EP4272272A1 - Verfahren zur herstellung einer porösen anode für eine lithium-ionen-sekundärbatterie, resultierende anode und batterie mit der anode - Google Patents

Verfahren zur herstellung einer porösen anode für eine lithium-ionen-sekundärbatterie, resultierende anode und batterie mit der anode

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Publication number
EP4272272A1
EP4272272A1 EP21835415.7A EP21835415A EP4272272A1 EP 4272272 A1 EP4272272 A1 EP 4272272A1 EP 21835415 A EP21835415 A EP 21835415A EP 4272272 A1 EP4272272 A1 EP 4272272A1
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EP
European Patent Office
Prior art keywords
tii
anode
porous
layer
coating
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EP21835415.7A
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English (en)
French (fr)
Inventor
Fabien Gaben
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I Ten SA
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I Ten SA
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Publication of EP4272272A1 publication Critical patent/EP4272272A1/de
Pending 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0457—Electrochemical coating; Electrochemical impregnation from dispersions or suspensions; Electrophoresis
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/362—Composites
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/626—Metals
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 invention relates to the field of electrochemistry, and more particularly to electrochemical systems. It relates more particularly to electrodes which can be used in batteries having a capacity greater than 1 mA h.
  • the invention relates to a new process for the manufacture of porous anodes which can be used in electrochemical systems such as high-power batteries (in particular lithium ion batteries). This process uses nanoparticles of an anode material.
  • the invention also relates to the anodes obtained by this process, which are mesoporous.
  • the invention also relates to batteries comprising such a porous anode.
  • the invention also relates to a process for preparing a lithium ion battery formed from such a mesoporous anode, which is in contact with a porous separator, the latter also being in contact with a cathode porous.
  • These porous electrode/separator assemblies can be impregnated with a liquid electrolyte.
  • the invention relates to anodes combining the following characteristics: a high volume capacity (expressed in mAh/cm 3 ), an insertion potential high enough to allow rapid recharging without inducing risks of "plating" of lithium, and the absence of significant variations in volume during the steps of charging and discharging the battery, so that said battery can be implemented in the form of a rigid structure, entirely solid and mesoporous one-piece.
  • the ideal batteries for powering autonomous electrical devices such as: telephones and portable computers, portable tools, autonomous sensors
  • traction of electric vehicles would have a long lifespan, would be able to store both large quantities of energy and power, could operate in a very wide temperature range and would present no risk of overheating or explosion.
  • these electrical devices are essentially powered by lithium ion batteries, which have the best energy density among the various storage technologies proposed.
  • the manufacturing processes for lithium ion batteries are presented in numerous articles and patents, and the books “Advances in Lithium-Ion Batteries” (Ed. W. van Schalkwijk and B.
  • the electrodes of lithium ion batteries can be manufactured using known coating techniques (in particular by coating techniques, such as roller coating (called “roll coating”), curtain (called “curtain coating” in English), coating through a slot (called “slot die coating” in English), scraping (called “doctor blade” in English), tape casting (called “tape casting “ in English)).
  • coating techniques such as roller coating (called “roll coating"), curtain (called “curtain coating” in English), coating through a slot (called “slot die coating” in English), scraping (called “doctor blade” in English), tape casting (called “tape casting " in English)).
  • the active materials used to make the electrodes are used in the form of suspensions of powders, the average particle size of which is between 5 ⁇ m and 15 ⁇ m in diameter. These particles are integrated into an ink which consists of these particles, organic binders, and a charge of a powder of an electronic conductive material (“conductive filler”), typically carbon black. This ink is deposited on the surface of a metal substrate, then dried in order to eliminate the organic solvents it contains and leave on the surface of the metal strip nothing more than a porous deposit consisting of particles of active materials mechanically bound between -they by organic binders and electrically connected by carbon black.
  • conductive filler typically carbon black
  • the inks (or pastes) deposited to form the electrodes contain particles of active materials, but also binders (organic), carbon powder making it possible to ensure electrical contact between the particles, and solvents which are evaporated during the electrode drying step.
  • a calendering step is performed on the electrodes. After this compression step, the active particles of the electrodes occupy approximately 60-70% of the volume of the deposit, which means that there generally remain 30 to 40% of porosities between the particles.
  • the electrode films with the highest volume energy densities are produced using vacuum deposition techniques, for example in PVD. These films are completely dense, and have no porosities. On the other hand, as these entirely solid films do not contain liquid electrolytes to facilitate ionic transport nor electronically conductive charge to facilitate the transport of electrical charges, their thickness remains limited to a few microns in order to prevent them from becoming too resistive.
  • the thickness of these electrodes can be greatly increased in comparison with what is possible with the techniques of vacuum deposition. These increases in thickness also contribute to the increase in the energy density of the battery cells.
  • the particles of active material have a size generally comprised between 5 ⁇ m and 15 ⁇ m.
  • the contact between two neighboring particles is essentially point-like, the particles being bonded together by an organic binder which is usually PVDF.
  • the liquid electrolytes used for the impregnation of the electrodes consist of aprotic solvents in which lithium salts have been dissolved. These organic electrolytes are highly flammable and can lead to violent combustion of battery cells, especially when the active cathode materials are stressed in voltage ranges outside their stability voltage range, or when hot spots appear locally. in the cell.
  • o Homogenize the particle sizes, in order to avoid local imbalances of states of charge which can lead during intensive discharges to locally soliciting active materials outside their conventional operating voltage ranges. This optimization would then be to the detriment of the energy density of the cell. o Homogenize the distribution and distribution of conductive charges (carbon black) in the electrode, in order to avoid locally having more electrically resistive zones which could lead to the formation of a hot spot during the power operation of the battery.
  • the manufacturing cost of the electrodes depends in part on the nature of the solvents used.
  • the manufacturing cost of the electrodes comes mainly from the complexity of the inks used (binders, solvents, carbon black, etc.).
  • NMP The main solvent used for the production of lithium ion battery electrodes.
  • NMP is an excellent solvent for dissolving PVDF which acts as a binder in the formulation of inks.
  • the drying of the NMP contained in the electrodes is a real economic issue.
  • the high boiling temperature of NMP coupled with a very low vapor pressure makes its drying difficult to achieve. Solvent vapors must be collected and reprocessed.
  • the drying temperature of the NMP must not be too high, which again tends to increase the drying time and its cost; this is described in the publication “Technical and economic analysis of solvent-based lithium-ion electrode drying with water and NMP" by D.L. Wood & al., published in the journal Drying Technology, vol. 36, n°2 (2018).
  • inks Other less expensive solvents can be used to make inks, including water and ethanol.
  • their surface tension is greater than that of NMP, and they therefore wet the surface of the metallic current collectors less well.
  • particles tend to agglomerate in water, especially carbon black nanoparticles. These agglomerations lead to a heterogeneous distribution of the components entering into the composition of the electrode (binders, carbon ).
  • traces of water can remain adsorbed on the surface of the particles of active materials, even after drying.
  • the energy stored in the batteries is the product of the capacity of the electrodes in Ah or in mAh multiplied by the operating voltage of the cell. This operating voltage is the difference between the lithium insertion potentials in the anodes and the cathodes.
  • anodes inserting lithium at a relatively high voltage (greater than 0.5V/Li) to avoid the formation of lithium dendrites during the fast charging phases. These anodes must also have very high mass capacities in order to compensate for energy losses by reducing the operating voltage by increasing their capacity. Have electrodes with a very large specific surface, and particle sizes (thickness of the insertion zones) as homogeneous as possible to avoid dynamic imbalances.
  • the present invention aims to provide a lithium ion battery which has at least some of these technical characteristics, and which preferably has all of these characteristics. According to the invention, this problem is solved by a judicious choice of the material of the anode and its structure, and by a manufacturing process which makes it possible to obtain an anode of such a structure.
  • the problem is solved by a process for manufacturing a porous anode for a battery designed to have a capacity greater than 1 mA h comprising an anode, a separator and a cathode, said anode having a porosity of between 25 and 50% by volume, and preferably approximately 35% by volume, and pores with an average diameter of less than 50 nm, according to a particular process which forms the first object of the invention.
  • the anode according to the invention is advantageously used in batteries designed to have a capacity greater than 1 mA h.
