CN111118344B - Multi-element gadolinium-containing rare earth hydrogen storage material, cathode, battery and preparation method - Google Patents
Multi-element gadolinium-containing rare earth hydrogen storage material, cathode, battery and preparation method Download PDFInfo
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- CN111118344B CN111118344B CN201911118362.XA CN201911118362A CN111118344B CN 111118344 B CN111118344 B CN 111118344B CN 201911118362 A CN201911118362 A CN 201911118362A CN 111118344 B CN111118344 B CN 111118344B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
- 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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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/70—Furnaces for ingots, i.e. soaking pits
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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
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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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
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
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- 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
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- 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
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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 gadolinium-containing rare earth hydrogen storage material, a negative electrode, a battery and a preparation method. The hydrogen storage material of the invention has the composition as shown in the general formula RExGdyNiz‑a‑b‑cMnaAlbMcIt does not contain Mg element; RE is selected from rare earth metal elements other than Gd; 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 respective elements; x is the number of>0, y is more than or equal to 0.5, and y + x is 6; z is more than or equal to 25 and more than or equal to 17; 7 is more than or equal to a + b>0；5≥c>0. The electrode prepared by the multi-element gadolinium-containing rare earth hydrogen storage material has longer service life and excellent electrochemical performance.
Description
Technical Field
The invention relates to a multi-element gadolinium-containing rare earth hydrogen storage material, a negative electrode, a battery and a preparation method.
Background
The hydrogen storage technology is the key point of the hydrogen energy application in industrialization and scale, and the hydrogen storage material is the important basis of the development of the hydrogen storage technology. The nickel-hydrogen power battery prepared by taking the rare earth hydrogen storage material as the cathode active material has the advantages of high safety, wide environment adaptive temperature range, environmental protection and the like, and is widely applied to the fields of new energy automobiles, smart grid energy storage, communication base station reserve power supplies and the like.
At present, the research and development of hydrogen storage materials with high capacity, long service life and excellent discharge performance are important core contents of the current energy storage technology. RE-Ni series rare earth hydrogen storage materials are widely concerned by researchers in various countries around the world due to excellent electrochemical performance and larger hydrogen storage capacity. However, in order to improve the electrochemical performance of the RE-Ni rare earth hydrogen storage material, Mg is often required to be added, the Mg is volatile and oxidized, and the volatile fine Mg powder is flammable and explosive, which becomes an important problem restricting the development and application of the material.
CN105220015A discloses a high-capacity magnesium-containing rare earth hydrogen storage alloy, which comprises the following chemical compositions in atomic number ratio: mmaMgbNixCoyAlzWherein Mm is one of La, Ce, Pr, Nd and YOne or more of a is more than 0.80 and less than 0.95, a + b is 1, x is more than 2.30 and less than 3.10, y is more than 0.45 and less than 0.70, z is more than 0.01 and less than 1, and x + y + z is more than or equal to 3.3 and less than or equal to 4.0. The hydrogen storage alloy has improved discharge capacity, but its self-discharge characteristics are not good; and because the alloy contains Mg element, the application of the hydrogen storage alloy in the practical production is restricted.
CN1165542A discloses a hydrogen storage alloy with a chemical composition of (R)1-xLx)(Ni1-yMy)zR can be La, Ce, Pr, Nd or a mixture thereof, L can be Gd, Tb, Dy, Ho, Er, Tm, Yb, Y, Sc, Mg, Ca or a mixture thereof, M can be Al, Mn, Fe, Cu, Zr, Ti, Mo, Si, V, Cr, Nb, Hf, Ta, W, B, C or a mixture thereof, x is 0.01-0.1, Y is 0-0.5, and z is 4.5-5. The metal L content of the hydrogen storage alloy is low, and the capacity of the battery is only 320mAh/g at most.
CN1072268C discloses a hydrogen storage alloy with a chemical composition of (R)1-xLx)(Ni1-yMy)zR can be La, Ce, Pr, Nd or a mixture thereof, L can be Gd, Tb, Dy, Ho, Er, Tm, Yb, Y, Sc, Mg, Ca, M can be Al, Mn, Fe, Cu, Zr, Ti, Mo, Si, V, Cr, Nb, Hf, Ta, W, B, C or a mixture thereof, x is 0.05-0.4, Y is 0-0.5, and z is 3-4.5. The metal L content of the hydrogen storage alloy is still low, so that the self-discharge characteristic is poor, and the activation period is long.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a hydrogen storage material containing a plurality of gadolinium-containing rare earths, which has excellent self-discharge characteristics. Further, the hydrogen storage material of the present invention has a longer service life. Furthermore, the complete activation of the hydrogen storage material of the present invention requires fewer cycles and has good cycle stability.
