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US20080085209A1 - Hydrogen-absorbing alloy for an alkaline storage battery - Google Patents

Hydrogen-absorbing alloy for an alkaline storage battery Download PDF

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Publication number
US20080085209A1
US20080085209A1 US11/679,504 US67950407A US2008085209A1 US 20080085209 A1 US20080085209 A1 US 20080085209A1 US 67950407 A US67950407 A US 67950407A US 2008085209 A1 US2008085209 A1 US 2008085209A1
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US
United States
Prior art keywords
alloy
alloy according
hydrogen
nickel
mass
Prior art date
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Abandoned
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US11/679,504
Inventor
Patrick Bernard
Bernard Knosp
Michel Latroche
Amelie Ferey
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SAFT Societe des Accumulateurs Fixes et de Traction SA
Centre National de la Recherche Scientifique CNRS
Original Assignee
SAFT Societe des Accumulateurs Fixes et de Traction SA
Centre National de la Recherche Scientifique CNRS
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Application filed by SAFT Societe des Accumulateurs Fixes et de Traction SA, Centre National de la Recherche Scientifique CNRS filed Critical SAFT Societe des Accumulateurs Fixes et de Traction SA
Publication of US20080085209A1 publication Critical patent/US20080085209A1/en
Priority to US12/430,451 priority Critical patent/US20090206302A1/en
Abandoned legal-status Critical Current

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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/242—Hydrogen storage electrodes
    • 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
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • 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
    • H01M4/26—Processes of manufacture
    • 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

  • a subject of the invention is a hydrogen-absorbing alloy comprising at least one crystalline phase of A 5 B 19 type, and an alkaline storage battery of nickel metal hydride type comprising at least one negative electrode (anode) containing said alloy.
  • Such a battery possesses a higher electrochemical capacity than the nickel metal hydride batteries of the prior art as well as a longer life.
  • Portable applications have increasing requirements for energy volume density and power, at a low cost as in wireless tools for example.
  • the batteries reach a limitation in terms of energy volume density, due to the optimization of the energy volume densities of each of the two electrodes constituting the battery: positive electrode based on nickel hydroxide and negative electrode based on hydrogen-absorbing alloy AB 5 .
  • the capacity by mass of an AB 5 type alloy is limited to 300-320 mAh/g.
  • compositions such as the AB 2 alloy families have been studied. However, although their initial capacity is greater than that of an AB 5 alloy, their power and their life spans are considerably reduced. Recently certain manufacturers have proposed the use of an A 2 B 7 type alloy. The following documents describe A 2 B 7 type alloys.
  • JP2001-316744 describes a hydrogen-absorbing alloy having the formula Ln 1 ⁇ x Mg x (Ni 1 ⁇ y T y ) z in which Ln is at least one element chosen from the lanthanide series, Ca, Sr, Sc, Y, Ti, Zr and the quantity of lanthanium represents from 10 to 50 atomic % of the lanthanides.
  • T is at least one element chosen from Li, V, Nb, Ta, Cr, Mo, Mn, Fe, Co, Al, Ga, Zn, Sn, In, Cu, Si, P and B; and x, y and z satisfy the relationships: 0.05 ⁇ x ⁇ 0.20; 0 ⁇ y ⁇ 0.5 and 2.8 ⁇ z ⁇ 3.9.
  • JP2002-069554 describes a hydrogen-absorbing alloy of formula R 1 ⁇ a Mg a Ni b Co c M d in which R represents at least two rare earth elements. R can also contain yttrium. M represents one or more elements chosen from Mn, Fe, V, Cr, Nb, Al, Ga, Zn, Sn, Cu, Si, P and B.
  • the stoichiometric indices a, b, c and d satisfy the following relationships: 0.15 ⁇ a ⁇ 0.35; 0 ⁇ c ⁇ 1.5; 0 ⁇ d ⁇ 0.2; and 2.9 ⁇ b+c+d ⁇ 3.5.
  • EP-A-1 026 764 describes a hydrogen-absorbing alloy of formula AM X , where A can be a rare earth element and/or magnesium and M is one or more elements which can be chosen from Cr, Mn, Fe, Co, Ni, Al, Cu and Sn and x satisfies the relationship: 2.7 ⁇ x ⁇ 3.8.
  • U.S. Pat. No. 6,214,492 describes a hydrogen-absorbing alloy comprising at least one crystalline phase consisting of a unit cell possessing at least one A 2 B 4 type sub-cell, and at least one AB 5 type sub-cell.
  • This alloy can optionally comprise a type AB 3 or type AB 3.5 crystalline phase.
  • US2004/0134569 describes a hydrogen-absorbing alloy of formula Ln 1 ⁇ x Mg x Ni y ⁇ a Al a in which Ln is at least one rare earth element; and x, y and a satisfy the relationships: 0.05 ⁇ x ⁇ 0.20; 2.8 ⁇ y ⁇ 3.9 and 0.10 ⁇ a ⁇ 0.25.
  • US2004/0146782 describes a hydrogen-absorbing alloy of formula Ln 1 ⁇ x Mg x Ni y ⁇ a Al a in which Ln is at least one rare earth element; M is chosen from the group consisting of Al, V, Nb, Ta, Cr, Mo, Mn, Fe, Co, Ga, Zn, Sn, In, Cu, Si and P; and x, y and a satisfy the relationships: 0.05 ⁇ x ⁇ 0.20; 2.8 ⁇ y ⁇ 3.9 and 0.10 ⁇ a ⁇ 0.50.
  • US2005/0100789 describes a hydrogen-absorbing alloy of formula RE 1 ⁇ x Mg x Ni y Al z M a in which RE is a rare earth element; M is an element other than a rare earth, and x, y, z and a satisfy the relationships: 0.10 ⁇ x ⁇ 0.30; 2.8 ⁇ y ⁇ 3.6; 0 ⁇ z ⁇ 0.30and 3.0 ⁇ y+z+a ⁇ 3.6.
