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WO2011111699A1 - Alliage de stockage d'hydrogène et batterie nickel-hydrogène - Google Patents

Alliage de stockage d'hydrogène et batterie nickel-hydrogène Download PDF

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Publication number
WO2011111699A1
WO2011111699A1 PCT/JP2011/055368 JP2011055368W WO2011111699A1 WO 2011111699 A1 WO2011111699 A1 WO 2011111699A1 JP 2011055368 W JP2011055368 W JP 2011055368W WO 2011111699 A1 WO2011111699 A1 WO 2011111699A1
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Prior art keywords
hydrogen storage
storage alloy
formula
atomic
nickel
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PCT/JP2011/055368
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English (en)
Japanese (ja)
Inventor
尾崎　哲也
学 金本
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株式会社Ｇｓユアサ
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Priority to JP2012504473A priority Critical patent/JP5796787B2/ja
Publication of WO2011111699A1 publication Critical patent/WO2011111699A1/fr

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Classifications

    • 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
    • H01M10/34—Gastight accumulators
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
    • C01B3/0047—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof
    • C01B3/0057—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof also containing nickel
    • 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
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0433—Nickel- or cobalt-based alloys
    • 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
    • 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
    • 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
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Definitions

  • the present invention relates to a hydrogen storage alloy and a nickel metal hydride storage battery including a negative electrode including the hydrogen storage alloy.
  • Nickel metal hydride storage batteries have high energy density, so they are used as power sources for small electronic devices such as digital cameras and notebook computers, and because the operating voltage is equivalent to and compatible with primary batteries such as alkaline manganese batteries. As a substitute for the primary battery, the battery is widely used, and the demand for the battery is expanding dramatically.
  • This type of nickel-metal hydride storage battery is usually configured to include a nickel electrode containing a positive electrode active material mainly composed of nickel hydroxide, a negative electrode mainly composed of a hydrogen storage alloy, a separator, and an alkaline electrolyte.
  • the hydrogen storage alloy which is the main material of the negative electrode, has a significant effect on the performance of nickel-metal hydride storage batteries such as discharge capacity and energy density, and various hydrogen storage alloys have been studied in the past. Has been.
  • rare earth-Mg a hydrogen storage alloy containing rare earth elements, Mg, and Ni
  • rare earth-Mg an alloy that can exhibit a discharge capacity that exceeds the discharge capacity when using an AB 5 rare earth-Ni hydrogen storage alloy.
  • Ni-based hydrogen storage alloy has attracted attention.
  • a rare earth element, Mg, and a combination of Ni and various metals have been proposed (Patent Document 1).
  • rare earth-Mg—Ni-based hydrogen storage alloys for example, in order to increase the discharge capacity of a nickel-metal hydride storage battery equipped with a negative electrode containing the hydrogen storage alloy, the type and amount of the metal blended in the hydrogen storage alloy are changed. Adjustments are made. However, the specific gravity of such rare earth-Mg—Ni-based hydrogen storage alloys may decrease depending on the type and amount of metal mixed in the hydrogen storage alloy, and the energy density of the battery cannot necessarily be increased.
  • the conventional rare earth-Mg-Ni-based hydrogen storage alloy has a relatively high specific gravity, so that the energy density of the battery can be made excellent, and the discharge capacity of the nickel-metal hydride storage battery is compared. There is a problem that it is not always possible to satisfy the high level.
  • the present invention is a hydrogen storage alloy that can be included in the negative electrode of a nickel-metal hydride storage battery, the specific gravity of which is relatively high, and the energy density of the battery is excellent, and It is an object of the present invention to provide a hydrogen storage alloy that simultaneously satisfies that the discharge capacity of a nickel metal hydride storage battery is relatively high. Another object of the present invention is to provide a nickel metal hydride storage battery including a negative electrode containing the hydrogen storage alloy.
  • the hydrogen storage alloy according to the present invention has a chemical composition represented by the following general formula (1): R1v Mgw Cax R2y Formula (1)
  • R1 is one or more elements selected from rare earth elements
  • R2 is Ni or a part of Ni is selected from the group consisting of Al, Co, Cu, Mn, Fe, Cr and Zn.
  • Formula (2) v, w, x, and y are the following formulas (3), (4), and (5).
  • the formula (5) is preferably represented by 1.0 ⁇ w / x ⁇ 2.5. According to the hydrogen storage alloy in which the formula (5) is represented by 1.0 ⁇ w / x ⁇ 2.5, it is possible to more reliably obtain the performance that the battery has an excellent energy density and a relatively high discharge capacity. Can do.
  • the hydrogen storage alloy according to the present invention is one or more elements selected from the group consisting of Al, Co, Cu, Mn, Fe, Cr, and Zn in which a part of Ni of R2 is substituted. Is preferably more than 0 atomic% and 2.2 atomic% or less. With this configuration, the capacity maintenance rate of the battery can be improved.
  • a part of Ni in R2 is substituted with Al and the Al content is more than 0 atomic% and not more than 2.2 atomic%. With this configuration, the capacity maintenance rate of the battery can be improved.
  • Ce as R1 is contained in an amount of 0 atomic% to 2.3 atomic%. With this configuration, the capacity maintenance rate of the battery can be improved.
  • the hydrogen absorbing alloy according to the present invention preferably contains a crystal phase having a Pr 5 Co 19 type crystal structure 11 mass% or more.
