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WO2024015971A2 - Séparateur de batterie multicouche comprenant une couche de polymère microporeux - Google Patents

Séparateur de batterie multicouche comprenant une couche de polymère microporeux Download PDF

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Publication number
WO2024015971A2
WO2024015971A2 PCT/US2023/070227 US2023070227W WO2024015971A2 WO 2024015971 A2 WO2024015971 A2 WO 2024015971A2 US 2023070227 W US2023070227 W US 2023070227W WO 2024015971 A2 WO2024015971 A2 WO 2024015971A2
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mol
poly
separator
acrylonitrile
polymer layer
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WO2024015971A3 (fr
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Steven J. LYLE
Jessica H. GOLDEN
Peter David FRISCHMANN
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Sepion Technologies Inc
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Sepion Technologies Inc
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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
    • 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
    • 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
    • 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
    • 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
    • H01M50/417—Polyolefins
    • 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
    • H01M50/426—Fluorocarbon polymers
    • 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
    • H01M2300/002—Inorganic electrolyte
    • H01M2300/0022—Room temperature molten salts
    • 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
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/0042—Four or more solvents
    • 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

  • Li-ion batteries have developed as the dominant high-energy chemistry due to their uniquely high energy density while maintaining high power and cyclability at acceptable prices.
  • the energy density of current commercial Li- ion battery chemistries is however approaching the technology’s theoretical limit, whereas demand for higher energy density batteries at lower unit cost is increasing with the rapid trend towards electrification of the transport and energy industries.
  • Replacing graphite anodes in Li-ion with lithium metal anodes provides an opportunity to significantly increase the energy density of lithium batteries.
  • lithium metal batteries suffer from irreversible capacity loss driven by electrolyte depletion and loss of lithium inventory due to parasitic reactivity between the highly reactive lithium metal anode and the electrolyte components. This process contnbutes to local non-uniformities in the lithium anode surface, propagating further uneven plating and stripping and resulting in physically isolated “dead” lithium. Further, uneven lithium plating increases the risk of dendrite formation, which can cause thermal runaway resulting in catastrophic cell failure, posing a significant hurdle to the commercialization of lithium metal batteries. Mitigation of dendrite formation in lithium metal batteries is critical to enabling their safe, stable use in commercial applications.
  • Battery separators are a critical component of Li-ion batteries since they isolate the electrodes, providing ion transport through large pores filled with electrolyte and insulating electronic conductivity that would otherwise induce a short circuit. Whereas separators are not involved directly in cell reactions, their physical properties play an important role in determining the performance of the battery including energy density, power density, and safety. Importantly, separators’ mechanical integrity throughout the entire lifetime of the battery cell is critical for prevention of internal short circuit.
  • porous membrane separator materials and composites are currently utilized in Li-ion batteries, such as separators made of made of polyolefin, for example polyethylene (PE), polypropylene (PP) and polypropylene-polyethylene-polypropylene (PP/PE/PP), as well as ceramic-coated separators, which include PP, PE or multilayer porous substrates with at least one surface coated with a ceramic composite layer.
  • the ceramic composite layer is intended to block dendrite growth and to prevent electronic shorting.
  • ceramic coated separators have been successfully utilized in Li-ion batteries to improve mechanical properties, their utility is limited in lithium metal batteries due to parasitic reactions induced at the anode by the binding materials which host the ceramic coatings and with some of the ceramic materials themselves.
  • WO 2018/106957 (Sepion Technologies, Inc et al.) describes the application of porous polymers (10-40% porosity, 0.5-2.0 nm pores) as templates that deliver solution- processed precursors of solid-state plus halide containing salts as a conformal coating between the Li-metal surface and the separator surface, in order to increase separator wettability and to increase Li-ion concentration and mobility at the separator-anode interface.
  • electrochemical cells including separators comprising several layers: a first polymer layer, comprising a planar species and a linker.
  • the separator may also comprise a porous support made of PP or PE, laminated to the first polymer layer.
  • the separator may also comprise a second membrane layer laminated to the porous support, such second layer comprising a ceramic material.
  • PIMs Intrinsic Microporosity
  • PIMs are composed of fused rings providing rigidity and sites of contortion, which may be provided by spiro-centers, by bent or bridged ring moieties, or by similar structural components which serve as a barrier preventing conformational relaxation of polymer chains.
  • PIMs have been described and studied since 2006, as they create continuous networks of interconnected voids used as gas separation membranes, hydrogen storage materials, adsorbents and heterogeneous catalysts.
  • the intrinsic microporosity of PIMs is defined as a continuous network of interconnected intermolecular voids, which form as a direct consequence of the shape and rigidity of the component macromolecules.
  • the article of Li et al. (Nano Lett. 2015, 15, 5724-5729) describes the use of PIMs as a membrane platform for achieving high-flux, ion-selective transport in nonaqueous electrolytes.
  • SEI solid-electrolyte-interphase
  • the composition and morphology of the SEI impacts the performance of the electrochemical cell.
  • the consumption of part of the lithium inventory inherent to the in situ SEI formation process reduces the coulombic efficiency of the electrochemical cell.
  • optimal SEI limits the further decomposition of electrolyte components and improves lithium-ion transport at the electrode-separator interface, improving the cycling performance and service life of the batteries.
  • Thin films of microporous polymers on porous supports such as a polyolefin battery separator (e.g., Celgard) are described in the examples.
  • a polyolefin battery separator e.g., Celgard
  • the article of Chengyin Fu et al. describes a lithium electrode laminated with a TBAF@PIM-1 coated polyolefin separator, i.e., a separator coated with microporous polymer host (e.g., PIM-1) in combination with tetrabutylammonium fluoride (TBAF), with the separator (Celgard 2325).
  • the coated separator was then assembled in either Li-Li or Li-NMC-622 cells along with a carbonate electrolyte containing an ionizable lithium salt (e.g., LiPF6).