  • US2005/0175896 describes a hydrogen-absorbing alloy of formula Ln 1 ⁇ x Mg x Ni y ⁇ a Al a in which Ln is a rare earth element; and x, y and a satisfy the relationships: 0.05 ⁇ x ⁇ 0.20; 2.8 ⁇ y ⁇ 3.9; and 0.10 ⁇ a ⁇ 0.25.
  • a part of the rare earth element or Ni is substituted by at least one element chosen from the group consisting of V, Nb, Ta, Cr, Mo, Mn, Fe, Co, Ga, Zn, Sn, In, Cu, Si, P and B.
  • US2005/0164083 describes a hydrogen-absorbing alloy of formula Ln 1 ⁇ x Mg x Ni y ⁇ a Al a in which Ln is at least one rare earth element, and x, y and a satisfy the relationships: 0.15 ⁇ x ⁇ 0.25; 3.0 ⁇ y ⁇ 3.6; and 0 ⁇ a ⁇ 0.3.
  • a part of the rare earth element or Ni is substituted by at least one element chosen from the group consisting of V, Nb, Ta, Cr, Mo, Mn, Fe, Co, Ga, Zn, Sn, In, Cu, Si, P and B.
  • JP 09-194971 describes a hydrogen-absorbing alloy represented by the formula: R 2 (Ni 7 ⁇ X ⁇ Y ⁇ Z Mn X A Y B Z ) n in which R is a rare earth element or a misch metal; A is one or more elements chosen from Co, Cr, Fe, Al, Zr, W, Mo, and Ti; B is one or more elements chosen from Cu, Nb and V; X, Y, Z and n satisfy the relationships: 0.3 ⁇ X ⁇ 1.5; 0 ⁇ Y ⁇ 1.0; 0 ⁇ Z ⁇ 1.0; Y+Z ⁇ 1.0; 0.96 ⁇ n ⁇ 1.1.
  • EP-A-0 783 040 describes a hydrogen-absorbing alloy of formula
  • R 1 ⁇ x L x (Ni 1y M y ), in which R represents La, Ce, Pr or Nd; L represents Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sc, Mg or Ca; M represents Co, Al, Mn, Fe, Cu, Zr, Ti, Mo, Si, V, Cr, Nb, Hf, Ta, W, B or C; and x, y and z satisfy the relationships: 0.05 ⁇ x ⁇ 0.4; 0 ⁇ y ⁇ 0.5; and 3.0 ⁇ z ⁇ 4.5.
  • JP 2004-115870 describes a hydrogen-absorbing alloy of formula Ln 1 ⁇ x Mg x Ni y M z in which Ln is Y, Sc or a rare earth element; M is Co, Mn, Al, Fe, V, Cr, Nb, Ga, Zn, Sn, Cu, Si, P or B, and x, y, and z satisfy the relationships: 0.1 ⁇ x ⁇ 0.5; 2.5 ⁇ y ⁇ 3.5 and 0 ⁇ z ⁇ 0.5; and 3.0 ⁇ y+z ⁇ 3.5.
  • a nickel metal hydride type alkaline storage battery is therefore sought, possessing a higher capacity than that of the batteries of the prior art as well as a long life span.
  • the invention therefore provides a hydrogen-absorbing alloy comprising at least one A 5 B 19 type crystalline phase having the formula R 1 ⁇ y Mg y Ni 3.8 ⁇ 0.1 ⁇ z M z , in which:
  • R represents one or more elements chosen from
  • M represents one or more elements chosen from
  • the invention extends to an electrode comprising an active material comprising said alloy. It also extends to a nickel metal hydride alkaline storage battery comprising at least one negative electrode comprising said alloy.
  • the invention also relates to the production process of said alloy.
  • the hydrogen-absorbing alloy according to the invention contains at least one A 5 B 19 type crystalline phase, corresponding to the formula: R 1 ⁇ y Mg y Ni 3.8 ⁇ 0.1 ⁇ z M z , where
  • R represents one or more elements chosen from La, Ce, Nd or Pr;
  • M represents one or more nickel substituents chosen from the elements Mn, Fe, Al, Co, Cu, Zr, Sn, and M does not contain the element Cr.
  • the presence of the element Cr as a nickel substituent is excluded from the invention as the presence of Cr reduces the power supplied by the battery.
  • composition of the alloy can be confirmed by elementary analysis (atomic absorption, inductive plasma technique), X-ray diffraction, electron probe microanalysis (EPMA) with wavelength dispersive spectroscopy (WDS).
  • elementary analysis atomic absorption, inductive plasma technique
  • X-ray diffraction X-ray diffraction
  • EPMA electron probe microanalysis
  • WDS wavelength dispersive spectroscopy
  • the sum of the stoichiometric indices of nickel and M is 3.8.
  • y 0.25.
  • y 0.15.
  • z 0.30.
  • the stoichiometric index of each of the nickel substituents is less than or equal to 0.20; preferably it is less than or equal to 0.15.
  • M represents one or more elements chosen from Co, Al and Mn.
  • M is Co a Al b , with a ⁇ 0.15 and b ⁇ 0.15.
  • the hydrogen-absorbing alloy comprises the A 5 B 19 crystalline phase as described previously and its overall composition has the formula: R 1 ⁇ u Mg u Ni t ⁇ v M v , where
  • the proportion of A 5 B 19 crystalline phase represents at least 50% by volume of the alloy.
  • the equilibrium pressure at 40° C. for 1% by mass of hydrogen inserted is less than 1.5 bar.
  • the size of the hydrogen-absorbing alloy particles is characterized by a Dv 50% of 30 to 120 ⁇ m, preferably of 50 to 100 ⁇ m. According to another embodiment, the size of the particles of hydrogen-absorbing alloy is characterized by a Dv 50% of 120 to 200 ⁇ m.
