, Nd, Y and Sc. More preferably, RE contains La, and La is 50-100 mol% of the total mole number of RE. According to an embodiment of the invention, RE is a combination of La and Ce, and La is 50-80 mol% of the total mole number of RE. x represents the mole fraction of the rare earth element RE, x > 0; preferably, 2> x > 0.5; more preferably, 1 ≧ x ≧ 0.5.
y represents the mole fraction of the rare earth metal element Sm. y is more than or equal to 0.1; preferably, y is equal to or greater than 0.5; more preferably, 3 ≧ y > 1. By adopting the RE element and the Sm element and adjusting the content of each element to be within the range defined by the invention, the maximum discharge capacity, the capacity retention rate after 100 times of circulation and the electrochemical activation performance of the hydrogen storage alloy can be improved simultaneously. In the present invention, x + y is 3.
z represents a mole fraction of the metal element Ni. In the invention, z is more than or equal to 9 and more than or equal to 7.5; preferably, 9.0. gtoreq.z.gtoreq.8; more preferably, 8.3. gtoreq.z.gtoreq.8.1. Controlling the mole fraction of Ni in the above range is not only beneficial to reducing the cycle number required by the complete activation of the electrode, but also can improve the maximum discharge capacity of the hydrogen storage alloy. Examples of hydrogen storage alloys meeting the above criteria include, but are not limited to, LaSm2Ni8.2Mn0.5Al0.3。
In the present invention, a represents the mole fraction of the metal element Mn; b represents the molar fraction of the metallic element Al. 4 is more than or equal to a + b and is more than 0; preferably, 2. gtoreq.a + b. gtoreq.0.3; more preferably, 1 ≧ a + b > 0.3. According to the invention, two metal elements of Mn and Al are controlled within the range, so that the capacity retention rate and the electrochemical activation performance of the hydrogen storage alloy battery can be improved after 100 cycles.
In the present invention, M is selected from one or more of Cu, Fe, Co, Sn, V, W, Cr, Zn, Mo and Si elements; preferably, M is selected from one or more of Cu, Fe, Co, V, Cr and Zn elements; more preferably, M is selected from one of Cu, Fe and V elements. c represents the mole fraction of the metal element M, and c is more than or equal to 0; preferably, 1 ≧ c ≧ 0; more preferably, 0.5. gtoreq.c.gtoreq.0.
In the invention, 9.5> a + b + c + z is more than or equal to 7.8; preferably, 9.5> a + b + c + z ≧ 8.5; more preferably, 9.5> a + b + c + z ≧ 9.
In certain embodiments of the invention, y/x.gtoreq.1.35. In other embodiments, 2.5. gtoreq.y/x. gtoreq.1.6. In still other embodiments, 3 ≧ y ≧ 2. The proportion of Sm rare earth metal elements and RE rare earth metal elements is controlled within the range, so that the maximum discharge capacity of the hydrogen storage alloy can be improved, and the electrochemical activation performance and the capacity retention rate of the hydrogen storage alloy after 100 times of circulation can be improved. Experiments prove that the maximum discharge capacity of the lithium secondary battery is greatly reduced by controlling the proportion of Sm rare earth metal elements and RE rare earth metal elements within y/x of less than 1.35.
According to one embodiment of the invention, 1.5. gtoreq.a + b. gtoreq.0.5, 1. gtoreq.c.gtoreq.0. According to another embodiment of the invention, 2.5. gtoreq.y/x. gtoreq.1.6; z is more than or equal to 9 and more than or equal to 8. According to one embodiment of the invention, 2.5. gtoreq.y/x. gtoreq.1.6; z is more than or equal to 9 and more than or equal to 8, and c is 0. According to yet another embodiment of the invention, RE contains La; x is 1, y is 2, 1.5 is more than or equal to a + b is more than or equal to 0.5, c is 0, 9 is more than or equal to z is more than or equal to 8.5.
Specific examples of the hydrogen occluding alloy of the present invention include, but are not limited to, alloys represented by one of the following formulas:
LaSm2Ni8.2Mn0.5Al0.3，
LaSm2Ni8.5Mn0.5，
LaSm2Ni8.5Al0.5，
La0.8Ce0.2Sm2Ni8Mn0.5Al0.5，
LaSm2Ni8Mn0.5Al0.3Cu0.2。
< preparation method >
The hydrogen occluding alloy of the present invention can be produced by various methods such as a mechanical alloying method, a powder sintering method, a high-temperature melting-gas atomization method, a reduction diffusion method, a displacement diffusion method, a combustion synthesis method, a self-propagating high-temperature synthesis method, a high-temperature melting casting method, a high-temperature melting-rapid quenching method, and a chemical method. Specifically, the method for producing a hydrogen occluding alloy of the present invention comprises: (1) preparing an alloy sheet or an alloy ingot; and (2) a heat treatment step.
