Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/362—Composites
  • H01M4/366—Composites as layered products
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/134—Electrodes based on metals, Si or alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
  • H01M10/0562—Solid materials
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/043—Processes of manufacture in general involving compressing or compaction
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
  • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/40—Alloys based on alkali metals
  • H01M4/405—Alloys based on lithium
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/624—Electric conductive fillers
  • H01M4/625—Carbon or graphite
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/64—Carriers or collectors
  • H01M4/66—Selection of materials
  • H01M4/661—Metal or alloys, e.g. alloy coatings
  • H01M4/662—Alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/64—Carriers or collectors
  • H01M4/66—Selection of materials
  • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/64—Carriers or collectors
  • H01M4/70—Carriers or collectors characterised by shape or form
  • H01M4/72—Grids
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/021—Physical characteristics, e.g. porosity, surface area
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/027—Negative electrodes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present application relates to electrodes comprising a film of electrode material having at least one modified surface, to their manufacturing methods and to the electrochemical cells comprising them.
• the liquid electrolytes used in lithium-ion batteries are flammable and slowly degrade to form a passivation layer on the surface of the lithium film or solid electrolyte interface (SEI for "solid electrolyte interface” or “solid electrolyte interphase” in English) irreversibly consuming lithium, which decreases the coulombic efficiency of the battery.
• SEI solid electrolyte interface
• solid electrolyte interphase solid electrolyte interphase
• a simple and more industrially transposable method for the protection of the surface of lithium is to cover its surface with a polymer or a polymer/lithium salt mixture by carrying out a coating by spraying, by immersion, using a centrifuge or again using the so-called doctor blade method (N. Delaporte, et al., Front. Mater., 2019, 6, 267).
• the chosen polymer must then be stable facing lithium and ionic conductor at low temperature.
• the polymer layer deposited on the lithium surface should be comparable to the solid polymer electrolytes (SPE) generally reported in the literature, which have a low glass transition (T v ). in order to remain rubbery at room temperature and maintain lithium conductivity similar to that of a liquid electrolyte.
• SPE solid polymer electrolytes
• T v glass transition
• the polymer must have good flexibility and must be characterized by a high Young's modulus.
• polymers used in this type of protective layer include polyacrylic acid (PAA) (N.-W. Li, et al., Angew. Chem. Int. Ed., 2018, 57, 1505-1509), poly(ethylene glycol) dimethacrylate (Y. M. Lee, et al., J. Power Sources, 2003, 119-121, 964-972), the PEDOT-co-PEG copolymer (G. Ma, et al., J. Mater. Chem. A, 2014, 2, 19355-19359 and I. S. Kang, et al., J. Electrochem.
• PAA polyacrylic acid
• PEDOT-co-PEG copolymer G. Ma, et al., J. Mater. Chem. A, 2014, 2, 19355-19359 and I. S. Kang, et al., J. Electrochem.
• inorganic fillers eg Al2O3, TiO2, BaTiOs
• organic-inorganic hybrid composite electrolyte e.g Al2O3, TiO2, BaTiOs
• SBR styrene butadiene rubber
• CU3N is converted into highly conductive lithium U3N.
• Li4TisOi2/Li (LTO/Li) cells were assembled with a liquid electrolyte and better electrochemical performances were obtained by using lithium protected by a mixture of CU3N and SBR.
• a 20 ⁇ m protective layer composed of ALCh particles (1.7 ⁇ m average diameter) and polyvinylidene-hexafluoropropylene fluoride (PVDF-HFP) deposited on the surface of the lithium has been proposed to improve the lifetime lithium-oxygen batteries (DJ Lee, et al., Electrochem. Commun., 2014, 40, 45-48).
• CO3O4- Super P/Li batteries with this protective layer and a liquid electrolyte.
• the effect of similarly modified lithium has also been studied by Gao and co-workers (HK Jing et al., J. Mater. Chem. A, 2015, 3, 12213-12219), although the focus is been on improving lithium-sulfur batteries.
• a 25 ⁇ m porous layer of polyimide with AhOs as filler (particle size of about 10 nm) in order to limit the growth of lithium has also been proposed (see Z. Peng et al., J. Mater. Chem. A, 2016, 4, 2427-2432).
• This method includes the formation of a film called "skin layer” by bringing lithium into contact with an additive present in the liquid electrolyte (such as fluoroethylene carbonate (FEC), vinylene carbonate (VC) or diisocyanate of hexamethylene (HDI)).
• FEC fluoroethylene carbonate
• VC vinylene carbonate
• HDI diisocyanate of hexamethylene
• the protective layers described in the previous three paragraphs are porous and suitable for use with a liquid electrolyte, which can penetrate them. This type of layer is therefore not suitable for use with a solid electrolyte which must be able to be in intimate contact with the surface of the electrode (or of its protective layer) and allow the conduction of the ions of the electrolyte. to the active electrode material.
• the present technology relates to an electrode comprising an electrode film modified by a first thin layer and a second thin layer, in which: the electrode film comprises a first and a second surface, the first surface being optionally pretreated; the first thin layer comprises an inorganic compound in a solvating polymer and optionally an ionic salt and/or a plasticizer, the first thin layer being disposed on the first surface of the electrode film and having an average thickness of about 15 ⁇ m or less , the "inorganic compound: solvating polymer" mass ratio in the first thin layer is in the range of about 1:20 to about 20:1; and the second thin layer comprises a solvating polymer, an ionic salt and optionally a plasticizer, the second thin layer being disposed on the first thin layer and having an average thickness of about 15 ⁇ m or less; wherein the solvating polymer of the first layer is the same as or different from the solvating polymer of the second layer.
• the solvating polymer of the first thin layer is crosslinked, and/or the solvating polymer of the second thin layer is crosslinked. In another embodiment, the solvating polymer of the first thin layer is uncrosslinked, and/or the solvating polymer of the second thin layer is uncrosslinked.
• the electrode film is a current collector, for example comprising a solid electron-conducting support, such as a sheet or a metal grid (such as copper, nickel, etc.), a film carbon or comprising carbon (such as carbon paper, self-supporting graphene, etc.), or other solid support (polymer, glass, etc.) comprising an electron-conducting layer (such as a current collector print).
• a solid electron-conducting support such as a sheet or a metal grid (such as copper, nickel, etc.), a film carbon or comprising carbon (such as carbon paper, self-supporting graphene, etc.), or other solid support (polymer, glass, etc.) comprising an electron-conducting layer (such as a current collector print).
• the electrode film comprises a metallic film, for example comprising lithium (for example comprising less than 1000 ppm (or less than 0.1% by mass) of impurities), or an alloy comprising lithium.
• the metal film comprises an alloy of lithium and an element selected from alkali metals other than lithium (such as Na, K, Rb, and Cs), alkaline earth metals (such as Mg, Ca , Sr, and Ba), rare earth metals (such as Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), zirconium, copper, silver, bismuth, cobalt, manganese, zinc, aluminum, silicon, tin, antimony, cadmium, mercury, lead, molybdenum, iron, boron, indium, thallium, nickel and germanium (eg Zr, Cu, Ag, Bi, Co, Zn, Al, Si, Sn , Sb, Cd
• the electrode film further comprises a pretreatment layer on the first surface, the latter being in contact with the first thin layer.
• the pretreatment layer comprises a compound chosen from a silane, a phosphonate, a borate, a salt or an organic compound, a carbon (such as graphite, graphene, etc.), a salt or an inorganic compound (such as LiF, LisN, U3P, UNO3, U3PO4, etc.), or a thin layer of an element other than a metal of the electrode film or forming an alloy with it on the surface (such as an element defined above with reference to alloys), said pretreatment layer having an average thickness of less than 5 ⁇ m, or less than 3 ⁇ m, or less than 1 ⁇ m, or less than 500 nm, or less than 200 nm , or less than 100 nm, or even less than 50 nm.
• the first surface of the electrode film is pretreated by stamping.
• the inorganic compound is in the form of particles (eg, spherical, rods, needles, etc.).
• the average particle size can be less than 1 ⁇ m, or less than 500nm, or less than 300nm, or less than 200nm, or between 1nm and 500nm, or between 10nm and 500nm, or even between 50nm and 500nm.
• 100nm and 500nm or between 1 nm and 300nm, or between 10nm and 300nm, or between 50nm and 300nm, or between 100nm and 300nm, or between 1 nm and 200nm, or between 10nm and 200nm, or even between 50nm and 200nm, or between 100nm and 200nm, or between 1nm and 100nm, or between 10nm and 100nm, or even between 25nm and 100nm, or between 50nm and 100nm.
• the inorganic compound comprises a ceramic.
• the inorganic compound is selected from Al2O3, Mg2B20s, Na2O-2B2O3, xMgO yB2O3-zH2O, TiO2, ZrO2, ZnO, Ti20s, SiO2, Cr20s, CeO2, B2O3, B2O, SrBi4Ti40i5, LLTO, LLZO, LAGP , l_ATP, Fe2O3, BaTiOs, Y-UAIO2, metal/carbon mixture (such as Sn+C, Zn+C, Ni2P+C), molecular sieves and zeolites (e.g. aluminosilicate, mesoporous silica), ceramics sulphides (like U7P3S11), glass ceramics (such as LIPON, etc.), and other ceramics, as well as combinations thereof.
• metal/carbon mixture such as Sn+C, Zn+C, Ni2P+C
• the particles of the inorganic compound further comprise organic groups grafted to their surface covalently, for example, said groups being chosen from crosslinkable groups (such as organic groups comprising acrylate, methacrylate, vinyl , glycidyl, mercapto, etc.), aryl groups, alkylene oxide or poly(alkylene oxide) groups, and other organic groups, or one of their combinations, optionally comprising a spacer group between the organic groups and the particles of the inorganic compound.
• the grafted organic groups comprise poly(alkylene oxide) chains attached to the particles of the inorganic compound by a spacer group.
• the spacer group is chosen from silane or halogenated silane, phosphonate, carboxylate, catechol, (meth)acrylate or poly(meth)acrylate, alkylene or polyalkylene groups, and combinations thereof.
• the particles of the inorganic compound have a small specific surface (for example, less than 80 m 2 /g, or less than 40 m 2 /g).
• the "inorganic compound: solvating polymer" mass ratio in the first thin layer is in the range of about 2:5 to about 4:1, or about 2:5 to about 2 :1, or about 1:2 to about 2:1, or about 4:5 to about 2:1, or about 1:1 to about 2:1, or about 4:5 to about 3:2.
• the particles of the inorganic compound have a large specific surface (for example, 80 m 2 /g and more, or 120 m 2 /g and more).
• the "inorganic compound: solvating polymer" mass ratio in the first thin layer is in the range of about 1:20 to about 2:1, or about 2:5 to about 2 : 1 , from about 2:5 to about 6:5, or from about 1:20 to about 6:5, or from about 2:5 to about 1:1 , or from about 1:20 to about 1:1, or about 2:5 to about 4:5, or about 1:20 to about 4:5.
• the average thickness of the first thin layer is between about 0.5 ⁇ m and about 15 ⁇ m, or between about 1 ⁇ m and about 15 ⁇ m, or between about 1 ⁇ m and about 12 ⁇ m, or between about 0, 5pm and approximately 10pm, or between approximately 1 pm and approximately 10pm, or between approximately 2pm and approximately 8pm, or between around 2pm and around 7pm, or between 2pm and around 5pm.