  • the alloy of the invention can be prepared by the following three processes:
  • the alloy of the invention may have undergone annealing.
  • the invention also proposes an electrode comprising an active ingredient comprising the alloy as described previously.
  • the invention extends to a nickel metal hydride alkaline storage battery comprising at least one negative electrode comprising the alloy according to the invention.
  • a yttrium compound with the active ingredient containing the alloy.
  • This compound can be an yttrium oxide, hydroxide or salt.
  • the yttrium-based compound is chosen from a non-exhaustive list comprising an yttrium-based oxide such as Y 2 O 3 , an yttrium-based hydroxide such as Y(OH) 3 or a yttrium-based salt.
  • the yttrium-based compound is yttrium oxide Y 2 O 3 .
  • the yttrium-based compound is mixed with the alloy in a proportion such that the mass of yttrium represents from 0.1 to 2% of the mass of the alloy, preferably from 0.2 to 1% of the mass of alloy, preferably also from 0.2 to 0.7% of the mass of the alloy.
  • the process of addition of the yttrium-based compound to the active ingredient during the manufacture of the anode is simple to implement industrially. It does not require complex devices.
  • the anode is manufactured by covering an electrically conductive support with a paste made up of an aqueous mixture of the composition of active ingredient according to the invention and additives.
  • the support can be a nickel foam, a flat or three-dimensional perforated strip made of nickel or nickel-plated steel.
  • the additives are intended to facilitate the use or the performances of the anode.
  • They can be thickeners such as carboxymethyl cellulose (CMC), hydroxypropylmethyl cellulose (HPMC), polyacrylic acid (PAA), poly(ethylene oxide) (PEO).
  • They can also be binders such as butadiene-styrene (SBR) copolymers, polystyrene acrylate (PSA), polytetrafluoroethylene (PTFE).
  • SBR butadiene-styrene
  • PSA polystyrene acrylate
  • PTFE polytetrafluoroethylene
  • They can also be polymer fibres, such as polyamide, polypropylene, polyethylene, etc., in order to improve the mechanical properties of the electrode.
  • They can also be conductive agents such as nickel powder, carbon powder or fibres, nanotubes.
  • the anode is covered with a surface layer intended to improve high-speed discharge and/or recombination with oxygen at the end of charging.
  • the invention also relates to a nickel metal hydride alkaline storage battery comprising said at least one anode.
  • the battery according to the invention typically comprises at least one anode, at least one nickel cathode, at least one battery separator and an alkaline electrolyte.
  • the cathode is constituted by the active cathode mass deposited on a support which can be a sintered support, a nickel foam, a flat or three-dimensional perforated strip made of nickel or nickel-plated steel.
  • the active cathode mass comprises the active cathode ingredient and additives intended to facilitate its implementation or its performances.
  • the active cathode ingredient is a nickel hydroxide Ni(OH) 2 which can be partially substituted by Co, Mg and Zn. This hydroxide can be partially oxidized and can be coated with a surface layer based on cobalt compounds.
  • CMC carboxymethyl cellulose
  • HPMC hydroxypropylmethyl cellulose
  • HPC hydroxypropyl cellulose
  • HEC hydroxyethyl cellulose
  • PAA polyacrylic acid
  • SMA polystyrene maleic anhydride
  • SBR optionally carboxylated butadiene-styrene copolymers
  • NBR acrylonitrile and butadiene
  • SEBS ⁇ copolymer of styrene, ethylene, butylene and styrene
  • SEBS a terpolymer of styrene, butadiene and vinylpyridine
  • SBVR polystyrene acrylate
  • PSA polytetrafluoroethylene
  • FEP fluorinated copolymer of ethylene and propylene
  • PPHF polyhexafluoropropylene
  • the battery separator is generally composed of polyolefin fibres (e.g. polypropylene) or nonwoven porous polyamide.
  • the electrolyte is a concentrated alkaline aqueous solution comprising at least one hydroxide (KOH, NaOH, LiOH), in a concentration generally of the order of several times normality.
  • the electrode pastes are prepared in a standard fashion, the electrodes are manufactured, then at least one cathode, a battery separator and an anode are superposed in order to constitute the electrochemical bundle.
  • the electrochemical bundle is introduced into a container and impregnated with an aqueous alkaline electrolyte. The battery is then closed.
  • the invention relates to any format of batteries: prismatic format (flat electrodes) or cylindrical format (spiral or concentric electrodes).
  • the battery according to the invention can be of the open (open or semi-open) type or of the sealed type.
  • the battery according to the invention is particularly well suited as an energy source for an electric vehicle or a portable device.
  • Alloys the overall composition of which has the formula (La, Ce, Nd, Pr) 1 ⁇ u Mg u (Ni, Mn, Al, Co) t , are produced by sintering prealloys
  • composition of the alloys in terms of crystalline phases is determined using the trace of X-ray diffraction diagrams, using the copper wavelength K ⁇ 1 .
  • the composition in terms of crystalline phases is determined by following the Rietveld method (Rietveld, H. M., A profile refinement method for nuclear and magnetic structures. Journal of Applied Crystallography, 1969, 2, 6571).
  • the compositions of alloys A, B and C in terms of crystalline phases are shown in Table 2. TABLE 2 Composition of the alloys in terms of phases. Phase (%) Alloy Type A 2 B 7 (R) Type A 2 B 7 (H) Type A 5 B 19 (R) Type AB 5 (H) A 0 100 0 0 B 9 1 82 8 C 11 7 24 58
  • the alloy of Example A of the prior art is constituted only by a hexagonal A 2 B 7 phase A 2 B 7 (H) of Ce 2 Ni 7 type.
  • the alloy of Example B according to the invention comprises 10% A 2 B 7 type phases (hexagonal of Ce 2 Ni 7 type or rhombohedral of Gd 2 Co 7 type,), 8% hexagonal AB 5 phase of CaCu 5 type and 82% rhombohedral A 5 B 19 type phase of Ce 5 Co 19 type.
