EP4272272A1

EP4272272A1 - Method for producing a porous anode for a lithium-ion secondary battery, resulting anode, and battery comprising said anode

Info

Publication number: EP4272272A1
Application number: EP21835415.7A
Authority: EP
Inventors: Fabien Gaben
Original assignee: I Ten SA
Current assignee: I Ten SA
Priority date: 2020-12-29
Filing date: 2021-12-23
Publication date: 2023-11-08
Also published as: FR3118535A1; IL304098A; JP2024503284A; CN117043984A; US20240063368A1; FR3118535B1; CA3206652A1; KR20230142713A; WO2022144726A1

Abstract

A method for producing an anode having a porosity of between 25% and 50% by volume, comprising: (a) supplying a substrate and a colloidal suspension or paste consisting of monodispersed primary nanoparticles, in agglomerate or dispersed form, of at least one active anode material A selected from niobium oxides and mixed oxides of niobium and titanium, germanium, cerium, lanthanum, copper, or tungsten, having an average primary diameter D₅₀ of between 2 nm and 100 nm; (b) depositing, on at least one face of the substrate, a layer from said colloidal suspension or paste supplied in step (a) using a method selected from the group made up of electrophoresis, a printing method, preferably inkjet printing or flexographic printing, and a coating method, preferably by means of knife coating, roller coating, curtain coating, dip coating, or slot-die coating; and (c) drying the layer obtained in step (b), and solidifying same, by pressing and/or heating, to obtain a porous layer.

Description

METHOD FOR MANUFACTURING A POROUS ANODE FOR A SECONDARY LITHIUM ION BATTERY, ANODE THUS OBTAINED, AND BATTERY COMPRISING THIS ANODE

Technical field of the invention

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. As such, 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.

More specifically, 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.

State of the art

The ideal batteries for powering autonomous electrical devices (such as: telephones and portable computers, portable tools, autonomous sensors) or for the 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. Currently, these electrical devices are essentially powered by lithium ion batteries, which have the best energy density among the various storage technologies proposed. There are different architectures and chemical compositions of electrodes making it possible to produce lithium ion batteries. 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. Scrosati), published in 2002 (Kluever Academie / Plenum Publishers), and “Lithium Batteries. Science and Technology” by C. Julien, A. Mauger, A. Vijh and K. Zaghib (Springer, Heidelberg 2016) provide a good overview.

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)).

With these methods, 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 μm and 15 μm 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.

These techniques make it possible to produce layers with a thickness of between about 20 μm and about 400 μm. Depending on the thickness of the layers, their porosity and the size of the active particles, the power and energy of the battery can be modulated.

According to the state of the art, 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. To improve the quality of the electrical contact between the particles and to compact the layers deposited, 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.

To best optimize the bulk energy density of lithium ion batteries produced with these conventional manufacturing processes, it can be very useful to reduce the porosity of the electrodes. This reduction in porosity, in other words the increase in the quantity of active material per unit volume of electrode, can be achieved in several ways.

In the extreme, 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.

With conventional inking techniques, it is also possible to increase the energy volume density by optimizing the size distribution of the deposited particles. Indeed, as shown for example in the article by J. Ma and L.C. Lim “Effect of particle size distribution on sintering of agglomerate-free submicron alumina powder compacts” published in 2002 in the journal J. European Ceramic Society 22 (2002) , p. 2197-2208, by optimizing the particle size distribution, it is possible to reach a density of around 70%. An electrode with 30% porosity, containing conductive fillers and impregnated with a conductive electrolyte of lithium ions will have a volume energy density approximately 35% higher than the same electrode with 50% porosity made up of particles monodispersed in size .

Furthermore, due to the impregnation by phases with very high ionic conductivity and the addition of electronic conductors, 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.

Although making it possible to increase the energy density of the electrodes, this distribution in size of the particles of active material is not without posing problems. particles of different sizes in an electrode, will have different capacities and under the effect of identical charging and/or discharging currents will be locally more or less charged and/or discharged according to their size. When the battery will no longer be under current demand, the local states of charge between particles will again be balanced, but during these transient phases, local imbalances can lead to locally stressed particles outside their stable voltage ranges. These local charge state imbalances will be all the more pronounced as the current densities are high. These imbalances consequently induce losses of performance in cycling, safety risks and a limitation of the power of the battery cell.

These effects of the particle size distribution of active materials on the current/voltage relationships of the electrodes have been studied and simulated by S. T. Taleghani et al. in the publication “A study on the effect of porosity and particles size distribution on Li-ion battery performance”, published in the journal J. Electrochemical Society, 164 (11) 2017, p. E3179-E3189.

With the electrode inking techniques of the prior art, the particles of active material have a size generally comprised between 5 μm and 15 μm. 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.

To solve these safety problems inherent in the structure of conventional lithium ion battery cells, it is necessary to: o Replace organic solvent-based electrolytes with ionic liquids that are extremely stable in temperature. However, ionic liquids do not wet on the surfaces of organic materials and the presence of PVDF and other organic binders in the electrodes of conventional batteries prevents the wetting of the electrodes by this type of electrolyte and the performance of the electrodes is thereby affected. . Ceramic separators have been developed to solve this problem at the level of the electrolytic junction between electrodes, but the fact remains that the presence of organic binders in the electrodes continues to pose problems for the use of electrolytes based on ionic liquids. 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.

As regards more particularly the manufacturing processes for battery electrodes according to the state of the art, their manufacturing cost depends in part on the nature of the solvents used. In addition to the intrinsic cost of the active materials, the manufacturing cost of the electrodes comes mainly from the complexity of the inks used (binders, solvents, carbon black, etc.).

The main solvent used for the production of lithium ion battery electrodes is NMP. 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. Furthermore, to guarantee better adhesion of the electrodes to the substrates, 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).

Other less expensive solvents can be used to make inks, including water and ethanol. However, their surface tension is greater than that of NMP, and they therefore wet the surface of the metallic current collectors less well. In addition, 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 ...). Moreover, whether with water or ethanol, traces of water can remain adsorbed on the surface of the particles of active materials, even after drying.

