WO2016140454A1 - Élément de batterie comprenant un séparateur doté d'une résistance d'adhésion renforcée - Google Patents

Élément de batterie comprenant un séparateur doté d'une résistance d'adhésion renforcée Download PDF

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Publication number
WO2016140454A1
WO2016140454A1 PCT/KR2016/001737 KR2016001737W WO2016140454A1 WO 2016140454 A1 WO2016140454 A1 WO 2016140454A1 KR 2016001737 W KR2016001737 W KR 2016001737W WO 2016140454 A1 WO2016140454 A1 WO 2016140454A1
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battery cell
hfp
battery
separator
electrode
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PCT/KR2016/001737
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English (en)
Korean (ko)
Inventor
최은석
안인구
윤수진
윤형구
김동명
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주식회사 엘지화학
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Publication of WO2016140454A1 publication Critical patent/WO2016140454A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L50/00—Electric propulsion with power supplied within the vehicle
    • B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
    • B60L50/60—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by batteries
    • B60L50/64—Constructional details of batteries specially adapted for electric vehicles
    • 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
    • H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/202—Casings or frames around the primary casing of a single cell or a single battery
    • 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
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/247—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders specially adapted for portable devices, e.g. mobile phones, computers, hand tools or pacemakers
    • 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
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/249—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders specially adapted for aircraft or vehicles, e.g. cars or trains
    • 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
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—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
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

Definitions

  • the present invention relates to a battery cell including a separator having enhanced adhesion.
  • a separator containing an excess of inorganic particles and a polymer binder is coated to form a porous coating layer.
  • a separator is also difficult to exert sufficient adhesive strength with the electrode, it was possible to exert sufficient adhesive strength only by forming a thick porous coating layer, in this case, the overall resistance is increased, the volume of the electrode assembly itself increases the volume to capacity There was a problem.
  • some prior art may configure a battery pack by stacking battery cells of different sizes.
  • a battery pack has a structure in which battery cells are stacked, so that the electrochemical reactions are not shared between the stacked battery cells, and as a result, the battery pack becomes thick and the battery capacity can be reduced due to such thickness. Due to the complexity of the electrical connection method in the design change process, it is also difficult to manufacture a battery cell that satisfies a desired condition.
  • the present invention aims to solve the problems of the prior art as described above and the technical problems that have been requested from the past.
  • inorganic particles including a mixture of a metal oxide and a metal hydroxide, and a PVdF-HFP polymer binder ('P HFP ) having a high content of hexafluoropropylene (HFP)
  • HFP hexafluoropropylene
  • Inorganic-inorganic porous coating layer using an organic-inorganic porous coating layer comprising a mixture of high ') and a low HFP content PVdF-HFP polymer binder (' P HFP low ') is formed on at least one side of the porous polymer substrate Even when the porous polymer substrate was coated with a thin thickness, it was confirmed that the adhesiveness with the excellent electrode can be exhibited and the thermal contraction rate of the separator can be improved, thus completing the present invention.
  • a battery cell in which an electrode assembly including a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode is embedded in a battery case,
  • the separator includes a porous polymer substrate and an organic-inorganic porous coating layer formed on at least one surface of the porous polymer substrate,
  • the organic-inorganic porous coating layer inorganic particles including a mixture of metal oxides and metal hydroxides, PVdF-HFP polymer binder ('P HFP high ') high in hexafluoropropylene (HFP) and PVdF low in HFP content
  • PVdF-HFP polymer binder 'P HFP high '
  • HFP hexafluoropropylene
  • PVdF low A mixture of HFP polymeric binder
  • the separation force between the separator and the positive electrode or the negative electrode is characterized in that more than 15gf / 25mm.
  • the organic-inorganic porous coating layer based on the cross section of the porous polymer substrate may be formed in a thickness of 0.5 micrometers to 5 micrometers, in detail, 1 micrometer to 3 micrometers.
  • the organic-inorganic porous coating layer in the above thickness range is an optimum range for imparting heat resistance to the separator without increasing internal resistance to the battery cell, and beyond the above range, it is not possible to add heat resistance to the separator if it is too thin.
