EP4356453A2 - Method for preparing a solvent-free electrode and electrode formulations obtainable by said method - Google Patents
Method for preparing a solvent-free electrode and electrode formulations obtainable by said methodInfo
- Publication number
- EP4356453A2 EP4356453A2 EP22734280.5A EP22734280A EP4356453A2 EP 4356453 A2 EP4356453 A2 EP 4356453A2 EP 22734280 A EP22734280 A EP 22734280A EP 4356453 A2 EP4356453 A2 EP 4356453A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrode
- formulation
- fluoropolymer
- tpu
- binder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 55
- 238000009472 formulation Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 24
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 23
- 239000004811 fluoropolymer Substances 0.000 claims abstract description 22
- 238000001125 extrusion Methods 0.000 claims abstract description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 22
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 22
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 20
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229920000459 Nitrile rubber Polymers 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 6
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 5
- 238000006731 degradation reaction Methods 0.000 claims description 5
- 239000007772 electrode material Substances 0.000 claims description 5
- 229920001169 thermoplastic Polymers 0.000 claims description 5
- 239000004416 thermosoftening plastic Substances 0.000 claims description 5
- 239000004812 Fluorinated ethylene propylene Substances 0.000 claims description 4
- 229920001774 Perfluoroether Polymers 0.000 claims description 4
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 229920009441 perflouroethylene propylene Polymers 0.000 claims description 4
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 4
- 229920006344 thermoplastic copolyester Polymers 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 206010061592 cardiac fibrillation Diseases 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 230000002600 fibrillogenic effect Effects 0.000 claims description 3
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 3
- FPBWSPZHCJXUBL-UHFFFAOYSA-N 1-chloro-1-fluoroethene Chemical group FC(Cl)=C FPBWSPZHCJXUBL-UHFFFAOYSA-N 0.000 claims description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 claims description 2
- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical group C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 claims description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims 1
- 210000000352 storage cell Anatomy 0.000 abstract 1
- 239000011149 active material Substances 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 11
- 239000011148 porous material Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052796 boron Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 239000010955 niobium Substances 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- 229910052758 niobium Inorganic materials 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 7
- 229910052727 yttrium Inorganic materials 0.000 description 7
- 229910052726 zirconium Inorganic materials 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 238000010008 shearing Methods 0.000 description 5
- 229910052693 Europium Inorganic materials 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 229910052772 Samarium Inorganic materials 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 239000010432 diamond Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010902 jet-milling Methods 0.000 description 3
- 238000002459 porosimetry Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 229910010401 Li2Na2Ti6O14 Inorganic materials 0.000 description 2
- 229910007404 Li2Ti3O7 Inorganic materials 0.000 description 2
- 229910007848 Li2TiO3 Inorganic materials 0.000 description 2
- 229910011469 Li4/3Ti5/3O4 Inorganic materials 0.000 description 2
- 229910012616 LiTi2O4 Inorganic materials 0.000 description 2
- 229910014704 LixTi2O4 Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010379 TiNb2O7 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical class [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011262 electrochemically active material Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000013072 incoming material Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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
- H01M4/62—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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/0402—Methods of deposition of the material
- H01M4/0411—Methods of deposition of the material by extrusion
-
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—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 invention relates to the field of energy storage, and more specifically to accumulators, in particular of the lithium type.
- lithium accumulators The operation of lithium accumulators is based on the reversible exchange of lithium ion between a positive electrode and a negative electrode, separated by a separator containing an electrolyte, the lithium inserting itself into the negative electrode during charging operation .
- the electrodes consist of a metal strip on which is applied an electrode formulation consisting of active material and possibly binder and conductive element.
- WO 2015/161289 describes an electrode composition based on polytetrafluoroethylene (PTFE) and co-binder(s), obtained by fibrillation of PTFE by a high shear process such as air jet grinding (jet -milling) in particular.
- PTFE polytetrafluoroethylene
- co-binder(s) obtained by fibrillation of PTFE by a high shear process such as air jet grinding (jet -milling) in particular.
- PTFE has the particularity when sheared well to produce fibrils which form a network which contributes to the formation of porosities within the electrode.
- the jet-milling step may require batch work, which is incompatible with continuous industrial operation. Furthermore, grinding by jet-milling can damage the fragile active material (such as graphite for example).
- the present invention thus relates to a new solvent-free route for the improved preparation of electrode formulations, in particular intended for Li-ion technology.
- the present invention relates to a method for preparing an electrode formulation comprising:
- fluoropolymer refers to fluorinated polymers whose repeating unit is a fluorocarbon, comprising multiple carbon-fluorine bonds.
- fluoropolymers mention may in particular be made of polytetrafluoroethylene (PTFE) and its derivatives, in particular its co-polymers such as chlorofluoroethylene, perfluoroalkoxy (PFA), polychlorotrifluoroethylene (PCTFE or PTFCE), fluorinated ethylene propylene (FEP), ethylene tetrafluoroethylene or poly(ethylene-co-tetrafluoroethylene) (ETFE), tetrafluoroethylene perfluoromethylvinylether (MFA), more particularly PTFE.
- PTFE polytetrafluoroethylene
- PFA perfluoroalkoxy
- PCTFE or PTFCE polychlorotrifluoroethylene
- FEP fluorinated ethylene propylene
- ETFE ethylene tetrafluoroethylene
- said fluoropolymers are of the fibrillable type.
- fibrillable means the types of fluoropolymers which are capable of fibrillating, that is to say which can form a network of fibers in the mixture with the pre-mix, under the extrusion conditions.
- the types of fluoropolymers can be of different shapes and/or grades.
- Pre-mix means a preliminary composition prepared beforehand before adding one or more additional ingredients; in this case the pre-mix comprises the mixture of the fluoropolymer and the active material, and optionally a conductive element, before subsequent addition of the co-binder.
- the pre-mix can also include one or more optional additives such as lubricants.
- the pre-mix can also comprise particles of solid electrolyte.
- the active electrode material can be chosen from electrochemically active materials. It depends on the type of electrode (positive or negative) and the type of battery considered. Thus in the case of lithium batteries, the negative electrode active material is in particular graphite, silicon, lithium, a lithium alloy or a lithiophilic material, alone or as a mixture, such as mixed active materials SiOx / graphite .
- the expression “lithiophile” here defines a material having an affinity for lithium, (ie) its ability to form alloys with lithium, such as silicon, silver, zinc and magnesium.
- TNO titanium and niobium oxide
- active materials - a titanium and niobium oxide TNO having the formula: LixTia-yMyNbb-zM'zO((x+4a+5b)/2)-c-dXc where 0 ⁇ x ⁇ 5 ; 0 ⁇ y ⁇ 1; 0 ⁇ z ⁇ 2; 1 ⁇ a ⁇ 5; 1 ⁇ b ⁇ 25; 0.25 ⁇ a/b ⁇ 2; 0 ⁇ c ⁇ 2 and 0 ⁇ d ⁇ 2; ay >0; bz >0; M and M' each represent at least one element selected from the group consisting of Li, Na, K, Mg, Ca, B, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Y, Zr, Nb, Mo, Ru, Ag, Sn, Sb, Ta, W, Bi, La, Pr, Eu, Nd and Sm; X represents
- the subscript d represents an oxygen vacancy.
- the index d may be less than or equal to 0.5.
- Said at least one titanium and niobium oxide can be chosen from TiNb2O7, Ti2Nb2O9 and Ti 2 Nb 10 O 29 . - a lithiated titanium oxide or a titanium oxide capable of being lithiated.
- LTO is chosen from the following oxides: Li xa M a Ti yb M' b O 4-cd X c in which 0 ⁇ x ⁇ 3;1 ⁇ y ⁇ 2.5;0 ⁇ a ⁇ 1;0 ⁇ b ⁇ 1; 0 ⁇ c ⁇ 2 and - 2.5 ⁇ d ⁇ 2.5; M represents at least one element selected from the group consisting of Na, K, Mg, Ca, B, Mn, Fe, Co, Cr, Ni, Al, Cu, Ag, Pr, Y and La; M' represents at least one element selected from the group consisting of B, Mo, Mn, Ce, Sn, Zr, Si, W, V, Ta, Sb, Nb, Ru, Ag, Fe, Co, Ni, Zn, Al , Cr, La, Pr, Bi, Sc, Eu, Sm, Gd, Ti, Ce, Y and Eu; X represents at least one element selected from the group consisting of S, F, Cl and Br; The subscript d represents an oxygen deficiency.
- the index d may be less than or equal to 0.5;
- HxTiyO4 in which 0 ⁇ x ⁇ 1; 0 ⁇ y ⁇ 2, and a mixture of the compounds Lix-aMaTiy-bM'bO4-c-dXc and HxTiyO4.
- lithium titanium oxides are spinel Li4Ti5O12, Li2TiO3, ramsdellite Li2Ti3O7, LiTi2O4, LixTi2O4, with 0 ⁇ x ⁇ 2 and Li2Na2Ti6O14.
- a preferred LTO compound has the formula Li4-aMaTi5-bM'bO4, for example Li4Ti5O12 which is also written Li4/3Ti5/3O4.
- the active material of the positive electrode is not particularly limited.