Finally, in addition to the problems of difficulty in formulating inks in order to have a high-performance electrode at low manufacturing cost, it is also important to bear in mind that, depending on the particle sizes of active materials, and indirectly on the porosity of the electrode deposits and their thicknesses, the ratio between the energy density and the power density of the electrodes can be adjusted. The article by J. Newman “Optimization of Porosity and Thickness of a Battery Electrode by Means of a Reaction-zone Model”, published in the journal J. Electrochem. Soc., Vol. 142, n°1 (1995), demonstrates the respective effects of the thickness of the electrodes and their porosity on their discharge rate (power) and energy density.

In addition to the architecture and manufacturing processes of battery cells, the choice of electrode materials is also fundamental. 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.

The more this insertion of lithium is carried out at low potential for the anodes, the more at isocapacitance, the energy of the battery will be important. However, anodes with low insertion potential, such as graphite, induce risks of lithium plating at high recharge current. Indeed, to carry out a rapid recharge of the battery, it is necessary to quickly insert a large quantity of lithium into the anodes. A high concentration of lithium at the surface of the anode, associated with a very low potential favors the precipitation of metallic lithium dendrites, which will induce short circuits in the cell.

Also, when seeking to obtain batteries with a very rapid recharging capacity, presenting no safety risks due to lithium plating, and for which the energy density of the cell would remain high, it would be necessary , at the same time :

Use 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.

Have electrodes with excellent ionic and electronic conduction.

Have very good ion conducting electrolytes with high transport numbers and giving low polarization resistances.

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.

Objects of the invention

According to the invention, 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:

(a) a substrate and a colloidal suspension or a paste composed of monodisperse primary nanoparticles, in the form of agglomerates or dispersed, of at least one anode active material A, with an average primary diameter D50 of between 2 nm and 100 nm, and preferably between 2 nm and 60 nm, it being understood that said colloidal suspension or said paste also comprises a liquid constituent, it being understood that said active anode material A is selected from niobium oxides and mixed oxides of niobium with titanium, germanium, cerium, lanthanum, copper, or tungsten, and preferably in the groups formed by: o Nb20s-s , NbisWieOgs-s , NbieWsOss-s with 0 S x < 1 and 0 s 5 < 2 o TiNb2C>7-8, Tii.xM ¹ xNb ₂ .yM ² yO7- _S , Li _w Tii. _x M ¹ xNb2-yM ² yO7-s wherein 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,

■ and in which 0<w<5 and 0<x<1 and 0<y<2 and z<0.3; 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. 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- xCe _x Nb2-yM ¹ yO7-zM ² _z , Li _w Tii-xCe _x Nb2-yM ¹ yO7-zM ² _z in which

■ M ¹ and M ² can be identical or different from each other,

■ and in which 0<w<5 and 0<x<1 and 0<y<2 and z<0.3; o Tii- _x Ge _x Nb2-yM ¹ yO7-z, Li _w Tii. _x Ge _x Nb2-yM ¹ yO7-z , Tii. _x Ce _x Nb2-yM ¹ yO7-z, Li _w Tii. _x Ce _x Nb2- yM ¹ _y O7-z in which

■ 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,

■ and in which 0<w<5 and 0<x<1 and 0<y<2andz<1, preferably in which 0<w<5 and 0<x<1 and 0<y<2andz<0.3;

(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 ;

(c) said layer obtained in step (b) is dried and consolidated, by pressing and/or heating, to obtain a porous layer. Advantageously, 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. _x M ¹ xNb2-yM ² yO7-s wherein 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 can be identical or different from each other,

■ M ³ is at least one halogen,

■ and in which 0<w<5 and 0<x<1 and 0<y<2 and z<0.3; 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. 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- xCe _x Nb2-yM ¹ yO7-zM ² z, Li _w Tii.xCe _x Nb2-yM ¹ yO7-zM ² zin which

■ M ¹ and M ² can be identical or different from each other,

■ and in which 0<w<5 and 0<x<1 and 0<y<2andz<1, preferably in which 0<w<5 and 0<x<1 and 0<y<2andz<0.3. Optionally, during step (c) said layer is heated to a temperature sufficient to remove the organic residues by evaporation and/or pyrolysis (step called debinding).

More generally, the treatments of 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. _x Cu _x Nb2- _y M ¹ _y O7-zM ² _z , Li _w Tii.xCe _x Nb2-yM ¹ yO7-zM ² _z and Li _w Tii.xCe _x Nb2-yM ¹ yO7-z , are supplied and deposited with w = 0 (ie without containing lithium): these materials have the ability to insert lithium during the first charge of the battery of which the anode is part.

In step (b) the deposition can be done on both sides of the substrate.

In a first embodiment, 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 μm and about 300 μm, or between 1 μm and 150 μm.

In a second embodiment, said substrate is an intermediate, temporary substrate, such as a polymer film. In this second embodiment, 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 μm and about 300 μm.

In both embodiments, when the layers are thick and resistive, it is advantageous to add step (d) according to which:

(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.

The electronic conductive material may be carbon. In this case, 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.

Advantageously, 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 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.

Advantageously, 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 (Ge), the doped oxides based on indium oxide, the doping preferably being at l tin (Sn), and/or gallium (Ga) 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 (Ge), oxides doped tin, the doping preferably being arsenic (As) and/or fluorine (F) and/or nitrogen (N) and/or niobium (Nb) and/or phosphorus (P ) and/or antimony (Sb) and/or aluminum (Al) and/or titanium (Ti), and/or gallium (Ga) and/or chromium (Cr) and/or cerium (Ce) and/or indium (In) and/or cobalt (Co) and/or nickel (Ni) and/or copper (Cu) and/or manganese (Mn) and/or germanium (Ge).

In general, 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.

In said second embodiment, 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 μm and 300 μm. It is advantageous to deposit a coating of an electronically conductive material, as has just been described.

In this second embodiment, 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 μm.

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. During this sintering, 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.

More precisely, it is possible either to stick mesoporous ceramic electrode plates (and in particular anodes according to the invention) on both sides of a metal substrate (we then find the same configuration as that resulting from the deposits on the two sides of a metal substrate). On this electrode/substrate/electrode (and in particular anode/substrate/anode) subassembly, the electrolyte film (separator) 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.