  • the adhesive strength can not be obtained even more than the desired value, on the contrary, if too thick, the overall volume increases, the volume-to-volume capacity is reduced, there is a problem that can act as an internal resistance is not preferable.
  • the PVdF-HFP polymer binder having a high hexafluoropropylene (HFP) content and inorganic particles comprising a separator according to the present invention, that is, a mixture of a metal oxide and a metal hydroxide ('P HFP high ') and an organic-inorganic porous coating layer containing a mixture of low HFP content PVdF-HFP polymer binder ('P HFP low ') using a separator formed on at least one side of the porous polymer substrate using an electrode and lamination
  • the adhesive force of the separator and the electrode can be improved to 15gf / 25mm or more, in detail 15gf / 25mm to 30gf / 25mm, the separation phenomenon of the membrane As it was confirmed that the safety of the battery cell can be improved.
  • the particle size is configured in two forms to maximize the packaging per unit area, and thus the thermal shrinkage of the separator may be further improved.
  • 'PVdF-HFP polymer binder' refers to a vinylidene fluoride air containing a structural unit derived from vinylidene fluoride (VdF) and a structural unit derived from hexafluoropropylene (HFP).
  • VdF vinylidene fluoride
  • HFP hexafluoropropylene
  • the molecular weight of the 'PVdF-HFP polymer binder' according to the present invention may be 100,000 g / mol to 1,000,000 g / mol, and specifically 200,000 g / mol to 700,000 g / mol.
  • 'P HFP high ' refers to a PVdF-HFP polymer binder having a relatively high HFP content
  • 'P HFP high ' refers to 8 to 20% by weight based on the weight in the polymer, more In particular, it may comprise 12 to 20% by weight of HFP.
  • 'P HFP low ' means a PVdF-HFP polymer binder having a relatively low HFP content
  • 'P HFP low ' is 3 to 15% by weight, more specifically, based on the weight in the polymer In particular, it may comprise 3 to 8% by weight of HFP.
  • HFP content of 'P HFP high ' and the HFP content of 'P HFP low ' in the mixture according to the present invention are included to satisfy the above range, and the HFP content of 'P HFP high ' is HFP of 'P HFP low ' More than the content.
  • HFP content of the difference between P and P high HFP HFP low preferably includes HFP the high HFP P, based on the weight of the polymeric binder, each lot more than 5% by weight of HFP than P low.
  • the difference in content is less than 5% by weight, it is not preferable because the desired degree of adhesion improvement, that is, the adhesive force of 15 gf / 25 mm or more, which is obtained by mixing two PVdF-HFP polymer binders cannot be exhibited.
  • the P HFP high and P HFP low may be mixed in an amount ratio of 1: 3 to 1:20 based on the weight.
  • the organic-inorganic porous coating layer may include other types of organic polymer binders in accordance with the object of the present invention, for example, polyvinylidene fluoride-trichloro Polyvinylidene fluoride-co-trichloroethylene (polyvinylidene), polymethylmethacrylate (polymethylmethacrylate), polybutylacrylate (polybutylacrylate), polyacrylonitrile, polyvinylpyrrolidone (polyvinylpyrrolidone), polyvinylacetate (polyvinylacetate) ), Ethylene vinyl co-vinyl acetate, polyethylene oxide, polyarylate, cellulose acetate, cellulose acetate butyrate, cellulose acetate pro Cypionate (cellulose acetate propionate), cyano Consisting of cyanoethylpullulan, cyanoethylpolyvinyl
  • the inorganic particles may be a mixture of a metal oxide and a metal hydroxide, wherein the metal hydroxide may be included in an amount of 0.01 to 0.3 moles per mole of the metal oxide.
  • metal hydroxide is less than 0.01 mole per mole of the metal oxide, it is not preferable because there is a problem that the effect of improving the membrane heat shrinkage of the desired degree of the present invention cannot be obtained.