In the step (1), the composition satisfies the formula RExSmyNizMnaAlbMcThe raw materials are put into a smelting device for smelting to obtain a smelting product; and (4) forming an alloy sheet by quickly quenching and throwing the smelted product or casting to obtain an alloy ingot. The method of the present invention may comprise an evacuation step. Vacuumizing a smelting device until the absolute vacuum degree is below 10 Pa; preferably, the smelting device is vacuumized until the absolute vacuum degree is below 8 Pa; more preferably, the melting apparatus is evacuated to an absolute vacuum degree of 5Pa or less. After vacuumizing, filling inert gas into the smelting device until the relative vacuum degree is-0.01 to-0.1 MPa; preferably-0.02 to-0.08 MPa; more preferably-0.03 to-0.06 MPa. At 1300-1500 ℃, preferably 1300-1450 ℃, more preferably 1350-1450 DEG CAnd (4) smelting.
And (3) after the raw materials in the smelting device are completely melted, preserving the heat for a certain time, and stopping heating, wherein the whole smelting process is about 10-60 min, preferably 15-50 min, and more preferably 15-20 min. Such smelting conditions are beneficial to prolonging the service life, improving the maximum discharge capacity and reducing self-discharge.
According to one embodiment of the invention, the smelting product is cast to a cooling copper roller for quick quenching and throwing to form an alloy sheet with the thickness of 0.1-0.4 mm. Preferably, the smelting product is cast to a cooling copper roller for quick quenching and casting to form an alloy sheet with the thickness of 0.2-0.4 mm. More preferably, the smelting product is cast to a cooling copper roller for quick quenching and throwing to form an alloy sheet with the thickness of 0.2-0.3 mm. According to another embodiment of the invention, the smelted product is cast into an alloy block with the diameter of 10-25 mm. Preferably, the smelting product is cast into an alloy block with the diameter of 15-25 mm. More preferably, the smelting product is cast into an alloy block with the diameter of 15-20 mm.
According to one embodiment of the invention, the smelting device is vacuumized until the absolute vacuum degree is less than or equal to 10 Pa; preferably less than or equal to 8 Pa; more preferably ≦ 5 Pa. Then argon is filled into the smelting device until the relative vacuum degree is-0.01 to-0.1 MPa, and preferably-0.02 to-0.08 MPa; more preferably-0.03 to-0.06 MPa. And then, the smelting device is arranged at 1300-1500 ℃, preferably 1300-1450 ℃, and more preferably 1350-1450 ℃. And (4) after the raw materials in the smelting device are completely melted, preserving the heat for a certain time, and stopping heating to obtain a smelting product. And finally, casting the smelting product to a cooling copper roller for quick quenching and casting to obtain an alloy sheet with the thickness of 0.2-0.3 mm.
In the step (2), the alloy sheet or the alloy block is subjected to heat treatment in a heat treatment device to obtain AB3The rare earth-samarium-nickel hydrogen storage alloy. In the present invention, the relative degree of vacuum in the heat treatment apparatus may be from-0.1 to-0.005 MPa, preferably from-0.08 to-0.01 MPa, and more preferably from-0.05 to-0.025 MPa. The heat treatment temperature can be 800-1050 ℃, preferably 850-950 ℃, and more preferably 800-900 ℃. The heat treatment time can be 10-48 h, preferably 10-36 h, and more preferably 10-24 h. Such heat treatment conditions are advantageous for improving the texture and electrochemical properties of the hydrogen occluding alloy.
In certain embodiments, the heat treatment is carried out under an inert gas blanket, which may be nitrogen or argon, preferably argon.
According to one embodiment of the invention, the heat treatment device is vacuumized, and then argon is filled into the heat treatment device until the relative vacuum degree is-0.05 to-0.025 MPa; then heat treatment is carried out for 10-24 h at 800-900 ℃.
