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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• 2006
  • 2006-02-28 FR FR0601751A patent/FR2897875B1/fr not_active Expired - Fee Related
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