WO2018128484A1 - Séparateur pour batterie auquel est appliqué un liant fonctionnel, et dispositif électrochimique l'appliquant - Google Patents

Séparateur pour batterie auquel est appliqué un liant fonctionnel, et dispositif électrochimique l'appliquant Download PDF

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WO2018128484A1
WO2018128484A1 PCT/KR2018/000309 KR2018000309W WO2018128484A1 WO 2018128484 A1 WO2018128484 A1 WO 2018128484A1 KR 2018000309 W KR2018000309 W KR 2018000309W WO 2018128484 A1 WO2018128484 A1 WO 2018128484A1
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Prior art keywords
binder
separator
battery
inorganic particles
substrate
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PCT/KR2018/000309
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English (en)
Korean (ko)
Inventor
남관우
윤수진
권혜진
김찬종
이제안
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주식회사 엘지화학
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Priority to EP18736258.7A priority Critical patent/EP3503256A4/fr
Priority to JP2019519709A priority patent/JP6824558B2/ja
Priority to US16/463,441 priority patent/US11258135B2/en
Priority to CN201880003626.4A priority patent/CN109792020B/zh
Priority claimed from KR1020180001926A external-priority patent/KR102137533B1/ko
Publication of WO2018128484A1 publication Critical patent/WO2018128484A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • 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
    • 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
    • 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 to which a functional binder is applied, and more particularly, to a separator including an inorganic particle coated on one surface of a polyolefin substrate and a functional binder having improved properties, and an electrochemical device including the same.
  • 'SRS' Safety Reinforced Separator
  • 'SRS' is a surface coated with inorganic particles and a binder on a polyolefin-based substrate.
  • the pore structure of the inorganic particles and the binder increases the space for the liquid electrolyte to increase the lithium ion conductivity and the electrolyte impregnation rate, thereby improving the performance and stability of the electrochemical device using the separator.
  • Patent Document 1 describes an organic / inorganic composite porous separator and an electrochemical device using the same.
  • the adhesion properties of the binder-inorganic and substrate-binder to prevent the inorganic material from falling off the surface of the polyolefin substrate is very important.
  • binders are PVDF-based, and since the adhesive property of the binder is low, it is necessary to develop a new binder to improve stability.
  • PVDF-based binders have excellent adhesion with the positive electrode, but have a disadvantage of poor adhesion with the negative electrode using SBR (Styrene-Butadiene Rubber) binder.
  • SBR Styrene-Butadiene Rubber
  • the PVDF-based binder is hydrophobic, the wettability of the separator with respect to the electrolyte is not good, and thus the output of the battery is reduced.
  • the SRS has a problem that it cannot cope with the dissolution of the cathode material transition metal in the high temperature / high voltage state that can occur frequently in the driving of an electric vehicle.
  • Conventional binders do not adsorb the eluted transition metal, which causes a problem of deterioration of battery life characteristics.
  • Non-Patent Document 1 is to improve the commercial PP (Polypropylene) membrane wettability characteristics of a lithium ion battery, and has developed a surface coating method of dipping a PP substrate into tannic acid, a natural vegetable polyphenyl.
  • tannic acid containing a large number of hydroxyl groups may not be evenly distributed on the surface of PP, and coating may not have sufficient durability in manufacturing and charging and discharging electrochemical devices using the same.
  • Non-Patent Document 2 is for improving the wetting properties of a PP substrate used as a separator of a lithium ion battery, and describes a method of coating using pyrogallic acid.
  • Non-Patent Literature 2 Also, as in Non-Patent Literature 1, since pyrogallic acid has a poor physical and chemical affinity with hydrophobic PP, a uniform coating can be obtained in a short time, but in the manufacture and charging / discharging of an electrochemical device using the coating, It does not have sufficient durability and uniformity.
  • Non-Patent Documents 3 to 6 a binder having a self-healing function, such as a capsule-shaped binder for improving the characteristics of a negative electrode containing silicon, is introduced.
  • a binder having a self-healing function such as a capsule-shaped binder for improving the characteristics of a negative electrode containing silicon.
  • Patent Document 2 describes a technique for adding a binder film to the SRS outermost layer in order to improve the wettability of the separator.
  • the hydrophilicity is improved due to the film of the outermost layer, but there is a problem in that the access of the pores formed by the inorganic particles and the binder is limited and thus the performance and stability of the electrochemical device cannot be found.
