WO2014195205A1 - Séparateurs de batterie modifiés et batteries au lithium - Google Patents

Séparateurs de batterie modifiés et batteries au lithium Download PDF

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Publication number
WO2014195205A1
WO2014195205A1 PCT/EP2014/061056 EP2014061056W WO2014195205A1 WO 2014195205 A1 WO2014195205 A1 WO 2014195205A1 EP 2014061056 W EP2014061056 W EP 2014061056W WO 2014195205 A1 WO2014195205 A1 WO 2014195205A1
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Prior art keywords
separator
separators
lithium
modified
batteries
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PCT/EP2014/061056
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German (de)
English (en)
Inventor
Henrik De Vries
Mario Joost
Martin Winter
Stefano Passerini
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Rockwood Lithium GmbH
Volkswagen Ag
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Publication of WO2014195205A1 publication Critical patent/WO2014195205A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/14—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles in several steps
    • B29C43/146—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles in several steps for making multilayered articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/18—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. compression moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0045—Room temperature molten salts comprising at least one organic ion
    • 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 novel separators, in particular for lithium metal batteries, their production and use, as well as corresponding lithium metal batteries containing these separators.
  • Rechargeable lithium batteries are among the most promising tools for the energy supply of the future.
  • these batteries supply most of the consumer electronics electronic devices. These batteries are also a good energy storage solution for battery-powered electric vehicles (BEV) with a long range. Furthermore, their potential for use in energy storage of renewable energy sources, such as solar or wind power, appears to be very high.
  • BEV battery-powered electric vehicles
  • Batteries containing lithium metal as the anode have the highest theoretical gravimetric power and energy densities. Combinations with sulfur or air cathodes are a desired solution.
  • the average theoretical energy densities of lithium-air (non-aqueous system) and lithium-sulfur batteries are 3505 and 2567 Wh / kg, respectively (P. Bruce et al., Nature 11 (2012) 19-29): This is 6, 5 to 9 times as high as a lithium-ion cell based on LiCoO 2 and graphite (387 Wh / kg) according to the current state of the art.
  • the latter is usually a mixture of two or more organic carbonates, for example ethylene carbonate (EC), diethylene carbonate (DEC), dimethyl carbonate (DMC), vinyl carbonate (VC), propylene carbonate (PC) or others, and a lithium salt, essentially lithium hexafluorophosphate (LiPF 6 ).
  • EC ethylene carbonate
  • DEC diethylene carbonate
  • DMC dimethyl carbonate
  • VC vinyl carbonate
  • PC propylene carbonate
  • LiPF 6 lithium essentially lithium hexafluorophosphate
  • Other usable lithium salts are lithium tetrafluoroborate (LiBF 4 ), lithium bis (oxalatoborate) (LIBOB), lithium bis (trifluoromethanesulfonyl) imide (LITFSI) or others.
  • LITFSI lithium bis (trifluoromethanesulfonyl) imide
  • the addition of one or more additives is practiced.
  • These may be: fluoroethylene carbonate, triphenylamine, succinic anhydride, 1,3-propane sultone, glutaric anhydride, 2,5-dihydrofuran, gamma-butyrolactone, biphenyl and others.
  • Deposition of metallic lithium in each cycle results in progressive degradation of the electrolytes on the fresh lithium surface.
  • the consumption of electrolyte in this type of parasitic side reactions can cause the cell to dry out, accompanied by a rapid decline in capacity. Massive growth of dendrites into the porous separator can also lead to internal short circuits of the cell, which can then lead to uncontrollable cell heating.
  • Polymer electrolytes based on polyethylene oxide (PEO), polypropylene oxide (PPO), poly (vinylidene fluoride) (PVdF), poly (vinylidene fluoride-hexafluoropropylene) (PVdF-HFP), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA) or other polymers show a promising solution for these safety concerns because they are able to form a stable lithium metal electrolyte granule surface and yet operate satisfactorily at temperatures above 100 ° C.
  • separator and electrolyte function in one part, resulting in a potential cost reduction.
