US20100221965A1 - Slurry for forming insulating layer, separator for electrochemical device, method for producing the same, and electrochemical device - Google Patents

Slurry for forming insulating layer, separator for electrochemical device, method for producing the same, and electrochemical device Download PDF

Info

Publication number
US20100221965A1
US20100221965A1 US12/676,806 US67680609A US2010221965A1 US 20100221965 A1 US20100221965 A1 US 20100221965A1 US 67680609 A US67680609 A US 67680609A US 2010221965 A1 US2010221965 A1 US 2010221965A1
Authority
US
United States
Prior art keywords
slurry
insulating layer
fine particles
separator
insulating
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.)
Abandoned
Application number
US12/676,806
Other languages
English (en)
Inventor
Hideaki Katayama
Hiroshi Abe
Nobuaki Matsumoto
Toshihiro Abe
Yasutaka Kuroki
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.)
Maxell Holdings Ltd
Original Assignee
Hitachi Maxell Ltd
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
Application filed by Hitachi Maxell Ltd filed Critical Hitachi Maxell Ltd
Assigned to HITACHI MAXELL, LTD. reassignment HITACHI MAXELL, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ABE, HIROSHI, ABE, TOSHIHIRO, KATAYAMA, HIDEAKI, KUROKI, YASUTAKA, MATSUMOTO, NOBUAKI
Publication of US20100221965A1 publication Critical patent/US20100221965A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. 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
    • 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.]
    • Y10T428/249987—With nonvoid component of specified composition
    • Y10T428/249991—Synthetic resin or natural rubbers
    • 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
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer

Definitions

  • the present invention relates to a slurry for forming an insulating layer suitable for the constituent of a separator for an electrochemical device, a separator for an electrochemical device having an insulating layer formed of the slurry and a method for producing the separator, and an electrochemical device including the separator.
  • a lithium secondary battery which is a type of an electrochemical device, is characterized by a high energy density and thus has been widely used as a power source for portable equipment such as a portable telephone and a notebook personal computer.
  • the capacity of the lithium secondary battery is likely to increase further as the performance of the portable equipment becomes higher. For this reason, it is important to ensure the safety of the lithium secondary battery.
  • a polyolefin microporous film with a thickness of about 20 to 30 ⁇ m is used as a separator that is interposed between a positive electrode and a negative electrode.
  • the separator may require a so-called shutdown function to improve the safety of the battery.
  • the shutdown function increases the internal resistance of the battery by melting the resin of the separator at a temperature not more than the abnormal heat generation temperature (thermal runaway temperature) of the battery so as to close the pores of the separator. Therefore, the material of the separator is preferably polyethylene having a low melting point.
  • the above separator may be formed of a uniaxially- or biaxially-oriented film. Since the separator is provided as an independent film, certain strength is needed in view of workability, and the drawing ensures the strength of the separator. In such a uniaxially- or biaxially-oriented however, the degree of crystallinity is increased, and the temperature at which a shutdown is to be effected (i.e., the shutdown temperature) is also raised close to the thermal runaway temperature of the battery. Thus, it is hard to say that the margin for safety of the battery is sufficient.
  • the film has been distorted by drawing and may shrink due to residual stress when it is subjected to high temperatures.
  • the shrinkage temperature is very close to the melting point of the resin of the film, namely the shutdown temperature. Therefore, when the polyolefin microporous film is used as a separator, a rise in temperature of the battery has to be prevented by reducing the current as soon as the temperature of the battery reaches the shutdown temperature due to charging anomaly or the like. If the pores are not sufficiently closed and the current cannot be immediately reduced, the temperature of the battery is easily raised to the shrinkage temperature of the separator, so that an internal short circuit can occur.
  • Patent Documents 1 and 2 As a technology for improving the reliability of the battery by preventing a short circuit due to the thermal shrinkage of the separator, e.g., an electrochemical device including a separator that includes a porous base having good heat resistance, inorganic fine particles, and a resin component for ensuring the shutdown function has been proposed (Patent Documents 1 and 2).
  • Patent Document 1 WO 2006/062153
  • Patent Document 2 WO 2007/066768
  • Patent Documents 1 and 2 can provide an electrochemical device that is not likely to cause thermal runaway even in the case of abnormal heat generation and achieves excellent safety.
  • Patent Documents 1 and 2 also disclose a method for producing a separator by using the inorganic fine particles and applying a slurry in which the inorganic fine particles are dispersed to the base or the like.
  • the inorganic fine particles have a higher specific gravity compared to the media such as water and an organic solvent, and therefore are likely to be settled in the slurry.
  • the particle size is 1 ⁇ m or less, the fine particles are likely to be agglomerated together. Thus, it may be difficult to maintain a stable dispersion state of the fine particles in the slurry.
  • the fine particles are agglomerated or settled during storage of the slurry.
  • the slurry in which the fine particles are agglomerated or settled is applied to the base or the like, the application tends to be not uniform.
  • the dispersion state of the fine particles in the slurry is particularly unstable, the fine particles are agglomerated or settled in the period of time between the application and drying of the slurry. This may result in non-uniformity of the surface to which the slurry is applied.
  • the non-uniform application of the slurry reduces the evenness of the separator produced. Consequently, in the lithium secondary battery, the ionic conduction is not uniform within the separator, which may cause a deficiency such as a deposition of lithium during charging of the battery particularly at a high current density. Moreover, if the deposited lithium becomes a dendrite crystal, a short circuit may occur due to the lithium dendrite.
  • a slurry for forming an insulating layer that is applicable to a separator for an electrochemical device and has both ion permeability and heat resistance, the slurry capable of achieving the uniform dispersion of fine particles and maintaining the dispersion state stably. It is also an object of the present invention to provide a separator for an electrochemical device that is produced using the slurry and a method for producing the separator. Moreover, it is also an object of the present invention to provide an electrochemical device including the separator.
  • a slurry for forming an insulating layer of the present invention is capable of being used to form an insulating layer of a separator for an electrochemical device and includes heat-resistant insulating fine particles, a thickening agent, and a dispersion medium.
  • the insulating fine particles are dispersed in the dispersion medium.
  • the slurry for forming an insulating layer has a viscosity of 5 to 500 mPa ⁇ s.
  • the proportion of particles with a particle size of 1 ⁇ m or less in the insulating fine particles is 30 vol % or more and the proportion of particles with a particle size of 3 ⁇ M or more in the insulating fine particles is 10 vol % or less.
  • a separator for an electrochemical device (which may be simply referred to as a “separator” in the following) of the present invention includes a porous insulating layer.
  • the insulating layer includes heat-resistant insulating fine particles and a binder.
  • the proportion of particles with a particle size of 1 ⁇ m or less in the insulating fine particles is 30 vol % or more and the proportion of particles with a particle size of 3 ⁇ m or more in the insulating fine particles is 10 vol % or less.
  • a method for producing a separator for an electrochemical device of the present invention produces a separator for an electrochemical device that includes a porous insulating layer.
  • the method includes applying the slurry for forming an insulating layer of the present invention to at least one base selected from the group consisting of a positive electrode, a negative electrode, and a porous base material and drying the base to which the slurry for forming an insulating layer is applied.
  • An electrochemical device of the present invention includes a positive electrode, a negative electrode, and the separator for an electrochemical device of the present invention.
  • the slurry for forming an insulating layer of the present invention is capable of achieving the uniform dispersion of the insulating fine particles and maintaining the dispersion state stably.
  • the separator for an electrochemical device of the present invention is produced using the slurry for forming an insulating layer of the present invention and thus can have excellent heat resistance.
  • the electrochemical device of the present invention includes the separator for an electrochemical device of the present invention and thus can have high reliability.
  • the method for producing a separator for an electrochemical device of the present invention can produce the separator stably and continuously.
  • FIG. 1 is a schematic view showing an example of a coating apparatus that is applicable to the production of a separator of the present invention.
  • the slurry for forming an insulating layer of the present invention is used to form a porous insulating layer that can constitute a separator for an electrochemical device, and is obtained by dispersing at least heat-resistant insulating fine particles (which may be simply referred to as “insulating fine particles” in the following) and a thickening agent in a dispersion medium.
  • the thickening agent may be dissolved in the dispersion medium.
  • the insulating fine particles have the effects of increasing the heat resistance of the separator, improving the dimensional stability of the separator at high temperatures, and suppressing the occurrence of a small short circuit due to the lithium dendrite.
  • the insulating fine particles are not particularly limited as long as they have electrical insulation and electrochemical stability, are stable to an organic electrolyte (which may be referred to as an “electrolyte” in the following and will be described in detail later) of an electrochemical device and to the dispersion medium of the slurry, and are not dissolved in the electrolyte under high temperature conditions.
  • organic electrolyte which may be referred to as an “electrolyte” in the following and will be described in detail later
  • the “insulating fine particles that are stable to the organic electrolyte” indicate the insulating fine particles that are neither deformed nor changed in chemical composition in the organic electrolyte (which is used as an electrolyte of the electrochemical device).
  • the “high temperature conditions” specifically require a temperature of 150° C. or higher.
  • the insulating fine particles can be any stable particles that are neither deformed nor changed in chemical composition in the electrolyte at a temperature in this range.
  • the heat resistance of the “heat-resistant insulating fine particles” means that the insulating fine particles are neither deformed nor changed in chemical composition in the electrolyte at least 150° C.
  • the phrase “electrochemically stable” means that no chemical change occurs during charging/discharging of the electrochemical device.
  • the insulating fine particles include the following: fine particles of oxides such as an iron oxide, Al 2 O 3 (alumina), SiO 2 (silica), TiO 2 , BaTiO 3 , and ZrO 2 ; fine particles of nitrides such as an aluminum nitride and a silicon nitride; fine particles of hardly-soluble ionic crystals such as a calcium fluoride, a barium fluoride, and a barium sulfate; fine particles of covalent crystals such as silicon and diamond; fine particles of clays such as talc and montmorillonite; and materials derived from the mineral resources such as boehmite, zeolite, apatite, kaoline, mullite, spinel, olivine, sericite, and bentonite or artificial products of these materials.
  • oxides such as an iron oxide, Al 2 O 3 (alumina), SiO 2 (silica), TiO 2 , BaTiO 3 , and ZrO 2
  • the insulating fine particles may be electrically insulating fine particles obtained by covering the surfaces of conductive fine particles with a material having electrical insulation (e.g., any of the above materials constituting the insulating fine particles).
  • a material having electrical insulation e.g., any of the above materials constituting the insulating fine particles.
  • the conductive fine particles include metal fine particles, oxide fine particles such as SnO 2 and an indium tin oxide (ITO), and carbonaceous fine particles such as carbon black and graphite.
  • ITO indium tin oxide
  • carbonaceous fine particles such as carbon black and graphite.
  • the fine particles of at least one selected from alumina, silica, and boehmite are suitable. These examples of the insulating fine particles may be used individually or in combinations of two or more.
  • the insulating fine particles can have any shape such as spherical, polyhedral, or plate-like particles, and preferably include the plate-like particles. Moreover, all the insulating fine particles may be in the form of plate-like particles. Various commercial products are available as the plate-like particles.
  • Examples of the commercial products include the following: SiO 2 , “SUNLOVELY (trade name)” manufactured by AGC Si-Tech Co., Ltd.; TiO 2 , a ground product of “NST-B1 (trade name)” manufactured by ISHIHARA SANGYO KAISHA, LTD.; a plate-like barium sulfate, “H series (trade name)” and “HL series (trade name)” manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD.; talc, “MICRON WHITE (trade name)” manufactured by Hayashi Kasei Co., Ltd.; bentonite, “BEN-GEL (trade name)” manufactured by Hayashi Kasei Co., Ltd.; boehmite, “BMM (trade name)” and “BMT (trade name)” manufactured by KAWAI LIME INDUSTRY CO., LTD.; alumina, “Serashyru BMT-B (trade name)” manufactured by KAWAI LIME INDUSTRY CO
  • the plate-like insulating fine particles when the plate-like insulating fine particles are oriented with their plane surfaces substantially parallel to the surface of the separator, the occurrence of a short circuit can be more successfully suppressed.
  • the reason for this is considered as follows.
  • the insulating fine particles are arranged so that their plane surfaces overlap with one another. Therefore, pores (through holes) going from one side to the other of the separator are formed in a curve rather than a line (i.e., a tortuosity factor of the pores is increased). This can prevent the lithium dendrite from passing through the separator and thus suppress the occurrence of a short circuit more successfully.
  • the aspect ratio (the maximum length of the plate-like particles/the thickness of the plate-like particles) is in the range of preferably 5, more preferably 10 to preferably 100, more preferably 50.
  • the average value of the ratios of length in the major axis direction and length in the minor axis direction (the length in the minor axis direction/the length in the major axis direction) of the plane surfaces of the plate-like particles is preferably 0.3 or more, and more preferably 0.5 or more. In this case, the average value may be 1, that is, the length in the major axis direction may be substantially the same as that in the minor axis direction.
  • the plate-like insulating fine particles have the aspect ratio and the average value of the ratios of length in the major axis direction and length in the minor axis direction of the plane surfaces, as described above, the effect of preventing a short circuit can be more effectively achieved.
  • the average value of the ratios of length in the major axis direction and length in the minor axis direction of the plane surfaces of the plate-like insulating fine particles can be determined, e.g., by analyzing the scanning electron microscope (SEM) images.
  • SEM scanning electron microscope
  • the aspect ratio of the plate-like insulating fine particles also can be determined by analyzing the SEM images.
  • the insulating fine particles preferably include secondary particles formed by agglomeration of primary particles, and all the insulating fine particles may be fine particles having a secondary particle structure.
  • the secondary particles can be agglomerates that are not easily separated into the primary particles in the general dispersion process.
  • the secondary particles can be formed by intergrowth of the primary particles. Examples of such fine particles include the following: boehmite, “C06 (trade name)” and “C20 (trade name)” manufactured by TAIMEI CHEMICALS CO., LLD.; CaCO 3 , “ED-1 (trade name)” manufactured by KOMESHO SEKKAI KOGYO CO., LTD.; and clay, “Zeolex 94HP (trade name)” manufactured by J. M. Huber Corporation.
  • the insulating fine particles include fine particles having a secondary particle structure in which the primary particles are agglomerated, the secondary particles impede the closest packing of the particles, so that the pores of the insulating layer can be made larger.
  • the electrochemical device such as a lithium secondary battery that includes the separator having this insulating layer is suitable for applications requiring higher power such as an electric vehicle, a hybrid vehicle, an electric motorcycle, a power-assisted bicycle, a power tool, and a shaver.
  • the average dispersion particle size of the insulating fine particles is in the range of preferably 0.01 ⁇ m, more preferably 0.1 ⁇ m to preferably 1.5 ⁇ m, more preferably 1 ⁇ m.
  • the proportion of particles with a particle size of 1 ⁇ m or less in all the dispersed particles is 30 vol % or more and the proportion of particles with a particle size of 3 ⁇ m or more in all the dispersed particles is 10 vol % or less.
  • the insulating fine particles including many fine particles although the insulating layer having better heat resistance can be easily formed, the fine particles are likely to be agglomerated together. Thus, it may be difficult to maintain a stable dispersion state of the fine particles in the slurry.
  • the slurry of the present invention can maintain the uniform dispersion state for a long time even if it includes many fine particles, as described above. As the proportion of coarse particles becomes smaller, the thickness of the insulating layer can be reduced while maintaining the excellent heat resistance. Therefore, the insulating fine particles dispersed in the dispersion medium include preferably 10 vol % or less of particles with a particles size of 3 ⁇ m or more, and more preferably 10 vol % or less of particles with a particles size of 2 ⁇ m or more.
  • the particle size of the insulating fine particles can be determined from a volume-based particle size distribution that is measured, e.g., with a laser diffraction particle size analyzer (“MT-3000 (trade name)” manufactured by NIKKISO CO., LTD.) by dispersing the insulating fine particles in a medium in which the insulating fine particles do not dissolve or swell (e.g., the dispersion medium used for the slurry). That is, the average particle size, the proportion of particles with a particle size of 1 ⁇ m or less, and the proportion of particles with a particle size of 3 ⁇ m or more can be determined from the cumulative frequency obtained by measuring the volume-based particle size distribution of the insulating fine particles.
  • MT-3000 laser diffraction particle size analyzer
  • the slurry for forming an insulating layer of the present invention includes the thickening agent.
  • the use of the thickening agent can adjust the viscosity of the slurry in a suitable range, make the dispersion of the insulating fine particles uniform, and maintain a good dispersion state stably.
  • the thickening agent is not particularly limited as long as it can control the slurry at a necessary viscosity without causing a side effect such as agglomeration of the insulating fine particles in the slurry. However, it is preferable that only a small amount of the thickening agent can effectively increase the viscosity. It is also preferable that the thickening agent can be well dissolved or dispersed in the dispersion medium used for the slurry. If many undissolved matters or agglomerates of the thickening agent are present in the slurry, the dispersion of the insulating fine particles is not uniform.
  • the number of residue on the filter is preferably one or less per 1 L of the slurry, and more preferably one or less per 5 L of the slurry.
  • the thickening agent include the following: synthetic polymers such as polyethylene glycol, a polyacrylic acid, polyvinyl alcohol, and a vinyl methyl ether-maleic anhydride copolymer; cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose; natural polysaccharides such as xanthan gum, welan gum, gellan gum, guar gum, and carrageenan; starches such as dextrin and a pregelatinized starch; clay minerals such as montmorillonite and hectorite; and inorganic oxides such as fumed silica, fumed alumina, and fumed titania.
  • synthetic polymers such as polyethylene glycol, a polyacrylic acid, polyvinyl alcohol, and a vinyl methyl ether-maleic anhydride copolymer
  • cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose
  • the thickening agent may be used individually or in combinations of two or more.
  • the clay minerals or the inorganic oxides it is preferable that they include primary particles with a smaller particle size (e.g., about several to several tens of nanometers) than the insulating fine particles and have a structure in which many primary particles are joined (e.g., fumed silica).
  • the natural polysaccharides are more preferred because they have high solubility in water (i.e., the dispersion medium suitable for the slurry for forming an insulating layer) and are highly effective in increasing the viscosity with a small amount.
  • the xanthan gum, the welan gum, and the gellan gum are further preferred, and the xanthan gum is particularly preferred.
  • the inorganic oxides such as fumed silica, fumed alumina, and fumed titania are preferably added.
  • the content of the thickening agent in the slurry varies depending on the predetermined viscosity of the slurry. For example, if the thickening agent does not evaporate in the drying process after the application of the slurry, it remains in the insulating layer. Therefore, the thickening agent should not be used in a large amount.
  • the content of the thickening agent is preferably 10 vol % or less, more preferably 5 vol % or less, and further preferably 1 vol % or less of the total volume of the solids in the slurry (i.e., the components other than the dispersion medium, which is true in the following).
  • the content of the thickening agent is preferably 0.1 vol % or more of the total volume of the solids in the slurry.
  • the slurry for forming an insulating layer of the present invention includes a dispersing agent.
  • the dispersing agent e.g., the dispersibility of the insulating fine particles in the slurry can be further improved, since the dispersing agent adheres to the surfaces of the insulating fine particles. This can prevent agglomeration of the insulating fine particles and thus maintain the dispersion state of the insulating fine particles more stably.
  • the plane surfaces of the individual particles may be arranged in layers depending on the manufacturing method (such as plate-like boehmite).
  • the insulating layer could not sufficiently provide the effect of preventing a short circuit due to the plate-like particles.
  • the slurry is prepared by using the dispersing agent along with the layered particles, the particles can be separated from one another and uniformly dispersed in the slurry. Therefore, even if the plate-like particles are used, the slurry including the dispersing agent can form an insulating layer that exhibits the above effect more suitably.
  • the dispersing agent include an anionic surface-active agent, a cationic surface-active agent, a nonionic surface-active agent, and polymer dispersing agents such as a polycarboxylic acid, a polyacrylic acid, a polymethacrylic acid, polycarboxylate, polyacrylate, and polymethacrylate.
