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
  • H01M4/244—Zinc electrodes
• • 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
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  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
  • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
  • C04B35/62605—Treating the starting powders individually or as mixtures
  • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
  • C04B35/6265—Thermal treatment of powders or mixtures thereof other than sintering involving reduction or oxidation
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/24—Alkaline accumulators
• • 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
• • 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
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/624—Electric conductive fillers
• • 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
  • H01M4/64—Carriers or collectors
  • H01M4/66—Selection of materials
  • H01M4/664—Ceramic materials
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
  • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
  • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
  • C04B2235/3234—Titanates, not containing zirconia
  • C04B2235/3236—Alkaline earth titanates
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/38—Non-oxide ceramic constituents or additives
  • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
  • C04B2235/3886—Refractory metal nitrides, e.g. vanadium nitride, tungsten nitride
• • 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

Definitions

• the present invention relates to the field of electrochemical generators, and more particularly to that of metal-air storage batteries and systems.
• the zinc electrode is well-known to the person skilled in the art for its high level of performance. It may furthermore be used in various secondary electrochemical systems: alkaline air-zinc, nickel-zinc and silver-zinc generators, bromine-zinc and chlorine-zinc generators with saline electrolytes.
• Zinc is an attractive anodic active material, having a strongly negative redox potential of ⁇ 1.25 V/NHE for the pair Zn/Zn(OH) 2 .
• the zinc electrode offers a theoretical gravimetric specific capacity of 820 Ah/kg. It accordingly makes it possible, for example, to achieve theoretical gravimetric specific energies of 334 Wh/kg for the nickel-zinc pair (NiZn), and of 1,320 Wh/kg for zinc-oxygen pair.
• the practical gravimetric specific energy may be between approximately 50 and 100 Wh/kg, the voltage furthermore being 1.65 volts, instead of the 1.2 volts for other alkaline systems.
• the present invention is based on the observation that insufficient drainage of charges within the active material promotes the formation of the zinc deposit during recharging at sites which represent only a limited percentage of the entire active mass.
• This zinc growth a phenomenon which most frequently gives rise to a chaotic deposit which may result in outgrowths through the separators or in densification of the deposit, accordingly proceeds from sites with a limited total surface area relative to the overall projected surface area of the anodic material.
• the technology described in the above-mentioned document shows that this mechanism may be greatly reduced if, by increasing the number of deposit formation sites, the same total quantity of zinc is deposited over a much larger surface area throughout the volume of the electrode.
• this technology results in the use, within the zinc anode, of two or three levels of electrical collection:
• the aim of the present invention is to improve the cyclability of the zinc electrode by prior treatment of the conductive ceramic, before the addition thereof to the active mass of the zinc electrode, the purpose of the treatment being to impart to said ceramic powder a second function of retaining the zincates formed on discharge of the zinc anode.
• titanates and hydrated titanium oxides have ion-exchange properties, which are utilised for treatment of effluents containing radioactive ions.
• titanium nitrides in particular in powder form, are not inert with regard to atmospheric oxygen, even at ambient temperature.
• Uncrystallised or slightly crystallised titanium oxynitrides and titanium oxides which may be detected by XPS analysis, form on the surface of the grains.
• RX analysis of TiN powders does not necessarily reveal the presence of titanium oxide, but a modification of the nitride lattice parameter corresponding to compounds which are sub-stoichiometric in nitrogen may be observed.
• TiN powders are generally produced by nitriding titanium. They always exhibit nitrogen deficits of 0.5 to 2% relative to the stoichiometric quantity, which is 22.62% by weight. This deficit may be even larger when the powders are prepared by methods such as nitriding of titanium dioxide with ammonia, or synthesis by a self-propagating thermal reaction from titanium oxide, titanium halides, etc.
• Titanium oxynitrides are of the general chemical formula TiN x O y , with x and y varying between 0.01 and 0.99.
• titanium oxynitrides At low oxygen contents, the (face-centred cubic) crystalline structure and the corresponding parameters of titanium oxynitrides are virtually identical to those of the nitride, which makes them difficult to identify by RX analysis. Titanium oxynitrides are black in colour, and if TiN is golden in colour, progressive oxidation of the TiN results in a colour change starting from bronze to brown and then to black.