  • the hydrogen storage alloy according to the present invention has a chemical composition represented by the following general formula (1 ′), R1v Mgw Cax R2y R3z Formula (1 ')
  • R1 is one or more elements selected from rare earth elements
  • R2 is Ni or a part of Ni is selected from the group consisting of Al, Co, Cu, Mn, Fe, Cr and Zn.
  • a hydrogen storage alloy that is substituted with one or more selected elements, and R3 is an element other than R1, Mg, Ca, and R2,
  • v, w, x, and y 100
  • Formula (2) v, w, x, and y are the following formulas (3), (4), and (5).
  • Formula (4) 0.8 ⁇ w / x ⁇ 2.5 (5)
  • z satisfies 0 ⁇ z ⁇ 0.4.
  • the hydrogen storage alloy according to the present invention has a chemical composition represented by the following general formula (1 ′), R1v Mgw Cax R2y R3z Formula (1 ')
  • R1 is one or more elements selected from rare earth elements
  • R2 is Ni or a part of Ni is selected from the group consisting of Al, Co, Cu, Mn, Fe, Cr and Zn.
  • a hydrogen storage alloy that is substituted with one or more selected elements, and R3 is an element other than R1, Mg, Ca, and R2,
  • v + w + x + y 100
  • Formula (2) v, w, x, y satisfy 13.0 ⁇ v ⁇ 18.0, 2.2 ⁇ w ⁇ 5.6, 2.0 ⁇ x ⁇ 5.0, 75.0 ⁇ y ⁇ 80.0
  • Z satisfies 0 ⁇ z ⁇ 0.4
  • w and x satisfy 0.8 ⁇ w / x ⁇ 2.5.
  • the nickel-metal hydride storage battery according to the present invention includes a negative electrode containing the hydrogen storage alloy.
  • the hydrogen storage alloy according to the present invention can be included in the negative electrode of a nickel metal hydride storage battery, and can have an excellent battery energy density due to its relatively high specific gravity, and discharge of the nickel metal hydride storage battery There is an effect of satisfying simultaneously that the capacity is relatively high.
  • the hydrogen storage alloy of the embodiment of the present invention has a chemical composition represented by the following general formula (1): R1v Mgw Cax R2y Formula (1)
  • R1 is one or more elements selected from rare earth elements
  • R2 is Ni or a part of Ni is selected from the group consisting of Al, Co, Cu, Mn, Fe, Cr and Zn.
  • Formula (2) v, w, x, and y are the following formulas (3), (4), and (5).
  • the hydrogen storage alloy of the embodiment of the present invention has a chemical composition represented by the following general formula (1 ′), R1v Mgw Cax R2y R3z Formula (1 ')
  • R1 is one or more elements selected from rare earth elements
  • R2 is Ni or a part of Ni is selected from the group consisting of Al, Co, Cu, Mn, Fe, Cr and Zn.
  • a hydrogen storage alloy that is substituted with one or more selected elements, and R3 is an element other than R1, Mg, Ca, and R2,
  • v, w, x, and y 100
  • Formula (2) v, w, x, and y are the following formulas (3), (4), and (5).
  • Formula (4) 0.8 ⁇ w / x ⁇ 2.5 (5)
  • z satisfies 0 ⁇ z ⁇ 0.4.
  • the hydrogen storage alloy contains rare earth elements, Mg, and Ni, and further Ca.
  • the number of Ni atoms is more than three times the total number of rare earth elements, Mg atoms, and Ca atoms. Greatly less than 5 times.
  • the number of Ni atoms is 3.4 times or more and 3.7 times or less of the total of the number of rare earth elements, the number of Mg atoms, and the number of Ca atoms. That is, the so-called B / A ratio is usually more than 3 and less than 5, preferably 3.4 or more and 3.7 or less.
  • A represents any element selected from the group consisting of rare earth elements and Mg
  • B represents any element selected from the group consisting of transition metal elements and Al.
  • a in the B / A ratio of the hydrogen storage alloy represents an element selected from the group consisting of rare earth elements such as La, Sm, Pr, and Nd, Mg, and Ca, and B represents Ni, It represents one or more elements selected from the group consisting of Al, Co, Cu, Mn, Fe, Cr and Zn.
  • R1 is preferably one or more elements selected from the group consisting of La, Ce, Pr, Nd, Sm, and Y. More preferably, the element contains at least La or Nd.
  • the hydrogen storage alloy preferably contains 2.3 atomic% or less of Ce.
  • Ce is contained in an amount of 2.3 atomic% or less, there is an advantage that the cycle characteristics of the battery and the capacity retention rate of the battery can be further improved.
  • atomic% refers to the percentage of the number of specific atoms with respect to the total number of atoms present. Therefore, for example, an alloy containing 1 atomic% of calcium contains one calcium atom out of 100 atoms of the alloy.
  • R2 is preferably Ni or a part of Ni substituted by Al or Co, and is Ni or a part of Ni. More preferably, is substituted with Al.
  • the hydrogen storage alloy preferably contains more than 0 atomic% and 2.2 atomic% or less of elements other than Ni in the R2. With this configuration, the capacity maintenance rate of the battery can be improved.
  • an element other than Ni in R2 is Al, and the Al content is more than 0 atomic% and not more than 2.2 atomic%. More preferably, R2 is Ni without containing Al.