  • examples of the dispersing agent include the following: “ADEKA TOL (trade name) series” and “ADEKA NOL (trade name) series” manufactured by ADEKA CORPORATION; “SN-Dispersant (trade name) series” manufactured by SAN NOPCO LIMITED; “POLITY (trade name) series”, “ARMEEN (trade name) series”, and “DUOMEEN (trade name) series” manufactured by LION CORPORATION; “HOMOGENOL (trade name) series”, “RHEODOL (trade name) series”, and “AMIET (trade name) series” manufactured by KAO CORPORATION; “FARPACK (trade name) series”, “CERAMISOL (trade name) series”, and “POLYSTER (trade name) series” manufactured by NOF CORPORATION; “AJISPER (trade name) series” manufactured by Ajinomoto Fine-Techno Co., Inc.; and “Aron Dispersant (trade name) series” manufactured by TOAGOSEI CO., LTD. These examples of the dispersing agent may be used individually
  • the dispersing agent including a plurality of ion-dissociable acid groups (such as a carboxyl group, a sulfonic group, an amino acid group, and a maleic acid group) or a plurality of ion-dissociable salt groups (such as a carboxylate group, a sulfonate group, and a maleate group) is preferred, and the polycarboxylate, the polyacrylate, and the polymethacrylate are more preferred.
  • the polymer dispersing agent is a salt (i.e., the polymer dispersing agent has a salt group)
  • an ammonium salt is suitable.
  • the content of the dispersing agent in the slurry is preferably 0.1 parts by mass or more, and more preferably 0.3 parts by mass or more per 100 parts by mass of the insulating fine particles so as to provide the effect of the dispersing agent more effectively. If the content of the dispersing agent in the slurry is too large, the effect of the dispersing agent becomes saturated, while the ratio of other components to the dispersing agent in the insulating layer is reduced, and thus the effects of the other components can be reduced. Therefore, the content of the dispersing agent in the slurry is preferably 5 parts by mass or less, and more preferably 1 part by mass or less per 100 parts by mass of the insulating fine particles.
  • the slurry for forming an insulating layer of the present invention may include a binder in order to bind the insulating fine particles to one another or to the other constituents (as will be described later) in the insulating layer to be formed.
  • the binder also can be used to bond the insulating layer with the base material or the like.
  • the type of the binder is not particularly limited as long as it is electrochemically stable in the electrochemical device and is stable to the electrolyte of the electrochemical device.
  • the above thickening agent having the function of a binder also can serve as a binder.
  • binder examples include the following: (meta) acrylic acid copolymers such as an ethylene-vinyl acetate copolymer (EVA having 20 to 35 mol % of a structural unit derived from vinyl acetate), an ethylene-ethyl acrylate copolymer, and an ethylene-ethyl methacrylate copolymer; fluoro-rubber; styrene-butadiene rubber (SBR); polyvinyl alcohol (PVA); polyvinyl butyral (PVB); polyvinyl pyrrolidone (PVP); poly-N-vinylacetamide; a crosslinked acrylic resin; polyurethane; and an epoxy resin.
  • EVA ethylene-vinyl acetate copolymer
  • PVA ethylene-ethyl acrylate copolymer
  • ethylene-ethyl methacrylate copolymer ethylene-ethyl methacrylate copolymer
  • fluoro-rubber SBR
  • the heat-resistant resins having heat resistance at 150° C. or higher are suitable.
  • highly flexible materials such as the ethylene-acrylic acid copolymer, the fluoro-rubber, and the SBR are more suitable.
  • the highly flexible materials include the following: EVA, “EVAFLEX series (trade mane)” manufactured by DU PONT-MITSUI POLYCHEMICALS CO., LTD.; EVA manufactured by NIPPON UNICAR CO., LTD.; an ethylene-acrylic acid copolymer, “EVAFLEX-EEA series (trade name)” manufactured by DU PONT-MITSUI POLYCHEMICALS CO., LTD.; EEA manufactured by NIPPON UNICAR, CO., LTD.; fluoro-rubber, “DAI-EL LATEX series (trade name)” manufactured by DAIKIN INDUSTRIES, Ltd.; SBR, “TRD-2001 (trade name)” manufactured by JSR Corporation; and SBR, “EM-400
  • the self-crosslinking (meta) acrylic acid copolymer is more preferred, and the self-crosslinking (meta) acrylic acid copolymer with a glass transition temperature (Tg) of ⁇ 20° or lower is further preferred.
  • this copolymer having the Tg include a copolymer in which the end of the side-chain ester group is an alkyl group with a carbon number of 2 to 10. More specifically, the copolymer in which the end of the side-chain ester group is mainly composed of n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, and n-hexyl group is even more preferred.
  • the Tg of the binder becomes higher, and the flexibility of the binder is reduced. If the carbon number of the end alkyl group of the side-chain ester group is too large, the side chains are crystallized, and the flexibility of the binder is reduced as well.
  • the insulating layer formed of the slurry of the present invention can be obtained in such a manner that the slurry is applied to a base material or the like and then dried to remove the solvent.
  • the slurry contains the self-crosslinking (meta) acrylic acid copolymer, the copolymer spontaneously crosslinks to form a crosslinked structure during the drying process. Therefore, since the binder acts to increase the adhesion between the insulating fine particles or between the insulating fine particles and the other constituents (such as a microporous film), the insulating layer can have good electrolyte resistance, and the stability of the slurry can be improved.
  • the insulating fine particles are held by a crosslinked body of the self-crosslinking (meta) acrylic acid copolymer.
  • the electrolyte resistance of the insulating layer can be improved, compared to the case where the binder is not self-crosslinkable. If the binder inherently has a crosslinked structure, the slurry is dried while the binder particles retain their shapes, so that the contact area of the binder with the insulating fine particles or the base material may be reduced.
  • the self-crosslinking (meta) acrylic acid copolymer spontaneously crosslinks to form a crosslinked structure during the drying process, and therefore can improve the binding properties of the insulating layer, compared to the binder inherently having a crosslinked structure.
  • the stability of the slurry may be reduced due to the crosslinking agent, although the electrolyte resistance and the adhesion of the binder to other members can be better.
  • the use of the self-crosslinking (meta) acrylic acid copolymer can maintain the stability of the slurry.
  • the self-crosslinking (meta) acrylic acid copolymer may be obtained by a conventionally known method.
  • a (meta) acrylic acid copolymer is synthesized in a usual manner using monomers that can impart self-cross linkage to the copolymer.
  • the monomer capable of imparting the self-cross linkage may be, e.g., an unsaturated monomer having a self-crosslinking functional group, or a combination of a monomer having a functional group such as a hydroxyl group or carboxyl group (including acrylates and methacrylates) and a functional monomer having a functional group that reacts with the hydroxyl group or carboxyl group.
  • Examples of the unsaturated monomer having a self-crosslinking functional group include the following: monomers containing a methylol group such as N-methylol methacrylamide, N-methylol acrylamide, N-butylol methacrylamide, and N-butylol acrylamide; monomers containing an epoxy group such as allyl glycidyl ether and glycidyl (meta) acrylate; monomers containing an alkoxyalkyl group such as methoxymethyl (meta) acrylate, ethoxymethyl (meta) acrylate, methoxyethyl (meta) acrylate, and butoxyethyl (meta) acrylate; acetoacetoxyalkyl (meta) acrylate derivatives such as 2-acetoacetoxyethyl (meta) acrylate, 3-acetoacetoxypropyl (meta) acrylate, and 4-acetoacetoxybutyl (meta) acrylate
  • Examples of the monomer having a functional group such as a hydroxyl group or carboxyl group include the following: a (meta) acrylic acid; a crotonic acid; an itaconic acid; a maleic acid; a maleic anhydride; a fumaric acid; ⁇ -hydroxyethyl (meta) acrylate; ⁇ -hydroxypropyl (meta) acrylate, and ⁇ -hydroxyethylvinyl ether.
  • Examples of the functional monomer having a functional group that reacts with the hydroxyl group or carboxyl group include the following: monomers containing an N-methylol group such as N-methylol acrylamide and N-butoxymethyl acrylamide; monomers containing an amino group such as dimethylaminoethyl (meta) acrylate and dimethylaminopropyl acrylamide; and monomers containing an epoxy group such as glycidyl (meta) acrylate.
  • the acrylic acid copolymer that has a low Tg and includes butyl acrylate as the main component of the monomer is particularly suitable.
  • a known resin may be mixed with an amine compound or a polyacrylic resin to enhance the flexibility or reduce the Tg of the binder.
  • a known plasticizer phthalate esters etc.
  • the adhesion properties of the binder can be improved by introducing a carboxyl group.
  • the Tg of the resin can be increased by a known method of introducing a crosslinked structure to increase the crosslink density or a rigid molecular structure (an aryl group etc.).
  • the Tg of the resin can be reduced by a known method of introducing a crosslinked structure with a low crosslink density or a long side chain.
  • the content of the binder in the slurry is preferably 1 or more, more preferably 5 or more, and further preferably 10 or more per 100 of the insulating fine particles when expressed as a volume ratio so as to provide the effect of the binder more effectively. If the content of the binder in the slurry is too large, the ion permeability of the insulating layer is reduced because the pores are filled, which may adversely affect the properties of the electrochemical device. Therefore, the content of the binder is preferably 30 or less, and more preferably 20 or less per 100 of the insulating fine particles when expressed as a volume ratio.
  • the dispersion medium of the slurry may include water as the main component or an organic solvent (e.g., aromatic hydrocarbons such as toluene, furans such as tetrahydrofuran, and ketones such as methyl ethyl ketone and methyl isobutyl ketone).
  • an organic solvent e.g., aromatic hydrocarbons such as toluene, furans such as tetrahydrofuran, and ketones such as methyl ethyl ketone and methyl isobutyl ketone.
  • the dispersion medium including water as the main component is suitable.
  • the “dispersion medium” indicates a portion of the slurry other than the solids that remain after the drying process to form the insulating layer.
  • the dispersion medium “including water as the main component” means that the amount of water is 70 mass % or more, and preferably 90 mass % or more of the components of the dispersion medium.
  • the remaining component of the dispersion medium can be, e.g., alcohols that are to be added to control the surface tension of the slurry (as will be described later).
  • the dispersion medium includes only water.
  • the viscosity of the slurry is 5 mPa ⁇ s or more, preferably 10 mPa ⁇ s or more, and more preferably 20 mPa ⁇ s or more so as to suppress the sedimentation of the insulating fine particles and improve the dispersion stability. If the viscosity of the slurry is too high, it is difficult to apply the slurry uniformly in a required thickness. Therefore, the viscosity of the slurry is 500 mPa ⁇ s or less, preferably 300 mPa ⁇ s or less, and more preferably 200 mPa ⁇ s or less.
  • the viscosity of the slurry is measured with an E-type viscometer by a method according to the Japanese Industrial Standard (JIS) R 1653 under the conditions of a temperature of 23° C. and a shear rate of 1000/s.
  • JIS Japanese Industrial Standard
  • the thickening agent when the thickening agent is, e.g., the natural polysaccharides or the like, the thickening agent may be decomposed by bacteria in the air. Therefore, a preservative or a germicide may be appropriately added to the slurry to suppress the decomposition of the thickening agent. This can improve the storage properties of the slurry including the natural polysaccharides.
  • preservative or the germicide include the following a benzoic acid; a p-hydroxybenzoic acid ester; alcohols (such as ethanol and methanol); chlorines (such as sodium hypochlorite); hydrogen peroxide; acids (such as a boric acid and an acetic acid); and alkalis (such as sodium hydroxide and potassium hydroxide).
  • an antifoaming agent can be used.
  • Various types of antifoaming agents such as mineral oil, silicon, acrylic, and polyether are available.
  • Specific examples of the antifoaming agent include the following: “FOAMLEX (trade name)” manufactured by NICCA CHEMICAL CO., LTD); “SURFYNOL (trade name) series” manufactured by Nisshin Chemical Industry Co., Ltd; “Awazeron (trade name) series” manufactured by Ebara Engineering Service Co., Ltd.; and “SN-Defoamer (trade name) series” manufactured by SAN NOPCO LIMITED.
  • an additive may be added to the slurry to control the surface tension.
  • the additive can be ethylene glycol, propylene glycol, or various propylene oxide glycol ethers such as monomethyl acetate.
  • alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and ethylene glycol
  • ethylene glycol can be used to control the surface tension.
  • the solid content including the insulating fine particles, the thickening agent, the dispersing agent, the binder, and thermofusible fine particles (as will be described later) in the slurry is, e.g., 10 to 80 mass %.
  • the slurry may be prepared by a conventionally known method.
  • the above materials such as the insulating fine particles, the thickening agent, the dispersing agent, the binder, the preservative, the germicide, the antifoaming agent, and the thermofusible fine particles (as will be described later)
  • the dispersion medium such as the insulating fine particles, the thickening agent, the dispersing agent, the binder, the preservative, the germicide, the antifoaming agent, and the thermofusible fine particles (as will be described later)
  • Some of these materials may be dissolved in the dispersion medium.
  • the dispersing device When the dispersing device generates strong shear, the molecular chains of polymeric materials such as the thickening agent and the binder may be cleaved.
  • the slurry is prepared in the following manner. First, the insulating fine particles and, if necessary, the dispersing agent or the like are dispersed in the dispersion medium with a high-shear dispersing device. Subsequently, the thickening agent, the binder, etc. are added to the dispersion medium and dispersed with a low-shear dispersing device (e.g., a propeller stirrer).
  • a low-shear dispersing device e.g., a propeller stirrer
  • dispersing device examples include the following: dispersing devices using a grinding medium such as a bead mill, a ball mill, a planetary mill, and a sand mill; and dispersing devices using no grinding medium such as a jet mill, a rod mill, a nanomizer, and a homogenizer.
  • a grinding medium such as a bead mill, a ball mill, a planetary mill, and a sand mill
  • no grinding medium such as a jet mill, a rod mill, a nanomizer, and a homogenizer.
  • the separator for an electrochemical device of the present invention includes a porous insulating layer.
  • the insulating layer includes heat-resistant insulating fine particles and a binder.
  • the proportion of particles with a particle size of 1 ⁇ m or less in the insulating fine particles is 30 vol % or more and the proportion of particles with a particle size of 3 ⁇ m or more in the insulating fine particles is 10 vol % or less.
  • the separator includes the insulating layer that has both ion permeability and heat resistance and is formed by the steps of: applying the slurry for forming an insulating layer of the present invention, as described in Embodiment 1, to at least one base selected from the group consisting of a positive electrode for an electrochemical device, a negative electrode for an electrochemical device, and a porous base material; and drying the base.
  • the “heat-resistant insulating layer” means that the insulating layer has a heat resistant temperature of 150° C. or more and is not substantially deformed at least 150° C. Specifically, when the insulating layer is heated at 150° C., no thermal shrinkage is found by visual observation.
  • the resultant separator can have a structure in which the insulating layer and the porous base material constitute separate layers, and these layers are integrated together, or a structure in which the components of the slurry and the porous base material are integrated into the insulating layer.
  • the separator may include another porous layer as well as the integrated layer of the insulating layer and the porous base material.
  • the porous layer may be combined with the integrated layer.
  • the porous layer may be independent of the integrated layer, and the separator may be formed by laminating these layers in the electrochemical device.
  • the separator may include either the insulating layer alone or the insulating layer and another porous layer.
  • the porous layer may be combined with the insulating layer.
  • the porous layer may be independent of the insulating layer, and the separator may be formed by laminating these layers in the electrochemical device.
  • the above positive and negative electrodes for the electrochemical device are to constitute the electrochemical device of the present invention such as a lithium secondary battery as will be described later.
  • the porous base material is not particularly limited as long as it has electrical insulation and is stable to both an electrochemical reaction inside the electrochemical device and the electrolyte, but is preferably a woven fabric, a nonwoven fabric, or a microporous film.
  • the microporous film may have the same structure as that of the microporous film used for the separator of a general lithium secondary battery.
  • the components of the porous base material include the following: resins such as cellulose, a modified product of the cellulose (such as carboxymethyl cellulose), polyolefins (such as polypropylene (PP), polyethylene (PE), and a copolymerized polyolefin in which the structural unit derived from ethylene is 85 mol % or more), polyesters (such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT)), polyacrylonitrile (PAN), aramid, polyamide-imide, and polyimide; and inorganic materials (inorganic oxides) such as glass, alumina, and silica.
  • resins such as cellulose, a modified product of the cellulose (such as carboxymethyl cellulose), polyolefins (such as polypropylene (PP), polyethylene (PE), and a copolymerized polyolefin in which the structural unit derived from ethylene is 85 mol
  • the copolymerized polyolefin may be, e.g., an ethylene-vinyl monomer copolymer, and specifically an ethylene-vinyl acetate copolymer (EVA), an ethylene-methyl acrylate copolymer, or an ethylene-ethyl acrylate copolymer.
  • EVA ethylene-vinyl acetate copolymer
  • the porous base material may include either one type or more than one type of these components.
  • the porous base material also may include various types of known additives (e.g., an antioxidant when the resin is used) as needed in addition to the above components.
  • the porous base material includes the components with higher heat resistance in those listed above (i.e., the heat-resistant resins such as polyesters, aramid, polyamide-imide, and polyimide and the inorganic materials).
  • the heat-resistant resins such as polyesters, aramid, polyamide-imide, and polyimide and the inorganic materials.
  • the porous base material melts and fills the pores of the separator to retard the ion conduction, thereby ensuring the safety of the electrochemical device. That is, the porous base material serves to impart a so-called shutdown function to the separator. Therefore, the porous base material preferably includes a component that melts and softens at a predetermined temperature.
  • the temperature at which the resin constituting the porous base material melts and softens is in the range of preferably 80° C., more preferably 100° C. to preferably 150° C., more preferably 140° C.
  • This temperature can be determined by a melting temperature that is measured with a differential scanning calorimeter (DSC) according to the regulations of JIS K 7121 (which is true for the thermofusible fine particles, as will be described later).
  • DSC differential scanning calorimeter
  • Such a component is preferably polyolefins, and more preferably PE.
  • a microporous film made of PE or a laminated microporous film having 2 to 5 layers of PE and PP is used to form the separator.
  • the porous base material includes both a thermoplastic resin with a melting point of 80° C. to 150° C. such as PE and a thermoplastic resin with a melting point of higher than 150° C. such as PP
  • the porous base material can be a microporous film obtained by mixing PE and a resin (such as PP) with a higher melting point than that of PE, or a laminated microporous film obtained by laminating a PE layer and a resin layer (such as a PP layer) made of a resin with a higher melting point than that of PE)
  • the resin (e.g., PE) with a melting point of 80° C. to 150° C. is preferably 30 mass % or more, and more preferably 50 mass % or more of the thermoplastic resin constituting the porous base material.
  • the porous base material may be surface-treated, e.g., with ultraviolet irradiation, corona discharge, a plasma treatment, or a surface-active agent to improve the adhesion to the insulating fine particles.
  • the slurry can be applied more uniformly, so that the insulating layer having higher homogeneity and excellent heat resistance can be easily formed. It is desirable that the surface treatment is performed only on the surface portion of the porous base material. In other words, low wettability of the inner surface of the pores of the porous base material with the slurry is better.
  • the slurry is not likely to enter the pores of the porous base material.
  • the slurry or the dispersion medium of the slurry can be prevented from passing through the pores to the opposite side of the porous base material from the surface to which the slurry is applied.
  • the critical surface tension (B) of the surface-treated porous base material is preferably the same as or larger than the surface tension (A) of the slurry at room temperature.
  • the difference [(A) ⁇ (B)] is preferably 0 mN/m or less, and more preferably ⁇ 10 mN/m or less.
  • the surface tension and the critical surface tension may be measured by a conventionally known method.
  • the surface tension can be measured, e.g., by a plate method, a pendant-drop method, or a maximum bubble pressure method.
  • the critical surface tension is preferably 50 mN/m or less.
  • the critical surface tension (B′) before the surface treatment is about 31 mN/m for polyethylene and about 29 mN/m for polypropylene at room temperature.
  • the surface treatment conditions of the porous base material can vary depending on the apparatus to be used, the critical surface tension (B′) of the porous base material before the surface treatment, and the surface tension (A) of the slurry.
  • the amount of discharge is preferably 25 to 100 W/min ⁇ m 2 .
