WO2024049152A1 - 전기화학소자용 분리막 및 이를 구비하는 전기화학소자 - Google Patents
전기화학소자용 분리막 및 이를 구비하는 전기화학소자 Download PDFInfo
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- WO2024049152A1 WO2024049152A1 PCT/KR2023/012756 KR2023012756W WO2024049152A1 WO 2024049152 A1 WO2024049152 A1 WO 2024049152A1 KR 2023012756 W KR2023012756 W KR 2023012756W WO 2024049152 A1 WO2024049152 A1 WO 2024049152A1
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- WIPO (PCT)
- Prior art keywords
- separator
- inorganic particles
- electrochemical device
- sulfonic acid
- coating layer
- Prior art date
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- 239000010954 inorganic particle Substances 0.000 claims abstract description 146
- 239000011247 coating layer Substances 0.000 claims abstract description 60
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 29
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011149 active material Substances 0.000 claims abstract description 16
- -1 hydrogen cations Chemical class 0.000 claims description 30
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- 229920005596 polymer binder Polymers 0.000 claims description 22
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- 229910001437 manganese ion Inorganic materials 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 17
- 239000011572 manganese Substances 0.000 claims description 16
- 238000001179 sorption measurement Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
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- 239000007774 positive electrode material Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910014689 LiMnO Inorganic materials 0.000 claims description 7
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 claims description 6
- 229910015645 LiMn Inorganic materials 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
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- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
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- 229920002258 tannic acid Polymers 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—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
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a separator for an electrochemical device and an electrochemical device comprising the same, and to a separator for minimizing capacity loss in an electrochemical device using a lithium-manganese-based positive electrode active material.
- Electrochemical devices convert chemical energy into electrical energy using an electrochemical reaction.
- lithium secondary batteries which have high energy density and voltage, long cycle life, and can be used in various fields, have been widely used.
- a lithium secondary battery may include an electrode assembly made of a positive electrode, a negative electrode, and a separator disposed between the positive electrode and the negative electrode, and the electrode assembly may be manufactured by being stored in a case together with an electrolyte solution.
- the positive electrode can provide lithium ions, and the lithium ions can pass through a separator made of a porous material and move to the negative electrode.
- the negative electrode can be made of a carbon-based active material that has an electrochemical reaction potential close to that of lithium metal and allows insertion and desorption of lithium ions.
- the positive electrode active material may contain lithium and various metal or transition metal elements.
- nickel can improve the capacity of electrochemical devices
- cobalt can improve the capacity and cycle stability of electrochemical devices
- manganese can improve the stability of electrochemical devices
- aluminum can improve electrochemical devices.
- the output characteristics of the device can be improved.
- nickel has low thermal stability, and nickel and cobalt are expensive, so interest in lithium manganese-based positive electrode active materials containing manganese is increasing recently.
- manganese ions may be eluted from the positive electrode during the charging and discharging process.
- the eluted manganese ions may move to the cathode, precipitate as impurities including manganese on the surface of the cathode, and form a non-uniform film, causing capacity degradation of the electrochemical device.
- separator for use in an electrochemical device containing a lithium manganese-based active material, it prevents deterioration of the cathode and the electrochemical device containing it by capturing manganese ions eluted from the anode and preventing them from moving to the cathode. Research is being conducted on separation membranes that can do this.
- the purpose of the present invention is to provide a separator for use in an electrochemical device containing a lithium manganese-based active material, capable of adsorbing manganese ions eluted from an anode.
- One aspect of the present invention includes a porous polymer substrate, first inorganic particles, and second inorganic particles having a larger specific surface area than the first inorganic particles, and a first porous coating layer formed on the first side of the porous polymer substrate, and a second porous coating layer formed on the second surface of the porous polymer substrate, wherein the second inorganic particles have sulfonic acid groups introduced to the surface, and at least some of the sulfonic acid groups have hydrogen cations replaced with lithium cations.
- a separator for an electrochemical device containing a lithium manganese-based active material.
- the first porous coating layer may include the first inorganic particles and the second inorganic particles in a weight ratio of 2:8 to 3:7.
- the second inorganic particle may be a mesoporous inorganic particle containing pores with an average diameter of 1.5 to 50 nm.
- the first inorganic particles may be different from the second inorganic particles and may not contain pores.
- the sulfonic acid group is selected from the group consisting of methane sulfonic acid, ethane sulfonic acid, trifluoromethane sulfonic acid, benzene sulfonic acid, p-toluene sulfonic acid, naphthalene sulfonic acid, phenylbenzimidazole sulfonic acid, and 2-acrylamido-2-methylpropane sulfonic acid. There may be more than one.