Another object of the present invention is to provide a method for preparing the above-mentioned multi-element gadolinium-containing rare earth hydrogen storage material, which can stably obtain a hydrogen storage material with excellent self-discharge characteristics.
It is still another object of the present invention to provide a hydrogen storage material negative electrode.
It is still another object of the present invention to provide a nickel-hydrogen secondary battery.
In one aspect, the invention provides a multi-element gadolinium-containing rare earth hydrogen storage material, the composition of the hydrogen storage material is shown as a general formula (1), and the hydrogen storage material does not contain Mg:
RExGdyNiz-a-b-cMnaAlbMc (1)
wherein RE is selected from rare earth metal elements other than Gd;
wherein 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 respective elements;
wherein x is greater than 0, y is greater than or equal to 0.5, and y + x is 6; z is more than or equal to 25 and more than or equal to 17; 7 is more than or equal to a + b and is more than 0; 5 is more than or equal to c and more than 0.
According to the hydrogen storage material of the present invention, preferably RE is selected from one or more of La, Ce, Pr, Nd, Y, Sm and Sc elements.
According to the hydrogen storage material of the present invention, y/x is preferably 1.6 or more.
According to the hydrogen storage material of the present invention, preferably, 3. gtoreq.x >1, 5> y. gtoreq.3.5, and y/x. gtoreq.1.8.
According to the hydrogen storage material of the present invention, preferably, 3. gtoreq.a.gtoreq.0.3, 2. gtoreq.b.gtoreq.0.2, 5. gtoreq.c >0, 23> z.gtoreq.18.
According to the hydrogen storage material of the present invention, preferably, M satisfies one of the following conditions:
(1) when M is Fe element, 25> z is more than or equal to 21;
(2) m contains one or more of Cu, Fe, Co, Zn, Sn and W elements, and M cannot contain Cu and Fe elements at the same time; or
(3) When M is W element, 22> z ≧ 18.
The hydrogen storage material according to the present invention preferably has a composition represented by one of the following formulae:
La2Gd4Ni18MnAlCo，
La2Gd4Ni18MnAlW，
La2Gd4Ni20.3MnAl0.5Cu，
La2Gd4Ni20.3MnAl0.5Fe，
La2Gd4Ni20.3MnAl0.5Sn，
La2Gd4Ni17.5MnAl0.5CoCu, or
La2Gd4Ni20.3MnAl0.5Zn0.5Cu0.5。
On the other hand, the invention also provides a preparation method for preparing the hydrogen storage material, which comprises the following steps:
(1) smelting a metal raw material with the integral composition meeting the general formula (1) in a vacuum smelting environment filled with inert gas, and then forming an alloy sheet or an alloy ingot; the relative vacuum degree of a vacuum smelting environment is-0.01 to-0.1 MPa, and the smelting temperature is 1200 to 1600 ℃;
(2) carrying out heat treatment on an alloy sheet or an alloy ingot in a vacuum heat treatment environment filled with inert gas to obtain the hydrogen storage material; the absolute vacuum degree of the vacuum heat treatment environment is 0.0001-0.05 Pa, the heat treatment temperature is 700-1000 ℃, and the heat treatment time is 10-60 h.
In still another aspect, the present invention also provides a hydrogen storage material negative electrode, including a negative electrode material, the negative electrode material including a negative electrode active material and a conductive agent, the negative electrode active material including the hydrogen storage material as described above.
In still another aspect, the present invention also provides a nickel-hydrogen secondary battery including 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, and the negative electrode is the negative electrode made of the hydrogen storage material.
The multi-element gadolinium-containing rare earth hydrogen storage material has excellent self-discharge characteristics. In the preferred technical scheme of the invention, the self-discharge characteristic of the hydrogen storage material is further improved and the service life of the hydrogen storage material is prolonged by adjusting the proportion of each element.
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.
In the present invention, the inert gas includes nitrogen, argon, or the like.
In the present invention, the alkali metal element means a metal element of group IA of the periodic table, for example, lithium, sodium, potassium, rubidium, and cesium.