  • the hydrogen storage alloy can surely improve the energy density of the battery and can surely improve the discharge capacity of the battery. 3 is preferable, and z ⁇ 0.2 is more preferable.
  • z is very close to 0, that is, the chemical composition is substantially the same as that represented by the general formula (1).
  • z 0, that is, the chemical composition is represented by the general formula (1).
  • the hydrogen storage alloy is provided with two or more crystal phases having different crystal structures, and preferably these two or more crystal phases are laminated in the c-axis direction of the crystal structure.
  • the crystal phase include a crystal phase composed of a rhombohedral La 5 MgNi 24 type crystal structure (hereinafter also simply referred to as La 5 MgNi 24 phase), and a crystal phase composed of a hexagonal Pr 5 Co 19 type crystal structure (hereinafter simply referred to as simply “La 5 MgNi 24 phase”).
  • Pr 5 Co 19 phase crystal phase composed of rhombohedral Ce 5 Co 19 type crystal structure (hereinafter also simply referred to as Ce 5 Co 19 phase), crystal phase composed of hexagonal Ce 2 Ni 7 type crystal structure (Hereinafter also simply referred to as Ce 2 Ni 7 phase), crystal phase composed of rhombohedral Gd 2 Co 7 type crystal structure (hereinafter also simply referred to as Gd 2 Co 7 phase), and hexagonal CaCu 5 type crystal structure crystalline phase (hereinafter, simply referred to as CaCu 5 phase), crystal phase comprising a cubic AuBe 5 type crystal structure (hereinafter, simply referred to as AuBe 5 phase) crystal phase comprising a rhombohedral PuNi 3 type crystal structure Hereinafter also referred to simply as PuNi 3-phase), and the like.
  • Ce 5 Co 19 phase crystal phase composed of hexagonal Ce 2 Ni 7 type crystal structure (Hereinafter also simply referred to as Ce 2 Ni 7 phase)
  • La 5 MgNi 24 phase, Pr 5 Co 19 phase, Ce 5 Co 19 phase, and the hydrogen storage alloy having two or more selected from the group consisting of Ce 2 Ni 7 phase is preferably used.
  • the hydrogen storage alloy having these crystal phases has excellent characteristics that the difference between the expansion and contraction ratios between the crystal phases is small, so that the distortion is not easily generated and the deterioration is not easily caused by repeated storage and release of hydrogen.
  • the hydrogen storage alloy is formed by laminating two or more crystal phases having different crystal structures in the c-axis direction of the crystal structure, distortion of the crystal phase when hydrogen is stored by charging is adjacent to the hydrogen storage alloy. Can be relaxed by other crystalline phases. Therefore, the inclusion of the hydrogen storage alloy has the advantage that the negative electrode is less likely to be pulverized and is less likely to deteriorate even if the storage and release of hydrogen are repeated by charging and discharging.
  • the La 5 MgNi 24 type crystal structure is a crystal structure in which 4 units of AB 5 units are inserted between A 2 B 4 units, and the Pr 5 Co 19 type crystal structure is A 2 B It is a crystal structure in which 3 units of AB 5 units are inserted between 4 units, and Ce 5 Co 19 type crystal structure is that 3 units of AB 5 units are inserted between 4 units of A 2 B 4 It is a crystal structure, and the Ce 2 Ni 7 type crystal structure is a crystal structure in which two AB 5 units are inserted between A 2 B 4 units. What is the Gd 2 Co 7 type crystal structure? , 2 units of AB 5 units are inserted between A 2 B 4 units, and the AuBe 5 type crystal structure is a crystal structure composed of only A 2 B 4 units.
  • the A 2 B 4 unit is a structural unit having a hexagonal MgZn 2 type crystal structure (C14 structure) or a hexagonal MgCu 2 type crystal structure (C15 structure), and the AB 5 unit is a hexagonal CaCu 5 It is a structural unit with a type crystal structure.
  • the stacking order of the crystal phases is not particularly limited, and a combination of specific crystal phases may be stacked with repeating periodicity.
  • the phase may be laminated randomly and without periodicity.
  • each crystal phase is not particularly limited, but the content of the crystal phase having the La 5 MgNi 24 type crystal structure is 0 to 50% by mass, and the Pr 5 Co 19 type crystal structure.
  • the rate is preferably 0 to 65% by mass.
  • the hydrogen storage alloy preferably contains 11 to 73% by mass, more preferably 37 to 73% by mass, of a crystal phase having a Pr 5 Co 19 type crystal structure containing Ca.
  • the crystal phase having each crystal structure can be identified by performing X-ray diffraction measurement on the ground alloy powder and analyzing the obtained X-ray diffraction pattern by the Rietveld method. Moreover, the content rate of the crystal phase which has each crystal structure is determined by the method described in the Example.
  • the denominator on the left side of the above formula (3) is A for all the number of sites in the hydrogen storage alloy obtained based on the fact that the hydrogen storage alloy is composed of A 2 B 4 units and AB 5 units.