- the first inorganic particles are BaTiO 3 , BaSO 4 , Pb(Zr,Ti)O 3 (PZT), Pb 1-x La x Zr 1-y Ti y O 3 (PLZT, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), Pb(Mg 1/3 Nb 2/3 )O 3 -PbTiO 3 (PMN-PT), hafnia (HfO 2 ), SrTiO 3 , SnO 2 , CeO 2 , MgO, Mg(OH) 2 , NiO, CaO, ZnO, ZrO 2 , Y 2 O 3 , SiO 2 , Al 2 O 3 , AlOOH, Al(OH) 3 , SiC, and TiO 2 .
- the first porous coating layer further includes a water-based polymer binder, wherein the water-based polymer binder binds the first inorganic particles to each other, the second inorganic particles to each other, and the first inorganic particles and the second inorganic particles, It may form an interstitial volume formed by gaps between inorganic particles.
- the water-based polymer binder is an acrylic polymer, polyacrylonitrile, polyvinylpyrrolidone, polyvinyl acetate, ethylene vinyl acetate copolymer, polyethylene oxide, polyarylate, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, At least one selected from the group consisting of cyanoethyl pullulan, cyanoethyl polyvinyl alcohol, cyanoethyl cellulose, cyanoethyl sucrose, pullulan, carboxymethyl cellulose, acrylonitrile-styrene-butadiene copolymer, and polyimide. You can.
- the first porous coating layer may face the cathode of the electrochemical device.
- the second porous coating layer may include the first inorganic particles and may not include the second inorganic particles.
- the average specific surface area of the first inorganic particles and the second inorganic particles included in the first porous coating layer may be 500 to 700 m 2 /g.
- the first porous coating layer may have a thickness of 1 to 6 ⁇ m.
- the separator for electrochemical devices may have an adsorption rate of manganese ions eluted from the positive electrode containing the lithium manganese-based active material of 20 to 50%.
- Another aspect of the present invention provides an electrochemical device including an anode, a cathode, and a separator disposed between the anode and the cathode, and the separator may be a separator for an electrochemical device according to an aspect of the present invention.
- the electrochemical device may be a lithium secondary battery.
- the separator for electrochemical devices introduces sulfonic acid groups on the surface of inorganic particles included in the porous coating layer, and replaces hydrogen cations contained in at least a portion of the sulfonic acid groups with lithium cations, thereby providing improved manganese ion adsorption capacity compared to the prior art. to provide.
- the separator for an electrochemical device controls the content ratio of inorganic particles into which a sulfonic acid group is introduced and inorganic particles without an introduced sulfonic acid group and the arrangement position of the porous coating layer containing the inorganic particles into which a sulfonic acid group is introduced, compared to the prior art.
- electrochemical device may mean a primary battery, secondary battery, super capacitor, etc.
- particle size means D50, which is the particle size corresponding to 50% of the cumulative distribution of particle numbers according to particle size, unless otherwise specified.
- One embodiment of the present invention includes a porous polymer substrate, first inorganic particles, and second inorganic particles having a larger specific surface area than the first inorganic particles, and a first porous coating layer formed on the first side of the porous polymer substrate. , and a second porous coating layer formed on the second side of the porous polymer substrate.
- the second inorganic particle has a sulfonic acid group introduced on its surface, and at least some of the sulfonic acid groups have hydrogen cations replaced with lithium cations, and the electrochemical device includes a lithium manganese-based active material.
- the porous polymer substrate electrically insulates the positive and negative electrodes to prevent short circuits, while providing pores through which lithium ions can pass.
- the porous polymer substrate may be resistant to the electrolyte solution of the electrochemical device, which is an organic solvent.
- the porous polymer substrate includes polyolefins such as polyethylene, polypropylene, and polybutene, polyvinyl chloride, polyethylene terephthalate, polycycloolefin, polyethersulfone, polyamide, polyimide, polyimideamide, polyaramide, It may include polymer resins such as polycycloolefin, nylon, polytetrafluoroethylene, and copolymers or mixtures thereof, but is not limited thereto.
- the porous polymer substrate includes a polyolefin-based polymer, has excellent slurry applicability for forming a porous coating layer, and may be advantageous for manufacturing a thin-thickness separator.
- the thickness of the porous polymer substrate may be 1 to 100 ⁇ m, preferably 1 to 30 ⁇ m, and more preferably 15 to 30 ⁇ m.
- the porous polymer substrate may include pores with an average diameter of 0.01 to 10 ⁇ m.
- a slurry may be applied and dried on at least one surface of the porous polymer substrate to form a porous coating layer, which will be described later.
- the slurry may include inorganic particles, polymer binder, dispersion medium, etc.
- surface treatment such as plasma treatment or corona discharge may be performed on the porous polymer substrate to improve impregnation with the electrolyte solution.
- the separator for an electrochemical device may include the porous polymer substrate and a porous coating layer.