Alternatively, 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.

In the two variants that have just been presented, welding by 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.

In the case where the layers or plates of electrodes (it is recalled here that in the expression "electrode plate", the term "plate" encompasses the "sheets") show sufficient electronic conductivity, it is not possible to provide a separate current collector. This variant applies above all to microbatteries and intermediate power batteries, and does not represent a preferred embodiment for batteries with a power greater than 1 mA h. In other embodiments of the assembly, which will be described below, a conductive adhesive (charged with graphite) or a sol-gel type deposit charged with conductive particles, or metal strips, preferably low melting point (eg aluminum); during the thermomechanical treatment (thermopressing) the metal strip can be deformed by creep and come to make this weld between the plates.

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:

- pores with an average diameter of less than 50 nm, 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. _x M ¹ xNb2-yM ² yO7-s , Li _w Tii. _x M ¹ xNb2-yM ² yO7-s wherein 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,

■ and in which 0 < w < 5 and 0 < x < 1 and 0 < y < 2 and z <0.3; o TiNb2C>7-zM ³ _z , Li _w TiNb2O7-zM ³ _z in which M ³ is at least one halogen, preferably chosen from F, Cl, Br, I or a mixture thereof, and 0 < z < 0.3, o Tii.xGexNb 2.yM ₁ yO7-z , Li _w Tii-xG6xNb2-yM ¹ yO7-z , Tii- _x C6xNb2-yM ¹ yO7-z , Li _w Tii-xCe _x Nb2- ^{yM 1} ^yO7 -z

■ 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;

■ 0 < w < 5 and 0 < x < 1 and 0 < y < 2 and z < 1, preferably in which 0 < w < 5 and 0 < x < 1 and 0 < y < 2 and z < 0.3 (with preferably 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. 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 yO7-z M ² _z , Li _w Tii-xCe _x Nb2-yM ¹ yO7-zM ² _z , in which

■ M ¹ and M ² can be identical or different from each other,

■ and in which 0 < w < 5 and 0 < x < 1 and 0 < y < 2 and z < 0.3; said anode being capable of being obtained by the process according to the invention.

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) providing a first substrate, a second substrate, and

- 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. _x M ¹ xNb2-yM ² yO _7-S , Li _w Tii-xM ¹ _x Nb2-yM ² yO7 wherein 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 can be identical or different from each other,

■ M ³ is at least one halogen,

■ and in which 0<w<5 and 0<x<1 and 0<y<2 and z<0.3; o TiNb2C>7-zM ³ _z , Li _w TiNb2O?-zM ³ _z in which M ³ is at least one halogen, preferably chosen from F, Cl, Br, I or a mixture thereof, and 0 < z <0.3, o Tii- _x Ge _x Nb2-yM ¹ yO7-z, Li _w Tii- _x Ge _x Nb2-yM ¹ yO7-z, Tii. _x Ce _x Nb2-yM ¹ yO7-z, Li _w Tii. _x Ce _x Nb2- yM ¹ _y O7-zin which

■ and in which 0<w<5 and 0<x<1 and 0<y<2etz<1, preferably in which 0<w<5 and 0<x<1 and 0<y<2etz<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. 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 yO7-zM ² _z , Li _w Tii-xCe _x Nb2-yM ¹ yO7-zM ² _z in which

■ M ¹ and M ² can be identical or different from each other,

■ and in which 0<w<5 and 0<x<1 and 0<y<2 and z<0.3; knowing that 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 is supplied 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 is supplied 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);

(b) 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;

(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;

(d) optionally, 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;

(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;

(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;

(g) 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;

(h) a 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.

The heat treatment in step (h) is done after the deposition on the electrodes of the separator film.

The product resulting from 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:

• an electrolyte composed of at least one aprotic solvent and at least one lithium salt;

• an electrolyte composed of at least one ionic liquid and at least one lithium salt;

• a mixture of at least one aprotic solvent and at least one ionic liquid and at least one lithium salt;

• a polymer made ionically conductive by the addition of at least one lithium salt; and

• a polymer made ionically conductive by the addition of a liquid electrolyte, either in the polymer phase or in the mesoporous structure.

These manufacturing processes make it possible to produce fully solid batteries with fine and ceramic separators. These separators impregnate very well with ionic liquids and are resistant to high temperatures.

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. In this case, 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.

In an advantageous embodiment of the invention, the battery has a surface capacity of the anodes lower than that of the cathodes; This improves your battery temperature resistance.

In general, 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. According to one of its essential characteristics, the process according to the invention uses nanoparticles, which makes it possible to reduce the sintering temperature. Furthermore, partial sintering is advantageously carried out to obtain mesoporous structures. In addition, 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. For the separator, 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.

tricks

[Fig. 1] shows a discharge curve obtained with an anode in Tio.gsGeo.osNbgO? according to the invention, for two different regimes.

detailed description

1. Definitions

In the context of this document, the size of a particle is defined by its largest dimension. By “nanoparticle”, is meant any particle or object of nanometric size having at least one of its dimensions less than or equal to 100 nm. As used herein, the term "electronic conductive oxide" includes electronic conductive oxides and electronic semiconductor oxides.

In the context of this document, 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 Ω-cm. By "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".

By "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. The term “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".

A presentation of the concepts of porosity (and of the terminology which has just been explained above) is given in the article “Texture of powdery or porous materials” by F. Rouquerol et al. published in the “Engineering Techniques” collection, treatise Analysis and Characterization, booklet P 1050; this article also describes porosity characterization techniques, in particular the BET method.

Within the meaning of the present invention, 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.

The term “agglomerate” means, according to IUPAC definitions, a strongly bound assembly of primary particles or aggregates.

Within the meaning of the present invention, the term “electrolyte layer” refers to the layer within an electrochemical device, this device being capable of operating according to its intended purpose. By way of example, in the case where said electrochemical device is a lithium ion secondary battery, 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.