  • the process for manufacturing the porous battery anode according to the invention comprises the following steps:
  • M 1 and M 2 are each at least one element selected from the group consisting of Nb, V, Ta, Fe, Co, Ti, Bi, Sb, As, P, Cr , Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs, Ce and Sn, M 1 and M 2 possibly being identical to or different from each other, and in which 0 ⁇ w ⁇ 5 and 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 2 and 0 ⁇ 5 ⁇ 0.3; o Tii. x M 1 xNb2-yM 2 yO7-zM 3 z , Li w Tii. x M 1 xNb2-yM 2 yO7-zM 3 z in which
  • ⁇ M 1 and M 2 are each at least one element chosen from the group consisting of Nb, V, Ta, Fe, Co, Ti, Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs, Ce and Sn,
  • ⁇ M 1 and M 2 can be identical or different from each other
  • ⁇ M 3 is at least one halogen
  • o TiNb2C>7-zM 3 z Li w TiNb2C>7-zM 3 z in which M 3 is at least one halogen, preferably chosen from F, Cl, Br, I or a mixture thereof, and0 ⁇ w ⁇ 5 and 0 ⁇ z ⁇ 0.3; o Tii-xGe x Nb2-yM 1 yO7-zM 2 z , Li w Tii-xGe x Nb2-yM 1 yO7-zM 2 z , Tii-xLa x Nb2-yM 1 yO7-zM 2 z , Li w Tii.
  • ⁇ M 1 and M 2 are each at least one element chosen from the group consisting of Nb, V, Ta, Fe, Co, Ti, Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs, Ce and Sn,
  • ⁇ M 1 and M 2 can be identical or different from each other
  • ⁇ M 1 is at least one element selected from the group consisting of Nb, V, Ta, Fe, Co, Ti, Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs, Ce and Sn,
  • step (b) depositing on at least one face of said substrate a layer from said colloidal suspension or paste provided in step (a), by a method selected from the group formed by: electrophoresis, extrusion, a printing process and preferably ink jet printing or flexographic printing, a coating process and preferably squeegee, roller, curtain, dipping, or through a die slot ;
  • said layer obtained in step (b) is dried and consolidated, by pressing and/or heating, to obtain a porous layer.
  • said anode active material A can also be selected from niobium oxides and mixed oxides of niobium with titanium, germanium, cerium, lanthanum, copper, or tungsten, and preferably from the groups formed by: o Nb20s-s , NbisWieOgs-s , NbieWsOss-s with 0 Sx ⁇ 1 and 0 ⁇ 5 s 2 o TiNb2C>7-8 with 0 ⁇ 5 ⁇ 0.3, Tii. x M 1 xNb2-yM 2 yO7-s , Li w Tii.
  • M 1 and M 2 are each at least one element selected from the group consisting of Nb, V, Ta, Fe, Co, Ti, Bi, Sb, As, P, Cr , Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs, Ce and Sn, M 1 and M 2 may be the same or different from each other , and wherein 0 ⁇ w ⁇ 5 and 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 2 and 0 ⁇ 5 ⁇ 0.3; o Tii-xM 1 xNb2-yM 2 y O7-zM 3 z , Li w Tii-xM 1 xNb2-yM 2 y O7-zM 3 z in which
  • ⁇ M 1 and M 2 are each at least one element chosen from the group consisting of Nb, V, Ta, Fe, Co, Ti, Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs, Ce and Sn,
  • ⁇ M 1 and M 2 can be identical or different from each other
  • ⁇ M 3 is at least one halogen
  • ⁇ M 1 and M 2 are each at least one element chosen from the group consisting of Nb, V, Ta, Fe, Co, Ti, Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs, Ce and Sn,
  • ⁇ M 1 and M 2 can be identical or different from each other
  • ⁇ M 1 is at least one element selected from the group consisting of Nb, V, Ta, Fe, Co, Ti, Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs, Ce and Sn,
  • step (c) said layer is heated to a temperature sufficient to remove the organic residues by evaporation and/or pyrolysis (step called debinding).
  • step (c) are carried out in several steps, or even during a continuous temperature ramp.
  • This treatment begins with drying, optionally followed by debinding if the deposit contains organic matter (this debinding is a heat treatment in air to pyrolyze or calcine the organic matter), and finally a consolidation treatment which may only be a treatment thermal and/or thermomechanical treatment.
  • the anode active materials A represented by formulas indicating the possible presence of lithium, namely U w Tii. x M 1 xNb2-yM 2 yO7, Li w Tii. x M 1 xNb2-yM 2 yO7-zM 3 z , Li w Tii. x Ge x Nb2-yM 1 yO7-zM 2 z , Li w Tii.xGe x Nb2-yM 1 yO7-z , Li w Tii.xLa x Nb2-yM 1 yO7-zM 2 z , Li w Tii.
  • step (b) the deposition can be done on both sides of the substrate.
  • said substrate may be a substrate capable of acting as an electric current collector.
  • the thickness of the layer after step (c) is advantageously between about 1 ⁇ m and about 300 ⁇ m, or between 1 ⁇ m and 150 ⁇ m.
  • said substrate is an intermediate, temporary substrate, such as a polymer film.
  • the layer can be separated from its substrate after drying, preferably before heating it, but at the latest at the end of step (c).
  • the thickness of the layer after step (c) is advantageously between about 5 ⁇ m and about 300 ⁇ m.
  • step (d) when the layers are thick and resistive, it is advantageous to add step (d) according to which:
  • Step (d) depositing, ie forming, on and inside the pores of said porous layer, a coating of an electronically conductive material, said electronically conductive material preferably being carbon or an electronically conductive oxide material.
  • Step (d) can be performed by ALD.
  • Step (d) may comprise the following successive steps, where during a step (d1), on and inside the pores of said porous layer, a layer of a precursor of an electronically conductive material is deposited , and during a step (d2), the precursor of an electronically conductive material, deposited during step (d1) on said porous layer, is transformed into an electronically conductive material, so that said layer present on and inside the pores, a layer of said electronically conductive material.
  • step (d1) is advantageously carried out by immersing the porous layer in a liquid phase comprising a carbon-rich compound, such as a carbohydrate, and said transformation into an electronically conductive material carried out during step ( d2) is, in this case, a pyrolysis, preferably carried out under an inert atmosphere, more preferably under nitrogen.
  • Step (d1) is advantageously carried out by immersing the porous layer in a liquid phase comprising a precursor of said electronically conductive material, and, in this case, said transformation of the precursor from an electronically conductive material into an electronically conductive material, during step (d2) is a heat treatment such as calcination, preferably carried out in air or in an oxidizing atmosphere.
  • said precursor of the electronically conductive material is chosen from organic salts containing one or more metallic elements capable, after heat treatment such as calcination, preferably carried out in air or under an oxidizing atmosphere, of forming an electronically conductive oxide.
  • metallic elements preferably these metallic cations, can advantageously be chosen from tin, zinc, indium, gallium, or a mixture of two or three or four of these elements.
  • the organic salts are preferably chosen from an alkoxide of at least one metallic element capable, after heat treatment such as calcination, preferably carried out in air or under an oxidizing atmosphere, of forming an electronic conductive oxide, an oxalate of au at least one metallic element capable, after calcination in air, of forming an electronically conductive oxide and an acetate of at least one metallic element capable, after heat treatment such as calcination, preferably carried out in air or in an oxidizing atmosphere, of forming an electronic conductive oxide.
  • said electronically conductive material may be an electronically conductive oxide material, preferably chosen from: tin oxide (SnC>2), zinc oxide (ZnO), indium oxide (ln 2 O 3 ), gallium oxide (Ga 2 O 3 ), a mixture of two of these oxides such as indium-tin oxide corresponding to a mixture of indium oxide (ln 2 O 3 ) and tin oxide (SnC>2), a mixture of three of these oxides or a mixture of four of these oxides, the doped oxides based on zinc oxide, the doping being preferably with gallium (Ga) and/or aluminum (Al) and/or boron (B) and/or beryllium (Be), and/or chromium (Cr) and/or cerium (Ce) and/or titanium (Ti) and/or indium (In) and/or cobalt (Co) and/ or nickel (Ni) and/or copper (Cu) and/or manganese (Mn) and/or germanium
  • said primary nanoparticles are advantageously in the form of aggregates or agglomerates, said aggregates or agglomerates having an average diameter D50 of between 50 nm and 300 nm, and preferably between 100 nm and 200 nm.
  • Said porous layer from step (c) has a specific surface of between 10 m 2 /g and 500 m 2 /g.
  • the deposition of said coating of electronically conductive material is carried out by the technique of deposition of atomic layers ALD or by immersion in a liquid phase comprising a precursor of said electronically conductive material, followed by the transformation of said precursor into electronically conductive material.
  • the process for manufacturing the porous battery anode uses an intermediate polymer substrate (such as PET) and results in a strip called “raw strip”.
  • This raw strip is then separated from its substrate; it then forms plates or sheets (the term “plate” is used hereafter, whatever its thickness). These plates can be cut before or after their separation from their intermediate substrate.
  • These plates are then calcined in order to eliminate the organic constituents.
  • These plates are then sintered in order to consolidate the nanoparticles until a mesoporous ceramic structure with a porosity of between 25 and 50% is obtained.
  • Said porous plate obtained in step (c) advantageously has a thickness of between 5 ⁇ m and 300 ⁇ m. It is advantageous to deposit a coating of an electronically conductive material, as has just been described.
  • a metal sheet is also supplied, covered on both sides with a thin intermediate layer of nanoparticles, preferably identical to those constituting the electrode plate.