• the average thickness of the second thin layer is between about 50 nm and about 15 ⁇ m, or between about 0.1 ⁇ m and about 15 ⁇ m, or between about 0.5 ⁇ m and about 15 ⁇ m, or between about 1 pm and approximately 3 pm, or between approximately 1 pm and approximately 12 pm, or between approximately 0.5 pm and approximately 10 pm, or between approximately 1 pm and approximately 10 pm, or between approximately 2 pm and approximately 8 pm, or between approximately 2 pm and approximately 7 pm, or between 2 pm and approximately 5 pm, or alternatively between 50 nm and approximately 5 pm, or between approximately 0.1 pm and approximately 2 pm.
• the total average thickness of the first and second thin layers being in the range of about 1 ⁇ m to about 30 ⁇ m, or about 1 ⁇ m to about 25 ⁇ m, or about 5pm to about 10pm, or from about 1pm to about 8pm, or from about 1pm to about 4pm, or from about 2pm to about 12pm, or from about 3pm to about 3pm, or from about 3pm to about 12pm, or from about 4pm to about 3pm, or from about 4pm to about 12pm.
• the solvating polymer is independently chosen from linear or branched polyether polymers (for example, PEO, PPO, or EO/PO copolymer), poly(dimethylsiloxanes), poly(alkylene carbonates), poly(alkylenesulfones), poly(alkylenesulfonamides), polyurethanes, poly(vinyl alcohol), polyacrylonitriles, polymethyl methacrylates, and copolymers thereof, optionally comprising crosslinked units originating from crosslinkable functions (such as acrylate functions, methacrylates, vinyls, glycidyls, mercapto, etc.).
• crosslinkable functions such as acrylate functions, methacrylates, vinyls, glycidyls, mercapto, etc.
• the first and second thin layers further comprises a plasticizer, for example, the first thin layer and the second thin layer further comprise a plasticizer.
• the plasticizer is chosen from liquids of the glycol diether type (such as tetraethylene glycol dimethyl ether (TEGDME)), carbonate esters (such as propylene carbonate, ethylene carbonate, fluoroethylene carbonate), lactones (such as ⁇ -butyrolactone), adiponitrile, ionic liquids and the like.
• TEGDME tetraethylene glycol dimethyl ether
• carbonate esters such as propylene carbonate, ethylene carbonate, fluoroethylene carbonate
• lactones such as ⁇ -butyrolactone
• adiponitrile such as ⁇ -butyrolactone
• At least one of the first and second thin layers further comprises a lithium salt.
• the first thin layer and the second thin layer further comprise a lithium salt.
• the lithium salt is chosen from lithium hexafluorophosphate (LiPFe), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyano-imidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (UBF4), lithium bis(oxalato)borate (LiBOB), lithium nitrate (UNO3), lithium chloride (LiCI), lithium bromide lithium (LiBr), lithium fluoride (LiPFe), lithium bis(triflu
• the electrode further comprises a current collector in contact with the second surface of the electrode film.
• the present technology relates to an electrochemical cell comprising a negative electrode and a positive electrode, in which at least one of the negative electrode and of the positive electrode is as defined above.
• the negative electrode is as defined above and the positive electrode comprises a film of positive electrode material comprising an electrochemically active positive electrode material, optionally a binder, and optionally a conductive material electronic.
• the positive electrode electrochemically active material is chosen from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides.
• the positive electrode electrochemically active material is in the form of optionally coated particles (e.g., polymer, ceramic, carbon, or a combination of two or more thereof).
• the film of positive electrode material comprises a first and a second surface, the first surface facing the negative electrode and bearing a third thin layer comprising a solvating polymer and an ionic salt, the third thin layer having an average thickness of about 50 ⁇ m or less, about 40 ⁇ m or less, or about 30 ⁇ m or less, or about 15 ⁇ m or less, or between about 0.5 ⁇ m and about 50pm, or between approximately 5pm and approximately 50pm, or between approximately 5pm and approximately 40pm, or between approximately 0.5pm and approximately 15pm, or between approximately 1 pm and approximately 15pm, or between approximately 1 pm and approximately 12pm, or between approximately 0 5 p.m. and about 10 p.m., or between about 1 p.m.
• the solvating polymer is as defined above.
• the salt is a lithium salt, for example as defined above.
• the third thin layer also comprises a plasticizer, for example as defined above.
• the electrochemical cell excludes the presence of a layer of solid polymer electrolyte.
• the electrochemical cell further comprises a layer of solid electrolyte comprising a polymer and a lithium salt.
• the polymer of the electrolyte is chosen from linear or branched polyether polymers (for example, PEO, PPO, or EO/PO copolymer), and optionally comprising crosslinkable units), poly(dimethylsiloxanes), poly(alkylene carbonate), poly(alkylenesulfones), poly(alkylenesulfonamides), polyurethanes, poly(vinyl alcohol), polyacrylonitriles, polymethyl methacrylates, and copolymers thereof, the solvating polymer optionally being crosslinked.
• the lithium salt of the solid electrolyte layer is chosen from lithium hexafluorophosphate (LiPFe), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyano-imidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (UBF4), lithium bis(oxalato)borate (LiBOB), lithium nitrate (UNO3), lithium chloride (LiCI), lithium bromide (LiBr), fluoride (LiF), lithium perchlorate (UCIO4), lithium hexafluoroarsenate (LiAsFe), lithium trifluorome
• the solid electrolyte further comprises a ceramic.
• the present technology relates to an electrochemical cell comprising a negative electrode and a positive electrode, in which:
• the negative electrode comprises a negative electrode film comprising a first and a second surface, the first surface being optionally pretreated, wherein said negative electrode comprises a first thin layer comprising an inorganic compound in a solvating polymer and optionally a ionic salt and/or a plasticizer, the first thin layer being provided on the first surface of the negative electrode film and having an average thickness of about 15 ⁇ m or less, the "inorganic compound: solvating polymer" mass ratio in the first thin film ranges from about 1:20 to about 20:1; And
• the negative electrode comprises a second thin layer comprising a solvating polymer, an ionic salt and optionally a plasticizer, the second thin layer being disposed on the first thin layer and having an average thickness of about 15 ⁇ m or less, in wherein the solvating polymer of the first layer is the same as or different from the solvating polymer of the second layer; and or the positive electrode comprises a film of positive electrode material comprising an electrochemically active positive electrode material, optionally a binder, and optionally an electronically conductive material, the film of positive electrode material comprising a first and a second surface, the first surface facing the negative electrode and carrying a third thin layer comprising a solvating polymer, an ionic salt, the third thin layer having an average thickness of about 50 ⁇ m or less; wherein the electrochemical cell excludes the presence of an additional solid polymer electrolyte layer.
• the electrochemical cell comprises the second thin layer, the solvating polymer of the second thin layer being crosslinked or non-crosslinked.
• the electrochemical cell comprises the third thin layer, the solvating polymer of the third thin layer being crosslinked or non-crosslinked.
• the electrochemical cell comprises the second thin layer and the third thin layer.
• the solvating polymer of the first thin layer is crosslinked. In an alternative embodiment, the solvating polymer of the first thin layer is non-crosslinked.
• the negative electrode film is a current collector, for example comprising a solid electron-conducting support, such as a sheet or a metallic grid (such as copper, nickel, etc.), a carbon film or comprising carbon (such as carbon paper, self-supporting graphene, etc.), or other solid support (polymer, glass, etc.) comprising an electron-conductive layer (such as a current collector print) .
• a solid electron-conducting support such as a sheet or a metallic grid (such as copper, nickel, etc.), a carbon film or comprising carbon (such as carbon paper, self-supporting graphene, etc.), or other solid support (polymer, glass, etc.) comprising an electron-conductive layer (such as a current collector print) .
• the negative electrode film comprises a metallic film, for example comprising lithium or an alloy comprising lithium.
• the metallic film comprises lithium comprising less than 1000 ppm (or less than 0.1% by mass) of impurities.
• the metallic film comprises an alloy of lithium and of an element chosen from alkali metals other than lithium (such as Na, K, Rb, and Cs), alkaline-earth metals (such as Mg, Ca, Sr, and Ba), rare earth metals (such as Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), zirconium, copper, silver, bismuth, cobalt, manganese, zinc, aluminum, silicon, tin, antimony, cadmium, mercury, lead, molybdenum, iron, boron, indium, thallium , nickel, and germanium (e.g., Zr, Cu, Ag, Bi, Co, Zr, Cu, Ag, Bi, Co
• the negative electrode film further comprises a pretreatment layer on the first surface, the latter being in contact with the first thin layer.
• the pretreatment layer comprises a compound chosen from a silane, a phosphonate, a borate, a salt or an organic compound, a carbon (such as graphite, graphene, etc.), a salt or inorganic compound (such as LiF, U3N, U3P, UNO3, U3PO4, etc.), or a thin layer of an element different from the metal of the metallic film or forming an alloy with it on the surface (such as an element defined above ), said pretreatment layer having an average thickness of less than 5 ⁇ m, or less than 3 ⁇ m, or less than 1 ⁇ m, or less than 500 nm, or less than 200 nm, or less than 100 nm, or even less than 50 nm.
• the first surface of the negative electrode film is pretreated by stamping.
• the inorganic compound is in the form of particles (e.g., spherical, rods, needles, etc.), for example, with an average size of less than 1 ⁇ m, less than 500 nm, or less than 300nm, or less than 200nm, or between 1nm and 500nm, or between 10nm and 500nm, or between 50nm and 500nm, or between 100nm and 500nm, or between 1nm and 300nm, or between 10nm and 300nm, or even between 50nm and 300nm, or between 100nm and 300nm, or between 1 nm and 200nm, or between 10nm and 200nm, or even between 50nm and 200nm, or between 100nm and 200nm, or between 1nm and 100nm, or between 10nm and 100nm, or even between 25nm and 100nm, or between 50nm and 100nm.
• particles e.g., spherical, rods, needles, etc
• the inorganic compound comprises a ceramic.
• the inorganic compound is chosen from Al2O3, Mg2B20s, Na2O-2B2O3, xMgO yB2O3-zH2O, TiO2, ZrO2, ZnO, Ti20s, SiO2, Cr20s, CeO2, B2O3, B2O, SrBi4Ti40i5, LLTO, LLZO, LAGP, LATP, Fe2O3, BaTiOs, Y-UAIO2, mixed metal/carbon (such as Sn+C, Zn+C, Ni2P+C), molecular sieves and zeolites (e.g. aluminosilicate, mesoporous silica), sulphide ceramics (such as U7P3S11), glass ceramics (such as LIPON, etc.), and other ceramics, as well as combinations thereof.
• zeolites e.g. aluminosilicate, mesoporous silic
• the particles of the inorganic compound further comprise organic groups grafted to their surface covalently, for example, said groups being chosen from crosslinkable groups (such as organic groups comprising acrylate, methacrylate, vinyl , glycidyl, mercapto, etc.), aryl groups, alkylene oxide or poly(alkylene oxide) groups, and other organic groups, or one of their combinations, optionally comprising a spacer group between the organic groups and the particles of the inorganic compound.
• the grafted organic groups comprise poly(alkylene oxide) chains attached to the particles of the inorganic compound by a spacer group.
• the spacer group can be chosen from silane or halogenated silane, phosphonate, carboxylate, catechol, (meth)acrylate or poly(meth)acrylate, alkylene or polyalkylene groups, and combinations thereof.
• the particles of the inorganic compound have a small specific surface (for example, less than 80 m 2 /g, or less than 40 m 2 /g).