  • the type of the metal oxide and the metal hydroxide are not limited to whether they include the same metal or different metals, but may include the same one or more metals in detail.
  • the metal is not limited as long as it can form a solid oxide and hydroxide, and examples thereof include Al, Ti, Sn, Ni, Mg, Ce, Sn, Sr, Pb, Si, Zn, Zr, Ca, and It may be at least one selected from the group consisting of Ba, in detail, the metal may be Al, the metal oxide is Al 2 O 3 , the metal hydroxide may be AlOOH.
  • the average particle diameter of the metal oxide of the inorganic particles may be in the range of 300 to 500 ⁇ m, and the average particle diameter of the metal hydroxide may be in the range of 150 to 400 nm.
  • the metal oxide and the metal hydroxide are included together in different particle sizes, they can be packaged in the same area and have an effect of improving the heat shrinkage rate.
  • the metal oxide and It is preferred to include all of the hydroxides.
  • the total content of the inorganic particles may be included in 50 to 95% by weight, specifically 60 to 95% by weight based on the total weight of the organic-inorganic porous coating layer.
  • the content of the polymer binder When included in less than 50% by weight out of the above range, the content of the polymer binder is too large to reduce the pore size and porosity due to the reduction of the void space formed between the inorganic particles may cause a decrease in battery performance If it is included in excess of 95% by weight, since the content of the polymer binder is too small, it is not preferable that the mechanical properties of the separator itself may be reduced due to the weakening of the adhesion between the inorganic materials.
  • the structure of the organic-inorganic porous coating layer including the inorganic particles and PVdF-HFP polymer binders is not limited, by the organic polymer binder in the state in which the inorganic particles are filled and in contact with each other It is bound to each other, and thus may have a structure in which interstitial volumes are formed between the inorganic particles.
  • the interstitial volume between the inorganic particles means a space defined by the inorganic particles that are substantially interviewed in the closed packed or densely packed structure.
  • the organic-inorganic porous coating layer may be formed by preparing a slurry for the porous coating layer using a solvent together with inorganic particles and a polymer binder, and applying the slurry to at least one surface of the porous polymer substrate and drying it. Specifically, after adding a poor solvent (for example, ethanol) to a solution in which the polymer binder is dissolved in its good solvent (for example, acetone), the polymer binder is applied onto a porous polymer substrate, and then By drying, the porous coating layer can be formed by the phase separation effect.
  • a poor solvent for example, ethanol
  • its good solvent for example, acetone
  • the organic-inorganic porous coating layer obtained by this method has the advantages of excellent infiltration and low resistance during operation of the battery, the adhesive strength is reduced due to swelling after pouring in the manufacturing process of the battery, but in the present invention
  • the mixed PVdF-HFP polymer binder and the mixed inorganic particles as described above, even if the organic-inorganic porous coating layer is applied in a thin thickness, it has excellent adhesion, and the maximum packaging per unit area has the effect of improving the thermal shrinkage of the separator. have.
  • the slurry for the porous coating layer may further include an additive commonly used in the art.
  • additives may be, for example, dispersants to further improve the dispersion of the inorganic particles.
  • the dispersant serves to keep the inorganic filler in a uniform dispersion state in the binder resin, and any one or more selected from oil-soluble polyamines, oil-soluble amine compounds, fatty acids, fatty alcohols, and sorbitan fatty acid esters may be used. Specifically, it may be a high molecular weight polyamine amide carboxylic acid salt.
  • the content of the dispersant may be 1 to 10 parts by weight based on 100 parts by weight of the inorganic particles.
  • the inorganic filler may be easily settled.
  • the adhesion strength of the organic-inorganic porous coating layer to the porous polymer substrate may be reduced, or impurities may be generated by reacting with the electrolyte when the secondary battery is manufactured.
  • the porous polymer substrate that can be used in the present invention is not limited as long as it is a planar porous polymer substrate commonly used in batteries, such as porous films or nonwoven fabrics formed of various polymers, and is generally used as a separator of a lithium secondary battery.
