CN111118345A - Multi-element samarium-nickel hydrogen storage material, negative electrode, battery and preparation method - Google Patents
Multi-element samarium-nickel hydrogen storage material, negative electrode, battery and preparation method Download PDFInfo
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- 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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- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
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- B22D11/0611—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by a single casting wheel, e.g. for casting amorphous metal strips or wires
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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
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- C22C30/04—Alloys containing less than 50% by weight of each constituent containing tin or lead
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- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/242—Hydrogen storage electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/383—Hydrogen absorbing alloys
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- 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 a multi-element samarium-nickel hydrogen storage material, a negative electrode, a battery and a preparation method. The component of the multi-element samarium nickel hydrogen storage material is RExSmyNiaMnbAlcMd(ii) a RE is one or more selected from rare earth metal elements except Sm, and x represents the mole fraction of RE; y represents the molar fraction of Sm; m is selected from one or more of Cu, Fe, Co, Sn, V, W, Cr, Zn, Mo and Si elements, and d represents the mole fraction of M; a represents the mole fraction of Ni; b represents the molar fraction of Mn; c represents the mole fraction of Al; x is the number of>0, y is more than or equal to 0.5, and y + x is 6; 23 is more than or equal to a and more than or equal to 12 and 7>b≥0，7>c≥0，5≥d>0, and 25 is more than or equal to a + b + c + d is more than or equal to 17. The negative electrode of the multi-element samarium nickel hydrogen storage material has excellent activation performance and electrochemical performance.
Description
Technical Field
The invention relates to a multi-element samarium-nickel hydrogen storage material, a negative electrode, a battery and a preparation method.
Background
With the development of industry and the improvement of people's living standard of matter, the demand of energy is increasing day by day. In recent years, energy is mainly derived from fossil fuel, and the use of the fossil fuel inevitably pollutes the environment, so that the search for renewable green energy is urgent. Hydrogen energy is a green energy source and an energy carrier with abundant reserves, wide sources and high energy density, and attracts people's extensive attention.
Hydrogen storage materials are a class of materials that can reversibly absorb and release hydrogen gas. Hydrogen storage alloys refer to intermetallic compounds that reversibly absorb, store, and release hydrogen in large quantities at a certain temperature and hydrogen pressure. Among hydrogen storage alloys, rare earth hydrogen storage materials have excellent dynamic properties and electrochemical properties, and are widely concerned. At present, rare earth hydrogen storage materials are mainly used as negative electrode materials of nickel-metal hydride (MH-Ni) secondary batteries.
CN101376941A discloses that the composition is LaaM1-aNixCuyFezCouMnvAlwM represents at least two kinds of rare earth metals other than La, and may be Sm, a is from 0.4 to 0.9, x is from 2.5 to 3.6, y is from 0.4 to 1.0, z is from 0 to 0.2, u is from 0 to 0.2 (excluding 0), v is from 0.4 to 0.7, w is from 0.2 to 0.4, and x + y + z + u + v + w is from 4.8 to 5.3. The complete activation times of the hydrogen storage alloy motor are more than 4 times, and the maximum discharge capacity is only less than 320mAh/g, so the activation performance and the electrochemical performance of the alloy are not good.
US5496424 discloses a composition R1-xAx(Ni5-yBy)zR can be La, A can be Sm, B can be Al or Mn, x is 0-0.5, y is 0-1 (excluding 0), and z is 0.8-1.2. The activation performance and electrochemical performance of the above alloy are also poor.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a samarium-nickel complex hydrogen storage material having excellent activation properties. Furthermore, the multielement samarium nickel hydrogen storage material has longer service life. Furthermore, the multi-element samarium nickel hydrogen storage material has higher maximum discharge capacity. The invention also aims to provide a preparation method of the multi-element samarium nickel hydrogen storage material. It is still another object of the present invention to provide a 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.
On one hand, the invention provides a samarium-nickel complex hydrogen storage material, which comprises the following components in formula (1):
RExSmyNiaMnbAlcMd(1)
wherein RE is selected from one or more of rare earth metal elements except Sm, and x represents the mole fraction of RE; y represents the molar fraction of Sm; m is selected from one or more of Cu, Fe, Co, Sn, V, W, Cr, Zn, Mo and Si elements, and d represents the mole fraction of M; a represents the mole fraction of Ni; b represents the molar fraction of Mn; c represents the mole fraction of Al;
wherein x is greater than 0, y is greater than or equal to 0.5, and y + x is 6; 23 is more than or equal to a and more than or equal to 12, 7 is more than or equal to b and more than or equal to 0, 7 is more than or equal to c and more than or equal to 0, 5 is more than or equal to d and more than or equal to 0, and 25 is more than or equal to a + b + c + d and more than or equal to 17.