< negative electrode >
The negative electrode of the present invention comprises a negative electrode material comprising a negative electrode active material and a conductive agent, the negative electrode active material comprising the above hydrogen storage alloy. The composition of the hydrogen storage alloy in the invention is RExSmyNizMnaAlbMcThe elements and their mole fractions are as described above and will not be described herein. In the present invention, the negative electrode material is supported on a current collector, which may be metallic copper or nickel foam, preferably nickel foam. The mass ratio of the negative electrode active material to the conductive agent is 1: 3-8; preferably 1: 3-6; more preferably 1: 3-5.
The hydrogen storage alloy may be used in the form of powder. In the present invention, the hydrogen absorbing alloy is used in the form of powder, and the particle size of the hydrogen absorbing alloy powder may be 100 to 400 mesh, preferably 100 to 300 mesh, and more preferably 200 to 300 mesh. The conductive agent may be nickel carbonyl powder.
According to one embodiment of the present invention, a hydrogen storage alloy is mechanically crushed into 200-mesh hydrogen storage alloy powder; mixing hydrogen storage alloy powder and nickel carbonyl powder in a mass ratio of 1: 4, and preparing into an electrode slice with the diameter of 15mm under 11 MPa; the electrode sheet was placed between two pieces of nickel foam, and a nickel tape as a tab was sandwiched, and a negative electrode was produced again at 11 MPa. And the close contact between the electrode plate and the nickel screen is ensured by spot welding around the electrode plate.
< Battery >
The battery comprises a battery shell, wherein an electrode group and alkaline electrolyte are hermetically arranged in the battery shell; the electrode group comprises a positive electrode, a negative electrode and a diaphragm; the negative electrode is the above negative electrode, and details are not described here.
In the present invention, the battery case may be made of a material that is conventional in the art. The positive electrode may be nickel hydroxide, preferably sintered Ni (OH) having an excess capacity2a/NiOOH electrode. The diaphragm can be porous vinylon non-woven fabric, nylon non-woven fabric or polypropylene fiber membrane, etc. The alkaline electrolyte can be KOH aqueous solution or KOH aqueous solution containing a small amount of LiOH; preferably 6 mol. L–1Aqueous KOH solution.
Examples 1 to 5 and comparative examples 1 to 3
AB was prepared according to the formulation of Table 1, as follows3Type rare earth-samarium-nickel hydrogen storage alloy:
(1) sequentially placing all raw materials into a smelting device from the bottom to the upper part of the smelting device, wherein the rare earth metal raw material is placed on the upper part, and other metal raw materials are placed on the bottom; then, the smelting device is vacuumized until the absolute vacuum degree is less than or equal to 5Pa, and argon is filled until the relative vacuum degree is-0.055 MPa; then heating the smelting device to 1400 ℃, keeping the temperature for 3min after the metal raw materials in the smelting device are completely melted, and stopping heating to obtain a smelting product; and casting the smelted product to a cooling copper roller, and quickly quenching and throwing to obtain an alloy sheet with the thickness of 0.3 mm.
(2) Placing the alloy sheet in a heat treatment device filled with argon and having a relative vacuum degree of-0.025 MPa, and performing heat treatment at 875 ℃ for 16h to obtain AB3The rare earth-samarium-nickel hydrogen storage alloy.
Examples of the experiments
The hydrogen occluding alloys of examples 1 to 12 were mechanically crushed into alloy powders of 200 mesh, respectively. Mixing the alloy powder and the conductive agent carbonyl nickel powder in a mass ratio of 1: 4, and preparing the mixture into an electrode slice with the diameter of 15mm under 11 MPa. The electrode plate is placed between two pieces of foamed nickel as a current collector, and a nickel strip as a tab is clamped at the same time, so that the hydrogen storage alloy negative electrode is prepared under 11 MPa. And the close contact between the electrode plate and the nickel screen is ensured by spot welding around the electrode plate.
The negative electrode in the open three-electrode system for testing electrochemical performance is a hydrogen storage alloy negative electrode, and the positive electrode adopts sintered Ni (OH) with excessive capacity2The NiOOH electrode, the reference electrode is Hg/HgO, and the electrolyte is 6 mol.L-1Potassium hydroxide solution. The assembled battery was left for 24h and electrochemical performance was measured by a constant current method using a LAND cell tester. The test environment temperature was 303K. The charging current density is 60mA g-1The charging time is 7.5 h; discharge current density 60mA g-1The discharge cut-off potential was 0.5V, and the charge/discharge pause time was 15 min. The test results are shown in Table 1.