  • the polyolefin-based porous film, a nonwoven fabric made of polyethylene terephthalate fiber, and the like can be used, and the material and shape thereof can be variously selected as desired.
  • the polyolefin-based porous film is, for example, a high-density polyethylene, linear low-density polyethylene, low-density polyethylene, ultra high molecular weight polyethylene, such as polyethylene, polypropylene, polybutylene, polypentene, or the like, respectively, or a mixture thereof.
  • the polymer may be formed, and the nonwoven fabric may also be made of a fiber using a polyolefin-based polymer or a polymer having higher heat resistance.
  • the thickness of the porous polymer substrate is not particularly limited, but may be 1 to 100 ⁇ m, and specifically 5 to 50 ⁇ m.
  • the pore size and porosity present in the porous polymer substrate is not particularly limited, the porosity is in the range of 10 to 95%, the pore size (diameter) is preferably 0.1 to 50 ⁇ m. When the pore size and porosity are less than 0.1 ⁇ m and 10%, respectively, it acts as a resistive layer, and when the pore size and porosity exceeds 50 ⁇ m and 95%, it is difficult to maintain mechanical properties.
  • the separator thus prepared is interposed between the positive electrode and the negative electrode to exert sufficient adhesive force, thereby preventing the separation of the separator and preventing a short circuit between the positive electrode and the negative electrode.
  • the battery cell including the separator according to the present invention is not particularly limited, and can be applied to all types and types of battery cells.
  • the battery cell including the separator according to the present invention is not particularly limited, and can be applied to all types and types of battery cells.
  • the separator may be more preferably applied to an amorphous battery cell.
  • the battery cell according to the present invention has an asymmetrical structure based on a line ('vertical center line') passing through the center of the battery cell in the protruding direction of the electrode terminal, or the battery cell in a vertical direction of the protruding direction of the electrode terminal.
  • the battery cell may have an asymmetrical structure based on a line passing through the center of the line ('horizontal centerline'), or may have a structure in which an opening is perforated therein. Of course, it may be asymmetrical with respect to both vertical and horizontal centerlines.
  • FIGS. 1 to 7 For convenience of understanding, one example according to the embodiment of the present invention of these structures is shown in FIGS. 1 to 7. However, the present invention is not limited to the examples shown in the following drawings.
  • the battery cell may be a secondary battery, and in detail, the battery cell may be a lithium secondary battery including a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.
  • the positive electrode is prepared by, for example, applying a mixture of the positive electrode active material, the conductive material, and the binder onto a positive electrode current collector, followed by drying. If necessary, a filler may be further added to the mixture.
  • the positive electrode active material is a lithium transition metal oxide, and includes two or more transition metals, and for example, layered compounds such as lithium cobalt oxide (LiCoO 2 ) and lithium nickel oxide (LiNiO 2 ) substituted with one or more transition metals.
  • the positive electrode current collector is generally made to a thickness of 3 to 500 ⁇ m. Such a positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery. For example, stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel Surface-treated with carbon, nickel, titanium, silver, and the like may be used.
  • the current collector may form fine irregularities on its surface to increase the adhesion of the positive electrode active material, and may be in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the conductive material is typically added in an amount of 1 to 50% by weight based on the total weight of the mixture including the positive electrode active material.
  • a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite such as natural graphite and artificial graphite; Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the binder is a component that assists in bonding the active material and the conductive material to the current collector, and is generally added in an amount of 1 to 50 wt% based on the total weight of the mixture including the positive electrode active material.
  • binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene , Polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butylene rubber, fluorine rubber, various copolymers and the like.
  • the filler is optionally used as a component for inhibiting expansion of the positive electrode, and is not particularly limited as long as it is a fibrous material without causing chemical change in the battery.
  • the filler include olefinic polymers such as polyethylene and polypropylene; Fibrous materials, such as glass fiber and carbon fiber, are used.
  • the negative electrode is manufactured by coating, drying, and pressing the negative electrode active material on a negative electrode current collector, and optionally, the conductive material, binder, filler, and the like as described above may be further included.