According to the invention, the "porous inorganic layer", preferably mesoporous, can be deposited electrophoretically, by the coating process by dipping hereinafter "dip-coating", by the inkjet printing process. hereinafter "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.

2. Preparation of nanopowder suspensions

In the context of the present invention, 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.

In general, compositions of the TNO (TiNb2O7) type have a very low electronic conductivity. In a battery, to be able to deliver high power, the particle size must be very small. Furthermore, as will be explained below, it is advantageous for the mesoporous network to be coated with a thin layer of an electronically conductive material in order to compensate for this low electronic conductivity of the anode material; a thin layer of graphitic carbon (and not diamond carbon) is used for this purpose.

It is known that 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. Alternatively, there are solid-state synthesis methods, which also require high temperature treatment to homogenize the chemical composition.

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.

According to one method, 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). A very homogeneous distribution of complexed and dilute cations is thus obtained. Subsequently, the polymer and the complexing organic molecule are eliminated by pyrolysis, leading to the formation of the targeted inorganic oxides. Calcination at approximately 700°C makes it possible to obtain crystallized nanoparticles. The process makes it possible to adjust the size of the particles which decreases when the concentration of cations in the polymer matrix decreases.

By way of example, to obtain a suspension of particles of cathode material, it is possible to synthesize a 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. After the calcination step at 600° C., 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. We prefer 0<x<1 and even more 0.1<x<1 because the presence of germanium in the composition of the anode reduces the resistance of the battery and increases its power. It can be seen that the oxidation-reduction properties of germanium make it possible to obtain in this compound a behavior on insertion of lithium almost identical to that of the analogous compound without germanium. Even if the oxidation-reduction potential of the Ge ⁴⁺ /Ge ³⁺ ions is slightly lower than that of the Ti ⁴⁺ /Ti ³⁺ pair, this potential remains high enough to avoid the deposition (plating) of lithium at the charging and increases the energy density of the anode.

Other 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 can be identical or different from each other,

■ and in which 0 < w < 5 and 0 < x < 1 and 0 < y < 2 and z < 0.3.

For each of these active anode materials, 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.

Concerning the Li _w Tii-xCu _x Nb2-yM ¹ yO7-zM ² _z , we prefer 0 < x < 1 and even more 0.1 < x < 1 because the presence of copper in this active anode material makes it possible to increase battery power.

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.

According to the invention, the cathode material is advantageously selected from the group formed by: LiCoPC; LiMm.sNio.sC; LiFe _x Coi. _x PO4 (where 0 < x <1);LiNii/xCoi/yMni/zC>2 with x+y+z = 10; Lii,2Nio,i3Mno,54Coo,i302; LiMm.sNio.s-xXxC where X is selected from Al, Fe, Cr, Co, Rh, Nd, Sc, Y, Lu, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and where 0 < x <0.1;LiNio.sCoo.isAlo.osC^; U2MPO4F (with M = Fe, Co, Ni or a mixture of these different elements); UMPO4F (with M = V, Fe, Ti or a mixture of these different elements); UMSO4F (with M = Fe, Co, Ni, Mn, Zn, Mg), LiNii/ _x Mni/ _y Coi/ _z O2 with x+y+z = 10; UCOO2.

For high capacity cathodes, LiNii/ _x Mni/ _y Coi/ _z O2 with x+y+z=10, LiNio.sCoo.isAlo.osC^, and UCOO2 are particularly preferred.

By way of example, LiNi _x Mn _y Co _z O2 (also known by the acronym "NMC") can be used, preferably with x + y + z = 1, and even more preferably with x:y:z = 4:3:3 (material known as "NMC433").

3. Deposition of the layers and their consolidation

In general, 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 deposition of the layers, their drying and their consolidation are likely to raise certain problems which will be discussed now. These problems are partly related to the fact that during the consolidation of the layers a shrinkage occurs which generates internal stresses.

According to a first embodiment, the layers of electrodes are each deposited on a substrate capable of acting as an electric current collector. In this regard, a metal strip (i.e. a laminated sheet of metal) is preferred. Layers comprising the suspension of nanoparticles or agglomerates of nanoparticles can be deposited on both sides, by the deposition techniques indicated above.

When one seeks to increase the thickness of the electrodes, one observes that 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. When this shear stress exceeds a threshold, the layer detaches from its substrate.

To avoid this phenomenon, it is preferred to increase 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. Alternatively, in a second variant, 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. Thus, during consolidation, 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.

According to a second embodiment, the electrode layers are not deposited on a substrate capable of acting as an electric current collector, but on an intermediate, temporary substrate. In particular, it is possible to deposit, from suspensions that are more concentrated in nanoparticles and/or agglomerates of nanoparticles (i.e. less fluid, preferably pasty), fairly thick layers (called “green sheets”). 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. For consolidation by heat treatment (and preferably already for their drying) they can be detached from their substrate; so-called “raw” electrode plates are thus obtained which, after calcination heat treatment and partial sintering, will give mesoporous and self-supporting ceramic plates.

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. In a variant, to facilitate bonding between the ceramic plates and the metal sheet, 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.

In all cases, a ceramic electrode is obtained, without organic binder, mesoporous, located on either side of a metallic substrate serving as an electrode current collector.

In a variant of the process according to the invention, batteries are produced without using metallic current collectors. This is possible in the case 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.

4. Deposition of the thin layer of an electronic conductor

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. For example, TNO (Titanium Niobium Oxide) is generally less conductive than NWO (Niobium Tungsten Oxide), and it is therefore an NWO anode layer which will, at equal thickness, need more this deposition of a thin layer of electronic conductor. Similarly, for the same material, the thicker electrode layers will need this deposition of a thin electronic conductor layer more than the thin electrode layers.

The anode materials (more particularly titanium oxides, niobium oxides and mixed oxides of titanium and niobium, and in particular TiNb2O? abbreviated TNO) and cathodes used in the context of the present invention 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. According to the invention, 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.

To remedy this problem, according to an optional feature of the present invention, a coating of an electronically conductive material is deposited on and inside the pores of said porous layer of anodic material.

Indeed, as explained above, during the consolidation of the layer of anode material, the nanoparticles of anodic material naturally “weld” together to generate a porous, rigid, three-dimensional structure, without organic binder; 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.