< hydrogen storage Material containing a plurality of rare earths containing gadolinium >
The composition of the multi-element gadolinium-containing rare earth hydrogen storage material is shown as a general formula (1):
RExGdyNiz-a-b-cMnaAlbMc (1)。
the multi-element gadolinium-containing rare earth hydrogen storage material of the invention does not contain other additional components except some inevitable impurities. According to one embodiment of the invention, the multi-component gadolinium-containing rare earth hydrogen storage material does not contain Mg; preferably, the Mg element and the alkali metal element are not contained. The raw material does not contain Mg element, so that the material is not inflammable and explosive any more, and the development of the multi-element gadolinium-containing rare earth hydrogen storage material is promoted.
RE of the present invention may be selected from one or more of rare earth metal elements except Gd. RE may be selected from one or more of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y), and scandium (Sc). Preferably, RE is selected from one or more of La, Ce, Pr, Nd, Y, Sm and Sc elements; more preferably, RE is selected from one or more of the La, Ce and Y elements. According to one embodiment of the invention, RE comprises La. According to another embodiment of the present invention, RE comprises La, and La is 50 to 100 mol% of the total mole number of RE. According to yet another embodiment of the invention RE is La.
In the present invention, x represents the mole fraction of RE. RE is an essential element, and x >0. Preferably, 4 ≧ x ≧ 1. More preferably, 3 ≧ x > 1. Most preferably, 2.5 ≧ x ≧ 2.
Gd is rare earth metal gadolinium. y represents the mole fraction of Gd. In the present invention, Gd is an essential element and y is 0.5 or more. Preferably, 5 ≧ y ≧ 1. More preferably, 5> y.gtoreq.3.5. Most preferably, 5> y ≧ 4.
The rare earth metal element and the Gd element are combined, the proportion of the rare earth metal element and the Gd element is adjusted, the content of the Gd element is obviously improved, and the service life of the hydrogen storage material is prolonged.
According to one embodiment of the invention, y/x.gtoreq.1.6; preferably, y/x is greater than or equal to 1.8; more preferably, 3.0. gtoreq.y/x. gtoreq.2.0. The mole ratio of Gd and RE is controlled in the range, so that the amorphization can be inhibited, the electrochemical performance of the hydrogen storage material can be improved, the cycling stability and the service life of the hydrogen storage material electrode can be prolonged, and the cycling times required by the complete activation of the hydrogen storage material electrode can be reduced. 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 reduced to two times or less, the capacity retention rate of the hydrogen storage material electrode at the 100 th time is improved, and the service life is prolonged.
In the present invention, x + y is 6. According to one embodiment of the invention, 3 ≧ x >1, 5> y ≧ 3.5, 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.
Mn is a metal element manganese, and a represents the molar fraction of Mn. In the invention, a is more than or equal to 3 and more than or equal to 0.3. Preferably, 2.5. gtoreq.a.gtoreq.0.35. More preferably, 2. gtoreq.a.gtoreq.1.
Al is a metal element aluminum, and b represents a mole fraction of Al. In the invention, b is more than or equal to 2 and more than or equal to 0.2. Preferably, 1.8. gtoreq.b.gtoreq.0.3. More preferably, 1.5. gtoreq.b.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, Zn, Sn and W. More preferably, M is selected from one or more of Cu, Fe, Co, Zn, Sn and W elements, and M cannot contain both Cu and Fe elements. c represents the mole fraction of M. In the present invention, 5. gtoreq.c >0. Preferably, 4 ≧ c > 0; more preferably, 2.5. gtoreq.c.gtoreq.0.5. The self-discharge performance of the hydrogen storage material can be improved by adopting the M element.
Ni is metallic element nickel, and z-a-b-c represents the mole fraction of Ni. In the present invention, Ni is an essential element, and z is 25. gtoreq.17. Preferably, 23> z ≧ 18. More preferably, 22.8. gtoreq.z.gtoreq.18. 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 and Al are both essential elements. In the present invention, 7. gtoreq.a + b >0. Preferably 5 ≧ a + b >0. More preferably, 3. gtoreq.a + b. gtoreq.1. In certain embodiments, 3. gtoreq.a.gtoreq.0.3, 2. gtoreq.b.gtoreq.0.2, 5. gtoreq.c >0, 23> z.gtoreq.18. In certain preferred embodiments, 1. gtoreq.a.gtoreq.0.5, 1.5. gtoreq.b.gtoreq.0.5, 2.5. gtoreq.c.gtoreq.0.5, 22.8> z.gtoreq.18 and 3. gtoreq.a + b.gtoreq.1. Controlling the contents of Mn and Al within the above ranges can further improve the high-temperature discharge characteristics and the self-discharge characteristics of the hydrogen storage material.