  • Said thin layer preferably has a thickness of less than 1 ⁇ m.
  • This sheet is then inserted between two porous electrode plates obtained previously (for example two porous anode plates).
  • the assembly is then heat-pressed so that said thin intermediate layer of nanoparticles is transformed by sintering and consolidates the electrode/substrate/electrode assembly to obtain a rigid and one-piece subassembly.
  • the bond between the electrode layer and the intermediate layer is established by diffusion of atoms; this phenomenon is known by the English term “diffusion bonding”.
  • This assembly is done with two electrode plates of the same polarity (typically between two anodes), and the metal sheet between these two electrode plates of the same polarity establishes a parallel connection between them.
  • One of the advantages of the second embodiment is that it makes it possible to use inexpensive substrates such as aluminum or copper strips. Indeed, these strips would not resist the heat treatments for consolidating the deposited layers; gluing them to the electrode plates after their heat treatment also prevents their oxidation.
  • This assembly by “diffusion bonding” can be carried out separately as has just been described, and the electrode/substrate/electrode subassemblies thus obtained can be used to manufacture a battery.
  • This assembly by diffusion bonding can also be carried out by stacking and thermopressing the entire structure of the battery; in this case, a multilayer stack is assembled comprising a first porous anode layer according to the invention, its metal substrate, a second porous anode layer according to the invention, a solid electrolyte layer, a first cathode layer, its metal substrate, a second cathode layer, a new solid electrolyte layer, and so on.
  • mesoporous ceramic electrode plates and in particular anodes according to the invention
  • mesoporous ceramic electrode plates and in particular anodes according to the invention
  • the electrolyte film is then deposited.
  • the necessary cutouts are then made to make a battery with several elementary cells, then the sub-assemblies are stacked (typically in “head to tail” mode) and thermocompression is carried out to weld the electrodes together at the level of the solid electrolyte.
  • the stack can be made comprising the first electrode plate, its substrate coated with the element used for bonding (typically an intermediate layer of nanoparticles of the material of the electrode to which this intermediate layer must be welded), the second electrode plate of the same polarity as the first, the solid electrolyte (separator), the electrode plate of opposite polarity, its substrate coated with the bonding element (typically an intermediate layer of nanoparticles of the material of the electrode to which this intermediate layer must be welded), and so on.
  • the final thermocompression is then carried out which is used both to weld the electrodes together at the level of the solid electrolyte but also to weld the electrode plates to the current collectors.
  • thermocompression is done at a relatively low temperature, which is possible thanks to the very small size of the nanoparticles. As a result, no oxidation of the metal layers of the substrate is observed.
  • Electrode plate the term “plate” encompasses the “sheets”
  • a conductive adhesive charged with graphite
  • a second object of the invention is a porous anode for a lithium ion battery designed to have a capacity greater than 1 mA h, comprising a porous layer with a porosity of between 25% and 50% by volume, preferably between 28 % and 43% by volume, and even more preferably between 30% and 40% by volume, characterized in that said porous layer comprises:
  • a porous network of a material A optionally comprising on and inside the pores forming said porous network a coating of an electronically conductive material, and characterized in that said material A is selected from niobium oxides and mixed oxides of niobium with titanium, germanium, cerium, lanthanum, copper, or tungsten, and preferably from the group formed by: o Nb20s-s , NbisWieOgs- s , NbieWsOss-s with 0 £ x ⁇ 1 and 0 s 5 ⁇ 2 o TiNb2C>7-8 , Tii.
  • M 1 and M 2 are each at least one element selected from the group consisting of Nb, V, Ta, Fe, Co, Ti, Bi, Sb, As, P, Cr , Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs and Sn, M 1 and M 2 possibly being the same or different from each other, and wherein 0 ⁇ w ⁇ 5 and 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 2 and 0 ⁇ S ⁇ 0.3; o Tii-xM 1 xNb2-yM 2 y O7-zM 3 z , Li w Tii-xM 1 xNb2-yM 2 y O7-zM 3 z in which
  • ⁇ M 1 and M 2 are each at least one element chosen from the group consisting of Nb, V, Ta, Fe, Co, Ti, Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs and Sn,
  • ⁇ M 1 and M 2 can be identical or different from each other
  • ⁇ M 3 is at least one halogen
  • ⁇ M 1 and M 2 are at least one element selected from the group consisting of Nb, V, Ta, Fe, Co, Ti, Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Ca , Ba, Pb, Al, Zr, Si, Sr, K, Cs, Ce and Sn;
  • ⁇ M 1 and M 2 are each at least one element chosen from the group consisting of Nb, V, Ta, Fe, Co, Ti, Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs, Ce and Sn,
  • ⁇ M 1 and M 2 can be identical or different from each other
  • a third object is a method for manufacturing a battery, preferably a lithium ion battery, implementing the method for manufacturing a porous anode according to the invention, or implementing a porous anode according to the invention. .
  • Such a process is a process for manufacturing a battery, comprising at least one porous anode according to the invention, at least one separator and at least one porous cathode, characterized in that:
  • a first colloidal suspension or a paste comprising aggregates or agglomerates of monodisperse primary nanoparticles of at least one anode active material A, with an average primary diameter D50 of between 2 and 100 nm, preferably between 2 and 60, is supplied nm, said aggregates or agglomerates having an average diameter D50 of between 50 nm and 300 nm (preferably between 100 nm and 200 nm), it being understood that said material A is selected from niobium oxides and mixed niobium oxides with the titanium, germanium, cerium, lanthanum, copper, or tungsten, and preferably from the group formed by: o Nb 2 O5-s , NbisWieOgs-s , NbieWsOss-s with 0 £ x ⁇ 1 and 0 s 5 ⁇ 2; o TiNb2C>7-8 , Tii.
  • M 1 and M 2 are each at least one element selected from the group consisting of Nb, V, Ta, Fe , Co, Ti, Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs and Sn, M 1 and M 2 which may be the same or different from each other, and wherein 0 ⁇ w ⁇ 5 and 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 2 and 0 ⁇ S ⁇ 0.3; o Tii-xM 1 xNb2-yM 2 y O7-zM 3 z , Li w Tii-xM 1 xNb2-yM 2 y O7-zM 3 z in which
  • ⁇ M 1 and M 2 are each at least one element chosen from the group consisting of Nb, V, Ta, Fe, Co, Ti, Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs and Sn,
  • ⁇ M 1 and M 2 can be identical or different from each other
  • ⁇ M 3 is at least one halogen
  • ⁇ M 1 is at least one element selected from the group consisting of Nb, V, Ta, Fe, Co, Ti, Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs, Ce and Sn,
  • ⁇ M 1 and M 2 are each at least one element chosen from the group consisting of Nb, V, Ta, Fe, Co, Ti, Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs, Ce and Sn,
  • ⁇ M 1 and M 2 can be identical or different from each other
  • said first and/or said second substrate may be a substrate capable of acting as an electric current collector, or an intermediate substrate,
  • a second colloidal suspension comprising aggregates or agglomerates of monodisperse primary nanoparticles of at least one cathode active material C, with an average primary diameter D50 of between 2 nm and 100 nm, preferably between 2 nm and 60 nm, said aggregates or agglomerates having an average diameter D50 of between 50 nm and 300 nm (preferably between 100 nm and 200 nm), and
  • a third colloidal suspension comprising aggregates or agglomerates of nanoparticles of at least one inorganic material E (which is preferably an electrical insulator), with an average primary diameter D50 of between 2 nm and 100 nm, preferably between 2 nm and 60 nm, said aggregates or agglomerates having an average diameter D50 of between 50 nm and 300 nm (preferably between 100 nm and 200 nm);
  • E which is preferably an electrical insulator
  • an anode layer from said first colloidal suspension provided in step (a) is deposited on at least one face of said first substrate, and a cathode layer is deposited on at least one face of said second substrate from said second colloidal suspension provided in step (a), by a process preferably selected from the group formed by: electrophoresis, extrusion, a printing process, preferably selected from jet printing of ink and flexographic printing, and a coating process, preferably selected from roller coating, curtain coating, doctor coating, coating by extrusion through a die in the form of slit, coating by dipping;
  • step (c) said anode and cathode layers obtained in step (b) are dried and, where appropriate after having separated said layer from its intermediate substrate, each layer is consolidated, by pressing and/or heating, to obtain respectively a porous anode layer, preferably mesoporous and inorganic, and a porous cathode layer, preferably mesoporous and inorganic;
  • a coating of an electronically conductive material is deposited on and inside the pores of said porous anode and/or cathode layers, so as to form said porous anodes and porous cathodes;
  • step (e) depositing on said porous anode and/or said porous cathode obtained in step (c) or (d), a porous inorganic layer from the third colloidal suspension supplied in step (a), by a technique selected from the group formed by: electrophoresis, extrusion, a printing process, preferably chosen from inkjet printing and flexographic printing, and a coating process, preferably chosen among roll coating, curtain coating, doctor coating, extrusion coating through a slot-shaped die, dip coating;
  • step (f) said porous inorganic layer of the structure obtained in step (e) is dried, preferably under a flow of air, and a heat treatment is carried out at a temperature above 130° C. and preferably between approximately 300°C and about 600°C, knowing that, where appropriate, the layer separated from its intermediate substrate is pressed onto a metal sheet capable of acting as a current collector, before carrying out said heat treatment;
  • step d the porous anode obtained in step d), or e) is successively stacked face to face with the porous cathode obtained in step d) or e), it being understood that in the stack obtained the layers d porous anode are separated from the porous cathode layers by at least one porous inorganic layer as obtained in step e) forming said separator;
  • thermocompression treatment is carried out at a temperature of between 120°C and 600°C of the stack obtained in step (g) in order to obtain a battery comprising at least one porous anode, at least one separator and at least one porous cathode.