- M' and M" being different from each other, and 1 ⁇ x ⁇ 1.4; 0 ⁇ y ⁇ 0.6; 0 ⁇ z ⁇ 0.2; - a compound (c) of formula Li x Fe 1-y M y PO 4 (LFMP) where M is chosen from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo; and 0.8 ⁇ x ⁇ 1.2; 0 ⁇ y ⁇ 0.6; - a compound (d) of formula Li x Mn 1-yz M' y M'' z PO 4 (LMP), where M' and M'' are different from each other and are chosen from the group consisting of in B, Mg, Al, Si, Ca, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo, with 0.8 ⁇ x ⁇ 1.2; 0 ⁇ y ⁇ 0.6; 0.0 ⁇ z ⁇ 0.2; - a compound (e) of formula xLi 2 M
- M represents at least one element chosen from the group consisting of Na, K, Mg, Ca, B, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Y, Zr, Nb, Mo, Ru, Ag, Sn, Sb, Ta, W, Bi, La, Pr, Eu, Nd and Sm and where 0 ⁇ x ⁇ 0.5 and 0 ⁇ y ⁇ 1;
- a conductive element can also be added for positive electrode preparation. It can be chosen from electronically conductive materials, such as graphite, carbon black, acetylene black, soot, graphene, carbon fibers, carbon nanotubes or a mixture thereof.
- the preparation of the pre-mix can be carried out by simple mixing of the constituents, typically in the form of powders, with stirring.
- the mixing step can advantageously be carried out at a temperature between 25°C and the degradation temperature of the fluoropolymer
- co-binder means a material which makes it possible to give the electrode the cohesion of the various components and its mechanical strength on the current collector, and/or to give a certain flexibility to the electrode. electrode for its implementation in the cell. More particularly, the co-binder according to the invention ensures the cohesion between the fluoropolymer and the active material.
- the co-binder is chosen from thermoplastic polyurethane (TPU), poly(styrene-butadiene-styrene) (SBS), poly(styrene-ethylene-butadiene-styrene) (SEBS), elastomers thermoplastics (TPE), vulcanized thermoplastics (TPV), thermoplastic copolyesters (TPC), polystyrene-b-poly(ethylene-butylene)-b-polystyrene (SEBS), butadiene-acrylonitrile copolymers also called “nitrile rubbers” (NBR ), hydrogenated butadiene-acrylonitrile copolymers, also called “hydrogenated nitrile rubbers” (HNBR), elastomers, thermoplastics or ethylene-acrylate terpolymers.
- TPU thermoplastic polyurethane
- SBS poly(styrene-butadiene-styrene)
- SEBS poly(s
- the co-binder is TPU.
- extrusion is meant a thermomechanical process according to which the formulation is forced to pass through a die, under the action of pressure and heat.
- the extrusion step can be adapted according to several parameters, such as the mixing temperature, the type of screw profile of the extruder, the type of die of the extruder, the rotation speed and/or the screw length.
- the extrusion can be carried out with a mono- or twin-screw type extruder, co-rotating or not.
- the screw profile used in the extruder is of the shearing type in order to cause the fluoropolymer to fibrillate in the extruder.
- the screw profile can contain one or more mixing zones. The number of mixing zones typically depends on the number of introduction zones. The position of the mixing zones in the extruder generally depends on the number of material introduction zones. After each material introduction zone, a mixing zone can be added.
- the type of screw element used to shear the material can be adapted to the type of active material contained in the pre-mix. If the active ingredient is sensitive to shearing, it is preferable to favor low or medium shearing elements. If the active material is not very sensitive to shearing, it is possible to use low, medium or high shearing elements.
- the rotational speed of the screw is generally the same throughout the screw. It is generally recommended to run it between 100rpm and 1000rpm, especially between 100 and 750 rpm.
- the speed of rotation of the screw is generally adapted according to the flow of material desired at the exit of the extruder. The lower the rotational speed of the screw, the lower the output flow rates. Note that low rotation speeds lead to longer residence times in the extruder. In such a case, if the material input flow is high, there may be a risk of clogging the extruder. In the case of a high screw rotation speed, the output flow rates can be fluctuating if the incoming material flow rates are too low.
- the extrusion step can advantageously be carried out at a temperature between 25° C. and the degradation temperature of the fluoropolymer, more particularly between the melting temperature of the co-binder and the melting temperature of the fluoropolymer under the extrusion conditions.
- the degradation and/or melting temperatures of the fluoropolymer under the extrusion conditions may be reduced due to the mechanical stresses exerted.
- the degradation temperature is approximately 350°C and the melting temperature is approximately 327°C, it being understood that due to the stresses exerted, the extrusion temperature is preferably lower or equal to 260°C.
- the present invention also relates to the electrode formulation capable of being obtained by the process according to the invention.
- the present invention also relates to an electrode formulation comprising:
- thermoplastic polyurethane TPU
- the fluoropolymer is as defined above.
- the aforementioned electrode formulations according to the invention may also comprise a conductive element. This is notably the case for the positive electrodes, as discussed above.
- the electrode formulations according to the invention may also comprise one or more additives chosen from lubricants such as oils or waxes or graphite.
- formulations according to the invention can also comprise a carbon additive.
- This additive is distributed in the electrode so as to form an electronic percolating network between the active material and the current collector.
- the carbonaceous additive can be comprised up to about 10% (by weight), in particular from 1 to 6% (weight) of the total content of the formulation.
- formulations according to the invention comprise (by weight):
- the electrode formulation according to the invention is suitable for positive or negative electrodes.
- negative electrode designates when the accumulator is discharging, the electrode functioning as an anode and when the accumulator is charging, the electrode functioning as a cathode, the anode being defined as the electrode where a electrochemical oxidation reaction (emission of electrons), while the cathode is the seat of reduction.
- negative electrode also designates the electrode from which the electrons leave, and from which the cations (Li+) are released in discharge.
- positive electrode designates the electrode where the electrons enter, and where the cations (Li+) arrive in discharge.
- the electrode formulation is porous, the porosity being imparted by the fluoropolymer fibrils generated by the extrusion.
- This porosity makes it possible in particular on the one hand to accommodate the lithium metal in the porosity of the negative electrode during charging, and on the other hand to maintain the mechanical strength of the electrode.
- the term "porous" means a pore size of less than 300 nm.
- the pore size corresponds to the structure of the material having an organized network of channels of variable very small pore size: typically a pore size of less than 1 ⁇ m, preferably less than 300 nm. This pore size gives the electrode a particularly large active surface per unit electrode surface.
- the electrode has a porosity of between 10 and 60%, preferably between 15 and 35%, the porosity representing the percentage of voids in the total volume of the formulation considered. Porosity can be measured by Hg porosimetry or by Helium porosimetry in general.
- the present invention also relates to an electrode comprising the electrode formulation according to the invention shaped.
- said electrode may consist of a conductive support used as a current collector which is coated with the formulation according to the shaped invention.
- current collector is meant an element such as a pad, plate, sheet or other, made of conductive material, connected to the positive or negative electrode, and ensuring the conduction of the flow of electrons between the electrode and the terminals of the battery.
- the current collector is preferably a two-dimensional conductive support such as a solid or perforated strip, based on metal, for example copper, nickel, steel, stainless steel or aluminum.
- Said electrode can in particular be a Li-ion type electrode.
- the latter advantageously consists of the formulation comprising PTFE, TPU and graphite shaped on a current collector such as a copper strip .
- the latter advantageously consists of the formulation comprising PTFE, TPU, an active positive electrode material, an electronically conductive element and a carbonaceous additive, shaped on a current collector such as aluminum foil.
- the electrodes according to the invention can be prepared by applying or adapting conventional methodologies for manufacturing electrodes.
- the formulation obtained at the end of the extrusion step is shaped, for example by pressing, to obtain a self-supporting formulation which will then be rolled by calendering, for example on the current collector.
- the present invention also relates to an electrochemical element comprising at least one electrode according to the invention.
- Electrochemical element means an elementary electrochemical cell made up of the positive electrode/electrolyte/negative electrode assembly, allowing the electrical energy supplied by a chemical reaction to be stored and returned in the form of current.
- the chemical elements according to the invention can be adapted to the different battery technologies and types of electrolytes.
- the electrochemical element can be of the lithium-ion type.
- Li-ion cells are based on the reversible exchange of lithium ion between a positive electrode and a negative electrode, separated by an electrolyte, the lithium being deposited at the negative electrode during charging operation.
- the positive electrode formulation comprises a lithiated transition metal oxide as active material and the negative electrode formulation comprises graphite as active material.
- the electrochemical element can also be of the “solid” or even “primary Li” type.
- solid designates elements with a solid electrolyte, such as oxides, halides, sulphides or a polymer.
- Li-primary refers to a non-rechargeable lithium cell.
- the present invention also relates to an electrochemical module comprising the stacking of at least two elements according to the invention, each element being electrically connected with one or more other element(s).
- module therefore designates here the assembly of several electrochemical elements, said assemblies possibly being in series and/or parallel.
- Another object of the invention is also a battery comprising one or more modules according to the invention.
- battery or accumulator is meant the assembly of several modules according to the invention.
- the batteries according to the invention are accumulators whose capacity is greater than 100 mAh, typically 1 to 100 Ah.
- Figure 1 represents the observation by SEM of the structure of an anode of 94% Graphite / 2% PTFE / 4% TPU formulation prepared according to the examples.