  • a carbonate electrolyte containing an ionizable lithium salt e.g., LiPF6
  • the composites are described to act as dendrite-suppressing sohd-ion conductors (SICs) in lithium metal batteries.
  • the present invention provides a multi-layer coated separator, comprising: a porous support having a first surface and a second opposing surface; a first polymer layer; and a microporous polymer layer comprising a first polymer of intrinsic microporosity (PIM), wherein the first poly mer layer is coated on the first surface of the porous support, and the microporous polymer layer is coated on the first polymer layer.
  • PIM intrinsic microporosity
  • the present invention provides a multi-layer coated separator, comprising: a porous support comprising polyethylene; a first polymer layer comprising a poly(acrylonitrile-co-methyl acry late) having a number average molecular weight (M n ) of greater than 10 kg/mol, and wherein the ratio of acrylonitrile to methyl acrylate is 99:1 to 50:50 (mol:mol); and a microporous polymer layer comprising PIM- 13 having a number average molecular weight (M n ) of greater than 10 kg/mol, wherein PIM-13 has the following formula: wherein the first polymer layer is coated on the porous support, and the microporous polymer layer is coated on the first polymer layer.
  • the present invention provides an electrolyte comprising: dimethyl carbonate in an amount of of from 25% to 75% (mol/mol); fluoroethylene carbonate in an amount of from 20% to 65% (mol/mol); tolylene-2,6-diisocyanate in an amount of from 0.1% to 10% (mol/mol); lithium bis(fluorosulfonyl)imide in an amount of from 1% to 20% (mol/mol); and lithium difluoro(oxalato)borate in an amount of from 0. 1% to 10% (mol/mol).
  • the present invention provides an electrochemical cell comprising: an anode; a cathode; a multi-layer coated separator of the present invention; and an electrolyte.
  • FIG. 1 shows solubility test of Poly(AN-co-MA) polymer used in the first polymer layer. No characteristic absorption for this material appears in a UV-VIS spectrum of LP40 carbonate-solvent based electrolyte after 1 hour of soaking at room temperature.
  • LP40 obtained commercially from Gotion, comprises ethylene carbonate and diethyl carbonate in 1 : 1 wt% composition.
  • FIG. 2 shows the directionality of the coated separator, wherein the cycle life of the battery cell is greatly improved when the PIM-13 microporous polymer layer coated upon the first poly(acrylonitrile co methyl acrylate) layer is interfaced with the anode compared to the cathode.
  • FIG. 3 shows a multi-layer coated separator of the present invention.
  • FIG. 4 shows an electrochemical cell of the present invention.
  • substituent groups are specified by their conventional chemical formulae, written from left to right, they equally encompass the chemically identical substituents that would result from writing the structure from right to left, e.g., -CH 2 O- is equivalent to - OCH 2 -.
  • Carbonate refers to a compound of the formula R'OC(O)OR”, where R’ and R” can be the same or different, or combined to form a cyclic structure.
  • R’ and R” can be alkyl, haloalkyl, or combined to form an alkylene that is optionally substituted with halogen.
  • Representative carbonates include, but are not limited to, dimethyl carbonate and fluoroethylene carbonate.
  • Electrochemical device refers to a device wherein an electric current is produced by a chemical reaction, wherein electrons are transferred directly between molecules and/or atoms in oxidation -reduction reactions.
  • Electrode refers to an electrically conductive material in a circuit that is in contact with a nonmetallic part of the circuit, such as the electrolyte.
  • the electrode can be a positive electrode or cathode.
  • the electrode can be a negative electrode or anode.
  • Electrode refers to a solution of the electrochemical cell that includes ions, such as metal ions and protons as well as anions, that provides ionic communication between the positive and negative electrodes.
  • Electrolyte Solvent refers to the molecules solvating ions in the liquid electrolyte, such as small organic carbonates or ethereal molecules, that enable diffusion of ions in the electrolyte.
  • the Electrolyte Solvent may also be an ionic liquid or a gas at standard temperature and pressure.
  • Lithium salt refers to an inorganic salt having a lithium ion, Li + , and an anionic counterion.
  • Separatator refers to an electrically insulating membrane between the positive and negative electrodes to prevent electrical shorts, i.e., provides electronic isolation.
  • the separator also allows the ions to move between the positive and negative electrodes.
  • the separator can include any suitable polymeric or inorganic material that is electrically insulating.
  • the separator can include several layers including one or more membrane layers, and a porous support material for the membrane layers.
  • First polymer layer refers to a layer of the separator that is permeable to a first species of the electrolyte while substantially impermeable to liquid electrolyte.
  • the membrane layer can be of any suitable material that can provide the selective permeability, such as composites of microporous polymers and inorganic materials.
  • Substantially impermeable refers to less than 10% of the electrolyte solvent passing through the membrane layer, or less than 1 %, or less than 0.1 %, or less than 0.01 %, or less than 0.001 % of the liquid electrolyte passing through the membrane layer.
  • Polymer of intrinsic microporosity refers to a polymer that exhibits microporosity due to the shape and rigidity of the molecular structure of the repeat units within the polymer, where the repeat units may align relative to one another such that spaces or openings are generated along the polymer chain. Additionally or alternatively, the repeat units may align in an aggregate of the polymer in a way that frustrates packing of the polymer molecules in the aggregate such that spaces or openings are generated between different polymer molecules and/or between segments of the same polymer molecule. These spaces within the aggregated polymer may, at least in part, provide the microporosity to such a polymer.
  • some polymers of intrinsic microporosity may exhibit high surface areas, such as a surface area selected from the range of 300 m 2 g _
  • Example polymers of intrinsic microporosity include, but are not limited to, those described in U.S. Application Publication Nos. 2017/0346104 and 2018/0085744, U.S. Patent Nos. 7,690,514, and 8,056,732, and PCT Publication Nos. WO 2005/012397, and WO 2005/1 13121, each of which is incorporated herein by reference.
  • Oxide refers to a chemical compound having an oxygen, such as metal oxides or molecular oxides.