- the porous coating layer may be provided in plural pieces and may include a first porous coating layer formed on the first side of the porous polymer substrate and a second porous coating layer formed on the second side of the porous polymer substrate.
- a first slurry is applied and dried on the first side of the porous polymer substrate to form a first porous coating layer
- a second slurry is applied and dried on the second side located opposite to the first side to form a second porous coating layer. can be formed.
- the porous coating layer may include inorganic particles to improve the mechanical properties and insulation properties of the porous polymer substrate and a polymer binder to improve adhesion between the electrode and the separator.
- the polymer binder provides adhesion between the electrode and the separator, and can also bond adjacent inorganic particles and maintain the bond.
- Inorganic particles can combine with adjacent inorganic particles to provide an interstitial volume, which is a void between the inorganic particles, and lithium ions can move through the interstitial volume.
- the first porous coating layer may include first inorganic particles and second inorganic particles having a larger specific surface area than the first inorganic particles.
- the second porous coating layer may include the same or different types of inorganic particles as the first inorganic particles, but may not include the second inorganic particles.
- the first inorganic particles may form a uniform thickness of the porous coating layer and do not cause a redox reaction within the operating voltage range of the applied electrochemical device.
- the first inorganic particle may have one or more characteristics of lithium ion transport ability, piezoelectricity, and flame retardancy.
- Inorganic particles capable of transporting lithium ions mean that they contain lithium element but have the function of moving lithium ions rather than storing lithium. Inorganic particles capable of transmitting lithium ions can transmit and move lithium ions due to a type of defect that exists inside the particle structure. Therefore, lithium ion conductivity in the electrochemical device is improved, thereby improving the performance of the electrochemical device.
- inorganic particles capable of transporting lithium ions include Li 3 PO 4 , Li x Ti y (PO 4 ) 3 (0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 3), Li x Al y Ti z (PO 4 ) 3 (0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 3), Li x La y TiO 3 (0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 3), Li x Ge y P z S w (0 ⁇ x ⁇ 4, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ w ⁇ 5), lithium nitride such as Li 3 N (Li x N y , 0 ⁇ x ⁇ 4, 0 ⁇ y ⁇ 2), SiS 2 series glass such as Li 3 PO 4 -Li 2 S-SiS 2 (Li x Si y S z , 0 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 2, 0 ⁇ z ⁇ 4), LiI-Li P 2 S 5 series glass such as 2 SP 2 S 5 (Li x P y S z ,
- Inorganic particles with piezoelectricity refer to materials that are insulators at normal pressure but have the property of conducting electricity due to changes in their internal structure when a certain pressure is applied.
- the inorganic particles can exhibit high dielectric constant characteristics with a dielectric constant of 100 or more, and when a certain pressure is applied and stretched or compressed, an electric charge is generated, so that one side is positively charged and the other side is negatively charged, thereby generating a potential difference between both sides.
- the inorganic particles coated on the separator not only prevent the anode and the cathode from coming into direct contact, but also prevent the anode and the cathode from coming into direct contact due to the piezoelectricity of the inorganic particles.
- a potential difference occurs within the particle, which causes electron movement between the anode and the cathode, that is, a fine current flow, which can gradually reduce the voltage of the electrochemical device and thereby improve safety.
- piezoelectric inorganic particles include BaTiO 3 , BaSO 4 , Pb(Zr,Ti)O 3 (PZT), Pb 1-x La x Zr 1-y Ti y O 3 (PLZT) (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), Pb(Mg 1/3 Nb 2/3 )O 3 -PbTiO 3 (PMN-PT), HfO 2 (Hafnia), and mixtures thereof. , but is not limited to this.
- Inorganic particles with flame retardancy can add flame retardant properties to the separator or prevent the temperature inside the electrochemical device from rapidly rising.
- flame-retardant inorganic particles include Sb 2 O 3 , Sb 2 O 4 , Sb2O 5 , SrTiO 3 , SnO 2 , CeO 2 , MgO, Mg(OH) 2 , NiO, CaO, ZnO, Zn 2 SnO 4 , ZnSnO 3 , ZnSn(OH) 6 , ZrO 2 , Y 2 O 3 , SiO 2 , Al 2 O 3 , AlOOH, Al(OH) 3 , SiC, TiO 2 , H 3 BO 3 , HBO 2 and mixtures thereof. It may be one or more selected from the group consisting of, but is not limited thereto.
- the average particle diameter of the first inorganic particles may be 50 to 5000 nm, preferably 200 to 1000 nm, and more preferably 300 to 700 nm. If the average particle diameter of the first inorganic particles is less than 50 nm, an additional polymer binder is required for bonding between the inorganic particles, which is disadvantageous in terms of electrical resistance. If the average particle diameter of the first inorganic particles exceeds 5000 nm, the uniformity of the surface of the coating layer decreases, and the separator and electrode may be damaged during lamination by the protruding particles after coating, resulting in a short circuit.