According to the samarium nickel hydride hydrogen storage material, RE is preferably one or more elements selected from La, Ce, Pr, Nd, Gd, Y and Sc.
According to the multi-element samarium nickel hydrogen storage material, preferably, M contains Co and one or more of Cu, Fe, Sn, V, W, Cr and Zn; 5 is more than or equal to b + c and is more than 1.
According to the multi-element samarium nickel hydrogen storage material, preferably, x is more than or equal to 4 and more than 1, y is more than or equal to 5 and more than or equal to 1, and y/x is more than or equal to 1.6.
According to the multi-element samarium nickel hydrogen storage material, 22 is preferably more than or equal to a and more than or equal to 13, 3 is more than or equal to b and more than 0, 3 is more than or equal to c and more than 0, and 4 is more than or equal to d and more than 0.
According to the samarium nickel hydrogen storage material, M preferably satisfies one of the following conditions:
1) 22> a >17 when M is Co;
2) 18> a >12, 2> b >0.5 when M is Fe;
3) when M is Cu, 19 is more than or equal to a + b + c + d is more than or equal to 17, or 25 is more than or equal to a + b + c + d and is more than or equal to 20.
The samarium nickel complex hydrogen storage material according to the present invention preferably has a composition represented by one of the following formulae:
La2Sm4Ni15MnAlCu，
La2Sm4Ni15MnAlFe，
La2Sm4Ni15MnAlCo，
La2Sm4Ni15MnAlSn，
La2Sm4Ni15MnAl(VFe)1，
La2Sm4Ni15MnAlW，
La2Sm4Ni17.5MnAl1.5Cu，
La2Sm4Ni17.5MnAl1.5Fe，
La2Sm4Ni17.5MnAl1.5Co，
La2Sm4Ni17.5MnAl1.5Sn，
La2Sm4Ni17.5MnAl1.5(VFe)1，
La2Sm4Ni17.5MnAl1.5W，
La2Sm4Ni20.3MnAl0.5Co，
La2Sm4Ni20.3MnAl0.5Cu，
La2Sm4Ni20.3MnAl0.5Fe，
La2Sm4Ni20.3MnAl0.5Sn，
La2Sm4Ni20.3MnAl0.5(VFe)1，
La2Sm4Ni20.3MnAl0.5W，
La2Sm4Ni17.5MnAl0.5CoCu，
La2Sm4Ni17.5Mn0.5Al0.5CoCuSn0.5，
La2Sm4Ni17.5Mn0.5Al0.5CoCuW0.5，
La2Sm4Ni20.3MnAl0.5Co0.5Cu0.5，
La2Sm4Ni20.3MnAl0.5Zn0.5Cu0.5，
La2Sm4Ni17.5Mn0.5Al0.5FeCuSn0.5，
La2Sm4Ni14.5MnAl0.5CuSn，
La2Sm4Ni14.5MnAl0.5CuCo，
La2Sm4Ni14MnAlCuW0.5Fe0.5，
La2Sm4Ni14.5MnAl(VFe)1Co0.5，
La2Sm4Ni17MnAl0.5W(VFe)1Sn0.5，
La2Sm4Ni19.3MnAl0.5Zn0.5Cu0.5(VFe)1。
on the other hand, the invention also provides a preparation method of the multi-element samarium nickel hydrogen storage material, which comprises the following steps:
1) a smelting step: putting the metal raw material into an environment with a relative vacuum degree of-0.01 to-0.1 MPa, and smelting at 1200-1600 ℃ to obtain a smelting product; the integral composition of the metal raw material is shown as a formula (1);
2) a forming step: rapidly quenching and casting the smelted product to obtain an alloy sheet or casting to obtain an alloy ingot;
3) a heat treatment step: and (3) placing the alloy sheet or the alloy ingot in an environment with the absolute vacuum degree of 0.0001-0.05 Pa, and carrying out heat treatment at 750-1050 ℃ for 10-60 h to obtain the samarium-nickel complex hydrogen storage material.
In another aspect, the invention provides a negative electrode, which comprises a negative electrode material, wherein the negative electrode material comprises a negative electrode active substance and a conductive agent in a mass ratio of 1: 3-8, and the negative electrode active substance comprises the above-mentioned samarium-nickel hydrogen storage material; the conductive agent is nickel powder, acetylene black or graphite.