• the oxidation temperature of TiN powders is closely related to the nature of the samples. Fine powders of a diameter of approximately 5 ⁇ m begin to oxidise at around 350° C., whereas coarser powders of 50 ⁇ m will begin to do so at around 500° C. (P. Lefort and al., Journal of Less Common Metals, no. 60, page 11, 1978).
• Extended, high-temperature treatment of TiN powder results in the formation of rutile-type titanium oxide.
• the oxidising pretreatment must be performed while avoiding the formation of a significant layer of titanium oxide, which would bring about an excessive reduction in the electron conduction of the grains, and would furthermore be totally inert with regard to the alkaline medium.
• This pretreatment depends on the nature and the particle size of the TiN used. The smaller is the size of the particles, the higher is the reactivity of the TiN with regard to oxygen.
• preferred TiN powders advantageously have a particle size essentially less than 10 microns.
• Pretreatment may more readily be performed in air. It is, however, also possible to use pure oxygen or mixtures of inert gas and oxygen.
• the inert gas may be nitrogen, helium or argon.
• the oxygen content may be between 1% and 99%.
• gas pressure is of little significance, and treatment may in particular be performed at ambient pressure in the case of air, or with a slightly elevated pressure in the case of oxygen or synthetic mixtures of gas, said elevated pressure being for example between 0.1 kPa and 5 kPa.
• the duration of treatment will depend mainly on the composition of the gas (in particular on the oxygen content), the temperature and the grain size.
• the temperature is between approximately 150 and 800° C., for treatment times of between 5 minutes and 15 hours. It must be ensured, when treating very fine TiN powders, that temperature is raised progressively in order to prevent abrupt oxidation of the powder by ignition.
• the titanium nitride powder modified according to the present invention obtained after such an oxidising pretreatment, may be handled without any particular precautions other than those recommended for titanium nitride powders produced according to the various production processes already mentioned above.
• the zinc anodes will preferably be produced according to the production processes described in French patent applications 99 00859 and 01 10488.
• the anode has two, or even three, electrical collection networks, which constitute as many sets of potential zinc nucleation sites during recharge, although the conductive ceramic powder is the first among these networks:
• the pretreated TiN particles which here constitute the conductive ceramic and will be the main conductive zincate binding sites, it may also be useful, as described in document FR 01 10488, to introduce into the anodic mass additives such as alkali metal or alkaline-earth metal titanates, and also to add to the mixture of conductive ceramic and titanates, or to the active mass, a quantity of an additive consisting of at least one compound based on aluminium and/or calcium, and/or a quantity of an additive consisting of at least one compound which, on contact with the alkaline electrolyte, forms soluble aluminium compounds, of between approximately 1 and 5% by weight relative to the zinc oxide.
• the anodic mass additives such as alkali metal or alkaline-earth metal titanates
• a quantity of an additive consisting of at least one compound based on aluminium and/or calcium and/or a quantity of an additive consisting of at least one compound which, on contact with the alkaline electrolyte, forms soluble aluminium compounds, of between approximately
• the electrolyte may also have added to it a quantity of an additive consisting of at least one soluble compound of aluminium and/or of calcium, of between approximately 1 and 5% by weight relative to the zinc oxide.
• the ion-exchange power of the ceramics pretreated according to the invention is improved by the addition of aluminium and/or calcium in various forms to the anodic active mass or to the electrolyte.
• the zinc anode used may advantageously be of the pasted/plasticised electrode type, and thus be produced by pasting, coating or filling by any means, in the liquid or dry phase, of a highly porous, three-dimensional support of the reticulate honeycomb metal foam type, with a paste in particular containing zinc oxide powder, the dispersion of ceramic particles, a plasticiser, and optionally a suspending agent.
• Nickel-zinc storage batteries are produced with pasted/plasticised nickel cathodes within a support of nickel foam.
• the zinc anodes are produced by pasting a copper foam support, covered with lead by electrolytic deposition, of grade 45 PPI (pores per inch) or 18 pores per linear centimetre.
• the density of the support is 450 g/m 2 .