- Figure 2 represents the comparison of the pore size distribution for a reference anode (represented by circles) and for anodes according to the invention (varying in terms of their PTFE or TPU content) ( samples 1 , 2 and 3 represented by squares, diamonds and triangles, respectively)
- Figure 3 represents the comparison of the amount of porosity for a reference anode (round) and for anodes according to the invention (varying by their PTFE or TPU content) (samples 1, 2 and 3 : squares, diamonds and triangles, respectively).
- Electrode formulations according to the invention are prepared by producing a premix of the active material (graphite) and the fibrillable PTFE. Then the pre-mix is mixed with the binder (TPU) using a twin-screw extruder, at a temperature between 70 and 260° C. and at a speed of rotation between 100 and 750 rpm.
- the mixture recovered at the exit of the extruder is then transferred to a mixer with external rollers to manufacture a self-supporting electrode (or pressed under a press) and to shape the electrode. Adhesion on strip is then obtained by co-lamination (by calendering) on a current collector.
- the SEM image in Figure 1 shows that the PTFE fibrils are well distributed in the electrode. They form a network which contributes to the formation of porosities within the electrode.
- the porosity was measured by porosimetry Fig.
- the reference electrode was produced by the solvent route.
- the active material (the graphite), the binder (the SBR) and the co-binder (the CMC) all in the form of powder, are first mixed in a dry process using a planetary-type mixer.
- a solvent NMP
- NMP solvent
- the formulation of the reference electrode is composed of 97% active material, 1.5% binder and 1.5% co-binder.
- the pre-mix/solvent mass ratio when adding the solvent is 40/60.
- the reference electrode is represented by circles, and the invention formulations 1, 2 and 3 above are represented by squares, diamonds and triangles, respectively.
- Figure 2 illustrates the size distribution of the pores contained in the reference electrode and in the electrodes made via the present invention. Two populations of pores are observed. It appears that the size distribution of the pores contained in the electrodes made by the process described in this invention is in the range of the size of the pores of the reference electrode prepared in the standard way (solvent way). In addition, Figure 2 shows that by changing the amount of PTFE and co-binder (here TPU) in the specific formulation, it is possible to control and modulate the amount of porosity produced but also the average pore size of the electrode.
- Figure 3 shows the amount of porosity contained in the reference electrode prepared by the solvent route and in electrodes prepared according to the method presented in the present invention.
- the amount of porosity of the electrodes prepared according to the method presented depends on the formulation. Moreover, it is shown that it is possible to modulate the amount of porosity of the electrode by adjusting the formulation, namely the content of active material, binder and co-binder.
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Abstract
The present application relates to fluoropolymer-based, solvent-free electrode formulations obtained by extrusion and/or comprising one or more co-binders, including TPU. The application further relates to the electrodes containing said formulations and to the corresponding electrochemical elements and storage cells.
Description
DESCRIPTION DESCRIPTION
TITRE : PROCEDE DE PREPARATION D’ELECTRODE SANS SOLVANT ET LES FORMULATIONS D’ELECTRODES SUSCEPTIBLES D’ETRE OBTENUES PAR LEDITTITLE: SOLVENT-FREE ELECTRODE PREPARATION PROCESS AND THE ELECTRODE FORMULATIONS LIKELY TO BE OBTAINED BY SAID
PROCEDE PROCESS
La présente invention concerne le domaine du stockage de l’énergie, et plus précisément les accumulateurs, notamment de type lithium. The present invention relates to the field of energy storage, and more specifically to accumulators, in particular of the lithium type.
Le fonctionnement des accumulateurs au lithium est basé sur l’échange réversible de l’ion lithium entre une électrode positive et une électrode négative, séparées par un séparateur contenant un électrolyte, le lithium s’insérant dans l’électrode négative pendant le fonctionnement en charge. The operation of lithium accumulators is based on the reversible exchange of lithium ion between a positive electrode and a negative electrode, separated by a separator containing an electrolyte, the lithium inserting itself into the negative electrode during charging operation .
Typiquement, les électrodes sont constituées d’un feuillard métallique sur lequel est appliquée une formulation d’électrode constituée de matière active et éventuellement liant et élément conducteur. Typically, the electrodes consist of a metal strip on which is applied an electrode formulation consisting of active material and possibly binder and conductive element.
En raison de l’augmentation constante des besoins en énergie et batteries, il est nécessaire d’améliorer leur fabrication, pour en faciliter l’industrialisation, en diminuer les coûts et améliorer leur impact environnemental. Due to the constant increase in energy and battery needs, it is necessary to improve their manufacture, to facilitate their industrialization, reduce their costs and improve their environmental impact.
Actuellement, une part très importante du coût de fabrication d’une électrode est lié à son procédé de fabrication, notamment pour la technologie Li-ion. En effet, le solvant qui sert à préparer l’encre (à base de matière active, charges conductrices et de liant) qui sera enduite sur le feuillard pour concevoir l’électrode, doit être évaporé. Cette étape implique donc l’utilisation de fours énergivores. Currently, a very significant part of the manufacturing cost of an electrode is linked to its manufacturing process, particularly for Li-ion technology. Indeed, the solvent used to prepare the ink (based on active material, conductive fillers and binder) which will be coated on the strip to design the electrode, must be evaporated. This step therefore involves the use of energy-intensive ovens.
Il est par ailleurs désirable de limiter l’utilisation de solvants dans une démarche environnementale. It is also desirable to limit the use of solvents in an environmental approach.
Dans un souci d’élimination de ces solvants et de réduction des coûts de fabrication des électrodes, de nouveaux procédés dits sans solvant sont actuellement en développement.
Ainsi, WO 2015/161289 décrit une composition d’électrode à base de polytétrafluoroéthylène (PTFE) et de co-liant(s), obtenue par fibrillation du PTFE par un procédé à cisaillement élevé tel que le broyage par jet d’air (jet-milling) notamment. With a view to eliminating these solvents and reducing the manufacturing costs of the electrodes, new so-called solvent-free processes are currently under development. Thus, WO 2015/161289 describes an electrode composition based on polytetrafluoroethylene (PTFE) and co-binder(s), obtained by fibrillation of PTFE by a high shear process such as air jet grinding (jet -milling) in particular.
Le PTFE a la particularité lorsqu’il est bien cisaillé de fabriquer des fibrilles qui forment un réseau qui contribue à la formation de porosités au sein de l’électrode. PTFE has the particularity when sheared well to produce fibrils which form a network which contributes to the formation of porosities within the electrode.
Néanmoins, l’étape de jet-milling peut nécessiter un travail en batch, incompatible avec une exploitation industrielle en continu. Par ailleurs, le broyage par jet-milling peut endommager la matière active fragile (telle que le graphite par exemple). However, the jet-milling step may require batch work, which is incompatible with continuous industrial operation. Furthermore, grinding by jet-milling can damage the fragile active material (such as graphite for example).
Il est donc nécessaire de mettre à disposition un procédé plus adapté et/ou aisément industrialisable. It is therefore necessary to provide a more suitable and/or easily industrializable process.
La présente invention concerne ainsi une nouvelle voie sans solvant pour la préparation améliorée de formulations d’électrodes, notamment destinées à la technologie Li-ion. The present invention thus relates to a new solvent-free route for the improved preparation of electrode formulations, in particular intended for Li-ion technology.
Selon un premier objet, la présente invention concerne un procédé de préparation d’une formulation d’électrode comprenant : According to a first object, the present invention relates to a method for preparing an electrode formulation comprising:
- La préparation d’un pré-mix comprenant une matière active d’électrode et un fluoropolymère; - The preparation of a pre-mix comprising an active electrode material and a fluoropolymer;
- Le mélange du pré-mix avec un co-liant ; - Mixing the pre-mix with a co-binder;
- La fibrillation du mélange obtenu par extrusion. - The fibrillation of the mixture obtained by extrusion.
Le terme « fluoropolymère » tel qu’utilisé ici fait référence aux polymères fluorés dont le motif de répétition est un fluorocarbure, comprenant de multiples liaisons carbone-fluor. Parmi ces fluoropolymères, on peut notamment citer le polytétrafluoroéthylène (PTFE) et ses dérivés, notamment ses co-polymères tels que le chlorofluoroéthylène, le perfluoroalkoxy (PFA), le polychlorotrifluoroéthylène (PCTFE ou PTFCE), éthylène propylène fluoré (FEP), éthylène tétrafluoroéthylène ou poly(éthylène-co- tétrafluoroéthylène) (ETFE), tétrafluoroéthylène perfluoromethylvinyléther (MFA), plus particulièrement le PTFE. De préférence, lesdits fluoropolymères sont de type fibrillable. On entend par « fibrillable » les types de fluoropolymères qui sont susceptibles de fibriller, c’est-à-dire qui peuvent former un réseau de fibres dans le mélange avec le pré-mix, dans les conditions d’extrusion. Les types de fluoropolymères peuvent être de différentes formes et/ou grades.