- the specific surface area of the first inorganic particle may be 1 to 50 m 2 /g. Preferably, the first inorganic particles do not contain pores.
- the second inorganic particles may include pores and have a larger specific surface area than the first inorganic particles, and may provide the first porous coating layer with the ability to substantially adsorb manganese ions.
- the second inorganic particle may be a mesoporous inorganic particle containing pores with an average diameter of 1.5 to 50 nm. Microporous inorganic particles with an average pore diameter of less than 1.5 nm have too small pores, and macroporous inorganic particles with an average pore diameter of more than 50 nm have a small specific surface area, which reduces the adsorption performance of manganese ions through the introduction of sulfonic acid groups. It is difficult to secure.
- the type of the second inorganic particle is not limited as long as a sulfonic acid group (HSO 3 ) can be introduced to the surface, but preferably it may be different from the first inorganic particle, and more preferably, before the introduction of a sulfonic acid group. Hydroxyl groups may exist on the surface of the inorganic particles.
- the surface may encompass a surface in which pores are not formed in the second inorganic particle and an inner surface of the pores.
- the second inorganic particle may be one or more selected from the group consisting of mesoporous silica nanoparticles, mesoporous titania nanoparticles, mesoporous zirconia nanoparticles, and mesoporous alumina nanoparticles.
- the second inorganic particle may be a mesoporous silica nanoparticle.
- the sulfonic acid group is one selected from the group consisting of methane sulfonic acid, ethane sulfonic acid, trifluoromethane sulfonic acid, benzene sulfonic acid, p-toluene sulfonic acid, naphthalene sulfonic acid, phenylbenzimidazole sulfonic acid, and 2-acrylamido-2-methylpropane sulfonic acid. It could be more than that.
- At least some of the sulfonic acid groups may have hydrogen cations replaced with lithium cations.
- Substitution of the lithium cation may be accomplished by adding lithium hydroxide to the dispersion of the second inorganic particles into which the sulfonic acid group is introduced and stirring.
- hydrogen cations contained in 50 to 100% of the sulfonic acid groups present in the second inorganic particle may be replaced with lithium cations, but the present invention is not limited to this.
- the lithium cation can be easily separated from the second inorganic particle compared to the hydrogen cation, thereby improving the manganese ion adsorption capacity of the second inorganic particle.
- lithium ions released from the second inorganic particles improve lithium ion conductivity within the electrochemical device, thereby improving the performance of the electrochemical device.
- the second inorganic particle is one in which a sulfonic acid group is introduced to the surface of the inorganic particle, and at least some hydrogen cations of the sulfonic acid group are replaced with lithium cations, and the average particle diameter may be 50 to 5000 nm, preferably It may be 200 to 1000 nm, more preferably 300 to 700 nm. If the average particle diameter of the second inorganic particles is less than 50 nm, an additional polymer binder is required for bonding between the inorganic particles, which is disadvantageous in terms of electrical resistance.
- the specific surface area of the second inorganic particle may be 500 to 1000 m 2 /g.
- the first porous coating layer includes both the first inorganic particles and the second inorganic particles, and can improve the mechanical properties of the porous polymer substrate and provide manganese ion adsorption capacity.
- the first porous coating layer may include the first inorganic particles and the second inorganic particles in a weight ratio of 2:8 to 3:7.
- the specific surface area of the first porous coating layer decreases rapidly, and the adsorption capacity for manganese ions decreases at a rate greater than the decrease in the specific surface area.
- thermal shrinkage of the separator may occur due to a decrease in thermal stability.
- the average specific surface area of the first inorganic particles and the second inorganic particles may be 500 to 700 m 2 /g.
- the porous coating layer may include a water-based polymer binder as a polymer binder.
- the weight average molecular weight of the water-based polymer binder may be 10,000 to 10,000,000.
- water-based polymer binders include acrylic polymers, polyacrylonitrile, polyvinylpyrrolidone, polyvinyl acetate, ethylene vinyl acetate copolymer, polyethylene oxide, polyarylate, cellulose acetate, cellulose acetate butyrate, cellulose acetate propio.
- nate cyanoethyl pullulan, cyanoethyl polyvinyl alcohol, cyanoethyl cellulose, cyanoethyl sucrose, pullulan, carboxymethyl cellulose, acrylonitrile-styrene-butadiene copolymer and polyimide. There may be more than one.
- the first porous coating layer may include an acrylate-based polymer as a water-based polymer binder, and the water-based polymer binder may be used between the first inorganic particles, between the second inorganic particles, and between the first inorganic particles and the By combining the second inorganic particles, an interstitial volume formed by gaps between the inorganic particles can be formed.
