WO2012011944A2 - Separators for electrochemical cells - Google Patents

Separators for electrochemical cells Download PDF

Info

Publication number
WO2012011944A2
WO2012011944A2 PCT/US2011/001274 US2011001274W WO2012011944A2 WO 2012011944 A2 WO2012011944 A2 WO 2012011944A2 US 2011001274 W US2011001274 W US 2011001274W WO 2012011944 A2 WO2012011944 A2 WO 2012011944A2
Authority
WO
WIPO (PCT)
Prior art keywords
aluminum oxide
organic
separator
acid
cell
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2011/001274
Other languages
French (fr)
Other versions
WO2012011944A3 (en
Inventor
Zhong Xu
Steven Allen Carlson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Optodot Corp
Original Assignee
Optodot Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to EP11761412.3A priority Critical patent/EP2596538B1/en
Application filed by Optodot Corp filed Critical Optodot Corp
Priority to CN201180035701.3A priority patent/CN103283060B/en
Priority to DK11761412.3T priority patent/DK2596538T3/en
Priority to PL11761412T priority patent/PL2596538T3/en
Priority to EP18198974.0A priority patent/EP3444867B1/en
Priority to KR1020137003965A priority patent/KR20140018171A/en
Priority to JP2013520699A priority patent/JP5990804B2/en
Priority to ES11761412T priority patent/ES2713517T3/en
Publication of WO2012011944A2 publication Critical patent/WO2012011944A2/en
Priority to US13/744,702 priority patent/US20130171500A1/en
Anticipated expiration legal-status Critical
Publication of WO2012011944A3 publication Critical patent/WO2012011944A3/en
Priority to US15/616,399 priority patent/US10833307B2/en
Priority to US17/088,351 priority patent/US11728544B2/en
Priority to US18/216,293 priority patent/US12327881B2/en
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/02—Diaphragms; Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M50/403—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
    • H01M50/411—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
    • 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
    • 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
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249978—Voids specified as micro