• the "inorganic compound: solvating polymer" mass ratio in the first thin layer is in the range of about 2:5 to about 4:1, or about 2:5 to about 2 : 1 , or about 1:2 to about 2:1 , or about 4:5 to about 2:1 , or about 1:1 to about 2:1 , or about 4:5 to about 3:2.
• the particles of the inorganic compound have a large specific surface (for example, 80 m 2 /g and more, or 120 m 2 /g and more).
• the "inorganic compound:solvating polymer" mass ratio in the first thin layer is in the range of about 1:20 to about 2:1, or about 2:5 to about 2:1, about 2:5 to about 6:5, or about 1:20 to about 6:5, or about 2:5 to about 1:1, or about 1:20 to about 1:1, or about 2:5 to about 4:5, or about 1:20 to about 4:5.
• the average thickness of the first thin layer is between about 0.5 ⁇ m and about 15 ⁇ m, or between about 1 ⁇ m and about 15 ⁇ m, or between about 1 ⁇ m and about 12 ⁇ m, or between about 0.5 ⁇ m and about 10pm, or between about 1m and approximately 10pm, or between approximately 2pm and approximately 8pm, or between approximately 2pm and approximately 7pm, or between 2pm and approximately 5pm.
• the average thickness of the second thin layer is between about 50 nm and about 15 ⁇ m, or between about 0.1 ⁇ m and about 15 ⁇ m, between about 0.5 ⁇ m and about 15 ⁇ m, or between about 1 ⁇ m and approximately 3 pm, or between approximately 1 pm and approximately 12 pm, or between approximately 0.5 pm and approximately 10 pm, or between approximately 1 pm and approximately 10 pm, or between approximately 2 pm and approximately 8 pm, or between approximately 2 pm and approximately 7 pm, or between 2 p.m. and about 5 p.m., or alternatively between 50 nm and about 5 p.m., or between about 0.1 p.m. and about 2 p.m.
• the second thin layer is present and the total average thickness of the first and second thin layers is in the range of about 1 ⁇ m to about 30 ⁇ m, or about 1 ⁇ m to about 10 p.m., or from about 5 p.m. to about 10 p.m., or from about 1 p.m. to about 8 p.m., or from about 1 p.m. to about 4 p.m., or from about 2 p.m. to about 12 p.m., or from about 3 p.m. to about 3 p.m. , or from about 3pm to about 12pm, or from about 4pm to about 3pm, or from about 4pm to about 12pm.
• the average thickness of the third thin layer is about 40 ⁇ m or less, or about 30 ⁇ m or less, or about 15 ⁇ m or less, or is between about 0.5 ⁇ m and about 50pm, or between about 5pm and about 50pm, or between about 5pm and about 40pm, or between about 0.5pm and about 3pm, or between about 1pm and about 3pm, or between about 1pm and about 12pm, or between about 0.5pm and about 10pm, or between about 1pm and about 10pm, or between about 2pm and about 8pm, or between about 2pm and about 7pm, or between 2pm and about 5pm.
• the second thin layer and the third thin layer are present and the total average thickness of the first, second and third thin layers is in the range of about 3 ⁇ m to about 60 ⁇ m, or about 10pm to about 50pm, or about 3pm to about 30pm, or about 3pm to about 30pm, or about 3pm to about 25pm, or about 5pm to about 25pm, or about 5pm to about 8pm , or from about 8 p.m. to about 3 p.m., or from about 8 p.m. to about 12 p.m., or from about 5 p.m. to about 3 p.m., or from about 5 p.m. to about 12 p.m., or from about 5 p.m. 9pm to around 3pm.
• the solvating polymer is independently chosen from linear or branched polyether polymers (for example, PEO, PPO, or EO/PO copolymer), poly(dimethylsiloxanes), poly(alkylene carbonates), poly(alkylenesulfones), poly(alkylenesulfonamides), polyurethanes, poly(vinyl alcohol), polyacrylonitriles, polymethyl methacrylates, and their copolymers, optionally comprising crosslinked units originating from crosslinkable functions (such as acrylate, methacrylate , vinyls, glycidyls, mercapto, etc.).
• linear or branched polyether polymers for example, PEO, PPO, or EO/PO copolymer
• poly(alkylene carbonates) poly(alkylenesulfones), poly(alkylenesulfonamides)
• polyurethanes poly(vinyl alcohol), polyacrylonitrile
• the first and second thin layers further comprises a plasticizer, or the first thin layer and the second thin layer further comprise a plasticizer, and/or the third thin layer further comprises a plasticizer.
• the plasticizer is chosen from liquids of the glycol diether type (such as tetraethylene glycol dimethyl ether (TEGDME)), carbonate esters (such as propylene carbonate, ethylene carbonate, fluoroethylene carbonate), lactones (such as y-butyrolactone), adiponitrile, ionic liquids and the like.
• TEGDME tetraethylene glycol dimethyl ether
• carbonate esters such as propylene carbonate, ethylene carbonate, fluoroethylene carbonate
• lactones such as y-butyrolactone
• adiponitrile such as y-butyrolactone
• the first, second and third thin layers further comprises a lithium salt, or the first, second and third thin layers further comprise a lithium salt.
• the lithium salt is chosen from lithium hexafluorophosphate (LiPFe), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), 2-trifluoromethyl lithium -4,5-dicyano-imidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (UBF4), lithium bis(oxalato)borate (LiBOB), lithium nitrate (UNO3), lithium chloride (LiCI), lithium bromide (LiBr), lithium fluoride (LiF),
• LiPFe lithium hexa
• the negative electrode further comprises a current collector in contact with the second surface of the negative electrode film.
• the positive electrode further comprises a current collector in contact with the second surface of the film of positive electrode material.
• the positive electrode electrochemically active material is chosen from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides.
• the present technology relates to an electrochemical accumulator comprising at least one electrochemical cell as defined above.
• the electrochemical accumulator is a lithium battery or a lithium-ion battery.
• the present technology relates to the use of an electrochemical accumulator as defined above, in a mobile device, an electric or hybrid vehicle, or in the storage of renewable energy.
• the mobile device is chosen from mobile phones, cameras, tablets and laptop computers.
• Figure 1 shows (a) the X-ray diffractogram and (b) a scanning microscope image of the Ni 2 P powder (Nii 2 Ps phase) obtained according to Example 1(a).
• Figure 2 presents (a) thermogravimetric curves of Al2O3 (—) and ALOa-polymer (—) powders, and (b) a photograph of a lithium strip with a 1 ⁇ m thin layer of Polymer 1 + AhCh ceramic -polymer according to Example 1(b).
• Figure 3 presents the conductivity measurements between 20°C and 80°C on stainless steel of the polymer films A1 to A5 described in Example 2(a).
• Figure 4 schematically illustrates different cell configurations comprising a polymer + inorganic compound layer on the anode and (a) a polymer electrolyte; (b) a polymer layer on the cathode and a polymer electrolyte, (c) a second layer without inorganic compound on the polymer + inorganic compound layer and a polymer electrolyte; (d) a second layer without inorganic compound on the polymer + inorganic compound layer (without polymer electrolyte); (e) a polymer layer on the cathode (without polymer electrolyte); and (f) a second layer without inorganic compound on the polymer layer + inorganic compound, a polymer layer on the cathode (without polymer electrolyte).
• Figure 5 presents the results (a) of galvanostatic cycling obtained at 50°C and at C/6 (2 cycles at C/12 every 20 cycles at C/6) for LFP/polymer electrolyte/Li batteries assembled with the lithium without modification (reference) and lithiums having layers B1(i) to B3(i) according to Example 3(a); and (b) the representation of the capacity drop during cycling for the same batteries.
• Figure 6 presents the results (a) of galvanostatic cycling obtained at 50°C and at C/6 (2 cycles at C/12 every 20 cycles at C/6) for LFP/polymer electrolyte/Li batteries assembled with the lithium without modification (reference) and lithiums having layers B1 to B3 according to Example 3(b); and (b) the representation of the capacity drop during cycling for the same batteries.
• Figure 7 presents the results (a) of galvanostatic cycling obtained at 50°C and at C/6 (2 cycles at C/12 every 20 cycles at C/6) for LFP/polymer electrolyte/Li batteries assembled with the lithium without modification (reference) and lithiums having layers B1 to B3 according to Example 3(c) (with percentage solids of 17, 21 and 24%); and (b) the representation of the capacity drop during cycling for the same batteries.
• Figure 8 shows the data of (a) galvanostatic cycling and (b) coulombic efficiencies obtained at 50°C and in C/3 for LFP/polymer electrolyte/Li batteries assembled with lithium without modification (reference) and a lithium having a 4 ⁇ m layer of Polymer 1 with 130% ALCh-polymer (C1 stacks according to Example 3(d)).
• the diagram shows the assembly of C1 batteries.
• Figure 9 shows the data of (a) galvanostatic cycling and (b) coulombic efficiencies obtained at 50°C and in C/3 for LFP/polymer electrolyte/Li batteries assembled with lithium without modification (reference) and a lithium having a 4 ⁇ m layer of Polymer 1 with 130% ALOa-polymer and an LFP cathode having a 2 or 4 ⁇ m Polymer layer (stacks C2-a and C2-b according to Example 3(d)).
• the diagram shows the assembly of batteries C2-a and C2-b.
• Figure 10 shows the data of (a) galvanostatic cycling and (b) coulombic efficiencies obtained at 50°C and in C/3 for LFP/polymer electrolyte/Li batteries assembled with lithium without modification (reference) and a lithium having a 4 ⁇ m layer of Polymer 1 with 130% ALCh-polymer and a second 4 ⁇ m layer of Polymer 1 (C3 stack according to Example 3(d)).
• the diagram represents the assembly of the C3 pile.
• Figure 11 shows the data of (a) galvanostatic cycling and (b) coulombic efficiencies obtained at 50°C and in C/3 for LFP/polymer electrolyte/Li batteries assembled with lithium without modification (reference) and a lithium having a 4 ⁇ m layer of Polymer 1 with 130% ALCh-polymer and a second 9 or 12 ⁇ m layer of Polymer 1 without polymer electrolyte (cells C4-a and C4-b according to Example 3(d)).
• the diagram shows the assembly of batteries C4-a and C4-b.
• Figure 12 shows the data of (a) galvanostatic cycling and (b) coulombic efficiencies obtained at 50°C and in C/3 for LFP/polymer electrolyte/Li batteries assembled with lithium without modification (reference) and a lithium having a 4 ⁇ m layer of Polymer 1 with 130% ALOa-polymer and an LFP cathode having a 5, 8, or 11 ⁇ m polymer layer without polymer electrolyte (stacks C5-a, C5-b, and C- 5-c according to Example 3(d)).
• the diagram shows the assembly of batteries C5-a, C5-b, and C-5-c.
• Figure 13 shows the data of (a) galvanostatic cycling and (b) coulombic efficiencies obtained at 50°C and in C/3 for LFP/polymer electrolyte/Li batteries assembled with lithium without modification (reference) and a lithium having a 4 ⁇ m layer of Polymer 1 with 130% ALCh-polymer and a second layer of 3 or 4 ⁇ m of Polymer 1 as well as an LFP cathode having a 4 ⁇ m polymer layer, without polymer electrolyte (batteries C6-a and C6-b according to Example 3(d)).
• the diagram shows the assembly of batteries C6-a and C6-b.
• Figure 14 shows the galvanostatic cycling obtained at 50°C and at C/3 for LFP/polymer electrolyte/Li batteries assembled with lithium without modification (reference), then with a lithium having a 5 ⁇ m layer of polymer 1 with 30% Ni2P and 17% carbon according to Example 3(e).
• Figure 15 shows data for (a) cycling stability (discharge capacity), (b) average voltage and (c) coulombic efficiencies obtained during galvanostatic cycling at 50°C and C/3 for two LFP/electrolyte batteries polymer/Li assembled with lithium without modification (reference) and two C7 batteries as described in Example 4.
• Figure 16 shows the data of (a) cycling stability (discharge capacity), and (b) coulombic efficiencies obtained during galvanostatic cycling at 50°C and at C/3 for two LFP/polymer electrolyte/Li batteries assembled with lithium without modification (reference) and three C8 batteries as described in Example 4.
• Figure 17 shows the data of (a) discharge capacity, and (b) coulombic efficiencies obtained during cycling at 50°C at speeds ranging from C/6 to 1C for an LFP/polymer electrolyte/Li battery assembled with the lithium without modification (reference) and two C9 batteries as described in Example 4.