In yet another aspect, the present invention provides a battery comprising a battery case, and an electrode group and an alkaline electrolyte sealed in the battery case; the electrode group comprises a positive electrode, a negative electrode and a diaphragm;
wherein the diaphragm is a porous vinylon non-woven fabric, a nylon non-woven fabric or a polypropylene fiber membrane;
the negative electrode comprises a negative electrode material, the negative electrode material comprises a negative electrode active substance and a conductive agent in a mass ratio of 1: 3-8, and the negative electrode active substance comprises the multi-element samarium nickel hydrogen storage material; the conductive agent is nickel powder, acetylene black or graphite.
The multi-element samarium nickel hydrogen storage material has excellent activation performance. The number of cycles required for complete activation of the electrode can be reduced to as low as about 1 cycle. In the preferred scheme of the invention, the electrode prepared from the samarium-nickel complex hydrogen storage material has higher maximum discharge capacity and longer service life. Furthermore, the electrode prepared from the samarium-nickel hydride hydrogen storage material has excellent self-discharge characteristics.
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. In the present invention, the alkali metal element means a metal element of group IA in the periodic table, for example, lithium, sodium, potassium, cesium and the like.
< multiple samarium Nickel Hydrogen storage Material >
The composition of the multi-element samarium nickel hydrogen storage material is shown as a formula (1):
RExSmyNiaMnbAlcMd(1)。
in the present invention, RE is selected from one or more of rare earth metal elements other than Sm. Specifically, the rare earth metal elements of the present invention include La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc elements. Preferably, RE is selected from one or more of La, Ce, Pr, Nd, Gd, Y and Sc elements; more preferably, the RE is selected from one or more of La, Ce and Y elements. In some embodiments, RE comprises La, and La comprises 50 to 100 mol% of the total moles of RE. In certain embodiments, RE is La. x represents the mole fraction of RE, x >0. Preferably, 4 ≧ x > 1. More preferably, 2.5. gtoreq.x.gtoreq.2.
Sm is samarium. y represents a molar fraction of Sm. y is more than or equal to 0.5. Preferably, 5> y.gtoreq.1. More preferably, 5> y.gtoreq.4.
In the present invention, x + y is 6. The invention obviously improves the activation performance of the hydrogen storage material by adjusting the contents of M and Sm in the hydrogen storage material. Further, this can improve the service life of the hydrogen storage material.
In the invention, y/x is more than or equal to 1.6; preferably, y/x is greater than or equal to 1.8; more preferably, 3.0. gtoreq.y/x. gtoreq.2.0. Controlling the molar ratio of Sm to RE in the above range can improve the electrochemical performance of the hydrogen storage material, prolong the service life of the hydrogen storage material electrode and reduce the cycle times required for the complete activation of the hydrogen storage material electrode. According to one embodiment of the present invention, y/x is 2.0. Therefore, the circulation frequency required by the complete activation of the hydrogen storage material electrode can be stabilized to 1 time, the capacity retention rate of the hydrogen storage material electrode at the 100 th time is improved, and the service life is prolonged.
According to one embodiment of the invention, 4 ≧ x >1, 5> y ≧ 1, x + y ≧ 6 and y/x ≧ 1.8. According to another embodiment of the invention 2.5 ≧ x ≧ 2, 5> y ≧ 4, x + y ≧ 6 and 3 ≧ y/x ≧ 2. According to yet another embodiment of the present invention, x is 2 and y is 4.
Ni is nickel. a represents the molar fraction of Ni. 23 is more than or equal to a and more than or equal to 12. Preferably, 22. gtoreq.a.gtoreq.13. More preferably, 20.3. gtoreq.z.gtoreq.14. Controlling the mole fraction of Ni in the above range is advantageous for reducing the number of cycles required for complete activation of the hydrogen storage material electrode.
Mn is manganese. b represents the molar fraction of Mn. 7> b.gtoreq.0. Preferably, 3 ≧ b >0. More preferably, 1.5. gtoreq.b.gtoreq.0.5.
Al is aluminum, and c represents the molar fraction of Al. 7> c.gtoreq.0. Preferably, 3 ≧ c >0. More preferably, 1.5. gtoreq.c.gtoreq.0.5.