  • 2 B Indicates the ratio of the number of A sites in 4 units. That is, the denominator on the left side of the formula (3) represents the number of A sites of A 2 B 4 units when the total number of sites in the hydrogen storage alloy represented by the chemical composition of the formula (1) is represented by v + w + x + y. . In detail, it is calculated
  • the number of sites where the A side element is arranged is represented by v + w + x with respect to the number of all sites represented by v + w + x + y in the crystal of the hydrogen storage alloy, and the number of sites where the B side element is arranged is y It is represented by On the other hand, the ratio of the number of AB 5 units to the number of A 2 B 4 units k, i.e., the ratio between the A 2 B 4 units and AB 5 units 1: When k, site A side element is arranged The number can also be expressed as (2 + k) ⁇ n. The number of sites where the B-side element is arranged can also be expressed as (4 + 5k) ⁇ n.
  • n means the number of crystal units when one A 2 B 4 unit and k AB 5 units are crystal units. From the above relationship, the following equation (A) can be obtained.
  • k can be represented by the following formula (C) by modifying the formula (B).
  • the number of A sites of A 2 B 4 units when the number of all sites is represented by v + w + x + y is represented by the following formula (D). That is, since the the AB 5 units against A 2 B 4 units 1 exists k, the total number of A site is represented by (2 + k) ⁇ n, the number of A-site in A 2 B 4 units is represented by 2n The The total number of A sites is also expressed as v + w + x. Therefore, the number of A sites of A 2 B 4 units when the total number of sites is represented by v + w + x + y is represented by the following formula (D).
  • the denominator of the left side of Formula (3) can be obtained by substituting Formula (E) and Formula (F) into Formula (D).
  • the value of the left side of the above formula (3) exceeds 0.8, that is, when the ratio of Ca and Mg to the ratio of A site in the A 2 B 4 unit exceeds 0.8, it is clear However, it is considered that Ca and Mg are difficult to enter the A site of the A 2 B 4 unit, and Ca is arranged at the A site of the AB 5 unit. As a result, the crystal lattice may expand and the specific gravity of the alloy may be reduced.
  • the value on the left side of the above formula (3) is preferably more than 0, more preferably 0.4 or more, further preferably 0.5 or more, and most preferably 0.6 or more. preferable.
  • Mg can be arranged at the A site of the A 2 B 4 unit, but is not arranged at the A site of the AB 5 unit, and is considered to segregate when it cannot enter the A site of the A 2 B 4 unit.
  • the hydrogen storage alloy when the above formula (4) is not satisfied, that is, when x is less than 2.0, the discharge capacity of the nickel-metal hydride storage battery including the negative electrode including the hydrogen storage alloy becomes insufficient. If x exceeds 5.0, the specific gravity of the hydrogen storage alloy may not be sufficiently large.
  • x is preferably a number satisfying 2.2 ⁇ x, more preferably a number satisfying 2.3 ⁇ x, further preferably a number satisfying 2.8 ⁇ x. Most preferred is a number satisfying 1 ⁇ x. Further, x is preferably a number that satisfies x ⁇ 4.7, more preferably a number that satisfies x ⁇ 4.4, and even more preferably a number that satisfies x ⁇ 4.1. When x is 2.2 or more, there is an advantage that the discharge capacity of the battery can be improved, and when it is 4.7 or less, the specific gravity of the hydrogen storage alloy can be increased. There are advantages.
  • w is preferably a number satisfying 2.2 ⁇ w, and more preferably a number satisfying 3.3 ⁇ w. Moreover, it is preferable that it is a number which satisfy
  • fills w ⁇ 5.6, and it is more preferable that it is a number which satisfy
  • fills w ⁇ 4.7.
  • w is 2.2 or more, there is an advantage that the specific gravity of the hydrogen storage alloy can be larger, and when w is 5.6 or less, the discharge capacity of the battery becomes better. There is an advantage of getting.
  • w / x is less than 0.8, that is, the ratio of Mg to Ca is less than 0.8, or w / x is If it exceeds 2.5, the specific gravity of the hydrogen storage alloy may not be sufficiently large.
  • w / x is a number satisfying 1.0 ⁇ w / x.
  • fills w / x ⁇ 2.0.
  • v is preferably a number satisfying 13.0 ⁇ v ⁇ 18.0, and is a number satisfying 14.0 ⁇ v ⁇ 17.0. It is more preferable.
  • y is preferably a number satisfying 75.0 ⁇ y ⁇ 80.0, and a number satisfying 77.0 ⁇ y ⁇ 79.0. It is more preferable that
  • the hydrogen storage alloy according to another embodiment has a chemical composition represented by the following general formula (1 ′): R1v Mgw Cax R2y R3z Formula (1 ')
  • R1 is one or more elements selected from rare earth elements
  • R2 is Ni or a part of Ni is selected from the group consisting of Al, Co, Cu, Mn, Fe, Cr and Zn.
  • a hydrogen storage alloy that is substituted with one or more selected elements, and R3 is an element other than R1, Mg, Ca, and R2,
  • v + w + x + y 100
  • Formula (2) v, w, x, y satisfy 13.0 ⁇ v ⁇ 18.0, 2.2 ⁇ w ⁇ 5.6, 2.0 ⁇ x ⁇ 5.0, 75.0 ⁇ y ⁇ 80.0
  • Z satisfies 0 ⁇ z ⁇ 0.4
  • w and x satisfy 0.8 ⁇ w / x ⁇ 2.5.
  • the structure similar to the hydrogen storage alloy of embodiment mentioned above is employable.
  • the hydrogen storage alloy preferably has a hydrogen equilibrium pressure of 0.07 MPa or less.