  • the alloy C which is outside the invention is characterized by the presence of 24% A 5 B 19 phase, 18% A 2 B 7 phase and 58% AB 5 phase.
  • a sample of alloy is coated with an epoxy resin, then polished. Different points on the polished sample are analyzed using a electronic microprobe with wavelength dispersive analysis in order to determine its composition.
  • the B/A ratio where B is the sum of the level of Ni and of the element(s) M, and A is the sum of the La, Ce, Nd, Pr and Mg levels, is determined for each point analyzed.
  • the alloy A of the prior art does not contain any A 5 B 19 phase.
  • the A 5 B 19 phase of the alloy B according to the invention has an Mg level y equal to 0.19 and a level z of element M equal to 0.16.
  • the A 5 B 19 phase of the alloy C which is outside the invention has an Mg level y equal to 0.21 and a level z of element M equal to 0.54.
  • the mass capacity of the alloys is determined in prismatic laboratory elements the capacity of which is limited by the anode.
  • the anodes comprising the alloys are constituted by a mixture of:
  • Yttrium oxide is added to the anode 3 of Table 4, at a level of 0.5% yttrium with respect to the alloy mass.
  • the cathode comprises a standard nickel foam type current collector and an active ingredient constituted by a nickel hydroxide partially substituted by Zn and Co, the conductive network of which, constituted by Co(OH) 2 has been formed beforehand.
  • the anode and the cathode are separated by a polyolefin battery separator and a membrane intended to prevent any recombination of oxygen, released at the cathode, on the anode.
  • the electrolyte is an aqueous solution of KOH at 8.7 mole/litre.
  • the alloy After a first charge for 16 hours with a current of 40 mA per gram of alloy (charge for 16 hours at 40 mA/g), the alloy is activated over 10 cycles under the following conditions:
  • alloy life span is meant the number of cycles corresponding to a discharged capacity equal to 80% of the maximum capacity measured during the activation period.
  • the maximum capacity restored during activation by the anode 1 for which the active ingredient is the alloy A of the prior art is equal to 367 mAh/g. However, it decreases rapidly during cycling in order to reach 80% of the initial capacity at cycle 153.
  • the maximum capacity restored during activation by the anode 2 for which the active ingredient is the alloy B of the invention is equal to 358 mAh/g.
  • the life span of this anode 2 is 257 cycles.
  • the anode 3 contains alloy B of the invention and yttrium oxide.
  • the maximum capacity restored during the activation by this series is 355 mAh/g and its life span is 398 cycles.
  • the capacity of the anodes 2 and 3 is greater than 320 mAh/g, which is the mass capacity of the NiMH batteries of the prior art.
  • the maximum capacity restored during activation by the anode 4, for which the active ingredient is the alloy C which is outside the invention, is equal to 323 mA/g. This is attributed to the large quantity of AB 5 type phase contained in this alloy. Its life span is limited to 174 cycles.

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Abstract

Therefore the invention provides a hydrogen-absorbing alloy comprising at least one A5B19 type crystalline phase having the formula R1−yMgyNi3.8±0.1−zMz, in which R represents one or more elements chosen from La, Ce, Nd or Pr; M represents one or more elements chosen from Mn, Fe, Al, Co, Cu, Zr, Sn and M does not contain Cr; 0≦y≦0.30; z≦0.5. The invention extends to an electrode comprising an active ingredient comprising said alloy. It also extends to a nickel metal hydride alkaline storage battery the negative electrode of which comprises said alloy. The invention also relates to the process for the manufacture of said alloy.

Description

    TECHNICAL FIELD
  • A subject of the invention is a hydrogen-absorbing alloy comprising at least one crystalline phase of A5B19 type, and an alkaline storage battery of nickel metal hydride type comprising at least one negative electrode (anode) containing said alloy. Such a battery possesses a higher electrochemical capacity than the nickel metal hydride batteries of the prior art as well as a longer life.
    • STATE OF THE ART
  • Portable applications have increasing requirements for energy volume density and power, at a low cost as in wireless tools for example. At present the batteries reach a limitation in terms of energy volume density, due to the optimization of the energy volume densities of each of the two electrodes constituting the battery: positive electrode based on nickel hydroxide and negative electrode based on hydrogen-absorbing alloy AB5. The capacity by mass of an AB5 type alloy is limited to 300-320 mAh/g.
  • When optimization of the battery's capacity is carried out, it is to the detriment of its life span. Conversely it is possible to carry out optimization of the life span of the battery, but to the detriment of the capacity by volume.
  • In order to increase the capacity by volume, compositions such as the AB2 alloy families have been studied. However, although their initial capacity is greater than that of an AB5 alloy, their power and their life spans are considerably reduced. Recently certain manufacturers have proposed the use of an A2B7 type alloy. The following documents describe A2B7 type alloys.
  • JP2001-316744 describes a hydrogen-absorbing alloy having the formula Ln1−xMgx(Ni1−yTy)z in which Ln is at least one element chosen from the lanthanide series, Ca, Sr, Sc, Y, Ti, Zr and the quantity of lanthanium represents from 10 to 50 atomic % of the lanthanides.
  • T is at least one element chosen from Li, V, Nb, Ta, Cr, Mo, Mn, Fe, Co, Al, Ga, Zn, Sn, In, Cu, Si, P and B; and x, y and z satisfy the relationships:
    0.05≦x<0.20; 0≦y≦0.5 and 2.8≦z≦3.9.
  • JP2002-069554 describes a hydrogen-absorbing alloy of formula R1−aMgaNibCocMd in which R represents at least two rare earth elements. R can also contain yttrium. M represents one or more elements chosen from Mn, Fe, V, Cr, Nb, Al, Ga, Zn, Sn, Cu, Si, P and B. The stoichiometric indices a, b, c and d satisfy the following relationships:
    0.15<a<0.35; 0≦c≦1.5; 0≦d≦0.2; and 2.9<b+c+d<3.5.