M is one or more selected from Cu, Fe, Co, Sn, V, W, Cr, Zn, Mo and Si. Preferably, M is selected from one or more of the elements Cu, Fe, Co, Sn, V, W, Cr and Zn. More preferably, M is selected from one or more of the elements Cu, Fe, Co, Sn, V, W and Cr. c represents the mole fraction of M. 5 is more than or equal to c and more than 0. Preferably, 4 ≧ c > 0; more preferably, 2.5. gtoreq.c.gtoreq.0.5. With the above amount of M, the self-discharge performance of the hydrogen storage material can be improved.
According to one embodiment of the present invention, M contains one or more of Cu, Fe, Sn, V, W, Cr, Zn and Co elements, and 5. gtoreq.b + c > 1. Thus, the hydrogen storage material with better electrochemical performance and service life can be obtained.
In the present invention, Ni and M are both essential elements, i.e., their contents are not zero. 25 is more than or equal to a + b + c + d is more than or equal to 17. Preferably 24. gtoreq.a + b + c + d. gtoreq.18. More preferably, 23. gtoreq.a + b + c + d. gtoreq.18. In certain embodiments, 22. gtoreq.a.gtoreq.13, 3. gtoreq.b >0, 3. gtoreq.c >0, 4. gtoreq.d >0. In certain preferred embodiments, 22. gtoreq.a.gtoreq.13, 3. gtoreq.b >0, 3. gtoreq.c >0, 4. gtoreq.d >0 and 24. gtoreq.a + b + c + d. gtoreq.18. Controlling the contents of the components within the above ranges can further improve the electrochemical properties of the hydrogen storage alloy, particularly the maximum discharge capacity.
According to one embodiment of the present invention, 22> a >17 when M is Co element.
According to still another embodiment of the present invention, 18> a >12, 2> b >0.5 when M is Fe element.
According to another embodiment of the present invention, when M is Cu, 19. gtoreq.a + b + c + d. gtoreq.17. This is more advantageous for obtaining hydrogen storage materials with better electrochemical properties and service life, especially maximum discharge capacity.
According to still another embodiment of the present invention, when M is Cu, 25. gtoreq.a + b + c + d > 20. This is more advantageous for obtaining hydrogen storage materials with better electrochemical properties and service life, especially maximum discharge capacity.
According to a preferred embodiment of the present invention, the samarium nickel polyatomic hydrogen storage material contains no additional components except some inevitable impurities. According to one embodiment of the invention, the multi-element rare earth hydrogen storage material does not comprise Mg; preferably, the Mg element and the alkali metal element are not contained. The raw material does not contain Mg. Therefore, Mg volatilization and oxidation in the process of preparing the hydrogen storage material can be avoided, the composition is easy to control, and burning explosion of Mg powder can not occur.
Specific examples of the samarium nickel polynary hydrogen storage material of the present invention include, but are not limited to, the following materials:
La2Sm4Ni15MnAlCu，
La2Sm4Ni15MnAlFe，
La2Sm4Ni15MnAlCo，
La2Sm4Ni15MnAlSn，
La2Sm4Ni15MnAl(VFe)1，
La2Sm4Ni15MnAlW，
La2Sm4Ni17.5MnAl1.5Cu，
La2Sm4Ni17.5MnAl1.5Fe，
La2Sm4Ni17.5MnAl1.5Co，
La2Sm4Ni17.5MnAl1.5Sn，
La2Sm4Ni17.5MnAl1.5(VFe)1，
La2Sm4Ni17.5MnAl1.5W，
La2Sm4Ni20.3MnAl0.5Co，
La2Sm4Ni20.3MnAl0.5Cu，
La2Sm4Ni20.3MnAl0.5Fe，
La2Sm4Ni20.3MnAl0.5Sn，
La2Sm4Ni20.3MnAl0.5(VFe)1，
La2Sm4Ni20.3MnAl0.5W，
La2Sm4Ni17.5MnAl0.5CoCu，
La2Sm4Ni17.5Mn0.5Al0.5CoCuSn0.5，
La2Sm4Ni17.5Mn0.5Al0.5CoCuW0.5，
La2Sm4Ni20.3MnAl0.5Co0.5Cu0.5，
La2Sm4Ni20.3MnAl0.5Zn0.5Cu0.5，
La2Sm4Ni17.5Mn0.5Al0.5FeCuSn0.5，
La2Sm4Ni14.5MnAl0.5CuSn，
La2Sm4Ni14.5MnAl0.5CuCo，
La2Sm4Ni14MnAlCuW0.5Fe0.5，
La2Sm4Ni14.5MnAl(VFe)1Co0.5，
La2Sm4Ni17MnAl0.5W(VFe)1Sn0.5，
La2Sm4Ni19.3MnAl0.5Zn0.5Cu0.5(VFe)1。
< preparation method >
The preparation method of the hydrogen storage alloy comprises a high-temperature smelting casting method, a high-temperature smelting-rapid quenching method, a mechanical alloying method, a powder sintering method, a high-temperature smelting-gas atomization method, a reduction diffusion method, a displacement diffusion method, a combustion synthesis method, a self-propagating high-temperature synthesis method and a chemical method. The texture and properties can be improved by heat treatment.