TABLE 1
Figure BDA0002450760530000101
Remarking: n is the number of times of circulation needed for complete activation of the alloy electrode, and the smaller the numerical value, the better the activation performance is. S100The larger the value of the capacity retention rate of the alloy electrode at the 100 th cycle, the longer the cycle life. CmaxThe larger the value is for the maximum discharge capacity of the alloy electrode, indicating the better performance.
As can be seen from Table 1, the maximum discharge capacity C of the hydrogen storage alloy battery can be improved simultaneously by controlling the types and the proportions of the rare earth metal elements and other elements in the hydrogen storage alloymaxCapacity retention ratio S at the 100 th week of the cycle100And the number of cycles N required for complete activation of the electrode.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.

Claims (8)

1. AB3A type rare earth-samarium-nickel hydrogen storage alloy characterized by having a composition represented by formula (1):
RExSmyNizMnaAlbMc (1)
wherein RE is selected from one or more of La, Ce, Pr, Nd, Gd and Sc rare earth metal elements; m is selected from one or more of Cu, Fe, Co, Sn, V, W, Cr, Zn, Mo and Si elements;
wherein x, y, z, a, b and c represent mole fractions of RE, Sm, Ni, Mn, Al and M, respectively;
wherein x is more than or equal to 1 and more than or equal to 0.5, y is more than or equal to 3 and more than 1, y/x is more than or equal to 1.35, and x + y is 3; 4 is more than or equal to a + b and is more than 0; c is more than or equal to 0, 9.5 is more than a + b + c + z is more than or equal to 7.8, and 9.0 is more than or equal to z is more than or equal to 8.
2. The AB of claim 13The rare earth-samarium-nickel hydrogen storage alloy is characterized in that a + b is more than or equal to 1.5 and more than or equal to 0.5, and c is more than or equal to 1 and more than or equal to 0.
3. The AB of claim 23The rare earth-samarium-nickel hydrogen storage alloy is characterized in that y/x is more than or equal to 2.5 and more than or equal to 1.6; z is more than or equal to 8.3 and more than or equal to 8.1.
4. The AB of claim 13The rare earth-samarium-nickel hydrogen storage alloy is characterized in that RE contains La, and La accounts for 50-100 mol% of the total mole number of RE.
5. The AB of claim 13A rare earth-samarium-nickel hydrogen storage alloy of the type having a composition represented by one of the following formulae:
LaSm2Ni8.2Mn0.5Al0.3，
LaSm2Ni8.5Mn0.5，
LaSm2Ni8.5Al0.5，
La0.8Ce0.2Sm2Ni8Mn0.5Al0.5，
LaSm2Ni8Mn0.5Al0.3Cu0.2。
6. an AB as claimed in any of claims 1 to 53The preparation method of the rare earth-samarium-nickel hydrogen storage alloy is characterized by comprising the following steps of:
1) placing the raw material as the formula (1) in a smelting device, vacuumizing the smelting device until the absolute vacuum degree is below 10Pa, then filling inert gas until the relative vacuum degree is-0.01 to-0.1 MPa, and smelting at 1300-1500 ℃ to obtain a smelting product; forming an alloy sheet from the smelted product through a quick quenching melt-spun strip or casting to obtain an alloy ingot;
2) placing the alloy sheet or the alloy ingot in a heat treatment device with the relative vacuum degree of-0.1 to-0.005 MPa, and carrying out heat treatment for 10-48 h at 800-1050 ℃ to obtain AB3The rare earth-samarium-nickel hydrogen storage alloy.
7. A hydrogen storage alloy negative electrode is characterized by comprising a negative electrode material, wherein the negative electrode material comprises a negative electrode active material and a conductive agent; wherein the mass ratio of the negative electrode active material to the conductive agent is 1: 3-8, and the negative electrode active material comprises AB as defined in any one of claims 1-53The rare earth-samarium-nickel hydrogen storage alloy.
8. The battery is characterized by comprising a battery shell, wherein an electrode group and alkaline electrolyte are hermetically arranged in the battery shell; the electrode group comprises a positive electrode, a negative electrode and a diaphragm; wherein the negative electrode is the hydrogen storage alloy negative electrode according to claim 7.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106463786A (en) * 2014-06-27 2017-02-22 Fdk株式会社 Nickel hydrogen secondary battery
CN110714139A (en) * 2018-07-13 2020-01-21 有研工程技术研究院有限公司 Rare earth-nickel-based hydrogen storage alloy material and preparation method thereof

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