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EP-4736244-A1 - PROCESS FOR MANUFACTURING A POROUS ELECTRODE, AND BATTERY CONTAINING SUCH AN ELECTRODE

EP4736244A1EP 4736244 A1EP4736244 A1EP 4736244A1EP-4736244-A1

Abstract

The present invention relates to a porous electrode for use in electrical energy storage or production devices, such as a lithium ion battery. Said porous electrode is a porous layer comprising at least an active electrode material P and an electronic conductive oxide material.

Inventors

  • GABEN, FABIEN
  • CAYREFOURCQ, IAN
  • GUIRONNET, Laure
  • SAYEGH, Adnan
  • DECHAUD, Loris
  • BOUMAHRAZ, Mehdi

Assignees

  • I-TEN

Dates

Publication Date
20260506
Application Date
20240627

Claims (20)

  1. 1. Method for manufacturing a porous electrode, in particular for devices for storing or producing electrical energy, said electrode being a porous layer comprising at least one active electrode material P and an electronically conductive oxide material, said electrode being free of binder, having a porosity of between 25% and 60% by volume, preferably between 25% and 50%, and pores with an average diameter of less than 100 nm, said manufacturing method being characterized in that: (a) a substrate is provided, at least one precursor of an electronically conductive oxide material, and a colloidal suspension or a paste comprising aggregates or agglomerates of primary nanoparticles, of at least one active electrode material P, with an average primary diameter Dso of between 2 nm and 400 nm, preferably between 2 nm and 100 nm, and more preferably between 2 nm and 60 nm, said aggregates or agglomerates having an average diameter Dso of between 50 nm and 900 nm, and preferably between 100 nm and 800 nm, knowing that said substrate may be a substrate capable of acting as an electric current collector, or be an intermediate substrate, (b) mixing said precursor(s) of an electronically conductive oxide material and said colloidal suspension or said paste comprising aggregates or agglomerates of primary nanoparticles, of at least one active electrode material P supplied in step (a), so as to form a mixture, (c) a layer is formed from the mixture obtained at the end of step (b), by a process selected from the group formed by: electrophoresis, an additive manufacturing process, extrusion, a printing process, preferably inkjet printing or flexographic printing, a coating process, preferably by doctor blade, roller, curtain, dip-shrink, or through a slot-shaped die, (d) said layer obtained in step (c) is dried so as to obtain a dried layer, where appropriate said dried layer is separated from its intermediate substrate after drying step (d), (e) the transformation of the precursor(s) of an electronically conductive oxide material into an electronically conductive oxide material is carried out, such that said dried layer comprises said electronically conductive oxide material, (f) said layer is consolidated, by thermal and/or mechanical treatment, preferably by sintering, to obtain a porous, preferably mesoporous, electrode, it being understood that steps (e) and (f) may be carried out during the same heat treatment.
  2. 2. A method of manufacturing a porous electrode according to claim 1, characterized in that step (b) is carried out by bringing into contact the colloidal suspension or the paste supplied in step (a) comprising aggregates or agglomerates of primary nanoparticles, of at least one active electrode material P with a liquid phase comprising at least one precursor of said electronically conductive oxide material, and in that said transformation of the precursor(s) of an electronically conductive oxide material into an electronically conductive oxide material during step (e) is carried out by heat treatment such as calcination, preferably carried out in air or in an oxidizing atmosphere.