  • EP-A-1 026 764 describes a hydrogen-absorbing alloy of formula AMX, where A can be a rare earth element and/or magnesium and M is one or more elements which can be chosen from Cr, Mn, Fe, Co, Ni, Al, Cu and Sn and x satisfies the relationship: 2.7<x<3.8.
  • U.S. Pat. No. 6,214,492 describes a hydrogen-absorbing alloy comprising at least one crystalline phase consisting of a unit cell possessing at least one A2B4 type sub-cell, and at least one AB5 type sub-cell. This alloy can optionally comprise a type AB3 or type AB3.5 crystalline phase.
  • US2004/0134569 describes a hydrogen-absorbing alloy of formula Ln1−xMgxNiy−aAla in which Ln is at least one rare earth element; and x, y and a satisfy the relationships:
    0.05≦x<0.20; 2.8≦y≦3.9 and 0.10≦a≦0.25.
  • US2004/0146782 describes a hydrogen-absorbing alloy of formula Ln1−xMgxNiy−aAla in which Ln is at least one rare earth element; M is chosen from the group consisting of Al, V, Nb, Ta, Cr, Mo, Mn, Fe, Co, Ga, Zn, Sn, In, Cu, Si and P; and x, y and a satisfy the relationships:
    0.05≦x<0.20; 2.8≦y≦3.9 and 0.10≦a≦0.50.
  • US2005/0100789 describes a hydrogen-absorbing alloy of formula RE1−xMgxNiyAlzMa in which RE is a rare earth element; M is an element other than a rare earth, and x, y, z and a satisfy the relationships:
    0.10≦x<0.30; 2.8≦y≦3.6; 0≦z≦0.30and
    3.0≦y+z+a≦3.6.
  • US2005/0175896 describes a hydrogen-absorbing alloy of formula Ln1−xMgxNiy−aAla in which Ln is a rare earth element; and x, y and a satisfy the relationships:
    0.05≦x<0.20; 2.8≦y≦3.9; and 0.10≦a≦0.25.
  • Preferably, a part of the rare earth element or Ni is substituted by at least one element chosen from the group consisting of V, Nb, Ta, Cr, Mo, Mn, Fe, Co, Ga, Zn, Sn, In, Cu, Si, P and B.
  • US2005/0164083 describes a hydrogen-absorbing alloy of formula Ln1−xMgxNiy−aAla in which Ln is at least one rare earth element, and x, y and a satisfy the relationships:
    0.15≦x≦0.25; 3.0≦y≦3.6; and 0<a≦0.3.
  • Preferably, a part of the rare earth element or Ni is substituted by at least one element chosen from the group consisting of V, Nb, Ta, Cr, Mo, Mn, Fe, Co, Ga, Zn, Sn, In, Cu, Si, P and B.
  • JP 09-194971 describes a hydrogen-absorbing alloy represented by the formula: R2(Ni7−X−Y−ZMnXAYBZ)n in which R is a rare earth element or a misch metal; A is one or more elements chosen from Co, Cr, Fe, Al, Zr, W, Mo, and Ti; B is one or more elements chosen from Cu, Nb and V; X, Y, Z and n satisfy the relationships:
    0.3≦X≦1.5; 0≦Y≦1.0; 0≦Z≦1.0; Y+Z≦1.0; 0.96≦n≦1.1.
  • EP-A-0 783 040 describes a hydrogen-absorbing alloy of formula
  • (R1−xLx)(Ni1yMy), in which R represents La, Ce, Pr or Nd; L represents Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sc, Mg or Ca; M represents Co, Al, Mn, Fe, Cu, Zr, Ti, Mo, Si, V, Cr, Nb, Hf, Ta, W, B or C; and x, y and z satisfy the relationships:
    0.05≦x≦0.4; 0≦y≦0.5; and 3.0≦z≦4.5.
  • JP 2004-115870 describes a hydrogen-absorbing alloy of formula Ln1−xMgxNiyMz in which Ln is Y, Sc or a rare earth element; M is Co, Mn, Al, Fe, V, Cr, Nb, Ga, Zn, Sn, Cu, Si, P or B, and x, y, and z satisfy the relationships:
    0.1≦x≦0.5; 2.5≦y≦3.5 and 0≦z<0.5; and 3.0≦y+z≦3.5.
  • However, although the initial capacity of the A2B7 alloys is greater than that of an AB5 alloy and comparable to that of an AB2 alloy, their life span is limited.
  • A nickel metal hydride type alkaline storage battery is therefore sought, possessing a higher capacity than that of the batteries of the prior art as well as a long life span.
    • SUMMARY OF THE INVENTION
  • The invention therefore provides a hydrogen-absorbing alloy comprising at least one A5B19 type crystalline phase having the formula R1−yMgyNi3.8±0.1−zMz, in which:
  • R represents one or more elements chosen from
  • La, Ce, Nd or Pr;
  • M represents one or more elements chosen from
  • Mn, Fe, Al, Co, Cu, Zr, Sn and M not containing Cr;
  • 0≦y≦0.30;
  • z≦0.5.
  • The invention extends to an electrode comprising an active material comprising said alloy. It also extends to a nickel metal hydride alkaline storage battery comprising at least one negative electrode comprising said alloy.
  • The invention also relates to the production process of said alloy.
    • DETAILED DISCLOSURE OF EMBODIMENTS OF THE INVENTION
  • The hydrogen-absorbing alloy according to the invention contains at least one A5B19 type crystalline phase, corresponding to the formula:
    R1−yMgyNi3.8±0.1−zMz, where
  • R represents one or more elements chosen from La, Ce, Nd or Pr;
  • M represents one or more nickel substituents chosen from the elements Mn, Fe, Al, Co, Cu, Zr, Sn, and M does not contain the element Cr.