- the thickness of the first porous coating layer may be 1 to 6 ⁇ m. If the thickness of the first porous coating layer is less than 1 ⁇ m, a problem occurs in which impurities including manganese are precipitated at the cathode. Even if the thickness of the first coating layer exceeds 6 ⁇ m, the manganese ion adsorption efficiency does not significantly increase. Preferably, the thickness of the first porous coating layer may be 3 to 5 ⁇ m.
- the first side of the porous polymer substrate may be disposed to face a negative electrode, and the second side may be disposed to face a positive electrode containing a lithium manganese-based active material.
- the first porous coating layer is disposed to face the cathode of the electrochemical device to delay or reduce precipitation of impurities on the cathode surface.
- the porous coating layer may further include a dispersant to further improve the dispersibility of the inorganic particles.
- the dispersant functions to maintain a uniform dispersion of inorganic particles within the polymer binder during slurry production.
- the dispersing agent may be one or more selected from oil-soluble polyamines, oil-soluble amine compounds, fatty acids, fatty alcohols, sorbitan fatty acid esters, tannic acid, and pyrogallic acid.
- the porous coating layer may contain 5% by weight or less of the dispersant.
- the slurry may contain inorganic particles and a polymer binder at a weight ratio of 90:10 to 10:90, preferably 80:20 to 20:80. If it is outside the above range, the movement of the polymer binder in the porous coating layer is hindered, making it impossible to secure sufficient adhesion between the electrode and the separator.
- an electrochemical device including an anode, a cathode, and a separator disposed between the anode and the cathode, wherein the separator is a separator for an electrochemical device according to the above-described embodiment.
- the electrochemical device may be a lithium secondary battery including a positive electrode containing a lithium manganese-based positive electrode active material.
- the positive electrode and the negative electrode may be formed by applying and drying an active material on at least one surface of each current collector.
- the current collector may be a material that has conductivity without causing chemical changes in the electrochemical device.
- current collectors for positive electrodes include aluminum, nickel, titanium, fired carbon, and stainless steel; It may be a surface of aluminum or stainless steel treated with carbon, nickel, titanium, silver, etc., but is not limited to this.
- current collectors for negative electrodes include copper, nickel, titanium, fired carbon, and stainless steel; It may be a surface of copper or stainless steel treated with carbon, nickel, titanium, silver, etc., but is not limited to this.
- the current collector may be in various forms, such as a thin metal plate, film, foil, net, porous material, or foam.
- the lithium manganese-based positive electrode active material may not contain nickel and cobalt, or may contain only one of nickel and cobalt.
- the lithium manganese-based positive electrode active material may be an LMO-based active material containing only lithium and manganese.
- the negative electrode active material includes carbon such as non-graphitized carbon and graphitic carbon; Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1 ) , Sn : Al, B, P, Si, elements of groups 1, 2, and 3 of the periodic table, halogen; metal complex oxides such as 0 ⁇ x ⁇ 1;1 ⁇ y ⁇ 3;1 ⁇ z ⁇ 8); lithium metal; lithium alloy; silicon-based alloy; tin-based alloy; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , and metal oxides such as Bi 2 O 5 ; Conductive polymers such as polyacetylene; It may include, but is not limited to, Li-Co-Ni based materials.
- the electrochemical device may include a separator disposed so that the first porous coating layer faces the positive electrode, and the adsorption rate of manganese ions eluted from the positive electrode containing the lithium manganese-based active material may be 20 to 50%. Within the above range, precipitation of impurities containing manganese in the cathode may be delayed or reduced.
- the electrochemical device can be manufactured by inserting the anode, cathode, separator, and electrolyte into a case or pouch and sealing it.
- the shape of the case or pouch is not limited.
- the electrochemical device may be a cylindrical, prismatic, coin-shaped, or pouch-shaped lithium secondary battery.
- the lithium secondary battery is packaged or modularized as a unit cell to be used in small devices such as computers, mobile phones, and power tools, and power tools that are powered by an electric motor; Electric vehicles, including Electric Vehicle (EV), Hybrid Electric Vehicle (HEV), Plug-in Hybrid Electric Vehicle (PHEV), etc.; Electric two-wheeled vehicles, including electric bicycles (E-bikes) and electric scooters (E-scooters); electric golf cart; It can be used in medium to large-sized devices such as power storage systems.
- Electric vehicles including Electric Vehicle (EV), Hybrid Electric Vehicle (HEV), Plug-in Hybrid Electric Vehicle (PHEV), etc.
- Electric two-wheeled vehicles including electric bicycles (E-bikes) and electric scooters (E-scooters)
- electric golf cart It can be used in medium to large-sized devices such as power storage systems.