  • step (h) is done after the deposition on the electrodes of the separator film.
  • step (h) can then be impregnated with an ionically conductive polymer or a polymer which has been made ionically conductive, or else with a liquid electrolyte containing at least one lithium salt, which are advantageously selected from the group formed by:
  • Yet another object of the invention is a lithium ion battery having a capacity greater than 1 mA h, capable of being obtained by the method according to the invention.
  • the battery comprises an anode according to the invention or capable of being obtained by the process according to the invention.
  • This anode advantageously has a mass capacity greater than 200 mAh/g, and preferably greater than 250 mAh/g.
  • a final object of the invention is the use of a battery according to the invention at a temperature below -10°C and/or at a temperature above 50°C, and preferably at a temperature below -20°C. C and/or at a temperature above 60°C, and even more preferably at a temperature below -30°C and/or at a temperature above 70°C.
  • the battery has a surface capacity of the anodes lower than that of the cathodes; This improves your battery temperature resistance.
  • the realization of entirely solid, sintered and multilayer structures poses many problems. It heats to high temperatures to achieve sintering, which can degrade electrode materials and induce interdiffusion at interfaces.
  • the process according to the invention uses nanoparticles, which makes it possible to reduce the sintering temperature.
  • partial sintering is advantageously carried out to obtain mesoporous structures.
  • this sintering can be carried out on the layers or plates of electrodes before assembly with the separator, which avoids that during sintering there are ceramic layers of different materials in contact.
  • a material is advantageously selected with a relatively low melting point and which is inert in contact with the electrodes in order to be able to carry out this assembly at a relatively low temperature.
  • FIG. 1 shows a discharge curve obtained with an anode in Tio.gsGeo.osNbgO? according to the invention, for two different regimes.
  • the size of a particle is defined by its largest dimension.
  • nanoparticle is meant any particle or object of nanometric size having at least one of its dimensions less than or equal to 100 nm.
  • electroconductive oxide includes electronic conductive oxides and electronic semiconductor oxides.
  • an electronically insulating material or layer preferably an electronically insulating and ion-conductive layer, is a material or a layer whose electrical resistivity (resistance to the passage of electrons) is greater than 10 5 ⁇ -cm.
  • ionic liquid is meant any liquid salt, capable of transporting electricity, differing from all molten salts by a melting temperature below 100°C. Some of these salts remain liquid at room temperature and do not solidify, even at very low temperatures. Such salts are called “ionic liquids at room temperature”.
  • mesoporous materials we mean any solid which has within its structure pores called “mesopores” having an intermediate size between that of micropores (width less than 2 nm) and that of macropores (width greater than 50 nm), namely a size between 2 nm and 50 nm.
  • This terminology corresponds to that adopted by IIIPAC (International Union for Pure and Applied Chemistry), which is a reference for those skilled in the art.
  • IIIPAC International Union for Pure and Applied Chemistry
  • nanopore is therefore not used here, even if the mesopores as defined above have nanometric dimensions within the meaning of the definition of nanoparticles, knowing that the pores of a size smaller than that of the mesopores are called by the skilled in the art of "micropores”.
  • the term “mesoporous layer” means a layer which has mesopores. As will be explained below, in these layers the mesopores contribute significantly to the total pore volume; this state of affairs is translated by the expression "Mesoporous layer of mesoporous porosity greater than X% by volume” used in the description below where X% is preferably greater than 25%, preferentially greater than 30% and even more preferentially between 30 and 50% of the total volume of the layer.
  • the term “aggregate” means, according to IUPAC definitions, a loosely bound assembly of primary particles. In this case, these primary particles are nanoparticles having a diameter which can be determined by transmission electron microscopy. An aggregate of aggregated primary nanoparticles can normally be destroyed (ie reduced to primary nanoparticles) in suspension in a liquid phase under the effect of ultrasound, according to a technique known to those skilled in the art.
  • agglomerate means, according to IUPAC definitions, a strongly bound assembly of primary particles or aggregates.
  • the term “electrolyte layer” refers to the layer within an electrochemical device, this device being capable of operating according to its intended purpose.
  • the term “electrolyte layer” designates the “porous inorganic layer” impregnated with a phase carrying lithium ions.
  • the electrolyte layer is an ion conductor, but it is electronically insulating.
  • Said porous inorganic layer in an electrochemical device is here also called “separator”, according to the terminology used by those skilled in the art.
  • the "porous inorganic layer”, preferably mesoporous, can be deposited electrophoretically, by the coating process by dipping hereinafter “dip-coating”, by the inkjet printing process.
  • dip-coating by the inkjet printing process.
  • ink-jet by roller coating (called “roll coating” in English), by curtain coating (called “curtain coating” in English) or by scraping hereinafter “doctor blade”, and this at from a suspension of aggregate or agglomerates of nanoparticles, preferably from a concentrated suspension containing agglomerates of nanoparticles.
  • monodisperse crystallized nanopowders with a primary particle size of less than 100 nm are preferably used for the layers of the electrodes and of the separator. This promotes sintering (necking) between the primary particles (in agglomerated form or not) during the consolidation treatment.
  • the consolidation can then take place at a relatively low temperature, knowing that insofar as the primary particles are already in the crystallized state, the object of this treatment is no longer to recrystallize them. For some chemical compositions, it must resort to specific synthesis methods to obtain populations of monodisperse crystallized nanoparticles.
  • compositions of the TNO (TiNb2O7) type have a very low electronic conductivity.
  • the particle size must be very small.
  • particles of the TNO (TiNb2O?) type can be synthesized hydrothermally, with a size dispersed between approximately 50 nm and approximately 300 nm; however, it is difficult to control this size, and the dispersion is wide.
  • This synthesis leads to amorphous particles which must then be crystallized by heat treatment at high temperature, for example around 1000°C for around 30 minutes. During this crystallization, the particles can grow in an uncontrolled manner, which widens the dispersion in size.
  • solid-state synthesis methods which also require high temperature treatment to homogenize the chemical composition.
  • nanoparticles In the context of the present invention, it is preferred to use primary nanoparticles, agglomerated or not, with a size of less than 100 nm, preferably less than 60 nm, and even more preferably less than 40 nm. Such nanoparticles can be obtained by various methods.
  • salts, complexes or alcoholates (such as ethanolates) of the cations of metallic elements entering into the composition of the desired phase are mixed together to obtain a perfectly homogenized distribution on the atomic scale, and polymers to freeze this distribution of molecules, ions or complexes comprising the metallic element.
  • These polymers are then eliminated by heat treatment and leave only the inorganic constituents at the atomic scale for which a simple calcination at relatively low temperature will make it possible to obtain the desired phase, crystallized, at the scale of nanoparticles. It is possible to add organic materials liable to strongly degas during the heat treatment phases, which will contribute to obtaining mesoporous agglomerates.
  • An example for such a synthesis is the “Pechini method”, a sol-gel type process in which the cations of the desired phase (in our case for example Nb, Ti and others) are complexed with an organic molecule (such as citric acid or EDTA (ethylene diamine tetra acetate)) and introduced into a polymer matrix (for example a polyalcohol such as polyethylene glycol or polyvinyl alcohol).
  • an organic molecule such as citric acid or EDTA (ethylene diamine tetra acetate)
  • a polymer matrix for example a polyalcohol such as polyethylene glycol or polyvinyl alcohol.
  • LiMn 2 C>4 powder consisting of clusters of nanoparticles using the Pechini method described in the article “Synthesis and Electrochemical Studies of Spinel Phase LiMn 2 O4 Cathode Materials Prepared by the Pechini Process”, W. Liu, GC Farrington, F. Chaput, B. Dunn, J. Electrochem. Soc., vol.143, No.3, 1996.
  • the powder contains clusters whose size is typically between 50 nm and 100 nm; the size of the primary nanoparticles, which are crystallized, is typically between 10 nm and 30 nm depending on the synthesis conditions.