On entend par « pré-mix » une composition préliminaire préalablement préparée avant ajout d’un ou plusieurs ingrédients additionnels ; en l’espèce le pré-mix comprend le mélange du fluoropolymère et de la matière active, et éventuellement un élément conducteur, avant ajout ultérieur du co-liant. Le pré-mix peut également comprendre un ou plusieurs additifs éventuels tels que les lubrifiants. Dans le cadre des batteries à électrolyte solide, le pré-mix peut également comprendre des particules d’électrolyte solide. La matière active d’électrode peut être choisie parmi les matériaux électrochimiquement actifs. Elle dépend du type d’électrode (positive ou négative) et du type de batterie considérée. Ainsi dans le cas des batteries au lithium, la matière active d’électrode négative est notamment le graphite, le silicium, le lithium, un alliage du lithium ou un matériau lithiophile, seuls ou en mélange, tel que les matières actives mixtes SiOx/graphite. L’expression « lithiophile » définissant ici un matériau présentant une affinité pour le lithium, (ie) sa capacité à former des alliages avec le lithium, tel que le silicium, l’argent, le zinc et le magnésium. On peut également citer les matières actives suivantes : - un oxyde de titane et de niobium TNO ayant pour formule : LixTia-yMyNbb-zM’zO((x+4a+5b)/2)-c-dXc où 0 ≤ x ≤ 5 ; 0 ≤ y ≤ 1 ; 0 ≤ z ≤ 2 ; 1 ≤ a ≤ 5 ; 1 ≤ b ≤ 25 ; 0,25 ≤ a/b ≤ 2 ; 0 ≤ c ≤ 2 et 0 ≤ d ≤ 2 ; a-y > 0 ; b-z > 0 ; M et M’ représentent chacun au moins un élément choisi dans le groupe constitué de Li, Na, K, Mg, Ca, B, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Y, Zr, Nb, Mo, Ru, Ag, Sn, Sb, Ta, W, Bi, La, Pr, Eu, Nd et Sm ; X représente au moins un élément choisi dans le groupe constitué de S, F, Cl et Br. L’indice d représente une lacune en oxygène. L’indice d peut être inférieur ou égal à 0,5. Ledit au moins un oxyde de titane et de niobium peut être choisi parmi TiNb2O7, Ti2Nb2O9 et Ti2Nb10O29. - un oxyde de titane lithié ou un oxyde de titane capable d’être lithié. LTO est choisi parmi les oxydes suivants : Lix-aMaTiy-bM’bO4-c-dXc dans lequel 0<x≤3 ; 1≤y≤2,5 ; 0≤a≤1 ; 0≤b≤1 ; 0≤c≤2 et - 2,5≤d≤2,5 ; M représente au moins un élément choisi dans le groupe constitué de Na, K, Mg, Ca, B, Mn, Fe, Co, Cr, Ni, Al, Cu, Ag, Pr, Y et La ;
M’ représente au moins un élément choisi dans le groupe constitué de B, Mo, Mn, Ce, Sn, Zr, Si, W, V, Ta, Sb, Nb, Ru, Ag, Fe, Co, Ni, Zn, Al, Cr, La, Pr, Bi, Sc, Eu, Sm, Gd, Ti, Ce, Y et Eu ; X représente au moins un élément choisi dans le groupe constitué de S, F, Cl et Br ; L’indice d représente une lacune en oxygène. L’indice d peut être inférieur ou égal à 0,5 ; Tels que Li4Ti5O12, Li2TiO3, la ramsdellite Li2Ti3O7, LiTi2O4, LixTi2O4, avec 0<x≤2 et Li2Na2Ti6O14, plus particulièrement Li4-aMaTi5-bM’bO4, par exemple Li4Ti5O12 (ou Li4/3Ti5/3O4). HxTiyO4 dans lequel 0≤x≤1 ; 0≤y≤2, et un mélange des composés Lix-aMaTiy-bM’bO4-c-dXc et HxTiyO4. Des exemples d’oxydes lithiés de titane sont la spinelle Li4Ti5O12, Li2TiO3, la ramsdellite Li2Ti3O7, LiTi2O4, LixTi2O4, avec 0<x≤2 et Li2Na2Ti6O14. Un composé LTO préféré a pour formule Li4-aMaTi5-bM’bO4, par exemple Li4Ti5O12 qui s’écrit encore Li4/3Ti5/3O4. Le matériau actif de l’électrode positive n’est pas particulièrement limité. Il peut être choisi dans les groupes suivants ou leurs mélanges : - un composé (a) de formule LixM1-y-z-wM’yM’’zM’’’wO2 (LMO2) où M, M’, M’’ et M’’’ sont choisis dans le groupe consistant en B, Mg, Al, Si, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, W et Mo à la condition qu'au moins M ou M’ ou M’’ ou M’’’ soit choisi parmi Mn, Co, Ni, ou Fe ; M, M’, M’’ et M’’’ étant différents les uns des autres; et 0,8≤x≤1,4 ; 0≤y≤0,5 ; 0≤z≤0,5 ; 0≤w≤0,2 et x+y+z+w<2,1 ; - un composé (b) de formule LixMn2-y-zM'yM''zO4 (LMO), où M' et M" sont choisis dans le groupe consistant en B, Mg, Al, Si, Ca, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb et Mo ;. M' et M" étant différents l’un de l’autre, et 1≤x≤1,4 ; 0≤y≤0,6 ; 0≤z≤0,2 ; - un composé (c) de formule LixFe1-yMyPO4 (LFMP) où M est choisi dans le groupe consistant en B, Mg, Al, Si, Ca, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Y, Zr, Nb et Mo; et 0,8≤x≤1,2 ; 0≤y≤0,6 ; - un composé (d) de formule LixMn1-y-zM’yM’’zPO4 (LMP), où M’ et M’’ sont différents l’un de l’autre et sont choisis dans le groupe consistant en B, Mg, Al, Si, Ca, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb et Mo, avec 0,8≤x≤1,2 ; 0≤y≤0,6 ; 0,0≤z≤0,2 ; - un composé (e) de formule xLi2MnO3; (1-x)LiMO2 où M est au moins un élément choisi parmi Ni, Co et Mn et x≤1.
- un composé (f) de formule Lii+xM02-yFy de structure cubique où M représente au moins un élément choisi dans le groupe constitué de Na, K, Mg, Ca, B, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Y, Zr, Nb, Mo, Ru, Ag, Sn, Sb, Ta, W, Bi, La, Pr, Eu, Nd et Sm et où 0 < x < 0,5 et 0 < y < 1 ; The term "fluoropolymer" as used herein refers to fluorinated polymers whose repeating unit is a fluorocarbon, comprising multiple carbon-fluorine bonds. Among these fluoropolymers, mention may in particular be made of polytetrafluoroethylene (PTFE) and its derivatives, in particular its co-polymers such as chlorofluoroethylene, perfluoroalkoxy (PFA), polychlorotrifluoroethylene (PCTFE or PTFCE), fluorinated ethylene propylene (FEP), ethylene tetrafluoroethylene or poly(ethylene-co-tetrafluoroethylene) (ETFE), tetrafluoroethylene perfluoromethylvinylether (MFA), more particularly PTFE. Preferably, said fluoropolymers are of the fibrillable type. The term "fibrillable" means the types of fluoropolymers which are capable of fibrillating, that is to say which can form a network of fibers in the mixture with the pre-mix, under the extrusion conditions. The types of fluoropolymers can be of different shapes and/or grades. “Pre-mix” means a preliminary composition prepared beforehand before adding one or more additional ingredients; in this case the pre-mix comprises the mixture of the fluoropolymer and the active material, and optionally a conductive element, before subsequent addition of the co-binder. The pre-mix can also include one or more optional additives such as lubricants. In the context of solid electrolyte batteries, the pre-mix can also comprise particles of solid electrolyte. The active electrode material can be chosen from electrochemically active materials. It depends on the type of electrode (positive or negative) and the type of battery considered. Thus in the case of lithium batteries, the negative electrode active material is in particular graphite, silicon, lithium, a lithium alloy or a lithiophilic material, alone or as a mixture, such as mixed active materials SiOx / graphite . The expression “lithiophile” here defines a material having an affinity for lithium, (ie) its ability to form alloys with lithium, such as silicon, silver, zinc and magnesium. Mention may also be made of the following active materials: - a titanium and niobium oxide TNO having the formula: LixTia-yMyNbb-zM'zO((x+4a+5b)/2)-c-dXc where 0 ≤ x ≤ 5 ; 0 ≤ y ≤ 1; 0 ≤ z ≤ 2; 1 ≤ a ≤ 5; 1 ≤ b ≤ 25; 0.25≤a/b≤2; 0 ≤ c ≤ 2 and 0 ≤ d ≤ 2; ay >0; bz >0; M and M' each represent at least one element selected from the group consisting of Li, Na, K, Mg, Ca, B, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Y, Zr, Nb, Mo, Ru, Ag, Sn, Sb, Ta, W, Bi, La, Pr, Eu, Nd and Sm; X represents at least one element selected from the group consisting of S, F, Cl and Br. The subscript d represents an oxygen vacancy. The index d may be less than or equal to 0.5. Said at least one titanium and niobium oxide can be chosen from TiNb2O7, Ti2Nb2O9 and Ti 2 Nb 10 O 29 . - a lithiated titanium oxide or a titanium oxide capable of being lithiated. LTO is chosen from the following oxides: Li xa M a Ti yb M' b O 4-cd X c in which 0<x≤3;1≤y≤2.5;0≤a≤1;0≤b≤1; 0≤c≤2 and - 2.5≤d≤2.5; M represents at least one element selected from the group consisting of Na, K, Mg, Ca, B, Mn, Fe, Co, Cr, Ni, Al, Cu, Ag, Pr, Y and La; M' represents at least one element selected from the group consisting of B, Mo, Mn, Ce, Sn, Zr, Si, W, V, Ta, Sb, Nb, Ru, Ag, Fe, Co, Ni, Zn, Al , Cr, La, Pr, Bi, Sc, Eu, Sm, Gd, Ti, Ce, Y and Eu; X represents at least one element selected from the group consisting of S, F, Cl and Br; The subscript d represents an oxygen deficiency. The index d may be less than or equal to 0.5; Such as Li4Ti5O12, Li2TiO3, ramsdellite Li2Ti3O7, LiTi2O4, LixTi2O4, with 0<x≤2 and Li2Na2Ti6O14, more particularly Li4-aMaTi5-bM'bO4, for example Li4Ti5O12 (or Li4/3Ti5/3O4). HxTiyO4 in which 0≤x≤1; 0≤y≤2, and a mixture of the compounds Lix-aMaTiy-bM'bO4-c-dXc and HxTiyO4. Examples of lithium titanium oxides are spinel Li4Ti5O12, Li2TiO3, ramsdellite Li2Ti3O7, LiTi2O4, LixTi2O4, with 0<x≤2 and Li2Na2Ti6O14. A preferred LTO compound has the formula Li4-aMaTi5-bM'bO4, for example Li4Ti5O12 which is also written Li4/3Ti5/3O4. The active material of the positive electrode is not particularly limited. It may be