  • Pore size refers to the average diameter of interstitial space not occupied by the pore forming material. This may include, but is not limited to, the space remaining between polymer chains due to inefficient packing, the space remaining between organic linkers and metal ions in a metal-organic framework, the space between layers and within the holes of stacked 2D material, and the space left in an amorphous or semicrystalline carbon due to unaligned covalent bonding.
  • the pore size may also change once wetted with electrolyte or it may stay the same.
  • “Surface area” refers to the surface area of a porous material as measured by a variety of methods, such as nitrogen adsorption BET.
  • “Microporous polymer” refers to an amorphous glassy polymer having interconnected pores with an average diameter of less than 10 nm, or less than 5, 4, 3, 2, or less than 1 nm.
  • Membrarosity refers to a layer of the membrane comprising pores of less than or equal to 2 nm in size.
  • Intransic microporosity is used herein to mean the polymer provides a continuous network of interconnected intermolecular voids (suitably of less than or equal to 2 nm in size), which forms as a direct consequence of the shape and rigidity of at least a proportion of the component monomers of the polymer.
  • intrinsic microporosity arises due to the structure of the monomers used to form the polymer and, as the term suggests, it is an intrinsic property of a polymer formed from such monomers.
  • the network polymers disclosed herein have a certain property (i.e. intrinsic microporosity).
  • Metal refers to elements of the periodic table that are metallic and that can be neutral, or negatively or positively charged as a result of having more or fewer electrons in the valence shell than is present for the neutral metallic element.
  • Metals useful in the present invention include the alkali metals, alkali earth metals, transition metals and post-transition metals.
  • Alkali metals include Li, Na, K, Rb and Cs.
  • Alkaline earth metals include Be, Mg, Ca, Sr and Ba.
  • Transition metals include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg and Ac.
  • Post-transition metals include Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, and Po.
  • Rare earth metals include Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
  • Porous support refers to any suitable material that is capable of supporting the membrane layer of the present invention, and is permeable to the electrolyte.
  • “Laminated” refers to the deposition of one layer on another, such as the microporous polymer layer or first polymer layer onto the porous support.
  • Mol% refers to the mole percentage of a component based on the total number of moles in the composition.
  • the present invention provides a multi-layer coated separator, comprising: a porous support having a first surface and a second opposing surface; a first polymer layer; and a microporous polymer layer comprising a first polymer of intrinsic microporosity (PIM), wherein the first polymer layer is coated on the first surface of the porous support, and the microporous polymer layer is coated on the first polymer layer.
  • PIM intrinsic microporosity
  • FIG. 3 shows multi-layer coated separator 100, having porous support 110 having a first surface 111 and a second opposing surface 112, a first polymer layer 120, and a microporous polymer layer 130.
  • the pore size of the porous support is between about 0.01 micrometers and 5 micrometers, more specifically between about 0.02 micrometers and 1.5 micrometers, or even more specifically between about 0.03 micrometers and 1 micrometers.
  • the porosity of porous support may be between about 20% and 85%, or more specifically, between about 30% and 60%.
  • pore sizes may be affected by the composition of electrolyte that is provided in the pores of separator. For example, some components of separator (e.g., porous support or first poly mer layer) may swell when come in contact with some materials of electrolyte causing the pore size to change.
  • the pore size and other like parameter refer to components of separator before they come in contact with electrolyte.
  • the thickness of porous support is between about 5 micrometers and 500 micrometers, or in specific embodiment between about 5 micrometers and 50 micrometers, or more specifically between about 10 micrometers and 30 micrometers. In the same or other embodiments, the thickness of porous support may be between about 1 to 50 times greater than the thickness of first polymer layer or, more specifically, between about 5 and 25 times greater.
  • suitable materials for porous support include, but are not limited, fluoro-polymeric fibers of poly(ethylene-co-tetrafluoroethylene (PETFE) and poly(ethylenechloro-co-tnfluoroethylene) (e.g., a fabric woven from these used either by itself or laminated with a fluoropolymeric microporous film), poly vinylidene difluoride, polytetrafluoroethylene (PTFE), polystyrenes, polyarylether sulfones, polyvinyl chlorides, polypropylene, polyethylene (including LDPE, LLDPE, HDPE, and ultrahigh molecular weight polyethylene), polyamides, polyimides, polyacrylics, polyacetals, polycarbonates, polyesters, polyetherimides, polyimides, polyketones, polyphenylene ethers, polyphenylene sulfides, polymethylpentene, polysulfones non-woven glass, glass fiber materials,
  • Porous support may also be supplied with an additional coating of a second suitable material including, but not limited to, PTFV, PVDF, and PETFE.
  • a second suitable material including, but not limited to, PTFV, PVDF, and PETFE.
  • the multi-layer coated separator is the separator wherein the porous support comprises polyethylene, polypropylene, poly(tetrafluoroethylene) (PTFE), poly(vinyl chloride) (PVC), poly(vinylidene difluoride) (PVDF), cellulose, a ceramic, or combinations thereof.
  • the multi-layer coated separator is the separator wherein the porous support comprises polyethylene.
  • the porous support may have a thickness of between about 3 micrometers and 200 micrometers, or between about 5 micrometers and 100 micrometers, or between about 10 micrometers and 50 micrometers, or between about 9 micrometers and 25 micrometers, or between about 10 micrometers and 20 micrometers, or more specifically between about 15 micrometers and 30 micrometers.
  • the porous support can have a thickness of about 5 micrometers, or about 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or about 20 micrometers.
  • Selective blocking characteristics of one or more polymer layers used in a separator come from the composition or specific pore architectures of these layers.
  • the term “blocking'’ is referred to as sieving, selecting, or excluding.
  • the pore architectures of polymer layer manifest as networks of interconnected pores with small pore sizes, narrow pore-size distribution, high surface area, and high porosity as further described below.
  • the pore architectures of polymer layer manifest as an array of channels with small pore sizes, narrow pore-size distribution, high surface area, and high porosity as further described below.