The preparation method of the multi-element samarium nickel hydrogen storage material comprises the following steps: (1) a smelting step, (2) a forming step and (3) a heat treatment step. As described in detail below.
In the smelting step, metal raw materials are smelted in a vacuum environment to obtain a smelting product. The metal raw material can be smelted by a vacuum smelting furnace. The overall composition of the metal raw material is shown as formula (1):
RExSmyNiaMnbAlcMd(1)。
the elements and their mole fractions are as described above and will not be described further herein. The vacuum environment may be filled with an inert gas. The inert gas may be high purity nitrogen or high purity argon, preferably argon.
In the smelting step, the metal raw material is placed in an environment with the relative vacuum degree of-0.01 to-0.1 MPa, and smelting is carried out at 1200-1600 ℃ to obtain a smelting product. Firstly, putting a metal raw material into a vacuum smelting furnace, then vacuumizing the vacuum smelting furnace, and recharging inert gas to obtain a vacuum environment. Vacuumizing the vacuum melting furnace until the absolute vacuum degree is less than or equal to 50 Pa; preferably, the vacuum melting furnace is vacuumized until the absolute vacuum degree is less than or equal to 10 Pa; more preferably, the vacuum melting furnace is vacuumized to the absolute vacuum degree of less than or equal to 5 Pa. Inert gas is filled into the vacuum smelting furnace 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. The smelting temperature is 1200-1600 ℃, preferably 1250-1500 ℃, and more preferably 1300-1400 ℃. Such smelting conditions are beneficial to prolonging the service life of the hydrogen storage material and improving the electrochemical performance of the hydrogen storage material.
In the forming step, the smelting product is rapidly quenched and spun to form an alloy sheet or cast to form an alloy ingot. In certain embodiments, the smelted product is cast onto a cooling copper roller to form an alloy sheet with the thickness of 0.1-0.4 mm through quick quenching and throwing; preferably, the alloy sheet with the thickness of 0.15-0.35 mm is formed by rapid quenching and spinning; more preferably, the rapid quenching melt-spun strip is an alloy sheet with the thickness of 0.2-0.3 mm.
In the heat treatment step, the alloy sheet or the alloy ingot is subjected to heat treatment in a vacuum environment to obtain the samarium-nickel complex hydrogen storage material. Specifically, the alloy sheet or the alloy ingot is placed in an environment with the absolute vacuum degree of 0.0001-0.05 Pa, and is subjected to heat treatment at the temperature of 750-1050 ℃ for 10-60 hours to obtain the samarium-nickel-polynary hydrogen storage material. The absolute vacuum degree of the vacuum environment may be 0.0001 to 0.05Pa, preferably 0.001 to 0.03Pa, and more preferably 0.01 to 0.02 Pa. The heat treatment temperature can be 750-1050 ℃, preferably 800-1000 ℃, and more preferably 850-925 ℃. The heat treatment time can be 10-60 h, preferably 15-50 h, and more preferably 15-35 h. The vacuum environment may be filled with an inert gas. The inert gas may be high purity nitrogen or high purity argon, preferably argon. Such heat treatment conditions are advantageous for extending the service life.
According to one embodiment of the present invention, the metal raw materials are placed in the vacuum melting furnace in the order of Ni, Mn, Al, M, RE, Sm from the bottom to the top. Vacuumizing the vacuum smelting furnace until the absolute vacuum degree is less than or equal to 50Pa, then filling inert gas argon to normal pressure, vacuumizing the vacuum smelting furnace until the absolute vacuum degree is less than or equal to 50Pa, and repeating the operation for 2-5 times; finally, filling inert gas until the relative vacuum degree is-0.01 to-0.1 MPa, and forming a vacuum environment; and then heating the vacuum smelting furnace to 1200-1600 ℃, and stopping heating (about 10-60 min is needed) after the raw materials in the vacuum smelting furnace are completely melted into smelting products. And casting the obtained smelting product to a cooling copper roller for quick quenching and throwing to obtain an alloy sheet with the thickness of 0.1-0.4 mm. And (3) placing the alloy sheet or the alloy ingot in a vacuum environment filled with argon and having an absolute vacuum degree of 0.01-0.02 Pa, heating to 850-800 ℃, and carrying out heat treatment for 15-35 h to obtain the samarium-nickel complex hydrogen storage material.