- Cetyltrimethylammonium chloride was added as a surfactant to a solution of water and ethanol mixed at a weight ratio of 1:1 at room temperature (25°C), and tetraethyl orthosilicate (TEOS) was added. Stirred for 10 minutes. Aqueous ammonia was added to the stirred solution and left for one day. The precipitate was filtered, washed, dried, and calcined to synthesize mesoporous silica nanoparticles with an average pore size of 10 nm and an average particle diameter of 300 nm.
- TEOS tetraethyl orthosilicate
- Mesoporous silica nanoparticles with sulfonic acid groups introduced were added to a solution of 25 g of LiOH ⁇ H 2 O dissolved in 500 mL of distilled water, and stirred for 12 hours.
- Second inorganic particles were prepared by replacing hydrogen contained in some of the sulfonic acid groups with lithium.
- aqueous dispersion medium 100 mL of distilled water was prepared as an aqueous dispersion medium at room temperature.
- acrylic polymer binder Toyo ink, CSB130, solid content 40%, particle size 177 nm
- carboxylmethylcellulose (GLChem, SG-L02):wetting agent was dispersed in a weight ratio of 8:5:1.
- a first slurry in which a polymer binder and inorganic particles were dispersed was prepared.
- aqueous dispersion medium 100 mL of distilled water was prepared as an aqueous dispersion medium at room temperature.
- acrylic polymer binder Toyo ink, CSB130, solid content 40%, particle size 177 nm
- carboxylmethylcellulose (GLChem, SG-L02):wetting agent was dispersed in a weight ratio of 8:5:1.
- a slurry for forming an organic/inorganic composite porous coating layer was prepared.
- 30 g of alumina with an average particle diameter of 500 nm as inorganic particles was added to the slurry and stirred for 120 minutes to prepare a second slurry in which the polymer binder and inorganic particles were dispersed.
- porous polymer substrate As a porous polymer substrate, a polyethylene porous film (thickness 9 ⁇ m, porosity 45%) was used. In particular, polypropylene film (PP) was used as a porous polymer substrate.
- PP polypropylene film
- the slurry was applied to one side of a polyethylene porous film using a bar coater on both sides of the polypropylene film, and then the first slurry and the second slurry were coated and dried, respectively, to prepare a separator.
- a porous coating layer with each coating having a thickness of 3 ⁇ m was formed to prepare a separator with a total thickness of about 15 ⁇ m.
- a separator was manufactured in the same manner as in Example 1, except that the first inorganic particles and the second inorganic particles were added at a weight ratio of 3:7 when preparing the first slurry.
- a separator was manufactured in the same manner as in Example 1, except that the first inorganic particles and the second inorganic particles were added at a weight ratio of 4:6 when preparing the first slurry.
- a separator was manufactured in the same manner as in Example 1, except that the first inorganic particles and the second inorganic particles were added at a weight ratio of 5:5 when preparing the first slurry.
- a separator was manufactured in the same manner as in Example 1, except that the first inorganic particles and the second inorganic particles were added at a weight ratio of 6:4 when preparing the first slurry.
- a separator was manufactured in the same manner as in Example 1, except that the first inorganic particles and the second inorganic particles were added at a weight ratio of 7:3 when preparing the first slurry.
- a separator was manufactured in the same manner as in Example 1, except that mesoporous silica nanoparticles into which sulfonic acid groups were introduced were used as the second inorganic particles.
- a separator was manufactured in the same manner as Example 1, except that both sides of the polypropylene film were coated with the second slurry.
- the thickness of the separators according to Examples 1 to 2 and Comparative Examples 1 to 6 and the first and second porous coating layers of each separator were confirmed with a thickness gauge (Mitutoyo, VL-50S-B), and the first porosity of each separator was measured.
- the average specific surface area of the inorganic particles included in the coating layer was measured and shown in Table 1 below.
- the separators according to Examples 1 to 2 and Comparative Examples 1 to 6 were completely immersed in a manganese sulfate solution (MnSO 4 ) (initial Mn 2+ concentration of 3,400 ppm) and maintained for 24 hours, and then the membranes were recovered and dried.
- MnSO 4 manganese sulfate solution
- the dried separator was analyzed by EDS (JEOL SEM, 15kV) and is shown in Table 2 below.
- Lithium manganese composite oxide LiMnO 2
- Conductive material Denka black
- PVdF binder
- NMP N-methylpyrrolidone
- a Li metal plate with a thickness of 200 ⁇ m was used as the cathode, and the anode and cathode were stacked with the separator of Example or Comparative Example in between, and then inserted into an aluminum pouch.
- ethylene carbonate (EC)/ethylmethyl carbonate (EMC) is mixed in a weight ratio of 3/7, and as additives, 3 mol of vinylene carbonate (VC), 1.5 mol of propane sultone (PS), and ethylene sulfate are added.