  • they have a low ionic conductivity at room temperature or lower temperatures, have a high internal cell resistance, which leads to poor efficiency of cycle rates, and they can not be used in pure form with porous electrodes because they have a reduced contact area (since the porous electrodes are currently produced by wet coating processes).
  • GPE gelled polymer electrolyte
  • GPEs have high conductivities and are considered less dangerous because a large proportion of the flammable electrolytes are "trapped" in the polymer.
  • GPE gelled polymer electrolyte
  • using GPE raises newer issues.
  • GPEs show rapid softening at elevated temperatures, which can reduce mechanical stability and cause internal short circuits.
  • the porous cathode can be blocked by penetrating polymer, which leads to increased internal resistance and decrease in the absolute capacity of the cell for the loading and unloading. Additional electrolyte is necessary to wet the porous cathode. Liquid organic electrolytes are still present in the gel, which can then be released at higher temperatures.
  • Ionic liquids are currently used in place of or as a mixture with conventional electrolytes, or incorporated into solid polymer electrolytes.
  • a coating with soluble polymers usually leads to increased surface film formation on the electrodes and to clogging of the porous electrodes (US 2007/0054184 A1). Furthermore, it may happen that the polymeric coating material is dissolved in the electrolyte, as long as no chemical connection between polymer and separator has been achieved. Combinations of separators and GPE are usually much thicker than the pure separators, with an average increase in thickness of 5 to 20 ⁇ is to be expected. The usual thickness of uncoated separators for rechargeable batteries in the consumer sector is currently up to 25 ⁇ (1 mil). Combinations with the latest thin-film polyethylene separators are designed to increase the energy density of the cells. The companies Asahi Kasei and Toning have already developed corresponding separators having a thickness of 16 ⁇ or 12 ⁇ .
  • Polyolefin separators coated on one or both sides by means of solvent-based processes are known, for example, from US 2004/0053122 A1 and US Pat. No. 6,444,359 B1.
  • Object of the present invention was to provide new separators available, which no longer have the disadvantages of the prior art and have very good properties. In particular, they should be used be suitable in lithium metal based batteries.
  • Not least object of the present invention was to provide corresponding uses of the new separators and new batteries containing these separators.
  • the term “and / or” includes both any and all combinations of the elements listed in the respective list
  • the term “coating polymer” describes the organic polymer which is used to coat the unmodified separator used and applied to this. Not included are inorganic polymers such as silicates or similar. Separators for the purposes of the present invention are those for use in batteries, in particular secondary batteries.
  • ionic liquid means organic salts which are liquid at temperatures below 100 ° C., without the salt being dissolved in a solvent such as water.
  • the present invention is first a modified separator, in particular for lithium metal-based secondary batteries, comprising or constructed of a separator, in particular in the form of a porous separator network, and a crosslinked polymer coating, characterized in that the polymer coating only on one side of the separator applied and chemically bonded to this.
  • the present invention likewise provides a solvent-free process for the preparation of the modified separators according to the invention.
  • the present invention furthermore relates to the use of the separators according to the invention in batteries, preferably secondary batteries, particularly preferably lithium-based secondary batteries, and particularly preferably in lithium metal-based secondary batteries.
  • the present invention furthermore relates to batteries, preferably secondary batteries, particularly preferably lithium-based secondary batteries and particularly preferably lithium metal-based secondary batteries containing the separators according to the invention.
  • Not least object of the present invention are modified separators in which a polymer coating is applied on both sides of the separator and chemically bonded thereto, the polymer coatings are different on the two sides.
  • separators according to the invention a separator was produced for the first time which suppresses dendritic formation as a polymer separator and forms a stable lithium metal electrolyte interface.
  • the separator of the present invention can still be used with conventional porous electrodes.
  • the separators of the present invention have all those properties that must be met for a good separator.
  • the separators of the present invention have the following properties:
  • the separators of the present invention have compatibility with electrodes of different physical and chemical properties.