  • Patent document 3 relates to a battery separator and a nonaqueous electrolyte battery using the same, wherein the battery separator includes a resin porous membrane having a thermoplastic resin as a main component and a multilayer porous membrane having a heat resistant porous layer containing heat resistant fine particles as a main component, wherein The thickness of a heat resistant porous layer is 1-15 micrometers, and the peeling strength in 180 degrees of the said resin porous film and the said heat resistant porous layer is 0.6 N / cm or more, It is related with the battery separator.
  • the binder of the present invention has an object that is never recognized in Patent Document 3, such as adhesion improvement, adsorption of a cathode material transition metal, and self-healing, and thus there is a large difference in the molecular structure of the binder.
  • the present invention is a binder containing a large number of -O and hydroxy (OH) functional groups in the molecule, while Patent Document 3 uses a polymer or water-soluble cellulose derivative of N-vinylacetamide and a crosslinked acrylic resin as a binder. There is a difference.
  • Patent Document 3 uses xanthan gum used as a binder in the present invention as a thickener.
  • the binder and the thickener are basically different in the amount used.
  • the composition ratio of a binder is 1.1 mass parts or more with respect to 100 mass parts of heat resistant fine particles
  • the composition ratio of a thickener uses 0.1 mass part or more with respect to 100 mass parts of heat resistant fine particles. Since the composition ratio is about 10 times the difference, it can be seen that the binder and the thickener are not mutually compatible.
  • this invention and patent document 3 have some similarities in using xanthan gum, since specific uses differ, it can be seen that patent document 3 does not grasp the technical characteristic of the binder used by this invention at all.
  • Non-Patent Document 7 is a review paper on natural materials used in an electrochemical energy storage device and describes that natural materials amylopectin, xanthan gum, and the like are used as binders. However, all of the binders of Non-Patent Document 7 differ in their use and function from those of the separator used in the present invention as binders of positive or negative electrodes. In particular, since the binder for the separator of the present invention has a completely different property from the material used in the anode or the cathode in that the separator contains an inorganic material, the technical field of the separator may be different.
  • the present invention is a separator comprising a porous polyolefin substrate, an organic-inorganic composite porous coating layer comprising a binder compound and inorganic particles formed on at least one surface of the substrate, while increasing the adhesive strength of the binder-inorganic, substrate-binder,
  • a self-healing function prevents internal short-circuit in advance and improves adhesion between the separator and the positive electrode and the negative electrode, and a functional binder capable of coping with dissolution of the positive electrode material transition metal and a battery separator including the same. It aims to provide.
  • the first aspect of the present invention for solving the above problems is (a) a polyolefin-based substrate; And (b) an active layer wherein at least one region selected from the group consisting of a surface of the substrate and a portion of the pores present in the substrate is coated with a mixture of inorganic particles and a binder, wherein the active layer is an inorganic material by a binder.
  • the separator for the battery is connected and fixed between the particles, the pore structure is formed due to the interstitial volume between the inorganic particles,
  • the binder provides a separator for a battery in which the proportion of hydroxy groups in each molecule is 10% by weight or more.
  • binder may be at least one or more of tannic acid, pyrogallic acid, amylose, amylopectin, xanthan gum, or 1) at least one or more of tannic acid, pyrogallic acid, amylose, amylopectin and xanthan gum.
  • the inorganic particles may be at least one selected from the group consisting of inorganic particles having a dielectric constant of 5 or more, inorganic particles having piezoelectricity, and inorganic particles having lithium ion transfer ability.
  • the inorganic particles having a dielectric constant of 5 or more are SrTiO 3 , SnO 2 , CeO 2 , MgO, NiO, CaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , TiO 2 or SiC;
  • the inorganic particles having piezoelectricity are BaTiO 3 , Pb (Zr, Ti) O 3 (PZT), Pb 1-x La x Zr 1-y Ti y O 3 (PLZT), PB (Mg 3 Nb 2 / 3 ) O 3 -PbTiO 3 (PMN-PT) or hafnia (HfO 2 );
  • the inorganic particles having the lithium ion transfer ability are lithium phosphate (Li 3 PO 4 ), lithium titanium phosphate (Li x Ti y (PO 4 ) 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 3), lithium aluminum titanium phosphate (Li x Al
  • the inorganic particles may include at least one of Al 2 O 3 , AlOOH, and Mg (OH) 2 .