  • the porous base material is a woven or nonwoven fabric, it is composed of fibers.
  • the fiber diameter may be not more than the thickness of the separator. Specifically, the fiber diameter is preferably 0.01 to 5 ⁇ m. If the fiber diameter is too large, entanglement of the fibers is insufficient, and the strength of the porous base material composed of these fibers is reduced. This can reduce the strength of the separator and make it difficult to handle the separator. If the fiber diameter is too small, the pores of the separator become excessively small. Therefore, the ion permeability tends to be low, and the load characteristics of the electrochemical device can be degraded.
  • the woven or nonwoven fabric may use a binder as needed in order to bind the fibers.
  • the binder can be any of the various types of binders included in the insulating layer (i.e., the slurry), as described above.
  • the porous base material is composed of fibers such as a woven or nonwoven fabric, and in particular the pore diameter of the porous base material is relatively large (e.g., 5 ⁇ m or more), this tends to cause a short circuit of the electrochemical device.
  • a part or the whole of the insulating fine particles is contained in the pores of the porous base material. It is more preferable that a part or the whole of the fine particles other than the insulating fine particles (such as the thermofusible fine particles as will be described later) is contained in the pores of the porous base material.
  • the insulating fine particles or the thermofusible fine particles can be present in the pores of the porous base material, e.g., by impregnating the slurry into the porous base material, allowing the porous base material to pass through a predetermined gap to remove the extra slurry, and subsequently drying the porous base material.
  • the nonwoven fabric and the microporous film are more preferred as the porous base material used for the separator of the present invention because the thickness can be reduced.
  • the nonwoven fabric and the microporous film may be produced by a conventionally known method. Specifically, the nonwoven fabric can be produced, e.g., by a spun-bond method, a melt-blow method, a wet process, a dry process, or an electrospinning process.
  • the microporous film can be produced, e.g., by a foaming process, a solvent extraction process, a dry drawing process, or a wet drawing process.
  • the separator also can have the shutdown function in such a manner that a material for imparting the shutdown function is included in the insulating layer, or that a layer for imparting the shutdown function is provided in the separator.
  • the porous base material includes a resin having high heat resistance, or the separator is formed without using the porous base material, the following methods are recommended to ensure the shutdown function of the separator.
  • the separator may have a structure that includes the integrated layer (of the insulating layer and the porous base material) and another porous layer, or a structure that includes the insulating layer and another porous layer.
  • the layer for imparting the shutdown function to the separator corresponds to this “another porous layer”.
  • the “another porous layer” may be, e.g., a porous base material (more preferably a microporous film) including the component that melts and softens at a predetermined temperature, as described above.
  • the layer (particularly the microporous film) for imparting the shutdown function is likely to cause thermal shrinkage at high temperatures.
  • the insulating layer including the insulating fine particles acts to suppress thermal shrinkage of the whole separator and thus can improve the dimensional stability of the separator at high temperatures. Even if the separator does not include a layer for imparting the shutdown function separately, the thermal shrinkage of the separator can be suppressed due to the effect of the insulating fine particles of the insulating layer. Therefore, the electrochemical device using the separator of the present invention can suppress an internal short circuit caused by shrinkage of the separator at high temperatures and improve both reliability and safety.
  • the material for imparting the shutdown function that is added to the insulating layer can be, e.g., thermofusible fine particles that melt and soften when the temperature of the electrochemical device is raised.
  • thermofusible fine particles melt and soften is in the range of preferably 80° C., more preferably 100° C. to preferably 150° C., more preferably 140° C.
  • components of the thermofusible fine particles include the following: PE; a copolymerized polyolefin in which the structural unit derived from ethylene is 85 mol % or more; PP; polyolefin derivatives (such as chlorinated polyethylene and chlorinated polypropylene); a polyolefin wax; a petroleum wax; and a carnauba wax.
  • the copolymerized polyolefin may be, e.g., an ethylene-vinyl monomer copolymer, and specifically EVA, an ethylene-methyl acrylate copolymer, or an ethylene-ethyl acrylate copolymer. Moreover, polycycloolefin etc. also can be used.
  • the thermofusible fine particles may include either one type or more than one type of these components. Among the above components, the PE, the polyolefin wax, or the EVA in which the structural unit derived from ethylene is 85 mol % or more is suitable.
  • the thermofusible fine particles also may include various types of known additives (e.g., an antioxidant when the resin is used) as needed in addition to the above components.
  • thermofusible fine particles is, e.g., in the range of preferably 0.01 ⁇ m, more preferably 0.1 ⁇ m to preferably 15 ⁇ m, more preferably 1 ⁇ m when expressed as a number-average particle size that is measured by the same measurement method as that of the insulating fine particles.
  • the shutdown function of the separator can be evaluated, e.g., by an increase in resistance with the temperature of a model cell.
  • the model cell including a positive electrode, a negative electrode, a separator, and an electrolyte is prepared. Then, this model cell is placed in a thermostatic bath, and the internal resistance value of the model cell is measured while the temperature is raised at 5° C./min. By determining the temperature at which the measured internal resistance value is at least five times as large as that before heating (i.e., the resistance value measured at room temperature), this temperature can be evaluated as a shutdown temperature of the separator.
  • the separator may have a plurality of insulating layers or a plurality of layers composed of the porous base material.
  • the separator may be formed by disposing the microporous films on both sides of the insulating layer or disposing the insulating layers on both sides of the microporous film.
  • the thickness of the separator increases with the number of layers, which may lead to an increase in the internal resistance or a reduction in the energy density of the electrochemical device. Therefore, the number of layers in the separator is preferably five layers or less.
  • the content of the insulating fine particles in the separator is preferably 10 vol % or more, more preferably 30 vol % or more, and further preferably 40 vol % or more of the total volume of components in the separator so as to provide the effect of the insulating fine particles more effectively.
  • the volume ratio of the insulating fine particles in the separator is preferably 80 vol % or less.
  • the volume ratio of the insulating fine particles in the separator can be even higher as long as it is, e.g., 95 vol % or less.
  • the separator uses the porous base material and also includes the thermofusible fine particles in the insulating layer to have the shutdown function, or the separator is composed of the porous base material (e.g., the microporous film) including a thermofusible resin and the insulating layer
  • the volume ratio of the insulating fine particles in the separator is preferably 60 vol % or less.
  • the volume ratio of the insulating fine particles in the separator can be even higher and is preferably 80 vol % or less.
  • the content of the thermofusible resin (i.e., the porous base material including the thermofusible resin or the thermofusible fine particles) in the separator is preferably 5 to 70 vol % of the total volume of components in the separator. If the content of the thermofusible resin in the separator is too small, the shutdown effect obtained by this resin can be reduced. If the content of the thermofusible resin is too large, the content of the insulating fine particles or the like in the separator is reduced, and thus the effects of these components can be reduced.
  • the slurry for forming an insulating layer of the present invention includes the above components in amount such that the content of each of the components in the resultant insulating layer can meet the appropriate value.
  • the thickness of the separator is preferably 3 ⁇ m or more, and more preferably 5 ⁇ m or more.
  • the thickness of the separator is preferably 50 ⁇ m or less, and more preferably 30 ⁇ m or less.
  • the thickness of the insulating layer may meet the appropriate thickness of the separator.
  • the separator when the separator includes the insulating layer and the porous base material as separate layers (in particular, the porous base material is a microporous film), it is preferable that the ratio of X and Y (Y/X) is 1 to 10, where X represents the thickness ( ⁇ m) of the insulating layer and Y represents the thickness ( ⁇ m) of the porous base material, and that the thickness of the whole separator meets the above appropriate value. If Y/X is too large, the insulating layer is excessively thin. As a result, e.g., when the dimensional stability of the porous base material at high temperature is poor, the effect of suppressing thermal shrinkage of the porous base material can be reduced.
  • Y/X is too small, the insulating layer is excessively thick. Therefore, the thickness of the whole separator is increased, and the load characteristics or the like of the electrochemical device can be degraded.
  • X represents the total thickness of the plurality of insulating layers.
  • Y represents the total thickness of the plurality of porous base materials.
  • the thickness of the porous base material is preferably in the range of 5 ⁇ m to 30 ⁇ m.
  • the thickness of the insulating layer i.e., the total thickness when the separator has a plurality of insulating layers
  • the porosity of the separator is preferably 20% or more, and more preferably 30% or more in a dry state.
  • the porosity of the separator is preferably 70% or less, and more preferably 60% or less in a dry state.
  • the porosity P (%) of the separator can be calculated from the thickness of the separator, the mass per unit area of the separator, and the densities of the components of the separator by obtaining a summation for each component i with the following formula.
  • a i represents the ratio of a component i expressed as a mass percentage
  • ⁇ i represents the density (g/cm 3 ) of the component i
  • m represents the mass (g/cm 2 ) per unit area of the separator
  • t represents the thickness (cm) of the separator.
  • the separator of the present invention has an air permeability of 10 to 300 sec, which is indicated by a Gurley value.
  • Gurley value is obtained by a method according to JIS P 8117 and expressed as the length of time (seconds) it takes for 100 ml air to pass through a membrane at a pressure of 0.879 g/mm 2 . If the air permeability is too large, the ion permeability can be reduced. If the air permeability is too small, the strength of the separator can be reduced. The air permeability can be ensured by the separator with the configuration as described above.
  • This method includes the steps of applying the slurry for forming an insulating layer of the present invention, as described in Embodiment 1, to at least one base selected from a positive electrode, a negative electrode, and a porous base material; and drying the base to which the slurry is applied.
  • the slurry may be applied to the surface of the base with a conventionally known coating apparatus such as a die coater, a gravure coater, a reverse roll coater, a squeeze roll coater, a curtain coater, a blade coater, or a knife coater.
  • a conventionally known coating apparatus such as a die coater, a gravure coater, a reverse roll coater, a squeeze roll coater, a curtain coater, a blade coater, or a knife coater.
  • FIG. 1 is a schematic view showing an example of the coating apparatus that is applicable to the production of the separator of the present invention.
  • the coating apparatus shown in FIG. 1 includes a corona discharge device 2 for performing a surface treatment on a porous base material 1 before the slurry is applied.
  • the separator of the present invention is produced by using the coating apparatus shown in FIG. 1 , first, the rein porous base material 1 that has been wound up into a roll is drawn out and then surface-treated with corona discharge 2 a by the corona discharge device 2 . Subsequently, the slurry for forming an insulating layer is applied to the surface of the porous base material 1 after the surface treatment by a die head 3 . Since the surface treatment is performed only on the surface portion of the porous base material 1 , the slurry or the dispersion medium of the slurry can be prevented from entering the pores of the porous base material 1 .
  • the slurry can be applied more uniformly, so that the homogeneity of the insulating layer can be improved.
  • FIG. 1 shows an example of producing the separator in which the heat-resistant porous insulating layer is formed on one side of the resin porous base material 1 .
  • the insulating layer may be formed on either one side or both sides of the porous base material.
  • the separator may include a plurality of porous base materials.
  • the process of surface-treating the porous base material and the process of forming the insulating layer by applying the slurry to the surface-treated porous base material are continuously performed. However, these processes may be independently performed.
  • the orientation of the plate-like insulating fine particles in the separator may be improved by subjecting the slurry to shear while it is applied to the base material.
  • the slurry may be subjected to shear by impregnating the slurry into the porous base material, allowing the porous base material to pass through a predetermined gap to remove the extra slurry, and subsequently drying the porous base material.
  • the orientation of the plate-like insulating fine particles in the separator can be further improved, e.g., by the following methods: a method of using a slurry that has a high solid concentration (e.g., 50 to 80 mass %); a method of using a slurry that is prepared by dispersing the insulating fine particles in a solvent with various types of mixing and stirring devices such as a disperser, an agitator, a homogenizer, a ball mill, an attritor, and a jet mill and mixing a binder (and the thermofusible fine particles as needed) with the dispersion thus obtained; a method of using a slurry that includes the insulating fine particles whose surfaces have been modified by the action of dispersing agents such as fats and oils, a surface-active agent, and a silane coupling agent; a method of using a slurry that includes the insulating fine particles with different shapes, diameters, or aspect ratios; a method of using a slurry that
  • the slurry of the present invention that has good dispersion stability of the insulating fine particles is used to form the insulating layer of the separator. Therefore, according to the production method of the present invention, the separator including the insulating layer with high homogeneity can be produced, e.g., even if the slurry used has been stored for a long time. Moreover, according to the production method of the present invention, even if a long separator is continuously produced, the separator can include the insulating layer with high homogeneity from the beginning to the end of the production and thus have stable quality.
  • the electrochemical device of the present invention includes the separator of the present invention having good heat resistance, as described in Embodiment 2. Therefore, even if the temperature in the electrochemical device becomes high, it is possible to suppress an internal short circuit caused by thermal shrinkage of the separator. Moreover, it is also possible to suppress a small short circuit caused by a deposition of the lithium dendrite by the separator. Thus, electrochemical device can achieve excellent safety and reliability.
  • the intended use of the electrochemical device of the present invention is not particularly limited.
  • the electrochemical device can be suitably used in any application requiring safety at high temperatures such as a lithium battery (primary and secondary batteries) including an organic electrolyte or a super capacitor.
  • a lithium battery primary and secondary batteries
  • an organic electrolyte or a super capacitor.
  • the electrochemical device of the present invention can employ various configurations/structures of various types of conventionally known electrochemical devices including an organic electrolyte (such as a lithium secondary battery, a lithium primary battery, and a super capacitor).
  • the lithium secondary battery may be in the form of a rectangular or circular cylinder and have an outer can made of steel or aluminum.
  • the lithium secondary battery may be a soft package battery using a metal-deposited laminated film as an outer package.
  • the positive electrode is not particularly limited as long as it has been used for a conventional lithium secondary battery, that is, it contains an active material capable of intercalating and deintercalating a Li ion.
  • the positive active material include the following: a lithium-containing transition metal oxide expressed as Li 1+x MO 2 (0.1 ⁇ x ⁇ 0.1, M: Co, Ni, Mn, Mg, Al, Zr, Ti, etc.); a lithium manganese oxide such as LiMn 2 O 4 ; LiMn x M (1 ⁇ x) O 2 in which a part of Mn of LiMn 2 O 4 is substituted with another element; an olivine-type LiMPO 4 (M: Co, Ni, Mn, Fe); LiMn 0.5 Ni 0.5 O 2 ; and Li (1+a) Mn x Co y Ni (1 ⁇ x ⁇ y) O 2 ( ⁇ 0.1 ⁇ a ⁇ 0.1, 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5).
  • the positive electrode may be produced in such a manner that a positive electrode mixture is prepared by adding a known conductive assistant (e.g., a carbon material such as carbon black) or a binder such as polyvinylidene fluoride (PVDF) appropriately to the above positive active materials, and then is formed into a compact (i.e., a positive electrode mixture layer) by using a current collector as a core material.
  • a known conductive assistant e.g., a carbon material such as carbon black
  • PVDF polyvinylidene fluoride
  • the current collector of the positive electrode may be, e.g., a foil, a punched metal, a mesh, or an expanded metal, which are made of aluminum or the like.
  • a foil e.g., a punched metal, a mesh, or an expanded metal, which are made of aluminum or the like.
  • an aluminum foil with a thickness of 10 to 30 ⁇ m can be suitably used.
  • a lead portion of the positive electrode is generally provided in the following manner.
  • a part of the current collector remains exposed without forming the positive electrode mixture layer when the positive electrode is produced, and this exposed portion can serve as the lead portion.
  • the lead portion does not necessarily need to be integrated with the current collector from the beginning and may be provided by connecting an aluminum foil or the like to the current collector afterward.
  • the negative electrode is not particularly limited as long as it has been used for a conventional lithium secondary battery, that is, it contains an active material capable of intercalating and deintercalating a Li ion.
  • the negative active material include one type of carbon materials capable of intercalating and deintercalating lithium such as graphite, pyrolytic carbons, coke, glassy carbons, a calcined organic polymer compound, mesocarbon microbeads (MCMB), and a carbon fiber or a mixture of two or more types of the carbon materials.
  • examples of the negative active material also include the following: elements such as Si, Sn, Ge, Bi, Sb, and In and their alloys; compounds that can be charged/discharged at a low voltage close to a lithium metal such as a lithium-containing nitride; a lithium metal; and a lithium/aluminum alloy.
  • the negative electrode may be produced in such a manner that a negative electrode mixture is prepared by adding the conductive assistant (e.g., a carbon material such as carbon black) or the binder (e.g., PVDF) appropriately to the above negative active materials, and then formed into a compact (i.e., a negative electrode mixture layer) by using a current collector as a core material.
  • a foil of the lithium metal or various alloys as described above can be used individually as the negative electrode.
  • a negative electrode layer may be formed by laminating a layer of the lithium metal or various alloys as described above and the current collector.
  • the current collector may be, e.g., a foil, a punched metal, a mesh, or an expanded metal, which are made of copper or nickel. In general, a cooper foil is used. If the thickness of the whole negative electrode is reduced to achieve a battery with high energy density, the current collector of the negative electrode preferably has a thickness of 5 to 30 ⁇ m.
  • a lead portion of the negative electrode is generally provided in the following manner. Apart of the current collector remains exposed without forming the negative electrode layer (including the negative active material layer and the negative electrode mixture layer) when the negative electrode is produced, and this exposed portion can serve as the lead portion.
  • the lead portion does not necessarily need to be integrated with the current collector from the beginning and may be provided by connecting a copper foil or the like to the current collector afterward.
  • the positive electrode and the negative electrode may be used in the form of an electrode assembly having a stacked structure in which these electrodes are stacked via the separator of the present invention, or in the form of an electrode assembly having a wound structure in which the electrode assembly having the stacked structure is wound.
  • the electrolyte (organic electrolyte) may be a solution obtained by dissolving a lithium salt in an organic solvent.
  • the lithium salt is not particularly limited as long as it dissociates in the solvent to produce a Li + ion and does not cause a side reaction such as decomposition in the working voltage range of a battery.
  • lithium salt examples include the following: inorganic lithium salts such as LiClO 4 , LiPF 6 , LiBF 4 , LiAsF 6 , and LiSbF 6 ; and organic lithium salts such as LiCF 3 SO 3 , LiCF 3 CO 2 , Li 2 C 2 F 4 (SO 3 ) 2 , LiN(CF 3 SO 2 ) 2 , LiC(CF 3 SO 2 ) 3 , LiC n F 2n+1 SO 3 (2 ⁇ n ⁇ 5), and LiN(RfOSO 2 ) 2 (where Rf represents a fluoroalkyl group).