  • the thickness of the polymer layer is considerably lower than that of conventional polymer separators.
  • the present invention combines conventional separators and a polymer coating in a solvent-free process.
  • the treated separator of the present invention may be mixed with various electrolytes including liquid organic electrolytes, ionic Liquids and mixtures of these two are used.
  • the separator of the present invention when used in lithium metal secondary batteries, is disposed between the anode and the cathode such that the polymer-coated side faces the lithium metal anode and the uncoated side of the porous separator faces the porous cathode.
  • the separators according to the invention can be used with any electrolyte commonly used for corresponding batteries.
  • electrolytes which are based on ionic liquids, in which case lithium salts are still added.
  • the lithium salts used for this purpose usually have the same or a similar anion as the ionic liquids.
  • ionic liquids are used as in situ source liquids.
  • ionic liquids for example: imidazolium, pyridinium, pyrrolidinium, guanidinium, uronium, thiouronium, piperidinium, morpholinium, ammonium and phosphonium.
  • anions can be used in the context of the present invention for the ionic liquids, for example: halides and more complex ions, such as tetrafluoroborates, trifluoroacetates, triflates, hexafluorophosphate phosphinates and tosylates, organic ions such as imides and amides.
  • complex ions such as tetrafluoroborates, trifluoroacetates, triflates, hexafluorophosphate phosphinates and tosylates
  • organic ions such as imides and amides.
  • the anions selected from the group consisting of bis (trifluoromethanesulfonyl) imide (TFSI), N-fluoro- (trifluoromethanesulfonyl) imide (FTFSI), bis (fluorosulfonyl) imide (FSI), N (SO 2 CF 2 CF 3 ) 2 " (BETI), hexafluorophosphate (PFe), trifluoromethanesulfonate (Tf),
  • TFSI bis (trifluoromethanesulfonyl) imide
  • FTFSI N-fluoro- (trifluoromethanesulfonyl) imide
  • FSI bis (fluorosulfonyl) imide
  • N SO 2 CF 2 CF 3 ) 2 "
  • BETI hexafluorophosphate
  • PFe trifluoromethanesulfonate
  • DFOB Difluoromono (oxalato) borate
  • BOB bis (oxalato) borate
  • the ionic liquid which can be used as preferred is N-methyl-N-butyl-pyrrolidinium-bis (trifluoromethanesulfonyl) imide (Pyn 4 TFSI).
  • Lithium salts to be preferably used together with the ionic liquids are those selected from the group consisting of lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium N-fluoroor- (trifluoromethanesulfonyl) imide (LiFTFSI), lithium bis (fluorosulfonyl) imide ( LiFSI), lithium N (SO 2 CF 2 CF 3 ) 2 " (LiBETI), lithium hexafluorophosphate (LiPF 6 ), lithium trifluoromethanesulfonate (LiTf), lithium difluoromono (oxalato) borate (LiDFOB), lithium bis (oxalato) borate (LiBOB ) and combinations thereof.
  • LiTFSI lithium bis (trifluoromethanesulfonyl) imide
  • LiFTFSI lithium N-fluoroor- (trifluoromethanesulfonyl)
  • ionic liquids are outstandingly suitable in particular for safety reasons, since the more temperature-stable ionic liquid surrounds the polymer chains and thus prevents the burning with atmospheric oxygen. Accordingly, a preferred embodiment of the present invention is to use the modified separators according to the invention together with ionic liquids as electrolytes. Likewise, batteries containing the modified separators and ionic liquids of the invention as electrolytes are a preferred embodiment of the present invention.
  • the new concept of the present invention is that coated and influenced only one side of the separator becomes.
  • This is inventively achieved in that a solvent-free hot press technology is used.
  • the inventive method for producing the new separators according to the invention is easy to carry out on a large scale, since thin film productions with corresponding components are already available and extrusion techniques are also already used in separator production.
  • the production method according to the invention comprises the following steps:
  • separators optionally pre-treatment of the separators to be used.
  • the separators are dried essentially at elevated temperatures, in particular using vacuum.