chosen from the following groups or mixtures thereof: - a compound (a) of formula LixM1-yz-wM'yM''zM'''wO2 (LMO2) where M, M', M'' and M''' are selected from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, W and Mo with the proviso that at least M or M' or M'' or M''' is chosen from Mn, Co, Ni or Fe; M, M', M'' and M''' being different from each other; and 0.8≤x≤1.4; 0≤y≤0.5; 0≤z≤0.5; 0≤w≤0.2 and x+y+z+w<2.1; - a compound (b) of formula Li x Mn 2-yz M' y M'' z O 4 (LMO), where M' and M" are chosen from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo;. M' and M" being different from each other, and 1≤x≤1.4; 0≤y≤0.6; 0≤z≤0.2; - a compound (c) of formula Li x Fe 1-y M y PO 4 (LFMP) where M is chosen from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo; and 0.8≤x≤1.2; 0≤y≤0.6; - a compound (d) of formula Li x Mn 1-yz M' y M'' z PO 4 (LMP), where M' and M'' are different from each other and are chosen from the group consisting of in B, Mg, Al, Si, Ca, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo, with 0.8≤x≤1.2; 0≤y≤0.6; 0.0≤z≤0.2; - a compound (e) of formula xLi 2 MnO 3 ; (1-x)LiMO 2 where M is at least one element chosen from Ni, Co and Mn and x≤1. - a compound (f) of formula Lii +x M0 2 -yF y of cubic structure where M represents at least one element chosen from the group consisting of Na, K, Mg, Ca, B, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Y, Zr, Nb, Mo, Ru, Ag, Sn, Sb, Ta, W, Bi, La, Pr, Eu, Nd and Sm and where 0 < x < 0.5 and 0 < y <1;
Un élément conducteur peut également être ajouté pour la préparation d’électrode positive. Il peut être choisi parmi les matériaux conducteurs électroniquement, tels que le graphite, le noir de carbone, le noir d'acétylène, la suie, le graphène, les fibres de carbone, les nanotubes de carbone ou un mélange de ceux-ci. A conductive element can also be added for positive electrode preparation. It can be chosen from electronically conductive materials, such as graphite, carbon black, acetylene black, soot, graphene, carbon fibers, carbon nanotubes or a mixture thereof.
La préparation du pré-mix peut être réalisée par simple mélange des constituants, typiquement sous forme de poudres, sous agitation. The preparation of the pre-mix can be carried out by simple mixing of the constituents, typically in the form of powders, with stirring.
L’étape de mélange peut être avantageusement réalisée à température comprise entre 25°C et la température de dégradation du fluoropolymère, The mixing step can advantageously be carried out at a temperature between 25°C and the degradation temperature of the fluoropolymer,
On entend par «co-liant » (aussi appelé « cobinder »), un matériau permettant de conférer à l'électrode la cohésion des différents composants et sa tenue mécanique sur le collecteur de courant, et/ou de conférer une certaine flexibilité à l'électrode pour sa mise en œuvre en cellule. Plus particulièrement, le co-liant selon l’invention assure la cohésion entre le fluoropolymère et la matière active. The term "co-binder" (also called "cobinder") means a material which makes it possible to give the electrode the cohesion of the various components and its mechanical strength on the current collector, and/or to give a certain flexibility to the electrode. electrode for its implementation in the cell. More particularly, the co-binder according to the invention ensures the cohesion between the fluoropolymer and the active material.
Selon un mode de réalisation, le co-liant est choisi parmi le polyuréthane thermoplastique (TPU), le poly(styrène-butadiène-styrène) (SBS), le poly(styrène-éthylène- butadiène-styrène) (SEBS), les élastomères thermoplastiques (TPE), thermoplastiques vulcanisés (TPV), les copolyesters thermoplastiques (TPC), polystyrène-b-poly(éthylène- butylène)-b-polystyrène (SEBS), les copolymères de butadiène-acrylonitrile aussi appelés « caoutchoucs nitrile » (NBR), les copolymères de butadiène-acrylonitrile hydrogénés, aussi appelés « caoutchoucs nitrile hydrogénés » (HNBR), les élastomères, les thermoplastiques ou les terpolymères éthylène-acrylate. According to one embodiment, the co-binder is chosen from thermoplastic polyurethane (TPU), poly(styrene-butadiene-styrene) (SBS), poly(styrene-ethylene-butadiene-styrene) (SEBS), elastomers thermoplastics (TPE), vulcanized thermoplastics (TPV), thermoplastic copolyesters (TPC), polystyrene-b-poly(ethylene-butylene)-b-polystyrene (SEBS), butadiene-acrylonitrile copolymers also called “nitrile rubbers” (NBR ), hydrogenated butadiene-acrylonitrile copolymers, also called “hydrogenated nitrile rubbers” (HNBR), elastomers, thermoplastics or ethylene-acrylate terpolymers.
Plus particulièrement, le co-liant est le TPU. More particularly, the co-binder is TPU.
On entend par « extrusion » un procédé thermomécanique selon lequel la formulation est contrainte de traverser une filière, sous l’action de la pression et de la chaleur.
L’étape d’extrusion peut être adaptée en fonction de plusieurs paramètres, tels que la température de mélange, le type de profil de vis de l’extrudeuse, le type de filière de l’extrudeuse, la vitesse de rotation et/ou la longueur des vis. By “extrusion” is meant a thermomechanical process according to which the formulation is forced to pass through a die, under the action of pressure and heat. The extrusion step can be adapted according to several parameters, such as the mixing temperature, the type of screw profile of the extruder, the type of die of the extruder, the rotation speed and/or the screw length.
Selon un mode de réalisation, l’extrusion peut être réalisée avec une extrudeuse de type mono- ou bi-vis, corotative ou non. According to one embodiment, the extrusion can be carried out with a mono- or twin-screw type extruder, co-rotating or not.
Selon un mode de réalisation, le profil de vis utilisé dans l’extrudeuse est de type cisaillant afin de faire fibriller le fluoropolymère dans l’extrudeuse. Le profil de vis peut contenir une ou plusieurs zones de mélange. Le nombre de zones de mélange dépend typiquement du nombre de zones d’introduction. La position des zones de mélange dans l’extrudeuse dépend généralement du nombre de zones d’introduction de matière. Après chaque zone d’introduction de matière, une zone de mélange peut être ajoutée. According to one embodiment, the screw profile used in the extruder is of the shearing type in order to cause the fluoropolymer to fibrillate in the extruder. The screw profile can contain one or more mixing zones. The number of mixing zones typically depends on the number of introduction zones. The position of the mixing zones in the extruder generally depends on the number of material introduction zones. After each material introduction zone, a mixing zone can be added.
Typiquement, le type d’élément de vis permettant de cisailler la matière peut être adapté au type de matière active contenue dans le pré-mix. Si la matière active est sensible au cisaillement, il est préférable de privilégier des éléments peu ou moyennement cisaillants. Si la matière active est peu sensible au cisaillement, il est possible d’utiliser des éléments peu, moyennement ou fortement cisaillants. Typically, the type of screw element used to shear the material can be adapted to the type of active material contained in the pre-mix. If the active ingredient is sensitive to shearing, it is preferable to favor low or medium shearing elements. If the active material is not very sensitive to shearing, it is possible to use low, medium or high shearing elements.
La vitesse de rotation de la vis est généralement la même sur toute la vis. Il est généralement recommandé de la faire tourner entre 100rpm et 1000rpm, notamment entre 100 et 750 rpm. La vitesse de rotation de la vis est généralement adaptée en fonction du débit de matière désiré en sortie d’extrudeuse. Plus la vitesse de rotation de la vis est faible, plus les débits de sortie seront faibles. A noter que les vitesses de rotation faibles entraînent des temps de résidence dans l’extrudeuse plus longs. Dans tel cas, si le débit d’entrée de matière est important un risque de boucher l’extrudeuse peut apparaître. Dans le cas d’une vitesse de rotation de vis importante, les débits de sortie peuvent être fluctuants si les débits de matière entrant sont trop faibles. The rotational speed of the screw is generally the same throughout the screw. It is generally recommended to run it between 100rpm and 1000rpm, especially between 100 and 750 rpm. The speed of rotation of the screw is generally adapted according to the flow of material desired at the exit of the extruder. The lower the rotational speed of the screw, the lower the output flow rates. Note that low rotation speeds lead to longer residence times in the extruder. In such a case, if the material input flow is high, there may be a risk of clogging the extruder. In the case of a high screw rotation speed, the output flow rates can be fluctuating if the incoming material flow rates are too low.