Very advantageously, 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, known as such, 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. Advantageously, 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.

Advantageously, 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 (Ge), the doped oxides based on indium oxide, the doping preferably being tin (Sn), and/or gallium (Ga ) 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 with copper (Cu) and/or with manganese (Mn) and/or with germanium (Ge), the doped tin oxides, the doping being preferably with arsenic (As) and/or with fluorinated (F) and/or nitrogen (N) and/or niobium (Nb) and/or phosphorus (P) and/or antimony (Sb) e t/or aluminum (Al) and/or titanium (Ti), and/or gallium (Ga) and/or chromium (Cr) and/or cerium (Ce) and/or indium (In) and/or cobalt (Co) and/or nickel (Ni) and/or copper (Cu) and/or manganese (Mn) and/or germanium (Ge).

To obtain a layer of an electronically conductive material, preferably an electronically conductive oxide material, from an alkoxide, an oxalate or an acetate, the porous layer can be immersed in a rich solution of the precursor of the desired electronic conductive material. Then 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. Thus, 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.

The presence of 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. Indeed, 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. It is particularly advantageous to use 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.

Moreover, due to the very large specific surface, the effect of these electronically conductive coatings in oxide form on the electronic conductivity of the electrode will be much more pronounced than in the case of a conventional electrode, where the surface specific is lower, even if the conductive coatings deposited have a small thickness. These electronically conductive coatings, deposited on and inside the pores of the porous layer, give the electrode excellent electronic conductivity.

It is essentially the synergistic combination of a 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.

Moreover, 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. Indeed, in the case of coatings in electronically conductive material in oxide form, 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.

In this variant of depositing a nanolayer of electronically conductive material, it is preferable that 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.

In the case of the deposition of self-supporting electrode plates, this treatment can be carried out on the mesoporous ceramic plate and before the "bonding" on the current conductors.

5. Selection of layer materials

To obtain high performance batteries it is necessary to optimize their mass capacity and voltage. This can lead to constraints in the choice of the different materials, which must be compatible with each other and stable under the potential conditions in which the battery operates.

In this chapter we will mainly expose the cathode materials. The anode 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.

As regards the cathode materials, in the process for manufacturing a battery according to the invention, as presented in the “Object of the invention” section above, in a first embodiment, when the porous cathode has a mass capacity > 120 mAh/g and operates at a voltage < 4.5V, said cathode active material C is advantageously selected from the group formed by: LiCoO2, LiNii/ _x Coi/ _y Mni/ _z O2 with x +y+z = 10, Lii,2Nio,i3Mno,54Coo,i302, LiNio,8Coo,i5Alo,o502, Li2FePO4F, UMSO4F with M = Fe, Co, Ni, Mn, Zn, Mg or a mixture of these different elements, said first and second substrates are selected from the group formed by metals Cu, Al, stainless steels, Mo, W, Ta, Ti, Cr, Ni and alloys consisting of at least one of these elements, knowing that if the layer cathode plate is a cathode plate initially deposited on an intermediate substrate and heat-treated after being separated from its initial substrate and before s brought into contact with a substrate capable of acting as an electric current collector, said plate can be plated on a low melting point substrate, such as aluminum foil, and the method is characterized more particularly as follows:

- during a step (i), between step (f) and step (g), 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:

• a polymer rendered ionically conductive by the addition of a liquid electrolyte, either in the polymer phase or in the mesoporous structure, and even more preferably, by an electrolyte selected from the group formed by:

• an electrolyte comprising N-butyl-N-methyl-pyrrolidinium 4,5-dicyano-2-(trifluoro methyl) imidazole (Pyr^TDI) and containing lithium salts of the LiTDI type,

• 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) .

The use of 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), bis(mandelato)borate (abbreviated BMB), bis (perfluoropinacolato) borate (abbreviated BPFPB).

As will be explained in greater detail in the following chapter, in a second embodiment of this method, at the end of step (h) during a step (i), said battery is impregnated with an electrolyte , preferably by a phase carrying lithium ions, selected from the group formed by:

• an electrolyte comprising N-butyl-N-methyl-pyrrolidinium 4,5-dicyano-2-(trifluoro methyl) imidazole (Pyr^TFSI) and containing lithium salts of the LiTDI type,

• 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).

As for 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.

6. Impregnation with a liquid electrolyte to form a battery

After assembly of the stack of layers intended to form the battery, followed by thermocompression, the assembly thus obtained must be impregnated with an electrolyte to form a battery. Said electrolyte must include a phase carrying lithium ions, as described in the previous section. The 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 lithium ion carrier phase may comprise a mixture of several ionic liquids. It is possible to use ionic liquids which are liquid at room temperature (RTIL=Room Temperature Ionic Liquids).

In general, 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 (abbreviated BMB), bis(perfluoropinacolato) borate (abbreviated BPFPB) .

The 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.

Thus, and by way of example, for a battery intended to operate at high temperature, 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%.

Additives can also be added to these formulations in order to reduce parasitic reactions at the surface of the electrodes and/or at the surface of the current collectors. Advantageously, 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 γ-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. Surprisingly, 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.

Advantageously, 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. In an advantageous embodiment, the liquid electrolyte contains at least 50% by weight of ionic liquid, which is preferably PyruTFSI.

Among the other cations which can be used in these ionic liquids, mention is also made of PMIM ⁺ . Among the other anions which can be used in these ionic liquids, mention is also made of BF4; PFe', BOB; the DFOB; BMB; the BPFPB'. To form an electrolyte, a lithium salt such as LiTFSI can be dissolved in the ionic liquid which serves as the solvent or in a solvent such as γ-butyrolactone. The γ-butyrolactone prevents the crystallization of ionic liquids inducing a greater temperature operating range of the latter, in particular at low temperature. Advantageously, when the porous cathode comprises a lithium phosphate, 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.

As just explained, a certain number of ionic liquids can be used, 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.