According to an embodiment of the present invention, when M is an Fe element, 25> z.gtoreq.21.
According to yet another embodiment of the present invention, M is selected from one or more of Cu, Fe, Co, Zn, Sn and W elements, and M cannot contain both Cu and Fe elements.
According to still another embodiment of the present invention, 22> z.gtoreq.18 when M is an element W.
In certain embodiments, 3 ≧ x >1, 5> y ≧ 3.5, x + y ≧ 6, y/x ≧ 1.8, 23> z ≧ 18, 5 ≧ a + b >0. The invention further prolongs the service life of the hydrogen storage material electrode by adjusting the molar ratio of each element, and has more excellent self-discharge performance.
In other embodiments, 2.5 ≧ x ≧ 2, 5> y ≧ 4, y/x ≧ 2.0, x + y ≧ 6, 2 ≧ a ≧ 1, 1.5 ≧ b ≧ 0.5, 2.5 ≧ c ≧ 0.5, 22.8 ≧ z ≧ 18 and 3 ≧ a + b ≧ 1. This allows for a compromise between service life and self-discharge performance, both of which remain at a high level.
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:
La2Gd4Ni18MnAlCo，
La2Gd4Ni18MnAlW，
La2Gd4Ni20.3MnAl0.5Cu，
La2Gd4Ni20.3MnAl0.5Fe，
La2Gd4Ni20.3MnAl0.5Sn，
La2Gd4Ni17.5MnAl0.5CoCu, or
La2Gd4Ni20.3MnAl0.5Zn0.5Cu0.5。
< preparation method >
The preparation method of the multi-element gadolinium-containing rare earth hydrogen storage material comprises a high-temperature smelting and 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.
Smelting metal raw materials, then forming an alloy sheet or an alloy ingot, and obtaining the multi-element gadolinium-containing rare earth hydrogen storage material through heat treatment, wherein the method comprises the following specific steps: (1) an alloy sheet or an alloy ingot forming step and (2) a heat treatment step.
In the step (1), the raw materials are smelted in a vacuum smelting environment filled with inert gas, and then an alloy sheet is obtained by adopting a quick quenching and melt-spinning belt or an alloy ingot is cast. The overall composition of the raw material satisfies the general formula (1) RExGdyNiz-a-b- cMnaAlbMc. The elements and their mole fractions are as described above and will not be described further herein. The inert gas may be high purity nitrogen or high purity argon, preferably argon.
The raw materials can be smelted by a vacuum smelting furnace. Firstly, the raw materials are placed in a vacuum smelting furnace, then the vacuum smelting furnace is vacuumized, and inert gas is charged again to obtain a vacuum smelting environment. In certain embodiments, the vacuum melting furnace is evacuated to an absolute vacuum of 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 until the absolute vacuum degree is 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 vacuum melting furnace is heated to start melting. The smelting temperature is 1200-1600 ℃, preferably 1250-1500 ℃, and more preferably 1300-1400 ℃. And after the metal raw materials in the furnace are completely melted, an alloy sheet is obtained by adopting a quick quenching melt-spun belt or an alloy ingot melt-spun belt is cast. Such smelting conditions are favorable for prolonging the service life of the hydrogen storage material and improving the self-discharge characteristic. According to one embodiment of the invention, the molten liquid is cast on a cooling copper roller and is spun into an alloy sheet with the thickness of 0.1-0.4 mm; preferably, the alloy sheet with the thickness of 0.15-0.35 mm is formed by spinning; more preferably, the strip is spun into an alloy sheet with the thickness of 0.2-0.3 mm.
In the step (2), the alloy sheet or the alloy ingot is subjected to heat treatment in a vacuum heat treatment environment filled with inert gas to obtain the multi-element gadolinium-containing rare earth 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 700-1000 ℃, preferably 750-950 ℃, and more preferably 850-900 ℃. The heat treatment time can be 10-60 h, preferably 15-50 h, and more preferably 15-35 h. 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 and reducing self-discharge.
According to one embodiment of the present invention, a metal raw material is placed in a vacuum melting furnace in the order of Ni, Mn, Al, M, RE, Gd, 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, inert gas is filled until the relative vacuum degree is-0.01 to-0.1 MPa, and a vacuum smelting environment is formed. And 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 molten liquid. Casting the molten liquid to a cooling copper roller, and casting the molten liquid into an alloy sheet with the thickness of 0.1-0.4 mm, and casting the alloy sheet into an alloy ingot.