  • Conventional hydrogen storage alloys have the property that they do not absorb hydrogen easily when the hydrogen equilibrium pressure is high and easily release the absorbed hydrogen. When the high-rate characteristics of the hydrogen storage alloy are improved, hydrogen self-releases. It is easy to do. However, it is a rare earth-Mg-Ni-based hydrogen storage alloy in which two or more crystal phases having different crystal structures are laminated, and particularly when the content of the crystal phase having a CaCu 5 type crystal structure is 15% by mass or less. In some hydrogen storage alloys, good high rate characteristics can be obtained even when the hydrogen equilibrium pressure is set to a low value of 0.07 MPa or less.
  • a nickel metal hydride battery using the hydrogen storage alloy as a negative electrode has excellent high rate characteristics and Hydrogen self-release (self-discharge in a battery) is unlikely to occur. This is considered to be because the diffusibility of hydrogen in the alloy was improved.
  • a cooling process for solidifying, an annealing process for annealing the cooled alloy in a pressurized inert gas atmosphere in a temperature range of 860 ° C. to 1000 ° C., and a pulverizing process for pulverizing the alloy are performed.
  • a predetermined amount of raw material ingot is weighed based on the chemical composition of the target hydrogen storage alloy.
  • the alloy raw material is put in a crucible and heated to, for example, 1200 ° C. or higher and 1600 ° C. or lower in an inert gas atmosphere or in a vacuum to melt the alloy raw material.
  • the cooling rate is preferably 1000 K / second or more (also called rapid cooling). By rapidly cooling at 1000 K / second or more, there is an effect that the alloy composition is refined and homogenized.
  • the cooling rate can be set in a range of 1000000 K / second or less.
  • a melt spinning method having a cooling rate of 100,000 K / sec or more, a gas atomizing method having a cooling rate of about 10,000 K / sec, or the like can be suitably used.
  • heating is performed at 860 ° C. or higher and 1000 ° C. or lower using, for example, an electric furnace in a pressurized state under an inert gas atmosphere.
  • the pressurizing condition is preferably 0.2 MPa (gauge pressure) or more and 1.0 MPa (gauge pressure) or less.
  • the processing time in this annealing process shall be 3 hours or more and 50 hours or less.
  • the pulverization step may be performed either before or after annealing, but since the surface area is increased by pulverization, it is desirable to perform the pulverization step after the annealing step from the viewpoint of preventing surface oxidation of the alloy.
  • the pulverization is preferably performed in an inert atmosphere to prevent oxidation of the alloy surface.
  • the pulverization means for example, mechanical pulverization, hydrogenation pulverization, or the like is used, and it is preferable that the particle size of the hydrogen storage alloy particles after pulverization is approximately 20 to 70 [ ⁇ m].
  • the nickel-metal hydride storage battery according to this embodiment includes a negative electrode containing the above-described hydrogen storage alloy as a hydrogen storage medium. That is, it is a nickel metal hydride storage battery provided with the negative electrode containing the hydrogen storage alloy mentioned above. Since the nickel-metal hydride storage battery of the present embodiment includes the hydrogen storage alloy in the negative electrode, the specific gravity of the hydrogen storage alloy is relatively high, the battery energy density is relatively high, and the discharge capacity of the battery is high. It can be relatively expensive.
  • the nickel metal hydride storage battery of the present embodiment includes a negative electrode mainly composed of the above-described hydrogen storage alloy, and further includes, for example, a positive electrode (nickel electrode) including a positive electrode active material mainly composed of nickel hydroxide, a separator, And an alkaline electrolyte.
  • a positive electrode nickel electrode
  • the negative electrode include those in which the hydrogen storage alloy powder is mixed with a conductive agent, a binder, a thickener, or the like, and pressed into a predetermined shape.
  • the nickel hydroxide composite which has nickel hydroxide as a main component and zinc hydroxide and cobalt hydroxide are mixed.
  • the positive electrode containing an oxide as a positive electrode active material is mentioned, Preferably, the positive electrode containing this nickel hydroxide complex oxide uniformly disperse
  • additives other than the nickel hydroxide composite oxide cobalt hydroxide, cobalt oxide and the like as a conductive modifier can be used, and the nickel hydroxide composite oxide is coated with cobalt hydroxide.
  • the positive electrode may contain a conductive agent, a binder, a thickener, and the like as other components in addition to the main components as described above.
  • the conductive agent is not limited as long as it is an electron conductive material that does not adversely affect the battery performance.
  • natural graphite such as scaly graphite, scaly graphite, earthy graphite
  • artificial graphite carbon black, acetylene black
  • examples thereof include ketjen black, carbon whisker, carbon fiber, vapor-grown carbon, metal (nickel, gold, etc.) powder, one kind of conductive material such as metal fiber, or a mixture of two or more kinds.
  • ketjen black carbon whisker, carbon fiber, vapor-grown carbon, metal (nickel, gold, etc.) powder
  • one kind of conductive material such as metal fiber, or a mixture of two or more kinds.
  • a method of mixing them a method that can be as uniform as possible is preferable.
  • a powder mixer such as a V-type mixer, an S-type mixer, a grinder, a ball mill, a planetary ball mill, or the like may be dry or wet.
  • the method used in the above can be adopted.