Definitions

  • the present invention relates generally to the field of porous membranes and to the fields of electric current producing cells and of separators for use in electric current producing cells. More particularly, this invention pertains to a porous separator membrane comprising an aluminum oxide and an organic polymer where the aluminum oxide has been surface modified by treatment with an organic acid to provide
  • the present invention pertains to electric current producing cells, such as lithium ion cells and capacitors, comprising such porous separators.
  • an electroactive material that has been fabricated into a structure for use in an electrochemical cell is referred to as an electrode.
  • the electrode on the electrochemically higher potential side is referred to as the positive electrode or the cathode, while the electrode on the
  • a battery may contain one or more electrochemical cells.
  • an electrolyte element is interposed between the cathode and the anode.
  • This electrolyte element must be electronically non-conductive to prevent short circuits, but must permit the transport of ions between the anode and the cathode.
  • the electrolyte element should also be stable electrochemically and chemically toward both the anode and the cathode.
  • the electrolyte element contains a porous material, referred to as a separator (since it separates or insulates the anode and the cathode from each other), and an aqueous or non-aqueous electrolyte, that usually comprises an ionic electrolyte salt and ionically conductive material, in the pores of the separator.
  • a separator since it separates or insulates the anode and the cathode from each other
  • an aqueous or non-aqueous electrolyte that usually comprises an ionic electrolyte salt and ionically conductive material, in the pores of the separator.
  • porous separator materials include polyolefins such as polyethylenes and polypropylenes, glass fiber filter papers, and ceramic materials.
  • separator materials are supplied as porous free-standing membranes that are interleaved with the anodes and the cathodes in the fabrication of electrochemical cells.
  • a liquid organic electrolyte containing organic solvents and lithium salts is typically used as the electrolyte in the pores of the separator in the electrolyte element for rechargeable or secondary lithium ion and non-rechargeable or primary lithium electrochemical cells.
  • a gel or solid polymer electrolyte containing an ionically conductive polymer and lithium salts, and optionally organic solvents, might be utilized instead of the liquid organic electrolyte.
  • the separator In addition to being porous and chemically stable to the other materials of the electric current producing cell, the separator should be flexible, thin, economical in cost, and have good mechanical strength and safety properties.
  • High porosity in the separator is important for obtaining the high ionic
  • the separator it is desirable for the separator to have a porosity of at least 30 percent, and preferably 40 percent or higher, in lithium ion batteries.
  • Another highly desirable feature of the separator in the electrolyte element is that it is readily wetted by the electrolyte materials that provide the ionic conductivity.
  • the separator material is a polyolefin material that has non-polar surface properties
  • the electrolyte materials (which typically have highly polar properties) often poorly wet the separator material. This results in longer times to fill the battery with electrolyte and potentially in low capacities in the battery due to a non-uniform distribution of electrolyte materials in the electrolyte element.
  • the separators used for lithium ion batteries are typically polyolefin separators, which melt at below 200°C and are very flammable.
  • the lithium ion batteries, as well as lithium primary batteries and some capacitors, utilize highly flammable organic solvents in their electrolytes.
  • a non-melting and flame retardant separator would help prevent the spread of any burning of the organic electrolyte, caused by an internal short circuit, thermal runaway, or other unsafe condition, that might spread into a larger area of the battery or capacitor and cause a major explosion.
  • lithium ion batteries are typically polyolefin separators, which melt at below 200°C and are very flammable.
  • the lithium ion batteries, as well as lithium primary batteries and some capacitors, utilize highly flammable organic solvents in their electrolytes.
  • a non-melting and flame retardant separator would help prevent the spread of any burning of the organic electrolyte, caused by an internal short circuit, thermal runaway, or other unsafe condition, that might spread into a larger area
  • the present invention utilizes non-flammable inorganic oxides, such as aluminum oxides, and preferably non-flammable organic polymers having fluorinated groups in the separators.
  • This invention utilizes various inorganic oxide particle pretreatment, mixing, coating, drying, and delaminating methods for preparing such separators.
  • One aspect of the present invention pertains to a separator for an electric current producing cell, wherein the separator comprises a microporous layer comprising (a) at least 50% by weight of an aluminum oxide and (b) an organic polymer, wherein the aluminum oxide is surface modified by treatment with an organic acid to form a modified aluminum oxide.
  • the organic acid is a sulfonic acid, preferably an aryl sulfonic acid, and more preferably a toluenesulfonic acid.
  • the organic acid is a carboxylic acid.
  • the aluminum oxide comprises a hydrated aluminum oxide of the formula Al 2 O 3 *xH 2 O, wherein x is in the range of 1.0 to 1.5, and wherein the hydrated aluminum oxide is surface modified by treatment with an organic acid to form a modified hydrated aluminum oxide.
  • the modified aluminum oxide has an Al 2 O 3 content in the range of 50 to 85% by weight.
  • the modified aluminum oxide has an AI2O3 content in the range of 65 to 80% by weight.
  • the separator comprises 60 to 90% by weight of the modified aluminum oxide.
  • the separator comprises 70 to 85%) by weight of the modified aluminum oxide.
  • the microporous layer is a xerogel layer.
  • the organic polymer comprises a polyvinylidene fluoride polymer.
  • the separator comprises a copolymer of a first fluorinated organic monomer and a second organic monomer.
  • the second organic monomer is a second fluorinated organic monomer.
  • the electric current producing cell is a secondary lithium ion cell. In one embodiment, the electric current producing cell is a primary lithium cell. In one embodiment, the electric current producing cell is a capacitor. In one embodiment, the separator does not melt at temperatures lower than 300°C. In one embodiment, the separator is a flame retardant separator.
  • an electrochemical cell comprising an anode, a cathode, an organic electrolyte comprising a lithium salt, and a separator interposed between the anode and the cathode, wherein the separator comprises a microporous layer comprising (a) at least 50% by weight of an aluminum oxide and (b) an organic polymer, wherein the aluminum oxide is surface modified by treatment with an organic acid.
  • the organic acid is a sulfonic acid, preferably an aryl sulfonic acid, and more preferably a toluenesulfonic acid.
  • the organic acid is a carboxylic acid.
  • the aluminum oxide comprises a hydrated aluminum oxide of the formula ⁇ 2 ⁇ 3 ⁇ 2 0, wherein x is in the range of 1.0 to 1.5, and wherein the hydrated aluminum oxide is surface modified by treatment with an organic acid to form a modified hydrated aluminum oxide.
  • the microporous layer is a xerogel layer.
  • the anode active material of the anode is lithium.
  • the modified aluminum oxide has an AI2O3 content in the range of 50 to 85% by weight. In one embodiment, the modified aluminum oxide has an AI2O3 content in the range of 65 to 80% by weight.
  • the organic polymer comprises a polyvinylidene fluoride polymer. In one embodiment, the organic polymer comprises a copolymer of a first fluorinated organic monomer and a second organic monomer. In one embodiment, the second organic monomer is a second fluorinated organic monomer. In one embodiment, the lithium salt is lithium
  • a capacitor comprising two electrodes, an organic electrolyte comprising a tetraalkyl ammonium salt, and a separator interposed between the two electrodes, wherein the separator comprises a microporous layer comprising (a) at least 50% by weight of an aluminum oxide and (b) an organic polymer, wherein the aluminum oxide is surface modified by treatment with an organic acid to form a modified aluminum oxide.
  • the inorganic oxide comprises a hydrated aluminum oxide of the formula ⁇ 2 ⁇ 3 ⁇ 2 ⁇
  • the organic acid is a sulfonic acid.
  • the microporous layer is a xerogel layer.
  • the organic polymer comprises a polyvinylidene fluoride polymer.
  • the organic polymer comprises a copolymer of a first fluorinated organic monomer and a second organic monomer.
  • the separators of the present invention provide superior safety and other key performance properties for use in electric current producing cells, including, but not limited to, lithium batteries and capacitors.
  • microporous xerogel separators for electrochemical cells are described in U.S. Pat. Nos. 6,153,337 and 6,306,545, and in U.S. Pat. Application 20020092155, all to Carlson et al.
  • the liquid mixture described in these references for coating xerogel separators comprises an inorganic oxide, an organic binder, and typically water as the volatile liquid in the mixture.
  • the liquid mixture comprises organic solvents, preferably protic organic solvents. Examples of protic organic solvents are alcohols and glycols.
  • the drying process to form a xerogel layer involves the removal of the liquid in the liquid mixture.
  • xerogel layer and “xerogel structure,” as used herein, is meant, respectively, a layer of a coating or the structure of a coating layer in which the layer and structure were formed by drying a liquid sol or sol-gel mixture to form a solid gel matrix as, for example, described in Chem. Mater., Vol. 9, pages 1296 to 1298 (1997) by Ichinose et al. for coating layers of inorganic oxide based xerogels.
  • the resulting gel layer or film is termed, as used herein, a xerogel layer.
  • the microporous xerogel layers of this invention comprise a dried microporous three- dimensional solid network with pores which are interconnected in a substantially continuous fashion from one outermost surface of the layer through to the other outermost surface of the layer.
  • a continuous xerogel coating layer has the materials of the xerogel in a continuous structure in the coating layer, i.e., the materials, such as inorganic oxide particles, are in contact and do not have discontinuities in the structure, such as a discontinuous layer of solid pigment particles that are separated from each other.
  • xerogel pigment particles may be formed by a xerogel process involving drying a liquid solution of a suitable precursor to the pigment to form a dried mass of xerogel pigment particles, which is typically then ground to a fine powder to provide xerogel pigment particles.
  • the microporous inorganic oxide layers of this invention may be, but are not limited to, xerogel layers.
  • the inorganic oxide layers of the present invention may also be discontinuous layers of solid pigment particles that are not a xerogel coating layer and have discontinuities of solid pigment particles that are separated from each other in the structure of the discontinuous layer. This separation typically involves organic polymer interposed between the pigment particles.
  • xerogel coating and "xerogel coating layer,” as used herein, are synonymous with the term “xerogel layer.”
  • microporous describes the material of a layer or coating, in which the material possesses pores of a diameter of about 1 micron or less.
  • nanoporous describes the material of a layer or coating, in which the material possesses pores of a diameter of about 100 nanometers or less.
  • these pores are connected in a substantially continuous fashion from one outermost surface of the microporous layer through to the other outermost surface of the layer.
  • This substantially continuous 3-dimensional microporous inorganic oxide network is efficient in allowing the diffusion of ions, such as lithium ions, through the separator during the charging and discharging of the electric current producing cell.
  • the amount of the pores in the separator may be characterized by the percent porosity or percent pore volume, which is the cubic centimeters of pores per cubic centimeters of the separator.
  • the porosity may be measured by filling the pores with a relatively non-volatile liquid having a known density and then calculated by the increase in weight of the separator with the liquid present divided by the known density of the liquid and then dividing this quotient by the volume of the separator, as calculated from the area and average thickness of the separator.
  • the average pore diameter of the microporous inorganic oxide layer is from 2 nm to 70 ran. Typically, the average pore diameter of the microporous inorganic oxide layer is from 30 to 50 nm.
  • the pore sizes of the separators of this invention may provide ion transport and conductivity with lithium ion battery electrolytes that is at least equal to that of polyolefin separators.
  • the inorganic oxide is an aluminum oxide.
  • Other inorganic oxides such as zirconium oxides and silicas, as known in the art of electrolyte elements and separators for electrochemical cells, may be utilized alone or in combination with other inorganic oxides including aluminum oxides.
  • Preferred aluminum oxides are aluminum boehmites.
  • the term "pseudo-boehmite,” as used herein, pertains to hydrated aluminum oxides having the chemical formula, ⁇ 1 2 0 3 ⁇ 2 ⁇ , wherein x is in the range of 1.0 to 1.5.
  • pseudo-boehmite include “aluminum boehmite,” “boehmite,” “AIOOH,” and “hydrated alumina.”
  • the materials referred to herein as “pseudo- boehmite” are distinct from anhydrous aluminum oxides or aluminas (AI2O3 such as alpha-alumina or gamma-alumina) and hydrated aluminum oxides of the formula Al 2 0 3 »xH 2 0 wherein x is less than 1.0 or greater than 1.5.
  • the weight percent of the aluminum oxide in the separator is greater than 50%. This loading of the aluminum oxide helps to provide the porosity of the separator that is needed for conductivity and for rapid wetting by the electrolyte when manufacturing the electric current producing cell.
  • One aspect of the present invention pertains to a separator for an electric current producing cell, wherein the separator comprises a microporous layer comprising (a) at least 50% by weight of an aluminum oxide and (b) an organic polymer, wherein the aluminum oxide is surface modified by treatment with an organic acid to form a modified aluminum oxide.
  • the separator may contain only the microporous layer of this invention or may contain additional microporous layers, such as porous polyolefin layers as typically used in lithium ion batteries.
  • the microporous layer of the present invention may be coated on one or both sides of a microporous polyolefin layer, such as Celgard 2500, the trade name for a polyolefin separator membrane available from
  • the thickness of a coating of the microporous layer of this invention onto a polyolefin microporous separator is typically in, but not limited to, the range of 1 to 4 microns.
  • the organic acid is a sulfonic acid, preferably an aryl sulfonic acid, and more preferably a toluenesulfonic acid.
  • the organic acid is a carboxylic acid.
  • One purpose of the surface modification of the aluminum oxide is to make the aluminum oxide particles dispersible in organic solvents, especially in aprotic organic solvents. This broader scope of dispersibility is advantageous in enabling a wider range of organic polymers that are soluble in aprotic organic solvents, but not in water and alcohols, to be used.
  • Other types of surface modification of inorganic oxides as known in the art of surface modification of inorganic oxides for excellent dispersibility in aprotic organic solvents may be utilized in the present invention.
  • the aluminum oxide comprises a hydrated aluminum oxide of the formula ⁇ 2 ⁇ 3 ⁇ 2 0, wherein x is in the range of 1.0 to 1.5, and wherein the hydrated aluminum oxide is surface modified by treatment with an organic acid to form a modified hydrated aluminum oxide.
  • the modified aluminum oxide has an AI2O3 content in the range of 50 to 85% by weight.
  • the modified aluminum oxide has an AI2O3 content in the range of 65 to 80% by weight.
  • the separator comprises 60 to 90% by weight of the modified aluminum oxide.
  • the separator comprises 70 to 85% by weight of the modified aluminum oxide.
  • the microporous layer is a xerogel layer.
  • the organic polymer comprises a polyvinylidene fluoride (PVDF) polymer, such as KYNAR HSV 900, the trade name for a PVDF polymer for lithium battery and other applications available from Arkema, Inc.
  • the separator comprises a copolymer of a first fluorinated organic monomer and a second organic monomer.
  • the second organic monomer is a second fluorinated organic monomer.
  • the electric current producing cell is a secondary lithium ion cell. In one embodiment, the electric current producing cell is a primary lithium cell. In one embodiment, the electric current producing cell is a capacitor. In one embodiment, the separator does not melt at temperatures lower than 300°C. The aluminum oxide or other inorganic oxide material is primarily responsible for providing this non-melting and dimensionally stable property at high temperatures. In one embodiment, the separator is a flame retardant separator. The aluminum oxide or other inorganic oxide is a flame retardant material and, in
  • an electrochemical cell comprising an anode, a cathode, an organic electrolyte comprising a lithium salt, and a separator interposed between the anode and the cathode, wherein the separator comprises a microporous layer comprising (a) at least 50% by weight of an aluminum oxide and (b) an organic polymer, wherein the aluminum oxide is surface modified by treatment with an organic acid.
  • the organic acid is a sulfonic acid, preferably an aryl sulfonic acid, and more preferably a toluenesulfonic acid.
  • the organic acid is a carboxylic acid.
  • the aluminum oxide comprises a hydrated duminum oxide of the formula ⁇ 1 2 ⁇ 3 ⁇ 2 ⁇ , wherein x is in the range of 1.0 to 1.5, and wherein the hydrated aluminum oxide is surface modified by treatment with an organic acid to form a modified hydrated aluminum oxide.
  • the microporous layer is a xerogel layer.
  • the anode active material of the anode is lithium.
  • the modified aluminum oxide has an AI2O3 content in the range of 50 to 85% by weight. In one embodiment, the modified aluminum oxide has an AI2O3 content in the range of 65 to 80% by weight.
  • the organic polymer comprises a polyvinylidene fluoride polymer. In one embodiment, the organic polymer comprises a copolymer of a first fluorinated organic monomer and a second organic monomer. In one embodiment, the second organic monomer is a second fluorinated organic monomer. In one embodiment, the lithium salt is lithium
  • a capacitor comprising two electrodes, an organic electrolyte comprising a tetraalkyl ammonium salt, and a separator interposed between the two electrodes, wherein the separator comprises a microporous layer comprising (a) at least 50% by weight of an aluminum oxide and (b) an organic polymer, wherein the aluminum oxide is surface modified by treatment with an organic acid to form a modified aluminum oxide.
  • the inorganic oxide comprises a hydrated aluminum oxide of the formula ⁇ 1 2 ⁇ 3 ⁇ 2 0 wherein x is in the range of 1.0 tol .5, wherein the aluminum oxide is surface modified by treatment with an organic acid to form a modified aluminum oxide.
  • the organic acid is a sulfonic acid.
  • the microporous layer is a xerogel layer.
  • the organic polymer comprises a polyvinylidene fluoride polymer.
  • the organic polymer comprises a copolymer of a first fluorinated organic monomer and a second organic monomer.
  • a 20% by weight dispersion of DISPAL lOSR the trade name for a surface- modified aluminum oxide available from SASOL North America, Houston, TX, in methyl ethyl ketone was prepared.
  • MSDS Material Safety Data Sheet
  • the aluminum oxide is an aluminum boehmite
  • the surface modification comprises p-toluenesulfonic acid (PTSA).
  • PTSA p-toluenesulfonic acid
  • NMP N-methyl pyrrolidone
  • This dispersion was coated onto a 3 mil thick silicone treated polyester (PET) film on the silicone release side to give a dry coating thickness of about 20 microns and then delaminated from the release substrate to provide a free standing aluminum oxide microporous separator with a porosity of about 43%.
  • PET silicone treated polyester
  • the aluminum oxide separator did not melt at temperatures below 300°C and was flame retardant, as shown by not burning when exposed to an open flame.
  • Example 2
  • Example 1 The aluminum oxide and fluoropolymer dispersion of Example 1 was coated onto a 20 micron thick polyolefin separator from Ube and dried at 90°C to avoid shrinkage and melting of the polyolefin separator. The thickness of the coating was varied from 1 to 4 microns dry and coated on one or both sides of the polyolefin separator. Button cells as described in Example 1 were prepared with a 2 micron thick aluminum oxide
  • microporous coating on one or both sides of the polyolefin separator gave
  • DISPAL 10F4 the trade name for a surface- modified aluminum boehmite available from SASOL North America, Houston, TX, in methyl ethyl ketone was mixed at 2200 rpm stirring for 40 minutes. No satisfactory dispersion was obtained, and nearly all of the pigment settled to the bottom of the mix container.
  • MSDS Material Safety Data Sheet
  • the surface modification comprises formic acid.
  • a 10% by weight solution of KYNAR HSV 900 in NMP was prepared.
  • the non-dispersed DISPAL 10F4 mix in methyl ethyl ketone was added to the stirred fluoropolymer solution at a dry weight ratio of 3:1 of the aluminum boehmite and fluoropolymer with continued stirring at 2200 rpm for 40 minutes. No satisfactory dispersion was obtained, and nearly all of the pigment settled to the bottom of the mix container. The mix was not suitable for coating a separator layer on a release substrate.
  • a 7.5% by weight solution of KYNAR HSV 900 in NMP was prepared.
  • DISPAL 10F4 in a dry weight ratio of 5:1 of the aluminum boehmite and fluoropolymer was added slowly with continued stirring at 2200 rpm for 40 minutes. No satisfactory dispersion was obtained, and nearly all of the pigment settled to the bottom of the mix container. The mix was not suitable for coating a separator layer on a release substrate.
  • Comparative Examples 1 and 2 show that surface modification of an aluminum oxide with formic acid does not provide dispersibility in aprotic solvents as represented by NMP and methyl ethyl ketone and consequently is not suitable for coating separators with polyvinylidene fluoride (PVdF) and other fiuoropolymers that require aprotic solvents such as NMP for solubility and for use in coatings, such as a separator or battery electrode coating.
  • PVdF polyvinylidene fluoride

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Cell Separators (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Secondary Cells (AREA)
  • Primary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Provided are separators for use in batteries and capacitors comprising (a) at least 50% by weight of an aluminum oxide and (b) an organic polymer, wherein the aluminum oxide is surface modified by treatment with an organic acid to form a modified aluminum oxide, and wherein the treatment provides dispersibility of the aluminum oxide in aprotic solvents such as N-methyl pyrrolidone. Preferably, the organic acid is a sulfonic acid, such as p-toluenesulfonic acid. Also preferably, the organic polymer is a fluorinated polymer, such as polyvinylidene fluoride. Also provided are electrochemical cells and capacitors comprising such separators.