  • the first polymer layer possesses various other properties making them suitable for electrochemical cell applications, such as chemical and electrochemical stability, wettability, thickness, thermal stability, and the like.
  • the blocking mechanism is based on chemical exclusion (non-wettable) or a sizeexclusion effect transpired at a nanometer to sub-nanometer scale where tortuous, ionically percolating, pathways are established in polymer layers.
  • a polymer layer may allow Li-ions (or other like species described below) to pass while blocking larger electrolyte solvent or the like.
  • the membrane may be formed from a ladder polymer with angular spiro centers and absence of rotatable bonds in the polymer backbone or bonds in the backbone with restricted bond rotation. These characteristics provide inefficient solid-state packing with porosity of between about 10% and 40% or, more specifically, between about 20% and 30% of the bulk powder. The pores may then be filled with an inorganic component leaving a non-porous or partially porous polymer layer.
  • the first polymer layer can include any suitable polymer.
  • the multi-layer coated separator is the separator wherein the first polymer layer is substantially insoluble in carbonate electrolytes. Representative carbonate electrolytes are described within.
  • the first polymer layer can be more than 50% insoluble in the carbonate electrolyte, or more than 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or more than 99% insoluble in the carbonate electrolyte.
  • the first polymer layer can include one or more different polymer layers.
  • the first polymer layer can include a first polymer layer, a second polymer layer, or more polymer layers.
  • the multi-layer coated separator is the separator wherein the first polymer layer comprises polyacrylonitrile, poly(acrylonitrile-co-methyl acrylate), poly(acrylonitrile-co-methacrylic acid), poly(acrylonitrile-acrylic acid), poly (acrylonitrile-itaconic acid), poly(acrylonitrile-methyl methacrylate), polyacrylonitrile- itaconic acid-methyl acrylate), poly(acrylonitrile-methacrylic acid-methyl acrylate), poly (aery lonitrile-vinyl pyridine), poly(acrylonitrile-vinyl chloride), poly(acrylonitrile-vinyl acetate), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP),
  • the multi-layer coated separator is the separator wherein the first polymer layer comprises poly(acrylonitrile-co-methyl acrylate), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), the second polymer of intrinsic microporosity different from the first polymer of intrinsic microporosity, or combinations thereof.
  • the first polymer layer comprises poly(acrylonitrile-co-methyl acrylate), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), the second polymer of intrinsic microporosity different from the first polymer of intrinsic microporosity, or combinations thereof.
  • the multi-layer coated separator is the separator wherein poly(acrylonitnle-co-methyl acrylate) having a number average molecular weight (Mn) of greater than 10 kg/mol, wherein the ratio of acrylonitrile to methyl acrylate is 99: 1 to 50:50 (mol:mol), a polymer blend comprising poly(acrylonitrile-co-methyl acry late) and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), wherein the ratio of poly(acrylonitrile-co-methyl acrylate) to (PVDF-HFP is 99:1 to 50:50 (wt/wt),
  • PIM-3-Me-OTf or combinations thereof.
  • the multi-layer coated separator is the separator wherein the first polymer layer comprises poly(acrylonitrile-co-methyl acrylate) having a number average molecular weight (M n ) of greater than 10 kg/mol, and wherein the ratio of acrylonitrile to methyl acrylate is 99: 1 to 50:50 (mol: mol).
  • Polymers of intrinsic microporosity useful in the electrochemical device of the present invention include those described in U.S. Patent Nos. 10,710,065, and 11,394,082, U.S. Publication No. 2021/0309802, and 2019/0326578, each of which is incorporated herein by reference in its entirety.
  • PIMs intrinsic microporosity
  • PIMs There are two different types of PIMs, i) non-network (linear) polymers which may be soluble in organic solvents, and ii) network polymers which are generally insoluble, depending on the monomer choice.
  • PIMs possess internal molecular free volume (IMFV), which is a measure of concavity and is defined by Swager as the difference in volume of the concave unit as compared to the non-concave shape [T M Long and T M Swager, "Minimization of Free Volume: Alignment of Tripty cenes in Liquid Crystals and Stretched Polymers", Adv.
  • IMFV internal molecular free volume
  • network PIMs possess greater microporosity than non-network PIMs due to their macrocyclization [N B McKewon, P M Budd, "Explotation of Intrinsic Microporosity in Polymer-Based materials", Macromolecules, 43, 5163-5176, 2010],
  • prior art network PIMs are not soluble, they can only be incorporated into a membrane if mixed as fillers with microporous soluble materials, which include soluble PIMs or other soluble polymers.
  • Non-network PIMs may be soluble, and so suitable for casting a membrane by phase inversion, or for use coating a support membrane to make a thin film composite.
  • their solubility in a range of solvents restricts their applications in organic solvent nanofiltration [Ulbricht M, Advanced functional polymer membranes. Single Chain Polymers, 47, 2217-2262, 2006],
  • U.S. Pat. No. 7,690,514 B2 describes materials of intrinsic microporosity comprising organic macromolecules comprised of a first generally planar species connected by linkers having a point of contortion such that two adjacent first planar species connected by a linker are held in non-coplanar orientation.
  • Preferred points of contortion are spiro groups, bridged ring moieties and sterically congested bonds around which there is restricted rotation.
  • These non-network PIMs may be soluble in common organic solvents, allowing them to be cast into membranes, or coated onto other support membranes to make a thin film composite.