  • the binder is usually a thermoplastic resin such as polytetrafluoroethylene (PTFE), polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butadiene rubber (SBR), fluoro rubber.
  • PTFE polytetrafluoroethylene
  • EPDM ethylene-propylene-diene terpolymer
  • SBR styrene butadiene rubber
  • fluoro rubber examples thereof include a single type of polymer having rubber elasticity such as a single type or a mixture of two or more types.
  • the addition amount of the binder is preferably 0.1 to 3% by mass with respect to the total amount of the positive electrode or the negative electrode.
  • the thickener include one kind of a polysaccharide such as carboxymethylcellulose, methylcellulose, and xanthan gum, or a mixture of two or more kinds.
  • the addition amount of the thickener is preferably 0.1 to 0.3% by mass with respect to the total amount of the positive electrode or the negative electrode.
  • the positive electrode and the negative electrode are prepared by mixing the active material, the conductive agent, and the binder in an organic solvent such as water, alcohol, and toluene, and then applying the obtained mixed liquid onto a current collector and drying it.
  • an organic solvent such as water, alcohol, and toluene
  • a method of applying an arbitrary thickness and an arbitrary shape using means such as roller coating such as an applicator roll, screen coating, blade coating, spin coating, and per coating is preferable. It is not limited to.
  • an electron conductor that does not adversely affect the exchange of electrons with the active material in the battery that is configured can be used without any particular limitation.
  • the current collector include those made of nickel or nickel-plated steel plate as a material from the viewpoint of reduction resistance and oxidation resistance.
  • the shape of the current collector include a foam, a molded product of a fiber group, a three-dimensional base material subjected to uneven processing, or a two-dimensional base material such as a punching plate.
  • the thickness of the current collector is not particularly limited, and is usually 5 to 700 ⁇ m.
  • the positive electrode those made of nickel having excellent corrosion resistance and oxidation resistance to alkali and having a porous structure having a structure excellent in current collection are preferable.
  • a punching plate obtained by nickel plating on an iron foil that is inexpensive and excellent in conductivity is preferable.
  • the punching diameter is preferably 2.0 mm or less, and the opening ratio is preferably 40% or more. This makes it possible to improve the adhesion between the negative electrode active material and the current collector even with a small amount of binder.
  • the separator of the nickel metal hydride storage battery is preferably composed of a porous film or a nonwoven fabric exhibiting excellent rate characteristics alone or in combination of two or more.
  • the material constituting the separator include polyolefin resins such as polyethylene and polypropylene, and nylon.
  • the basis weight of the separator is preferably 40 g / m 2 to 100 g / m 2 . If it is less than 40 g / m 2 , the short circuit and the self-discharge performance may be deteriorated, and if it exceeds 100 g / m 2 , the ratio of the separator per unit volume increases, so the battery capacity tends to decrease.
  • the air permeability of the separator is preferably 1 cm / sec to 50 cm / sec. If it is less than 1 cm / sec, the internal pressure of the battery may increase, and if it exceeds 50 cm / sec, the short circuit and the self-discharge performance may be deteriorated.
  • the average fiber diameter of the separator is preferably 1 ⁇ m to 20 ⁇ m. When the thickness is less than 1 ⁇ m, the strength of the separator decreases, and the defect rate in the battery assembly process may increase. When the thickness exceeds 20 ⁇ m, the short circuit and the self-discharge performance may decrease. Further, the separator is preferably subjected to a hydrophilic treatment.
  • separator examples include those obtained by subjecting the surface of a polyolefin resin fiber such as polypropylene to a sulfonation treatment, a corona treatment, a fluorine gas treatment, a plasma treatment, or a mixture of those already subjected to these treatments. .
  • separators that have been sulfonated have a high ability to adsorb impurities such as NO 3 ⁇ , NO 2 ⁇ , and NH 3 ⁇ that cause the shuttle phenomenon and elements eluted from the negative electrode. ,preferable.
  • the alkaline electrolyte constituting the nickel metal hydride storage battery preferably contains at least one of sodium ion, potassium ion and lithium ion, and the total ion concentration is 9.0 mol / liter or less, and the total ion concentration is What is 5.0-8.0 mol / liter is still more preferable.
  • additives may be added to the electrolytic solution in order to improve the corrosion resistance of the alloy, improve the overvoltage at the positive electrode, improve the corrosion resistance of the negative electrode, and improve self-discharge.
  • the additive include oxides such as yttrium, ytterbium, erbium, calcium, and zinc, one kind of a hydroxide or the like, or a mixture of two or more kinds.
  • the nickel-metal hydride storage battery of this embodiment is an open-type nickel-metal hydride storage battery
  • the battery sandwiches the negative electrode with the positive electrode via a separator and fixes these electrodes so that a predetermined pressure is applied to these electrodes. Then, an electrolytic solution made of an aqueous solution containing KOH and LiOH is injected, and an open cell is assembled.
  • the nickel metal hydride storage battery of this embodiment is a sealed nickel metal hydride storage battery
  • the battery is injected with the electrolyte before or after the positive electrode, the separator, and the negative electrode are stacked, and is sealed with an exterior material.
  • the electrolyte is injected into the power generation element before or after winding.
  • an injection method it is possible to inject at normal pressure, but a vacuum impregnation method, a pressure impregnation method, and a centrifugal impregnation method can also be used.