  3. 3. Method for manufacturing a porous electrode according to claim 1 or 2, characterized in that after step (f) the pores of said porous electrode are impregnated with an electrolyte, preferably with a phase carrying lithium ions, sodium ions or potassium ions selected from the group formed by: - an electrolyte composed of at least one aprotic solvent and at least one lithium, sodium or potassium salt; - an electrolyte composed of at least one ionic liquid and at least one lithium, sodium or potassium salt; - a mixture of at least one aprotic solvent and at least one ionic liquid and at least one lithium, sodium or potassium salt; - an ionic liquid polymer; - a polymer made ionically conductive by the addition of at least one lithium, sodium or potassium salt; and - a polymer made ionically conductive by the addition of a liquid electrolyte, either in the polymer phase or in the porous structure of the porous electrode, or by an ionically conductive polymer, preferably chosen from polyethylene oxide (PEO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), poly(propylene carbonate) (PPC), poly(ethylene carbonate) (PEC), poly(vinyl carbonate) (PVC), polyvinylidene fluoride (PVDF), polypropylene glycol (PPG), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polydimethylsiloxane (PDMS), poly(E-caprolactone) (PCL) and poly(tri methylene carbonate) (PTMC).
  4. 4. A method of manufacturing a porous electrode according to any one of claims 1 to 3, characterized in that said precursor(s) of the electronically conductive oxide material 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, these organic salts preferably being chosen from - an alcoholate 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 electronically conductive oxide, - a nitrate 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 electronically conductive oxide, - an oxalate 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 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 electronically conductive oxide, - and/or in that, preferably, the metallic element is chosen from tin, zinc, indium, gallium, molybdenum or a mixture of two or three or four or five of these elements.
  5. 5. Method for manufacturing a porous electrode according to any one of claims 1 to 4, characterized in that said electronically conductive oxide material is chosen from: - tin oxide (SnC>2), zinc oxide doped with aluminium (ZnO:Al, preferably having a Zn:Al molar ratio of between 1:0.015 and 1:0.05), indium oxide (In 2 O 3 ), gallium oxide (Ga 2 O 3 ), molybdenum oxide (MoO 3 ), molybdenum and strontium oxide (SrMoCh), a mixture of two of these oxides such as indium-tin oxide corresponding to a mixture of indium oxide (In 2 O 3 ) and tin oxide (SnC>2), a mixture of three of these oxides, a mixture of four of these oxides, a mixture of five of these oxides or a mixture of six of these oxides, - doped oxides based on zinc oxide, the doping preferably being gallium (Ga) and/or aluminium (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) and/or molybdenum (Mo), - 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 copper (Cu) and/or manganese (Mn) and/or germanium (Ge) and/or molybdenum (Mo), - doped tin oxides, 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 aluminium (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) and/or molybdenum (Mo), - doped oxides based on molybdenum oxide, the doping preferably being lithium (Li) and/or sodium (Na) and/or potassium (K) and/or beryllium (Be) and/or magnesium (Mg) and/or calcium (Ca) and/or scandium (Sc) and/or titanium (Ti) and/or vanadium (V) and/or chromium (Cr) and/or manganese (Mn) and/or iron (Fe) and/or cobalt (Co) and/or nickel (Ni) and/or copper (Cu) and/or zinc (Zn) and/or gallium (Ga) and/or germanium (Ge) and/or arsenic (As) and/or rubidium (Rb) and/or cesium (Cs) and/or yttrium (Y) and/or zirconium (Zr), and/or strontium (Sr) and/or niobium (Nb) and/or tritium (T) and/or rhenium and/or iridium (Ir) and/or platinum (Pt) and/or gold (Au) and/or mercury (Hg) and/or lead (Pb) and/or bismuth (Bi).