  • separators those are used which have a pore structure or network structure, so that on the one hand the coating polymers can penetrate into these pores / mesh openings and on the other hand, so that a charge transport in the cell is ensured. Accordingly, the usable separators
  • Tissue or membrane shape These generally have a porosity of 40-60% with a pore size of 10 to 2000 nm and a thickness of 5 to 40 ⁇ or 15 to 30 ⁇ on.
  • Examples of usable separator materials are: PET, polybutylene terephthalate, polyacetals, polyesters, polyamides,
  • Polycarbonates polyimides, polyetheretherketones, polyethersulfones, polyphenylene oxides, polyophenylene sulfides, polyethylene naphthalenes, polyvinylidene fluorides, PE, PP, polyacrylonitrile, PVdF-HFP, PEO, polytetrafluoroethylene, polyvinyl chloride, cellulose, cotton, glass fibers or mixtures thereof.
  • these materials may also already be coated, for example with ceramic layers, silica or the like.
  • Examples of commercially available separators which can be used with preference are ceramic-coated polymers such as PE, PP, PET, in particular PET coated with ceramics, polyalkanes such as PE or multilayered polyalkane separators (for example PE / PP / PE or PP / PE / PP).
  • the polymer is dried substantially at elevated temperatures, in particular using vacuum.
  • the coating polymer used may preferably be substances selected from the group consisting of PEO, PVdF, PVdF-HFP, PMMA, PAN, Nafion and mixtures thereof. Especially preferred is PEO.
  • polystyrene resin polystyrene resin having an average molecular weight of 100,000 to 8 million, preferably 2 to 6 million, especially about 4 million. In a preferred variant, these are molecular weights by weight average.
  • a photoinitiator to be added to the coating polymer may also be pretreated as above, in particular dried.
  • photoinitiators known in the art can be used.
  • Preferred photoinitiators are those selected from the group consisting of benzophenone, thioxanthones, alpha-acyl oxime esters, alpha-sulfonyloxy ketones, triarylsulfonium compounds, monoacylphosphioxides, diacylphosphine oxides, acetophenones, benz monoketals and mixtures thereof.
  • a particularly preferred example of a usable photoinitiator is benzophenone.
  • a photoinitiator may be used if the coating polymer and / or separator are not reactive enough or it is desired to increase their reactivity.
  • a photoinitiator is used.
  • the amount of photoinitiator is generally between 1 and 15% by weight, preferably between 3 and 10% by weight, in each case based on the polymer. 4.
  • the photoinitiator, if used, is mixed with the coating polymer. If necessary, both components can be precomminuted in order to improve the miscibility.
  • any known device can be used for comminution and mixing. For smaller quantities, e.g. crushed in a mortar and mixed.
  • the mixture is preferably subjected to a homogenization step.
  • the mixture is filled into suitable vessels, vacuum-sealed and heated for a suitable period, for example for 24 hours at 100 ° C.
  • the components are subjected to a melting process. It is possible to solidify this melt and then store it in a solidified form.
  • the homogenized mixture is then first with a Hot pressing method to between 20 and 40 ⁇ thick layers, in particular about 30 ⁇ thick films pressed. This is usually done at temperatures between 50 and 150 ° C, preferably between 50 to 130 ° C, in particular at about 100 ° C, and pressures between 100 and 500 bar, preferably between 200 and 400 bar, in particular at about 300 bar. Usual pressing times are within the scope of the present invention at 1 to 10 minutes. The pressing preferably takes place between siliconized polyester film.
  • the layers are then further pressed in a conventional calender to between 5 and 15 m thick layers, in particular about 10 m thick films.
  • the calendering roll is tempered to temperatures between 15 and 75 ° C, preferably 20 to 50 ° C. It is chosen a fixed gap thickness and a continuous feed takes place. The pressing preferably takes place between siliconized polyester film.
  • the calendering roll is not heated in a variant of the present invention, but the polymer films are previously heated briefly under pressure to mechanically relax the films. Usual pressing times are within the scope of the present invention at 1 to 10 minutes.