Description

SEPARATORS FOR ELECTROCHEMICAL CELLS
FIELD OF THE INVENTION
The present invention relates generally to the field of porous membranes and to the fields of electric current producing cells and of separators for use in electric current producing cells. More particularly, this invention pertains to a porous separator membrane comprising an aluminum oxide and an organic polymer where the aluminum oxide has been surface modified by treatment with an organic acid to provide
dispersibility in aprotic organic solvents. Also, the present invention pertains to electric current producing cells, such as lithium ion cells and capacitors, comprising such porous separators.
BACKGROUND
An electroactive material that has been fabricated into a structure for use in an electrochemical cell is referred to as an electrode. Of a pair of electrodes used in an electrochemical cell, the electrode on the electrochemically higher potential side is referred to as the positive electrode or the cathode, while the electrode on the
electrochemically lower potential side is referred to as the negative electrode, or the anode. A battery may contain one or more electrochemical cells.
To prevent the undesirable flow of the electrons in a short circuit internally from the anode to the cathode, an electrolyte element is interposed between the cathode and the anode. This electrolyte element must be electronically non-conductive to prevent short circuits, but must permit the transport of ions between the anode and the cathode. The electrolyte element should also be stable electrochemically and chemically toward both the anode and the cathode.
Typically, the electrolyte element contains a porous material, referred to as a separator (since it separates or insulates the anode and the cathode from each other), and an aqueous or non-aqueous electrolyte, that usually comprises an ionic electrolyte salt and ionically conductive material, in the pores of the separator. A variety of materials have been used for the porous layer or separator of the electrolyte element in electrochemical cells. These porous separator materials include polyolefins such as polyethylenes and polypropylenes, glass fiber filter papers, and ceramic materials.
Usually these separator materials are supplied as porous free-standing membranes that are interleaved with the anodes and the cathodes in the fabrication of electrochemical cells.
A liquid organic electrolyte containing organic solvents and lithium salts is typically used as the electrolyte in the pores of the separator in the electrolyte element for rechargeable or secondary lithium ion and non-rechargeable or primary lithium electrochemical cells. Alternatively, a gel or solid polymer electrolyte containing an ionically conductive polymer and lithium salts, and optionally organic solvents, might be utilized instead of the liquid organic electrolyte.
In addition to being porous and chemically stable to the other materials of the electric current producing cell, the separator should be flexible, thin, economical in cost, and have good mechanical strength and safety properties.
High porosity in the separator is important for obtaining the high ionic
conductivity needed for effective performance in most batteries, except, for example, those batteries operating at relatively low charge and discharge rates, and for efficiency in capacitors, such as supercapacitors. It is desirable for the separator to have a porosity of at least 30 percent, and preferably 40 percent or higher, in lithium ion batteries.
Another highly desirable feature of the separator in the electrolyte element is that it is readily wetted by the electrolyte materials that provide the ionic conductivity. When the separator material is a polyolefin material that has non-polar surface properties, the electrolyte materials (which typically have highly polar properties) often poorly wet the separator material. This results in longer times to fill the battery with electrolyte and potentially in low capacities in the battery due to a non-uniform distribution of electrolyte materials in the electrolyte element.
The separators used for lithium ion batteries are typically polyolefin separators, which melt at below 200°C and are very flammable. The lithium ion batteries, as well as lithium primary batteries and some capacitors, utilize highly flammable organic solvents in their electrolytes. A non-melting and flame retardant separator would help prevent the spread of any burning of the organic electrolyte, caused by an internal short circuit, thermal runaway, or other unsafe condition, that might spread into a larger area of the battery or capacitor and cause a major explosion. As lithium ion batteries are
increasingly utilized for high power applications, such as for electric vehicles, the need for improved safety is greatly increased because of the very large size and high power rates of these vehicle batteries.
A separator that is applicable for lithium ion and other electric current producing cells and that has flame retardant and non-melting properties that provide safety against internal short shorts and thermal runaway, while maintaining the chemical stability of the electrolyte and of the separator, would be of great value to the battery and capacitor industry.
SUMMARY OF THE INVENTION To achieve increased safety in separators for use in electric current producing cells such as batteries and capacitors, the present invention utilizes non-flammable inorganic oxides, such as aluminum oxides, and preferably non-flammable organic polymers having fluorinated groups in the separators. This invention utilizes various inorganic oxide particle pretreatment, mixing, coating, drying, and delaminating methods for preparing such separators.
One aspect of the present invention pertains to a separator for an electric current producing cell, wherein the separator comprises a microporous layer comprising (a) at least 50% by weight of an aluminum oxide and (b) an organic polymer, wherein the aluminum oxide is surface modified by treatment with an organic acid to form a modified aluminum oxide. In one embodiment, the organic acid is a sulfonic acid, preferably an aryl sulfonic acid, and more preferably a toluenesulfonic acid. In one embodiment, the organic acid is a carboxylic acid. In one embodiment, the aluminum oxide comprises a hydrated aluminum oxide of the formula Al2O3*xH2O, wherein x is in the range of 1.0 to 1.5, and wherein the hydrated aluminum oxide is surface modified by treatment with an organic acid to form a modified hydrated aluminum oxide. In one embodiment, the modified aluminum oxide has an Al2O3 content in the range of 50 to 85% by weight. In one embodiment, the modified aluminum oxide has an AI2O3 content in the range of 65 to 80% by weight. In one embodiment, the separator comprises 60 to 90% by weight of the modified aluminum oxide. In one embodiment, the separator comprises 70 to 85%) by weight of the modified aluminum oxide. In one embodiment, the microporous layer is a xerogel layer. In one embodiment, the organic polymer comprises a polyvinylidene fluoride polymer. In one embodiment, the separator comprises a copolymer of a first fluorinated organic monomer and a second organic monomer. In one embodiment, the second organic monomer is a second fluorinated organic monomer.
In one embodiment of the separators of this invention, the electric current producing cell is a secondary lithium ion cell. In one embodiment, the electric current producing cell is a primary lithium cell. In one embodiment, the electric current producing cell is a capacitor. In one embodiment, the separator does not melt at temperatures lower than 300°C. In one embodiment, the separator is a flame retardant separator.
Another aspect of the present invention pertains to an electrochemical cell comprising an anode, a cathode, an organic electrolyte comprising a lithium salt, and a separator interposed between the anode and the cathode, wherein the separator comprises a microporous layer comprising (a) at least 50% by weight of an aluminum oxide and (b) an organic polymer, wherein the aluminum oxide is surface modified by treatment with an organic acid. In one embodiment, the organic acid is a sulfonic acid, preferably an aryl sulfonic acid, and more preferably a toluenesulfonic acid. In one embodiment, the organic acid is a carboxylic acid. In one embodiment, the aluminum oxide comprises a hydrated aluminum oxide of the formula Αΐ2θ3·χΗ20, wherein x is in the range of 1.0 to 1.5, and wherein the hydrated aluminum oxide is surface modified by treatment with an organic acid to form a modified hydrated aluminum oxide.
In one embodiment of the electrochemical cells of this invention, the microporous layer is a xerogel layer. In one embodiment, the anode active material of the anode is lithium. In one embodiment, the modified aluminum oxide has an AI2O3 content in the range of 50 to 85% by weight. In one embodiment, the modified aluminum oxide has an AI2O3 content in the range of 65 to 80% by weight. In one embodiment, the organic polymer comprises a polyvinylidene fluoride polymer. In one embodiment, the organic polymer comprises a copolymer of a first fluorinated organic monomer and a second organic monomer. In one embodiment, the second organic monomer is a second fluorinated organic monomer. In one embodiment, the lithium salt is lithium
hexafluorophosphate.
Another aspect of the present invention relates to a capacitor comprising two electrodes, an organic electrolyte comprising a tetraalkyl ammonium salt, and a separator interposed between the two electrodes, wherein the separator comprises a microporous layer comprising (a) at least 50% by weight of an aluminum oxide and (b) an organic polymer, wherein the aluminum oxide is surface modified by treatment with an organic acid to form a modified aluminum oxide. In one embodiment, the inorganic oxide comprises a hydrated aluminum oxide of the formula Αΐ2θ3·χΗ2θ| wherein x is in the range of 1.0 to 1.5, wherein the aluminum oxide is surface modified by treatment with an organic acid to form a modified aluminum oxide. In one embodiment, the organic acid is a sulfonic acid. In one embodiment, the microporous layer is a xerogel layer. In one embodiment, the organic polymer comprises a polyvinylidene fluoride polymer. In one embodiment, the organic polymer comprises a copolymer of a first fluorinated organic monomer and a second organic monomer.
DETAILED DESCRIPTION OF THE INVENTION
The separators of the present invention provide superior safety and other key performance properties for use in electric current producing cells, including, but not limited to, lithium batteries and capacitors.
Methods of preparing microporous xerogel separators for electrochemical cells are described in U.S. Pat. Nos. 6,153,337 and 6,306,545, and in U.S. Pat. Application 20020092155, all to Carlson et al. The liquid mixture described in these references for coating xerogel separators comprises an inorganic oxide, an organic binder, and typically water as the volatile liquid in the mixture. Optionally, the liquid mixture comprises organic solvents, preferably protic organic solvents. Examples of protic organic solvents are alcohols and glycols. The drying process to form a xerogel layer involves the removal of the liquid in the liquid mixture. As is known in the art of inorganic oxide xerogel coatings, as the liquid is removed, the colloidal particles of inorganic oxide sol form a gel that, upon further loss of liquid, forms a 3 -dimensional microporous network of inorganic oxide. By the terms "xerogel layer" and "xerogel structure," as used herein, is meant, respectively, a layer of a coating or the structure of a coating layer in which the layer and structure were formed by drying a liquid sol or sol-gel mixture to form a solid gel matrix as, for example, described in Chem. Mater., Vol. 9, pages 1296 to 1298 (1997) by Ichinose et al. for coating layers of inorganic oxide based xerogels.
Thus, if the liquid of the gel formed in the liquid sol-gel mixture is removed substantially, for example, through the formation of a liquid-vapor boundary phase, the resulting gel layer or film is termed, as used herein, a xerogel layer. Thus, the microporous xerogel layers of this invention comprise a dried microporous three- dimensional solid network with pores which are interconnected in a substantially continuous fashion from one outermost surface of the layer through to the other outermost surface of the layer. A continuous xerogel coating layer has the materials of the xerogel in a continuous structure in the coating layer, i.e., the materials, such as inorganic oxide particles, are in contact and do not have discontinuities in the structure, such as a discontinuous layer of solid pigment particles that are separated from each other.
In contrast, xerogel pigment particles may be formed by a xerogel process involving drying a liquid solution of a suitable precursor to the pigment to form a dried mass of xerogel pigment particles, which is typically then ground to a fine powder to provide xerogel pigment particles. The microporous inorganic oxide layers of this invention may be, but are not limited to, xerogel layers. The inorganic oxide layers of the present invention may also be discontinuous layers of solid pigment particles that are not a xerogel coating layer and have discontinuities of solid pigment particles that are separated from each other in the structure of the discontinuous layer. This separation typically involves organic polymer interposed between the pigment particles. The terms "xerogel coating" and "xerogel coating layer," as used herein, are synonymous with the term "xerogel layer." As used herein, the term "microporous" describes the material of a layer or coating, in which the material possesses pores of a diameter of about 1 micron or less. As used herein, the term "nanoporous" describes the material of a layer or coating, in which the material possesses pores of a diameter of about 100 nanometers or less.