< negative electrode of Hydrogen storage Material >
The negative electrode of the hydrogen storage material comprises a negative electrode material, and the negative electrode material comprises a negative electrode active substance and a conductive agent. The negative active material comprises a gadolinium-containing rare earth hydrogen storage material as described above. The negative electrode material is supported on a negative electrode current collector. The negative current collector includes, but is not limited to, nickel foam. The general formula of the composition of the multi-element gadolinium-containing rare earth hydrogen storage material is RExGdyNiz-a-b-cMnaAlbMc. The elements and the mole fractions thereof in the multi-element gadolinium-containing rare earth hydrogen storage material are as described above. The negative electrode of the multi-element gadolinium-containing rare earth hydrogen storage material has long service life and excellent self-discharge characteristic.
In some embodiments, the particle size of the multi-element gadolinium-containing rare earth 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 gadolinium-containing rare earth hydrogen storage material loaded on the negative current collector is 200-300 meshes; the mass ratio of the multi-element gadolinium-containing rare earth 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 hydrogen storage material powder containing multiple gadolinium-containing rare earth 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.
< Nickel-hydrogen secondary Battery >
The nickel-hydrogen secondary 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 cathode is the hydrogen storage material cathode as described above.
In the present invention, the battery case may be made of a material that is conventional in the art. The alkaline electrolyte may be an aqueous potassium hydroxide solution or an aqueous potassium hydroxide solution containing a small amount of LiOH. The diaphragm in the electrode group can be porous vinylon non-woven fabric, nylon non-woven fabric or polypropylene fiber membrane, etc.; the positive electrode can be nickel hydroxide, e.g., sintered Ni (OH) with excess capacity2a/NiOOH electrode.
Example 1
According to the formulation of Table 1, the metal raw materials Ni, Mn, Al, M, La and Gd were placed in the vacuum melting furnace in sequence from the bottom to the top of the vacuum melting furnace. In this example, M is Cu and Zn. Vacuumizing the vacuum melting furnace to an absolute vacuum degree of 20Pa, then filling inert gas argon to normal pressure, vacuumizing the vacuum melting furnace to an absolute vacuum degree of 20Pa, 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 ℃, stopping heating after the raw materials in the vacuum smelting furnace are completely melted, casting to a cooling copper roller, and spinning to obtain an alloy sheet with the thickness of 0.3 mm.
And (3) placing the alloy sheet in an environment with argon filled absolute vacuum degree of 0.01Pa, and carrying out heat treatment for 16h at 875 ℃ to obtain the multi-element gadolinium-containing rare earth hydrogen storage material.
Examples 2 to 30
A multi-component gadolinium-containing rare earth hydrogen storage material was prepared according to the formulation of table 1, following the procedure of example 1.
Comparative example 1
The raw materials were formulated according to the formulation of table 1 with a composition of 8.3 parts by weight La, 16.3 parts by weight Ce, 1.7 parts by weight Pr, 6.9 parts by weight Nd, 0.75 parts by weight Gd, 50.4 parts by weight Ni, 1.3 parts by weight Al, 7.6 parts by weight Co, 6.5 parts by weight Mn and 0.3 parts by weight Fe. And (3) putting the raw materials into a vacuum melting furnace in an argon atmosphere for melting to prepare an alloy melt. And casting the alloy melt to a cooling copper roller, and spinning to obtain an alloy sheet with the thickness of 0.3 mm. The obtained alloy sheet was heat-treated at 950 ℃ for 4 hours in an argon atmosphere to obtain a hydrogen storage material.
Experimental example 1
The multi-element gadolinium-containing rare earth hydrogen storage materials prepared in examples 1 to 30 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 arranged between two pieces of foamed nickel serving as a current collector, and a nickel belt serving as a tab is clamped at the same time to prepare the gadolinium-containing rare earth hydrogen storage material cathode 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 an open type three-electrode system for testing electrochemical performance is a gadolinium-containing rare earth 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 open cell 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. S100The larger the value is for the capacity retention ratio of the electrode at 100 th time,indicating 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, the Gd content of the rare earth hydrogen storage material electrodes prepared in examples 1 to 30 is significantly increased compared with the hydrogen storage material electrode prepared in comparative example 1. The 100 th time capacity retention rate of the hydrogen storage material electrode is more than 92 percent and can reach as high as 98.2 percent; capacity retention rate SD after 72 hours storage72Above 92%, up to 94.6%; the number of times required for electrode activation is 2 or less, and the cycle stability is high. Therefore, the content of gadolinium (Gd) in the hydrogen storage material is increased, the proportion of other elements is adjusted, the service life of the electrode can be prolonged, and the electrochemical performance of the electrode is improved.