  • the negative electrode active material examples include carbon and graphite materials such as natural graphite, artificial graphite, expanded graphite, carbon fiber, non-graphitizable carbon, carbon black, carbon nanotube, fullerene, and activated carbon; Metals such as Al, Si, Sn, Ag, Bi, Mg, Zn, In, Ge, Pb, Pd, Pt, Ti which can be alloyed with lithium, and compounds containing these elements; Complexes of metals and compounds thereof with carbon and graphite materials; Lithium-containing nitrides; and the like.
  • carbon-based active materials, silicon-based active materials, tin-based active materials, or silicon-carbon-based active materials are more preferable, and these may be used alone or in combination of two or more.
  • the negative electrode current collector is generally made of a thickness of 3 ⁇ 500 ⁇ m.
  • a negative electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • the surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver, and the like, aluminum-cadmium alloy, and the like can be used.
  • fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the battery case in which the electrode assembly including the positive electrode, the negative electrode, and the separator are embedded includes an outer coating layer made of weather resistant polymer, an inner sealant layer made of a heat sealable polymer, and an interposed between the outer coating layer and the inner sealant layer.
  • It may be a pouch type battery case made of a laminate sheet comprising a barrier layer to be, in detail, may be a pouch type battery case made of an aluminum laminate sheet is a barrier layer Al.
  • the battery cell according to the present invention further includes, in addition to the electrode assembly, a lithium salt-containing nonaqueous electrolyte in the battery case.
  • the battery cell according to the present invention has a structure in which a lithium salt-containing nonaqueous electrolyte is impregnated in the electrode assembly.
  • the lithium salt-containing nonaqueous electrolyte is composed of a nonaqueous electrolyte and lithium.
  • a nonaqueous organic solvent, an organic solid electrolyte, an inorganic solid electrolyte and the like are used as the nonaqueous electrolyte, but are not limited thereto.
  • non-aqueous organic solvent examples include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, and gamma Butyl lactone, 1,2-dimethoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxorone, formamide, dimethylformamide, dioxolon , Acetonitrile, nitromethane, methyl formate, methyl acetate, phosphate triester, trimethoxy methane, dioxorone derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbo Aprotic organic solvents such as nate derivatives, tetrahydrofuran derivatives, ethers, methyl pyroionate and ethyl propionate can be
  • organic solid electrolytes examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, polyedgetion lysine, polyester sulfides, polyvinyl alcohols, polyvinylidene fluorides, Polymerizers containing ionic dissociating groups and the like can be used.
  • Examples of the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Nitrides, halides, sulfates and the like of Li, such as Li 4 SiO 4 -LiI-LiOH, Li 3 PO 4 -Li 2 S-SiS 2 , and the like, may be used.
  • the lithium salt is a good material to be dissolved in the non-aqueous electrolyte, for example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, (CF 3 SO 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium tetraphenyl borate and imide.
  • pyridine triethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitro Benzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrroles, 2-methoxy ethanol, aluminum trichloride and the like may be added. .
  • a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride may be further included, and carbon dioxide gas may be further included to improve high temperature storage characteristics, and FEC (Fluoro-Ethylene) may be further included. Carbonate), PRS (Propene sultone) may be further included.
  • lithium salts such as LiPF 6 , LiClO 4 , LiBF 4 , LiN (SO 2 CF 3 ) 2, and the like, may be prepared by cyclic carbonate of EC or PC as a highly dielectric solvent and DEC, DMC or EMC as a low viscosity solvent.
  • Lithium salt-containing non-aqueous electrolyte can be prepared by adding to a mixed solvent of linear carbonate.
  • the present invention also provides a battery module including the battery cell as a unit battery, a battery pack including the battery module, and a device including the battery pack.
  • the device include a mobile phone, a portable computer, a smartphone, a tablet PC, a smart pad, a netbook, a wearable electronic device, a light electronic vehicle (LEV), an electric vehicle (EV), and a hybrid electric vehicle (Hybrid Electric).