Preferably for battery and capacitor separator applications, these pores are connected in a substantially continuous fashion from one outermost surface of the microporous layer through to the other outermost surface of the layer. This substantially continuous 3-dimensional microporous inorganic oxide network is efficient in allowing the diffusion of ions, such as lithium ions, through the separator during the charging and discharging of the electric current producing cell.
The amount of the pores in the separator may be characterized by the percent porosity or percent pore volume, which is the cubic centimeters of pores per cubic centimeters of the separator. The porosity may be measured by filling the pores with a relatively non-volatile liquid having a known density and then calculated by the increase in weight of the separator with the liquid present divided by the known density of the liquid and then dividing this quotient by the volume of the separator, as calculated from the area and average thickness of the separator.
In one embodiment of the separators of this invention, the average pore diameter of the microporous inorganic oxide layer is from 2 nm to 70 ran. Typically, the average pore diameter of the microporous inorganic oxide layer is from 30 to 50 nm. These extremely small pores, that are about 5 to 10 times smaller than the average pore dimensions of polyolefin separators, present no limitation to high conductivity with lithium salt electrolytes. Thus, the pore sizes of the separators of this invention may provide ion transport and conductivity with lithium ion battery electrolytes that is at least equal to that of polyolefin separators.
In one embodiment of the separators of this invention, the inorganic oxide is an aluminum oxide. Other inorganic oxides, such as zirconium oxides and silicas, as known in the art of electrolyte elements and separators for electrochemical cells, may be utilized alone or in combination with other inorganic oxides including aluminum oxides.
Preferred aluminum oxides are aluminum boehmites. The term "pseudo-boehmite," as used herein, pertains to hydrated aluminum oxides having the chemical formula, Α1203·χΗ2θ, wherein x is in the range of 1.0 to 1.5. Terms used herein, which are synonymous with "pseudo-boehmite," include "aluminum boehmite," "boehmite," "AIOOH," and "hydrated alumina." The materials referred to herein as "pseudo- boehmite" are distinct from anhydrous aluminum oxides or aluminas (AI2O3 such as alpha-alumina or gamma-alumina) and hydrated aluminum oxides of the formula Al203»xH20 wherein x is less than 1.0 or greater than 1.5. In one embodiment of the separators of the present invention, the weight percent of the aluminum oxide in the separator is greater than 50%. This loading of the aluminum oxide helps to provide the porosity of the separator that is needed for conductivity and for rapid wetting by the electrolyte when manufacturing the electric current producing cell.
One aspect of the present invention pertains to a separator for an electric current producing cell, wherein the separator comprises a microporous layer comprising (a) at least 50% by weight of an aluminum oxide and (b) an organic polymer, wherein the aluminum oxide is surface modified by treatment with an organic acid to form a modified aluminum oxide. The separator may contain only the microporous layer of this invention or may contain additional microporous layers, such as porous polyolefin layers as typically used in lithium ion batteries. For example, the microporous layer of the present invention may be coated on one or both sides of a microporous polyolefin layer, such as Celgard 2500, the trade name for a polyolefin separator membrane available from
Polypore, Inc., of Charlotte, NC. Whereas a thickness of 5 to 20 microns is typical for the separators of this invention that contain only the microporous layers of this invention, the thickness of a coating of the microporous layer of this invention onto a polyolefin microporous separator is typically in, but not limited to, the range of 1 to 4 microns.
In one embodiment of the separators of the present invention, the organic acid is a sulfonic acid, preferably an aryl sulfonic acid, and more preferably a toluenesulfonic acid. In one embodiment, the organic acid is a carboxylic acid. One purpose of the surface modification of the aluminum oxide is to make the aluminum oxide particles dispersible in organic solvents, especially in aprotic organic solvents. This broader scope of dispersibility is advantageous in enabling a wider range of organic polymers that are soluble in aprotic organic solvents, but not in water and alcohols, to be used. Other types of surface modification of inorganic oxides, as known in the art of surface modification of inorganic oxides for excellent dispersibility in aprotic organic solvents may be utilized in the present invention.
In one embodiment of the separators of this invention, the aluminum oxide comprises a hydrated aluminum oxide of the formula Αΐ2θ3·χΗ20, wherein x is in the range of 1.0 to 1.5, and wherein the hydrated aluminum oxide is surface modified by treatment with an organic acid to form a modified hydrated aluminum oxide. In one embodiment, the modified aluminum oxide has an AI2O3 content in the range of 50 to 85% by weight. In one embodiment, the modified aluminum oxide has an AI2O3 content in the range of 65 to 80% by weight. In one embodiment, the separator comprises 60 to 90% by weight of the modified aluminum oxide. In one embodiment, the separator comprises 70 to 85% by weight of the modified aluminum oxide. In one embodiment, the microporous layer is a xerogel layer. In one embodiment, the organic polymer comprises a polyvinylidene fluoride (PVDF) polymer, such as KYNAR HSV 900, the trade name for a PVDF polymer for lithium battery and other applications available from Arkema, Inc. In one embodiment, the separator comprises a copolymer of a first fluorinated organic monomer and a second organic monomer. In one embodiment, the second organic monomer is a second fluorinated organic monomer.
In one embodiment of the separators of this invention, the electric current producing cell is a secondary lithium ion cell. In one embodiment, the electric current producing cell is a primary lithium cell. In one embodiment, the electric current producing cell is a capacitor. In one embodiment, the separator does not melt at temperatures lower than 300°C. The aluminum oxide or other inorganic oxide material is primarily responsible for providing this non-melting and dimensionally stable property at high temperatures. In one embodiment, the separator is a flame retardant separator. The aluminum oxide or other inorganic oxide is a flame retardant material and, in
combination with a highly fluorinated organic polymer which is also flame retardant, provides a flame retardant separator.
Another aspect of the present invention pertains to an electrochemical cell comprising an anode, a cathode, an organic electrolyte comprising a lithium salt, and a separator interposed between the anode and the cathode, wherein the separator comprises a microporous layer comprising (a) at least 50% by weight of an aluminum oxide and (b) an organic polymer, wherein the aluminum oxide is surface modified by treatment with an organic acid. In one embodiment, the organic acid is a sulfonic acid, preferably an aryl sulfonic acid, and more preferably a toluenesulfonic acid. In one embodiment, the organic acid is a carboxylic acid. In one embodiment, the aluminum oxide comprises a hydrated duminum oxide of the formula Α12θ3·χΗ2θ, wherein x is in the range of 1.0 to 1.5, and wherein the hydrated aluminum oxide is surface modified by treatment with an organic acid to form a modified hydrated aluminum oxide.
In one embodiment of the electrochemical cells of this invention, the microporous layer is a xerogel layer. In one embodiment, the anode active material of the anode is lithium. In one embodiment, the modified aluminum oxide has an AI2O3 content in the range of 50 to 85% by weight. In one embodiment, the modified aluminum oxide has an AI2O3 content in the range of 65 to 80% by weight. In one embodiment, the organic polymer comprises a polyvinylidene fluoride polymer. In one embodiment, the organic polymer comprises a copolymer of a first fluorinated organic monomer and a second organic monomer. In one embodiment, the second organic monomer is a second fluorinated organic monomer. In one embodiment, the lithium salt is lithium
hexafluorophosphate.
Another aspect of the present invention relates to a capacitor comprising two electrodes, an organic electrolyte comprising a tetraalkyl ammonium salt, and a separator interposed between the two electrodes, wherein the separator comprises a microporous layer comprising (a) at least 50% by weight of an aluminum oxide and (b) an organic polymer, wherein the aluminum oxide is surface modified by treatment with an organic acid to form a modified aluminum oxide. In one embodiment, the inorganic oxide comprises a hydrated aluminum oxide of the formula Α12θ3·χΗ20 wherein x is in the range of 1.0 tol .5, wherein the aluminum oxide is surface modified by treatment with an organic acid to form a modified aluminum oxide. In one embodiment, the organic acid is a sulfonic acid. In one embodiment, the microporous layer is a xerogel layer. In one embodiment, the organic polymer comprises a polyvinylidene fluoride polymer. In one embodiment, the organic polymer comprises a copolymer of a first fluorinated organic monomer and a second organic monomer. EXAMPLES
Several embodiments of the present invention are described in the following examples, which are offered by way of illustration and not by way of limitation.
Example 1
A 20% by weight dispersion of DISPAL lOSR, the trade name for a surface- modified aluminum oxide available from SASOL North America, Houston, TX, in methyl ethyl ketone was prepared. According to the Material Safety Data Sheet (MSDS) by SASOL for DISPAL 10SR, the aluminum oxide is an aluminum boehmite, and the surface modification comprises p-toluenesulfonic acid (PTSA). Separately, a 10% by weight solution of KYNAR HSV 900 in N-methyl pyrrolidone (NMP) was prepared. The aluminum oxide dispersion was added to the stirred fluoropolymer solution to prepare a dispersion containing the aluminum oxide and fluoropolymer in a dry weight ratio of 5:1. The % solids of this dispersion was about 17%.
This dispersion was coated onto a 3 mil thick silicone treated polyester (PET) film on the silicone release side to give a dry coating thickness of about 20 microns and then delaminated from the release substrate to provide a free standing aluminum oxide microporous separator with a porosity of about 43%. Evaluation of this alurninum oxide microporous separator in a typical lithium ion button cell with a graprute-containing anode, a lithium hexfluorophosphate-containing electrolyte in organic carbonate solvents, and a cobalt oxide-containing cathode showed equal or better chemical stability at 55°C, cycling, and ionic conductivity at 1C and 5C charge, in comparison to a control button cell with an Ube polyolefin separator of the same thickness substituted for the aluminum oxide separator.
The aluminum oxide separator did not melt at temperatures below 300°C and was flame retardant, as shown by not burning when exposed to an open flame. Example 2
The aluminum oxide and fluoropolymer dispersion of Example 1 was coated onto a 20 micron thick polyolefin separator from Ube and dried at 90°C to avoid shrinkage and melting of the polyolefin separator. The thickness of the coating was varied from 1 to 4 microns dry and coated on one or both sides of the polyolefin separator. Button cells as described in Example 1 were prepared with a 2 micron thick aluminum oxide
microporous coating on one or both sides of the polyolefin separator and gave
comparable stability at 55°C, cycling, and conductivity to control button cells with the polyolefin separator only.
Comparative Example 1
A 20% by weight dispersion of DISPAL 10F4, the trade name for a surface- modified aluminum boehmite available from SASOL North America, Houston, TX, in methyl ethyl ketone was mixed at 2200 rpm stirring for 40 minutes. No satisfactory dispersion was obtained, and nearly all of the pigment settled to the bottom of the mix container. According to the Material Safety Data Sheet (MSDS) by SASOL for DISPAL 10F4, the surface modification comprises formic acid. Separately, a 10% by weight solution of KYNAR HSV 900 in NMP was prepared. The non-dispersed DISPAL 10F4 mix in methyl ethyl ketone was added to the stirred fluoropolymer solution at a dry weight ratio of 3:1 of the aluminum boehmite and fluoropolymer with continued stirring at 2200 rpm for 40 minutes. No satisfactory dispersion was obtained, and nearly all of the pigment settled to the bottom of the mix container. The mix was not suitable for coating a separator layer on a release substrate.
Comparative Example 2
A 7.5% by weight solution of KYNAR HSV 900 in NMP was prepared. To this fluoropolymer solution with stirring at 2200 rpm, DISPAL 10F4 in a dry weight ratio of 5:1 of the aluminum boehmite and fluoropolymer was added slowly with continued stirring at 2200 rpm for 40 minutes. No satisfactory dispersion was obtained, and nearly all of the pigment settled to the bottom of the mix container. The mix was not suitable for coating a separator layer on a release substrate.
Comparative Examples 1 and 2 show that surface modification of an aluminum oxide with formic acid does not provide dispersibility in aprotic solvents as represented by NMP and methyl ethyl ketone and consequently is not suitable for coating separators with polyvinylidene fluoride (PVdF) and other fiuoropolymers that require aprotic solvents such as NMP for solubility and for use in coatings, such as a separator or battery electrode coating.
While the invention has been described in detail and with reference to specific and general embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims

What is claimed is:
1. A separator for an electric current producing cell, wherein said separator
comprises a microporous layer comprising (a) at least 50% by weight of an aluminum oxide and (b) an organic polymer, wherein said aluminum oxide is surface modified by treatment with an organic acid to form a modified aluminum oxide, and wherein said treatment provides dispersibility of said aluminum oxide in aprotic solvents, and said organic polymer comprises a first fluorinated organic monomer and a second organic monomer or said organic polymer comprises a polyvinylidene fluoride polymer.
2. The separator of claim 1, wherein said organic acid is a sulfonic acid.
3. The separator of claim 2, wherein said sulfonic acid is an aryl sulfonic acid, preferably a toluenesulfonic acid.
4. The separator of claim 1, wherein said organic acid is a carboxylic acid.
5. The separator of any of the preceding claims, wherein said aluminum oxide
comprises a hydrated aluminum oxide of the formula Α12θ3·χΗ20, wherein x is in the range of 1.0 to 1.5, and wherein said hydrated aluminum oxide is surface modified by treatment with an organic acid to form a modified hydrated aluminum oxide.
6. The separator of any of the preceding claims, wherein said separator comprises 60 to 90% by weight of said modified aluminum oxide.
7. The separator of any of the preceding claims, wherein said microporous layer is a xerogel layer with an average pore diameter from 2 nm to 70 nm.
The separator of any of the preceding claims, wherein said electric current producing cell is a secondary lithium ion cell, a primary lithium cell, or a capacitor.
The separator of any of the preceding claims, wherein said mircroporous layer is coated on one or both sides of at least one microporous polyolefin layer.
An electrochemical cell comprising an anode, a cathode, an organic electrolyte comprising a lithium salt, and a separator interposed between said anode and said cathode, wherein said separator comprises a microporous layer comprising (a) at least 50% by weight of an aluminum oxide and (b) an organic polymer, wherein said aluminum oxide is surface modified by treatment with an organic acid to form a modified aluminum oxide, and wherein said treatment provides dispersibility of said aluminum oxide in aprotic solvents, and said organic polymer comprises a first fluorinated organic monomer and a second organic monomer or said organic polymer comprises a polyvinylidene fluoride polymer.
11. The cell of claim 10, wherein said organic acid is a sulfonic acid.
12. The cell of claim 11, wherein said sulfonic acid is an aryl sulfonic acid, preferably a toluenesulfonic acid.
13. The cell of claim 10, wherein said organic acid is a carboxylic acid.
14. The cell of any of the claims 10 to 13, wherein said aluminum oxide comprises a hydrated aluminum oxide of the formula Al2C>3*xH20, wherein x is in the range of 1.0 to 1.5, and wherein said hydrated aluminum oxide is surface modified by treatment with an organic acid to form a modified hydrated aluminum oxide.
15. The cell of any of the claims 10 to 14, wherein said microporous layer is a xerogel layer with an average pore diameter from 2 nm to 70 nm.
16. The cell of any of the claims 10 to 15, wherein said microporous layer is coated on one or both sides of least one microporous polyolefin layer.
17. The cell of any of the claims 10 to 16, wherein the anode active material of said anode is lithium.
18. The cell of any of the claims 10 to 17, wherein said lithium salt is lithium
hexafluorophosphate.
19. A capacitor comprising two electrodes, an organic electrolyte comprising a
tetraalkyl ammonium salt, and a separator interposed between said two electrodes, wherein said separator comprises a microporous layer comprising (a) at least 50% by weight of an aluminum oxide and (b) an organic polymer, wherein said aluminum oxide is surface modified by treatment with an organic acid to form a modified aluminum oxide, and wherein said treatment provides dispersibility of said aluminum oxide in aprotic solvents, and said organic polymer comprises a first fluorinated organic monomer and a second organic monomer or said organic polymer comprises a polyvinylidene fluoride polymer.
20. The capacitor of claim 19, wherein said organic acid is a sulfonic acid.
21. The capacitor of claim 20, wherein said sulfonic acid is an aryl sulfonic acid, preferably a toluenesulfonic acid.
22. The capacitor of claim 19, wherein said organic acid is a carboxylic acid.
23. The capacitor of any of the claims 19 to 22, wherein said inorganic oxide
comprises a hydrated aluminum oxide of the formula Αΐ2θ3·χΗ20 wherein x is in the range of 1.0 to 1.5, and wherein said aluminum oxide is surface modified by treatment with an organic acid to form a modified aluminum oxide.
24. The capacitor of any of the claims 19 to 23, wherein said microporous layer is a xerogel layer with an average pore diameter from 2 nm to 70 nm.
25. The capacitor of any of the claims 19 to 24, wherein said microporous layer is coated on one or both sides of at least one microporous polyolefin layer.
26. Use of the separator of any of the claims 1 to 9 in an electric current producing cell.
27. Use of claim 26, wherein the electric current producing cell is a secondary lithium ion cell, a primary lithium cell, or a capacitor.
PCT/US2011/001274 2010-07-19 2011-07-18 Separators for electrochemical cells Ceased WO2012011944A2 (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
ES11761412T ES2713517T3 (en) 2010-07-19 2011-07-18 Separators for electrochemical cells
CN201180035701.3A CN103283060B (en) 2010-07-19 2011-07-18 Separators for electrochemical cells
DK11761412.3T DK2596538T3 (en) 2010-07-19 2011-07-18 SEPARATORS FOR ELECTROCHEMICAL CELLS
PL11761412T PL2596538T3 (en) 2010-07-19 2011-07-18 Separators for electrochemical cells
EP18198974.0A EP3444867B1 (en) 2010-07-19 2011-07-18 Separators for electrochemical cells
KR1020137003965A KR20140018171A (en) 2010-07-19 2011-07-18 Separators for electrochemical cells
JP2013520699A JP5990804B2 (en) 2010-07-19 2011-07-18 Electrochemical battery separator
EP11761412.3A EP2596538B1 (en) 2010-07-19 2011-07-18 Separators for electrochemical cells
US13/744,702 US20130171500A1 (en) 2010-07-19 2013-01-18 Separators for electrochemical cells
US15/616,399 US10833307B2 (en) 2010-07-19 2017-06-07 Separators for electrochemical cells
US17/088,351 US11728544B2 (en) 2010-07-19 2020-11-03 Separators for electrochemical cells
US18/216,293 US12327881B2 (en) 2010-07-19 2023-06-29 Separators for electrochemical cells

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US39988310P 2010-07-19 2010-07-19
US61/399,883 2010-07-19

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/744,702 Continuation US20130171500A1 (en) 2010-07-19 2013-01-18 Separators for electrochemical cells

Publications (2)

Publication Number Publication Date
WO2012011944A2 true WO2012011944A2 (en) 2012-01-26
WO2012011944A3 WO2012011944A3 (en) 2013-02-28

Family

ID=44681400

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2011/001274 Ceased WO2012011944A2 (en) 2010-07-19 2011-07-18 Separators for electrochemical cells

Country Status (9)

Country Link
US (4) US20130171500A1 (en)
EP (2) EP2596538B1 (en)
JP (2) JP5990804B2 (en)
KR (1) KR20140018171A (en)
CN (2) CN106784556A (en)
DK (1) DK2596538T3 (en)
ES (1) ES2713517T3 (en)
PL (1) PL2596538T3 (en)
WO (1) WO2012011944A2 (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2830125A1 (en) 2013-07-22 2015-01-28 Sihl GmbH Separator for an electrochemical cell and method for producing the same
JP2016517161A (en) * 2013-04-29 2016-06-09 マディコ インコーポレイテッド Nanoporous composite separator with enhanced thermal conductivity
JPWO2014021292A1 (en) * 2012-07-30 2016-07-21 帝人株式会社 Nonaqueous electrolyte battery separator and nonaqueous electrolyte battery
US10381623B2 (en) 2015-07-09 2019-08-13 Optodot Corporation Nanoporous separators for batteries and related manufacturing methods
US10505168B2 (en) 2006-02-15 2019-12-10 Optodot Corporation Separators for electrochemical cells
US10833307B2 (en) 2010-07-19 2020-11-10 Optodot Corporation Separators for electrochemical cells
US12040506B2 (en) 2015-04-15 2024-07-16 Lg Energy Solution, Ltd. Nanoporous separators for batteries and related manufacturing methods
US12278344B2 (en) 2022-12-16 2025-04-15 24M Technologies, Inc. Systems and methods for minimizing and preventing dendrite formation in electrochemical cells
US12401089B2 (en) 2021-04-29 2025-08-26 24M Technologies, Inc. Electrochemical cells with multiple separators, and methods of producing the same
US12431545B1 (en) 2024-03-26 2025-09-30 24M Technologies, Inc. Systems and methods for minimizing and preventing dendrite formation in electrochemical cells

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014046131A1 (en) * 2012-09-20 2014-03-27 旭化成株式会社 Lithium ion capacitor
EP3353844B1 (en) 2015-03-27 2022-05-11 Mason K. Harrup All-inorganic solvents for electrolytes
US20170098857A1 (en) * 2015-04-15 2017-04-06 Optodot Corporation Coated stacks for batteries and related manufacturing methods
KR20180031628A (en) * 2015-04-15 2018-03-28 옵토도트 코포레이션 Coated stacks for batteries and related manufacturing methods
CA2987938C (en) * 2015-06-01 2023-09-26 Pneumaticoat Technologies Llc Nano-engineered coatings for anode active materials, cathode active materials, and solid-state electrolytes and methods of making batteries containing nano-engineered coatings
JP6638315B2 (en) * 2015-10-22 2020-01-29 株式会社ジェイテクト Lithium ion capacitor
CN105932210A (en) * 2016-05-19 2016-09-07 湖南锂顺能源科技有限公司 Lithium ion battery alumina hydrate coating membrane and preparation method thereof
US10707531B1 (en) 2016-09-27 2020-07-07 New Dominion Enterprises Inc. All-inorganic solvents for electrolytes
TWI778006B (en) 2017-01-16 2022-09-21 日商巴川製紙所股份有限公司 Self-heating sheet-like material for absorbing and desorbing moisture, moisture absorbing and desorbing body, and moisture absorbing and desorbing device using the same
US20200395583A1 (en) 2017-10-09 2020-12-17 Optodot Corporation Separator for electrochemical cells and method of making the same
CN116581479A (en) 2017-10-13 2023-08-11 株式会社Lg新能源 Multilayer nanoporous separators
EP4007035A4 (en) 2019-08-16 2023-01-04 Lg Energy Solution, Ltd. SEPARATOR HAVING A HEAT-RESISTANT LAYER FOR ELECTROCHEMICAL DEVICE AND SECONDARY BATTERY COMPRISING THE SAME
US20240030501A1 (en) * 2020-10-02 2024-01-25 Battelle Energy Alliance, Llc Electrochemical cells including anodes comprising a protective layer, and related methods
EP4170807B1 (en) 2020-10-21 2026-02-11 LG Energy Solution, Ltd. Separator for lithium secondary battery and lithium secondary battery including the same
US20220158298A1 (en) * 2020-11-19 2022-05-19 Solaredge Technologies Ltd. Coated Beohmite Particles for Battery Separators
CN113594632A (en) * 2021-07-30 2021-11-02 中材锂膜有限公司 Low-moisture solvent type PVDF coating diaphragm
KR102834635B1 (en) * 2021-12-27 2025-07-16 에스케이이노베이션 주식회사 A method for production of sheet phase pseudo-boehmite using couette-taylor vortex reaction