  • examples of the material for the outer package of the sealed nickel-metal hydride storage battery include nickel-plated iron, stainless steel, polyolefin resin, and the like.
  • the configuration of the sealed nickel-metal hydride storage battery is not particularly limited, and batteries including a positive electrode, a negative electrode, and a single-layer or multi-layer separator, such as a coin battery, a button battery, a square battery, a flat battery, Alternatively, a cylindrical battery having a roll-shaped positive electrode, a negative electrode, and a separator can be given.
  • the present invention is not limited to the above exemplified hydrogen storage alloy and the above exemplified nickel metal hydride storage battery. That is, various forms used in a general hydrogen storage alloy can be adopted as long as the effects of the present invention are not impaired. Moreover, the various aspects used in a general nickel hydride storage battery can be employ
  • the hydrogen storage alloy whose chemical composition is represented by the formula (1) is an element not defined by the general formula as long as the general formula is satisfied as long as the effect of the present invention is not impaired. Can be included.
  • the chemical composition of the hydrogen storage alloy containing an element not defined by the formula (1) can also be represented by the formula (1 ′).
  • the content of R3 in the formula (1 ′) is an amount that does not impair the effects of the present invention. That is, it is proved that the effect of the present invention is not impaired if z defining the amount of R3 in the formula (1 ′) satisfies z ⁇ 0.4.
  • the reason why the R3 element is contained in the hydrogen storage alloy is that impurities are contained in the raw material ingot. Therefore, the amount of R3 in the hydrogen storage alloy can be controlled by controlling the purity of the raw material ingot.
  • Example 1 An open-type nickel metal hydride storage battery was produced by the method described below. Preparation of hydrogen storage alloy A predetermined amount of raw material ingot was weighed into a crucible so that the chemical composition would be Example 1 of Table 1, and heated to 1500 ° C. using a high frequency melting furnace in a reduced pressure argon gas atmosphere. Melted. After melting, it was quenched by applying a melt spinning method to solidify the alloy. Next, after heat-treating the obtained alloy at 910 ° C. in an argon gas atmosphere pressurized to 0.2 MPa (gauge pressure, the same applies hereinafter), the obtained hydrogen storage alloy was pulverized and averaged A hydrogen storage alloy powder having a particle size (D 50 ) of 20 ⁇ m was obtained.
  • D 50 particle size
  • An open-type nickel-metal hydride storage battery was manufactured by using the hydrogen storage alloy powder for the negative electrode. Specifically, after adding 3 parts by weight of nickel powder (INCO, # 210) to 100 parts by weight of the hydrogen storage alloy powder obtained as described above, the thickener (methylcellulose) is dissolved. After adding the prepared aqueous solution and further adding 1.5 parts by weight of a binder (styrene butadiene rubber) to a paste, it was applied to both sides of a 45 ⁇ m-thick perforated steel sheet (opening ratio 60%) and dried. , Pressed to a thickness of 0.36 mm to obtain a negative electrode.
  • nickel powder INCO, # 210
  • the thickener methylcellulose
  • a binder styrene butadiene rubber
  • the positive electrode an excess capacity sintered nickel hydroxide electrode was used.
  • an electrode was manufactured as prepared above open type battery sandwiched between the positive electrode through the separator, it is bolted to a pressure of 1 kgf / cm 2 to these electrodes such, assembled into open type cell.
  • the electrolytic solution a mixed solution composed of a 6.8 mol / L KOH solution and a 0.8 mol / L LiOH solution was used.
  • Nickel-metal hydride storage batteries were produced in the same manner as in Example 1 except that the compositions of the hydrogen storage alloys were changed to those shown in Examples 2 to 15 in Table 1.
  • ⁇ Content of crystal phase in hydrogen storage alloy> The hydrogen storage alloy powders obtained in each example and each comparative example were measured by X-ray diffraction, and further analyzed by the Rietveld method to identify the crystal structure contained in the hydrogen storage alloy. As a result, a crystal phase having a Pr 5 Co 19 type crystal structure, a crystal phase having a Ce 2 Ni 7 type crystal structure, and a crystal phase having a Gd 2 Co 7 type crystal structure were identified. Also, measure factor of each phase obtained from the Rietveld analysis, the unit cell volume, formula number, by using a chemical formula weight to determine the content of the crystal phase having a Pr 5 Co 19 type crystal structure. Table 1 shows the results of the hydrogen storage alloys of the examples and comparative examples.
  • ⁇ Nickel metal hydride storage capacity maintenance rate Using each of the produced nickel metal hydride storage batteries, charging in a water bath at 20 ° C. under a condition of 150% at 0.1 It (A), and a stop potential of ⁇ 0.6 V (vs Hg / v) at 0.2 It (A) Charging / discharging was repeated 50 cycles, with the discharge under the condition of HgO) as one cycle. Then, the discharge capacity at the 50th cycle with respect to the discharge capacity at the 1st cycle was obtained as a capacity retention rate.
  • ⁇ Discharge capacity of nickel metal hydride storage battery> The maximum discharge capacity of the nickel-metal hydride storage batteries produced in each Example and each Comparative Example was measured by the method described below. Using each produced nickel metal hydride storage battery, a charge / discharge test was performed under the following conditions. The charging conditions were constant current and constant voltage charging with a charging current of 0.1 ItmA and a charging time of 15 hours, and the discharging conditions were constant current discharging with a discharge current of 0.1 ItmA.