  • a particularly preferred anode material is Li w Tii.xGe x Nb2-yM 1 yO7-zM 3 z wherein M 1 is at least one member selected from the group consisting of Nb, V, Ta, Fe, Co, Ti , Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs, Ce and Sn, and wherein 0 ⁇ w ⁇ 5, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 2 and z ⁇ 0.3.
  • M 3 is at least one halogen.
  • anode active materials A are particularly preferred; these are the Tii type materials. x Ge x Nb2- y M 1 y O7-zM 2 z , Li w Tii. x Ge x Nb2- y M 1 y O7-zM 2 z , Tii. x La x Nb2- y M 1 y O7-zM 2 z , Li w Tii.xLa x Nb2-yM 1 yO7-zM 2 z , Tii.xCu x Nb2-yM 1 yO7-zM 2 z , Li w Tii-xCu x Nb2-yM 1 yO7-zM 2 z , Tii. x Ce x Nb2- yM 1 yC>7-z M 2 z , Li w Tii-xCe x Nb2-yM 1 yO7-zM 2 z in which
  • ⁇ M 1 and M 2 are each at least one element chosen from the group consisting of Nb, V, Ta, Fe, Co, Ti, Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs, Ce and Sn,
  • ⁇ M 1 and M 2 can be identical or different from each other
  • 0 ⁇ x ⁇ 1 and even more 0.1 ⁇ x ⁇ 1 are preferred because the presence of germanium, cerium, lanthanum or copper in the composition of the anode improves the battery cycling performance.
  • a battery with a mesoporous anode made from this material can be recharged very quickly, and has a very good volumetric energy density, higher than that obtained with a Li4Ti50i2 anode according to the state of the art.
  • a layer of a suspension of nanoparticles is deposited on a substrate, by any appropriate technique, and in particular by a selected process in the group formed by: electrophoresis, extrusion, a printing process and preferably inkjet printing or flexographic printing, a coating process and preferably with a doctor blade, a roller , curtain, dipping, or through a slot-shaped die.
  • the suspension is typically in the form of an ink, that is to say a fairly fluid liquid, but can also have a pasty consistency.
  • the deposition technique and the conduct of the deposition process must be compatible with the viscosity of the suspension, and vice versa.
  • the deposited layer will then be dried.
  • the layer is then consolidated to obtain the desired ceramic mesoporous structure.
  • This consolidation will be described below. It includes a thermal and possibly thermomechanical treatment, typically a thermocompression. During this thermomechanical treatment, the electrode layer will be freed of any constituent and organic residue (such as the liquid phase of the suspension of nanoparticles and any surfactants): it becomes an inorganic layer (ceramic).
  • the consolidation of a plate is preferably carried out after its separation from its intermediate substrate, because the latter would risk being degraded during this treatment.
  • the layers of electrodes are each deposited on a substrate capable of acting as an electric current collector.
  • a metal strip i.e. a laminated sheet of metal
  • Layers comprising the suspension of nanoparticles or agglomerates of nanoparticles can be deposited on both sides, by the deposition techniques indicated above.
  • the shrinkage generated by the consolidation can lead either to the cracking of the layers, or to a shearing stress at the level of the interface between the substrate (which is fixed dimension) and the ceramic electrode.
  • this shear stress exceeds a threshold, the layer detaches from its substrate.
  • the thickness of the electrodes by a succession of deposition-sintering operation.
  • This first variant of the first embodiment of depositing the layers gives a good result, but is not very productive.
  • layers of greater thickness are deposited on both sides of a perforated substrate.
  • the perforations must have a sufficient diameter so that the two layers of the front and the back are in contact at the level of the perforations.
  • the nanoparticles and/or agglomerates of nanoparticles of electrode material in contact through the perforations in the substrate weld together, forming a point of attachment (weld point between the deposits on the two faces). This limits the loss of adhesion of the layers on the substrate during the consolidation steps.
  • the electrode layers are not deposited on a substrate capable of acting as an electric current collector, but on an intermediate, temporary substrate.
  • a substrate capable of acting as an electric current collector
  • These thick layers are deposited, for example, by a coating process, referred to as a doctor blade (technique known in English as “doctor blade” or “tape casting”).
  • Said intermediate substrate can be a polymer sheet, for example poly(ethylene terephthalate), abbreviated PET. When drying, these layers do not crack.
  • a stack of three layers is then produced, namely two plates of electrodes of the same polarity separated by a metal sheet capable of acting as an electric current collector.
  • This stack is then assembled by thermomechanical treatment, comprising pressing and heat treatment, preferably simultaneously.
  • the interface can be coated with a layer allowing electronic conductive bonding.
  • This layer can be a sol-gel layer (preferably of the type allowing the chemical composition of the electrodes to be obtained after heat treatment) possibly loaded with particles of an electronically conductive material, which will make a ceramic weld between the mesoporous electrode and the sheet metallic.
  • This layer can also consist of a thin layer of non-sintered electrode nanoparticles, or of a thin layer of a conductive glue (loaded with graphite particles for example), or even a metallic layer of a metal with low melting point.
  • Said metal sheet is preferably a rolled sheet, ie obtained by rolling. Rolling may optionally be followed by final annealing, which may be softening (total or partial) or recrystallization annealing, depending on the terminology of metallurgy. It is also possible to use a sheet deposited by electrochemical means, for example an electrodeposited copper sheet or an electrodeposited nickel sheet.
  • a ceramic electrode is obtained, without organic binder, mesoporous, located on either side of a metallic substrate serving as an electrode current collector.
  • batteries are produced without using metallic current collectors.
  • the electrode plates are sufficiently electronically conductive, to ensure the passage of electrons on the ends of the electrodes.
  • Sufficient electronic conductivity can be observed either in the case where the electrode material intrinsically presents a very high electronic conductivity (in the case of materials such as UCOO2 or Nb WsOss), or in the case where the mesoporous surface has been coated with an electronic conductive layer.
  • This step is optional. Indeed, depending on the desired power of the electrode (which also influences its thickness) and the conductivity of the electrode materials, it may or may not be necessary to carry out this treatment to improve the conductivity of the electrode.
  • TNO Tianium Niobium Oxide
  • NWO Niobium Tungsten Oxide
  • the thicker electrode layers will need this deposition of a thin electronic conductor layer more than the thin electrode layers.
  • the anode materials are of poor electronic conductors.
  • a battery which contains them would therefore present a high series resistance, which implies an ohmic loss of energy, and this all the more so as the electrodes are thick.
  • a nanolayer of an electronically conductive material is deposited in the mesoporosity network, ie inside the pores, to ensure good electronic conductivity of the electrodes. This need to increase the conductivity is all the more important as the deposits are thick. It is thus possible to have thick electrodes, endowed with high power, which have a low series resistance.
  • a coating of an electronically conductive material is deposited on and inside the pores of said porous layer of anodic material.
  • this porous layer preferably mesoporous, is perfectly suited to the application of a surface treatment, by gaseous or liquid means, which goes into the depth of the open porous structure of the layer.
  • this deposit if it is carried out, is carried out by a technique allowing an encapsulating coating (also called "conformal deposit”), i.e. a deposit which faithfully reproduces the atomic topography of the substrate on which it is applied, and which enters deeply into the layer's open porosity network.
  • Said electronic conductive material may be carbon.
  • the ALD (Atomic Layer Deposition) or CSD (Chemical Solution Deposition) techniques may be suitable. They can be implemented on the electrodes after manufacture, before and/or after deposition of separator particles and before and/or after assembly of the cell.
  • the ALD deposition technique is done layer by layer, by a cyclic process, and makes it possible to produce an encapsulating coating which faithfully reproduces the topography of the substrate; the coating lines the entire surface of the electrodes.
  • This conformal coating typically has a thickness of between 1 nm and 5 nm.
  • ALD deposition is carried out at a temperature typically between 100°C and 300°C. It is important that the layers be free of organic matter: they must not contain any organic binder, any residues of stabilizing ligands used to stabilize the suspension must have been eliminated by purification of the suspension and/or during the heat treatment of the layer after drying. Indeed, at the temperature of the ALD deposition, the organic materials forming the organic binder (for example the polymers contained in the electrodes made by tape casting ink) may decompose and pollute the ALD reactor. Furthermore, the presence of residual polymers in contact with the particles of active electrode material can prevent the ALD coating from coating all of the surfaces of the particles, which is detrimental to its effectiveness.
  • the CSD deposition technique also makes it possible to produce an encapsulating coating with a precursor of the electronically conductive material which faithfully reproduces the topography of the substrate; it lines the entire surface of the electrodes.
  • This conformal coating typically has a thickness of less than 5 nm, preferably between 1 nm and 5 nm. It must then be transformed into electronic conductive material. In the case of a carbon precursor, this will be done by pyrolysis, preferably under inert gas (such as nitrogen).
  • a layer of an electronically conductive material can be formed, very advantageously, by immersion in a liquid phase comprising a precursor of said electronically conductive material followed by the transformation of said precursor from an electronically conductive material into an electronically conductive material by heat treatment.