  6. 6. Method for manufacturing a porous electrode according to any one of claims 1 to 5, characterized in that said porous electrode obtained at the end of step (f) has a specific surface area of between 10 m 2 /g and 500 m 2 /g and/or a thickness of between 2 pm and 400 pm, preferably between 2 pm and 300 pm, more preferably between 3 pm and 200 pm.
  7. 7. A method of manufacturing a porous electrode according to any one of claims 1 to 5, characterized in that said porous electrode obtained at the end of step (f) has a specific surface area of between 10 m 2 /g and 500 m 2 /g; and/or a thickness of between 2 pm and 20 pm when the substrate is a substrate capable of acting as an electric current collector, and/or a thickness of between 25 pm and 500 pm, preferably between 50 pm and 400 pm, when the substrate is an intermediate substrate.
  8. 8. A method of manufacturing a porous electrode according to any one of claims 1 to 5, characterized in that when said substrate is an intermediate substrate, said layer is separated from said intermediate substrate in step (d) after drying said layer, to form a porous plate.
  9. 9. A method of manufacturing a porous electrode according to any one of claims 1 to 8, characterized in that said colloidal suspension or paste supplied in step (a) comprises organic additives, such as ligands, stabilizers, binders or residual organic solvents, and a heat treatment is carried out, preferably in an oxidizing atmosphere, of said dried layer obtained at the end of step d) according to any one of claims 1 to 7, or of said porous plate according to claim 8, it being understood that this heat treatment and steps (e) and/or (f) can be carried out during the same heat treatment.
  10. 10. A method of manufacturing a porous electrode according to any one of claims 1 to 9, wherein said electrode active material P is selected from group (A) formed by: - the oxides LiMn2O4, Ui +x Mn2-xO4 with 0 < x < 0.15, LiCoO2, LiNiC>2, LiMn1.5Nio.5O4, LiMni,sNio,5-xX x 040where X is selected from Al, Fe, Cr, Co, Rh, Nd, other rare earths such as Sc, Y, Lu, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and where 0 < x < 0.1 , LiMn2-xM x O4 with M = Er, Dy, Gd, Tb, Yb, Al, Y, Ni, Co, Ti, Sn, As, Mg or a mixture of these compounds and where 0 < x < 0.4, LiFeO2, LiMni/3Nii/3Coi/3O2 , LiNi0.8Co0.15AI0.05O2, LiAl x Mn2-xO4 with0 < x < 0.15, LiNii/ x Coi/ y Mni/ z O2 with x+y+z =10 ; - Li x M y O2 where 0.6<y<0.85;0<x+y<2; and M is selected from Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Sn, and Sb or a mixture of these elements; Li1.20Nbo.20Mno.60O2; - Lii+xNbyMe z ApO2 where Me is at least one transition metal selected from: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, and where 0.6<x<1;0<y<0.5;0.25<z<1; with A Me and A Nb, and 0<p<0.2; - LixNby. a N a M z .bPbO 2 -cFc where 1.2<x<1.75;0<y<0.55;0.1<z<1;0<a<0.5;0<b<1;0<c<0.8; and where M, N, and P are each at least one of the elements selected from the group consisting of Ti, Ta, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Zr, Y, Mo, Ru, Rh, Ce and Sb; - Li1.25Nbo.25Mno.50O2; Li1.3Nbo.3Mno.40O2; Li1.3Nbo.3Feo.40O2; Li1.3Nbo.43Nio.27O2; Li1.3Nb0.43Co0.27O2; Li1.4Nbo.2Mno.53O2; - LixNi0.2Mn0.eOy where 0.00<x<1.52; 1.07<y<2.4; Li1.2Nio.2Mno.6O2; - LiNi x Co y Mni-x-yO2 where 0 < x and y <0.5; LiNi x Ce z Co y Mni-x-yO2 where 0 < x and y < 0.5 and 0 <z; - phosphates LiFePO4, LiMnPÛ4, UCOPO4, LiNiPÛ4, Li3V2(PO4)3, U2MPO4F with M = Fe, Co, Ni or a mixture of these different elements, UMPO4F with M = V, Fe, T or a mixture of these different elements; phosphates of formula LiMM'PCU, with M and M' (M M') selected from Fe, Mn, Ni, Co, V such that LiFe x Coi. x PO4and where 0 < x <1; - Feo.gCoo OF ; FeFs; UMSO4F with M = Fe, Co, Ni, Mn, Zn, Mg; - titanium oxysulfides (TiO y S z with z=2-y and 0.3<y<1), tungsten oxysulfides (WOySz with 0.6<y<3 and 0.1 <z<2), CuS, CUS2, Li x V 2 Os with 0 < x < 2, LLVsOs with 0 < x < 1 ,7, Li x TiS 