  • Steps 4 and 5 can be made by using a heated thermoplastic material
  • Extrusion screw can be made even lighter and more compact in one operation. This is the preferred variant for large-scale production.
  • the resulting polymer film is then subsequently placed on the (dry) separator surface and pressed. This is done for example by means of static hot pressing in a hot press at temperatures between 40 and 150 ° C, preferably between 50 and 100 ° C, in particular at about 80 ° C and a pressure between 5 and 50, preferably between 5 and 20 bar, especially at about 10 bar. Usual pressing times are within the scope of the present invention at 1 to 10 minutes.
  • the polymer is crosslinked, preferably in a still warm state, by one or both, preferably both, sides by means of UV radiation.
  • the introduced radiation dose is usually between 1 and 6 ⁇ m 2 , preferably between 2 and 4 cm 2 U.
  • the temperature in the UV chamber is usually between 20 and 80 ° C., preferably between 40 and 80 ° C.
  • This crosslinking not only results in the formation of chemical bonds between the various molecules of the coating polymer, but also between the molecules of the coating polymer and CH 2 and / or CH 3 groups of the separator.
  • the result is a coating which, among other things, is insoluble in the separator due to its chemical bonds; ie the coating is not dissolved by the electrolyte in the interior of a cell.
  • the polymer coating is also physically connected to the separator.
  • the polymer fills the surface pores in a non-crosslinked state, and after swelling of the electrolyte, the polymer is "clamped" in the surface pores, that is, physically anchored.
  • the bond is chemically bonded to the separator to a lesser extent due to the ceramic coating, and is physically structured to a greater extent and therefore not so rigid.
  • the radiation power is adjusted according to general knowledge.
  • the process is continuous, in particular using an extruder in steps 4 and 5, performed.
  • the opposite side of the separator now coated on one side still has the original separator surface and is unaffected by the coating on the other side.
  • the result is a modified separator, which is coated on one side with a polymer, and the other side has no coating.
  • a coating of the cathode side of the separator is particularly useful in connection with sulfur electrodes. This prevents diffusion of the polysulfides. Thus, this represents a preferred variant of the present invention.
  • the new use for the separators according to the invention in lithium batteries, in particular in secondary batteries based on lithium metal found.
  • the modified separator is disposed between the anode and cathode, with it being preferred to face the coated side of the anode.
  • batteries are obtained by placing the modified separator between a lithium metal anode and a porous cathode such that the polymer-coated side faces the lithium, and the untreated separate surface faces the porous cathode.
  • the separators according to the invention are suitable for the Use in a battery based on a lithium iron phosphate (LFP) cathode and a lithium metal anode.
  • LFP lithium iron phosphate
  • the most preferred modified separator of the present invention is constructed of ceramic coated PET, PE or PE / PP / PE as a separator coated with polyethylene oxide, especially with an average molecular weight of 4 million daltons, with the photoinitiator being benzophenone.
  • the inventively preferred substances PEO and benzophenone are cheap materials and available on a large scale.
  • the separators according to the invention can be connected to the electrodes by means of adhesives or adhesive layers.
  • the coatings of the separators according to the invention are in this sense not to be understood as adhesive layers; they have no special adhesive properties that they can act as independent adhesive layers.
  • the separators according to the invention have very good thermal stability of over 135 ° C in a pure oxygen atmosphere, which can even be increased to over 175 ° C, when ionic liquids are used as electrolytes.
  • the coating polymer and electrolytes based on ionic liquids form a completely amorphous polymer electrolyte layer inside the battery (cell) according to the invention. This effect occurs especially when using poly (ethylene oxide) as a coating polymer.
  • a separator having different properties on both its sides By obtaining, according to the invention, a separator having different properties on both its sides, it is possible to adapt this separator in its properties to the respective electrodes to be used. This is especially important when electrodes with different surface properties in a cell are to be used.