  • inorganic lithium salts such as LiClO 4 , LiPF 6 , LiBF 4 , LiAsF 6 , and LiSbF 6
  • organic lithium salts such as LiCF 3 SO 3 , LiCF 3 CO 2 , Li 2 C 2 F 4 (SO 3 ) 2 , LiN(CF 3 SO 2 ) 2 , LiC(CF 3 SO 2 ) 3 , LiC n F
  • the organic solvent used for the electrolyte is not particularly limited as long as it dissolves the lithium salt and does not cause a side reaction such as decomposition in the working voltage range of a battery
  • the organic solvent include the following: cyclic carbonates such as an ethylene carbonate, a propylene carbonate, a butylene carbonate, and a vinylene carbonate; chain carbonates such as a dimethyl carbonate, a diethyl carbonate, and a methyl ethyl carbonate; chain esters such as methyl propionate; cyclic esters such as ⁇ -butyrolactone; chain ethers such as dimethoxyethane, diethyl ether, 1,3-dioxolane, diglyme, triglyme, and tetraglyme; cyclic ethers such as dioxane, tetrahydrofuran, and 2-methyltetrahydrofuran; nitriles such as acetonitrile, propionitrile
  • the above examples of the organic solvent may be used individually or in combinations of two or more.
  • a combination of the materials capable of achieving a high conductivity e.g., a mixed solvent of the ethylene carbonate and the chain carbonate is preferred for better characteristics of the battery.
  • additives such as vinylene carbonates, 1,3-propane sultone, diphenyl disulfide, cyclohexylbenzene, biphenyl, fluorobenzene, and t-butylbenzene can be appropriately added to the electrolyte.
  • the concentration of the lithium salt in the electrolyte is preferably 0.5 to 1.5 mold, and more preferably 0.9 to 1.25 mol/l.
  • room temperature molten salts such as ethyl-methylimidazolium trifluoromethyl sulfonium imide, heptyl-trimethylammonium trifluoromethyl sulfonium imide, pyridinium trifluoromethyl sulfonium imide, and guadinium trifluoromethyl sulfonium imide also can be used.
  • a polymeric material that contains and gelatinizes the electrolyte may be added, and the gelled electrolyte may be used in the battery.
  • the polymeric material for gelatinizing the electrolyte include known host polymers capable of forming a gelled electrolyte such as PVDF, a vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), PAN, a polyethylene oxide, a polypropylene oxide, an ethylene oxide-propylene oxide copolymer, a crosslinked polymer having an ethylene oxide chain in the main or side chain, and a crosslinked poly (meta) acrylic ester.
  • the electrochemical device of the present invention can be used as a power source for various equipment such as portable equipment (a portable telephone, a notebook personal computer, etc.), an electric vehicle, a hybrid vehicle, an electric motorcycle, a power-assisted bicycle, a power tool, and a shaver.
  • portable equipment a portable telephone, a notebook personal computer, etc.
  • electric vehicle a hybrid vehicle
  • electric motorcycle a power-assisted bicycle
  • power tool a power tool
  • a shaver a power-assisted bicycle
  • a median diameter (d 50 ) in the volume-based particle size distribution of the insulating fine particles, a 10% value (d 10 ) of the cumulative distribution, a 30% value (d 30 ) of the cumulative distribution, and a 90% value (d 90 ) of the cumulative distribution were determined, and the median diameter was defined as an average particle size of the insulating fine particles.
  • d 30 it was confirmed from d 30 that the proportion of particles with a particle size of 1 ⁇ m or less was 30 vol % or more.
  • d 90 the proportion of particles with a particle size of 3 ⁇ m or more was 10 vol % or less.
  • plate-like boehmite (insulating fine particles) with an aspect ratio of 10 were added 1000 g of water (dispersion medium) and 1 part by mass of ammonium polyacrylate (dispersing agent) with respect to 100 parts by mass of boehmite, and then mixed in a bench ball mill for 6 days, so that the plate-like boehmite was dispersed in water.
  • d 10 , d 30 , d 50 , and d 90 of the boehmite in the resultant dispersion were 0.40 ⁇ m, 0.68 ⁇ m, 0.98 ⁇ m, and 1.86 ⁇ m, respectively, that the average particle size was 0.98 ⁇ m, and that the proportion of particles with a particle size of 1 ⁇ m or less was 50 vol % or more and the proportion of particles with a particle size of 3 ⁇ m or more was 10 vol % or less.
  • an emulsion of a self-crosslinking acrylic acid copolymer including butyl acrylate as the main component of the monomer was used as a binder, and 3 parts by mass of the emulsion with respect to 100 parts by mass of boehmite was added to the dispersion. Moreover, 2 g of xanthan gum was added to the dispersion as a thickening agent. This mixture was stirred with a Three-One Motor for 1 hour and dispersed, resulting in a uniform slurry for forming an insulating layer.
  • the viscosity of the slurry thus obtained was measured with an E-type viscometer at 20° C., and was 200 mPa ⁇ s.
  • the stability of the slurry was evaluated with a Turbiscan (“MA-2000 (trade name)” manufactured by EKO INSTRUMENTS CO., LTD.) by measuring a height of sedimentation in a sample tube.
  • the slurry was injected into the sample tube at a height of 60 mm, and the back scattering light intensity was measured. Then, the height to the point at which the scattered light intensity was 1 or more was measured and defined as the height of sedimentation.
  • the height of sedimentation one week after the start of the measurement was 54 mm.
  • a slurry for forming an insulating layer was produced in the same manner as Example 1 except that polyhedral alumina was used instead of the plate-like boehmite. It was confirmed that d 10 , d 30 , d 50 , and d 90 of the alumina dispersed in water were 0.40 ⁇ m, 0.47 ⁇ m, 0.54 ⁇ m, and 1.15 ⁇ m, respectively, that the average particle size was 0.54 ⁇ m, and that the proportion of particles with a particle size of 1 ⁇ m or less was 50 vol % or more and the proportion of particles with a particle size of 3 ⁇ m or more was 10 vol % or less. As a result of the measurement of the slurry thus obtained in the same manner as Example 1, the viscosity was 180 mPa ⁇ s and the height of sedimentation after one week was 53 mm.
  • a slurry for forming an insulating layer was produced in the same manner as Example 1 except that plate-like alumina with an aspect ratio of 25 was used instead of the plate-like boehmite. It was confirmed that d 10 , d 30 , d 50 , and d 90 of the alumina dispersed in water were 0.43 ⁇ m, 0.78 ⁇ m, 1.05 ⁇ m, and 1.20 ⁇ m, respectively, that the average particle size was 1.05 ⁇ m, and that the proportion of particles with a particle size of 1 ⁇ m or less was 30 vol % or more and the proportion of particles with a particle size of 3 ⁇ m or more was 10 vol % or less. As a result of the measurement of the slurry thus obtained in the same manner as Example 1, the viscosity was 190 mPa ⁇ s and the height of sedimentation after one week was 55 mm.
  • a slurry for forming an insulating layer was produced in the same manner as Example 1 except that boehmite having a second particle structure was used instead of the plate-like boehmite. It was confirmed that d 10 , d 30 , d 50 , and d 90 of the boehmite dispersed in water were 0.34 ⁇ m, 0.48 ⁇ m, 0.71 ⁇ m, and 1.24 ⁇ m, respectively, that the average particle size was 0.71 ⁇ m, and that the proportion of particles with a particle size of 1 ⁇ m or less was 50 vol % or more and the proportion of particles with a particle size of 3 ⁇ m or more was 10 vol % or less. As a result of the measurement of the slurry thus obtained in the same manner as Example 1, the viscosity was 220 mPa ⁇ s and the height of sedimentation after one week was 56 mm.
  • a slurry for forming an insulating layer was produced in the same manner as Example 1 except that polyhedral silica was used instead of the plate-like boehmite, and the amount of the thickening agent was changed to 10 g. It was confirmed that d 10 , d 30 , d 50 , and d 90 of the silica dispersed in water were 0.11 ⁇ m, 0.16 ⁇ m, 0.20 ⁇ m, and 0.39 ⁇ m, respectively, that the average particle size was 0.20 ⁇ m, and that the proportion of particles with a particle size of 1 ⁇ m or less was 90 vol % or more and the proportion of particles with a particle size of 3 ⁇ m or more was 10 vol % or less. As a result of the measurement of the slurry thus obtained in the same manner as Example 1, the viscosity was 200 mPa ⁇ s and the height of sedimentation after one week was 50 mm.
  • a slurry for forming an insulating layer was produced by further adding 1 g of a p-hydroxybenzoic acid ester (serving as a preservative) to the slurry of Example 1.
  • a p-hydroxybenzoic acid ester serving as a preservative
  • the viscosity and the height of sedimentation after one week were the same as those of the slurry of Example 1.
  • a slurry for forming an insulating layer was produced by further adding 0.1 g of a polyether antifoaming agent (polyether-modified organopolysiloxane) to the slurry of Example 1.
  • a polyether antifoaming agent polyether-modified organopolysiloxane
  • a slurry for forming an insulating layer was produced in the same manner as Example 1 except that the thickening agent was not added.
  • the viscosity was 3 mPa ⁇ s and the height of sedimentation after one week was 34 mm.
  • Example 7 Each of the slurries of Examples 1 to 7 was uniformly stirred and defoamed. Then, a PET nonwoven fabric (porous base material) with a thickness of 15 ⁇ m was immersed in and removed from the slurry, so that the slurry was applied to the nonwoven fabric. Subsequently, this nonwoven fabric was allowed to pass through a predetermined gap and dried, thereby providing a separator with a thickness of 20 ⁇ m. However, since the slurry of Example 7 included the antifoaming agent, the defoaming treatment was not necessary.
  • Example 7 Each of the slurries of Examples 1 to 7 and Comparative Example 1 was uniformly stirred and defoamed. Then, the slurry was applied to one surface of a PE microporous film (porous base material) with a thickness of 16 ⁇ m using a die coater and dried, thereby providing a separator with a thickness of 20 ⁇ m. However, since the slurry of Example 7 included the antifoaming agent, the defoaming treatment was not necessary.
  • Each of the slurries of Examples 1 to 7 was applied to the surface of a copper foil using an applicator and dried, thereby forming a porous insulating layer with a thickness of 20 ⁇ m. Moreover, the copper foil having the insulating layer was heated at 150° C., and the presence or absence of thermal shrinkage was checked by visual observation. Consequently, no thermal shrinkage of the insulating layer was found.
  • the heat resistance of the separators of Examples 8 to 21 was evaluated in the following manner. First, two sheets of cardboard with a thickness of 1 mm were prepared, each of which was cut to 9 cm ⁇ 9 cm and provided with a hole of 3 cm square in the center. Then, a double-faced tape was attached to the four sides around the hole of one sheet, and the separator to be tested was placed at the center of this sheet and bonded. Moreover, the other sheet was disposed on the separator so that the separator was sandwiched between the two sheets and fixed. Subsequently, the separator held between the two sheets of cardboard was hanged in a thermostatic chamber at 150° C. and allowed to stand for 3 hours. Thereafter, the separator was taken out, and the presence or absence of fracture in the separator was observed. For comparison purposes, the PE microporous film (with a thickness of 20 ⁇ m) for a lithium secondary battery also evaluated in the same mariner.
  • a positive electrode mixture containing paste was prepared by mixing 85 parts by mass of LiCoO 2 (positive active material), 10 parts by mass of acetylene black (conductive assistant), and 5 parts by mass of PVDF (binder) uniformly by using N-methyl-2-pyrrolidone (NMP) as a solvent.
  • This paste was intermittently applied to both surfaces of an aluminum foil (current collector) with a thickness of 15 ⁇ m so that the applied length was 320 mm on the upper surface and 250 mm on the lower surface, which then was dried and calendered.
  • the thicknesses of the positive electrode mixture layers were adjusted so that the total thickness was 150 p.m.
  • the current collector having the positive electrode mixture layers was cut into a width of 43 mm, thus producing a positive electrode with a length of 340 mm and a width of 43 mm. Moreover, a lead portion was connected to the exposed portion of the aluminum foil of the positive electrode.
  • a negative electrode mixture containing paste was prepared by mixing 90 parts by mass of graphite (negative active material) and 5 parts by mass of PVDF (binder) uniformly by using NMP as a solvent. This paste was intermittently applied to both surfaces of a copper foil (current collector) with a thickness of 10 ⁇ m so that the applied length was 320 mm on the upper surface and 260 mm on the lower surface, which then was dried and calendered. The thicknesses of the negative electrode mixture layers were adjusted so that the total thickness was 142 ⁇ m. Subsequently, the current collector having the negative electrode mixture layers was cut into a width of 45 mm, thus producing a negative electrode with a length of 330 mm and a width of 45 mm. Moreover, a lead portion was connected to the exposed portion of the copper foil of the negative electrode.
  • the positive electrode and the negative electrode thus obtained were stacked with the separator of Example 8 interposed between them, and then wound in a spiral fashion to form an electrode assembly having a wound structure.
  • the electrode assembly was placed in a cylindrical battery case with a diameter of 14 mm and a height of 50 mm.
  • an electrolyte i.e., a solution obtained by dissolving LiPF 6 at a concentration of 1.2 mol/l in a solvent containing an ethylene carbonate and an ethyl methyl carbonate at a volume ratio of 1:2
  • LiPF 6 a solution obtained by dissolving LiPF 6 at a concentration of 1.2 mol/l in a solvent containing an ethylene carbonate and an ethyl methyl carbonate at a volume ratio of 1:2
  • Lithium secondary batteries of Examples 23 to 28 were produced in the same manner as Example 22 except that the separators of Examples 9 to 14 were used, respectively.
  • Lithium secondary batteries of Examples 29 to 35 were produced in the same manner as Example 22 except that the separators of Examples 15 to 21 were used, respectively, and the separator was interposed between the positive electrode and the negative electrode so that the PE microporous film faced the negative electrode.
  • Table 1 shows the separator and the slurry for forming an insulating layer used for the lithium secondary battery in each of the examples.
  • Example 21 Slurry Lithium secondary battery for forming insulating layer Separator Example 22
  • Example 1 Example 8
  • Example 2 Example 9
  • Example 10 Example 25
  • Example 4 Example 11
  • Example 26 Example 5
  • Example 12 Example 27
  • Example 6 Example 13
  • Example 28 Example 7
  • Example 14 Example 29
  • Example 15 Example 30
  • Example 2 Example 16
  • Example 31 Example 3
  • Example 17 Example 32
  • Example 4 Example 18
  • Example 5 Example 19
  • Example 34 Example 6 Example 20 Example 35
  • Example 21 Slurry Lithium secondary battery for forming insulating layer Separator Example 22
  • Example 1 Example 8
  • Example 2 Example 9
  • Example 10 Example 25
  • Example 12 Example 27
  • Example 6 Example 13
  • Example 28 Example 7
  • Example 14 Example 29
  • Example 15 Example 30
  • Example 16 Example 31
  • Example 3 Example 17
  • Example 32 Example 4
  • Example 18 Example 33
  • Example 5 Example 19
  • Example 34 Example 6
  • Example 20 Example 35
  • Example 21 Example 21
  • a constant-current charge was performed at 150 mA until the voltage reached 4.2 V so that the electrical quantity was 20% of a rated capacity of 750 mAh of the battery, and subsequently a constant-voltage charge was performed at 4.2 V.
  • the total charge time of the constant-current charge and the constant-voltage charge was 6 hours.
  • a constant-current discharge was performed on the charged battery at 150 mA until the voltage was reduced to 3 V. In this manner, a conversion treatment of the battery was performed.
  • the lithium secondary batteries of Examples 22 to 35 after the conversion treatment were charged by performing a constant-current charge at 150 mA to 4.2 V and a constant-voltage charge at 4.2 V for 15 hours in total, and then discharged at 150 mA until the voltage was reduced to 3V. Consequently, all the batteries of Examples 22 to 35 achieved the discharge capacity comparable to the rated capacity. In this case, the ratio of the discharge capacity to the charge capacity was approximately 100% in each of the batteries. Thus, it was confirmed that these batteries had good charge-discharge characteristics and reliability.
  • the self-crosslinking acrylic resin was used as a binder added to the slurry for forming an insulating layer, the flexibility of the insulating layer (separator) formed of the slurry was improved. Therefore, it was possible to suppress cracking of the separator or peeling of the insulating fine particles in the innermost portion of the electrode assembly having a wound structure. Thus, a small short circuit caused by a deposition of the lithium dendrite could be sufficiently suppressed, so that the separator was considered to have higher reliability.
  • a slurry for forming an insulating layer was produced in the same manner as Example 1 except that the ammonium polyacrylate (dispersing agent) was not used. It was confirmed that d 10 , d 30 , d 50 , and d 90 of the plate-like boehmite dispersed in water were 1.05 ⁇ m, 1.83 ⁇ m, 2.72 ⁇ m, and 4.82 ⁇ m respectively, that the average particle size was 2.72 ⁇ m, and that the proportion of particles with a particle size of 1 or less was less than 10 vol % and the proportion of particles with a particle size of 3 or more was 50 vol % or more.
  • a slurry for forming an insulating layer was produced in the same manner as Example 2 except that the ammonium polyacrylate (dispersing agent) was not used. It was confirmed that d 10 , d 30 , d 50 , and d 90 of the alumina dispersed in water were 0.53 ⁇ m, 0.70 ⁇ m, 0.85 ⁇ m, and 1.32 ⁇ m, respectively, that the average particle size was 0.85 ⁇ m, and that the proportion of particles with a particle size of 1 ⁇ m or less was 50 vol % or more and the proportion of particles with a particle size of 3 ⁇ m or more was 10 vol % or less.
  • a slurry for forming an insulating layer was produced in the same manner as Example 3 except that the ammonium polyacrylate (dispersing agent) was not used. It was confirmed that d 10 , d 30 , d 50 , and d 90 of the plate-like alumina dispersed in water were 0.55 ⁇ m, 0.88 ⁇ m, 1.22 ⁇ m, and 1.43 ⁇ m, respectively, that the average particle size was 1.22 ⁇ m, and that the proportion of particles with a particle size of 1 ⁇ m or less was 30 vol % or more and the proportion of particles with a particle size of 3 ⁇ m or more was 10 vol % or less.
  • each of the slurries was applied to the surface of a copper foil using an applicator and dried, thereby forming a porous insulating layer (with a thickness of 20 ⁇ m) having both ion permeability and heat resistance.
  • An evaluation cell was prepared in such a manner that metallic lithium was arranged opposite to the insulating layer of the copper foil, and both the copper foil having the insulating layer and the metallic lithium were immersed in the electrolyte.
  • the electrolyte was a solution obtained by dissolving LiPF 6 at a concentration of 1 mol/l in a solvent containing an ethylene carbonate and a dimethyl carbonate at a volume ratio of 1:2.
  • the insulating layers formed of the slurries of Examples 1 to 3 including the dispersing agent had a larger short circuit current compared to those formed of the slurries of Examples 36, 37 and Comparative Example 2 including no dispersing agent, and it was clear that the occurrence of a short circuit was suppressed.
  • the reason for this is considered as follows.
  • the insulating fine particles are more uniformly dispersed in the slurries of Examples 1 to 3 than in the slurries of Examples 36, 37 and Comparative Example 2. Therefore, the use of the slurries of Examples 1 to 3 can provide the insulating layer with higher homogeneity.
  • the movement of lithium ions in the insulating layer becomes more uniform, and the growth of dendrite due to current concentration can be suppressed.
  • the short circuit current is significantly increased by the addition of the dispersing agent, and thus the effect of improving the dispersibility of the particles by the dispersing agent is increased.
  • Example 7 Each of the slurries of Examples 1 to 7 was uniformly stirred and defoamed. Then, the slurry was applied to both surfaces of the same negative electrode as that produced in Example 22 using a die coater and dried, so that a separator including the insulating layer with a thickness of 20 ⁇ m per one surface was formed on the surface of the negative electrode. However, since the slurry of Example 7 included the antifoaming agent, the defoaming treatment was not necessary.
  • Example 22 The same positive electrode as that used in Example 22 and the above negative electrode integrated with the separator were stacked and wound in a spiral fashion to form an electrode assembly having a wound structure.
  • Lithium secondary batteries of Examples 38 to 44 were produced in the same manner as Example 22 except that this electrode assembly was used. Table 3 shows the slurries used for the production of the lithium secondary batteries of Examples 38 to 44.
  • the charge-discharge characteristics of the lithium secondary batteries of Examples 38 to 44 including the negative electrode integrated with the insulating layer (separator) composed of the respective slurries of Examples 1 to 7, were evaluated in the same manner as the lithium secondary batteries of Examples 22 to 35. The evaluation confirmed that all the batteries of Examples 38 to 44 achieved the discharge capacity comparable to the rated capacity, and had good charge-discharge characteristics and reliability.
  • the slurry for forming an insulating layer of the present invention is capable of achieving the uniform dispersion of the insulating fine particles and maintaining the dispersion state stably.
  • the separator for an electrochemical device of the present invention is produced using the slurry for forming an insulating layer and thus can have excellent heat resistance.
  • the electrochemical device of the present invention includes the separator for an electrochemical device and thus can have high reliability.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Cell Separators (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Secondary Cells (AREA)
US12/676,806 2008-01-29 2009-01-29 Slurry for forming insulating layer, separator for electrochemical device, method for producing the same, and electrochemical device Abandoned US20100221965A1 (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP2008017004 2008-01-29
JP2008-017004 2008-01-29
JP2008-040972 2008-02-22
JP2008040972 2008-02-22
JP2008205040 2008-08-08
JP2008-205040 2008-08-08
PCT/JP2009/051429 WO2009096451A1 (ja) 2008-01-29 2009-01-29 絶縁層形成用スラリー、電気化学素子用セパレータおよびその製造方法、並びに電気化学素子