However, TFSI-type lithium salts tend to corrode substrates. For this reason, among the ionic liquids and associated salts, 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. It is observed that the simple addition of LiTDI type salts to the LiTFSI type salts already reduces the corrosive effect ionic liquid compared to metallic substrates. 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.

In general, it is advantageous for the phase bearing lithium ions to 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 γ-butyrolactone, glyme or PC.

In an advantageous embodiment, 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.

Advantageously, 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, γ-butyrolactone, PC, glymes;

- optionally additives such as VC to stabilize the interfaces and limit parasitic reactions.

In another embodiment, the lithium ion carrier phase comprises:

- between 30 and 40% by mass of a solvent, preferably between 30 and 40% by mass of y-butyrolactone, or PC or glyme, and more than 50% by mass of at least one ionic liquid, preferably more than 50% mass of PYRuTFSI. By way of example, the phase carrying lithium ions can be an electrolytic solution comprising PYR14TFSI, LiTFSI and γ-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.

7. Description of advantageous embodiments

We describe here several embodiments of the battery according to the invention.

In general, in the context of the present invention, 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 μm. 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). They are partially sintered, that is to say that the primary nanoparticles, following the thermomechanical consolidation treatment, are welded together by the phenomenon of "necking" (known to those skilled in the art, see for example "Particulate Composites by R. M. German, Springer International Publishing 2016, p. 26/27) to form a continuous mesoporous three-dimensional network.

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. Advantageously, a nanolayer of an electronic conductor (for example carbon) is deposited on the mesoporous surface.

According to the invention, 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. By surface, we mean here not the geometric surface of the layer but its entire mesoporous surface: the coating is also applied inside the pores. Said coating may be a carbon conductive coating.

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.

More particularly, 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.

With these electrodes, and in particular such an anode in TiNb2O? with a mesoporous volume of about 35% as described above, lithium ion batteries can be made. To enable those skilled in the art to carry out the invention, we describe here five embodiments; this in no way limits the scope of the invention.

In a first embodiment, an attempt was made to increase the energy of the battery, by choosing a cathode operating at high voltage.

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 μm and 20 μm. The cathode is LiCoPC with a mesoporous volume of approximately 35%. The thickness of the cathode is about 90 µm; 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 µm 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 μm and 20 μm. In the second embodiment of the invention, where the anode was initially deposited on an intermediate (or extruded) substrate, it is also possible to use an aluminum electrode for example. The anode in TiNb2C>7 with a mesoporous volume of about 35% exhibited a thickness of about 50 µm.

In all cases, and more particularly in the second embodiment of the invention (in which the anode is manufactured in the form of a plate), 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).

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.

One of the disadvantages of this battery is the high cost of the cathode material, due to its high cobalt content.

In a second embodiment, 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 μm, a mesoporous volume of about 35%, with deposit of a carbon nanolayer; this cathode is dimensioned for a capacity of approximately 120 mAh/g.

The separator, the anode, the cathodic and anode current collectors, as well as the ionic liquid used for the impregnation of the cell were the same as in the first embodiment. 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.

In a third embodiment, a cathode operating at low voltage has been used.

The cathode was in Lii,2Nio,i3Mno,54Coo,i302 had a thickness of about 90 μm 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 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 μm and 20 μm. The TiNb2O anode? with a mesoporous volume of about 35% had a thickness of about 80 µm; a carbon nanolayer was deposited on the mesoporous surface.

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.

It should be noted that 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 μm and 20 μm. One can use an aluminum sheet if the nanoparticles from which the cathode was made are already perfectly crystallized, or the collector is glued on the electrodes after sintering in the case where the electrode was made in the form of a electrode plate.

The cathode was in Lii,2Nio,i3Mno,54Coo,i302 had a thickness of about 16 μm, 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 anode current collector is a sheet of Cu, Ni, Al or Mo; its thickness is typically between 5 μm and 20 μm. The TiNb2O anode? with a mesoporous volume of about 35% had a thickness of about 14 µm; a carbon nanolayer was deposited on the mesoporous surface.

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.

These battery cells and batteries have excellent low temperature performance. They are capable of operating at temperatures below the crystallization temperature of the liquid electrolyte. When the impregnation is made with a polymer, the conduction properties of the polymer are increased over a wide temperature range. 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 μm and 8 μm. 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. In particular, 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”.

For example, a cell is made according to the fourth embodiment described above, by multiplying the thicknesses of the electrodes by a factor of six. Thus, with an anode with a thickness of around 50 μm to 80 μm, 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.

Examples

In addition to certain very specific embodiments which have been described in the "Detailed Description" section above, we give here other examples to enable those skilled in the art to reproduce the invention. These examples do not limit the invention. Example 1: Synthesis of TNO nanopowders that can be used to produce an anode according to the invention

A formulation of nanoparticle agglomerates of Tio.gsGeo.osl^O? from the following alkoxides:

(i) Ge(OC2Hs)4, molar mass 252.88 g/mol, density 1.14 g/cm ³ ;

(ii) Ti(OC2Hs)4, molar mass 228.11 g/mol, density 1.09 g/cm ³ ;

(iii) Nb(OC2Hs)4, molar mass 318.21 g/mol, density 1.268 g/cm ³ .

In a first step, citric acid was dissolved in ethylene glycol by heating to 80°C. At the same time, the mixture of ethoxides was prepared in a glove box, respecting the stoichiometry of the target component.

In a second step, 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. We then obtain agglomerates of nanoparticles (of elementary sizes of 40 nm) crystallized in the space group 12/m JCPDS: 39-1407. These are pure monoclinic crystals.

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.

These plates are very useful for the manufacture of high power batteries.