  • the polyolefin-based substrate may be at least one selected from the group consisting of high density polyethylene, low density polyethylene, linear low density polyethylene, ultra high molecular weight polyethylene, and polypropylene.
  • a second aspect according to the present invention comprises the steps of 1) dissolving a binder in a solvent to prepare a binder solution; 2) adding and mixing the inorganic particles to the binder solution of step 1); 3) A method of manufacturing a battery separator comprising coating and drying at least one region selected from the group consisting of a surface of a polyolefin-based substrate and a part of pores in the substrate with the solution of step 2).
  • a method for manufacturing a battery separator according to the present invention wherein the proportion of hydroxyl groups in the molecule is 10% by weight or more.
  • the solvent has a mixed weight ratio of water and acetone of 100: 0 to 0: 100, preferably 95: 5 to 0: 100, more preferably 75:25 to 0: 100, even more preferably 60:40 to 0: 100. Even more preferably 50:50 to 0: 100.
  • the most preferred range is 40:60 to 0: 100.
  • the optimal ratio according to an embodiment of the present invention is 75:25.
  • an electrochemical device including the battery separator of the present invention.
  • the electrochemical device may be a lithium secondary battery.
  • FIG. 1 illustrates a unit structure of Amylose, which is an embodiment of the binder of the present invention.
  • Figure 2 shows the unit structure of Amylopectin (Amylopectin) which is one embodiment of the binder of the present invention.
  • FIG 3 shows a unit structure of Xanthan Gum, which is one embodiment of the binder of the present invention.
  • FIG. 4 illustrates hydrogen bonding between an electrode and a separator when tannic acid is used as a binder according to an embodiment of the present invention.
  • Figure 5 is an illustration for the improvement of the wettability according to the use of tannic acid according to an embodiment of the present invention.
  • FIG. 6 is an illustration of the adsorption mechanism for the cathode material transition metal by hydrogen bonding.
  • Figure 9 conceptually shows the self-healing function according to the application of the binder of the present invention.
  • 11 is a measure of the physical properties of the separator according to the concentration of acetone according to an embodiment of the present invention.
  • the present invention not only exhibits excellent thermal safety, electrochemical stability, excellent lithium ion conductivity, electrolyte impregnation rate, self-healing function, etc., compared with the polyolefin-based separators used as conventional battery separators, but also contains a large amount of hydrophilic functional groups.
  • the present invention provides a battery separator and a method of manufacturing the same, in which a binding force of the battery-separation membrane is improved and a functional binder capable of adsorbing a transition metal eluted from the positive electrode is applied.
  • the present invention (a) a polyolefin-based substrate; And (b) an active layer wherein at least one region selected from the group consisting of a surface of the substrate and a portion of the pores present in the substrate is coated with a mixture of inorganic particles and a binder, wherein the active layer is an inorganic material by a binder.
  • the separator for the battery is connected and fixed between the particles, the pore structure is formed due to the interstitial volume between the inorganic particles,
  • the binder provides a separator for a battery in which the proportion of hydroxy groups in each molecule is 10% by weight or more.
  • the proportion of hydroxy groups in each molecule is preferably 12 wt% or more and 50 wt% or less, more preferably 15 wt% or more and 45 wt% or less, even more preferably 18 wt% or more and 40 wt% or less, even more preferably Preferably it is 18 weight% or more and 38 weight% or less.
  • the weight ratio of the hydroxy group is less than 10% by weight, the hydrogen bonding functional group of the binder is not sufficient, and thus the desired function in the present invention is not sufficiently realized.
  • the weight ratio of the hydroxy group is more than 50% by weight, there may be a problem that the movement of the electrolyte is limited due to the strong hydrogen bond.
  • binder may be at least one or more of tannic acid, pyrogallic acid, amylose, amylopectin, xanthan gum, or 1) at least one or more of tannic acid, pyrogallic acid, amylose, amylopectin and xanthan gum.
  • polyvinylidene fluoride-co-hexafluoropropylene polyvinylidene fluoride-co-trichloroethylene
  • polymethylmethacryl Polymethylmethacrylate polyacrylonitrile
  • polyvinylpyrrolidone polyvinylacetate
  • ethylene vinyl acetate copolymer polyethylene oxide
  • Cellulose acetate, cellulose acetate butyrate Cellulose acetate propionate
  • cyanoethylpullulan cyanoethylpolyvinylalcohol
  • cyanoethylcellulose cyanoethylsucrose
  • pullulan It may be a mixture with a mixture comprising at least one of pullulan, carboxyl methyl cellulose, acrylonitrilestyrene-butadiene copolymer, polyimide.