  • PIM-1 (soluble PIM) membranes exhibit gas permeabilities which are exceeded only by very high free volume polymers such as Teflon AF2400 and PTMSP, presenting selectivities above Robeson's 1991 upper bound for gas pairs such as CO2/CH4 and O2/N2. Studies have shown that permeability is enhanced by methanol treatment, helping flush out residual casting solvent and allowing relaxation of the chains [P M Budd and N B McKewon, D Fritsch, "Polymers of Intrinsic Microporosity (PIMs): High free volume polymers for membrane applications", Macromol Symp, 245-246, 403-405, 2006],
  • PIM-Polyimides A range of polyimides with characteristics similar to a microporous polymer (PIM) were prepared by Ghanem et al. and membrane gas permeation experiments showed these PIM-Polyimides to be among the most permeable of all polyimides and to have selectivities close to the upper bound for several important gas pairs [B G Ghanem, N B McKeown, P M Budd, N M Al-Harbi, D Fritsch, K Heinrich, L Starannikova, A Tokarev and Y Yampolskii, "Synthesis, characterization, and gas permeation properties of a novel group of polymers with intrinsic micro porosity: PIM-polyimides", Macromolecules, 42, 7781-7888, 2009],
  • U.S. Pat. No. 7,410,525 Bl describes polymer/polymer mixed matrix membranes incorporating soluble polymers of intrinsic microporosity as microporous fillers for use in gas separation applications.
  • a microporous polymer layer comprises a polymer having a chain comprised of repeating units bonded to each other.
  • Each unit may include a first generally planar species comprising at least one aromatic ring and also comprising a rigid linker having a site of contortion, which is a spiro group, a bridged ring moiety, or a sterically congested single covalent bond.
  • the rigid linker restricts rotation of the first planar species in a non-coplanar orientation.
  • At least 50% by mole (or 70%, 80%, or even 90%) of the first planar species in the chain are connected by the rigid linkers to a maximum of two other planar species and being such that it does not have a cross-linked, covalently bonded 3 -dimensional structure.
  • this polymer may include rigid linkers having a site of contortion. Since these polymer chains do not pack together by virtue of their rigid contorted structure, the microporous polymer layer possesses intrinsic microporosity and, in some cases, nanoporosity. As such, this combination of non-packed and non-crosslinked polymer chains extends in three dimensions. It may be also considered as a non-network polymer. Cross-linked polymers are also within the scope.
  • the surface area of the PIM polymer layer (as measured by nitrogen adsorption or a related technique of the dry powder prior to membrane processing) prior to infilling with an inorganic component may be at least 200 m 2 /g or at least 500 m 2 /g such as between 200 m 2 /g and 2200 m 2 /g or more specifically between 600 m 2 /g and 900 m 2 /g.
  • Representative methods for measuring surface area include nitrogen adsorption BET.
  • the surface area is directly related to the porosity, essential for efficient transport of supporting electrolyte between electrodes and higher power cell operation. Typical porosities range from 20% to 70% or more specifically 30% to 60%.
  • the surface area of the PIM polymer layer can be from 100 m 2 /g to 3000 m 2 /g, such as 100 m 2 /g, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1 100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, or 3000 m 2 /g.
  • the multi-layer coated separator is the separator wherein the microporous polymer layer has a surface area of from 100 m 2 /g to 3000 m 2 /g, as measured by nitrogen adsorption BET.
  • the multi-layer coated separator is the separator wherein the average pore diameter of the microporous polymer layer prior to infilling with an inorganic component is of less than 100 nm, or from about 0. 1 nm to about 20 nm, or from about 0.1 nm to about 10 nm, or from about 0.1 nm to about 5 nm, or from about 0.1 nm to about 2 nm, or from about 0.1 nm to about 1 nm.
  • the average pore diameter of the microporous polymer layer can be less than about 10 nm, or less than about 9, 8, 7, 6, 5, 4, 3, 2, or 1 nm.
  • the average pore diameter of the microporous polymer layer can be about 10 nm, or about 9, 8, 7, 6, 5, 4, 3, 2, or 1 nm. This pore diameter ensures that some materials (e.g., materials that have unit sizes greater than the pore diameter) are blocked by the microporous polymer layer, while other materials are allowed to pass (e.g., materials with smaller unit sizes).
  • the multi-layer coated separator is the separator wherein the microporous polymer layer has an average pore diameter of from 0.1 nm to 10 nm. In some embodiments, the multi-layer coated separator is the separator wherein the microporous polymer layer has an average pore diameter of from 0. 1 nm to 2 nm. In some embodiments, the multi-layer coated separator is the separator wherein the microporous polymer layer has an average pore diameter of from 0. 1 nm to 1 nm.
  • the multi-layer coated separator is the separator wherein the number average molecular weight (M n ) of the microporous polymer layer is between 1x10 3 and 2000xl0 3 kg/mol or, more specifically, between 15xl0 3 and 500xl0 3 kg/mol or between 20x10 3 and 200x10 3 kg/mol. Larger number average molecular weight polymers contribute to enhanced mechanical properties of the formed membrane.
  • the microporous polymer layer can be a film cast, sprayed or coated from solution (e.g., onto the porous support), a composite comprised of a plurality of individual membrane layers, a free-standing film, or a supported film (e.g., by a porous support).
  • the multi-layer coated separator is the separator wherein the microporous polymer layer has a thickness of between about 5 nanometers and 20 micrometers, or between about 100 nanometers and 10 micrometers, or more specifically between about 500 nanometers and 5 micrometers.
  • microporosity of a polymer layer is demonstrated by its high surface area (approximately 680 - 850 m 2 /g) determined using nitrogen adsorption measurements (BET calculation).
  • BET calculation nitrogen adsorption measurements
  • the presence of the cyano and methyl groups is optional, they may be omitted or replaced with other simple substituents.
  • Each phenyl goup may contain one or more substituents. Additionally, the nature and arrangement of substituents on the spiro-indane moiety may be chosen to provide any desirable configuration around the carbon atom common to both 5 -membered rings.
  • the multi-layer coated separator is the separator wherein the first polymer of intrinsic microporosity has the following formula: or combinations thereof.