  • Table 1 shows the specific gravity of the hydrogen storage alloys produced in each example and each comparative example, the initial maximum discharge capacity measured in the charge / discharge test using each nickel metal hydride storage battery, and the capacity retention rate of the battery. As can be seen from Table 1, in the examples, specific gravity of 7.5 or more and maximum discharge capacity of 370 mAh / g or more can be achieved. In addition, Example 10 and Example 18 in which the Al content was 2.2 atomic% or less were significantly superior in capacity retention compared to Example 19 in which the Al content was 3.3 atomic%. It is a thing.

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Abstract

L'invention concerne un alliage de stockage d'hydrogène intégré dans l'électrode négative d'une batterie nickel-hydrogène. L'alliage de stockage d'hydrogène spécifiquement décrit respecte simultanément les conditions d'une densité d'énergie supérieure pour la batterie grâce à une gravité spécifique comparativement élevée de l'alliage de stockage d'hydrogène, et d'une capacité de décharge comparativement élevée pour la batterie nickel-hydrogène. L'invention concerne également une batterie nickel-hydrogène pour vue d'un allige de stockage hydrogène, et dont l'électrode négative contient cet alliage de stockage d'hydrogène. La composition chimique de celui-ci est donnée par la formule générale (1) : R1vMgwCaxR2y (1). R1 représente un ou plusieurs éléments choisis parmi les terres rares. R2 représente Ni ou un alliage de stockage d'hydrogène dans lequel le nickel est remplacé en partie par un ou plusieurs éléments choisis dans le groupe constitué par Al, Co, Cu, Mn, Fe, Cr et Zn. Quand v, w, x et y sont définis de manière à respecter la formule (2), v, w, x et y pour l'alliage de stockage d'hydrogène décrit et l'électrode contenant cet alliage respectent également les formules (3), (4) et (5) : v+w+x+y = 100 (2), 2,0 ≤ x ≤ 5,0 (4), 0,8 ≤ w/x ≤ 2,5 (5).
PCT/JP2011/055368 2010-03-12 2011-03-08 Alliage de stockage d'hydrogène et batterie nickel-hydrogène WO2011111699A1 (fr)

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
EP2628812A1 (fr) * 2012-02-20 2013-08-21 GS Yuasa International Ltd. Alliage de stockage d'hydrogène, électrode, batterie rechargeable à hydrure métallique de nickel et procédé de production d'un alliage de stockage d'hydrogène
JP2013199703A (ja) * 2012-02-20 2013-10-03 Gs Yuasa Corp 水素吸蔵合金、電極、ニッケル水素蓄電池及び水素吸蔵合金の製造方法
JP2014114476A (ja) * 2012-12-07 2014-06-26 Gs Yuasa Corp 水素吸蔵合金、電極、ニッケル水素蓄電池及び水素吸蔵合金の製造方法
JP2015187301A (ja) * 2014-03-27 2015-10-29 株式会社Ｇｓユアサ 水素吸蔵合金、電極、及び蓄電素子
CN106854715A (zh) * 2015-12-08 2017-06-16 北京有色金属研究总院 一种含有钇元素的镧-镁-镍系ab3型储氢合金及其制备工艺
CN108493436A (zh) * 2018-03-09 2018-09-04 燕山大学 一种2h型a5b19超堆垛结构镧–m–镁–镍基四元贮氢合金电极材料及其制备方法

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Publication number Priority date Publication date Assignee Title
JPH11323469A (ja) * 1997-06-17 1999-11-26 Toshiba Corp 水素吸蔵合金及び二次電池
WO2009060666A1 (fr) * 2007-11-09 2009-05-14 Gs Yuasa Corporation Batterie au nickel-métal-hydrure et procédé pour produire un alliage de stockage d'hydrogène

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11323469A (ja) * 1997-06-17 1999-11-26 Toshiba Corp 水素吸蔵合金及び二次電池
WO2009060666A1 (fr) * 2007-11-09 2009-05-14 Gs Yuasa Corporation Batterie au nickel-métal-hydrure et procédé pour produire un alliage de stockage d'hydrogène

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2628812A1 (fr) * 2012-02-20 2013-08-21 GS Yuasa International Ltd. Alliage de stockage d'hydrogène, électrode, batterie rechargeable à hydrure métallique de nickel et procédé de production d'un alliage de stockage d'hydrogène
JP2013199703A (ja) * 2012-02-20 2013-10-03 Gs Yuasa Corp 水素吸蔵合金、電極、ニッケル水素蓄電池及び水素吸蔵合金の製造方法
JP2014114476A (ja) * 2012-12-07 2014-06-26 Gs Yuasa Corp 水素吸蔵合金、電極、ニッケル水素蓄電池及び水素吸蔵合金の製造方法
JP2015187301A (ja) * 2014-03-27 2015-10-29 株式会社Ｇｓユアサ 水素吸蔵合金、電極、及び蓄電素子
CN106854715A (zh) * 2015-12-08 2017-06-16 北京有色金属研究总院 一种含有钇元素的镧-镁-镍系ab3型储氢合金及其制备工艺
CN108493436A (zh) * 2018-03-09 2018-09-04 燕山大学 一种2h型a5b19超堆垛结构镧–m–镁–镍基四元贮氢合金电极材料及其制备方法

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