Claims

48 CLAIMS

1 . 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 comprising a porous layer having a porosity of between 25% and 50% by volume, preferably about 35% by volume, and pores with an average diameter of less than 50 nm, said manufacturing method being characterized in that:

(a) a substrate and a colloidal suspension or a paste composed of monodisperse primary nanoparticles, in the form of agglomerates or dispersed, of at least one anode active material A, with an average primary diameter D50 of between 2 nm and 100 nm, and preferably between 2 nm and 60 nm, it being understood that said colloidal suspension or said paste also comprises a liquid constituent, it being understood that said active anode material A is selected from niobium oxides and mixed oxides of niobium with titanium, germanium, cerium, lanthanum, copper, or tungsten, and preferably in 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.xM ¹ xNb ₂ .yM ² yO7- _S , Li _w Tii. _x M ¹ xNb2-yM ² yO7 in which 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 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-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 can be identical or different from each other,

■ M ³ is at least one halogen,

■ and wherein 0 < w < 5 and 0 < x < 1 and 0 < y < 2 and z <0.3; 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, and 0 < w < 5 and and 0 < z <0.3; o Tii-xGe _x Nb2-yM ¹ yO7-z , Li _w Tii-xGe _x Nb2-yM ¹ yO7-z , Tii-xLa _x Nb2-yM ¹ yO7-z , Li _w Tii. _x La _x Nb2- yM ¹ _y O7-z , Tii-xCe _x Nb2-yM ¹ yO7-z , Li _w Tii-xCe _x Nb2-yM ¹ yO7-z in which 49

■ and in which 0<w<5 and 0<x<1 and 0<y<2andz<1, preferably in which 0<w<5 and 0<x<1 and 0<y<2andz<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. xLa _x Nb2-yM ¹ _y O7-zM ² _z , Tii- _x Cu _x Nb2-yM ¹ _y O7-zM ² _z , Li _w Tii- _x Cu _x Nb2-yM ¹ _y O7-zM ² _z , Tii- xCe _x Nb2-yM ¹ _y O7-zM ² _z , Li _w Tii- _x Ce _x Nb2-yM ¹ _y O7-zM ² _z in which

■ 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 and Sn;

■ 0<w<5 and 0<x<1 and 0<y<2 and z<0.3;

(c) said layer obtained in step (b) is dried and consolidated, by pressing and/or heating, to obtain a porous layer.

2. Method according to claim 1, characterized in that the method is continued by a step (d):

(d) depositing, on and inside the pores of said porous layer, a coating of an electronically conductive material, which is preferably chosen from among carbon or an electronically conductive oxide material, and wherein said conductive oxide material electronics is preferably chosen from: tin oxide (SnO2), 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 (SnO2), 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 (Ge), 50 doped oxides based on indium oxide, the doping preferably being with tin (Sn), and/or gallium (Ga) 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 (Ge), doped tin oxides, the doping being preferably with arsenic (As) and/or with fluoride (F) and/or with nitrogen (N) and/or with niobium (Nb) and/or phosphorus (P) and/or antimony (Sb) and/or aluminum (Al) and/or titanium (Ti), and/or gallium (Ga) and /or chromium (Cr) and/or cerium (Ce) and/or indium (In) and/or cobalt (Co) and/or nickel (Ni) and/or copper (Cu) and /or manganese (Mn) and/or germanium (Ge).

3. Method according to claim 2, characterized in that 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 said precursor in electronically conductive material.

4. Method according to claim 3, characterized in that said precursor is a carbon-rich compound, such as a carbohydrate, and in that said transformation into electronic conductive material is pyrolysis, preferably under an inert atmosphere, or in that that said precursor is chosen from organic salts containing one or more metallic elements capable, after heat treatment such as calcination, of forming an electronically conductive oxide, and in that said transformation into an electronically conductive material is a heat treatment such as calcination, preferably carried out in air or in an oxidizing atmosphere.

5. Method according to any one of claims 1 to 4, characterized in that the organic salts are preferably chosen from an alcoholate of at least one metallic element capable, after heat treatment such as calcination, preferably carried out under air or under an oxidizing atmosphere, of forming an electronically conductive oxide, an oxalate of at least one metallic element capable, after heat treatment such as calcination, preferably carried out under air or under an oxidizing atmosphere, 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 a conductive oxide 51 electronics, and / or in that the metallic element is selected from tin, zinc, indium, gallium, or a mixture of two or three or four of these elements.

6. Method according to any one of claims 1 to 5, characterized in that said primary nanoparticles are 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.

7. Method according to any one of claims 1 to 6, characterized in that said porous layer resulting from step (c) has a specific surface of between 10 m ² /g and 500 m ² /g.

8. Method according to any one of claims 1 to 7, in which said layer obtained in step (c) has a thickness of between 1 μm and 150 μm.

9. Method according to any one of claims 1 to 8, characterized in that said substrate is an intermediate substrate, from which said layer is separated in step (c) after its drying, to form a porous anode plate.

10. 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:

- pores with an average diameter of less than 50 nm, a porous network of material A 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 Nb ₂ O ₅ ^ , NbisWieOgs- s , NbieWsOss-s with 0 S x < 1 and 0 s 5 <2; o TiNb2C>7-8 , Tii.xM ¹ xNb ₂ .yM ² yO7- _S , Li _w Tii. _x M ¹ xNb2-yM ² yO7-s wherein 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 < 5 <0.3; o Tii-xM ¹ xNb2-yM ² _y O7-zM ³ _z , Li _w Tii-xM ¹ xNb2- _y M ² yO7-zM ³ _z in which

■ M ¹ and M ² can be identical or different from each other,

■ M ³ is at least one halogen,

■ and in which 0<w<5 and 0<x<1 and 0<y<2 and z<0.3; 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, and 0 < z < 0.3, o Tii- _x Ge _x Nb2-yM ¹ yO7-z, Li _w Tii. _x Ge _x Nb2-yM ¹ yO7-z , Tii. _x Ce _x Nb2-yM ¹ yO7-z, Li _w Tii. _x Ce _x Nb2- yM ¹ _y O7-z in which

■ and in which 0<w<5 and 0<x<1 and 0<y<2 and z 1, preferably in which 0<w<5 and 0<x<1 and 0<y<2 and 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. 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- xCe _x Nb2-yM ¹ yO7-zM ² _z , Li _w Tii-xCe _x Nb2-yM ¹ yO7-zM ² _z in which

■ 0<w<5 and 0<x<1 and 0<y<2 and z<0.3; said anode being capable of being obtained by the process according to any one of claims 1 to 9.