  • Electric vehicles and electric power storage devices including vehicles, HEVs, Plug-in Hybrid Electric Vehicles (PHEVs), and the like, but are not limited thereto.
  • FIG. 1 is a view of a line passing through the center of a battery cell in a protruding direction of an electrode terminal (a vertical center line) and a line passing through the center of a battery cell in a vertical direction of the electrode terminal protruding direction (a horizontal center line).
  • a vertical center line a line passing through the center of a battery cell in a protruding direction of an electrode terminal
  • a horizontal center line a line passing through the center of a battery cell in a vertical direction of the electrode terminal protruding direction
  • FIG. 2 is an example of an amorphous battery cell having an asymmetrical structure with respect to a line passing through the center of the battery cell ('horizontal center line') in the vertical direction of the electrode terminal protruding direction and cutting the separators of the lower edge parts accordingly.
  • 3 is an example of an amorphous battery cell having an asymmetric structure with respect to a line ('vertical center line') passing through the center of the battery cell in the protruding direction of the electrode terminal;
  • FIG. 4 is another example of an amorphous battery cell having an asymmetrical structure with respect to a line ('horizontal center line') passing through the center of the battery cell in a direction perpendicular to the protruding direction of the electrode terminal;
  • FIG. 5 is another example of an amorphous battery cell having an asymmetrical structure with respect to a line ('horizontal center line') passing through the center of the battery cell in a direction perpendicular to the protruding direction of the electrode terminal;
  • FIG. 6 is a line passing through the center of the battery cell in the protruding direction of the electrode terminal ('vertical center line') and a line passing through the center of the battery cell in the vertical direction of the electrode terminal protruding direction ('horizontal center line').
  • Another example is an amorphous battery cell having an asymmetric structure.
  • FIG. 7 is a line passing through the center of the battery cell in the protruding direction of the electrode terminal ('vertical center line') and a line passing through the center of the battery cell in the vertical direction of the electrode terminal protruding direction ('horizontal center line').
  • Another example is an amorphous battery cell having an asymmetric structure.
  • HFP18 a PVdF-HFP polymer binder
  • HFP5" a PVdF-HFP polymer binder
  • a ball mill ball mill
  • the slurry for the organic-inorganic porous coating layer was coated by 2.5 ⁇ m by dip coating on both surfaces of the porous film, and then dried in an oven at 70 ° C. to prepare a separator.
  • LiCoO 2 as a positive electrode active material
  • acetylene black as a conductive agent
  • PVDF as a binder
  • EMC Ethyl methyl carbonate
  • BPO benzoyl peroxide
  • An electrode assembly was prepared by laminating the separator prepared in Preparation Example 1 between a plurality of positive electrodes and a negative electrode to form an anode / separator / cathode / separator / anode / separator / cathode structure, followed by lamination, to prepare an electrolyte assembly in the electrode assembly.
  • the composition was poured and vacuum packed and left at room temperature for 15 hours. Thereafter, polymerization was performed at 80 ° C. for 4 hours to prepare a battery cell.
  • a separator was prepared in the same manner as in Preparation Example 1, except that HFP18 and HFP5 were prepared in a weight ratio of 0.5: 7.0, and a battery cell was prepared in the same manner as in Example 1 except for using the same.
  • a separator was prepared in the same manner as in Preparation Example 1, except that HFP18 and HFP5 were prepared to have a weight ratio of 2.0: 6.0, and a battery cell was prepared in the same manner as in Example 1 except for using the same.
  • a separator was prepared in the same manner as in Preparation Example 1, except that HFP18 and HFP5 were prepared in a weight ratio of 0: 8.5, and a battery cell was prepared in the same manner as in Example 1 except for using the same.
  • a separator was prepared in the same manner as in Preparation Example 1, except that HFP18 and HFP5 were prepared in a weight ratio of 8.5: 0, and a battery cell was prepared in the same manner as in Example 1 except for using the same.
  • a battery cell was manufactured in the same manner as in Example 1, except that a polyolefin porous film having a thickness of 14 ⁇ m was used as a separator.