- a cell was manufactured by injecting 1 g of an electrolyte solution containing 1 mol of (ESa) and 1 mol of the lithium salt LiPF 6 and sealing the pouch.
- the manufactured cell was charged and discharged once at 0.1 C in a voltage range of 3.0 V to 4.35 V in a 25°C chamber, and performance maintenance was confirmed by repeating 0.33 C charging and 0.33 C discharging 400 times.
- the performance maintenance rate was calculated as the ratio of the discharge capacity after repeating 400 cycles to the initial discharge capacity.
- the resistance was measured before and after the 400 cycles to confirm the resistance increase rate.
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Abstract
Description
원단 | 다공성 코팅층 | 분리막 두께 (㎛) |
제1/제2 다공성 코팅층 두께 (㎛/㎛) |
제1 다공성 코팅층 중의 무기물 입자 평균 비표면적 (m2/g) |
||
제1 무기물 입자와 제2 무기물 입자의 중량 비율 | 제2 무기물 입자 표면 처리 여부 (+SO3-Li) | |||||
실시예 1 | PP | 2:8 | ○ | 15.1 | 3/3 | 620 |
실시예 2 | PP | 3:7 | ○ | 15.2 | 3/3 | 550 |
비교예 1 | PP | 4:6 | ○ | 15.4 | 3/3 | 240 |
비교예 2 | PP | 5:5 | ○ | 15.1 | 3/3 | 126 |
비교예 3 | PP | 6:4 | ○ | 15.2 | 3/3 | 94 |
비교예 4 | PP | 7:3 | ○ | 15.3 | 3/3 | 70 |
비교예 5 | PP | 2:8 | × | 15.2 | 3/3 | 580 |
비교예 6 | PP | 10:0 | - | 15.4 | 3/3 | 6.3 |
EDS mapping 결과 (Mn2+ 이온의 비율, %) |
분리막의 Mn2+ 이온 흡착량 (ppm) | Mn2+ 이온 흡착율 (%) | |
실시예 1 | 3.12 | 1150 | 33.82 |
실시예 2 | 2.64 | 800 | 23.53 |
비교예 1 | 1.95 | 124 | 3.65 |
비교예 2 | 0.75 | 94 | 2.76 |
비교예 3 | 0.64 | 82 | 2.41 |
비교예 4 | 0.58 | 50 | 1.47 |
비교예 5 | 0.66 | 142 | 4.17 |
비교예 6 | 0.02 | 17 | 0.51 |
400 사이클 후 셀 성능 유지율(%) | 400 사이클 후 저항 증가율(%) | |
실시예 1 | 88.8 | 5.65 |
실시예 2 | 87.2 | 6.54 |
비교예 1 | 75.4 | 23.45 |
비교예 2 | 74.8 | 35.89 |
비교예 3 | 73.9 | 37.87 |
비교예 4 | 73.5 | 39.42 |
비교예 5 | 78.2 | 22.40 |
비교예 6 | 72.1 | 41.87 |
Claims (15)
- 다공성 고분자 기재;제1 무기물 입자 및 상기 제1 무기물 입자보다 비표면적이 더 큰 제2 무기물 입자를 포함하며, 상기 다공성 고분자 기재의 제1 면에 형성되는 제1 다공성 코팅층; 및상기 다공성 고분자 기재의 제2 면에 형성되는 제2 다공성 코팅층을 포함하며,상기 제2 무기물 입자는,표면에 술폰산기가 도입된 것이며, 상기 술폰산기 중 적어도 일부는 수소 양이온이 리튬 양이온으로 치환된 것인, 리튬망간계 활물질을 포함하는 전기화학소자용 분리막.
- 제1항에 있어서,상기 제1 다공성 코팅층은,상기 제1 무기물 입자와 상기 제2 무기물 입자를 2:8 내지 3:7의 중량 비율로 포함하는 것인, 전기화학소자용 분리막.
- 제1항에 있어서,상기 제2 무기물 입자는,평균 직경이 1.5 내지 50 nm인 기공을 포함하는 메조포러스 무기물 입자인, 전기화학소자용 분리막.
- 제3항에 있어서,상기 제1 무기물 입자는,상기 제2 무기물 입자와는 상이한 것이며, 기공을 포함하지 않는 것인, 전기화학소자용 분리막.
- 제1항에 있어서,상기 술폰산기는,메탄 술폰산, 에탄 술폰산, 트리플루오로메탄 술폰산, 벤젠 술폰산, p-톨루엔 술폰산, 나프탈렌 술폰산, 페닐벤지미다졸 술폰산 및 2-아크릴아미도-2-메틸프로판 술폰산으로 이루어진 군으로부터 선택되는 하나 이상인, 전기화학소자용 분리막.