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6153337A (en) 1997-12-19 2000-11-28 Moltech Corporation Separators for electrochemical cells

Family Cites Families (178)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3625771A (en) 1969-03-27 1971-12-07 Mc Donnell Douglas Corp Battery separator
US3647554A (en) 1969-04-17 1972-03-07 Mc Donnell Douglas Corp Battery separator and method of producing same
EP0143562A1 (en) 1983-11-02 1985-06-05 Raychem Limited Electrode article
MX168606B (en) * 1986-12-12 1993-06-01 Ici American Ine METHOD FOR THE PREPARATION OF MERCAPTOBENZOATES.
US4894301A (en) 1989-08-03 1990-01-16 Bell Communications Research, Inc. Battery containing solid protonically conducting electrolyte
DE3926977A1 (en) 1989-08-16 1991-02-21 Licentia Gmbh HIGH-ENERGY SECONDARY BATTERY
US5162175A (en) 1989-10-13 1992-11-10 Visco Steven J Cell for making secondary batteries
US5208121A (en) 1991-06-18 1993-05-04 Wisconsin Alumni Research Foundation Battery utilizing ceramic membranes
US5194341A (en) 1991-12-03 1993-03-16 Bell Communications Research, Inc. Silica electrolyte element for secondary lithium battery
CA2068290C (en) 1992-05-08 1999-07-13 Michel Gauthier Electrical connecting on lithium anodes
JP3116643B2 (en) 1992-09-11 2000-12-11 三菱電機株式会社 Electrochemical element, assembled battery, and method of manufacturing electrochemical element
US5326391A (en) 1992-11-18 1994-07-05 Ppg Industries, Inc. Microporous material exhibiting increased whiteness retention
CA2110097C (en) 1992-11-30 2002-07-09 Soichiro Kawakami Secondary battery
US5418091A (en) 1993-03-05 1995-05-23 Bell Communications Research, Inc. Polymeric electrolytic cell separator membrane
US5340669A (en) 1993-04-19 1994-08-23 Valence Technology, Inc. Allyl polyalkylene ether polymers and solid electrolytes for an electrochemical cell
US5350645A (en) 1993-06-21 1994-09-27 Micron Semiconductor, Inc. Polymer-lithium batteries and improved methods for manufacturing batteries
DE69404602T2 (en) 1993-10-07 1998-01-29 Matsushita Electric Ind Co Ltd Manufacturing method of a separator for a lithium secondary battery and a lithium secondary battery with organic electrolyte using such a separator
US5314765A (en) 1993-10-14 1994-05-24 Martin Marietta Energy Systems, Inc. Protective lithium ion conducting ceramic coating for lithium metal anodes and associate method
US5439760A (en) 1993-11-19 1995-08-08 Medtronic, Inc. High reliability electrochemical cell and electrode assembly therefor
US5569520A (en) 1994-01-12 1996-10-29 Martin Marietta Energy Systems, Inc. Rechargeable lithium battery for use in applications requiring a low to high power output
US5549717A (en) 1994-03-03 1996-08-27 Wilson Greatbatch Ltd. Method of making prismatic cell
JPH10512390A (en) 1995-01-13 1998-11-24 エス・アール・アイ・インターナシヨナル Organic liquid electrolyte and plasticizer
JPH08255615A (en) 1995-03-20 1996-10-01 Nippondenso Co Ltd Non-aqueous electrolyte battery
US6365299B1 (en) 1995-06-28 2002-04-02 Fuji Photo Film Co., Ltd. Nonaqueous secondary battery
JPH0927343A (en) 1995-07-10 1997-01-28 Hitachi Ltd Non-aqueous secondary battery and method for producing the battery
CA2226366C (en) 1995-08-28 2002-05-21 Asahi Kasei Kogyo Kabushiki Kaisha Novel battery and method for producing the same
US5948464A (en) 1996-06-19 1999-09-07 Imra America, Inc. Process of manufacturing porous separator for electrochemical power supply
CN1096481C (en) 1996-08-20 2002-12-18 大曹株式会社 Solid polyelectrolyte
FR2753159B1 (en) 1996-09-10 1999-03-26 Ampafrance DEVICE FOR HANGING A CARRYCOT ON A CHILDREN'S STROLLER, STROLLER AND SUPPORT EQUIPPED WITH SUCH A DEVICE
US5840087A (en) 1996-09-18 1998-11-24 Bell Communications Research, Inc. Method for making laminated rechargeable battery cells
JPH10214639A (en) 1997-01-31 1998-08-11 Toshiba Battery Co Ltd Manufacture of battery
US20040188880A1 (en) 1997-03-27 2004-09-30 Stephan Bauer Production of molded articles for lithium ion batteries
US5894656A (en) 1997-04-11 1999-04-20 Valence Technology, Inc. Methods of fabricating electrochemical cells
US5778515A (en) 1997-04-11 1998-07-14 Valence Technology, Inc. Methods of fabricating electrochemical cells
US5882721A (en) 1997-05-01 1999-03-16 Imra America Inc Process of manufacturing porous separator for electrochemical power supply
CA2237457A1 (en) 1997-05-19 1998-11-19 Richard S. Bogner Battery cell with spray-formed separator
KR100220449B1 (en) 1997-08-16 1999-09-15 손욱 Lithium ion polymer secondary battery manufacturing method
WO1999031751A1 (en) 1997-12-18 1999-06-24 Mitsubishi Denki Kabushiki Kaisha Lithium ion secondary battery and its manufacture
US6811928B2 (en) 1998-01-22 2004-11-02 Mitsubishi Denki Kabushiki Kaisha Battery with adhesion resin layer including filler
JPH11233144A (en) 1998-02-18 1999-08-27 Matsushita Electric Ind Co Ltd Manufacturing method of organic electrolyte battery
US6753114B2 (en) 1998-04-20 2004-06-22 Electrovaya Inc. Composite electrolyte for a rechargeable lithium battery
US6214061B1 (en) 1998-05-01 2001-04-10 Polyplus Battery Company, Inc. Method for forming encapsulated lithium electrodes having glass protective layers
US6444344B1 (en) 1998-07-13 2002-09-03 Nisshinbo Industries, Inc. Material for fuel cell separator and fuel cell separator made from said material
US6190426B1 (en) 1998-12-17 2001-02-20 Moltech Corporation Methods of preparing prismatic cells
US6277514B1 (en) 1998-12-17 2001-08-21 Moltech Corporation Protective coating for separators for electrochemical cells
US6194098B1 (en) 1998-12-17 2001-02-27 Moltech Corporation Protective coating for separators for electrochemical cells
JP3471244B2 (en) 1999-03-15 2003-12-02 株式会社東芝 Manufacturing method of non-aqueous electrolyte secondary battery
US6148503A (en) 1999-03-31 2000-11-21 Imra America, Inc. Process of manufacturing porous separator for electrochemical power supply
US6451484B1 (en) 1999-04-21 2002-09-17 Samsung Sdi Co., Ltd. Lithium secondary battery and manufacturing method thereof
JP2000323129A (en) 1999-05-14 2000-11-24 Matsushita Electric Ind Co Ltd Battery electrode manufacturing method
AU5731400A (en) 1999-06-09 2000-12-28 Moltech Corporation Methods of preparing electrochemical cells
JP3068092B1 (en) 1999-06-11 2000-07-24 花王株式会社 Method for producing positive electrode for non-aqueous secondary battery
WO2000079618A1 (en) 1999-06-22 2000-12-28 Mitsubishi Denki Kabushiki Kaisha Separator for cell, cell, and method for producing separator
DE19931204A1 (en) * 1999-07-07 2001-01-18 Rwe Dea Ag Process for the production of metal oxides dispersible in organic solvents
US6224846B1 (en) * 1999-08-21 2001-05-01 Condea Vista Company Method for making modified boehmite alumina
US6724512B2 (en) 1999-11-03 2004-04-20 Optodot Corporation Optical switch device
WO2001039294A2 (en) 1999-11-23 2001-05-31 Moltech Corporation Methods of preparing electrochemical cells
US7066971B1 (en) 1999-11-23 2006-06-27 Sion Power Corporation Methods of preparing electrochemical cells
WO2001039293A2 (en) 1999-11-23 2001-05-31 Moltech Corporation Methods of preparing electrochemical cells
JP5106732B2 (en) * 1999-11-23 2012-12-26 シオン・パワー・コーポレーション Lithium negative electrode for electrochemical cells
US7247408B2 (en) 1999-11-23 2007-07-24 Sion Power Corporation Lithium anodes for electrochemical cells
US6328770B1 (en) 1999-11-23 2001-12-11 Valence Technology (Nevada), Inc. Method of making multi-layer electrochemical cell devices
US7155516B2 (en) 2000-02-08 2006-12-26 Mips Technologies, Inc. Method and apparatus for overflowing data packets to a software-controlled memory when they do not fit into a hardware-controlled memory
CA2373904C (en) 2000-03-07 2010-01-26 Teijin Limited Lithium ion secondary battery, separator, battery pack and charging method
CN1236507C (en) 2000-03-17 2006-01-11 Tdk株式会社 Electrochemical device
US6432586B1 (en) * 2000-04-10 2002-08-13 Celgard Inc. Separator for a high energy rechargeable lithium battery
US6344293B1 (en) 2000-04-18 2002-02-05 Moltech Corporation Lithium electrochemical cells with enhanced cycle life
US6645670B2 (en) 2000-05-16 2003-11-11 Wilson Greatbatch Ltd. Efficient cell stack for cells with double current collectors sandwich cathodes
US6488721B1 (en) 2000-06-09 2002-12-03 Moltech Corporation Methods of preparing electrochemical cells
JP2002042882A (en) 2000-07-28 2002-02-08 Matsushita Electric Ind Co Ltd Manufacturing method of organic electrolyte battery
DE60144235D1 (en) 2000-08-12 2011-04-28 Lg Chemical Ltd COMPILED FILM WITH SEVERAL COMPONENTS AND METHOD FOR THE PRODUCTION THEREOF
KR100378007B1 (en) 2000-11-22 2003-03-29 삼성에스디아이 주식회사 Positive electrode for lithium-sulfur battery and lithium-sulfur battery comprising same
KR100406690B1 (en) 2001-03-05 2003-11-21 주식회사 엘지화학 Electrochemical device using multicomponent composite membrane film
US6497700B1 (en) 2001-06-28 2002-12-24 Lahaye Leon C. Multi-function surgical instrument for facilitating ophthalmic laser surgery
US7070632B1 (en) 2001-07-25 2006-07-04 Polyplus Battery Company Electrochemical device separator structures with barrier layer on non-swelling membrane
EP1435673B1 (en) 2001-09-19 2011-07-27 Kawasaki Jukogyo Kabushiki Kaisha Threedimensional cell, its electrode structure, and method for manufacturing electrode material of threedimensional cell
JP3729112B2 (en) 2001-09-20 2005-12-21 ソニー株式会社 Solid electrolyte battery
JP3904935B2 (en) 2002-01-29 2007-04-11 三菱化学株式会社 Method for producing lithium polymer secondary battery
US7118828B2 (en) 2002-03-11 2006-10-10 Quallion Llc Implantable battery
CN1723575A (en) 2002-06-05 2006-01-18 瑞威欧公司 Layered electrochemical cell and manufacturing method therefor
NL1020965C2 (en) 2002-06-28 2004-01-13 Tno Biofuel cell.
US20040043295A1 (en) 2002-08-21 2004-03-04 Rafael Rodriguez Rechargeable composite polymer battery
DE10238943B4 (en) 2002-08-24 2013-01-03 Evonik Degussa Gmbh Separator-electrode unit for lithium-ion batteries, method for their production and use in lithium batteries and a battery, comprising the separator-electrode unit
KR100484642B1 (en) 2002-09-23 2005-04-20 삼성에스디아이 주식회사 Positive active material for lithium-sulfur battery and method for preparing the same
DE10255121B4 (en) 2002-11-26 2017-09-14 Evonik Degussa Gmbh Separator with asymmetric pore structure for an electrochemical cell
US6933077B2 (en) 2002-12-27 2005-08-23 Avestor Limited Partnership Current collector for polymer electrochemical cells and electrochemical generators thereof
US7115339B2 (en) 2003-02-21 2006-10-03 Matsushita Electric Industrial Co., Ltd. Lithium ion secondary battery
US7396612B2 (en) 2003-07-29 2008-07-08 Matsushita Electric Industrial Co., Ltd. Lithium ion secondary battery
EP1667252B1 (en) 2003-08-06 2011-06-22 Mitsubishi Chemical Corporation Separator for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery including the same