2 with 0 < x < 1 , titanium and lithium oxysulfides Li x TiO y S z with z=2-y, 0.3<y<1 and 0 < x < 1 , Li x WO y S z with z=2-y, 0.3<y<1 and 0 < x < 1 , Li x CuS with 0 < x < 1 , Li x CuS 2 with 0 < x <1; or in group (B) formed by: transition metal oxides: o Na x MO 2+z with M chosen from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te with z < 0.3 and 0 < x < 1 , preferably 0 < x < 0.44 or 0.44 < x < 0.67 or 0.67 < x <1; o Na x M u / 2 M'v/ 2 O 2+z with u + v = 2 and M, M' selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te with z < 0.3 and 0 < x < 1 , preferably 0 < x < 0.44 or 0.44 < x < 0.67 or 0.67 < x <1; o Na x M u /3M'v/3M”w/3O 2+z with u + v + w = 3 and M, M', M” selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te with z < 0.3 and O < x < 1 , preferably 0 < x < 0.44 or 0.44 < x < 0.67 or 0.67 < x <1; o Na x Mn y Ni z Feo.iMgo.i0 2 with 0.67 < x <1.0; 0.5 < y < 0.7 and 0.1 < z <0.3; Prussian blue and/or Prussian blue analogues known by the acronym PBA from the English “prussian blue analogues”: o Na x M 1 [M 2 '(CN)e] y .nH 2 O, M 1 being a transition metal or a transition metal alloy, M 2 ' being a transition metal, the transition metal and the transition metal alloy being selected from Fe, Ni, Co and Mn, with 0 < x <2; y < 1 and 0 < n <12; polyanionic compounds: o Na x M 2 (XO4) 3 with 0 < x < 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W, such as Na3V 2 (PO4) 3 ; o Na x M3 (XO4) 2 (X 2 O?) with 0 < x < 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W ; o Na x M (X 2 O?) with 0 < x < 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W ; o Na x M2(XC>4)2F3 with 0 < x < 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; o Na x M2(XO4)2F3-yO y with 0 < x < 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and O.07 < y < 0.12 and X = P, S, As, Si, Mo or W; o Na x M2C>2(XO4)2F with 0 < x < 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; o Na x MXO4 with 0 < x < 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; or in the group (C) formed by: transition metal oxides: o K X MO 2+Z with M chosen from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te with z < 0.3 and 0 < x < 1 , preferably 0 < x < 0.44 or 0.44 < x < 0.67 or 0.67 < x <1; o K X M U /2M'V/2O2+Z with u + v = 2 and M, M' chosen from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te with z < 0.3 and 0 <x < 1, preferably 0 < x < 0.44 or O.44 < x < 0.67 or 0.67 < x <1; o K X M U /3M'V/3M”W/3O2+Z with u + v + w = 3 and M, M', M” selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te with z < 0.3 and O < x < 1, preferably 0 < x < 0.44 or 0.44 < x < 0.67 or 0.67 < x <1; o K x Mn y Ni z Feo.iMgo.i02 with 0.67 < x <1.0; 0.5 < y < 0.7 and 0.1 < z <0.3; Prussian blue and/or Prussian blue analogues known by the acronym PBA for "Prussian blue analogues": o K x M 1 [M 2 '(CN)e]y.nH2O, M 1 being a transition metal or a transition metal alloy, M 2 ' being a transition metal, the transition metal and the transition metal alloy being selected from Fe, Ni, Co and Mn, , with 0 < x <2; y < 1 and 0 < n <12; polyanionic compounds: o K X M2(XO4)3 with 0 < x < 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W, such as NasX^PCLh; o K X M3(XO4)2(X2O?) with 0 < x < 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; o K X M(X2O?) with 0 < x < 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; o K x M2(XO4)2F3 with 0 < x < 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; o K x M2(XO4)2F3-yO y with 0 < x < 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and 0.07 < y < 0.12 and X = P, S, As, Si, Mo or W; o K X M2O2(XC>4)2F with 0 < x < 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; o K x MXO 4 with 0 < x < 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W.
  11. 11. A method of manufacturing a porous electrode according to any one of claims 1 to 9, wherein said electrode active material P is selected from the group (D) formed by: • Li4TisOi2, Li4Tis-xM x Oi2 with M = V, Zr, Hf, Nb, Ta and 0 < x <0.25; • niobium oxides and mixed oxides of niobium with titanium, germanium, cerium or tungsten, and preferably in the group formed by: Nb 2 O 5±5 , Nbi2WO33±s, Nbi4W3O44±s, NbisWi6O93±8 , NbieWsOss a with 0 s S < 2, LiNbO 3 , TiNb2C>7±8, LiwTiNb2C>7 with w>0, Tii-xM 1 x Nb2-yM 2 yO7±8 or Li w Tii-xM 1 x Nb2- yM 2 yC>7±8 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 being the same or different from each other. the other, and in which 0 < w < 5 and 0 < x < 1 and 0 < y < 2 and 0 < ô <0.3; La x Tii-2xNb2+xO7 where 0<x<0.5; M x Tii-2xNb2+xO7±5in which M is an element whose oxidation state is +III, more particularly M is at least one of the elements selected from the group consisting of Fe, Ga, Mo, Al, B, and where 0<x<0.20 and -0.3< 5 sO.3; Ga0.10Ti0.80Nb2.10O7; Fe0.10Ti0.80Nb2.10O7; M x Ti 2 -2xNbio + x029± 5 in which M is an element whose oxidation state is +III, more particularly M is at least one of the elements selected from the group consisting of Fe, Ga, Mo, Al, B, and where 0<x<0.40 and -0.3<5 <0.3; Tii-xM 1 x Nb2-yM 2 yO7-zM 3 z or Li w Tii-xM 1 xNb2-yM 2 yO7-zM 3 z 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 may 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;TiNb2C>7-zM 3 z or Li w TiNb2O7- z M 3 z in which M 3 is at least one halogen, preferably selected from F, Cl, Br, I or a mixture thereof, and 0 < z < 0.3 and 0 < w <5; Tii-xGe 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 , UwTii- 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 and Sn; - 0 < w < 5 and 0 < x < 1 and 0 < y < 2 and z <0.3; Tii- x Ge x Nb2-yM 1 yO7-zM 2 z , Li w Tii- x Ge x Nb2-yM 1 yO7-zM 2 z, Tii- x Ce x Nb2-yM 1 yO7- z M 2 z , LiwTii- x Ce x Nb2-yM 1 yO7-zM 2 z , 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, Ce and Sn, - M 1 and M 2 may 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; • TiO2 ; TiO x Ny with x<2 and 0<y<0.2 ; • LiSiTON, tin and silicon-based oxynitrides, and more particularly the formulation SiSno,870i,2oNi,72 and their lithiated forms; • nitrides and oxynitrides of type MO x N y where M is at least one element chosen from Ge, Si, Sn, Zn, Co, Ni, Cu, Fe or a mixture of one or more of these elements, and where x>0 and y>0.3; • Li3-xM x N with M is at least one element selected from Cu, Ni, Co or a mixture of one or more of these elements and 0 < x <1; • Li3-xM x N with M being cobalt (Co) and 0 < x <0.5; Li3-xM x N with M being nickel (Ni) and 0 < x <0.6; Li3-xM x N with M being copper (Cu) and 0 < x <0.3; • lithium iron phosphate, with the typical formula LiFePO4; • mixed silicon and tin oxynitrides, of typical formula Si a SnbO y N z with a>0, b>0, a+b<2, 0<y<4, 0<z<3, also called SiTON, and in particular SiSno,870i,2Ni,72; as well as oxynitride-carbides of typical formula SiaSnbCcOyNz with a>0, b>0, a+b<2, 0<c<10, 0<y<24, 0<z<17; • nitrides of the type Si x N y , in particular with x=3 and y=4; Sn x N y , in particular with x=3 and y=4, Zn x N y , in particular with x=3 and y=2; Li3- X M X N with 0<x<0.5 for M=Co, 0<x<0.6 for M=Ni, 0<x<0.3 for M=Cu; Si3- X M X N4 with M=Co or Fe and 0<x<3. • the oxides SnC>2, SnO, Li2SnO3, SnSiCh, Li x SiO y with x>=0 and 2>y>0, Li4Ti50i2, TiNb2O7, CO3O4, SnBo,ePo,402,9 and TiO2, • Si, Sn, SiC>2, SnC>2, SiN, SnN and their mixtures, • TiNb2O7 composite oxides comprising between 0% and 10% by mass of carbon, preferably the carbon being chosen from graphene and carbon nanotubes. or in the group (E) formed by: alloys based on Si, Ge, Sn, Sb, Bi or P and alloys of these different compounds, MXenes. MXenes constitute a class of 2D materials of stoichiometry of the type M n +iX n T x with M a transition metal, preferably selected from Sc, Ti, V, Cr, Y, Zr, Nb, Mo, Hf, Ta, W and X is selected from C and/or N and T a surface termination selected from F, Cl, I, Br, O, S, Se, Te, OH, NH 2 , 1 < n < 4 conversion anode materials such as o oxides of the type G2TisO7, G4TisOi2, GTi2(PÛ4)3, G being Na or K o oxides, sulfides, selenides, phosphide of the following elements or their alloys: Si, Ge, Sn, Sb, Bi.