- 제1항에 있어서,상기 제1 무기물 입자는,Li3PO4, LixTiy(PO4)3 (0<x<2, 0<y<3), LixAlyTiz(PO4)3 (0<x<2, 0<y<1, 0<z<3), LixLayTiO3 (0<x<2, 0<y<3), LixGeyPzSw (0<x<4, 0<y<1, 0<z<1, 0<w<5), LixNy (0<x<4, 0<y<2), LixSiySz (0<x<3, 0<y<2, 0<z<4), LixPySz (0<x<3, 0<y<3, 0<z<7), Li7La3Zr2O12, BaTiO3, BaSO4, Pb(Zr,Ti)O3 (PZT), Pb1-xLaxZr1-yTiyO3 (PLZT, 0<x<1 , 0<y<1), Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT), HfO2, Sb2O3, Sb2O4, Sb2O5, SrTiO3, SnO2, CeO2, MgO, Mg(OH)2, NiO, CaO, ZnO, Zn2SnO4, ZnSnO3, ZnSn(OH)6, ZrO2, Y2O3, SiO2, Al2O3, AlOOH, Al(OH)3, SiC, TiO2, H3BO3 및 HBO2 로 이루어진 군으로부터 선택되는 하나 이상인, 전기화학소자용 분리막.
- 제1항에 있어서,상기 제1 다공성 코팅층은,수계 고분자 바인더를 더 포함하며,상기 수계 고분자 바인더는,상기 제1 무기물 입자 상호간, 상기 제2 무기물 입자 상호간 및 상기 제1 무기물 입자와 상기 제2 무기물 입자를 결합시켜, 무기물 입자 사이 간극으로 형성되는 인터스티셜 볼륨을 형성하는 것인, 전기화학소자용 분리막.
- 제7항에 있어서,상기 수계 고분자 바인더는,아크릴계 고분자, 폴리아크릴로니트릴, 폴리비닐피롤리돈, 폴리비닐아세테이트, 에틸렌 비닐 아세테이트 공중합체, 폴리에틸렌옥사이드, 폴리아릴레이트, 셀룰로오스 아세테이트, 셀룰로오스 아세테이트 부티레이트, 셀룰로오스 아세테이트 프로피오네이트, 시아노에틸풀루란, 시아노에틸폴리비닐알코올, 시아노에틸셀룰로오스, 시아노에틸수크로오스, 풀루란, 카복실메틸셀룰로오스, 아크릴로니트릴-스티렌-부타디엔 공중합체 및 폴리이미드로 이루어진 군으로부터 선택되는 하나 이상인, 전기화학소자용 분리막.
- 제1항에 있어서,상기 제1 다공성 코팅층은,상기 전기화학소자의 음극과 대면하는 것인, 전기화학소자용 분리막.
- 제9항에 있어서,상기 제2 다공성 코팅층은,상기 제1 무기물 입자를 포함하고, 상기 제2 무기물 입자는 포함하지 않는 것인, 전기화학소자용 분리막.
- 제1항에 있어서,상기 리튬망간계 활물질은,Li1+xMn2-xO4 (0≤x≤0.33), LiMnO3, LiMn2O3, LiMnO2, LiNi1-xMnxO2 (0.01≤x≤0.3), LiMn2-xMxO2 (M=Co, Ni, Fe, Cr, Zn 또는 Ta이고, 0.01≤x≤0.1), Li2Mn3MO8 (M=Fe, Co, Ni, Cu 또는 Zn), LiNixMn2-xO4 (0<x<0.5) 및 LiMn2O4로 이루어진 군으로부터 선택되는 하나 이상의 양극 활물질인, 전기화학소자용 분리막.
- 제1항에 있어서,상기 제1 다공성 코팅층에 포함된 상기 제1 무기물 입자 및 상기 제2 무기물 입자의 평균 비표면적은 500 내지 700 m2/g인, 전기화학소자용 분리막.
- 제1항에 있어서,상기 제1 다공성 코팅층은,두께가 1 내지 6 ㎛인, 전기화학소자용 분리막.
- 제1항에 있어서,상기 리튬망간계 활물질을 포함하는 양극으로부터 용출되는 망간 이온의 흡착율이 20 내지 50%인, 전기화학소자용 분리막.
- 양극, 음극 및 상기 양극과 상기 음극 사이에 배치되는 분리막을 포함하는 전기화학소자로서,상기 분리막은 제1항 내지 제14항 중 어느 한 항에 따른 전기화학소자용 분리막인, 전기화학소자.
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KR20130126445A (ko) * | 2012-05-10 | 2013-11-20 | 삼성에스디아이 주식회사 | 세퍼레이터 및 그 제조 방법과 상기 세퍼레이터를 포함하는 리튬 이차 전지 |
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