JP4529903B2 (en) 2003-08-29 2010-08-25 宇部興産株式会社 Battery separator and lithium secondary battery
PL2290738T3 (en) 2003-09-23 2020-01-31 Innolith Assets Ag Electrochemical battery cell
US7595130B2 (en) 2003-11-06 2009-09-29 Ube Industries, Ltd. Battery separator and lithium secondary battery
JP3953026B2 (en) 2003-12-12 2007-08-01 松下電器産業株式会社 Electrode plate for lithium ion secondary battery, lithium ion secondary battery and method for producing the same
WO2005067080A1 (en) 2004-01-09 2005-07-21 Matsushita Electric Industrial Co., Ltd. Lithium ion secondary cell
KR100666821B1 (en) 2004-02-07 2007-01-09 주식회사 엘지화학 Electrode with organic / inorganic composite porous coating layer and electrochemical device comprising the same
DE602005021292D1 (en) 2004-02-20 2010-07-01 Panasonic Corp METHOD FOR PRODUCING A LITHIUM ION SECONDARY BATTERY
JP4454340B2 (en) 2004-02-23 2010-04-21 パナソニック株式会社 Lithium ion secondary battery
KR100790280B1 (en) 2004-03-30 2008-01-02 마쯔시다덴기산교 가부시키가이샤 Nonaqueous Electrolyte Secondary Battery
KR100856638B1 (en) 2004-03-30 2008-09-03 마쯔시다덴기산교 가부시키가이샤 Lithium ion secondary battery and charge/discharge controlling system thereof
CN100541867C (en) 2004-04-13 2009-09-16 株式会社Lg化学 Electrochemical device comprising electrode lead with protector element
WO2005104270A1 (en) 2004-04-19 2005-11-03 Matsushita Electric Industrial Co., Ltd. Lithium ion secondary battery and method for producing same
WO2005117169A1 (en) 2004-05-27 2005-12-08 Matsushita Electric Industrial Co., Ltd. Wound nonaqueous secondary battery and electrode plate used therein
JP4781263B2 (en) 2004-06-22 2011-09-28 パナソニック株式会社 Secondary battery and manufacturing method thereof
ES3010715T3 (en) 2004-07-07 2025-04-04 Lg Energy Solution Ltd New organic/inorganic composite porous film and electrochemical device prepared thereby
JP2006020804A (en) 2004-07-07 2006-01-26 Olympus Corp Endoscope
TWI318018B (en) 2004-09-02 2009-12-01 Lg Chemical Ltd Organic/inorganic composite porous film and electrochemical device prepared thereby
US7638230B2 (en) 2004-09-03 2009-12-29 Panasonic Corporation Lithium ion secondary battery
WO2006045339A2 (en) 2004-10-21 2006-05-04 Degussa Ag Inorganic separator-electrode-unit for lithium-ion batteries, method for the production thereof and use thereof in lithium batteries
KR100775310B1 (en) 2004-12-22 2007-11-08 주식회사 엘지화학 Organic/inorganic composite microporous membrane and electrochemical device prepared thereby
KR100578158B1 (en) * 2004-12-23 2006-05-10 비나텍주식회사 The electric double layer capacitors
WO2006068143A1 (en) 2004-12-24 2006-06-29 Matsushita Electric Industrial Co., Ltd. Rechargeable battery with nonaqueous electrolyte
CN100553025C (en) 2005-01-26 2009-10-21 松下电器产业株式会社 Negative electrode for lithium secondary battery, lithium secondary battery using the same, and their manufacturing method
US7981548B2 (en) 2005-01-28 2011-07-19 Nec Energy Devices, Ltd. Multilayer secondary battery and method of making same
KR101223554B1 (en) 2005-02-02 2013-01-17 삼성에스디아이 주식회사 Hybrid Fuel Cell System
EP1780820A4 (en) 2005-03-02 2009-09-09 Panasonic Corp LITHIUM ION SECONDARY BATTERY AND METHOD OF MANUFACTURING THE SAME
JP5183016B2 (en) 2005-03-25 2013-04-17 三菱化学株式会社 Porous separator for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery using the same
CN100502139C (en) 2005-04-04 2009-06-17 松下电器产业株式会社 Cylindrical lithium secondary battery
KR100850157B1 (en) 2005-04-15 2008-08-04 마쯔시다덴기산교 가부시키가이샤 Rectangular lithium secondary battery
WO2006108302A1 (en) 2005-04-15 2006-10-19 Avestor Limited Partnership LITHIUM RECHARGEABLE CELL HAVING AN EXCESS OF LiFePO4 BASED CATHODE RELATIVE TO A Li4Ti5O12 BASED ANODE
KR100659851B1 (en) 2005-04-27 2006-12-19 삼성에스디아이 주식회사 Lithium secondary battery
US7935442B2 (en) 2005-05-17 2011-05-03 Lg Chem, Ltd. Polymer binder for electrochemical device comprising multiply stacked electrochemical cells
KR100770105B1 (en) 2005-07-06 2007-10-24 삼성에스디아이 주식회사 Lithium secondary battery
KR100933427B1 (en) 2005-08-16 2009-12-23 주식회사 엘지화학 Electrochemical device consisting of cross separator
BRPI0620590B1 (en) 2005-12-06 2019-07-09 Lg Chem, Ltd. ORGANIC / INORGANIC COMPOSITE SEPARATOR, METHOD FOR MANUFACTURING AN ORGANIC / INORGANIC COMPOSITE SEPARATOR AND ELECTROCHEMICAL DEVICE
JP4151852B2 (en) 2005-12-08 2008-09-17 日立マクセル株式会社 Electrochemical element separator and manufacturing method thereof, and electrochemical element and manufacturing method thereof
JP2007188777A (en) 2006-01-13 2007-07-26 Sony Corp Separator and non-aqueous electrolyte battery
US8192858B2 (en) 2006-02-07 2012-06-05 Panasonic Corporation Electrode plate for battery and method and apparatus for forming the same
WO2007095348A2 (en) * 2006-02-15 2007-08-23 Steven Allen Carlson Separators for electrochemical cells
US20070189959A1 (en) * 2006-02-15 2007-08-16 Steven Allen Carlson Methods of preparing separators for electrochemical cells
US20080182174A1 (en) 2006-02-15 2008-07-31 Carlson Steven A Microporous separators for electrochemical cells
US8883354B2 (en) * 2006-02-15 2014-11-11 Optodot Corporation Separators for electrochemical cells
JP2007220452A (en) 2006-02-16 2007-08-30 Matsushita Electric Ind Co Ltd Nonaqueous electrolyte secondary battery separator and nonaqueous electrolyte secondary battery
JP5135822B2 (en) 2006-02-21 2013-02-06 日産自動車株式会社 Lithium ion secondary battery and battery pack using the same
JP2007227136A (en) * 2006-02-23 2007-09-06 Matsushita Electric Ind Co Ltd Electricity storage device
WO2007120763A2 (en) 2006-04-12 2007-10-25 Steven Allen Carlson Safety shutdown separators
JP5061502B2 (en) 2006-05-20 2012-10-31 日産自動車株式会社 Battery structure
WO2007135790A1 (en) 2006-05-23 2007-11-29 Incorporated National University Iwate University Total solid rechargeable battery
US7595133B2 (en) 2006-07-01 2009-09-29 The Gillette Company Lithium cell
JP4945189B2 (en) 2006-08-04 2012-06-06 株式会社東芝 Electrode manufacturing method
JP5093882B2 (en) 2006-10-16 2012-12-12 日立マクセル株式会社 Electrochemical element separator, electrochemical element and method for producing electrochemical element
US20080166202A1 (en) 2007-01-08 2008-07-10 Dunlap William L Conical nut
KR100727248B1 (en) 2007-02-05 2007-06-11 주식회사 엘지화학 Organic / inorganic composite membrane coated with porous active layer and electrochemical device
JP5213007B2 (en) 2007-02-23 2013-06-19 日立マクセル株式会社 Battery separator and non-aqueous electrolyte battery
KR100754746B1 (en) 2007-03-07 2007-09-03 주식회사 엘지화학 Organic / inorganic composite membrane coated with porous active layer and electrochemical device
KR101147255B1 (en) 2007-06-04 2012-05-18 에스케이이노베이션 주식회사 A Stacking Method of High Power Lithium Battery
KR100987260B1 (en) 2007-07-25 2010-10-12 주식회사 엘지화학 Electrochemical Device and Manufacturing Method Thereof
EP2201628B1 (en) 2007-08-21 2015-02-18 A123 Systems, Inc. Separator for electrochemical cell and method for its manufacture
US9105938B2 (en) * 2008-08-05 2015-08-11 Sion Power Corporation Application of force in electrochemical cells
CN101809801B (en) 2007-09-28 2014-03-26 A123系统公司 Batteries with inorganic/organic porous membranes
US9166251B2 (en) 2007-10-03 2015-10-20 Hitachi Maxell, Ltd. Battery separator and nonaqueous electrolyte battery
KR100976862B1 (en) 2007-11-21 2010-08-23 주식회사 엘지화학 Secondary battery having an improved storage performance and a method of manufacturing the same.
KR100983161B1 (en) * 2008-01-11 2010-09-20 삼성에스디아이 주식회사 Electrode assembly and secondary battery having same
US20100221965A1 (en) * 2008-01-29 2010-09-02 Hitachi Maxell, Ltd. Slurry for forming insulating layer, separator for electrochemical device, method for producing the same, and electrochemical device
JP5102056B2 (en) 2008-01-31 2012-12-19 株式会社オハラ Solid battery and method of manufacturing electrode thereof
EP2272117A1 (en) 2008-02-12 2011-01-12 Massachusetts Institute of Technology Small-scale batteries and electrodes for use thereof
KR20100137530A (en) 2008-03-25 2010-12-30 에이일이삼 시스템즈 인코포레이티드 High energy high power electrodes and batteries
EP2166057B1 (en) 2008-08-26 2011-12-28 Basf Se Adhesive compound for self-adhesive, detachable item on the basis of adhesive polymers and organic nanoparticles
JP2010056036A (en) * 2008-08-29 2010-03-11 Teijin Ltd Non-aqueous electrolyte battery separator, method of manufacturing the same, and non-aqueous electrolyte secondary battery using the separator
CN102388483B (en) 2009-01-12 2016-04-06 A123系统有限责任公司 Laminate battery and its preparation method
RU2513988C2 (en) 2009-05-26 2014-04-27 Оптодот Корпорейшн Battery having electrodes in form of coating deposited directly on nanoporous separators
WO2011040474A1 (en) 2009-09-30 2011-04-07 日本ゼオン株式会社 Porous membrane for secondary battery, and secondary battery
CN101786668A (en) 2010-01-13 2010-07-28 桂林理工大学 Low-temperature preparation method of Co ferrite Nano powder
KR101117126B1 (en) 2010-04-19 2012-02-24 한국과학기술연구원 Metal oxide ultrafine fiber-based composite separator with heat resistance and secondary battery using same
PL2596538T3 (en) * 2010-07-19 2019-06-28 Optodot Corporation Separators for electrochemical cells
KR101198806B1 (en) 2010-12-06 2012-11-07 현대자동차주식회사 Electrode of secondary cell including por0us insulating layer and manufacturing thereof
KR101845117B1 (en) 2010-12-14 2018-04-03 교리쯔 가가꾸 산교 가부시키가이샤 Battery electrode or separator surface protective agent, battery electrode or separator protected by same, and battery having battery electrode or separator
US20120258348A1 (en) 2011-04-05 2012-10-11 Kazuhisa Hayakawa Binder for Separator of Non-Aqueous Electrolyte Battery Comprising 2-Cyanoethyl Group-Containing Polymer and Separator and Battery Using the Same
KR101297769B1 (en) 2011-04-08 2013-08-20 데이진 가부시키가이샤 Nonaqueous secondary battery separator and nonaqueous secondary battery
CN102437302A (en) 2011-11-25 2012-05-02 东莞市比比克电子科技有限公司 Lithium ion battery diaphragm and high temperature thermal-stable lithium ion battery
WO2013146126A1 (en) 2012-03-30 2013-10-03 リンテック株式会社 Lithium ion secondary battery separator with process film and manufacturing method for same
CA2886154A1 (en) 2012-09-27 2014-04-03 Zpower, Llc Cathode
CN104837773A (en) 2012-11-06 2015-08-12 河合石灰工业株式会社 High thermal conductivity boehmite and manufacturing method thereof
JP5751454B2 (en) 2012-12-14 2015-07-22 トヨタ自動車株式会社 Nonaqueous electrolyte secondary battery
JP6292906B2 (en) 2013-02-01 2018-03-14 株式会社日本触媒 Anion conductive material and battery
JP2015018635A (en) 2013-07-09 2015-01-29 日東電工株式会社 Electrode for power storage device and process of manufacturing the same, and power storage device using the same
US20150162586A1 (en) 2013-12-05 2015-06-11 Sion Power Corporation New separator
US20170098857A1 (en) 2015-04-15 2017-04-06 Optodot Corporation Coated stacks for batteries and related manufacturing methods
US10381623B2 (en) 2015-07-09 2019-08-13 Optodot Corporation Nanoporous separators for batteries and related manufacturing methods