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/051429 A-371-Of-International WO2009096451A1 (ja) 2008-01-29 2009-01-29 絶縁層形成用スラリー、電気化学素子用セパレータおよびその製造方法、並びに電気化学素子

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US14/682,783 Division US9972816B2 (en) 2008-01-29 2015-04-09 Slurry for forming insulating layer, separator for electrochemical device, method for producing the same, and electrochemical device

Publications (1)

Publication Number Publication Date
US20100221965A1 true US20100221965A1 (en) 2010-09-02

Family

ID=40912802

Family Applications (2)

Application Number Title Priority Date Filing Date
US12/676,806 Abandoned US20100221965A1 (en) 2008-01-29 2009-01-29 Slurry for forming insulating layer, separator for electrochemical device, method for producing the same, and electrochemical device
US14/682,783 Active US9972816B2 (en) 2008-01-29 2015-04-09 Slurry for forming insulating layer, separator for electrochemical device, method for producing the same, and electrochemical device

Family Applications After (1)

Application Number Title Priority Date Filing Date
US14/682,783 Active US9972816B2 (en) 2008-01-29 2015-04-09 Slurry for forming insulating layer, separator for electrochemical device, method for producing the same, and electrochemical device

Country Status (5)

Country Link
US (2) US20100221965A1 (zh)
JP (2) JP5753657B2 (zh)
KR (1) KR101111710B1 (zh)
CN (1) CN101796669B (zh)
WO (1) WO2009096451A1 (zh)

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110052987A1 (en) * 2007-10-03 2011-03-03 Hideaki Katayama Battery separator and nonaqueous electrolyte battery
CN103000848A (zh) * 2012-11-29 2013-03-27 东莞新能源科技有限公司 复合多孔性隔膜及其制备方法
EP2680340A1 (en) * 2012-06-25 2014-01-01 Hou, Dong Membrane
US20140050989A1 (en) * 2012-08-20 2014-02-20 Samsung Sdi Co., Ltd. Separator for rechargeable lithium battery and rechargeable lithium battery including same
EP2784843A1 (en) * 2012-11-30 2014-10-01 LG Chem, Ltd. Slurry with improved dispersibility and use therefor
US20150017512A1 (en) * 2012-01-30 2015-01-15 Evonik Litarion Gmbh Separator comprising an organic-inorganic adhesion promoter
EP2618406B1 (en) * 2010-09-14 2016-06-22 Hitachi Maxell, Ltd. Nonaqueous secondary cell
EP2549564B1 (en) * 2010-03-17 2016-10-12 LG Chem, Ltd. Separator and electrochemical device having same
EP3085432A1 (en) 2015-04-22 2016-10-26 Karlsruher Institut für Technologie Separator for an electrochemical device and method for the production thereof
US9765459B2 (en) 2011-06-24 2017-09-19 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
US9827755B2 (en) 2011-06-23 2017-11-28 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
US9827696B2 (en) 2011-06-17 2017-11-28 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
US9837650B2 (en) 2014-07-29 2017-12-05 Sumitomo Chemical Company, Limited Porous membrane
US10062888B2 (en) * 2014-07-29 2018-08-28 Sumitomo Chemical Company, Limited Porous membrane
US10211442B2 (en) 2015-11-27 2019-02-19 Sumitomo Chemical Company, Limited Nonaqueous electrolyte secondary battery insulating porous layer and nonaqueous electrolyte secondary battery laminated separator
US10249869B2 (en) * 2016-05-25 2019-04-02 Toyota Jidosha Kabushiki Kaisha Method of producing electrode body and method of producing battery
US10305081B2 (en) * 2015-11-06 2019-05-28 Samsung Sdi Co., Ltd. Separator for rechargeable battery and rechargeable battery including the same
US10369769B2 (en) 2011-06-23 2019-08-06 Fiberweb, Inc. Vapor-permeable, substantially water-impermeable multilayer article
US10418608B2 (en) 2011-07-28 2019-09-17 Sumitomo Chemical Company, Limited Laminated porous film and non-aqueous electrolyte secondary battery
US10811658B2 (en) 2012-09-19 2020-10-20 Asahi Kasei Kabushiki Kaisha Separator and method of preparing the same, and lithium ion secondary battery
US10833307B2 (en) * 2010-07-19 2020-11-10 Optodot Corporation Separators for electrochemical cells
EP3703158A4 (en) * 2018-01-18 2020-12-23 Lg Chem, Ltd. SEPARATOR FOR SECONDARY BATTERY AND LITHIUM SECONDARY BATTERY WITH IT
EP3706198A4 (en) * 2018-01-18 2021-01-06 Lg Chem, Ltd. SEPARATOR FOR LITHIUM SECONDARY BATTERY AND LITHIUM SECONDARY BATTERY WITH IT
CN113300047A (zh) * 2021-05-24 2021-08-24 万邦特种材料股份有限公司 一种碱性电池专用高性能复合隔膜材料的制备方法
US11404694B2 (en) * 2015-09-17 2022-08-02 Nec Corporation Resin composition
US11404746B2 (en) 2018-03-07 2022-08-02 Toyota Jidosha Kabushiki Kaisha Battery and method of producing the same
CN115050926A (zh) * 2022-06-22 2022-09-13 多氟多新能源科技有限公司 一种锂离子电池水系正负极片保护涂层制备方法
EP4053986A3 (en) * 2018-10-11 2022-11-30 Asahi Kasei Kabushiki Kaisha Lithium ion battery using crosslinkable separator
US11670822B2 (en) 2018-10-11 2023-06-06 Asahi Kasei Kabushiki Kaisha Separator having silane-modified polyolefin and polyethylene, and method for producing the same
EP4235899A3 (en) * 2020-04-13 2024-04-10 Asahi Kasei Kabushiki Kaisha Composite single-layer chemically cross-linked separator