It is understood from the comparison of examples 2, 8 and 15 that when M is Fe, the value of z is in the range of 25 to 21, and the self-discharge performance of the gadolinium-rich rare earth hydrogen storage material can be better.
It is understood from the comparison of examples 6, 12 and 18 that when M is W, the value of z is in the range of 22 to 18, and the self-discharge performance of the gadolinium-rich rare earth hydrogen storage material can be improved.
As can be seen from the comparison of the examples 24, 27 and 30 with other examples, the multielement gadolinium-containing rare earth hydrogen storage material is used for improving the electrochemical performance of the hydrogen storage material electrode by adding one or more of Cu, Fe, Co, Zn, Sn and W elements; however, when M contains both Cu and Fe elements, the improvement effect is reduced.
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 (9)
1. The hydrogen storage material is characterized in that the composition of the hydrogen storage material is shown as a general formula (1), and the hydrogen storage material does not contain Mg:
RExGdyNiz-a-b-cMnaAlbMc (1)
wherein RE is selected from one or more of La, Ce, Pr, Nd, Sm and Sc elements;
wherein 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 respective elements;
wherein, x is more than or equal to 3 and more than 1, y is more than or equal to 5 and more than or equal to 3.5, y/x is more than or equal to 1.8, and y + x is 6; z is more than or equal to 22.8 and more than or equal to 18; a + b is more than or equal to 3 and more than or equal to 1; a is more than or equal to 1 and more than or equal to 0.5; b is more than or equal to 1.5 and more than or equal to 0.5; 2.5 is more than or equal to c and is more than 0.5.
2. Hydrogen storage material according to claim 1, characterized in that RE is La.
3. Hydrogen storage material according to claim 1, characterized in that 3.0. gtoreq.y/x. gtoreq.2.0.
4. Hydrogen storage material according to claim 1, characterized in that 2.5. gtoreq.x.gtoreq.2, 5> y.gtoreq.4 and 3. gtoreq.y/x.gtoreq.2.
5. A hydrogen storage material according to claim 1, characterized in that M fulfils one of the following conditions:
(1) when M is Fe element, 25> z is more than or equal to 21;
(2) m is selected from one or more of Cu, Fe, Co, Zn, Sn and W elements, and M cannot simultaneously contain Cu and Fe elements; or
(3) When M is W element, 22> z ≧ 18.
6. Hydrogen storage material according to claim 1, characterized in that it has a composition represented by one of the following formulae:
La2Gd4Ni18MnAlCo，
La2Gd4Ni18MnAlW，
La2Gd4Ni20.3MnAl0.5Cu，
La2Gd4Ni20.3MnAl0.5Fe，
La2Gd4Ni20.3MnAl0.5Sn，
La2Gd4Ni17.5MnAl0.5CoCu, or
La2Gd4Ni20.3MnAl0.5Zn0.5Cu0.5。
7. A method for producing a hydrogen storage material according to any one of claims 1 to 6, comprising the steps of:
(1) smelting a metal raw material with the integral composition meeting the general formula (1) in a vacuum smelting environment filled with inert gas, and then forming an alloy sheet or an alloy ingot; the relative vacuum degree of a vacuum smelting environment is-0.01 to-0.1 MPa, and the smelting temperature is 1200 to 1600 ℃;
(2) carrying out heat treatment on an alloy sheet or an alloy ingot in a vacuum heat treatment environment filled with inert gas to obtain the hydrogen storage material; the absolute vacuum degree of the vacuum heat treatment environment is 0.0001-0.05 Pa, the heat treatment temperature is 700-1000 ℃, and the heat treatment time is 10-60 h.
8. A hydrogen storage material negative electrode, characterized by comprising a negative electrode material, wherein the negative electrode material comprises a negative electrode active material and a conductive agent, and the negative electrode active material comprises the hydrogen storage material according to any one of claims 1 to 6.
9. A nickel-hydrogen secondary battery is characterized by comprising a battery shell, an electrode group and an 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, wherein the negative electrode is the hydrogen storage material negative electrode in claim 8.
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