< negative electrode >
The negative electrode comprises a negative electrode material, wherein the negative electrode material comprises a negative electrode active material and a conductive agent in a mass ratio of 1: 3-8. The negative active material includes a samarium-nickel polyatomic hydrogen storage material as described above. Negative electrode current collector with negative electrode material loadedThe above. The negative current collector includes, but is not limited to, nickel foam. The composition of the multi-element samarium nickel hydrogen storage material is RExSmyNiaMnbAlcMd. The individual elements and their mole fractions in the hydrogen storage material of the invention are as described above. The negative pole of the hydrogen storage material has higher maximum discharge capacity and service life.
In some embodiments, the particle size of the samarium-nickel complex hydrogen storage material loaded on the negative current collector is 200 to 500 meshes, preferably 200 to 350 meshes, and more preferably 200 to 300 meshes. In other embodiments, the particle size of the multi-element samarium nickel hydrogen storage material loaded on the negative current collector is 200-300 meshes; the mass ratio of the multi-element samarium nickel hydrogen storage material loaded on the negative current collector to the conductive agent can be 1: 3-8, preferably 1: 3-6, and more preferably 1: 3-5. The conductive agent can be nickel powder, acetylene black or graphite; preferably nickel powder; more preferably carbonyl nickel powder.
According to one embodiment of the invention, the samarium-nickel complex hydrogen storage material is crushed into hydrogen storage material powder with the particle size of 200-300 meshes; then mixing the hydrogen storage material powder and the nickel carbonyl powder in a mass ratio of 1: 4, and preparing an electrode slice with the diameter of 15-25 mm under the pressure of 12-16 MPa; the electrode plate is placed between two pieces of foamed nickel, a nickel strip serving as a tab is clamped at the same time, and then the hydrogen storage material cathode is prepared under the pressure of 12-16 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, an electrode group and alkaline electrolyte, wherein the electrode group and the alkaline electrolyte are sealed in the battery shell; the electrode group comprises a positive electrode, a negative electrode and a diaphragm; the diaphragm is a porous vinylon non-woven fabric, a nylon non-woven fabric or a polypropylene fiber membrane; the negative electrode comprises a negative electrode material, the negative electrode material comprises a negative electrode active substance and a conductive agent in a mass ratio of 1: 3-8, and the negative electrode active substance is the above-mentioned multi-element samarium nickel hydrogen storage material; the conductive agent is nickel powder, acetylene black or graphite.
In the present invention, the battery case may be made of a material that is conventional in the art. The alkaline electrolyte can be aqueous potassium hydroxide solution or aqueous potassium hydroxide solutionAn aqueous potassium hydroxide solution with a small amount of LiOH. The positive electrode can be nickel hydroxide, e.g., sintered Ni (OH) with excess capacity2a/NiOOH electrode.
Example 1
According to the formula (M is Cu) in Table 1, the polybasic samarium nickel hydrogen storage material is prepared by the following steps:
(1) sequentially placing metal raw materials of Ni, Mn, Al, M, La and Sm into a vacuum smelting furnace from the bottom to the upper part of the vacuum smelting furnace; vacuumizing the vacuum melting furnace to the absolute vacuum degree of 5Pa, then filling inert gas argon to the normal pressure, vacuumizing the vacuum melting furnace to the absolute vacuum degree of 5Pa, and repeating the operation for 2 times; and finally, filling argon to the relative vacuum degree of-0.055 MPa, heating the vacuum smelting furnace to 1300 ℃ for smelting, and stopping heating after the raw materials in the vacuum smelting furnace are completely melted into a smelting product to obtain the smelting product.
(2) 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.
(4) And (3) placing the alloy sheet in an environment filled with argon and with the absolute vacuum degree of 0.01Pa, and carrying out heat treatment at 875 ℃ for 16h to obtain the multi-element samarium nickel hydrogen storage material.
Examples 2 to 30
A samarium-nickel multicomponent hydrogen storage material was prepared according to the procedure of example 1, according to the formulation of table 1.