Families Citing this family (69)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5753657B2 (ja) * 2008-01-29 2015-07-22 日立マクセル株式会社 絶縁層形成用スラリー、電気化学素子用セパレータの製造方法、及び電気化学素子
JP5778378B2 (ja) * 2008-02-28 2015-09-16 帝人株式会社 非水電解質電池セパレータ及び非水電解質二次電池
JP5213534B2 (ja) * 2008-06-17 2013-06-19 三洋電機株式会社 非水電解質二次電池及びその製造方法
KR101237331B1 (ko) * 2009-06-10 2013-02-28 히다치 막셀 가부시키가이샤 전기 화학 소자용 세퍼레이터 및 그것을 사용한 전기 화학 소자
DE102009058606A1 (de) * 2009-12-17 2011-06-22 Li-Tec Battery GmbH, 01917 Lithium-Ionen-Batterie
JP2011204587A (ja) * 2010-03-26 2011-10-13 Teijin Ltd 非水系二次電池用セパレータ、非水系二次電池、および非水系二次電池用セパレータの製造方法
JP5793332B2 (ja) * 2010-04-09 2015-10-14 川研ファインケミカル株式会社 非水電解液電池用セパレータおよびリチウムイオン二次電池
WO2011129169A1 (ja) * 2010-04-16 2011-10-20 日立マクセル株式会社 電気化学素子用セパレータおよびそれを用いた電気化学素子、並びにその電気化学素子用セパレータの製造方法
CN103119755B (zh) * 2010-07-23 2015-07-15 日本瑞翁株式会社 二次电池多孔膜、二次电池多孔膜用浆料及二次电池
JP5614578B2 (ja) * 2010-07-27 2014-10-29 トヨタ自動車株式会社 水性組成物の製造方法
KR20130043186A (ko) * 2010-08-02 2013-04-29 셀가드 엘엘씨 높은 용융 온도 미세다공성 리튬-이온 2차 전지 세퍼레이터 및 제조방법 및 용도
WO2012023197A1 (ja) * 2010-08-19 2012-02-23 トヨタ自動車株式会社 リチウムイオン二次電池および該電池用セパレータ
JP5664138B2 (ja) * 2010-11-08 2015-02-04 ソニー株式会社 耐収縮性微多孔膜、電池用セパレータ及びリチウムイオン二次電池
CN105206774B (zh) * 2010-11-24 2018-09-11 丰田自动车株式会社 电池
JP2013089308A (ja) * 2011-10-13 2013-05-13 Kawaken Fine Chem Co Ltd 非水電解液電池用セパレータおよびリチウムイオン二次電池
KR102087564B1 (ko) * 2011-11-18 2020-03-10 스미또모 가가꾸 가부시끼가이샤 적층 다공질 필름 및 그 제조 방법, 그리고 비수 전해액 2 차 전지용 세퍼레이터, 적층 전극 시트 및 비수 전해액 2 차 전지
JP5699916B2 (ja) * 2011-11-24 2015-04-15 トヨタ自動車株式会社 非水系二次電池用セパレータ
KR101369326B1 (ko) * 2011-12-27 2014-03-04 주식회사 엘지화학 세퍼레이터의 제조방법 및 이에 따라 제조된 세퍼레이터를 구비한 전기화학소자
JP6221447B2 (ja) * 2012-07-19 2017-11-01 東レ株式会社 多孔質フィルムおよび蓄電デバイス用セパレータ
JP5841510B2 (ja) * 2012-08-27 2016-01-13 三菱製紙株式会社 金属イオン二次電池セパレータ用塗液及び金属イオン二次電池セパレータ
JP5875487B2 (ja) * 2012-08-29 2016-03-02 株式会社日立製作所 リチウムイオン二次電池の製造方法及び製造装置
KR101662638B1 (ko) * 2012-10-22 2016-10-05 주식회사 엘지화학 바인더층을 갖는 분리막, 상기 분리막을 포함하는 전기화학소자, 및 상기 분리막의 제조방법
KR102053259B1 (ko) * 2012-10-31 2019-12-09 아사히 가세이 이-매터리얼즈 가부시키가이샤 다층 다공막 및 그의 제조 방법, 및 비수 전해액 전지용 세퍼레이터
JP2014149935A (ja) * 2013-01-31 2014-08-21 Nippon Zeon Co Ltd 二次電池用セパレータ、二次電池用セパレータの製造方法及び二次電池
JP6049520B2 (ja) * 2013-03-28 2016-12-21 三菱製紙株式会社 リチウムイオン二次電池用セパレータの製造装置および製造方法
JP6264055B2 (ja) * 2014-01-22 2018-01-24 トヨタ自動車株式会社 リチウム二次電池用電極の製造方法および造粒物
JP6340826B2 (ja) * 2014-02-26 2018-06-13 日本ゼオン株式会社 二次電池多孔膜用スラリー、製造方法、二次電池用多孔膜、及び二次電池
WO2015129408A1 (ja) * 2014-02-27 2015-09-03 日本ゼオン株式会社 二次電池多孔膜用バインダー組成物、二次電池多孔膜用スラリー、二次電池用多孔膜及び二次電池
JP2015176815A (ja) * 2014-03-17 2015-10-05 株式会社豊田自動織機 蓄電装置用電極の製造方法、蓄電装置用電極の絶縁層形成用スラリー、蓄電装置用電極、及び、蓄電装置
WO2015145551A1 (ja) * 2014-03-24 2015-10-01 日産自動車株式会社 電気デバイスのセパレータ接合方法および電気デバイスのセパレータ接合装置
JP6425484B2 (ja) * 2014-09-30 2018-11-21 旭化成株式会社 電池用セパレータ
CN106328869B (zh) * 2015-06-30 2020-09-15 比亚迪股份有限公司 锂离子电池用陶瓷隔膜及锂离子电池
JP2017033871A (ja) * 2015-08-05 2017-02-09 株式会社豊田自動織機 負極及びリチウムイオン二次電池並びにその製造方法
JP6710920B2 (ja) * 2015-09-15 2020-06-17 東レ株式会社 セラミックスラリー及びそれを用いた電池用セパレータ
JP6682790B2 (ja) * 2015-09-28 2020-04-15 日本製紙株式会社 非水電解質二次電池セパレータ用カルボキシメチルセルロース又はその塩
JP6122936B1 (ja) * 2015-11-30 2017-04-26 住友化学株式会社 非水電解液二次電池用セパレータおよびその利用
JP2017135055A (ja) * 2016-01-29 2017-08-03 株式会社日立ハイテクファインシステムズ セパレータ用粉体及びセパレータ用スラリ並びにリチウムイオン電池及びその製造方法
JP6718258B2 (ja) * 2016-03-01 2020-07-08 株式会社日本触媒 アニオン伝導性膜
JP6950151B2 (ja) * 2016-06-14 2021-10-13 住友ゴム工業株式会社 シリカの製造方法およびシリカ
CN109075296B (zh) * 2016-07-25 2021-03-12 东丽株式会社 电池用隔膜
PL3444866T3 (pl) * 2016-08-09 2021-01-11 Lg Chem, Ltd. Separator i zawierające go urządzenie elektrochemiczne
JP6579383B2 (ja) * 2016-08-10 2019-09-25 荒川化学工業株式会社 リチウムイオン二次電池用セパレータ、リチウムイオン二次電池用セパレータの製造方法、及びリチウムイオン二次電池
KR101909864B1 (ko) * 2016-09-09 2018-10-18 스미또모 가가꾸 가부시끼가이샤 알루미나 분말, 알루미나 슬러리, 알루미나 함유 코트층, 적층 분리막 및 이차 전지
JP6360531B2 (ja) * 2016-09-15 2018-07-18 住友化学株式会社 非水電解液二次電池用積層セパレータ、非水電解液二次電池用部材および非水電解液二次電池
JP2018060606A (ja) * 2016-09-30 2018-04-12 日立オートモティブシステムズ株式会社 リチウムイオン二次電池および蓄電装置
JP6588170B2 (ja) 2016-10-24 2019-10-09 住友化学株式会社 セパレータ、およびセパレータを含む二次電池
CN109863623B (zh) 2016-10-24 2020-08-25 住友化学株式会社 间隔件和包含间隔件的二次电池
US10573866B2 (en) 2016-10-24 2020-02-25 Sumitomo Chemical Company, Limited Separator and secondary battery including the separator
CN106782763A (zh) * 2016-12-19 2017-05-31 东莞珂洛赫慕电子材料科技有限公司 一种含片状氧化铝的铝基介质浆料及其制备方法
CN106876632A (zh) * 2017-01-12 2017-06-20 广东骏东科技有限公司 一种锂离子电池用陶瓷隔膜及其制备方法
US20180254449A1 (en) * 2017-03-02 2018-09-06 GM Global Technology Operations LLC Composite porous separator including lithium ion-exchanged zeolite particles
US20180301679A1 (en) * 2017-04-14 2018-10-18 Sumitomo Chemical Company, Limited Coating material for nonaqueous electrolyte secondary battery
JP6567126B2 (ja) * 2017-04-28 2019-08-28 住友化学株式会社 非水電解液二次電池用絶縁性多孔質層
JP7103760B2 (ja) * 2017-06-20 2022-07-20 旭化成株式会社 パターン塗工用スラリー
KR102469471B1 (ko) * 2017-12-14 2022-11-21 주식회사 엘지에너지솔루션 리튬 이차 전지용 양극 및 이를 포함하는 이차 전지
CN110890544A (zh) * 2018-09-11 2020-03-17 深圳格林德能源有限公司 一种石墨烯复合导电浆料及其制备方法
CN112640170A (zh) * 2018-09-11 2021-04-09 麦克赛尔控股株式会社 圆柱形非水电解液一次电池
CN109524601B (zh) * 2018-10-16 2021-09-24 上海恩捷新材料科技有限公司 一种动力锂离子电池隔膜及其制备方法
JP2020136268A (ja) 2019-02-18 2020-08-31 旭化成株式会社 蓄電デバイス用微多孔膜
KR102280521B1 (ko) 2019-04-15 2021-07-26 아사히 가세이 가부시키가이샤 폴리올레핀 적층 미다공막
KR20210061137A (ko) * 2019-11-19 2021-05-27 주식회사 엘지에너지솔루션 전기화학소자용 분리막 및 이를 포함하는 전기화학소자
CN111072317B (zh) * 2019-12-04 2022-05-17 乐凯胶片股份有限公司 陶瓷浆料、陶瓷隔膜和锂离子电池
CN111312967B (zh) * 2020-02-27 2022-06-07 河北金力新能源科技股份有限公司 一种陶瓷涂覆浆料及其制备方法、锂电池隔膜、锂电池
EP4009436A1 (en) 2020-04-13 2022-06-08 Asahi Kasei Kabushiki Kaisha Composite-type stacked chemically-crosslinked separator
CN112588534A (zh) * 2020-11-30 2021-04-02 华中科技大学 一种致密Al2O3陶瓷涂层及其制备方法
JP7286696B2 (ja) * 2021-03-15 2023-06-05 本田技研工業株式会社 電池用部材の製造方法及び製造装置
CN113363667A (zh) * 2021-05-06 2021-09-07 惠州锂威新能源科技有限公司 一种电池隔膜的生产设备及隔膜
JP2024519898A (ja) * 2021-05-20 2024-05-21 アリゾナ ボード オブ リージェンツ オン ビハーフ オブ アリゾナ ステート ユニバーシティ γ－アルミナセパレーターにより有効化された急速充電準固体状態Ｌｉ金属バッテリー
KR20230060924A (ko) * 2021-10-28 2023-05-08 주식회사 티세라 나노 크기를 갖는 다면체 α-알루미나 입자 및 그 제조 방법

Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5830603A (en) * 1993-09-03 1998-11-03 Sumitomo Electric Industries, Ltd. Separator film for a storage battery
JPH1180395A (ja) * 1997-09-09 1999-03-26 Nitto Denko Corp 多孔質膜および非水電解液電池用セパレータ
US20010005560A1 (en) * 1999-06-22 2001-06-28 Mitsubishi Denki Kabushiki Kaisha Separator for battery, battery and process for preparing the separator
US20020055046A1 (en) * 2000-08-22 2002-05-09 Michio Ono Electrolyte composition and electrochemical battery using the same
US6387564B1 (en) * 1997-02-28 2002-05-14 Asahi Kasei Kabushiki Kaisha Non-aqueous secondary battery having an aggregation layer
US6447958B1 (en) * 1998-04-27 2002-09-10 Sumitomo Chemical Co., Ltd. Non-aqueous electrolyte battery separator
US20030235685A1 (en) * 2002-06-14 2003-12-25 Lofton Elizabeth P. Water-based adhesives
JP2005022540A (ja) * 2003-07-03 2005-01-27 Nifco Inc カップホルダ装置
US20060127753A1 (en) * 2003-08-06 2006-06-15 Mitsubishi Chemical Corporation Nonaqueous electrolyte solution secondary battery separator and nonaqueous electrolyte solution secondary battery using the same
US20060188786A1 (en) * 1998-12-08 2006-08-24 Sang-Young Lee Separator for secondary battery and porous film made of polyolefin blend and process for preparing the same
US20070082261A1 (en) * 2005-10-11 2007-04-12 Samsung Sdi Co., Ltd. Lithium rechargeable battery
US20070122716A1 (en) * 2005-11-28 2007-05-31 Le Chem, Ltd. Organic/inorganic composite porous membrane and electrochemical device using the same
US20070264577A1 (en) * 2004-12-08 2007-11-15 Hideaki Katayama Separator for Electrochemical Device, and Electrochemical Device
US20080038631A1 (en) * 2004-12-13 2008-02-14 Kensuke Nakura Lithium Ion Secondary Battery
US20080139737A1 (en) * 2005-12-13 2008-06-12 Keith Allen Alderfer Polymer composition
US20090181200A1 (en) * 2007-09-19 2009-07-16 Borenstein Jeffrey T Microfluidic Structures for Biomedical Applications
US20090326074A1 (en) * 2007-10-05 2009-12-31 Acucela Inc. Alkoxy compounds for disease treatment
US20100173187A1 (en) * 2007-06-19 2010-07-08 Teijin Limited Separator for nonaqueous secondary battery, method for producing the same, and nonaqueous secondary battery
US20100190063A1 (en) * 2006-07-06 2010-07-29 Yusuke Fukumoto Method and apparatus for manufacturing member for secondary battery and secondary battery using the same
US20100285348A1 (en) * 2007-01-30 2010-11-11 Hiroshi Murata Multilayer porous membrane and production method thereof
US20110294007A1 (en) * 2009-03-05 2011-12-01 Kenji Hosaka Bipolar secondary battery and method for producing the same
US20120045642A1 (en) * 2009-10-22 2012-02-23 Showa Denko K.K. Graphite material, carbonaceous material for battery electrodes, and batteries

Family Cites Families (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5827797A (en) * 1989-08-28 1998-10-27 Cass; Richard B. Method for producing refractory filaments
US5180647A (en) * 1989-09-18 1993-01-19 Evanite Fiber Corporation Battery separator and method of making same
US5216207A (en) * 1991-02-27 1993-06-01 David Sarnoff Research Center, Inc. Low temperature co-fired multilayer ceramic circuit boards with silver conductors
JP3348965B2 (ja) * 1994-03-31 2002-11-20 三井化学株式会社 高分子量ポリエチレンと高分子量ポリプロピレンの組成物よりなる微孔性二軸延伸フィルム、その製法およびその用途
JP3429558B2 (ja) * 1994-05-17 2003-07-22 三洋化成工業株式会社 分散剤およびその製造法
JPH09245836A (ja) * 1996-03-08 1997-09-19 Fuji Photo Film Co Ltd 非水電解質二次電池
JPH10162826A (ja) 1996-11-28 1998-06-19 Sanyo Electric Co Ltd 非水電解液二次電池
JP3797729B2 (ja) 1996-12-16 2006-07-19 日東電工株式会社 電池用セパレータ
JPH10223195A (ja) * 1997-02-03 1998-08-21 Asahi Chem Ind Co Ltd 新規な電池
JP2001138457A (ja) 1998-12-25 2001-05-22 Tokuyama Corp 積層体
FR2822296A1 (fr) 2001-03-19 2002-09-20 Atofina Elements de batteries lithium-ion fabriques a partir d'une poudre microcomposite a base d'une charge et d'un fluoropolymere
KR100399785B1 (ko) * 2001-04-07 2003-09-29 삼성에스디아이 주식회사 겔형 고분자 전해질을 포함하는 권취형 리튬 2차 전지용세퍼레이터 및 그 제조방법
JP2003020647A (ja) 2001-07-05 2003-01-24 Nippon Steel Corp 回転杭貫入装置
WO2003014251A1 (en) 2001-08-09 2003-02-20 Hitachi Maxell, Ltd. Non-magnetic particles having a plate shape and method for production thereof, abrasive material, polishing article and abrasive fluid comprising such particles
JP4543634B2 (ja) * 2003-08-14 2010-09-15 日本ゼオン株式会社 電極層形成用材料
KR100767560B1 (ko) * 2004-02-18 2007-10-17 마쯔시다덴기산교 가부시키가이샤 2차전지
JP4753870B2 (ja) * 2004-02-20 2011-08-24 パナソニック株式会社 リチウムイオン二次電池の製造法
JP2006066141A (ja) 2004-08-25 2006-03-09 Matsushita Electric Ind Co Ltd 二次電池
JP4819342B2 (ja) * 2004-11-08 2011-11-24 エレクセル株式会社 リチウム電池用正極及びこれを用いたリチウム電池
JP4651486B2 (ja) * 2004-11-19 2011-03-16 三井・デュポンフロロケミカル株式会社 含フッ素重合体水性分散液
JP4743747B2 (ja) 2004-12-08 2011-08-10 日立マクセル株式会社 セパレータおよびその製造方法、並びに非水電解質電池
EP1780820A4 (en) * 2005-03-02 2009-09-09 Panasonic Corp LITHIUMION SECONDARY CELL AND MANUFACTURING METHOD THEREFOR
US8405957B2 (en) * 2005-12-08 2013-03-26 Hitachi Maxell, Ltd. Separator for electrochemical device and method for producing the same, and electrochemical device and method for producing the same
AU2006246467B2 (en) * 2005-12-13 2011-11-10 Rohm And Haas Company Polymer composition
JP5196780B2 (ja) * 2005-12-22 2013-05-15 旭化成イーマテリアルズ株式会社 多層多孔膜およびその製造方法
JP4958484B2 (ja) * 2006-03-17 2012-06-20 三洋電機株式会社 非水電解質電池及びその製造方法
WO2007108426A1 (ja) * 2006-03-17 2007-09-27 Sanyo Electric Co., Ltd. 非水電解質電池及びその製造方法
KR20080105162A (ko) 2006-03-17 2008-12-03 산요덴키가부시키가이샤 비수전해질 전지 및 그 제조 방법
WO2007108424A1 (ja) 2006-03-17 2007-09-27 Sanyo Electric Co., Ltd. 非水電解質電池及びその製造方法
JP5611505B2 (ja) * 2006-03-29 2014-10-22 日立マクセル株式会社 電池用セパレータおよびリチウム二次電池
JP2008016313A (ja) * 2006-07-06 2008-01-24 Matsushita Electric Ind Co Ltd 二次電池用部材の製造方法および製造装置
JP5055865B2 (ja) 2006-07-19 2012-10-24 パナソニック株式会社 リチウムイオン二次電池
KR100977965B1 (ko) * 2006-08-25 2010-08-24 주식회사 엘지화학 리튬의 삽입이 가능한 고가역성 전극활물질, 그 제조방법,이를 포함하는 전극, 및 이차전지
KR100983161B1 (ko) 2008-01-11 2010-09-20 삼성에스디아이 주식회사 전극조립체 및 이를 구비한 이차전지
JP5753657B2 (ja) * 2008-01-29 2015-07-22 日立マクセル株式会社 絶縁層形成用スラリー、電気化学素子用セパレータの製造方法、及び電気化学素子
US8203161B2 (en) * 2009-11-23 2012-06-19 Koninklijke Philips Electronics N.V. Wavelength converted semiconductor light emitting device
KR102183992B1 (ko) * 2014-02-07 2020-11-27 삼성에스디아이 주식회사 양극 활물질, 이를 채용한 양극과 리튬 전지, 및 상기 양극 활물질의 제조방법