• the active mass for the zinc electrodes is prepared to form a paste of the following composition:
• the TiN powder used for the type A electrode is a commercial product.
• the TiN powder used for the type B electrodes is identical to the powder used for the electrodes A, but has undergone an oxidation pretreatment of 30 minutes at 250° C. in air according to the present invention.
• the solid particles constituting the active mass were subjected to thorough kneading before the addition of water, in order to ensure that they were mixed intimately and as homogeneously as possible.
• the electrolyte used is potassium hydroxide (KOH) of a concentration of 5 N. It is saturated with zincates and contains 10 g/l of lithium hydroxide (LiOH).
• the active mass is dried, and the resultant zinc anode is compacted under a compaction pressure of 80 kg per square centimetre. Thickness is reduced 0.8 mm.
• the electrolyte used is potassium hydroxide (KOH) of a concentration of 5 N. It is saturated with zincates and contains 10 g/l of lithium hydroxide (LiOH).
• Open nickel-zinc storage battery assemblies were produced by associating two nickel cathodes with one zinc anode, such that the latter defines the capacity of the storage battery and the properties thereof may be monitored during testing.
• a combination of two separators is used between the electrodes of opposite polarity.
• One is a microporous membrane, such as that offered for sale under the brand “Celgard” by the company Hoescht Celanese.
• the other is a nonwoven polyamide or polypropylene separator, such as the reference product “FS 2115” from Carl Freudenberg.
• the storage batteries produced in this manner are subjected to long-term cycling tests in accordance with standardised methods.
• the type of charge-discharge cycle used, at a set current, is as follows: C/4 mode (charge and discharge each performed in 4 hours, the applied current corresponding to one quarter of the nominal capacity of the element) with a depth of discharge of approx. 80%; one cycle comprising total discharge (100% depth) is performed every ten cycles.
• the type A electrodes retain more than 80% of their nominal capacity for 300 to 400 cycles depending on the particular electrode before their capacity drops off very rapidly.
• the type B electrodes retained more than 80% of their nominal capacity for more than 1,000 cycles, and achieved more than 1,500 cycles with a capacity greater than 70% of nominal capacity. Cycling was stopped after 2000 cycles without any abrupt drop in capacity being observed.
• said titanium oxides and oxynitrides may in turn change into partially crystallised titanates so forming zincate binding zones and imparting to the ceramic particles their second function of retaining zincates as the site of formation thereof (by oxidation of metallic zinc on discharge).
• This function is in addition to the primary electron conduction function of the ceramic particles, which latter function promotes the in situ reduction of said zincates into metallic zinc when the generator is charged.
• This twin function of the pretreated ceramic additive according to the invention thus makes it possible to avoid over the very long term the morphological changes to the zinc anode which are usually observed and would result in a short cycle life.
• the invention may be performed by being associated with some or all of the additives or charging procedures described in the literature and applied to the use of zinc electrodes.

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• 2002
  • 2002-07-30 FR FR0209644A patent/FR2843235B1/fr not_active Expired - Lifetime
• 2003
  • 2003-07-25 ES ES03766408T patent/ES2280804T3/es not_active Expired - Lifetime
  • 2003-07-25 CA CA2517830A patent/CA2517830C/fr not_active Expired - Lifetime
  • 2003-07-25 EP EP03766408A patent/EP1572598B1/fr not_active Expired - Lifetime
  • 2003-07-25 CN CNB03818270XA patent/CN100448069C/zh not_active Expired - Lifetime
  • 2003-07-25 RU RU2005105932/03A patent/RU2335482C2/ru active IP Right Revival
  • 2003-07-25 KR KR1020057001656A patent/KR101077951B1/ko not_active Expired - Fee Related
  • 2003-07-25 DE DE60311309T patent/DE60311309T2/de not_active Expired - Lifetime
  • 2003-07-25 WO PCT/EP2003/050334 patent/WO2004013064A2/fr not_active Ceased
  • 2003-07-25 JP JP2004525427A patent/JP4560404B2/ja not_active Expired - Lifetime
  • 2003-07-25 AU AU2003262539A patent/AU2003262539A1/en not_active Abandoned
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