  • the multi-layer coated separator is the separator wherein the first polymer of intrinsic microporosity has the following formula:
  • the multi-layer coated separator is the separator wherein the first polymer of intrinsic microporosity has the following formula:
  • the multi-layer coated separator is the separator wherein the first polymer of intrinsic microporosity has the following formula: [0072] In some embodiments, the multi-layer coated separator is the separator wherein the microporous polymer layer comprises PIM-13 having a number average molecular weight (M n ) of greater than 10 kg/mol, wherein PIM-13 has the following formula:
  • the multi-layer coated separator is the separator comprising: a porous support comprising polyethylene; a first polymer layer comprising a poly(acrylonitrile-co-methyl acrylate) having a number average molecular weight (M n ) of greater than 10 kg/mol, and wherein the ratio of acrylonitrile to methyl acrylate is 99:1 to 50:50 (mol:mol); and a microporous polymer layer comprising PIM-13 having a number average molecular weight (M n ) of greater than 10 kg/mol, wherein PIM-13 has the following formula: wherein the first polymer layer is coated on the porous support, and the microporous polymer layer is coated on the first polymer layer.
  • the multi-layer coated separator of the present invention is the multi-layer coated separator comprising: the porous support comprising polyethylene; and the first polymer layer comprises a poly(acrylonitrile-co-methyl acrylate) having a number average molecular weight (M n ) of about 194 kg/mol, and wherein the ratio of acrylonitrile to methyl acrylate is 99: 1 to 80:20 (mokmol); and the microporous polymer layer comprises PIM-13 having a number average molecular weight (M n ) of greater than 25 kg/mol.
  • the present invention also includes an electrolyte for use with the coated separator.
  • the electrolyte can include a variety of components, such as a carbonate electrolyte.
  • the electrolyte is a carbonate electrolyte.
  • the carbonate electrolytes can include a variety of carbonates such as, but not limited to, fluorinated carbonates.
  • the electrolyte is a carbonate electrolyte comprising a fluorinated carbonates.
  • the carbonate electrolyte may comprise from 20 % to 65 % (mol/mol) of a fluorinated carbonate, based on the total number of moles in the electrolyte, or from 25% to 60% (mol/mol), from 30% to 50%, from 32% to 48% (mol/mol), or from 35% to 45%.
  • the carbonate electrolyte can include additional components, such as one or more lithium salts.
  • the electrolyte is a carbonate electrolyte comprising a fluorinated carbonate and a lithium salt.
  • An exemplary electrolyte of the present invention includes a liquid electrolyte solvent which is a fluorinated carbonate solvent and a lithium salt.
  • Another exemplary electrolyte of the present invention includes a liquid electrolyte solvent which is a fluorinated carbonate solvent and a lithium salt which is a fluorinated lithium salt.
  • the electrolyte is a carbonate electrolyte comprising a fluorinated carbonate, an alkyl carbonate and a lithium salt.
  • An exemplary electrolyte of the present invention includes two liquid electrolyte solvents which are an alky l carbonate solvent and a fluorinated carbonate solvent, and a lithium salt.
  • the electrolyte is a carbonate electrolyte comprising a fluorinated carbonate, an alkyl carbonate and two distinct lithium salts.
  • An exemplary electrolyte of the present invention includes two liquid electrolyte solvents which are an alkyd carbonate solvent and a fluorinated carbonate solvent, and two distinct lithium salts.
  • the present invention also includes an electrolyte having an alkyl carbonate, a fluorinated carbonate, a diisocyanate, and a lithium salt.
  • the present invention provides an electrolyte comprising an alkyl carbonate, a fluorinated carbonate, a diisocyanate, and a first lithium salt.
  • the electrolyte comprises a second lithium salt different from the first lithium salt.
  • Representative al ky 1 carbonates of the electrolyte include, but are not limited to, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, n-propyl propionate, vinylene carbonate, ethylene carbonate, fluoroethylene carbonate, or propylene carbonate.
  • the alkyl carbonate is dimethyl carbonate.
  • Representative fluorinated carbonates of the electrolyte include, but are not limited to, fluoroethylene carbonate, CH3OC(O)OCH 2 CF3, CH3OC(O)OCH 2 CF 2 CHF 2 , CH3OC(O)OCH 2 CF 2 CHF 2 , CF 3 CH 2 OC(O)OCH 2 CF3, CH 3 OC(O)OCH 2 CF 2 CF3, CH 3CH 2 OC(O)OCH 2 CF 2 CHF 2 , or CH 3 OC(O)OCH 2 CF 2 CF 2 CF3
  • Representative diisocyanates of the electrolyte include, but are not limited to, tolylene-2,4-diisocyanate, or tolylene-2,6-diisocyanate.
  • the lithium salt of the electrolyte compositions of the present invention can be any suitable lithium salt.
  • suitable lithium salts include, but are not limited to, lithium bis(fluorosulfonyl)imide, lithium hexafluorophosphate, lithium 4,5-dicyano-2- (trifluoromethyl)imidazolium, lithium difluoro(oxalato)borate, lithium bis(trifluoromethanesulfonyl)imide, lithium difluorophosphate, lithium nitrate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, or combinations thereof.
  • the lithium salt can be lithium bis(fluorosulfonyl)imide, lithium hexafluorophosphate, lithium 4,5-dicyano-2-(trifluoromethyl)imidazolium, lithium difluoro(oxalato)borate, lithium bis(trifluoromethanesulfonyl)imide, lithium difluorophosphate, lithium nitrate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, or combinations thereof.
  • the electrolyte composition is the electrolyte composition wherein the first lithium salt includes lithium bis(fluorosulfonyl)imide (LiFSi), lithium hexafluorophosphate, or combinations thereof. In some embodiments, the electrolyte composition is the electrolyte composition wherein the first lithium salt includes lithium bis(fluorosulfonyl)imide (LiFSi).
  • the first lithium salt can be present in the electrolyte composition in any suitable amount.
  • the first lithium salt can be present in the electrolyte composition in an amount of from 0.1 to 20 mol%, from 0.1 to 20 mol%, from 1 to 20 mol%, from 5 to 20 mol%, from 5 to 15 mol%, from 8 to 12 mol%, or from 9 to 11 mol%.