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6153337A (en) 1997-12-19 2000-11-28 Moltech Corporation Separators for electrochemical cells
US6306545B1 (en) 1997-12-19 2001-10-23 Moltech Corporation Separators for electrochemical cells
US20020092155A1 (en) 1997-12-19 2002-07-18 Carlson Steven A. Separators for electrochemical cells

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ICHINOSE, CHEM. MATER., vol. 9, 1997, pages 1296 - 1298

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11121432B2 (en) 2006-02-15 2021-09-14 Optodot Corporation Separators for electrochemical cells
US12046774B2 (en) 2006-02-15 2024-07-23 Lg Energy Solution, Ltd. Separators for electrochemical cells
US10505168B2 (en) 2006-02-15 2019-12-10 Optodot Corporation Separators for electrochemical cells
US10797288B2 (en) 2006-02-15 2020-10-06 Optodot Corporation Separators for electrochemical cells
US11522252B2 (en) 2006-02-15 2022-12-06 Lg Energy Solution, Ltd. Separators for electrochemical cells
US11264676B2 (en) 2006-02-15 2022-03-01 Optodot Corporation Separators for electrochemical cells
US12327881B2 (en) 2010-07-19 2025-06-10 Lg Energy Solution, Ltd. Separators for electrochemical cells
US10833307B2 (en) 2010-07-19 2020-11-10 Optodot Corporation Separators for electrochemical cells
US11728544B2 (en) 2010-07-19 2023-08-15 Lg Energy Solution, Ltd. Separators for electrochemical cells
JPWO2014021292A1 (en) * 2012-07-30 2016-07-21 帝人株式会社 Nonaqueous electrolyte battery separator and nonaqueous electrolyte battery
US9692028B2 (en) 2012-07-30 2017-06-27 Teijin Limited Separator for nonaqueous electrolyte battery, and nonaqueous electrolyte battery
JP2021093379A (en) * 2013-04-29 2021-06-17 オプトドット コーポレイションＯｐｔｏｄｏｔ Ｃｏｒｐｏｒａｔｉｏｎ Nano-porous composite separator having enhanced heat conductivity
US10879513B2 (en) 2013-04-29 2020-12-29 Optodot Corporation Nanoporous composite separators with increased thermal conductivity
JP2016517161A (en) * 2013-04-29 2016-06-09 マディコ インコーポレイテッド Nanoporous composite separator with enhanced thermal conductivity
US11217859B2 (en) 2013-04-29 2022-01-04 Optodot Corporation Nanoporous composite separators with increased thermal conductivity
US11387521B2 (en) 2013-04-29 2022-07-12 Optodot Corporation Nanoporous composite separators with increased thermal conductivity
US12567651B2 (en) 2013-04-29 2026-03-03 24M Technologies, Inc. Nanoporous composite separators with increased thermal conductivity
JP2023080287A (en) * 2013-04-29 2023-06-08 オプトドット コーポレイション Nanoporous Composite Separator with Enhanced Thermal Conductivity
EP2830125A1 (en) 2013-07-22 2015-01-28 Sihl GmbH Separator for an electrochemical cell and method for producing the same
US12040506B2 (en) 2015-04-15 2024-07-16 Lg Energy Solution, Ltd. Nanoporous separators for batteries and related manufacturing methods
US12322832B2 (en) 2015-04-15 2025-06-03 Lg Energy Solution, Ltd. Nanoporous separators for batteries and related manufacturing methods
US10381623B2 (en) 2015-07-09 2019-08-13 Optodot Corporation Nanoporous separators for batteries and related manufacturing methods
US11355817B2 (en) 2015-07-09 2022-06-07 Lg Energy Solution, Ltd. Nanoporous separators for batteries and related manufacturing methods
US11050119B2 (en) 2015-07-09 2021-06-29 Optodot Corporation Nanoporous separators for batteries and related manufacturing methods
US12401088B2 (en) 2021-04-29 2025-08-26 24M Technologies, Inc. Electrochemical cells with multiple separators, and methods of producing the same
US12456780B2 (en) 2021-04-29 2025-10-28 24M Technologies, Inc. Electrochemical cells with multiple separators, and methods of producing the same
US12407065B2 (en) 2021-04-29 2025-09-02 24M Technologies, Inc. Electrochemical cells with multiple separators, and methods of producing the same
US12401089B2 (en) 2021-04-29 2025-08-26 24M Technologies, Inc. Electrochemical cells with multiple separators, and methods of producing the same
US12322762B2 (en) 2022-12-16 2025-06-03 24M Technologies, Inc. Systems and methods for minimizing and preventing dendrite formation in electrochemical cells
US12334518B1 (en) 2022-12-16 2025-06-17 24M Technologies, Inc. Systems and methods for minimizing and preventing dendrite formation in electrochemical cells
US12322763B2 (en) 2022-12-16 2025-06-03 24M Technologies, Inc. Systems and methods for minimizing and preventing dendrite formation in electrochemical cells
US12476288B2 (en) 2022-12-16 2025-11-18 24M Technologies, Inc. Systems and methods for minimizing and preventing dendrite formation in electrochemical cells
US12500278B2 (en) 2022-12-16 2025-12-16 24M Technologies, Inc. Systems and methods for minimizing and preventing dendrite formation in electrochemical cells
US12278344B2 (en) 2022-12-16 2025-04-15 24M Technologies, Inc. Systems and methods for minimizing and preventing dendrite formation in electrochemical cells
US12580231B2 (en) 2022-12-16 2026-03-17 24M Technologies, Inc. Systems and methods for minimizing and preventing dendrite formation in electrochemical cells
US12431545B1 (en) 2024-03-26 2025-09-30 24M Technologies, Inc. Systems and methods for minimizing and preventing dendrite formation in electrochemical cells
US12542306B2 (en) 2024-03-26 2026-02-03 24M Technologies, Inc. Systems and methods for minimizing and preventing dendrite formation in electrochemical cells

Also Published As

Publication number Publication date
WO2012011944A3 (en) 2013-02-28
CN103283060B (en) 2017-02-15
PL2596538T3 (en) 2019-06-28
JP2017004961A (en) 2017-01-05
EP3444867A1 (en) 2019-02-20
JP2013535773A (en) 2013-09-12
US20170271638A1 (en) 2017-09-21
CN103283060A (en) 2013-09-04
EP3444867B1 (en) 2020-03-25
ES2713517T3 (en) 2019-05-22
DK2596538T3 (en) 2019-04-01
US20210175581A1 (en) 2021-06-10
US10833307B2 (en) 2020-11-10
US20130171500A1 (en) 2013-07-04
US20240113392A1 (en) 2024-04-04
EP2596538A2 (en) 2013-05-29
JP5990804B2 (en) 2016-09-14
EP2596538B1 (en) 2018-12-19
US12327881B2 (en) 2025-06-10
US11728544B2 (en) 2023-08-15
JP6505052B2 (en) 2019-04-24
KR20140018171A (en) 2014-02-12
CN106784556A (en) 2017-05-31

Similar Documents

Publication Publication Date Title
US12327881B2 (en) Separators for electrochemical cells
US12046774B2 (en) Separators for electrochemical cells
CN109314207B (en) Separator and electrochemical device including the same
JP6630811B2 (en) Separator and electrochemical device including the same
EP2541644B1 (en) Manufacturing method for separator
US20140295285A1 (en) Method of preparing separator, separator prepared therefrom, and electrochemical device having the same
US20070189959A1 (en) Methods of preparing separators for electrochemical cells
JP2019501500A (en) Separator and electrochemical device including the same
US20080182174A1 (en) Microporous separators for electrochemical cells
JP2019505974A (en) Separator and electrochemical device including the same
JP2010135313A (en) Electrochemical element
WO2007095348A2 (en) Separators for electrochemical cells
KR20170112248A (en) Method for manufacturing a separator and the separator manufactured by the method

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11761412

Country of ref document: EP

Kind code of ref document: A2

ENP Entry into the national phase

Ref document number: 2013520699

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20137003965

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2011761412

Country of ref document: EP