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5830603A (en) * 1993-09-03 1998-11-03 Sumitomo Electric Industries, Ltd. Separator film for a storage battery
US6387564B1 (en) * 1997-02-28 2002-05-14 Asahi Kasei Kabushiki Kaisha Non-aqueous secondary battery having an aggregation layer
JPH1180395A (ja) * 1997-09-09 1999-03-26 Nitto Denko Corp 多孔質膜および非水電解液電池用セパレータ
US6447958B1 (en) * 1998-04-27 2002-09-10 Sumitomo Chemical Co., Ltd. Non-aqueous electrolyte battery separator
US20060188786A1 (en) * 1998-12-08 2006-08-24 Sang-Young Lee Separator for secondary battery and porous film made of polyolefin blend and process for preparing the same
US20010005560A1 (en) * 1999-06-22 2001-06-28 Mitsubishi Denki Kabushiki Kaisha Separator for battery, battery and process for preparing the separator
US20020055046A1 (en) * 2000-08-22 2002-05-09 Michio Ono Electrolyte composition and electrochemical battery using the same
US20030235685A1 (en) * 2002-06-14 2003-12-25 Lofton Elizabeth P. Water-based adhesives
JP2005022540A (ja) * 2003-07-03 2005-01-27 Nifco Inc カップホルダ装置
US20060127753A1 (en) * 2003-08-06 2006-06-15 Mitsubishi Chemical Corporation Nonaqueous electrolyte solution secondary battery separator and nonaqueous electrolyte solution secondary battery using the same
US20070264577A1 (en) * 2004-12-08 2007-11-15 Hideaki Katayama Separator for Electrochemical Device, and Electrochemical Device
US20080038631A1 (en) * 2004-12-13 2008-02-14 Kensuke Nakura Lithium Ion Secondary Battery
US20070082261A1 (en) * 2005-10-11 2007-04-12 Samsung Sdi Co., Ltd. Lithium rechargeable battery
US20070122716A1 (en) * 2005-11-28 2007-05-31 Le Chem, Ltd. Organic/inorganic composite porous membrane and electrochemical device using the same
US20080139737A1 (en) * 2005-12-13 2008-06-12 Keith Allen Alderfer Polymer composition
US20100190063A1 (en) * 2006-07-06 2010-07-29 Yusuke Fukumoto Method and apparatus for manufacturing member for secondary battery and secondary battery using the same
US20100285348A1 (en) * 2007-01-30 2010-11-11 Hiroshi Murata Multilayer porous membrane and production method thereof
US20100173187A1 (en) * 2007-06-19 2010-07-08 Teijin Limited Separator for nonaqueous secondary battery, method for producing the same, and nonaqueous secondary battery
US20090181200A1 (en) * 2007-09-19 2009-07-16 Borenstein Jeffrey T Microfluidic Structures for Biomedical Applications
US20090326074A1 (en) * 2007-10-05 2009-12-31 Acucela Inc. Alkoxy compounds for disease treatment
US20110294007A1 (en) * 2009-03-05 2011-12-01 Kenji Hosaka Bipolar secondary battery and method for producing the same
US20120045642A1 (en) * 2009-10-22 2012-02-23 Showa Denko K.K. Graphite material, carbonaceous material for battery electrodes, and batteries

Cited By (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9166251B2 (en) 2007-10-03 2015-10-20 Hitachi Maxell, Ltd. Battery separator and nonaqueous electrolyte battery
US20110052987A1 (en) * 2007-10-03 2011-03-03 Hideaki Katayama Battery separator and nonaqueous electrolyte battery
US9666849B2 (en) 2010-03-17 2017-05-30 Lg Chem, Ltd. Separator having improved porous coating layer having high packing density and electrochemical device comprising the same
EP2549564B1 (en) * 2010-03-17 2016-10-12 LG Chem, Ltd. Separator and electrochemical device having same
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
EP2618406B1 (en) * 2010-09-14 2016-06-22 Hitachi Maxell, Ltd. Nonaqueous secondary cell
US9827696B2 (en) 2011-06-17 2017-11-28 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
US10800073B2 (en) 2011-06-17 2020-10-13 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
US10850491B2 (en) 2011-06-23 2020-12-01 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
US11383504B2 (en) 2011-06-23 2022-07-12 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
US9827755B2 (en) 2011-06-23 2017-11-28 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
US11123965B2 (en) 2011-06-23 2021-09-21 Fiberweb Inc. Vapor-permeable, substantially water-impermeable multilayer article
US10369769B2 (en) 2011-06-23 2019-08-06 Fiberweb, Inc. Vapor-permeable, substantially water-impermeable multilayer article
US10900157B2 (en) 2011-06-24 2021-01-26 Berry Global, Inc. Vapor-permeable, substantially water-impermeable multilayer article
US10253439B2 (en) 2011-06-24 2019-04-09 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
US11866863B2 (en) 2011-06-24 2024-01-09 Berry Global, Inc. Vapor-permeable, substantially water-impermeable multilayer article
US9765459B2 (en) 2011-06-24 2017-09-19 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
US10418608B2 (en) 2011-07-28 2019-09-17 Sumitomo Chemical Company, Limited Laminated porous film and non-aqueous electrolyte secondary battery
US9680141B2 (en) * 2012-01-30 2017-06-13 Litarion GmbH Separator comprising an organic-inorganic adhesion promoter
US20150017512A1 (en) * 2012-01-30 2015-01-15 Evonik Litarion Gmbh Separator comprising an organic-inorganic adhesion promoter
EP2680340A1 (en) * 2012-06-25 2014-01-01 Hou, Dong Membrane
US20140050989A1 (en) * 2012-08-20 2014-02-20 Samsung Sdi Co., Ltd. Separator for rechargeable lithium battery and rechargeable lithium battery including same
US9105906B2 (en) * 2012-08-20 2015-08-11 Samsung Sdi Co., Ltd. Separator for rechargeable lithium battery and rechargeable lithium battery including same
US10811658B2 (en) 2012-09-19 2020-10-20 Asahi Kasei Kabushiki Kaisha Separator and method of preparing the same, and lithium ion secondary battery
CN103000848A (zh) * 2012-11-29 2013-03-27 东莞新能源科技有限公司 复合多孔性隔膜及其制备方法
EP2784843A1 (en) * 2012-11-30 2014-10-01 LG Chem, Ltd. Slurry with improved dispersibility and use therefor
EP2784843A4 (en) * 2012-11-30 2015-08-05 Lg Chemical Ltd BOILING WITH BETTER DISPERSIBILITY AND USE THEREIN
US9991491B2 (en) 2012-11-30 2018-06-05 Lg Chem, Ltd. Slurry including inorganic particles with improve dispersibility by controlling particle size and slurry viscosity
US11031656B2 (en) 2012-11-30 2021-06-08 Lg Chem, Ltd. Composite separator including porous coating layer made from slurry having improved dispersibility
US10062888B2 (en) * 2014-07-29 2018-08-28 Sumitomo Chemical Company, Limited Porous membrane
US9837650B2 (en) 2014-07-29 2017-12-05 Sumitomo Chemical Company, Limited Porous membrane
EP3085432A1 (en) 2015-04-22 2016-10-26 Karlsruher Institut für Technologie Separator for an electrochemical device and method for the production thereof
US11404694B2 (en) * 2015-09-17 2022-08-02 Nec Corporation Resin composition
US10305081B2 (en) * 2015-11-06 2019-05-28 Samsung Sdi Co., Ltd. Separator for rechargeable battery and rechargeable battery including the same
US10211442B2 (en) 2015-11-27 2019-02-19 Sumitomo Chemical Company, Limited Nonaqueous electrolyte secondary battery insulating porous layer and nonaqueous electrolyte secondary battery laminated separator
US10249869B2 (en) * 2016-05-25 2019-04-02 Toyota Jidosha Kabushiki Kaisha Method of producing electrode body and method of producing battery
DE102017110825B4 (de) 2016-05-25 2023-12-07 Toyota Jidosha Kabushiki Kaisha Verfahren zur herstellung eines elektrodenkörpers und verfahren zur herstellung einer batterie
EP3706198A4 (en) * 2018-01-18 2021-01-06 Lg Chem, Ltd. SEPARATOR FOR LITHIUM SECONDARY BATTERY AND LITHIUM SECONDARY BATTERY WITH IT
US11929519B2 (en) 2018-01-18 2024-03-12 Lg Energy Solution, Ltd. Separator including coating layer with ethylenically unsaturated binder, and secondary battery including polymer network formed by gel polymer electrolyte and ethylenically unsaturated binder in coating layer of separator
EP3703158A4 (en) * 2018-01-18 2020-12-23 Lg Chem, Ltd. SEPARATOR FOR SECONDARY BATTERY AND LITHIUM SECONDARY BATTERY WITH IT
EP4270580A3 (en) * 2018-01-18 2024-01-03 LG Energy Solution, Ltd. Separator for secondary battery, and lithium secondary battery comprising same
US11404746B2 (en) 2018-03-07 2022-08-02 Toyota Jidosha Kabushiki Kaisha Battery and method of producing the same
EP4053986A3 (en) * 2018-10-11 2022-11-30 Asahi Kasei Kabushiki Kaisha Lithium ion battery using crosslinkable separator
EP4235940A3 (en) * 2018-10-11 2023-10-25 Asahi Kasei Kabushiki Kaisha Lithium ion battery using crosslinkable separator
EP4235939A3 (en) * 2018-10-11 2023-11-01 Asahi Kasei Kabushiki Kaisha Lithium ion battery using crosslinkable separator
US11837750B2 (en) 2018-10-11 2023-12-05 Asahi Kasei Kabushiki Kaisha Lithium ion battery using crosslinkable separator
US11670822B2 (en) 2018-10-11 2023-06-06 Asahi Kasei Kabushiki Kaisha Separator having silane-modified polyolefin and polyethylene, and method for producing the same
US11588208B2 (en) 2018-10-11 2023-02-21 Asahi Kasei Kabushiki Kaisha Lithium ion battery using crosslinkable separator
EP4235899A3 (en) * 2020-04-13 2024-04-10 Asahi Kasei Kabushiki Kaisha Composite single-layer chemically cross-linked separator
CN113300047A (zh) * 2021-05-24 2021-08-24 万邦特种材料股份有限公司 一种碱性电池专用高性能复合隔膜材料的制备方法
CN115050926A (zh) * 2022-06-22 2022-09-13 多氟多新能源科技有限公司 一种锂离子电池水系正负极片保护涂层制备方法

Also Published As

Publication number Publication date
JP5829261B2 (ja) 2015-12-09
JP5753657B2 (ja) 2015-07-22
CN101796669A (zh) 2010-08-04
WO2009096451A1 (ja) 2009-08-06
US9972816B2 (en) 2018-05-15
JPWO2009096451A1 (ja) 2011-05-26
CN101796669B (zh) 2013-05-08
JP2014056843A (ja) 2014-03-27
US20150236318A1 (en) 2015-08-20
KR101111710B1 (ko) 2012-03-13
KR20100040955A (ko) 2010-04-21

Similar Documents

Publication Publication Date Title
US9972816B2 (en) Slurry for forming insulating layer, separator for electrochemical device, method for producing the same, and electrochemical device
US8771859B2 (en) Separator for battery and nonaqueous electrolyte battery using same
JP5588437B2 (ja) 電気化学素子用セパレータ及びそれを用いた電気化学素子
JP5805160B2 (ja) 電池用セパレータ、電池用セパレータの製造方法およびリチウム二次電池
JP5183435B2 (ja) 電池用セパレータおよびリチウム二次電池
JP5213158B2 (ja) 多層多孔質膜の製造方法、リチウムイオン電池用セパレータおよびリチウムイオン電池
JP5576740B2 (ja) 電気化学素子
EP1826842A1 (en) Separator for electrochemical device and electrochemical device
JP4994054B2 (ja) 電池用セパレータおよびリチウム二次電池
JP5247657B2 (ja) 非水電解液電池
JP5451426B2 (ja) 電池用セパレータおよびそれを用いたリチウムイオン二次電池
WO2015046126A1 (ja) 非水電池用多孔質層、非水電池用セパレータ、非水電池用電極および非水電池
JP2019501500A (ja) セパレータ及びそれを含む電気化学素子
CN111149237B (zh) 多孔隔膜和包含其的电化学装置
JP2011018589A (ja) 絶縁層形成用スラリー、リチウムイオン二次電池用セパレータおよびその製造方法、並びにリチウムイオン二次電池
WO2012005152A1 (ja) 非水電池用セパレータおよび非水電池
KR102413378B1 (ko) 세퍼레이터의 제조 방법, 이로부터 제조된 세퍼레이터 및 이를 포함하는 전기화학소자
KR102652724B1 (ko) 이차전지용 분리막
JP2023551958A (ja) 二次電池用分離膜
KR20150051506A (ko) 전기화학소자용 분리막 및 이를 포함하는 전기화학소자
JPWO2013051079A1 (ja) 耐熱性多孔質膜、非水電池用セパレータおよび非水電池

Legal Events

Date Code Title Description
AS Assignment

Owner name: HITACHI MAXELL, LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KATAYAMA, HIDEAKI;ABE, HIROSHI;MATSUMOTO, NOBUAKI;AND OTHERS;REEL/FRAME:024124/0420

Effective date: 20100218

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION