METHOD FOR MANUFACTURED A POROUS ELECTRODE, AND A BATTERY CONTAINING SUCH AN ELECTRODE

Abstract

The present invention relates to a porous electrode usable in electrical energy storage or production devices, such as a lithium-ion battery. This porous electrode is a porous layer comprising at least one active electrode material P and an electronically conductive oxide material.

Claims

1. Claims 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, 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 D50 of between 2 nm and 400 nm, preferably between 2 nm and 100 nm, and more preferably between 2 nm and 60 nm, are provided, said aggregates or agglomerates having an average diameter D50 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, so that said dried layer comprises said

2.

3. 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) can be carried out during the same thermal treatment. A method of manufacturing a porous electrode according to claim 1, characterized in that step (b) is carried out by bringing the colloidal suspension or paste supplied in step (a) comprising aggregates or agglomerates of primary nanoparticles, of at least one active electrode material P into contact 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. 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), po- vinylidene 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. 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 being, preferably, 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. Method of 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 (SnO2), zinc oxide doped with aluminum (ZnO:Al, preferably having a Zn:Al molar ratio of between 1:0.015 and 1:0.05), indium oxide (In2O3), gallium oxide (Ga2O3), molybdenum oxide (MoO3), molybdenum and strontium oxide (SrMoO3), a mixture of two of these oxides such as oxide indium-tin corresponding to a mixture of indium oxide (In2O3) and tin oxide (SnO2), 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 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) 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 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) 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 caesium (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. 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 m2 / g and 500 m2 / g and / or a thickness of between 2 μm and 400 pm, preferably between 2 pm and 300 pm, more preferably between 3 pm and 200 pm.

7. 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 of said layer, to form a porous plate.

8. A method of manufacturing a porous electrode according to any one of claims 1 to 7, 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 6, or of said porous plate according to claim 7, it being understood that this heat treatment and steps (e) and / or (f) can be carried out during the same heat treatment.

9. A method of manufacturing a porous electrode according to any one of claims 1 to 8, wherein said electrode active material P is selected from the group consisting of: - the oxides LiMn2O4, Lii+xMn2 XO4 with 0 < x < 0.15, LiCoO2, LiNiO2, LiMn2j5Nio>504, LiMn|3Ni03xXxO4 where 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 XMXO4 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 LiNio.sCoo.15 Al0.05O2LiAlxMn2.xO4with0< x < 0.15, LiNii / xCoi / yMni / zO2 with x+y+z =10; - LixMy02 where 0.6 <y<0.85; 0<x+y<2; et M est choisi parmi Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Sn, and Sb ou un mélange de ces éléments ; Lii.2oNbo.2oMn0.6o02 ; - Lii+xNbyMezApO2 where Me is at least one transition metal chosen 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<l; 0<y<0.5; 0.25<z<l; avec A Me et A Nb, et 0<p<0.2 ; - LixNby_aNaMz_bPbO2_cFc où 1.2<x<1.75; 0<y<0.55; 0.1<z<l; 0<a<0.5; 0<b<l; 0<c<0.8; et où M, N, et P sont chacun au moins un des éléments choisi dans le groupe constitué par Ti, Ta, V, Cr, Mn, Fe, Co, Ni, Cu,. Zn, Al, Zr, Y, Mo, Ru, Rh, Ce and Sb; ■ Lit25Nb0.25Mn0.50O2; Lit3Nb0.3Mn0.40O2; Lit3Nb0.3Fe0.40O2; Li1.3Nbo.43Ni 0.27O2; Lit3Nb0.43Co0.27O2; Lit4Nbo.2Mno.53O2 ; - LixNi0.2Mn0.6Oy where 0.00 <x<1.52; 1.07<y<2.4 ; Lit2Nio.2Mno.6O2; - LiNixCoyMni_x_yO2 where 0 < x and y < 0.5; LiNixCezCoyMni x yO2 where 0 < x and y < 0.5 and 0 < z; - the phosphates LiFePO4, LiMnPO4, LiCoPO4, LiNiPO4, Li3V2(PO4)3j Li 2MPO4F with M = Fe, Co, Ni or a mixture of these different elements, LiMPO4F with M = V, Fe, T or a mixture of these different elements; the phosphates of formula LiMM'PO4, with M and M' (M M') selected from Fe, Mn, Ni, Co, V such as LiFexCotxPO4et where 0 < x < 1; - Fe0.9Co0.1OF; FeF3; LiMSO4F with M = Fe, Co, Ni, Mn, Zn, Mg; - titanium oxysulfides (TiOySz with z=2-y and 0.3 <y<l), les oxy-sulfures de tungstène (WOySz avec 0.6<y<3 et 0.1<z<2), CuS, CuS2, Lix V2O5avec 0 < x < 2, LixV3O8avec 0 < x < 1,7, LixTiS2 avec 0 < x < 1, les oxysulfures de titane et de lithium LixTiOySzavec z=2-y, 0,3<y<l et 0 < x < 1, LixWOySzavec z=2-y, 0,3<y<l et 0 < x < 1, LixCuS avec 0 < x < 1, LixCuS2avec 0 < x < 1.

10. A method of manufacturing a porous electrode according to any one of claims 1 to 8, wherein said electrode active material P is selected from the group consisting of: • Li4Ti50i2, Li4Ti5 xMxOi2 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: • Nb2O5±ô, Nb12WO33±ô, Nb14W3O44±ô, Nb18W16O93±ô, Nb16W5O55± g with 0 < ô < 2, LiNbO3, • TiMhCF+g, LiwTiNb2O7 with w>0, Tii xM'xNb2 yM2yO7±ô or Li wTii_xM1xNb2_yM2yO7±ô in which M1 and M2 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, M1 and M2 being the same or different from each other, and in which 0 < w < 5 and 0 < x < let0 <y<2et0<ô< 0,3 ; • LaxTii 2xNb2+xO7 where 0 <x<0.5 ; • MxTii_2xNb2+xO7±ôin which M is an element whose oxidation state is +III, more particularly M is at least one of the elements chosen from the group consisting of Fe, Ga, Mo, Al, B, and where 0 <x<0.20 et -0.3<ô <0.3 ; Ga0.10Ti0.80Nb7.10O7 ; Fe o.ioTio.8oNb2.10O7 ; • MxTi2 2xNbio+x029±ôin which M is an element whose oxidation state is +III, more particularly M is at least one of the elements chosen from the group consisting of Fe, Ga, Mo, Al, B, and where 0 <x<0.40 et -0.3<ô <0.3 ; • Ti ijM^NboyM^CX or LiwTii_xM1xNb2_yM2yO7_zM3zdans which ones - M1 and M2 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, - M1 and M2 may be identical or different from each other, - M3 is at least one halogen, - and in which 0 <w<5et0<x<let0<y<2etz< 0,3 ; • TiNb2O7 ZM3Z or LiwTiNb2O7 ZM3Z in which M3 is at least one halogen, preferably chosen from F, Cl, Br, I or a mixture thereof, and 0 < z < 0.3 and 0 < w < 5; • Tii.xGexNb2.yM1yO7±z XCTii^GeJ'Jb^M'^+z Tii^Ce^b^yM'y O7±z ,LiwTii xCcxNb2 yM 1yO7±z in which - M1 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<5et0<x<let0<y<2etz< 0,3 ; • Ti, xGcxNb2yM'yO7ZM2Z, LiwTi, xGcxNb2yM'yO7ZM2Z, Til xCex Nb^yM'yO?^ M2Z, LCTii^CexNb^yM'yO^zM^ in which - M1 and M2 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, - M1 and M2 may be identical or different from each other, - and in which 0 <w<5et0<x<let0<y<2etz< 0,3 ; • TiO2; TiOxNy 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 the MOxNy type 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 xMxN with M is at least one element chosen from Cu, Ni, Co or a mixture of one or more of these elements and 0 < x < 1; • Li3.xMxN with M being cobalt (Co) and 0 < x < 0.5; Li3_xMx N with M being nickel (Ni) and 0 < x < 0.6; Li3 xMxN with M being copper (Cu) and 0 < x < 0.3; • lithium iron phosphate, with the typical formula LiFePO4; • mixed silicon and tin oxynitrides, with typical formula SiaSnbOyNz with a>0, b>0, a+b<2, 0 <y<4, 0<z<3, appelés aussi SiTON, et en particulier le SiSno,870i,2Ni,72 ; ainsi que les oxynitrures-carbures de formule typique SiaSnbCcOyNz avec a> 0, b>0, a+b<2, 0 <c<10, 0<y<24, 0<z<17; • nitrides of type SixNy, in particular with x=3 and y=4; Snx Ny, in particular with x=3 and y=4, ZnxNy, in particular with x=3 and y=2; Li3 xMxN with 0 <x<0,5 pour M=Co, 0<x<0,6 pour M=Ni, 0<x<0,3 pour M=Cu; Si3 xMxN4 avec M=Co ou Fe et 0<x<3. • the oxides SnO2, SnO, Li2SnO3, SnSiO3, LixSiOy with x>=0 and 2>y>0, Li4Ti50i2, TiNb2O7, Co3O4, SnB0.6Po.402.9 and TiO2, • Si, Sn, SiO2, SnO2, 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.

11. Porous electrode obtainable by the method according to any one of claims 1 to 10.

12. 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 10, or implementing a porous electrode according to claim 11.

13. Method according to claim 12, 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, photovoltaic cells, photoelectrochemical cells and batteries such as lithium ion batteries, sodium ion batteries, potassium ion batteries.

14. The method of claim 13, wherein said device is a lithium ion battery.

15. Method according to any one of claims 12 to 13, wherein 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 or in the porous structure, 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(trimethylene carbonate) (PTMC).

16. Device for storing or producing electrical energy capable of being obtained by the method according to any one of claims 12 to 15.

17. Device for storing or producing electrical energy according to claim 16, 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.