  • amylose see FIG. 1
  • amylopectin see FIG. 2
  • xanthan gum see FIG. 3
  • tannic acid see FIG. 4
  • OH occupies 18%, 25%, and 32% in each of amylose, amylopectin and xanthan gum. It can be seen that the specific gravity of all the hydroxy (OH) groups is 10% by weight or more and can generate strong hydrogen bonds.
  • an OH group is excluded and carboxyl (COOH) is excluded.
  • the binder according to the present invention has an advantage of excellent bonding strength for both the positive electrode and the negative electrode by the hydrophilic functional group.
  • the binding relationship in the molecular unit about this is shown typically in FIG.
  • the conventional PE substrate has a poor affinity for water as a hydrophobic material, but it can be seen that the result of applying the tannin acid as the binder according to the present invention changes to hydrophilicity (see FIG. 5).
  • Figure 6 shows an example of the adsorption mechanism for the positive electrode material transition metal by the binder containing a hydrophilic group according to the present invention.
  • FIG. 8 The conceptual diagram of the separator according to the present invention is shown in FIG.
  • Conventional binders do not have a large attractive force between the binder ends or the middle, but the binder according to the present invention maintains strong hydrogen bonds due to -O / -OH groups.
  • Triangle in FIG. 8 means a hydroxy group or a hydrophilic group.
  • Circle means inorganic particles.
  • Example 1 Preparation of a separator for a lithium ion battery to which a functional binder is applied.
  • PVdF-CTFE Polyvinylidene fluoride-chlorotrifluoroethylene copolymer
  • BaTiO 3 particle diameter of the slurry thus prepared may be controlled according to the size (particle size) of the beads used in the ball mill method and the application time of the ball mill method, but in Example 1, the slurry was pulverized to about 400 nm.
  • the slurry thus prepared was coated on a polyethylene separator (porosity 45%) having a thickness of about 18 ⁇ m by using a dip coating method, and the coating thickness was adjusted to about 3 ⁇ m.
  • the pore size and porosity in the active layer coated on the polyethylene separator were 0.5 ⁇ m and 58%, respectively, as measured by a porosimeter.
  • Example 2 was prepared by changing the weight ratio of the binder and the inorganic material to 15:85 in the coating composition.
  • Comparative Example 1 was prepared under the same conditions as in Example 2, but did not use tannic acid in the binder. Comparative Examples 1 and 2 were coated with a thickness of 5 ⁇ m and 3 ⁇ m, respectively.
  • Example 2 according to the present invention showed excellent physical properties compared to the conventional separation membrane (Comparative Example 1) does not contain tannic acid.
  • Comparative Example 1 exhibited poor heat shrinkage properties compared to Example 2, although the thickness of the coating was thicker.
  • MD is a machine direction and TD is a transverse direction, respectively, and shows the length of a horizontal direction and a vertical direction, respectively.
  • Numerical values at the top of each table indicate the MD / TD shrinkage percentage (%) before and after heat shrink.
  • Examples 3, 4 and 5 were prepared in the same manner as in Example 1.
  • the inorganic particles alumina and boehmite were used in a 85:15 weight ratio, and a mixing ratio of the inorganic material and the binder was 75:25 weight ratio.
  • a binder a binder containing PVdF-HFP: PVdF-CTFE: hydroxy group was prepared in a 22: 1: 2 weight ratio, and the solvent was 100% acetone.
  • Xanthan gum, tannic acid, and amylose were used as the hydroxyl group-containing binder, respectively.
  • PP was used for the polyolefin substrate.
  • the fabric means a polyolefin substrate.
  • the weight ratio of the hydroxyl group in the binder was increased, the adhesion between the substrate and the inorganic coating layer was increased, and the ionic conductivity was also increased.
  • the electrical resistance of the separator did not appear to change significantly.
  • the separator / fabric interface adhesion strength is a measure of the separation strength of the inorganic coating layer and the substrate when the substrate is separated after adhering the inorganic coating layer of the SRS to the remaining surface of the double-sided tape after attaching the double-sided tape on the glass surface
  • Separator / electrode interface adhesion is a measure of the separation strength of the electrode and the SRS when the substrate is separated after adhering the electrode to the other side of the double-sided tape after attaching the double-sided tape on the glass surface.