Comparative example 1
According to the formula shown in Table 1, each raw material metal was weighed, placed in a medium frequency induction melting furnace (500 kg capacity, manufactured by Jinzhou electric furnace Co., Ltd.), melted at 1450 ℃ for 3 hours, and cast to obtain a rare earth alloy ingot.
Comparative examples 2 to 4
Samarium Nickel Hydrogen storage materials were prepared according to the procedure of example 1, according to the formulations of Table 1.
Experimental example 1
The polybasic samarium-nickel hydrogen storage material prepared in the embodiment 1-30, the rare earth alloy ingot prepared in the comparative example 1 and the samarium-nickel hydrogen storage material prepared in the comparative examples 2-4 are mechanically crushed into alloy powder of 200 meshes 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 the pressure of 12 MPa. The electrode plate is placed between two pieces of foamed nickel as a current collector, and a nickel belt as a tab is clamped at the same time, so that the gadolinium-nickel-containing hydrogen storage material cathode is prepared under the pressure of 12 MPa. And the close contact between the electrode plate and the nickel screen is ensured by spot welding around the electrode plate.
The cathode of the open three-electrode system for testing electrochemical performance is a gadolinium-nickel-containing hydrogen storage material cathode, and the anode 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 was 7.5 hours, and the discharge current density was usually 60mA · g-1(unless otherwise stated), the 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
Remarking: n is the number of times of circulation required for complete activation of the electrode, and the smaller the value, the better the activation performance is. CmaxThe larger the numerical value is, the better the electrochemical performance of the electrode is; s100For a capacity retention of 100 cycles of the electrode, a larger value indicates a longer cycle life. SD72For the capacity retention rate (self-discharge characteristic) after 72 hours of storage, a larger value indicates less self-discharge. (VFe) represents a ferrovanadium alloy with a vanadium to iron weight ratio of 1: 1.
As can be seen from Table 1, compared with comparative example 1, the activation performance and electrochemical performance of the hydrogen storage material cathodes prepared in examples 1 to 30 are obviously improved, the number of complete activation cycles of the electrodes is one, and the capacity retention rate SD is obtained after 72-hour storage72Up to 94%The maximum discharge capacity is above 361mAh/g, and the maximum discharge capacity is above 374 mAh/g. Therefore, the hydrogen storage material can improve the activation performance and the electrochemical performance.
Compared with comparative examples 2 to 4, in examples 1 to 30, the electrochemical performance of the negative electrode of the hydrogen storage material, especially the maximum discharge capacity and the self-discharge characteristic, is improved by using the multi-element metal alloy and the rare earth alloy in a matching manner; and the capacity retention rate of the electrode for 100 cycles is improved, and the service life of the negative electrode is prolonged.
By comparing the examples 2, 8, 15 and 4, when M is Fe, the value of a + b + c + d is between 17 and 19 or between 20 and 25, the electrochemical performance of the negative electrode of the samarium-nickel hydrogen storage material can be better, and the service life is longer.
Compared with other examples, the comparison of the examples 24, 27 and 30 shows that the electrochemical performance of the negative electrode of the samarium-nickel hydrogen storage material is better and the service life is longer when the value of a is 12-18 and the value of b is 0.5-2.
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 (10)
1. A samarium-nickel complex hydrogen storage material is characterized by comprising the following components in formula (1):
RExSmyNiaMnbAlcMd(1)
wherein RE is selected from one or more of rare earth metal elements except Sm, and x represents the mole fraction of RE; y represents the molar fraction of Sm; m is selected from one or more of Cu, Fe, Co, Sn, V, W, Cr, Zn, Mo and Si elements, and d represents the mole fraction of M; a represents the mole fraction of Ni; b represents the molar fraction of Mn; c represents the mole fraction of Al;
wherein x is greater than 0, y is greater than or equal to 0.5, and y + x is 6; 23 is more than or equal to a and more than or equal to 12, 7 is more than or equal to b and more than or equal to 0, 7 is more than or equal to c and more than or equal to 0, 5 is more than or equal to d and more than or equal to 0, and 25 is more than or equal to a + b + c + d and more than or equal to 17.
2. The samarium nickel hydride storage material of claim 1 wherein RE is selected from one or more of La, Ce, Pr, Nd, Gd, Y and Sc elements.
3. The samarium nickel polyatomic hydrogen storage material of claim 1 wherein M comprises Co and further comprises one or more of Cu, Fe, Sn, V, W, Cr, and Zn elements; 5 is more than or equal to b + c and is more than 1.