  • This method is simple, fast, easy to implement and is less expensive than the ALD atomic layer deposition technique.
  • said precursor of the electronically conductive material is chosen from organic salts containing one or more metallic elements capable, after heat treatment such as calcination, preferably carried out in air or under an oxidizing atmosphere, of forming an electronically conductive oxide.
  • These metallic elements, preferably these metallic cations can advantageously be chosen from tin, zinc, indium, gallium, or a mixture of two or three or four of these elements.
  • the organic salts are preferably chosen from an alkoxide of at least one metal cation capable, after heat treatment such as calcination, preferably carried out in air or under an oxidizing atmosphere, of forming an electronic conductive oxide, an oxalate of au at least one metal cation capable, after heat treatment such as calcination, preferably carried out in air or under an oxidizing atmosphere, of forming an electronically conductive oxide and an acetate of at least one metal cation capable, after heat treatment such as calcination, preferably carried out in air or under an oxidizing atmosphere, to form an electronically conductive oxide.
  • said electronically conductive material may be an electronically conductive oxide material, preferably chosen from: tin oxide (SnC>2), zinc oxide (ZnO), indium oxide (ln 2 O 3 ), gallium oxide (Ga 2 O 3 ), a mixture of two of these oxides such as indium tin oxide corresponding to a mixture of indium oxide (ln 2 O 3 ) and tin oxide (SnC>2), a mixture of three of these oxides or a mixture of four of these oxides, the doped oxides containing zinc oxide, the doping preferably being gallium (Ga) and/or aluminum (Al) and/or boron (B) and/or beryllium (Be), and/or chromium (Cr ) and/or cerium (Ce) and/or titanium (Ti) and/or indium (In) and/or cobalt (Co) and/or nickel (Ni) and/or copper (Cu ) and/or manganese (Mn) and/or germanium
  • an electronically conductive material preferably an electronically conductive oxide material
  • the porous layer can be immersed in a rich solution of the precursor of the desired electronic conductive material.
  • the electrode is dried and subjected to a heat treatment, preferably in air or in an oxidizing atmosphere, at a temperature sufficient to pyrolyze the precursor of the electronic conductor material of interest.
  • a coating of electronically conductive material is formed, preferably a coating of an electronically conductive oxide material, more preferably of SnO2, ZnO, ln 2 O3, Ga2Os, or indium-tin oxide, over the entire surface. inside the electrode, perfectly distributed.
  • an electronically conductive coating in the form of an oxide instead of a carbonaceous coating on and inside the pores of the porous layer gives the electrode better electrochemical performance at high temperature, and makes it possible to significantly increase the stability of the electrode.
  • the fact of using an electronically conductive coating in the form of an oxide instead of a carbonaceous coating confers, among other things, better electronic conduction at the final electrode.
  • the presence of this electronically conductive oxide layer on and inside the pores of the porous layer or plate, in particular because the conductive coating electron or in oxide form, makes it possible to improve the final properties of the electrode, in particular to improve the voltage resistance of the electrode, its temperature resistance during sintering, to improve the electrochemical stability of the electrode, in particular when it is in contact with a liquid electrolyte, to reduce the polarization resistance of the electrode, and this even when the electrode is thick.
  • an electronically conductive coating in the form of an oxide, in particular of the I ⁇ Ch, SnC>2, ZnO, Ga2O3 type or a mixture of one or more of these oxides, on and at the inside the pores of the porous layer of an active electrode material, when the electrode is thick, and/or when the active materials of the porous layer are too resistive.
  • the electrode according to the invention is porous, preferably mesoporous, and its specific surface is large.
  • the increase in the specific surface of the electrode multiplies the exchange surfaces, and consequently, the power of the battery, but it also accelerates the parasitic reactions.
  • the presence of these electronically conductive coatings in the form of oxide on and inside the pores of the porous layer will make it possible to block these parasitic reactions.
  • porous layer or plate made from an active electrode material, and an electronically conductive coating in the form of an oxide placed on and inside the pores of said layer. or porous plate which makes it possible to improve the final properties of the electrode, in particular to obtain thick electrodes without increasing the internal resistance of the electrode.
  • the electronic conductive coating in the form of oxide on and inside the pores of a porous layer is easier and less expensive to achieve than a carbonaceous coating.
  • the transformation of the precursor of the electronically conductive material into an electronically conductive coating does not need to be carried out under an inert atmosphere, unlike the carbonaceous coating.
  • the diameter D50 of the primary particles of electrode material be of at least 10 nm in order to prevent the conductive layer from blocking the open porosity of the electrode layer.
  • this treatment can be carried out on the mesoporous ceramic plate and before the "bonding" on the current conductors.
  • the cathode materials have been presented above; these are formulations of oxides containing niobium. These anode materials have mass capacities greater than 160 mAh/g and lithium insertion voltages greater than 0.5V/Li, allowing rapid recharging without the risk of lithium plating. Furthermore, these anode materials used according to the invention do not exhibit significant variations in volume during the charging and discharging steps, so that they can be used in entirely solid cells.
  • step (i) the structure obtained after step (f) is impregnated, or, after step (h) said battery, by an electrochemically stable electrolyte up to at least 4.5V, selected from the group formed by:
  • an electrolyte comprising 1-Methyl-3-propylimidazolium 4,5-dicyano-2-(trifluoro-methyljimidazolide (PMIM-TDI) and lithium 4,5-dicyano-2-(trifluoro-methyl)imidazolide (LiTDI) .
  • conductive adhesives or conductive layers electronically deposited by a sol-gel process can protect the metallic substrate against corrosion, and in this case it is possible to use first and/or second substrates made of a metal less noble than the metals which just mentioned, and in particular aluminum and copper.
  • the RTILs used are an association of a cationic group with an anionic group.
  • the cations are preferentially selected from the group formed by the following cationic compounds and families of cationic compounds: imidazolium (such as the 1-pentyl-3-methylimidazolium cation, abbreviated PMIM), ammonium, pyrrolidinum, and/or the anions are preferentially selected from the group formed by the following anionic compounds and families of anionic compounds bis(trifluoromethanesulfonyl)imide, bis(trifluorosulfonyl)imide, trifluoromethylsulfonate, tetra-fluoroborate, hexafluorophosphate, 4,5-dicyano-2-(trifluoromethyl)imidazolium (abbreviated TDI), bis(oxlate) borate (abbreviated BOB), oxalyldifluoroborate (abbreviated DFOB),
  • said battery is impregnated with an electrolyte , preferably by a phase carrying lithium ions, selected from the group formed by:
  • an electrolyte comprising 1-Methyl-3-propylimidazolium 4,5-dicyano-2-(trifluoro-methyl)imidazolide (PMIM-TFSI) and lithium 4,5-dicyano-2-(trifluoro-methyl)imidazolide ( LiTDI).
  • PMIM-TFSI 1-Methyl-3-propylimidazolium 4,5-dicyano-2-(trifluoro-methyl)imidazolide
  • LiTDI lithium 4,5-dicyano-2-(trifluoro-methyl)imidazolide
  • the inorganic material E it must be an electronic insulator. It is possible to use oxides of the Al2O3, ZrO2, SiO2 type, or alternatively phosphates or borates. Nanoparticles of this material E form the mesoporous electrolyte separator layer.
  • Impregnation can be done at different stages of the process. Impregnation, especially with a liquid electrolyte, can be especially on stacked and thermocompressed cells, that is to say once the battery is finished. Impregnation, especially with a liquid electrolyte, can also be done after encapsulation, starting from the cut edges.
  • the lithium ion carrier phase may be an organic liquid containing lithium salts.
  • the lithium ion carrier phase can also be an ionic liquid (or a mixture of several ionic liquids) containing lithium salts, possibly diluted with an organic solvent or with a mixture of organic solvents containing a lithium salt which may be different of that or of the mixture dissolved in the ionic liquid.
  • the cations of this ionic liquid are preferentially selected from the group formed by the following cationic compounds and families of cationic compounds: imidazolium (such as the 1-pentyl-3-methylimidazolium cation, abbreviated PMIM), ammonium, pyrrolidinum, and/or the anions of this ionic liquid are preferentially selected from the group formed by the following anionic compounds and families of anionic compounds bis(trifluoromethanesulfonyl)imide, bis(trifluorosulfonyl)imide, trifluoromethylsulfonate, tetra-fluoroborate, hexafluorophosphate, 4, 5-dicyano-2-(trifluoromethyl)imidazolium (abbreviated TDI), bis(oxlate) borate (abbreviated BOB), oxalyldifluoroborate (abbreviated DFOB), bis(mandelato)borate (abbrevi
  • composition of the impregnation electrolyte and its concentration of lithium salts can be adjusted to meet the needs of temperature resistance, power, etc. of the intended application of the battery.
  • RTIL-based electrolytes of the Pyr ⁇ FSI or Pyr ⁇ TFSI type with LiFSI and/or LiTFSI and/or LiTDI as lithium salt are preferred.