  12. 12. Porous electrode capable of being obtained by the method according to any one of claims 1 to 11.
  13. 13. Method for manufacturing a device for storing or producing electrical energy, implementing the method for manufacturing a porous electrode according to one of claims 1 to 11, or implementing a porous electrode according to claim 12.
  14. 14. Method according to claim 13, characterized in that said device for storing or producing electrical energy is selected from the group formed by: capacitors, supercapacitors, hybrid supercapacitors such as lithium ion hybrid supercapacitors, sodium ion hybrid supercapacitors, potassium ion hybrid supercapacitors, cells photovoltaic cells, photoelectrochemical cells and batteries such as lithium ion batteries, sodium ion batteries, potassium ion batteries.
  15. 15. The method of claim 14, wherein said device is a lithium ion battery and the method for manufacturing a porous electrode according to claim 10 is carried out to manufacture a cathode with the active electrode material P selected from group (A) or the method of claim 11 is carried out to manufacture an anode with the active electrode material P selected from group (D).
  16. 16. The method of claim 14, wherein said device is a sodium ion battery and the method for manufacturing a porous electrode according to claim 10 is carried out to manufacture a cathode with the active electrode material P selected from group (B) or the method of claim 11 is carried out to manufacture an anode with the active electrode material P selected from group (E).
  17. 17. The method of claim 14, wherein said device is a potassium ion battery and the method for manufacturing a porous electrode according to claim 10 is carried out to manufacture a cathode with the active electrode material P selected from group (C) or the method of claim 11 is carried out to manufacture an anode with the active electrode material P selected from group (E).
  18. 18. Method according to any one of claims 13 to 17, in which said device is a lithium, sodium or potassium ion battery and said porous electrode is impregnated with an electrolyte, preferably with a phase carrying lithium ions, sodium ions, potassium ions selected from the group formed by: - an electrolyte composed of at least one aprotic solvent and at least one lithium, sodium or potassium salt; - an electrolyte composed of at least one ionic liquid and at least one lithium, sodium or potassium salt; - a mixture of at least one aprotic solvent and at least one ionic liquid and at least one lithium, sodium or potassium salt; - an ionic liquid polymer; - a polymer made ionically conductive by the addition of at least one lithium, sodium or potassium salt; and - a polymer made ionically conductive by the addition of a liquid electrolyte, either in the polymer phase, either in the porous structure, or by an ionically conductive polymer preferably selected from polyethylene oxide (PEO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), poly(propylene carbonate) (PPC), poly(ethylene carbonate) (PEC), poly(vinyl carbonate) (PVC), polyvinylidene fluoride (PVDF), polypropylene glycol (PPG), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polydimethylsiloxane (PDMS), poly(E-caprolactone) (PCL) and poly(tri methylene carbonate) (PTMC).
  19. 19. Device for storing or producing electrical energy capable of being obtained by the method according to any one of claims 13 to 18.
  20. 20. Device for storing or producing electrical energy according to claim 19, characterized in that it is a capacitor, a supercapacitor, a hybrid supercapacitor such as a lithium ion hybrid supercapacitor, a sodium ion hybrid supercapacitor, a potassium ion hybrid supercapacitor, a photovoltaic cell, a photoelectrochemical cell, or a battery such as a lithium ion battery, a sodium ion battery or a potassium ion battery.