  • Representative amounts of the first lithium salt in the electrolyte compositions of the present invention include, but are not limited to, about 5 mol%, or about 6, 7, 8, 9, 10, 11, 12, 13, 14, or about 15 mol%.
  • the electrolyte composition of the present invention can include one or more lithium salts.
  • the electrolyte composition can include 1, 2, 3, 4, or more different lithium salts as defined above.
  • the electrolyte composition is the electrolyte composition comprising a single lithium salt.
  • the electrolyte composition is the electrolyte composition comprising two different lithium salts.
  • the electrolyte composition is the electrolyte composition comprising three different lithium salts.
  • the electrolyte compositions of the present invention can also include a second lithium salt that is different from the first lithium salt.
  • the electrolyte composition is the electrolyte composition including a second lithium salt that is different from the first lithium salt.
  • the electrolyte composition is the electrolyte composition wherein the second lithium salt comprises lithium 4,5-dicyano-2- (trifluoromethyl)imidazolium, lithium difluoro(oxalato)borate (LiDFOB), lithium bis(tri Huoromethanesulfony1)imide. lithium difluorophosphate, lithium nitrate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, or combinations thereof.
  • the second lithium salt comprises lithium 4,5-dicyano-2- (trifluoromethyl)imidazolium, lithium difluoro(oxalato)borate (LiDFOB), lithium bis(tri Huoromethanesulfony1)imide. lithium difluorophosphate, lithium nitrate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, or combinations thereof.
  • the electrolyte composition is the electrolyte composition wherein the second lithium salt comprises lithium 4,5-dicyano-2- (trifluoromethyl)imidazolium, lithium difluoro(oxalato)borate (LiDFOB), or combinations thereof.
  • thee electrolyte composition is the electrolyte composition wherein the second lithium salt comprises lithium 4,5-dicyano-2- (trifluoromethyl)imidazolium.
  • the electrolyte composition is the electrolyte composition wherein the second lithium salt comprises lithium difluoro(oxalato)borate (LiDFOB).
  • the electrolyte composition is the electrolyte composition wherein the second lithium salt comprises lithium nitrate.
  • the second lithium salt can be present in the electrolyte composition in any suitable amount.
  • the second lithium salt can be present in the electrolyte composition in an amount of from 0. 1 to 10 mol%, from 0. 1 to 5 mol%, from 0.5 to 5 mol%, from 0.5 to 4 mol%, from 0.5 to 3.5 mol%, from 1 to 3 mol%, from 1.0 to 2.5 mol%, or from 1.5 to 2.5 mol%, based on the total number of moles in the electrolyte.
  • Representative amounts of the second lithium salt in the electrolyte compositions of the present invention include, but are not limited to, about 1.5 mol%, or about l.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, or about 2.5 mol%.
  • the electrolyte composition is the electrolyte composition wherein the second lithium salt is present in the electrolyte composition in an amount of from 0. 1 to 5 mol%. In some embodiments, the electrolyte composition is the electrolyte composition wherein the second lithium salt is present in the electrolyte composition in an amount of from 0.5 to 3.5 mol%. In some embodiments, the electrolyte composition is the electrolyte composition wherein the second lithium salt is present in the electrolyte composition in an amount of 1 to 3 mol%. In some embodiments, the electrolyte composition is the electrolyte composition wherein the second lithium salt is present in the electrolyte composition in an amount of from 1.5 to 2.5 mol%.
  • An exemplary electrolyte of the present invention includes two distinct lithium salts, in particular two distinct fluorinated lithium salts.
  • the electrolyte may comprise lithium bis(fluorosulfonyl)imi de (LiFSi) and lithium difluoro(oxalato)borate (LiDFOB).
  • the present invention provides an electrolyte comprising, based on the total number of moles in the electrolyte: dimethyl carbonate in an amount of from 25% to 75% (mol/mol); fluoroethylene carbonate in an amount of from 20% to 65% (mol/mol); tolylene-2,6-diisocyanate in an amount of from 0.1% to 10% (mol/mol); lithium bis(fluorosulfonyl)imide (LiFSi)in an amount of from 1% to 20% (mol/mol); and lithium difluoro(oxalato)borate (LiDFOB) in an amount of from 0.1% to 10% (mol/mol).
  • dimethyl carbonate in an amount of from 25% to 75% (mol/mol)
  • fluoroethylene carbonate in an amount of from 20% to 65% (mol/mol)
  • tolylene-2,6-diisocyanate in an amount of from 0.1% to 10% (mol/mol)
  • LiFSi lithium bis(fluorosulfonyl)imide
  • the present invention provides an electrolyte comprising, based on the total number of moles in the electrolyte: dimethyl carbonate in an amount of from 30% to 70% (mol/mol), or from 40% to 60%; fluoroethylene carbonate in an amount of from 25% to 60% (mol/mol), or from 30% to 50%; tolylene-2,6-diisocyanate in an amount of from 0.5% to 5% (mol/mol), or from 0.7% to 3%; lithium bis(fluorosulfonyl)imide (LiFSi) in an amount of from 5% to 15% (mol/mol), or from 7% to 13%; andlithium difluoro(oxalato)borate (LiDFOB) in an amount of from 0.5% to 5% (mol/mol), or from 0.7% to 2%.
  • dimethyl carbonate in an amount of from 30% to 70% (mol/mol), or from 40% to 60%
  • fluoroethylene carbonate in an amount of from 25% to 60% (mol/mol), or from 30% to 50%
  • the present invention provides an electrolyte comprising, based on the total number of moles in the electrolyte: dimethyl carbonate in an amount of about 48% (mol/mol); fluoroethylene carbonate in an amount of about 39% (mol/mol); tolylene-2,6-dnsocyanate in an amount of about 1% (mol/mol); lithium bis(fluorosulfonyl)imide (LiFSi) in an amount of about 10% (mol/mol); and lithium difluoro(oxalato)borate (LiDFOB) in an amount of about 2% (mol/mol).