L’étape d’extrusion peut être avantageusement réalisée à température comprise entre 25°C et la température de dégradation du fluoropolymère, plus particulièrement entre la température de fusion du co-liant et la température de fusion du fluoropolymère dans les conditions de l’extrusion, étant entendu que les températures de dégradation et/ou fusion du fluoropolymère dans les conditions de l’extrusion peuvent être diminuées en raison des contraintes mécaniques exercées. A titre illustratif, pour le PTFE, la température de dégradation est d’environ 350°C et la température de fusion est de environ 327°C, étant entendu que du fait des contraintes exercées, la température d’extrusion est de préférence inférieure ou égale à 260°C.
Selon un autre objet, la présente invention concerne également la formulation d’électrode susceptible d’être obtenue par le procédé selon l’invention. The extrusion step can advantageously be carried out at a temperature between 25° C. and the degradation temperature of the fluoropolymer, more particularly between the melting temperature of the co-binder and the melting temperature of the fluoropolymer under the extrusion conditions. , it being understood that the degradation and/or melting temperatures of the fluoropolymer under the extrusion conditions may be reduced due to the mechanical stresses exerted. By way of illustration, for PTFE, the degradation temperature is approximately 350°C and the melting temperature is approximately 327°C, it being understood that due to the stresses exerted, the extrusion temperature is preferably lower or equal to 260°C. According to another object, the present invention also relates to the electrode formulation capable of being obtained by the process according to the invention.
Selon un autre objet, la présente invention vise également une formulation d’électrode comprenant : According to another object, the present invention also relates to an electrode formulation comprising:
- une matière active d’électrode ; - an active electrode material;
- un fluoropolymère; - a fluoropolymer;
- le polyuréthane thermoplastique (TPU) à titre de co-liant. - thermoplastic polyurethane (TPU) as a co-binder.
Le fluoropolymère est tel que défini ci-avant. The fluoropolymer is as defined above.
Selon un mode de réalisation, les formulations d’électrode précitées selon l’invention peuvent en outre comprendre un élément conducteur. Ceci est notamment le cas pour les électrodes positives, tel que discuté ci-avant. According to one embodiment, the aforementioned electrode formulations according to the invention may also comprise a conductive element. This is notably the case for the positive electrodes, as discussed above.
Selon un mode de réalisation, les formulations d’électrode selon l’invention peuvent en outre comprendre un ou plusieurs additifs choisis parmi les lubrifiants tel que les huiles ou les cires ou le graphite. According to one embodiment, the electrode formulations according to the invention may also comprise one or more additives chosen from lubricants such as oils or waxes or graphite.
De plus, les formulations selon l’invention peuvent également comprendre un additif carboné. Cet additif est réparti dans l’électrode de manière à former un réseau percolant électronique entre le matériau actif et le collecteur de courant. In addition, the formulations according to the invention can also comprise a carbon additive. This additive is distributed in the electrode so as to form an electronic percolating network between the active material and the current collector.
Lorsqu’il est présent, l’additif carboné peut être compris jusqu’à environ 10% (en poids), notamment de 1 à 6% (poids) de la teneur totale de la formulation. When it is present, the carbonaceous additive can be comprised up to about 10% (by weight), in particular from 1 to 6% (weight) of the total content of the formulation.
Ainsi, selon un mode de réalisation, les formulations selon l’invention comprennent (en poids) : Thus, according to one embodiment, the formulations according to the invention comprise (by weight):
De 80 à 98,5 % de matière active ; From 80 to 98.5% active ingredient;
- De 0.1 à 5 % de PTFE ; - From 0.1 to 5% PTFE;
- De 0.1 à 5 % de TPU ; - From 0.1 to 5% TPU;
De 0 à 5% de lubrifiant ; et From 0 to 5% lubricant; and
De 0 à 10% de carbone percolant. From 0 to 10% percolating carbon.
La formulation d’électrode selon l’invention convient aux électrodes positives ou négatives.
Le terme « électrode négative » désigne lorsque l'accumulateur est en décharge, l'électrode fonctionnant en anode et lorsque l'accumulateur est en charge, l'électrode fonctionnant en cathode, l’anode étant définie comme l’électrode où a lieu une réaction électrochimique d'oxydation (émission d'électrons), tandis que la cathode est le siège de la réduction. Le terme électrode négative désigne également l’électrode d’où partent les électrons, et d’où sont libérés les cations (Li+) en décharge. The electrode formulation according to the invention is suitable for positive or negative electrodes. The term "negative electrode" designates when the accumulator is discharging, the electrode functioning as an anode and when the accumulator is charging, the electrode functioning as a cathode, the anode being defined as the electrode where a electrochemical oxidation reaction (emission of electrons), while the cathode is the seat of reduction. The term negative electrode also designates the electrode from which the electrons leave, and from which the cations (Li+) are released in discharge.
Le terme « électrode positive » désigne l’électrode où entrent les électrons, et où arrivent les cations (Li+) en décharge. The term "positive electrode" designates the electrode where the electrons enter, and where the cations (Li+) arrive in discharge.
Selon l’invention, la formulation d’électrode est poreuse, la porosité étant conférée par les fibrilles de fluoropolymère générées par l’extrusion. Cette porosité permet notamment d’une part d’accueillir le lithium métal dans la porosité de l’électrode négative lors de la charge, et d’autre part de maintenir une tenue mécanique de l’électrode. According to the invention, the electrode formulation is porous, the porosity being imparted by the fluoropolymer fibrils generated by the extrusion. This porosity makes it possible in particular on the one hand to accommodate the lithium metal in the porosity of the negative electrode during charging, and on the other hand to maintain the mechanical strength of the electrode.
On entend ici par « poreux » selon l’invention une taille de pores inférieure à 300 nm. La taille de pores correspond à la structure du matériau présentant un réseau organisé de canaux de taille de pore très petite variable : typiquement une taille de pores inférieure à 1 pm, préférentiellement inférieure à 300 nm. Cette taille de pores confère à l’électrode une surface active par unité de surface d’électrode particulièrement grande. Here, the term "porous" according to the invention means a pore size of less than 300 nm. The pore size corresponds to the structure of the material having an organized network of channels of variable very small pore size: typically a pore size of less than 1 μm, preferably less than 300 nm. This pore size gives the electrode a particularly large active surface per unit electrode surface.
Selon un mode de réalisation, l’électrode présente une porosité comprise entre 10 et 60%, préférentiellement, entre 15 et 35%, la porosité représentant le pourcentage des vides dans le volume total de la formulation considérée. La porosité peut être mesurée par porosimétrie Hg ou par porosimétrie Hélium en général. According to one embodiment, the electrode has a porosity of between 10 and 60%, preferably between 15 and 35%, the porosity representing the percentage of voids in the total volume of the formulation considered. Porosity can be measured by Hg porosimetry or by Helium porosimetry in general.
Selon un autre objet, la présente invention vise encore une électrode comprenant la formulation d’électrode selon l’invention mise en forme. According to another object, the present invention also relates to an electrode comprising the electrode formulation according to the invention shaped.
Selon un mode de réalisation, ladite électrode peut être constituée d’un support conducteur utilisé comme collecteur de courant qui est revêtu de la formulation selon l’invention mise en forme. According to one embodiment, said electrode may consist of a conductive support used as a current collector which is coated with the formulation according to the shaped invention.
On entend par collecteur de courant un élément tel que plot, plaque, feuille ou autre, en matériau conducteur, relié à l’électrode positive ou négative, et assurant la conduction du flux d’électrons entre l’électrode et les bornes de la batterie.
Le collecteur de courant est de préférence un support conducteur bidimensionnel tel qu'un feuillard plein ou perforé, à base de métal, par exemple en cuivre, en nickel, en acier, en acier inoxydable ou en aluminium. By current collector is meant an element such as a pad, plate, sheet or other, made of conductive material, connected to the positive or negative electrode, and ensuring the conduction of the flow of electrons between the electrode and the terminals of the battery. . The current collector is preferably a two-dimensional conductive support such as a solid or perforated strip, based on metal, for example copper, nickel, steel, stainless steel or aluminum.
Ladite électrode peut notamment être une électrode de type Li-ion. Said electrode can in particular be a Li-ion type electrode.
Lorsqu’il s’agit d’une électrode négative de type Li-ion, celle-ci est constituée avantageusement de la formulation comprenant du PTFE, du TPU et du graphite mise en forme sur un collecteur de courant tel qu’un feuillard de cuivre. When it is a negative electrode of the Li-ion type, the latter advantageously consists of the formulation comprising PTFE, TPU and graphite shaped on a current collector such as a copper strip .
Lorsqu’il s’agit d’une électrode positive, celle-ci est constituée avantageusement de la formulation comprenant du PTFE, du TPU, un matériau actif d’électrode positive, un élément conducteur électroniquement et un additif carboné, mise en forme sur un collecteur de courant tel qu’un feuillard d’aluminium. When it is a positive electrode, the latter advantageously consists of the formulation comprising PTFE, TPU, an active positive electrode material, an electronically conductive element and a carbonaceous additive, shaped on a current collector such as aluminum foil.