• Figure 18 shows the galvanostatic cycling obtained at 50°C in C/3 (a) and C/6 (b) for LFP/polymer electrolyte/Li batteries assembled with lithium without modification (reference), and with lithiums modified with (a) an inorganic molecule (PCh) and (b) a thin layer of metal (Zn) according to Example 5.
• Figure 19 shows photographs of lithium strips having received (a) treatment with PCI3 and (b) treatment with PCI3 followed by deposition of polymer 1 + Al2O3-polymer according to Example 5.
• alkyl refers to saturated hydrocarbon groups having 1 to 20 carbon atoms, including linear or branched alkyl groups.
• alkyls can include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, tert-butyl, sec-butyl, isobutyl groups and the like.
• an “alkylene” group designates an alkyl group located between two other groups. Examples of alkylene groups include methylene, ethylene, propylene, etc.
• the terms "Ci- Cn alkyl” and "Ci- Cn alkylene” refer to an alkyl or alkylene group having from 1 to "n" number of carbon atoms.
• the surface modification of an electrode film is modified by a stack of at least two thin layers, each about 15 ⁇ m or less in thickness.
• this electrode film may consist of a metal film, for example comprising an alkali metal (such as lithium) or an alloy mainly comprising an alkali metal (such as lithium).
• the electrode film is a current collector, for example comprising a solid electron-conducting support, such as a sheet or a metal grid (such as copper, nickel, etc.), a film of carbon or comprising carbon (such as carbon paper, self-supporting graphene, etc.), or other solid support (polymer, glass, etc.) comprising an electron-conducting layer (such as a current collector print).
• a solid electron-conducting support such as a sheet or a metal grid (such as copper, nickel, etc.)
• a film of carbon or comprising carbon such as carbon paper, self-supporting graphene, etc.
• other solid support polymer, glass, etc.
• an electron-conducting layer such as a current collector print
• This lithiation process then generally occurs at the surface of the electron-conducting solid support or inside the meshes for a grid, or inside a pretreatment layer, in one case as in the other, the lithiation occurs on the surface of the electron-conducting solid support in contact with the first thin layer.
• surface modification is meant the application of a succession of two thin layers that conduct ions and serve as a barrier to the formation of dendrites without however reacting in a substantial way with the surface of the film of electrode, the elements of the thin layers being mostly non-reactive.
• the surface of the electrode film is modified by applying to one of its surfaces a first thin layer comprising an inorganic compound in a solvating polymer, optionally comprising an ionic salt and/or a plasticizer.
• the first thin layer has an average thickness of about 15 ⁇ m or less.
• the inorganic compound is present in the first thin layer according to a mass ratio “inorganic compound: solvating polymer” in the first thin layer is located in the interval from about 1:20 to about 20:1.
• the solvating polymer of the first layer can be crosslinked or not.
• the second thin layer includes a solvating polymer, an ionic salt, and optionally a plasticizer, the second thin layer being disposed over the first thin layer and having an average thickness of about 15 ⁇ m or less.
• the solvating polymer of the first layer is identical to or different from the solvating polymer of the second layer.
• the inorganic compound is preferably in the form of particles (eg, spherical, rods, needles, etc.).
• the average size of the particles is preferably nanometric, for example, less than 1 ⁇ m, less than 500nm, or less than 300nm, or less than 200nm, or between 1 nm and 500nm, or between 10nm and 500nm, or even between 50nm and 500nm, or between 10Onm and 500nm, or between 1 nm and 300nm, or between 10nm and 300nm, or between 50nm and 300nm, or between 100nm and 300nm, or between 1 nm and 200nm, or between 10nm and 200nm, or again between 50nm and 200nm, or between 100nm and 200nm, or between 1nm and 100nm, or between 10nm and 100nm, or even between 25nm and 100nm, or between 50nm and 100nm.
• Non-limiting examples of inorganic compounds include Al2O3, Mg2B20s, Na2O-2B2O3, xMgO yB2O3 zH2O, TiO2, ZrO2, ZnO, Ti2O3, SiO2, Cr20s, CeO2, B2O3, B2O, SrBi4Ti40i5, LLTO, LLZO, LAGP, LATP , Fe2C>3, BaTiCh, y-LiAICh, a metal/carbon mixture (such as Sn+C, Zn+C, Ni2P+C), molecular sieve or a zeolite (e.g. aluminosilicate, mesoporous silica) , a sulfide ceramic (such as U7P3S11), a glass ceramic (such as LIPON, etc.), and other ceramics, as well as combinations thereof.
• a metal/carbon mixture such as Sn+C, Zn+C, Ni2P+C
• the surface of the particles of the inorganic compound can also be modified by organic groups grafted to their surface in a covalent manner.
• the groups can be chosen from crosslinkable groups (such as organic groups comprising acrylate, methacrylate, vinyl, glycidyl, mercapto, etc. functions), aryl groups, alkylene oxide or poly(oxide of alkylene), and other organic groups, or one of their combinations, optionally comprising a spacer group between the organic groups and the particles of the inorganic compound.
• the grafted organic groups comprise poly(alkylene oxide) chains fixed to the particles of the inorganic compound by a spacer group.
• the crosslinkable groups can comprise silane or halogenated silane, phosphonate, carboxylate, catechol, (meth)acrylate or poly(meth)acrylate, alkylene or polyalkylene functions, and combinations thereof.
• Scheme 1 presents an example of a method for grafting silanes comprising propyl methacrylate groups.
• the methacrylate group present on the propylsilane function can then be reacted with compatible groups, for example, in order to form a polymer chain such as a polyether.
• compatible groups for example, in order to form a polymer chain such as a polyether.
• the particles of the inorganic compound have a small specific surface (for example, less than 80 m 2 /g, or less than 40 m 2 /g).
• concentration of inorganic compound in the first thin layer can then be relatively high.
• the "inorganic compound:solvating polymer" mass ratio in the first thin layer can be in the range of about 2:5 to about 4:1, or about 2:5 to about 2:1, or about 1:2 to about 2:1, or about 4:5 to about 2:1, or about 1:1 to about 2:1, or about 4:5 to about 3: 2.
• the particles of the inorganic compound have a large specific surface (for example, 80 m 2 /g and more, or 120 m 2 /g and more).
• the greater porosity of the inorganic compound may then require a greater amount of polymer and the concentration of the inorganic compound in the first thin layer will be lower.
• the "inorganic compound: solvating polymer" mass ratio in the first thin layer can then be in the range of about 1:20 to about 2:1, or about 2:5 to about 2:1 , about 2:5 to about 6:5, or about 1:20 to about 6:5, or about 2:5 to about 1:1, or about 1:20 to about 1: 1, or about 2:5 to about 4:5, or about 1:20 to about 4:5.
• the average thickness of the first and second thin layers is such that the latter is considered a modification of the electrode surface rather than an electrolyte layer.
• the average thickness of the first thin layer and the second thin layer is respectively less than 15 ⁇ m.
• the average thickness may be between about 0.5 ⁇ m and about 15 ⁇ m, or between about 1 ⁇ m and about 15 ⁇ m, or between about 1 ⁇ m and about 12 ⁇ m, or between about 0.5 pm and approximately 10 pm, or between approximately 1 pm and approximately 10 pm, or between approximately 2 pm and approximately 8 pm, or between approximately 2 pm and approximately 7 pm, or further between 2 pm and approximately 5 pm.
• its average thickness may be between approximately 50 nm and approximately 15 ⁇ m, or between approximately 0.1 ⁇ m and approximately 15 ⁇ m, or between approximately 0.5 ⁇ m and approximately 15 ⁇ m, or between approximately 1 ⁇ m and approximately 1 ⁇ m. approximately 3pm, or between approximately 1 pm and approximately 12 pm, or between approximately 0.5 pm and approximately 10 pm, or between approximately 1 pm and approximately 10 pm, or between approximately 2 pm and approximately 8 pm, or between approximately 2 pm and approximately 7 pm, or between 2 pm and about 5 ⁇ m, or else between 50 nm and about 5 ⁇ m, or between about 0.1 ⁇ m and about 2 ⁇ m.
• the total average thickness of the first and second thin layers may range from about 1 ⁇ m to about 30 ⁇ m, or from about 1 ⁇ m to about 25 ⁇ m, or from about 5 ⁇ m to about 10 p.m., or from about 1 p.m. to about 8 p.m., or from about 1 p.m. to about 4 p.m., or from about 2 p.m. to about 12 p.m., or from about 3 p.m. to about 3 p.m., or from about 3 p.m. to about 12 p.m., or from about 4pm to about 3pm, or from about 4pm to about 12pm.
• the polymer present in the first and/or the second layer is independently chosen from polymers comprising solvating units of ions, in particular of ions lithium.
• solvating polymers include linear or branched polyether polymers (e.g., PEO, PPO, or EO/PO copolymer), poly(dimethylsiloxanes), poly(alkylene carbonates), poly(alkylenesulfones), poly (alkylenesulfamides), polyurethanes, poly(vinyl alcohol), polyacrylonitriles, polymethyl methacrylates, and their copolymers, and optionally comprising crosslinked units originating from crosslinkable functions (such as acrylate, methacrylate, vinyl, glycidyl, mercapto , etc.).
• crosslinkable functions such as acrylate, methacrylate, vinyl, glycidyl, mercapto , etc.
• the first and second thin layers further comprises a plasticizer.
• the first thin layer and the second thin layer can each comprise a plasticizer.
• only the first thin layer additionally comprises a plasticizer.
• the plasticizers used are those generally known as compatible with electrochemical cells and cycling conditions. They generally include organic liquids with relatively high boiling points.
• Non-limiting examples of plasticizers include liquids such as glycol diethers (such as tetraethylene glycol dimethyl ether (TEGDME)), carbonate esters (such as propylene carbonate, ethylene carbonate, fluoroethylene carbonate), lactones (such as y -butyrolactone), adiponitrile, ionic liquids and the like.
• At least one of the first and second thin layers further comprises a lithium salt, for example both layers can comprise a lithium salt.
• lithium salts include lithium hexafluorophosphate (LiPFe), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), 2-trifluoromethyl-4,5 -lithium dicyano-imidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (UBF4), lithium bis(oxalato)borate (LiBOB), lithium nitrate (UNO3), lithium chloride (LiCI), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (
• the electrode film can comprise a metallic film, which is preferably a film of lithium or of an alloy comprising lithium, optionally on a current collector.
• a metallic film which is preferably a film of lithium or of an alloy comprising lithium, optionally on a current collector.
• the metal film is a lithium film, the latter consists of lithium comprising less than 1000 ppm (or less than 0.1% by weight) of impurities.
• a lithium alloy may comprise at least 75% by weight lithium, or between 85% and 99.9% by weight lithium.
• the alloy can then comprise an element chosen from alkali metals other than lithium (such as Na, K, Rb, and Cs), alkaline-earth metals (such as Mg, Ca, Sr, and Ba), rare earth metals (such as Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), zirconium, copper, silver, bismuth, cobalt, manganese, zinc, aluminum , silicon, tin, antimony, cadmium, mercury, lead, molybdenum, iron, boron, indium, thallium, nickel and germanium (e.g. Zr, Cu, Ag, Bi, Co, Zn, Al, Si, Sn, Sb, Cd, Hg, Pb, Mn, B, In, Tl, Ni, or Ge).
• alkali metals other than lithium such as Na, K, Rb, and Cs
• alkaline-earth metals such
• the electrode film can also comprise a pretreatment layer on the first surface, the latter being in contact with the first thin layer.
• the pretreatment layer comprises a compound selected from a silane, a phosphonate, a borate, a salt or an organic compound, a carbon (such as graphite, graphene, etc.), a salt or inorganic compound (such as LiF , U3N, U3P, UNO3, U3PO4, etc.), or a thin layer of an element other than a metal of the electrode film or forming an alloy with it on the surface (e.g.
• pretreatment layer having an average thickness of less than 1 ⁇ m, or less than 500 nm, or less than 200 nm, or less than 100 nm, or even less than 50 nm.
• pretreatment is generally produced by contacting the first surface of the electrode film with an organic or inorganic compound according to known methods. For example, contacting a film of lithium with PCI3 generally produces U3P and/or U3PO4 Similarly, the application of a very thin powder or film of an element metal different from a metal of the electrode film, for example, chosen from the elements defined above can produce a thin layer of alloy.
• the pretreatment layer is formed on the electrode film before the addition of the first thin layer.
• the surface of the electrode film can also be treated before the application of the first thin layer, for example by stamping.
• the electrode comprises a current collector in contact with the second surface of the electrode film.
• Electrochemical cells comprising the present surface modified electrode are also contemplated.
• an electrochemical cell comprises a negative electrode and a positive electrode, in which at least one of the negative electrode and the positive electrode is as defined herein and can be illustrated, for example, in Figures 4(c), (d) and (f).
• the negative electrode is as defined here and comprises an electrode film as defined above; and the positive electrode comprises a film of positive electrode material comprising an electrochemically active positive electrode material, optionally a binder, and optionally an electronically conductive material.
• the electrochemically active material of the positive electrode can be chosen from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides, but also other materials such as sulfur, elemental selenium or iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, and carbon-based active materials.
• the electrochemically active material of the positive electrode is preferably in the form of particles which can optionally be coated, for example, with polymer, ceramic, carbon or a combination of two or more thereof.
• electronically conductive materials that can be included in the electrode material include carbon black (such as Ketjen TM , Denka TM , Shawinigan carbons, acetylene black, etc.) graphite, graphene, nanotubes carbon, carbon fibers (including carbon nanofibers, gas-phase formed carbon fibers (VGCF), etc.), non-powdery carbon obtained by carbonization of an organic precursor (for example, in the form of coating on particles), or a combination of two or more thereof.
• carbon black such as Ketjen TM , Denka TM , Shawinigan carbons, acetylene black, etc.
• graphite graphene
• nanotubes carbon carbon fibers (including carbon nanofibers, gas-phase formed carbon fibers (VGCF), etc.
• Non-limiting examples of electrode material binders include the polymeric binders described above in connection with thin films or below for the electrolyte, but also rubber-like binders such as SBR (styrene-butadiene rubber). , NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), and ACM (acrylate rubber), or fluoropolymer type binders such as PVDF (polyvinylidene fluoride), PTFE ( polytetrafluoroethylene), and combinations thereof. Certain binders, such as those of the rubber type, may also include an additive such as CMC (carboxymethylcellulose).
• CMC carboxymethylcellulose
• additives may also be present in the electrode material, such as lithium salts or inorganic particles of the ceramic or glass type, or even other compatible active materials (for example, sulfur).
• the film of positive electrode material comprises a first and a second surface, the first surface facing the negative electrode and carrying a third thin layer comprising a solvating polymer (for example, as defined above ), an ionic salt (eg, as defined above), the third thin layer having an average thickness of about 50 ⁇ m or less, about 40 ⁇ m or less, or about 30 ⁇ m or less, or about 15 p.m. or less, or about 10 p.m. or less, or is between about 0.5 p.m. and about 50 p.m., or between about 5 p.m. and about 50 p.m., or between about 5 p.m. and about 40 p.m., or between about 0.5 p.m.
• a solvating polymer for example, as defined above
• an ionic salt eg, as defined above
• the third thin layer can also comprise a plasticizer, for example as defined above.
• the positive electrode material can be applied to a current collector (eg aluminum, copper). According to one example, the current collector is made of carbon-coated aluminum.
• the electrochemical cell excludes the presence of a layer of solid polymer electrolyte, excluding, for example, an electrolyte layer with a thickness of more than 15 ⁇ m, or of 20 ⁇ m or more. It is understood that the cell also does not include any other type of electrolyte, for example, liquid or gel impregnating a separator.
• the electrochemical cell further comprises a layer of solid electrolyte comprising a polymer and a lithium salt.
• the polymer of the electrolyte can be chosen from linear or branched polyether polymers (for example, PEO, PPO, or EO/PO copolymer), and optionally comprising crosslinkable units), poly(dimethylsiloxanes), poly (Alkylene carbonate), poly(alkylenesulfones), poly(alkylenesulfonamides), polyurethanes, poly(vinyl alcohol), polyacrylonitriles, polymethyl methacrylates, and copolymers thereof, the solvating polymer optionally being crosslinked.
• the lithium salt can be as defined above with reference to thin layers.
• the solid electrolyte may further comprise a ceramic.
• the present document also relates to an electrochemical cell comprising a negative electrode and a positive electrode, in which the negative electrode comprises a film of negative electrode and the positive electrode comprises a film of electrode material positive comprising a positive electrode electrochemically active material, optionally a binder, and optionally an electronically conductive material, and in which:
• the negative electrode film comprises a first and a second surface, the first surface being optionally pretreated, wherein said negative electrode comprises a first thin layer comprising an inorganic compound in a solvating polymer and optionally an ionic salt and/or a plasticizer, the first thin layer being disposed on the first surface of the negative electrode film and having an average thickness of about 15 ⁇ m or less, the "inorganic compound: solvating polymer" mass ratio in the first thin layer is within the range of about 1:20 to about 20:1; And (b) the negative electrode comprises a second thin layer comprising a solvating polymer, an ionic salt and optionally a plasticizer, the second thin layer being disposed on the first thin layer and having an average thickness of about 15 ⁇ m or less, in wherein the solvating polymer of the first layer is the same as or different from the solvating polymer of the second layer; and/or the film of positive electrode material comprises a first and a second surface, the first surface facing the negative electrode and bearing
• the electrochemical cell also excludes any other type of additional electrolyte, thereby also excluding the use of electrolytes of the liquid or gel type, for example, impregnating a separator. Examples of such a cell are shown in Figures 4(d), (e) and (f).
• the electrochemical cell comprises the second thin layer. According to another example, the electrochemical cell comprises the third thin layer. According to yet another example, the electrochemical cell comprises the second and the third thin layer.
• the solvating polymer of each of the thin layers is independently as defined herein and may be independently crosslinked or uncrosslinked. According to one example, the solvating polymer of at least one of the first, second and third layers is non-crosslinked. According to one example, the solvating polymer of the first layer is non-crosslinked. According to another example, the solvating polymer of the second layer is non-crosslinked. The solvating polymer of each of the first, second and third layers can be uncrosslinked. Or the polymer of the third layer is crosslinked and that of the first and second layers is uncrosslinked. Alternatively, the solvating polymer of each of the first, second and third layers can be crosslinked.
• the negative electrode film of the present electrochemical cell can be a current collector, for example comprising a electron-conductive solid support, such as a metallic foil or grid (such as copper, nickel, etc.), a film of carbon or including carbon (such as carbon paper, self-supporting graphene, etc.), or the like solid support (polymer, glass, etc.) comprising an electron-conducting layer (such as a current collector print).
• a current collector for example comprising a electron-conductive solid support, such as a metallic foil or grid (such as copper, nickel, etc.), a film of carbon or including carbon (such as carbon paper, self-supporting graphene, etc.), or the like solid support (polymer, glass, etc.) comprising an electron-conducting layer (such as a current collector print).
• the negative electrode film may comprise a metallic film, for example comprising lithium or an alloy comprising lithium, the film of lithium and its alloys also being able to be defined as above.
• the present negative electrode film may also include a
• the inorganic material of the first thin layer is as defined above and can be comprised in the same mass ratios described above.
• the average thickness of the first thin layer can be between about 0.5 ⁇ m and about 15 ⁇ m, or between about 1 ⁇ m and about 15 ⁇ m, or between about 1 ⁇ m and about 12 ⁇ m, or between about 0.5 ⁇ m and about 10 ⁇ m, or between approximately 1 pm and approximately 10 pm, or between approximately 2 pm and approximately 8 pm, or between approximately 2 pm and approximately 7 pm, or between 2 pm and approximately 5 pm.
• the average thickness of the second thin layer can, for its part, be between about 50 nm and about 15 ⁇ m, or between about 0.1 ⁇ m and about 15 ⁇ m, between about 0.5 ⁇ m and about 15 ⁇ m, or between about 1 ⁇ m and about 3 pm, or between approximately 1 pm and approximately 12 pm, or between approximately 0.5 pm and approximately 10 pm, or between approximately 1 pm and approximately 10 pm, or between approximately 2 pm and approximately 8 pm, or between approximately 2 pm and approximately 7 pm, or between 2 pm and approximately 5 pm, or alternatively between 50 nm and approximately 5 pm, or between approximately 0.1 pm and approximately 2 pm.
• the total average thickness of the first and second thin layers is preferably in the range of about 1 ⁇ m to about 30 ⁇ m, or about 1 ⁇ m to about 10 p.m., or from about 5 p.m. to about 10 p.m., or from about 1 p.m. to about 8 p.m., or from about 1 p.m. to about 4 p.m., or from about 2 p.m. to about 12 p.m., or from about 3 p.m. to about 3 p.m., or from about 3pm to about 12pm, or from about 4pm to about 3pm, or from about 4pm to about 12pm.
• the average thickness of the third thin layer is about 40 ⁇ m or less, or about 30 ⁇ m or less, or about 15 ⁇ m or less, or is between about 0.5 ⁇ m and about 50 ⁇ m, or between approximately 5pm and approximately 50pm, or between approximately 5pm and approximately 40pm, or approximately 0.5pm and approximately 15pm, or between approximately 1 pm and approximately 15pm, or between approximately 1 m and approximately 12 pm, or between approximately 0.5 pm and approximately 10 pm, or between approximately 1 pm and approximately 10 pm, or between approximately 2 pm and approximately 8 pm, or between approximately 2 pm and approximately 7 pm, or between 2 pm and approximately 5 pm.
• the layer present may have a slightly greater thickness.
• the second thin layer and the third thin layer are both present, the latter may be thinner, and the total average thickness of the first, second and third thin layers may be in the range of about 3 ⁇ m to about 60 ⁇ m , or from approximately 10pm to approximately 50pm, or from approximately 15pm to approximately 30pm, or from approximately 3pm to approximately 30pm, or from approximately 3pm to approximately 25pm, or from approximately 5pm to approximately 25pm, or from approximately 5pm to approximately 8pm, or from approximately 8pm to approximately 15pm, or from approximately 8pm to approximately 12pm, or from approximately 5pm to approximately 15pm, or from approximately 5pm to approximately 12pm, or from approximately 5pm to approximately 15pm, or from about 9pm to about 3pm.
• At least one of the first and second thin layers additionally comprises a plasticizer, preferably the first thin layer and the second thin layer additionally comprise a plasticizer.
• the third thin layer can also further comprise a plasticizer.
• the plasticizer is also as defined above.
• at least one of the first, second and third thin layers may further comprise a lithium salt, preferably each of the three layers. The lithium salt is also as defined above.
• the negative electrode may also further comprise a current collector in contact with the second surface of the negative electrode film.
• the positive electrode may also further comprise a current collector in contact with the second surface of the film of positive electrode material.
• the positive electrode material is also as defined with reference to the previous electrochemical cell.
• an electrochemical accumulator comprising at least one electrochemical cell as defined here.
• the electrochemical accumulator is a lithium or lithium-ion battery.
• the electrochemical accumulators of the present application are intended for use in mobile devices, for example telephones laptops, cameras, tablets or laptops, in electric or hybrid vehicles, or in the storage of renewable energy.
• This document also relates to a process for the preparation of a surface-modified electrode as described herein.
• This method comprises (i) mixing an inorganic compound and a solvating polymer in a solvent, optionally comprising a salt and/or a plasticizer; (ii) spreading the mixture obtained in (i) on the surface of the electrode; (iii) removal of the solvent to obtain a first thin layer; (iv) mixing a solvating polymer and a salt in a solvent, optionally including a plasticizer; (v) spreading the mixture obtained in (iv) on the first thin layer obtained in (iii); and (vi) solvent removal.
• steps (i) and/or (iv) further comprise a crosslinking agent
• the process may further comprise a step of crosslinking the polymer (for example by ionic, thermal or irradiation route), before, after or during steps (iii) and/or (vi), respectively.
• steps (ii), (iii), (v), and/or (vi) are preferably carried out under vacuum, or in an anhydrous enclosure which can be filled with a inert gas like argon.
• the process can exclude the presence of solvent and steps (iii) and/or (vi) can be avoided.
• the mixing steps can be carried out by various methods used in the field of the present technology.
• such methods may include planetary, ball, disc, ultrasonic (e.g., sonotrode) mixers, homogenizers (such as a rotor-stator type homogenizer), etc.
• Spreading can be done by conventional methods, for example, using a roller, such as a sheeter roller, coated with the mixture (including a continuous roll-to-roll method), with a doctor blade (" Doctor blade”), by spraying (“spray coating”), by centrifugation, by printing, etc.
• a roller such as a sheeter roller
• coated with the mixture including a continuous roll-to-roll method
• Doctor blade doctor blade
• spraying spraying
• centrifugation by printing, etc.
• the organic solvent used can be any solvent which is non-reactive with the electrode film, for example, non-reactive with lithium when the electrode film comprises lithium metallic.
• examples include tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), heptane, toluene or a combination thereof.
• Ni2P nanoparticles are synthesized by the liquid route using a vacuum ramp ("Schlenk line"), but could also be synthesized by other known means, for example, under solvothermal conditions under pressure using of an autoclave.
• the mixture is then allowed to cool very slowly to room temperature and then centrifuged at 10,000 RPM for 30 minutes in small 25 mL centrifuge tubes.
• the powder is easier to recover thanks to the absence of surfactant.
• the light brown supernatant is removed, the powder is redispersed in ethanol and the resulting black liquid is centrifuged again. This step is repeated three more times. A black powder is obtained with a yield of almost 90%.
• Figure 1(a) shows the X-ray powder diffractogram of the resulting material. The peaks obtained are relatively broad and not very intense, which confirms a nanometric size of the Ni2P particles. There is only one phase obtained which is in fact a Ni ⁇ Ps phase.
• Figure 1(b) shows a scanning microscope image of the Ni ⁇ Ps powder. A single phase is clearly visible and composed of small spherical particles with a diameter of about 20 nm.
• the attachment of a polymer to the surface of a ceramic is done in two steps.
• a powder of ALCh shape of needles, -164 m 2 /g
• a silanization reaction on the surface of the ALCh particles is carried out to fix crosslinkable groups there.
• Diagram 2 shows this first stage of surface modification.
• the second step consists of the polymerization on the surface of the ALO particles of polyethylene glycol units.
• Scheme 3 shows the reaction protocol.
• M n 500 g/mol
• AIBN azobisisobutyronitrile
• FIG. 2(a) shows the thermogravimetric curves of Al2O3 ( — ) and ALOa-polymer ( — ) powders. The continuous mass loss between 200 and 600°C for the modified powder makes it possible to determine that there is approximately 10% polymer in the final composite.
• Figure 2(b) shows an example of coating (thin layer of 1 ⁇ m) made on a lithium strip with an ink composed of Polymer 1 + ALOa-polymer.
• Polymer 1 refers to a polymer detailed in US Patent No. US 6,903,174 comprising crosslinkable groups.
• Example 2 Formulation of inks for electrode surface modification
• a plasticizer tetraethylene glycol dimethyl ether (TEGDME) is used.
• LiTFSI lithium salt
• TEGDME a crosslinking agent
• lrgacure-651 MC was also added at 0.5% by mass relative to the mass of Polymer 1.
• the depositions were made with a squeegee (“doctor blade”) on stainless steel strips with a thickness of 50 ⁇ m on a coating table.
• the strips are left under the fume hood for 5 minutes before being inserted into a box under nitrogen flow equipped with an ultraviolet (UV) lamp. After 5 minutes of purging with nitrogen, the films are crosslinked under UV light for 2 minutes.
• UV ultraviolet
• an adequate quantity of Polymer 1 is introduced with a quantity of LiTFSI salt adjusted so as to obtain an O:Li molar ratio of 20:1.
• An anhydrous solvent, tetrahydrofuran (THF) is added in sufficient quantity to have, after mixing, an 18.5% solid solution (polymer + salt).
• THF tetrahydrofuran
• the solution is mixed in the planetary mixer at 2000 RPM for 3 minutes. This mixing step is repeated seven times.
• TEGDME TEGDME which amounts to 44% in the polymer-inorganic compound films and the polymer films, in order to promote the mixing of the ceramic particles, adhesion and good conductivity of the deposited layers.
• the polymer solution is prepared as follows.
• a plastic container compatible with a planetary mixer of the Thinky type an adequate quantity of Polymer 1 is introduced with a quantity of LiTFSI salt in such a way as to obtain an O:Li molar ratio of 20:1.
• 44% by weight of TEGDME relative to the polymer is added and the whole is mixed in the planetary mixer at 2000 RPM for three minutes.
• the THF is added in sufficient quantity to have after mixing a solution with 18.1% solid (polymer + salt).
• the solution is mixed in the planetary mixer at 2000 RPM for 3 minutes. This mixing step is repeated six times.
• A9 polymer ink for second layer spray application
• Polymer 2 refers to a polymer detailed in US Patent No. US 6,903,174 but not comprising crosslinkable groups.
• a quantity of LiTFSI salt is added so as to obtain an O:Li molar ratio of 20:1.
• THF solvent is added so as to obtain a very dilute solution of salted polymer.
• a solution comprising 4% solids is obtained (salt+polymer). The solution is quickly homogeneous by simply mixing by hand.
• Table 1 Composition of polymer inks and films To. The percentages are by weight relative to the mass of Polymer 1.
• Procedure 1 (B1-B3 with ceramic AC-polymer): In a plastic container compatible with a planetary mixer of the Thinky type, an adequate quantity of Polymer 1 is introduced with a quantity of LiTFSI salt of such a way as to obtain an O:Li molar ratio of 20:1. Then, 44% by weight of TEGDME relative to the polymer is added and the whole is mixed in the planetary mixer at 2000 RPM for three minutes. After 2 min of rest, a quantity of Al2O3-polymer ceramic corresponding to a ratio of 56% to 130% of the mass of the polymer is added and the whole is again mixed for 3 minutes at 2000 RPM. This mixing step is repeated four times. The ink obtained, homogeneous and without agglomerates, is diluted with anhydrous THF in order to obtain a 17% solution of solid (polymer + salt + ceramic). The solution is mixed twice for 3 minutes at 2000 RPM.
• compositions (apart from the solvent) of the inks B1 to B3 are described in Table 2.
• Irgacure MC (0.5% by weight relative to the polymer) was also added as a crosslinking agent. These compositions may then be designated B1(i) to B3(i), where (i) indicates the additional presence of Irgacure TM .
• a quantity of Sn, Zn or Ni2P (of Ni ⁇ Ps phase prepared according to Example 1(a)) comprised between 30 and 90% by mass with respect to the polymer is introduced into the plastic container. Subsequently, from 10% to 20% by mass of carbon is added. Everything is mixed with the disc mixer at 2500 RPM for 8 minutes. THF is added in sufficient quantity to obtain, after mixing, a 17% solid solution (polymer + salt + carbon + metal). Finally, after introducing the THF, the solution is mixed one last time with the disc mixer at 2500 RPM for 2 minutes.
• the B4 ink presented in Table 2 is an example of an ink comprising a mixture of Ni2P and carbon.
• Procedure 3 (B5-a and B5-b with AI2O3): In a plastic container, a certain amount of unmodified alumina (unscreened AKPG15 type) is mixed with THF using a sonotrode (50% power) for 4 minutes (B5-a ink) or d an IKA-type rotor-stator homogenizer at maximum power for 10 min (Ink B5-b). During this time, a polymer solution is prepared. It contains a quantity of Polymer 1 equivalent in mass to that of alumina, the LiTFSI salt is added so as to obtain an O:Li molar ratio of 20:1. A mass of plasticizer (TEGDME) equivalent to 100% of the mass of polymer is added, without addition of crosslinking agent.
• TEGDME plasticizer
• the polymer solution is mixed in the planetary mixer at 2000 RPM for 3 times 10 minutes. Finally, the solution is poured into the plastic container containing the ceramic and the THF solvent. The final solution contains about 21% solid (polymer + salt + ceramic + TEGDME). This is stirred one last time in a conical vortex tube before coating with lithium.
• FIGS 4(a) to 4(f) Examples of cell configurations studied (according to the invention and as comparisons) are presented in Figures 4(a) to 4(f).
• the batteries in 4(a) to 4(c) are with polymer electrolyte, while the batteries in Figures 4(d) to 4(f) are without electrolyte polymer.
• All lithiums used contain at least a first thin layer of inorganic compound in a polymer (represented as Polymer 1 + Al2O3-polymer).
• the cells of Figures 4(c), 4(d) and 4(f) include a second layer of non-ceramic Polymer 1 which is applied to the surface of the first layer.
• the cells of Figures 4(b), 4(e) and 4(f) include a layer of Polymer 1 with a lithium salt, but no ceramic or plasticizer on the cathode surface.
• Button cells were assembled with a cathode of LFP (8 mg/cm 2 , composition: LFP coated with carbon: carbon black: Polymer 1: LiTFSI in proportions of about 73: 1: 19: 7), lithiums with a layer of polymer 1 + ALOs-polymer and a self-supporting film of electrolyte based on branched polyethylene oxide with functions of the allyl ether type (25 ⁇ m thick) (hereinafter referred to as EPS).
• Polymer 1 + AhCh-polymer B1(i), B2(i) and B3(i) inks were prepared (see Example 2(b) and Table 2). It should be noted that for this example, the films deposited on lithium were crosslinked (with 0.5% by mass of Irgacure MC ).
• the coatings with these inks were carried out on the surface of the lithium using a doctor blade on a coating table at a speed of 10 mm/s.
• the lithiums are left for 5 minutes under the hood then 5 minutes in an oven at 50° C. to evaporate the remaining THF.
• the films are then placed in a box under nitrogen flow equipped with a UV lamp. After 5 minutes of purging with nitrogen, the films are crosslinked under UV light for 2 minutes.
• the thicknesses of the deposits are approximately 4 ⁇ m after the drying and crosslinking stages.
• the typical assembly is as shown in Figure 4(a) (varying the levels of Al2O3-polymer according to those of inks B1(i) to B3(i)).
• the assemblies are therefore made with three lithiums covered with a layer having different contents of ceramic modified with polymer.
• Figure 5(a) shows the galvanostatic cycling performed in C/6 at 50°C for the different batteries as well as for the reference (LFP cathode and lithium anode without modification and self-supported polymer electrolyte).
• Figure 5(b) is a representation of the capacity drop during cycling for the same batteries. Two batteries are cycled by lithium and the cycles are relatively reproducible. Compared to the cycling for the reference battery, those for the batteries with the layer of polymer + ceramic give greater discharge capacities. The larger the amount of ceramic, the higher the capacity and the cycling is stable.
• Figure 8 presents (a) the galvanostatic cyclings and (b) the coulombic efficiencies obtained at 50°C and in C/3 for LFP/polymer electrolyte/Li batteries assembled with lithium without modification (reference) and a lithium having a 4 ⁇ m layer of Polymer 1 with 130% ALOa-polymer (C1 stack). Polymer films are not cross-linked. Compared to the three reference cells, the two C1 cells with the modified lithium have better reproducibility and do not show a gradual gain in capacity over the first two cycles. The specific discharge capacity is also slightly higher for batteries with modified lithium. In addition, a better coulombic efficiency (-99%) is obtained from the second cycle for the batteries assembled with the lithium containing the ceramic layer, whereas around 91-92% of coulombic efficiency is obtained for the reference batteries.
• Figure 9 presents (a) the galvanostatic cyclings and (b) the coulombic efficiencies obtained at 50°C and in C/3 for LFP/polymer electrolyte/Li batteries assembled with lithium and the LFP cathode without modification (reference) , then with lithium having a 4 ⁇ m layer of Polymer 1 with 130% ALOa-polymer and an LFP cathode having a 2 or 4 ⁇ m polymer layer (stacks C2-a and C2-b, respectively). Polymer films are not cross-linked.
• the configuration for assembling cells with modified lithium is inset in Figure 9(b).
• an LFP cathode with a thin layer of polymer was used for the cells of Figure 9 (except for the references).
• the overall resistance of the batteries was reduced thanks to the addition of this polymer layer on the cathode of LFP since discharge capacities of approximately 112 and 115 mAh/g were obtained when layers of 4 and 2 ⁇ m were deposited on the surface of the cathode, respectively. Without this added layer on the cathode, the discharge capacities were around 100 mAh/g (see Figure 8(a)). Again, reproducibility is very good using polymer layers on lithium and on cathode as shown by the two cells cycled with the cathode having a 4 ⁇ m polymer layer.
• the amount of ceramic in the polymer layer deposited on the surface of the lithium was set at 130%, because beyond that, the layer loses its mechanical properties, but also its bonding.
• a second sticky layer containing no ceramic, but only the polymer, the salt and the TEGDME is deposited on the surface of the first layer of Polymer 1 + AhCh-polymer to decrease the interfacial resistance between the anode and the polymer electrolyte. Polymer films are not cross-linked.
• Figure 10 presents (a) the galvanostatic cyclings and (b) coulombic efficiencies obtained at 50°C and in C/3 for LFP/polymer electrolyte/Li batteries assembled with lithium without modification (reference), then with lithium having a first 4 ⁇ m layer of Polymer 1 with 130% ALOs-polymer and a second 4 ⁇ m layer of Polymer 1 (C3 stack).
• the inset image ( Figure 10(b)) allows better visualization of the two layers deposited on the surface of the lithium.
• the improved interface between the self-supporting polymer electrolyte and the anode is clearly visible since an initial discharge capacity of 121 mAh/g was obtained whereas approximately 100 mAh/g was obtained with the C1 batteries when only the ALOs-polymer layer was deposited on lithium (see cycling in Figure 8(a )). However, a progressive loss of capacity is observed. It is possible that the layer is not optimal in this case.
• the coulombic efficiency reaches 80% in the first cycle for the C3 battery cycled with the lithium containing the two layers of polymer (62 to 66% for the reference batteries).
• FIG. 11(b) represents the tested assembly.
• a second layer of Polymer 1 with TEGDME was deposited on the lithium surface with relatively high thicknesses of 9 and 12 ⁇ m (stacks C4-a and C4-b in Table 3, respectively).
• Figure 11 presents (a) the galvanostatic cycling and (b) coulombic efficiencies obtained at 50°C and in C/3 for LFP/polymer electrolyte/Li batteries assembled with lithium without modification (reference), then for C4 batteries -a and C4-b. Polymer films are not cross-linked.
• the capacity difference is huge by removing the self-supporting polymer electrolyte which brings a lot of resistance and interface problems in the battery.
• the first cycle discharge capacity is approximately 145-149 mAh/g for the batteries without the polymer electrolyte against 85-90 mAh/g for the reference batteries.
• the interface between the cathode, which has surface defects, and the second layer of Polymer 1 deposited on the surface of the lithium is not optimal. Indeed, we can see small variations in the discharge capacity (Figure 11(a)), but above all larger variations in the coulombic efficiencies (Figure 11(b)), typical of an interface problem.
• the electrochemical results seem more stable with a thicker second polymer layer (12 ⁇ m versus 9 ⁇ m), but the determining factor remains the optimization of the interface between the surface of this polymer layer and the surface of the cathode.
• Figure 12 presents (a) the galvanostatic cycling and (b) coulombic efficiencies obtained at 50°C and in C/3 for these batteries as well as for the references for comparison.
• the electrochemical results are remarkable, the three cells are very reproducible so that one hardly sees any difference in the cycling of these ( Figure 12(a)).
• the initial specific capacity in discharge is about 145 mAh/g. A gradual drop in capacity is observed, but seems to stabilize as cycling progresses.
• Coulombic efficiencies close to 99% are obtained during the first cycle, which is much better than the 62 to 66% for the reference batteries. It is important to note that the thickness of the deposit on the cathode (5, 8 or 11 ⁇ m) does not influence the electrochemical cycling under the conditions tested.
• the cyclings are very similar to those obtained in Figure 12 and perfectly demonstrate the usefulness of depositing thin layers directly on the surface of the cathode and the anode to overcome a self-supported polymer electrolyte.
• the lithium has the layer rich in Al2O3-polymer which makes it possible to stabilize the lithium.
• fillers of inorganic compounds other than ALOs-polymer were also used.
• a carbon/metal (M) mixture was tested in order to form a Li-M alloy during the plating of lithium from the cathode to the lithium anode. Carbon is also present for the conduction of electrons in the polymer layer.
• two metals were tested (namely Sn and Zn) as well as a nickel phosphide Ni2P. Only one type of carbon has been tested, but others could be used.
• Figure 14 shows the galvanostatic cycling obtained at 50°C and at C/3 for LFP/polymer electrolyte/Li batteries assembled with lithium without modification (reference), then with a lithium having a 5 ⁇ m layer of polymer 1 with 30% Ni2P and 17% carbon (layer B4 of Table 2).
• Polymer films are not cross-linked. This is a first result, but confirms that the concept works. We see an increase in the initial capacity compared to the reference batteries. A gradual drop in capacity is however observable as the cycling progresses.
• This type of layer could benefit from a stack configuration such as those shown in Figures 4(d) to 4(f), particularly that of Figure 4(f) corresponding to the C6 stack (a or b) shown below. above where AhCh-polymer could be replaced by the present carbon/metal mixture.
• Example 4 Surface-modified electrodes with spray-applied second layer and electrochemical properties
• the first thin layer of inorganic compound in a polymer is however formed of Polymer 1 and unmodified alumina (Al2O3).
• the second thin layer on the lithium is applied by vaporization (spray) in a very thin layer and includes Polymer 2 rather than Polymer 1 and does not include a plasticizer.
• the cells also include a layer of different thickness of Polymer 1 with a lithium salt and a plasticizer, but without ceramic on the surface of the cathode.
• Cathode The A7 ink prepared in Example 2 is applied with a doctor blade to the surface of an LFP cathode, as described in Example 3(a), so as to obtain after crosslinking a thickness of 40 ⁇ m. Once coated, the cathode is left under the extractor hood for 5 minutes then in an airtight box under nitrogen for 5 minutes and then cross-linked under UV for 10 minutes.
• the free surface of the polymer on the cathode is then applied to the polymeric surface of the second layer present on the anode.
• the resulting multilayer material is pressed together and sachet-like batteries are formed from this material.
• the C8 Cell is prepared as for the C7 Cell, applying a 30 ⁇ m layer on the cathode rather than 40 ⁇ m.
• Ink B5-a is also replaced by Ink B5-b resulting in a layer thickness of approximately 7-8 ⁇ m.
• the C9 Cell is prepared the same way as the C7 Cell, where a 20 ⁇ m layer on the cathode rather than 40 ⁇ m.
• Stack composition (items in order) a To. The composition of layers A7, A9 and B5(a and b) is defined in Example 2. b. LFP cathode composition defined in Example 3(a). vs. Ultra-thin layer (thickness not measured)
• Figures 15 to 17 present the electrochemical results obtained during the cycling of C7 to C9 cells in comparison with an LFP/polymer electrolyte/Li cell assembled with lithium without modification (reference).
• Figure 15(a) demonstrates that the C7 Cell is more stable during cycling than the reference cell. This aspect is all the more visible in Figure 15(c) where a marked drop in coulombic efficiency is observed around the 20th cycle for the reference cells, whereas this remains stable for the C7 cells.
• Figure 15(b) also demonstrates a higher average voltage for the C7 cells compared to the reference cells.
• Figures 16(a) and 16(b) show cycling stability and coulombic efficiency results for C8 cells that are relatively similar to those obtained for C7 cells.
• Figure 17 shows the capacity rate results obtained with C9 cells for 5 cycles at each of the cycling rates of C/6, C/4, C/3, C/2 and 1C.
• Example 5 Pretreated Electrodes with Modified Surface and Electrochemical Properties
• An organic, inorganic or metallic pretreatment of the surface of the metallic electrode film can also be carried out in order to form a pretreatment layer which may consist of the formation of a passivation layer, in the formation or the deposition of a compound, an organic or inorganic salt, or an alloy with a metal different from that of the electrode film.
• FIG. 18 shows the galvanostatic cycling obtained at 50°C in C/3 (a) and C/6 (b) for LFP/polymer electrolyte/Li batteries assembled with lithium without modification (reference), and with lithiums pretreated with (a) an inorganic molecule (PCh) and (b) a thin layer of metal (Zn). These lithiums have been shown to help stabilize cycling.
• the goal is to have cumulative effects with the layer of polymer + inorganic compound and possibly a second layer.
• FIG 19 shows photographs of lithium strips that received (a) treatment with PCh and (b) treatment with PCI3 followed by a deposit of polymer 1 + ALCh-polymer.
• the first deposit with PCh is very uniform and gives a light brown color (see Figure 19(a)).
• the integrity and quality of this first deposition are not affected by the deposition of the polymer layer 1 + Al2O3-polymer as shown in Figure 19(b).

Landscapes

• Chemical & Material Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Composite Materials (AREA)
• Physics & Mathematics (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• General Physics & Mathematics (AREA)
• Inorganic Chemistry (AREA)
• Battery Electrode And Active Subsutance (AREA)
• Secondary Cells (AREA)
• Cell Electrode Carriers And Collectors (AREA)

Priority Applications (6)

Applications Claiming Priority (2)

Publications (1)

Family

ID=85173697

Family Applications (1)

Country Status (7)

Families Citing this family (1)

Citations (9)

Family Cites Families (3)

• 2021
  • 2021-08-13 CA CA3128220A patent/CA3128220A1/fr active Pending
• 2022
  • 2022-08-12 WO PCT/CA2022/051231 patent/WO2023015396A1/fr not_active Ceased
  • 2022-08-12 EP EP22854839.2A patent/EP4385083A4/fr active Pending
  • 2022-08-12 CN CN202280055033.9A patent/CN117795705A/zh active Pending
  • 2022-08-12 US US18/681,918 patent/US20250226392A1/en active Pending
  • 2022-08-12 CA CA3228241A patent/CA3228241A1/fr active Pending
  • 2022-08-12 JP JP2024507907A patent/JP2024530037A/ja active Pending
  • 2022-08-12 KR KR1020247007106A patent/KR20240045252A/ko active Pending

Patent Citations (9)

Non-Patent Citations (5)

Also Published As

Similar Documents

Legal Events