4. The samarium nickel hydride storage material of claim 1 wherein 4 > x >1, 5> y >1 and y/x > 1.6.
5. The samarium nickel hydride storage material of claim 1 wherein 22. gtoreq.a.gtoreq.13, 3. gtoreq.b >0, 3. gtoreq.c >0, 4. gtoreq.d >0.
6. The samarium nickel polyatomic hydrogen storage material of claim 1 wherein M meets one of the following conditions:
1) 22> a >17 when M is Co;
2) 18> a >12, 2> b >0.5 when M is Fe;
3) when M is Cu, 19 is more than or equal to a + b + c + d is more than or equal to 17, or 25 is more than or equal to a + b + c + d and is more than or equal to 20.
7. The samarium nickel polynary hydrogen storage material of claim 1 having a composition represented by one of the following formulae:
La2Sm4Ni15MnAlCu，
La2Sm4Ni15MnAlFe，
La2Sm4Ni15MnAlCo，
La2Sm4Ni15MnAlSn，
La2Sm4Ni15MnAl(VFe)1，
La2Sm4Ni15MnAlW，
La2Sm4Ni17.5MnAl1.5Cu，
La2Sm4Ni17.5MnAl1.5Fe，
La2Sm4Ni17.5MnAl1.5Co，
La2Sm4Ni17.5MnAl1.5Sn，
La2Sm4Ni17.5MnAl1.5(VFe)1，
La2Sm4Ni17.5MnAl1.5W，
La2Sm4Ni20.3MnAl0.5Co，
La2Sm4Ni20.3MnAl0.5Cu，
La2Sm4Ni20.3MnAl0.5Fe，
La2Sm4Ni20.3MnAl0.5Sn，
La2Sm4Ni20.3MnAl0.5(VFe)1，
La2Sm4Ni20.3MnAl0.5W，
La2Sm4Ni17.5MnAl0.5CoCu，
La2Sm4Ni17.5Mn0.5Al0.5CoCuSn0.5，
La2Sm4Ni17.5Mn0.5Al0.5CoCuW0.5，
La2Sm4Ni20.3MnAl0.5Co0.5Cu0.5，
La2Sm4Ni20.3MnAl0.5Zn0.5Cu0.5，
La2Sm4Ni17.5Mn0.5Al0.5FeCuSn0.5，
La2Sm4Ni14.5MnAl0.5CuSn，
La2Sm4Ni14.5MnAl0.5CuCo，
La2Sm4Ni14MnAlCuW0.5Fe0.5，
La2Sm4Ni14.5MnAl(VFe)1Co0.5，
La2Sm4Ni17MnAl0.5W(VFe)1Sn0.5，
La2Sm4Ni19.3MnAl0.5Zn0.5Cu0.5(VFe)1。
8. the method for preparing samarium nickel hydride storage material of any of claims 1 to 7, comprising the steps of:
1) a smelting step: putting the metal raw material into an environment with a relative vacuum degree of-0.01 to-0.1 MPa, and smelting at 1200-1600 ℃ to obtain a smelting product; the integral composition of the metal raw material is shown as a formula (1);
2) a forming step: rapidly quenching and casting the smelted product to obtain an alloy sheet or casting to obtain an alloy ingot;
3) a heat treatment step: and (3) placing the alloy sheet or the alloy ingot in an environment with the absolute vacuum degree of 0.0001-0.05 Pa, and carrying out heat treatment at 750-1050 ℃ for 10-60 h to obtain the samarium-nickel complex hydrogen storage material.
9. A 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 in a mass ratio of 1: 3-8, and the negative electrode active material comprises the samarium-nickel hydride storage material as claimed in any one of claims 1-7; the conductive agent is nickel powder, acetylene black or graphite.
10. A battery, comprising a battery case, and an electrode group and an alkaline electrolyte sealed in the battery case; the electrode group comprises a positive electrode, a negative electrode and a diaphragm;
wherein the diaphragm is a porous vinylon non-woven fabric, a nylon non-woven fabric or a polypropylene fiber membrane;
wherein the negative electrode comprises a negative electrode material, the negative electrode material comprises a negative electrode active material and a conductive agent in a mass ratio of 1: 3-8, and the negative electrode active material comprises the samarium nickel hydride storage material as claimed in any one of claims 1-7; the conductive agent is nickel powder, acetylene black or graphite.
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