Les électrodes selon l’invention peuvent être préparées par application ou adaptation des méthodologies classiques de fabrication d’électrodes. The electrodes according to the invention can be prepared by applying or adapting conventional methodologies for manufacturing electrodes.
Ainsi typiquement, la formulation obtenue à l’issue de l’étape d’extrusion est mise en forme par exemple par pressage, pour obtenir une formulation autosupportée qui sera ensuite laminée par calandrage par exemple sur le collecteur de courant. Thus typically, the formulation obtained at the end of the extrusion step is shaped, for example by pressing, to obtain a self-supporting formulation which will then be rolled by calendering, for example on the current collector.
Selon un autre objet, la présente invention concerne également un élément électrochimique comprenant au moins une électrode selon l’invention. According to another object, the present invention also relates to an electrochemical element comprising at least one electrode according to the invention.
On entend par « élément électrochimique » une cellule électrochimique élémentaire constituée de l’assemblage électrode positive/électrolyte/électrode négative, permettant d’emmagasiner l’énergie électrique fournie par une réaction chimique et de la restituer sous forme de courant. “Electrochemical element” means an elementary electrochemical cell made up of the positive electrode/electrolyte/negative electrode assembly, allowing the electrical energy supplied by a chemical reaction to be stored and returned in the form of current.
Les éléments chimiques selon l’invention peuvent être adaptés aux différentes technologies de batterie et types d’électrolytes. The chemical elements according to the invention can be adapted to the different battery technologies and types of electrolytes.
Ainsi selon un mode de réalisation, l’élément électrochimique peut être de type Lithium-ion. Thus according to one embodiment, the electrochemical element can be of the lithium-ion type.
Les éléments Li-ion sont basés sur l’échange réversible de l’ion lithium entre une électrode positive et une électrode négative, séparées par un électrolyte, le lithium se déposant à l’électrode négative pendant le fonctionnement en charge. Typiquement, pour ces accumulateurs, la formulation d’électrode positive comprend un oxyde de métal de transition lithié à titre de matière active et la formulation d’électrode négative comprend du graphite à titre de matière active.
Selon un mode de réalisation, l’élément électrochimique peut également être de type «solide » ou encore « Li primaire ». Li-ion cells are based on the reversible exchange of lithium ion between a positive electrode and a negative electrode, separated by an electrolyte, the lithium being deposited at the negative electrode during charging operation. Typically, for these accumulators, the positive electrode formulation comprises a lithiated transition metal oxide as active material and the negative electrode formulation comprises graphite as active material. According to one embodiment, the electrochemical element can also be of the “solid” or even “primary Li” type.
Le terme « solide » désigne les éléments à électrolyte solide, tel que les oxydes, halogénures, sulfures ou un polymère. The term “solid” designates elements with a solid electrolyte, such as oxides, halides, sulphides or a polymer.
Le terme « Li-primaire » désigne un élément au lithium non rechargeable. The term "Li-primary" refers to a non-rechargeable lithium cell.
Selon un autre objet, la présente invention concerne également un module électrochimique comprenant l’empilement d’au moins deux éléments selon l’invention, chaque élément étant connecté électriquement avec un ou plusieurs autre(s) élément(s). Le terme « module » désigne donc ici l’assemblage de plusieurs éléments électrochimiques, lesdits assemblages pouvant être en série et/ou parallèle. According to another object, the present invention also relates to an electrochemical module comprising the stacking of at least two elements according to the invention, each element being electrically connected with one or more other element(s). The term “module” therefore designates here the assembly of several electrochemical elements, said assemblies possibly being in series and/or parallel.
Un autre objet de l’invention est encore une batterie comprenant un ou plusieurs modules selon l’invention. Another object of the invention is also a battery comprising one or more modules according to the invention.
On entend par « batterie » ou accumulateur, l’assemblage de plusieurs modules selon l’invention. By “battery” or accumulator is meant the assembly of several modules according to the invention.
Selon un mode de réalisation, les batteries selon l’invention sont des accumulateurs dont la capacité est supérieure à 100 mAh, typiquement 1 à 100Ah. According to one embodiment, the batteries according to the invention are accumulators whose capacity is greater than 100 mAh, typically 1 to 100 Ah.
Figures tricks
[Fig 1] La Figure 1 représente l’observation par MEB de la structure d’une anode de formulation 94%Graphite / 2%PTFE / 4%TPU préparée selon les exemples. [Fig 1] Figure 1 represents the observation by SEM of the structure of an anode of 94% Graphite / 2% PTFE / 4% TPU formulation prepared according to the examples.
[Fig 2] La Figure 2 représente la comparaison de la distribution de la taille des pores pour une anode de référence (représentée par des ronds) et pour des anodes selon l’invention (variant de par leur teneur en PTFE ou en TPU) (échantillons 1 , 2 et 3 représentés par des carrés, losanges et triangles, respectivement) [Fig 2] Figure 2 represents the comparison of the pore size distribution for a reference anode (represented by circles) and for anodes according to the invention (varying in terms of their PTFE or TPU content) ( samples 1 , 2 and 3 represented by squares, diamonds and triangles, respectively)
[Fig 3] La Figure 3 représente la comparaison de la quantité de porosité pour une anode de référence (ronds) et pour des anodes selon l’invention (variant de par leur teneur en PTFE ou en TPU) (échantillons 1 , 2 et 3 : carrés, losanges et triangles, respectivement). [Fig 3] Figure 3 represents the comparison of the amount of porosity for a reference anode (round) and for anodes according to the invention (varying by their PTFE or TPU content) (samples 1, 2 and 3 : squares, diamonds and triangles, respectively).
Exemples Examples
1 . Préparation des électrodes
Des formulations d’électrode selon l’invention sont préparées en réalisant un pré-mélange de la matière active (graphite) et du PTFE fibrillable. Puis le pré-mix est mélangé au coliant (TPU) à l’aide d’une extrudeuse bi-vis, à température comprise entre 70 et 260°C et à une vitesse de rotation comprise entre 100 et 750 rpm. 1 . Preparation of the electrodes Electrode formulations according to the invention are prepared by producing a premix of the active material (graphite) and the fibrillable PTFE. Then the pre-mix is mixed with the binder (TPU) using a twin-screw extruder, at a temperature between 70 and 260° C. and at a speed of rotation between 100 and 750 rpm.
Les formulations suivantes ont été préparées : The following formulations were prepared:
[Table 1]
[Table 1]
Le mélange récupéré en sortie de l’extrudeuse est ensuite transféré dans un mélangeur à rouleaux externes pour fabriquer une électrode autosupportée (ou pressé sous une presse) et pour mise en forme de l’électrode. L’adhésion sur feuillard est ensuite obtenue par colamination (par calandrage) sur un collecteur de courant. The mixture recovered at the exit of the extruder is then transferred to a mixer with external rollers to manufacture a self-supporting electrode (or pressed under a press) and to shape the electrode. Adhesion on strip is then obtained by co-lamination (by calendering) on a current collector.
L’image MEB de la Figure 1 montre que les fibrilles de PTFE sont bien réparties dans l’électrode. Elles forment un réseau qui contribue à la formation de porosités au sein de l’électrode. The SEM image in Figure 1 shows that the PTFE fibrils are well distributed in the electrode. They form a network which contributes to the formation of porosities within the electrode.
2. Caractérisation des électrodes 2.1 La porosité des électrodes obtenues selon l’exemple 1 a été analysée pour les différentes compositions, et comparée à celle d’une électrode de référence. 2. Characterization of the electrodes 2.1 The porosity of the electrodes obtained according to example 1 was analyzed for the different compositions, and compared with that of a reference electrode.
La porosité a été mesurée par porosimétrie Fig. The porosity was measured by porosimetry Fig.
L’électrode de référence a été réalisée par voie solvant. La matière active (le graphite), le liant (le SBR) et le co-liant (la CMC) tous sous forme de poudre, sont d’abord mélangés en voie sèche à l’aide d’un mélangeur de type planétaire. Un solvant (la NMP) est ajouté ensuite pour produire une encre. Cette encre est ensuite enduite sur un collecteur de courant de type cuivre. Le solvant est ensuite évaporé à l’aide d’un système permettant d’aspirer et de recycler le solvant. La formulation de l’électrode de référence est composée de 97% de matière active, de 1.5 % de liant et de 1 .5% de co-liant. Le ratio massique pré- mix/solvant lors de l’ajout du solvant est de 40/60.
Sur les graphiques de la Figure 2, l’électrode de référence est représentée par des ronds, et les formulations de l’invention 1, 2 et 3 ci-dessus sont représentées par des carrés, losanges et triangles, respectivement. The reference electrode was produced by the solvent route. The active material (the graphite), the binder (the SBR) and the co-binder (the CMC) all in the form of powder, are first mixed in a dry process using a planetary-type mixer. A solvent (NMP) is then added to produce an ink. This ink is then coated on a copper type current collector. The solvent is then evaporated using a system for sucking up and recycling the solvent. The formulation of the reference electrode is composed of 97% active material, 1.5% binder and 1.5% co-binder. The pre-mix/solvent mass ratio when adding the solvent is 40/60. In the graphs of Figure 2, the reference electrode is represented by circles, and the invention formulations 1, 2 and 3 above are represented by squares, diamonds and triangles, respectively.