  • the thickness and the adhesive force of the separator obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were measured and shown in Table 1 below. At this time, the adhesive force was measured by using a tensile strength meter to prepare a unit cell of the anode / separator / cathode.
  • Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Polymer Binder Composition (HFP18: HFP5) 1: 7.5 0.5: 7.0 2.0: 6.0 0: 8.5 8.5: 0 - Mineral particles Al 2 O 3 + ALOOH Al 2 O 3 + ALOOH Al 2 O 3 + ALOOH Al 2 O 3 + ALOOH Al 2 O 3 + ALOOH - Thickness ( ⁇ m) 14.0 14.0 14.0 14.0 14.0 14.0 14.0 Adhesive force (gf / 25mm) 20 15 27 13 5 0
  • the shape of the electrode in the battery cells of Example 1 and Comparative Examples 1, 2 and 3 was performed as shown in FIG. 2 to cut the separators of the lower edge parts accordingly.
  • the resulting defective rate was confirmed, and the results are shown in Table 2 below.
  • the defective rate was confirmed in 10 battery cells and measured by whether there is a possibility of a short circuit because a separator is not interposed between the positive electrode and the negative electrode due to the sliding phenomenon of the separator.
  • the battery cell of Example 1 had a defective rate of 0%, but a defective rate of about 10% to 30% occurred in the battery cells of Comparative Examples 1 and 2, and about 80% of the battery cells of Comparative Example 3 A defective rate occurred. This is because the adhesive strength of the separators of Comparative Examples 1, 2 and 3 was weak and the adhesion with the electrodes was not good.
  • the battery cell according to the present invention includes inorganic particles including a mixture of a metal oxide and a metal hydroxide, a PVdF-HFP polymer binder ('P HFP high ') having a high hexafluoropropylene (HFP) content and a low HFP content.
  • inorganic particles including a mixture of a metal oxide and a metal hydroxide, a PVdF-HFP polymer binder ('P HFP high ') having a high hexafluoropropylene (HFP) content and a low HFP content.
  • the organic-inorganic porous coating layer comprising a mixture of PVdF-HFP polymer binder ('P HFP low ') includes a separator formed on at least one side of the porous polymer substrate, whereby the organic-inorganic porous coating layer of the separator is more than the porous polymer substrate Even when coated with a thin thickness, excellent adhesion to the electrode can be obtained, which can effectively prevent short-circuit between electrodes due to charging and discharging, and can also prevent thermal shrinkage of the separator, and the separator has a thinner thickness. It can be manufactured, thereby ensuring high capacity and high density of battery characteristics and battery safety.
  • the separator when the separator has sufficient adhesive force with the electrode, the separator may be cut during the manufacturing of an amorphous battery cell in which the shape of the electrode assembly itself is changed according to the shape of the device. By preventing the phenomenon, it is possible to cut more accurately, and also to prevent the short circuit between the electrodes caused by the sliding phenomenon, there is an effect that the safety of the battery cell is further improved.

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Abstract

La présente invention concerne un élément de batterie présentant un ensemble électrode incorporé dans un boîtier de batterie, l'ensemble électrode comprenant une cathode, une anode, et un séparateur intercalé entre la cathode et l'anode, lequel séparateur comprend un substrat polymère poreux et une couche de revêtement poreuse organique/inorganique formée sur au moins une surface du substrat polymère poreux, laquelle couche de revêtement poreuse organique/inorganique comprend des particules inorganiques comprenant un mélange d'un oxyde métallique et d'un hydroxyde métallique, et un mélange d'un liant polymère PVdF-HFP (« PHFP high ») ayant une teneur élevée en hexafluoropropylène (HFP) et d'un liant polymère PVdF-HFP (« PHFP low ») ayant une faible teneur en HFP, et la résistance d'adhésion du séparateur et de la cathode ou de l'anode étant supérieure ou égale à 15 gf/25 mm.
PCT/KR2016/001737 2015-03-05 2016-02-23 Élément de batterie comprenant un séparateur doté d'une résistance d'adhésion renforcée WO2016140454A1 (fr)

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