  • 0≦y≦0.30;
  • z≦0.5.
  • The presence of the element Cr as a nickel substituent is excluded from the invention as the presence of Cr reduces the power supplied by the battery.
  • The composition of the alloy can be confirmed by elementary analysis (atomic absorption, inductive plasma technique), X-ray diffraction, electron probe microanalysis (EPMA) with wavelength dispersive spectroscopy (WDS).
  • According to a preferred embodiment, the sum of the stoichiometric indices of nickel and M is 3.8.
  • According to an embodiment, y≦0.25.
  • According to an embodiment, y>0.15.
  • According to an embodiment, z≦0.30.
  • According to an embodiment, the stoichiometric index of each of the nickel substituents is less than or equal to 0.20; preferably it is less than or equal to 0.15.
  • According to an embodiment, M represents one or more elements chosen from Co, Al and Mn.
  • According to a preferred embodiment, M is CoaAlb, with a≦0.15 and b≦0.15.
  • According to an embodiment, the hydrogen-absorbing alloy comprises the A5B19 crystalline phase as described previously and its overall composition has the formula:
    R1−uMguNit−vMv, where
  • 0≦u≦0.25;
  • 3.5≦t≦4.3;
  • v≦0.5.
  • According to a preferred embodiment, the proportion of A5B19 crystalline phase represents at least 50% by volume of the alloy.
  • According to a second preferred embodiment, the equilibrium pressure at 40° C. for 1% by mass of hydrogen inserted is less than 1.5 bar.
  • According to an embodiment, the size of the hydrogen-absorbing alloy particles is characterized by a Dv 50% of 30 to 120 μm, preferably of 50 to 100 μm. According to another embodiment, the size of the particles of hydrogen-absorbing alloy is characterized by a Dv 50% of 120 to 200 μm.
  • The alloy of the invention can be prepared by the following three processes:
  • by melting the constitutive single elements of the alloy followed by slow freezing (standard metallurgy), by quenching (rapid freezing) as strip casting on a single roll or between double rolls, by hyperquenching (ultra-rapid cooling) using melt spinning techniques or rapid freezing on a single roll or between doubles rolls (“planar flow casting”)
  • by powder metallurgy (sintering) from single elements or prealloys,
  • by mechanosynthesis.
  • Other alloy manufacturing processes can also be envisaged.
  • The alloy of the invention may have undergone annealing.
  • The invention also proposes an electrode comprising an active ingredient comprising the alloy as described previously. The invention extends to a nickel metal hydride alkaline storage battery comprising at least one negative electrode comprising the alloy according to the invention.
  • It is advantageous, in order to obtain a still longer life span of the negative electrode, to mix a yttrium compound with the active ingredient containing the alloy. This compound can be an yttrium oxide, hydroxide or salt.
  • The yttrium-based compound is chosen from a non-exhaustive list comprising an yttrium-based oxide such as Y2O3, an yttrium-based hydroxide such as Y(OH)3 or a yttrium-based salt. Preferably, the yttrium-based compound is yttrium oxide Y2O3.
  • The yttrium-based compound is mixed with the alloy in a proportion such that the mass of yttrium represents from 0.1 to 2% of the mass of the alloy, preferably from 0.2 to 1% of the mass of alloy, preferably also from 0.2 to 0.7% of the mass of the alloy.
  • The process of addition of the yttrium-based compound to the active ingredient during the manufacture of the anode is simple to implement industrially. It does not require complex devices.
  • The anode is manufactured by covering an electrically conductive support with a paste made up of an aqueous mixture of the composition of active ingredient according to the invention and additives.
  • The support can be a nickel foam, a flat or three-dimensional perforated strip made of nickel or nickel-plated steel.
  • The additives are intended to facilitate the use or the performances of the anode. They can be thickeners such as carboxymethyl cellulose (CMC), hydroxypropylmethyl cellulose (HPMC), polyacrylic acid (PAA), poly(ethylene oxide) (PEO). They can also be binders such as butadiene-styrene (SBR) copolymers, polystyrene acrylate (PSA), polytetrafluoroethylene (PTFE). They can also be polymer fibres, such as polyamide, polypropylene, polyethylene, etc., in order to improve the mechanical properties of the electrode. They can also be conductive agents such as nickel powder, carbon powder or fibres, nanotubes.
  • Advantageously, the anode is covered with a surface layer intended to improve high-speed discharge and/or recombination with oxygen at the end of charging. The invention also relates to a nickel metal hydride alkaline storage battery comprising said at least one anode.
  • The battery according to the invention typically comprises at least one anode, at least one nickel cathode, at least one battery separator and an alkaline electrolyte.
  • The cathode is constituted by the active cathode mass deposited on a support which can be a sintered support, a nickel foam, a flat or three-dimensional perforated strip made of nickel or nickel-plated steel.
  • The active cathode mass comprises the active cathode ingredient and additives intended to facilitate its implementation or its performances. The active cathode ingredient is a nickel hydroxide Ni(OH)2 which can be partially substituted by Co, Mg and Zn. This hydroxide can be partially oxidized and can be coated with a surface layer based on cobalt compounds.
  • Among the additives there can be mentioned, without this list being exhaustive, carboxymethyl cellulose (CMC), hydroxypropylmethyl cellulose (HPMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), polyacrylic acid (PAA), polystyrene maleic anhydride (SMA), optionally carboxylated butadiene-styrene copolymers (SBR), a copolymer of acrylonitrile and butadiene (NBR), α copolymer of styrene, ethylene, butylene and styrene (SEBS), a terpolymer of styrene, butadiene and vinylpyridine (SBVR), polystyrene acrylate (PSA), polytetrafluoroethylene (PTFE), a fluorinated copolymer of ethylene and propylene (FEP), polyhexafluoropropylene (PPHF), ethylvinyl alcool (EVA), zinc oxide ZnO, fibres (Ni, C, polymers), powders of compounds based on cobalt such as Co, Co(OH)2, CoO, LixCoO2, HxCoO2, NaxCoO2.
  • The battery separator is generally composed of polyolefin fibres (e.g. polypropylene) or nonwoven porous polyamide.
  • The electrolyte is a concentrated alkaline aqueous solution comprising at least one hydroxide (KOH, NaOH, LiOH), in a concentration generally of the order of several times normality.
  • The electrode pastes are prepared in a standard fashion, the electrodes are manufactured, then at least one cathode, a battery separator and an anode are superposed in order to constitute the electrochemical bundle. The electrochemical bundle is introduced into a container and impregnated with an aqueous alkaline electrolyte. The battery is then closed.
  • The invention relates to any format of batteries: prismatic format (flat electrodes) or cylindrical format (spiral or concentric electrodes).
  • The battery according to the invention can be of the open (open or semi-open) type or of the sealed type.
  • The battery according to the invention is particularly well suited as an energy source for an electric vehicle or a portable device.
    • EXAMPLES
  • Alloys, the overall composition of which has the formula
    (La, Ce, Nd, Pr)1−uMgu(Ni, Mn, Al, Co)t, are produced by sintering prealloys
  • (La, Ce, Nd, Pr)(Ni, Mn, Al, Co)x (1<x<=5) and Mg2Ni in sealed crucibles under argon and annealed at temperatures comprised between 800 and 1100° C. for periods comprised between 1 hour and 10 days.
  • The elemental composition of these alloys is indicated in Table 1
    TABLE 1
    Elemental composition of the alloys
    Al-
    loy La Ce Nd Pr Mg Ni Mn Al Co t
    A 0.7 0 0 0 0.30 2.80 0 0 0.5 3.3
    B 0.20 0 0.20 0.45 0.15 3.58 0.02 0.05 0.05 3.7
    C 0.60 0.18 0.07 0.03 0.12 4.02 0.13 0.10 0.25 4.5
  • The alloy of Example A of the prior art is characterized by an Mg level equal to u=0.30, a value of t=3.3 and a value of v=0.5.
  • The alloy of Example B according to the invention has a magnesium level of u=0.15, a stoichiometry of t=3.7, and a partial substitution of the nickel by Mn, Al and Co at the level v=0.12.
  • The magnesium level of the alloy C which is outside the invention is equal to u=0.12, its stoichiometry is equal to t=4.5 and the nickel is substituted by Mn, Al and Co at the level v=0.48.
  • The composition of the alloys in terms of crystalline phases is determined using the trace of X-ray diffraction diagrams, using the copper wavelength Kα1. The composition in terms of crystalline phases is determined by following the Rietveld method (Rietveld, H. M., A profile refinement method for nuclear and magnetic structures. Journal of Applied Crystallography, 1969, 2, 6571). The compositions of alloys A, B and C in terms of crystalline phases are shown in Table 2.
    TABLE 2
    Composition of the alloys in terms of phases.
    Phase (%)
    Alloy Type A2B7(R) Type A2B7(H) Type A5B19(R) Type AB5(H)
    A 0 100 0 0
    B 9 1 82 8
    C 11 7 24 58
  • The alloy of Example A of the prior art is constituted only by a hexagonal A2B7 phase A2B7(H) of Ce2Ni7 type.
  • The alloy of Example B according to the invention comprises 10% A2B7 type phases (hexagonal of Ce2Ni7 type or rhombohedral of Gd2Co7 type,), 8% hexagonal AB5 phase of CaCu5 type and 82% rhombohedral A5B19 type phase of Ce5Co19 type.
  • The alloy C which is outside the invention is characterized by the presence of 24% A5B19 phase, 18% A2B7 phase and 58% AB5 phase.
  • A sample of alloy is coated with an epoxy resin, then polished. Different points on the polished sample are analyzed using a electronic microprobe with wavelength dispersive analysis in order to determine its composition. The B/A ratio where B is the sum of the level of Ni and of the element(s) M, and A is the sum of the La, Ce, Nd, Pr and Mg levels, is determined for each point analyzed.
  • The results of the analysis by electronic microprobe of the A5B19 phase of alloys A, B and C are shown in Table 3.
    TABLEAU 3
    Composition of the A5B19 phase of the alloys.
    Alloy La Ce Nd Pr Mg Ni Mn Al Co B/A
    A No A5B19 phase
    B 0.16 0.14 0.39 0.19 3.58 0.03 0.06 0.07 3.74
    C 0.45 0.12 0.05 0.02 0.21 3.31 0.12 0.14 0.28 3.85
  • The alloy A of the prior art does not contain any A5B19 phase.
  • The A5B19 phase of the alloy B according to the invention has an Mg level y equal to 0.19 and a level z of element M equal to 0.16.
  • The A5B19 phase of the alloy C which is outside the invention has an Mg level y equal to 0.21 and a level z of element M equal to 0.54.
  • The mass capacity of the alloys is determined in prismatic laboratory elements the capacity of which is limited by the anode.
  • The anodes comprising the alloys are constituted by a mixture of:
  • 65% (by weight) of the alloy reduced to powder the particle size distribution of which is characterized by a Dv 50% corresponding to a size of 40 μm
  • 30% (by weight) of nickel powder as conductive compound
  • 5% of PTFE as binder.
  • Yttrium oxide is added to the anode 3 of Table 4, at a level of 0.5% yttrium with respect to the alloy mass.
  • The cathode comprises a standard nickel foam type current collector and an active ingredient constituted by a nickel hydroxide partially substituted by Zn and Co, the conductive network of which, constituted by Co(OH)2 has been formed beforehand.
  • The anode and the cathode are separated by a polyolefin battery separator and a membrane intended to prevent any recombination of oxygen, released at the cathode, on the anode.
  • The electrolyte is an aqueous solution of KOH at 8.7 mole/litre.
  • After a first charge for 16 hours with a current of 40 mA per gram of alloy (charge for 16 hours at 40 mA/g), the alloy is activated over 10 cycles under the following conditions:
  • Discharge at 80 mA/g, cut-off voltage=0.9 V.
  • recharge for 16 hours at 40 mA/g
  • rest for 1 hour.
  • Then the batteries are cycled under the following conditions:
  • discharge for 48 minutes at 400 mA/g, cut-off voltage=0.9 V.
  • recharge for 52 minutes at 400 mA/g.
  • By alloy life span is meant the number of cycles corresponding to a discharged capacity equal to 80% of the maximum capacity measured during the activation period.
  • The capacities and life span in an open element is shown in Table 4.
    TABLE 4
    Discharged initial capacity and life span of the anodes
    Anode
    1 2 3 4
    Alloy A B B C
    Y2O3 (Y/alloy = 0.5% by mass) no no yes no
    Q (mAh/g) 367 358 355 323
    Life span (cycles) 153 257 398 174
  • The maximum capacity restored during activation by the anode 1 for which the active ingredient is the alloy A of the prior art is equal to 367 mAh/g. However, it decreases rapidly during cycling in order to reach 80% of the initial capacity at cycle 153.
  • The maximum capacity restored during activation by the anode 2 for which the active ingredient is the alloy B of the invention is equal to 358 mAh/g. The life span of this anode 2 is 257 cycles.
  • The anode 3 contains alloy B of the invention and yttrium oxide. The maximum capacity restored during the activation by this series is 355 mAh/g and its life span is 398 cycles.
  • The capacity of the anodes 2 and 3 is greater than 320 mAh/g, which is the mass capacity of the NiMH batteries of the prior art.
  • The addition of yttrium oxide to the anode 3 makes it possible to prolong the life span of the anode by 141 cycles compared with the anode 2.
  • The maximum capacity restored during activation by the anode 4, for which the active ingredient is the alloy C which is outside the invention, is equal to 323 mA/g. This is attributed to the large quantity of AB5 type phase contained in this alloy. Its life span is limited to 174 cycles.

Claims (23)

1. Hydrogen-absorbing alloy comprising at least one crystalline phase of type A5B19 having the formula R1−yMgyNi3.8±0.1−zMz, in which:
R represents one or more elements chosen from
La, Ce, Nd or Pr;
M represents one or more elements chosen from
Mn, Fe, Al, Co, Cu, Zr, Sn and M does not contain Cr;
0≦y≦0.30;
z≦0.5.
2. Alloy according to claim 1, in which the sum of the stoichiometric indices of nickel and M is 3.8.
3. Alloy according to claim 1, in which y≦0.25.
4. Alloy according to claim 1, in which y>0.15.
5. Alloy according to claim 1, in which z≦0.30.
6. Alloy according to claim 1, in which the stoichiometric index of each of the nickel substituents is less than or equal to 0.20.
7. Alloy according to claim 6, in which the stoichiometric index of each of the nickel substituents is less than or equal to 0.15.
8. Alloy according to claim 1, in which M represents one or more elements chosen from Co, Al and Mn.
9. Alloy according to claim 1, in which M is CoaAlb, with a≦0.15 and b≦0.15.
10. Alloy comprising a crystalline phase A5B19 as defined in claim 1, and the overall composition of which has the formula:

R1−uMguNit−vMv where
0≦u≦0.25;
3.5≦t≦4.3;
v≦0.5.
11. Alloy according to claim 10 in which the crystalline phase AbB19 represents at least 50% by volume of the alloy.
12. Alloy according to claim 1, in which the equilibrium pressure at 40° C., for 1% by mass of hydrogen inserted, is less than 1.5 bar.
13. Alloy according to claim 1, in which the size of the particles is characterized by a Dv 50% of 30 to 120 μm, preferably of 50 to 100 μm.
14. Alloy according to claim 1, in which the size of the particles is characterized by a Dv 50% of 120 to 200 μm.
15. Electrode comprising an active ingredient comprising the alloy according to claim 1.
16. Electrode according to claim 15 also comprising an yttrium-based compound.
17. Electrode according to claim 16, in which the yttrium compound is an oxide such as Y2O3, an hydroxide such as Y(OH)3 or an yttrium salt.
18. Electrode according to claim 17, in which the mass of yttrium represents from 0.1 to 2% of the mass of the alloy, preferably from 0.2 to 1% of the mass of the alloy, also preferably from 0.2 to 0.7% of the mass of the alloy.
19. Nickel metal hydride alkaline storage battery comprising with at least one negative electrode according to claim 15.
20. Process for the manufacture of an alloy according to claim 1 comprising the stages of:
melting the single elements of the alloy
quenching or hyperquenching.
21. Process for the manufacture of an alloy according to claim 1 comprising the stage of:
sintering from the single elements of the alloy or
sintering from prealloys.
22. Process for the manufacture of an alloy according to claim 1 comprising a stage of mechanosynthesis.
23. Process according to claim 20 for the manufacture of an alloy comprising an annealing stage.
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US20090011332A1 (en) * 2007-07-06 2009-01-08 Saft Groupe Sa Negative active material for nickel-metal hydride accumulator
EP2487270A1 (en) 2010-11-29 2012-08-15 Saft Active material for a negative electrode of a nickel-metal hydride alkaline accumulator
CN106207143A (en) * 2016-07-20 2016-12-07 燕山大学 A kind of single-phase super stacking provisions Pr Mg Ni base hydrogen-storing alloy and preparation method thereof
CN114203999A (en) * 2020-08-31 2022-03-18 Fdk株式会社 Hydrogen storage alloy, negative electrode containing hydrogen storage alloy and nickel-hydrogen secondary battery containing negative electrode

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US20090206302A1 (en) 2009-08-20
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EP1826283A1 (en) 2007-08-29
FR2897875B1 (en) 2008-12-05

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