  • Solvents resistant to high temperature such as for example GBL can be added at contents lower than 50%.
  • the lithium ion carrier phase comprises at least one ionic liquid, preferably at least one ionic liquid at room temperature, such as PYR14TFSI, optionally diluted in at least one solvent, such as ⁇ -butyrolactone.
  • the lithium ion carrier phase may contain, for example, LiPFe or UBF4 dissolved in an aprotic solvent, or an ionic liquid containing lithium salts. It is also possible to use ionic liquids, optionally dissolved in an appropriate solvent, and/or mixed with organic electrolytes. It is possible, for example, to mix at 50% by mass the LiPFe dissolved in EC/DMC with an ionic liquid containing lithium salts of the LiTFSI YRuTFSI type (molar ratio 1:9). It is also possible to produce mixtures of ionic liquids which can operate at low temperature, such as for example the mixture LiTFSI YR FSI YRuTFSI (molar ratio 2:9:9).
  • EC is the common abbreviation for ethylene carbonate (CAS no: 96-49-1).
  • DMC is the common abbreviation for dimethyl carbonate (CAS no: 616-38-6).
  • LITFSI is the common abbreviation for lithium bis-trifluoromethanesulfonimide (CAS no: 90076-65-6).
  • PYR13FSI is the common abbreviation for N-Propyl-N-Methylpyrrolidinium bis(fluorosulfonyl)imide.
  • PYR14TFSI is the common abbreviation for 1-butyl-1-methylpyrrolidinium bis(trifluoro-methanesulfonyl)imide.
  • the phase carrying lithium ions can be an electrolytic solution comprising an ionic liquid.
  • the ionic liquid consists of a cation associated with an anion; this anion and this cation are chosen so that the ionic liquid is in the liquid state in the operating temperature range of the accumulator.
  • the ionic liquid has the advantage of having high thermal stability, reduced flammability, of being non-volatile, of being of low toxicity and good wettability of ceramics, which are materials that can be used as electrode materials.
  • the mass percentage of ionic liquid contained in the lithium ion carrier phase can be greater than 50%, preferably greater than 60% and even more preferably greater than 70%, and this unlike lithium ion batteries.
  • lithium of the prior art where the percentage by mass of ionic liquid in the electrolyte must be less than 50% by mass so that the battery retains a capacity and a high voltage in discharge as well as good stability in cycling. Beyond 50% by mass, the capacity of the battery of the prior art deteriorates, as indicated in application US 2010/209 783 A1. This can be explained by the presence of polymeric binders within the electrolyte of the battery of the prior art; these binders are slightly wetted by the ionic liquid inducing poor ionic conduction within the phase carrying lithium ions, thus causing a degradation of the capacity of the battery.
  • PYRuTFSI and LiTFSI can be used; these abbreviations will be defined below.
  • the ionic liquid can be a cation of the 1-Ethyl-3-methylimidazolium type (also called EMI + or EMIM + ) and/or n-propyl-n-methylpyrrolidinium (also called PYRn*) and/or n- butyl-n-methylpyrrolidinium (also called PYRi4 + ), combined with anions of the bis(trifluoromethanesulfonyl)imide (TFSI”) and/or bis(fluorosulfonyl)imide (FSI-) type.
  • the liquid electrolyte contains at least 50% by weight of ionic liquid, which is preferably PyruTFSI.
  • a lithium salt such as LiTFSI can be dissolved in the ionic liquid which serves as the solvent or in a solvent such as ⁇ -butyrolactone.
  • the ⁇ -butyrolactone prevents the crystallization of ionic liquids inducing a greater temperature operating range of the latter, in particular at low temperature.
  • the phase carrying lithium ions comprises a solid electrolyte such as LiBFL or a mixture of UBH4 with one or more compounds chosen from LiCl, Lil and LiBr.
  • UBH4 is a good conductor of lithium and has a low melting point facilitating its impregnation in porous electrodes, in particular by dipping. Due to its extremely reducing properties, LiBFL is rarely used as an electrolyte. The use of a protective film on the surface of the porous lithium phosphate electrode prevents the reduction of the cathode materials by the LiBFL and avoids its degradation.
  • ionic liquids mainly PyruTFSI-LiTFSI and EMIM-TFSI.
  • the latter is more fluid than Pyru-TFSI.
  • the main difference between these two ionic liquids is in the range of stability potential in which they can be used.
  • the EMIM-TFSI is stable from 1 V up to 4.7 V while the Pyru-TFSI is stable from 0 V up to 5.0 V; for this reason, Pyru-TFSI is preferred, despite its lower fluidity.
  • TFSI-type lithium salts tend to corrode substrates.
  • LiTDI is preferred instead or in complement of the LiTFSI as an anionic group of ionic liquid and/or lithium salts, when the cathode operates at more than 4.3 V.
  • LiTFSI contains sulfur which tends to corrode substrates especially during high temperature operation. LiTDI does not corrode substrates.
  • TFSI can be used with substrates coated with a protective layer, or with substrates made of a material which is more resistant to the corrosive action of TFSI; such substrates are Mo, W, Cr, Ti, Ta.
  • phase bearing lithium ions comprise between 10% and 40% by weight of a solvent, preferably between 30 and 40% by weight of a solvent, and even more preferably between 30 and 40% by mass of ⁇ -butyrolactone, glyme or PC.
  • the phase carrying lithium ions comprises more than 50% by mass of at least one ionic liquid and less than 50% of solvent, which limits the risks of safety and of inflammation in the event of a malfunction.
  • batteries comprising such a carrier phase of lithium ions.
  • the lithium ion carrier phase comprises: a lithium salt or a mixture of lithium salts chosen from the group formed: LiTFSI, LiFSI, LiBOB, LiDFOB, LiBMB, LiBPFPB and LiTDI; the lithium salt concentration is preferably between 0.5 mol/L and 4 mol/L; the applicant has found that the use of an electrolyte with a high concentration of lithium salts promotes very fast charging performance; a solvent or a solvent mixture with a mass content of less than 40% and preferably less than or equal to 20%; This solvent can be, for example, ⁇ -butyrolactone, PC, glymes;
  • the lithium ion carrier phase comprises:
  • the phase carrying lithium ions can be an electrolytic solution comprising PYR14TFSI, LiTFSI and ⁇ -butyrolactone, preferably an electrolytic solution comprising approximately 90% by mass of PYR14TFSI, 0.7 M of LiTFSI, 2% LiTDI and 10% y-butyrolactone by mass.
  • the electrodes can be mesoporous. They can be thick (typically between ten micrometers to a hundred micrometers), and more particularly their thickness can be greater than 10 ⁇ m. They can be prepared by deposition of agglomerates of nanoparticles. These agglomerates can have polydisperse sizes and/or two different sizes (bimodal particle size). In the finished state, these electrodes do not contain any binder (they may contain binders when depositing the suspension or paste of nanoparticles, but these binders will be eliminated during the heat treatment of calcination).
  • the porous anode according to the invention advantageously has a mesoporosity of less than 50% and preferably between 20% and 45%, and preferably between 25% and less than 40%; a value of about 35% is adequate.
  • a nanolayer of an electronic conductor for example carbon is deposited on the mesoporous surface.
  • these mesoporous electrodes are coated with a layer of nanometric thickness (this thickness being typically between about 0.8 nm to 10 nm) which extends over their entire surface.
  • a layer of nanometric thickness this thickness being typically between about 0.8 nm to 10 nm
  • the coating is also applied inside the pores.
  • Said coating may be a carbon conductive coating.
  • this electrode After being coated with a conductive layer, this electrode is impregnated with a conductive phase of lithium ions.
  • This phase can be liquid or solid. If it is solid, it can be organic or inorganic.
  • This electrode is bonded and sintered on a substrate resistant to high temperature heat treatments; said substrate can for example be made of W, Mo, Cr, Ti, and all alloys containing at least one of these elements. Stainless steel may be suitable. It is noted that in the case where self-supporting electrode plates are prepared, this constraint of resistance of the substrate or current collector to oxidation at the heat treatment temperature of the electrode no longer exists, because at the time of the heat treatment the electrode is not yet in contact with its current collector.
  • the anode can be more particularly a TiNb2O anode? (abbreviated “TNO”), but the following description also applies to other active anode materials.
  • TNO TiNb2O anode?
  • a TiNb2O? anode can be used. with a mesoporous volume of about 35%. This anode is sized for a capacity of approximately 230 mAh/g.
  • lithium ion batteries can be made.
  • the cathodic current collector is a sheet of Mo, W, Ta, Ti, Al, stainless steel, Cr or any alloy containing at least one of these elements; its thickness is typically between 5 ⁇ m and 20 ⁇ m.
  • the cathode is LiCoPC with a mesoporous volume of approximately 35%. The thickness of the cathode is about 90 ⁇ m; a nanolayer of an electronic conductor (in this case carbon) has been deposited on the mesoporous surface. This cathode is sized for a capacity of approximately 145 mAh/g.