Description

DESCRIPTION Title: METHOD FOR MANUFACTURING A POROUS ELECTRODE, AND BATTERY CONTAINING SUCH AN ELECTRODE Technical field of the invention The invention relates to energy storage or production devices. It relates more specifically to electrodes that can be used in energy storage or production devices such as capacitors, photovoltaic cells or ion insertion batteries, in particular lithium ion, sodium ion or potassium ion batteries. The invention applies to negative electrodes and positive electrodes. It relates to porous electrodes that can be impregnated with an ionic conductive phase such as a solid electrolyte without a liquid phase or a liquid electrolyte. The invention also relates to a method for preparing such a porous electrode which uses aggregates or agglomerates of nanoparticles of an electrode material and at least one precursor of an electronically conductive oxide material, and the electrodes thus obtained. The invention also relates to a method for manufacturing an energy storage or production device, in particular a method for manufacturing a lithium ion battery comprising at least one of these electrodes, and the batteries thus obtained. State of the art Lithium-ion batteries have the best energy density among the various electrochemical storage technologies available on the market. There are different electrode architectures and chemical compositions for producing these batteries. The manufacturing processes for lithium-ion batteries are presented in numerous articles and patents; an overview is given in the book "Advances in Lithium-Ion Batteries" (ed. W. van Schalkwijk and B. Scrosati), published in 2002 (Kluever Academic / Plenum Publishers). There is a growing need for very small rechargeable batteries, capable of being integrated on electronic cards; these electronic circuits can be used in many fields, for example in cards to secure transactions, in electronic labels, in implantable medical devices, in various micromechanical systems. There is also a growing need for high-capacity rechargeable batteries, particularly to power transport devices (electric bicycles, scooters, motorcycles electric vehicles, electric cars, electric utility vehicles) and for the storage of electrical energy, for example to store electricity produced by intermittent electricity generators (wind turbines, photovoltaic panels) or to stabilize an electricity network subject to highly fluctuating supply and demand. There is also a growing need for intermediate-sized rechargeable batteries for various stand-alone and portable devices (e.g. mobile phones, laptops, power tools, intermittent-use kitchen appliances). In all these applications, the ability to quickly recharge the battery is a highly valued feature. Similarly, these batteries must not present a risk of thermal runaway. And finally, it is desirable that they can operate over a wide temperature range. According to the state of the art, the electrodes of lithium ion batteries can be manufactured using coating techniques, in particular by coating. These processes make it possible to deposit on the surface of a substrate, an ink consisting of particles of active materials in the form of powder; the particles constituting this powder have an average particle size which is typically between 5 pm and 15 pm in diameter. These deposition techniques, particularly by coating, make it possible to produce layers with a thickness of between approximately 20 pm and approximately 400 pm. The power and energy of the battery can be modulated by adapting the thickness and porosity of the layers, the size of the active particles that constitute them and by the presence of various constituents within the layer such as binders or electronic conductive materials. To produce microbatteries, it is desired to have a lower thickness for each layer constituting the microbattery. In addition to the issues related to the formulation of inks to obtain a high-performance electrode at low manufacturing cost, it should be kept in mind that the ratio between the energy density and the power density of the electrodes can be adjusted according to the particle size of active materials, and indirectly by the specific surface area of the electrode layers and their thickness. The article by J. Newman ("Optimization of Porosity and Thickness of a Battery Electrode by Means of A Reaction-Zone Model", J. Electrochem. Soc., 142 (1), p. 97-101 (1995)) demonstrates the respective effects of the electrode thicknesses and their porosity on their discharge regime (power) and energy density. Binder-free mesoporous electrode layers for lithium-ion batteries can be deposited by electrophoresis; this is known from WO 2019/215 407 (l-TEN). They can be impregnated with a liquid electrolyte, but their electrical resistivity remains quite high. To increase the low electronic conductivity of electrodes, especially when these electrodes are of high thickness or made from electrode active materials with poor ele