  • dimethyl carbonate in an amount of about 48% (mol/mol); fluoroethylene carbonate in an amount of about 39% (mol/mol); tolylene-2,6-dnsocyanate in an amount of about 1% (mol/mol); lithium bis(fluorosulfonyl)imide (LiFSi) in an amount of about 10% (mol/mol); and lithium difluoro(oxala
  • the electrochemical device is an electrochemical cell.
  • an electrochemical cell includes a positive electrode, a negative electrode, a separator, and an electrolyte.
  • the present invention provides an electrochemical cell comprising: an anode; a cathode; a multi-layer coated separator of the present invention; and an electrolyte.
  • FIG. 4 shows the electrochemical cell 200, having anode 210, cathode 220, and the multi-layer coated separator 100.
  • the separator 100 is disposed between the anode 210 and the cathode 220.
  • the separator provides electronic isolation between the anode and the cathode. At least a portion of the electrolyte is disposed within the separator.
  • the electrochemical cell is the electrochemical cell wherein the multi-layer coated separator is between the anode and the cathode. In some embodiments, the electrochemical cell is the electrochemical cell wherein the multi-layer coated separator is oriented such that the first surface of the support material is oriented towards the anode.
  • the electrochemical cell of the present invention is the electrochemical cell wherein the electrolyte is an electrolyte of the present invention.
  • the electrochemical device is a lithium-ion battery with a carbon-based, metallic, or metalloid anode and a metal oxide or conversion cathode.
  • P(AN-co-MA) poly(acrylonitrile-co-methyl acrylate) (94 wt% acrylonitrile) from Sigma-Aldrich:
  • PCL poly caprolactone (Mw: 150 kg/mol) from Scientific Polymer Products.
  • PEG 8000 polyethylene glycol 8000 from Sigma-Aldrich.
  • PVDF-HFP poly(vinylidene fluoride-co-hexafluoropropylene) Kynar® 2801 from Arkema:
  • PAN polyacrylonitrile (Mw: 150 kD) from Sigma- Aldrich: PIM-13: Compound 13, as described in paragraph [0179] of WO 2020/037246 Al (The
  • Molecular weight information for poly(AN-co-MA) and PVDF-HFP were determined using a Malvern OMNISEC SEC equipped with a refractive index, light scattering, and intrinsic viscosity triple detector and a using DMF + 0.2% LiBr mobile phase. A combination of specific refractive index increment and light scattering signal were used to calculate molecular weight, and a viscometer used to calculate intrinsic viscosity.
  • An electrolyte mixture was prepared by mixing the following components (mol %): dimethyl carbonate 48%, fluoroethylene carbonate 39%, tolylene-2,6-diisocyanate 1%, Lithium bis(fluorosulfonyl)imide 10%, Lithium difluoro(oxalato)borate 2%.
  • the coating solutions were prepared by stirring the polymer in an appropriate solvent for 24 hours, followed by filtration through a 1 -micron pore glass fiber syringe filter.
  • the list of solvents used, along with their concentration is detailed in Table 1 below.
  • the concentrations of coating solutions are determined by drying a known mass of ink and collecting the mass of the residual solids.
  • a carbonate-based electrolyte was used in the present examples.
  • the coat weights and Gurley numbers of the layers are then measured to qualify the samples for cell testing.
  • Coat weight is determined gravimetrically, in which a 12 cm2 area of coated material is weighed, the coating stripped using an appropriate solvent, and the separator weighted again. The coat weight is determined by subtracting these two values and normalizing to the surface area of the test sample.
  • Gurley measurement is designed to ensure that the polymer layer(s) coated onto the porous support comprise a conformal layer over the support and is exempt of pinhole defects.
  • a coated material with a Gurley value greater than 10,000 validates the material as free of pinhole defects and appropriate for testing in cells. All of the coated separators described below present a Gurley value greater than 10,000.
  • Lithium metal cells containing these polymer coated separators are constructed by first generating a stack containing: a lithium metal anode (20 pm), one of the coated separators exemplified below, with the multilayer polymer coating facing the anode, and a cathode (NMC-811).
  • the stack is then either laminated or not.
  • the stack is laminated, it is placed in a laminate pouch, which is then sealed on three sides.
  • This dry interlayer-containing cell is then laminated by compressing a stack of the dry cell with 90A durometer polyurethane rubber on each side in a pneumatic press under a specified pressure, temperature, and time.
  • the stack is not laminated, it is placed in a pouch and sealed.
  • Electrolyte 2.0 g/Ah
  • Cells are then formed with three symmetric cycles at 0.38 mA/cm2, then cycled symmetrically at 1.27 mA/cm2.

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Abstract

La présente invention concerne un séparateur revêtu multicouche, comprenant un support poreux et une couche de membrane multicouche sur le support poreux, une telle couche de membrane comprenant au moins une couche de polymère microporeux, par exemple un polymère de microporosité intrinsèque (PMI) et au moins une couche polymère distincte, la couche de polymère microporeux agissant en tant que couche sélective d'ions et la couche polymère fournissant une barrière physique à la migration de la couche de polymère microporeux.
PCT/US2023/070227 2022-07-15 2023-07-14 Séparateur de batterie multicouche comprenant une couche de polymère microporeux Ceased WO2024015971A2 (fr)

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US12084544B2 (en) 2018-08-17 2024-09-10 The Regents Of The University Of California Diversity-oriented polymers of intrinsic microporosity and uses thereof
US12327835B2 (en) 2016-09-28 2025-06-10 Sepion Technologies, Inc. Electrochemical cells with ionic sequestration provided by porous separators

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US10363546B2 (en) * 2016-05-02 2019-07-30 Liso Plastics LLC Multilayer polymeric membrane
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12327835B2 (en) 2016-09-28 2025-06-10 Sepion Technologies, Inc. Electrochemical cells with ionic sequestration provided by porous separators
US12084544B2 (en) 2018-08-17 2024-09-10 The Regents Of The University Of California Diversity-oriented polymers of intrinsic microporosity and uses thereof

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