11. Anode according to claim 10, characterized in that the electronically conductive material is chosen from carbon, electronically conductive oxide materials, preferably chosen from: tin oxide (SnO2), 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 (SnO2), a mixture of three of these oxides or a mixture of four of these oxides, doped oxides based on zinc oxide, doping being preferably 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 (Ge), the doped oxides based on d indium, the doping preferably being tin (Sn), and/or gallium (Ga) 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 (Ge), doped tin oxides, the doping being preferably with arsenic (As) and/or fluorine (F) and/or nitrogen (N) and/or niobium (Nb) and/or phosphorus ( P) and/or antimony (Sb) and/or aluminum (Al) and/or titanium (Ti), and/or gallium (Ga) and/or chromium (Cr) and/or cerium (Ce) and/or indium (In) and/or cobalt (Co) and/or nickel (Ni) and/or copper (Cu) and/or manganese (Mn) and/or germanium (Ge).

12. A method of manufacturing a battery designed to have a capacity greater than 1 mA h, preferably a lithium ion battery, implementing the method of manufacturing a porous anode according to one of claims 1 to 9 , or implementing a porous anode according to claim 10.

13. A method of manufacturing a battery, comprising at least one porous anode according to claim 10 or 11, at least one separator and at least one porous cathode, characterized in that:

(a) supplying a first substrate, a second substrate, and supplying a first colloidal suspension or a paste comprising aggregates or agglomerates of monodisperse primary nanoparticles of at least one anode active material A, of mean primary diameter D ₅ o between 2 and 100 nm, preferably between 2 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), it being understood 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 TiNb2O?-s , Tii. _x M ¹ xNb2-yM ² yO ₇ -5 , Li _w Tii-xM ¹ _x Nb2-yM ² yO7-s wherein 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 ^M2 54 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<S<0.3; o Tii. _x M ¹ xNb2-yM ² yO7-zM ³ _z , Li _w Tii-xM ¹ _x Nb2-yM ² yO7-zM ³ _z in which

■ M ¹ and M ² can be identical or different from each other,

■ M ³ is at least one halogen,

■ and in which 0<w<5 and 0<x<1 and 0<y<2 and z<0.3; 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. 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 _y O7-zM ² _z , Li _w Tii-xCe _x Nb2-yM ¹ yO7-zM ² _z in which

■ 0<w<5 and 0<x<1 and 0<y<2 and z<0.3; o Tii- _x Ge _x Nb2-yM ¹ yO7-z, Li _w Tii. _x Ge _x Nb2-yM ¹ yO7-z , Tii. _x Ce _x Nb2-yM ¹ yO7-z, Li _w Tii. _x Ce _x Nb2- yM ¹ _y O7-z in which

■ and in which 0<w<5 and 0<x<1 and 0<y<2 and z<1, preferably in which 0<w<5 and 0<x<1 and 0<y<2 and z<0.3; knowing that 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 is supplied comprising aggregates or agglomerates of monodispersed primary nanoparticles of at least one cathode active material C, with an average primary diameter D50 of between 2 and 100 nm, preferably between 2 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 nm), and a third colloidal suspension comprising aggregates or agglomerates of nanoparticles of at least one inorganic material E, of 55 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);

(c) drying said anode and cathode layers obtained in step (b), if necessary after having separated said layer from its intermediate substrate, and consolidating each layer, 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;

(e) depositing on said porous anode and/or said porous cathode obtained in step (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 from coating roller, curtain coating, doctor coating, extrusion coating through a slot-shaped die, dip coating;

(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 approximately 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;

(g) 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 56 the stack obtained comprises at least one porous inorganic layer as obtained in step e) forming said separator;

14. Method according to claim 13, characterized in that said inorganic material E is an electrical insulator.

15. Process according to claim 13 or 14, in which the product resulting from step (h) is impregnated with an electrolyte, preferably with a phase carrying lithium ions, selected from the group formed by:

• an electrolyte comprising N-butyl-N-methyl-pyrrolidinium 4,5-dicyano-2- (trifluoromethyl) imidazole (Pyr^TDI),

16. Method according to any one of claims 1 to 9 or 12 to 15, in which said cathode active material C is selected from the group formed by: LiCoPC , LiMni.sNio.sC , LiFe _x Coi. _x PO4 and where 0 < x < 1 , LiNii/ _x Coi/ _y Mni/ _z O2 with x+y+z = 10, Lii,2Nio,i3Mno,54Coo,i302, LiMni,5Nio,5- _x X _x 04 where X is selected from Al, Fe, Cr, Co, Rh, Nd, Sc, Y, Lu, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and where 0 < x < 0.1 , LiNio,8Coo,i5Alo,o502, U2MPO4F with M = Fe, Co, Ni or a mixture of these different 57 elements, LiMPC F with M = V, Fe, T or a mixture of these different elements, UMSO4F with M = Fe, Co, Ni, Mn, Zn, Mg, UCOO2.

17. Lithium ion battery having a capacity greater than 1 mA h, obtainable by the method according to any one of claims 12 to 16.

18. Battery according to claim 17, characterized in that its liquid electrolyte contains at least 50% by mass of ionic liquid, which is preferably Pyr^TFSI.

19. Battery according to any one of claims 17 or 18 dependent on any one of claims 13 to 16, characterized in that:

- its cathodic current collector is made of a material selected from the group formed by: Mo, Ti, W, Ta, Cr, Al, alloys based on the aforementioned elements, stainless steel;

- its cathode is made of NMC and preferably of NMC433, and it has a pore volume of between 30 and 40%, 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 μm and 8 μm;

- Its anode is a layer of TiNb2O?-s, with 0<5<0.3, preferably doped with a halide and/or germanium, 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.

20. Battery according to any one of claims 17 to 19, characterized in that it has electrodes with a thickness greater than 10 μm.

21. Battery according to any one of claims 17 to 20, characterized in that it comprises an anode according to claim 10 or 11, or capable of being obtained by the method according to any one of claims 1 to 9, and in that said anode has a mass capacity greater than 200 mAh/g, and preferably greater than 250 mAh/g.

22. Use of a battery according to any one of claims 17 to 20 at a temperature below -10°C and/or at a temperature above 50°C.