  • the special structure of the separators according to the invention has proven particularly advantageous for cells in which a lithium metal and a porous electrode are used. The reason why lithium metal is not normally used in modern lithium cells is the uncontrollable formation of dendrites when the lithium metal is used with conventional porous separators.
  • novel modified separators according to the invention which are coated on a page-specific basis, provide the necessary surfaces for lithium metal on the one hand and for conventional porous electrodes on the other hand.
  • lithium metal-based batteries can be made available which have higher capacities.
  • membranes in the batteries according to the invention which act as intrinsic moisture barriers.
  • the use of the inventively modified separators in cells (batteries) thus allows the use of air cathodes without having to use additional moisture barriers in the form of other membranes.
  • An advantage of the present invention is also that the manufacturing process of the separators according to the invention, in contrast to the prior art, is simple and inexpensive. Because it is achieved by the application of solvent-based coating techniques, the u.a. a long and energy-intensive drying require to be bypassed.
  • the coating polymer it is readily possible for the coating polymer to be easily extruded and then laminated to the separator.
  • Another advantage of the present invention is that the modified separators already prepared are readily storable.
  • the present invention also relates to modified separators which have been coated by the process according to the invention.
  • the benzophenone was then ground in a mortar and poly (ethylene oxide) blended into the benzophenone powder.
  • the amount of benzophenone was 4.5 to 9 wt.%.
  • the mixture was filled into pouch bags, vacuum sealed and heated at 100 ° C for 24 hours to homogenize the mixture.
  • the homogenized mixture was then pressed first with a hot pressing process to about 30 ⁇ thick films and then further compressed in a conventional Kalendriermaschine to about 10 ⁇ thick films.
  • the resulting polymer film was then pressed onto dry separator surfaces and crosslinked from both sides by UV radiation for 3 minutes.
  • the modified separator was placed between a lithium metal anode and a porous cathode such that the polymer-coated side faces the lithium and the untreated separate surface faces the porous cathode.
  • the vacuum was in each case 1 to 10 mbar.
  • the separators produced in accordance with the invention exhibited very good thermal stabilities of> 135 ° C. in a pure oxygen atmosphere.
  • the thermal stability could still be increased to over 175 ° C when ionic liquids were used as the electrolyte.
  • Lithium iron phosphate (LFP) cathode achieved stable capacities of 140 to

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
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  • General Physics & Mathematics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Cell Separators (AREA)

Abstract

L'invention concerne des séparateurs modifiés, lesquels sont revêtus unilatéralement de polymères et sont liés chimiquement. L'invention concerne également la fabrication et l'utilisation desdits séparateurs, ainsi que des batteries contenant ces séparateurs.
PCT/EP2014/061056 2013-06-03 2014-05-28 Séparateurs de batterie modifiés et batteries au lithium WO2014195205A1 (fr)

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DE201310105676 DE102013105676A1 (de) 2013-06-03 2013-06-03 Modifizierte Batterieseparatoren und Lithiummetall-Batterien
DE102013105676.8 2013-06-03

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CN111916638A (zh) * 2020-08-04 2020-11-10 珠海冠宇电池股份有限公司 一种电池隔膜、制备方法和电池
CN115498248A (zh) * 2022-07-26 2022-12-20 吉林省东驰新能源科技有限公司 一种夹层结构固态电解质及其制备方法和应用、固态锂离子电池

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DE102013111853A1 (de) 2013-10-28 2015-04-30 Rockwood Lithium GmbH Kohlenstoffbeschichtetes Lithiumsulfid
CN115312972B (zh) * 2021-05-07 2024-04-30 中国科学院过程工程研究所 一种适用于有机锂液流电池的液晶改性Nafion隔膜及制备方法

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CN111916638A (zh) * 2020-08-04 2020-11-10 珠海冠宇电池股份有限公司 一种电池隔膜、制备方法和电池
CN115498248A (zh) * 2022-07-26 2022-12-20 吉林省东驰新能源科技有限公司 一种夹层结构固态电解质及其制备方法和应用、固态锂离子电池

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