  • ER and ionic conductivity were measured by the conventional method, and the membrane Gurely was measured for air permeability, and the air permeability was measured using Toyoseiki's Gurley type Densometer (No. 158) according to Japanese Industrial Standard Gurley measurement method. Measured.
  • air permeability refers to the time (in seconds) that 100 cc of air passes through a 1 inch square membrane under constant air pressure of 4.8 inches.
  • Examples 6, 7, 8, 9, and 10 prepared a separator by the same method as in Example 3. At this time, tannic acid was used as the binder having a hydroxyl group. In the preparation of the solvent, the weight ratio of water and acetone was 100: 0, 95: 5, 50:50, 25:75, and 0: 100, respectively. The change in physical properties according to the weight ratio of water and acetone, respectively, is shown in FIG. 11.
  • the ratio of water and acetone was 25:75.
  • the ratio of water and acetone was in the range of 50:50 or more and 0: 100.
  • the optimum point may be changed by the proportion of hydroxy groups in the binder, and considering the ratio of hydroxy groups according to the present invention, from 60:40 to It can be extended to 0: 100.
  • the present invention is a separator comprising a porous polyolefin substrate, an organic-inorganic composite porous coating layer comprising a binder compound and inorganic particles formed on at least one surface of the substrate, while increasing the adhesive strength of the binder-inorganic, substrate-binder, Self-healing function prevents internal short circuits in advance for some damage to the separator, improves the adhesion between the separator and the anode and the cathode, and can cope with the elution of the transition material of the cathode material.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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Abstract

La présente invention concerne : un liant fonctionnel dans un séparateur qui comprend un substrat de polyoléfine poreux et une couche de revêtement poreux composite organique-inorganique qui comprend un mélange d'un composé liant avec des particules inorganiques formé sur au moins une surface du substrat ; et un séparateur comprenant celui-ci, le liant fonctionnel pouvant augmenter l'adhérence entre un liant et un matériau inorganique et entre un substrat et un liant tout en préemptant un court-circuit interne par l'intermédiaire d'une fonction d'auto-réparation pour un endommagement partiel du séparateur, améliorer l'adhérence du séparateur à une cathode et à une anode, et répondre à l'élution d'un métal de transition de matériau de cathode. Dans le liant selon la présente invention, la proportion de groupe hydroxyle dans chaque molécule est de 10 % en poids ou plus.
PCT/KR2018/000309 2017-01-06 2018-01-05 Séparateur pour batterie auquel est appliqué un liant fonctionnel, et dispositif électrochimique l'appliquant WO2018128484A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP18736258.7A EP3503256A4 (fr) 2017-01-06 2018-01-05 Séparateur pour batterie auquel est appliqué un liant fonctionnel, et dispositif électrochimique l'appliquant
JP2019519709A JP6824558B2 (ja) 2017-01-06 2018-01-05 機能性バインダーが適用された電池用分離膜及びこれを適用した電気化学素子
US16/463,441 US11258135B2 (en) 2017-01-06 2018-01-05 Battery separator including functional binder and electrochemical device comprising the same
CN201880003626.4A CN109792020B (zh) 2017-01-06 2018-01-05 包括功能性粘合剂的电池隔板以及包括该电池隔板的电化学装置

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Application Number Priority Date Filing Date Title
KR20170002219 2017-01-06
KR10-2017-0002219 2017-01-06
KR20170030566 2017-03-10
KR10-2017-0030566 2017-03-10
KR1020180001926A KR102137533B1 (ko) 2017-01-06 2018-01-05 기능성 바인더가 적용된 전지용 분리막 및 이를 적용한 전기화학 소자
KR10-2018-0001926 2018-01-05

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Cited By (4)

* Cited by examiner, † Cited by third party
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CN112292783A (zh) * 2019-05-09 2021-01-29 株式会社Lg化学 包括分散剂的用于二次电池的隔板及其制造方法
CN114512769A (zh) * 2020-10-23 2022-05-17 中国石油化工股份有限公司 一种锂硫电池隔膜及其制备方法和锂硫电池
CN114744363A (zh) * 2022-03-29 2022-07-12 中材锂膜(宁乡)有限公司 锂离子电池隔膜浆料、其制备方法及隔膜
CN115803956A (zh) * 2020-07-28 2023-03-14 宁德时代新能源科技股份有限公司 一种隔膜、包括该隔膜的电学装置及其制备方法

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