  • the separator is a layer of U3PO4 about 6 ⁇ m thick with a mesoporous volume of about 50%.
  • the anode current collector is a sheet of Mo, W, Ta, Ti, Cu, Cr, Ni, Al, stainless steel or any alloy containing at least one of these elements; its thickness is typically between 5 ⁇ m and 20 ⁇ m.
  • an aluminum electrode for example.
  • the surface of the collector intended to be in contact with the electrode can be coated with a conductive coating, which, in the case of the second embodiment of the invention, will also serve to make the bonding.
  • the cell was impregnated with an ionic liquid of the RTIL type (Room Temperature Ionic Liquid) consisting of a mixture of Pyr14TFSI (1-Butyl-1-methylpyrrolidinium bis(trifluoro-methylsulfonyl)imide; CAS No. 223437-11-4) with 20% GBL and LiTFSI (Lithium bis(trifluoromethanesulfonyl)imide; CAS No. 90076-65-6; 0.7M concentration).
  • RTIL type Room Temperature Ionic Liquid
  • the following mixture can also be used: 0.7M LiTFSI+Pyr3TFSI+10% GBL+2% LiTDI.
  • Such a battery achieves a volume capacity density of about 200 mAh/cm 3 and a volume energy density of about 610 mWh/cm 3 . It can provide continuous power of around 50°C. It can operate over a very wide temperature range, typically between around -40°C and around +60°C. It presents no risk of thermal runaway.
  • the cathode material UCOPO4 was replaced by another cathode material operating at high voltage, not containing cobalt, namely a material of the spinel type, the LiMni.sNio.sO ⁇ It contains manganese, and for this reason the high temperature resistance of this cell is a little more limited than in the first embodiment.
  • the LiMni,5Nio,504 cathode had a thickness of about 90 ⁇ m, a mesoporous volume of about 35%, with deposit of a carbon nanolayer; this cathode is dimensioned for a capacity of approximately 120 mAh/g.
  • This battery achieves a volume capacity density of 210 mAh/cm 3 and a volume energy density of 625 mWh/cm 3 . It can provide direct current in excess of 50°C. It can operate over a very wide temperature range, typically between around -40°C and around +60°C. It presents no risk of thermal runaway. These batteries are compatible with rapid recharging; they can be recharged in less than 5 minutes without the risk of lithium precipitates forming.
  • a cathode operating at low voltage has been used.
  • the cathode was in Lii,2Nio,i3Mno,54Coo,i302 had a thickness of about 90 ⁇ m and a mesoporous volume of about 35%, with deposition of a carbon nanolayer; this cathode is dimensioned for a capacity of approximately 200 mAh/g.
  • the separator is a layer of U3PO4 about 6 ⁇ m thick with a mesoporous volume of about 50%.
  • the anode current collector is a sheet of Cu, Ni, W, Ta, Al, Cr, stainless steel, Ti, or Mo and any alloy comprising at least one of these elements; its thickness is typically between 5 ⁇ m and 20 ⁇ m.
  • the cell was impregnated with an ionic liquid of the RTIL type, which was comprised of a mixture of LiTDI and LiTFSI, and which consisted more precisely of Pyr14TFSI, with 0.7M of LiTFSI and 2% of LiTDI.
  • This battery achieves a volume capacity density of 285 mAh/cm 3 and a volume energy density of 720 mWh/cm 3 . It can provide direct current in excess of 50°C. It can operate over a very wide temperature range, typically between around -40°C and around +70°C. It presents no risk of thermal runaway. These batteries are compatible with rapid recharging; they can be recharged in less than 5 minutes without the risk of lithium precipitates forming.
  • this battery can operate in a wide temperature range (up to about +85°C) when the surface capacity of the cathode is lower than the surface capacity of the anode.
  • a fourth embodiment relates to a high capacity microbattery with a cathode operating at low voltage.
  • the cathodic current collector is a sheet of Mo, W, Ta, Ti, Al, stainless steels, Cr or any alloy containing at least one of these elements; its thickness is typically between 5 ⁇ m and 20 ⁇ m.
  • the cathode was in Lii,2Nio,i3Mno,54Coo,i302 had a thickness of about 16 ⁇ m, a mesoporous volume of about 35%, with deposition of a carbon nanolayer; this cathode is dimensioned for a capacity of approximately 200 mAh/g.
  • the separator is a layer of U3PO4 about 6 ⁇ m thick with a mesoporous volume of about 50%.
  • the anode current collector is a sheet of Cu, Ni, Al or Mo; its thickness is typically between 5 ⁇ m and 20 ⁇ m.
  • the cell was impregnated with an ionic liquid of the RTIL type, which consisted of Pyr14TFSI, with 0.7M of LiTFSI and 2% of LiTDI
  • This microbattery reaches a volume capacity density of 215 mAh/cm 3 and a volume energy density of 535 mWh/cm 3 . It can provide a continuous current greater than 50°C. It can operate in a very wide temperature range, typically between around -40°C and around +70°C. It presents no risk of thermal runaway. These batteries are also compatible with fast recharges. As noted above, the operating temperature range can be extended to approximately +85°C when the battery is sized such that the cathode areal capacity is less than the anode areal capacity.
  • An advantageous battery according to the invention has a cathodic current collector made of a material selected from the group formed by: Mo, Ti, W, Ta, Cr, Al, alloys based on the aforementioned elements, stainless steel; it also has a cathode with a porous volume of between 30 and 40%, which can be made of NMC and preferably of NMC433, a conductive layer of carbon being deposited in the pores.
  • Its separator is a mesoporous layer of U3PO4, preferably with a thickness of between 6 ⁇ m and 8 ⁇ m.
  • Its anode is a layer of TiNb2O?, preferably doped with a halide and/or cerium and/or germanium and/or lanthanum and/or copper, said layer being impregnated with a liquid electrolyte containing lithium salts.
  • Its anode current collector is selected from the group formed by: Mo, Cu, Ni, alloys based on the aforementioned elements, stainless steel. Aluminum can also be used. Other separator materials can be used.
  • the batteries according to the invention can be produced with very different powers.
  • using the method according to the invention it is possible to manufacture lithium ion batteries with a capacity greater than 1 mA h. They are of particular interest in the form of high-power batteries, in particular for use in electric vehicles. With intermediate powers they can be used in various mobile electronic devices such as mobile phones, laptops, portable reading devices.
  • a battery having a capacity not exceeding 1 mA h is referred to herein as a “microbattery”.
  • a cell is made according to the fourth embodiment described above, by multiplying the thicknesses of the electrodes by a factor of six.
  • anode with a thickness of around 50 ⁇ m to 80 ⁇ m, we obtain a battery with more than 550 Wh/I, operating in a very wide temperature range and which can be recharged in less than 15 minutes.
  • This battery is in fact particularly well suited to the needs of hybrid vehicles and fast-charging electric vehicles.
  • citric acid was dissolved in ethylene glycol by heating to 80°C.
  • the mixture of ethoxides was prepared in a glove box, respecting the stoichiometry of the target component.
  • the mixture of alkoxides was introduced with vigorous stirring into a citric acid/ethylene glycol solution at room temperature.
  • the reaction mixture is stirred for 12 hours at 80° C., which results in the solution gelling.
  • the gel is then extracted to be placed in an alumina crucible.
  • the crucibles are placed in a heating chamber at 250° C. for 12 hours. This heating step will eliminate the excess ethylene glycol and activate the esterification reactions.
  • the product is then calcined at 600° C. for 1 hour to eliminate a large part of the organics.
  • a second heat treatment is then carried out at 800° C.
  • Figure 1 shows the electrochemical characteristics of an anode prepared according to this example.
  • Example 2 Manufacture of a mesoporous anode plate according to the invention
  • a slurry composed of agglomerates of crystallized nanoparticles of TNO was prepared. These agglomerates were approximately 100 nm in size and consisted of primary particles 15 nm in diameter. These nanoparticle agglomerates were integrated into a slurry of the following composition (in mass percent): 20% TNO nanoparticle agglomerates, 36% 2-butanone and 24% ethanol acting as solvent, 3% ester phosphoric acting as a dispersant, 8.5% of dibutylphthalate acting as a plasticizer, 8.5% methacrylate resin acting as a binder.
  • This slip was cast in a strip, then cut into a plate and dried. These plates were then annealed at 600°C for 1 hour in air to obtain the mesoporous ceramic plate which will serve as an electrode. This plate was then impregnated with a glucose solution and annealed at 400°C under N2 in order to produce a conductive carbon nanocoating over the entire mesoporous surface of the electrode.

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EP21835415.7A 2020-12-29 2021-12-23 Verfahren zur herstellung einer porösen anode für eine lithium-ionen-sekundärbatterie, resultierende anode und batterie mit der anode Pending EP4272272A1 (de)

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