La Figure 2 illustre la distribution de taille des pores contenus dans l’électrode de référence et dans les électrodes réalisées via la présente invention. Deux populations de pores sont observées. Il apparait que la distribution de taille des pores contenus dans les électrodes faites par le procédé décrit dans cette invention est dans la gamme de la taille des pores de l’électrode de référence préparée en voie standard (voie solvant). De plus, la Figure 2 montre qu’en changeant la quantité de PTFE et de co-liant (ici le TPU) dans la formulation spécifique, il est possible de contrôler et moduler la quantité de porosité fabriquée mais également la taille moyenne des pores de l’électrode. La Figure 3 présente la quantité de porosité contenue dans l'électrode de référence préparée par voie solvant et dans des électrodes préparées selon le procédé présenté dans la présente invention. Il apparait que la quantité de porosité des électrodes préparées selon le procédé présenté dépend de la formulation. Par ailleurs, il est montré qu’il est possible de moduler la quantité de porosité de l’électrode en jouant sur la formulation à savoir la teneur en matière active, en liant et en co-liant. Figure 2 illustrates the size distribution of the pores contained in the reference electrode and in the electrodes made via the present invention. Two populations of pores are observed. It appears that the size distribution of the pores contained in the electrodes made by the process described in this invention is in the range of the size of the pores of the reference electrode prepared in the standard way (solvent way). In addition, Figure 2 shows that by changing the amount of PTFE and co-binder (here TPU) in the specific formulation, it is possible to control and modulate the amount of porosity produced but also the average pore size of the electrode. Figure 3 shows the amount of porosity contained in the reference electrode prepared by the solvent route and in electrodes prepared according to the method presented in the present invention. It appears that the amount of porosity of the electrodes prepared according to the method presented depends on the formulation. Moreover, it is shown that it is possible to modulate the amount of porosity of the electrode by adjusting the formulation, namely the content of active material, binder and co-binder.
2.2 Durée de vie 2.2 Lifespan
Les expérimentations effectuées ont montré une durée de vie supérieure à 30 cycles, à 60°C et en régime C/5.
The experiments carried out have shown a lifetime greater than 30 cycles, at 60° C. and in C/5 conditions.
Claims
1. Procédé de préparation d’une formulation d’électrode comprenant :1. Process for preparing an electrode formulation comprising:
- La préparation d’un pré-mix comprenant une matière active d’électrode et un fluoropolymère; - The preparation of a pre-mix comprising an active electrode material and a fluoropolymer;
- Le mélange du pré-mix avec un co-liant ; - Mixing the pre-mix with a co-binder;
- La fibrillation du mélange obtenu par extrusion. - The fibrillation of the mixture obtained by extrusion.
2. Procédé selon la revendication 1 tel que l’extrusion est réalisée avec une extrudeuse de type mono- ou bi-vis. 2. Method according to claim 1 such that the extrusion is carried out with a mono- or twin-screw type extruder.
3. Procédé selon la revendication 1 ou 2 tel que le fluoropolymère est choisi parmi le polytétrafluoroéthylène (PTFE) et ses co-polymères, tels que le chlorofluoroéthylène, le perfluoroalkoxy (PFA), le polychlorotrifluoroéthylène (PCTFE ou PTFCE), éthylène propylène fluoré (FEP), éthylène tétrafluoroéthylène ou poly(éthylène-co-tétrafluoroéthylène) (ETFE), tétrafluoroéthylène perfluoromethylvinyléther (MFA). 3. Method according to claim 1 or 2 such that the fluoropolymer is chosen from polytetrafluoroethylene (PTFE) and its co-polymers, such as chlorofluoroethylene, perfluoroalkoxy (PFA), polychlorotrifluoroethylene (PCTFE or PTFCE), fluorinated ethylene propylene ( FEP), ethylene tetrafluoroethylene or poly(ethylene-co-tetrafluoroethylene) (ETFE), tetrafluoroethylene perfluoromethylvinylether (MFA).
4. Procédé selon l’une quelconque des revendications précédentes tel que le fluoropolymère est le PTFE. 4. Method according to any one of the preceding claims, such that the fluoropolymer is PTFE.
5. Procédé selon l’une quelconque des revendications précédentes tel que le co-liant est choisi parmi le polyuréthane thermoplastique (TPU), le poly(styrène- butadiène-styrène) (SBS), le poly(styrène-éthylène-butadiène-styrène) (SEBS), les élastomères thermoplastiques (TPE), thermoplastiques vulcanisés (TPV), les copolyesters thermoplastiques (TPC), polystyrène-b-poly(éthylène-butylène)-b- polystyrène (SEBS), les copolymères de butadiène-acrylonitrile aussi appelés « caoutchoucs nitrile » (NBR), les copolymères de butadiène-acrylonitrile hydrogénés, aussi appelés « caoutchoucs nitrile hydrogénés » (HNBR), les élastomères, les thermoplastiques ou les terpolymères éthylène-acrylate. 5. Method according to any one of the preceding claims, such that the co-binder is chosen from thermoplastic polyurethane (TPU), poly (styrene-butadiene-styrene) (SBS), poly (styrene-ethylene-butadiene-styrene ) (SEBS), thermoplastic elastomers (TPE), vulcanized thermoplastics (TPV), thermoplastic copolyesters (TPC), polystyrene-b-poly(ethylene-butylene)-b-polystyrene (SEBS), butadiene-acrylonitrile copolymers also called “nitrile rubbers” (NBR), hydrogenated butadiene-acrylonitrile copolymers, also called “hydrogenated nitrile rubbers” (HNBR), elastomers, thermoplastics or ethylene-acrylate terpolymers.
6. Procédé selon l’une quelconque des revendications précédentes tel que le co-liant est le TPU. 6. Method according to any one of the preceding claims, such that the co-binder is TPU.
7. Procédé selon l’une quelconque des revendications précédentes tel que l’étape de mélange sous contrainte mécanique est réalisée à température comprise entre 25°C et la température de dégradation du fluoropolymère.
7. Process according to any one of the preceding claims, such that the step of mixing under mechanical stress is carried out at a temperature between 25° C. and the degradation temperature of the fluoropolymer.
8. Formulation d’électrode susceptible d’être obtenue par le procédé selon l’une quelconque des revendications précédentes. 8. Electrode formulation obtainable by the process according to any one of the preceding claims.
9. Formulation d’électrode de type Li-ion comprenant : 9. Li-ion type electrode formulation comprising:
- une matière active d’électrode ; - an active electrode material;
- un fluoropolymère; - a fluoropolymer;
- le polyuréthane thermoplastique (TPU) à titre de co-liant. - thermoplastic polyurethane (TPU) as a co-binder.
10. Formulation selon la revendication 9 telle qu’elle comprend en outre un élément conducteur. 10. Formulation according to claim 9 such that it further comprises a conductive element.
11. Formulation selon la revendication 9 ou 10 telle qu’elle comprend (en poids) : 11. Formulation according to claim 9 or 10 as it comprises (by weight):
De 80 à 98,5 % de matière active ; From 80 to 98.5% active ingredient;
- De 0,1 à 5 % de PTFE ; - From 0.1 to 5% PTFE;
- De 0,1 à 5 % de TPU ; - From 0.1 to 5% TPU;
De 0 à 5 % de lubrifiant ; et De 0 à 10 % de carbone percolant. From 0 to 5% lubricant; and From 0 to 10% percolating carbon.
12. Formulation selon l’une quelconque des revendications 8 à 11 présentant une porosité comprise entre 15 et 35%. 12. Formulation according to any one of claims 8 to 11 having a porosity of between 15 and 35%.
13. Electrode de type Li-ion comprenant la formulation d’électrode selon l’une quelconque des revendications 8 à 12 mise en forme sur un collecteur de courant. 13. Li-ion type electrode comprising the electrode formulation according to any one of claims 8 to 12 shaped on a current collector.
14. Electrode selon la revendication 13, telle qu’il s’agit d’une électrode négative, et telle que la formulation comprend du PTFE, du TPU, du graphite.14. Electrode according to claim 13, such that it is a negative electrode, and such that the formulation comprises PTFE, TPU, graphite.
15. Elément électrochimique de type Li-ion comprenant une électrode selon la revendication 13 ou 14.
15. Li-ion type electrochemical element comprising an electrode according to claim 13 or 14.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR2106383A FR3124327A1 (en) | 2021-06-16 | 2021-06-16 | SOLVENT-FREE ELECTRODE PREPARATION PROCESS AND ELECTRODE FORMULATIONS LIKELY TO BE OBTAINED BY SUCH PROCESS |
| PCT/EP2022/066388 WO2022263555A2 (en) | 2021-06-16 | 2022-06-15 | Method for preparing a solvent-free electrode and electrode formulations obtainable by said method |
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| US (1) | US20240290981A1 (en) |
| EP (1) | EP4356453A2 (en) |
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| TW201432748A (en) * | 2013-01-25 | 2014-08-16 | Corning Inc | Method for manufacturing carbon electrode material |
| US10741843B2 (en) | 2014-04-18 | 2020-08-11 | Maxwell Technologies, Inc. | Dry energy storage device electrode and methods of making the same |
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| WO2022263555A3 (en) | 2023-03-09 |
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| WO2022263555A2 (en) | 2022-12-22 |
| CA3222861A1 (en) | 2022-12-22 |
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