WO2019205589A1 - Procédé de préparation de séparateur de polymère de para-aramide fabriqué par électrofilage et utilisé pour une batterie au lithium-ion - Google Patents

Procédé de préparation de séparateur de polymère de para-aramide fabriqué par électrofilage et utilisé pour une batterie au lithium-ion Download PDF

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WO2019205589A1
WO2019205589A1 PCT/CN2018/115437 CN2018115437W WO2019205589A1 WO 2019205589 A1 WO2019205589 A1 WO 2019205589A1 CN 2018115437 W CN2018115437 W CN 2018115437W WO 2019205589 A1 WO2019205589 A1 WO 2019205589A1
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Prior art keywords
para
aramid polymer
aramid
lithium ion
electrospinning
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PCT/CN2018/115437
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English (en)
Chinese (zh)
Inventor
吴迪
唐凯
陈文建
马海兵
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烟台泰和新材料股份有限公司
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Publication of WO2019205589A1 publication Critical patent/WO2019205589A1/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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • D01F6/905—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides of aromatic polyamides
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/4334—Polyamides
    • D04H1/4342—Aromatic polyamides
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • 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
    • H01M50/44—Fibrous 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
    • 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 invention relates to the technical field of lithium ion battery and polymer material production, and particularly relates to a preparation method of a para-aramid polymer separator which can be used for a lithium ion battery prepared by an electrospinning method.
  • Lithium-ion batteries are widely used in portable electronic products, electric vehicles, and energy storage systems due to their high voltage, high energy, no memory effect, and rapid charge and discharge. Research hotspots in the energy field. Lithium-ion batteries are mainly composed of positive and negative electrodes, separators and electrolytes. The membrane is located between the positive and negative materials, because the membrane has a large number of micropores which are bent and penetrated, and the electrolyte ions are freely passed through to form a charge and discharge circuit. When the battery is overcharged or the temperature rises, the membrane passes the closed hole function to the battery. The positive and negative poles are separated to prevent short circuit.
  • the performance of the diaphragm determines the internal resistance of the battery and the internal interface structure, which in turn affects the battery capacity, charge and discharge performance, cycle performance and safety performance. Therefore, the quality of the diaphragm has an important influence on the overall performance of the lithium ion battery.
  • Electrospinning is a process in which a polymer solution or a polymer melt forms fibers under the action of a high-voltage electrostatic field.
  • the main principle is to cause a charged polymer solution or melt to flow, split and deform in an electrostatic field, and then The solvent is evaporated or melt cooled to solidify, and finally a fiber membrane is obtained.
  • Fibers prepared by electrospinning techniques can range in diameter from a few hundred nanometers to between microns. Electrospinning technology is suitable for the preparation of the film direction because of its simple spinning equipment, short operating time and low dosage of spinning solution.
  • the prepared film has excellent characteristics such as a large specific surface area, a high porosity, and a small pore size. These properties make microfiber membranes have considerable potential applications in filtration, electrical, optical, biomedical, battery separators and water treatment.
  • the para-aramid polymer has become a new material for the production of lithium ion battery separators because of its excellent physical and chemical properties such as solvent resistance, heat resistance and low thermal expansion coefficient.
  • the phase transition occurs in the production process of the para-aramid polymer.
  • the final product exists in the form of solid particles, and is only soluble in a very small amount of strong protonic acid such as concentrated sulfuric acid or benzenesulfonic acid, which is not conducive to post-processing, which becomes a para-positional Polyester polymer materials are the biggest obstacles in the field of lithium ion battery separators.
  • the invention provides a preparation method of a para-aramid polymer separator which can be used for a lithium ion battery prepared by an electrospinning method, in order to overcome the deficiencies of the prior art, the present invention dissolves in a solvent by adding a cosolvent to an organic solvent. Under the premise of retaining the excellent physicochemical properties of the para-aramid polymer, it imparts good fluidity, and forms a porous structure with ceramic particles, and additionally forms a film by an electrospinning method, and the process is simple and easy.
  • a preparation method of a para-aramid polymer separator which can be used for a lithium ion battery prepared by an electrospinning method comprising the following steps:
  • the inorganic/organic composite film is dried to remove the residual organic solvent in the composite film, that is, the para-aramid polymer separator which can be used for the lithium ion battery obtained by the electrospinning method.
  • the co-solvent A described in the step 1) is one or both of potassium sec-butoxide and potassium t-butoxide; the co-solvent B is one or two of methanol and ethanol;
  • the amount of cosolvent A added is one time the equivalent of the nitrogen element in the para-aramid polymer or the para-aramid fiber; the amount of the co-solvent B is four in the para-aramid polymer or the para-aramid fiber in the equivalent of the nitrogen element. Times.
  • the organic solvent described in the step 1) is N,N-dimethylformamide, N,N-dimethylacetamide, acetone, N-methylpyrrolidone, tetrahydrofuran and dimethyl sulfoxide. One or two.
  • the mass of the para-aramid polymer or the para-aramid fiber in the step 1) is 0.6 of the sum of the para-aramid polymer or the para-aramid fiber and the organic solvent and the mass of the co-solvent A and the co-solvent B. % ⁇ 9.8%.
  • the nano-scale inorganic ceramic particles described in the step 1) are one or two of zirconium dioxide, aluminum oxide, titanium dioxide, silicon dioxide, magnesium oxide, zinc oxide, and nano-scale inorganic ceramic particles.
  • the particle diameter is 10 to 130 nm, preferably 20 to 98 nm.
  • the mass ratio of the para-aramid polymer or the para-aramid fiber to the nano-scale inorganic ceramic particles in the step 1) is (0.75 to 0.85): (0.15 to 0.25).
  • the ultrasonic dispersion time in step 2) is 15 to 28 min.
  • the spinning rate in the step 3) is 0.5 to 1.6 mL/h
  • the distance between the spinning port and the receiving device is 10 to 16 cm
  • the spinning voltage is 10 to 18 kV.
  • drying temperature in the step 4) is 50 to 220 ° C, and the time is 1 to 1.5 hours.
  • the para-aramid polymer separator obtained in the step 4) has a thickness of 22 to 48 ⁇ m, a tensile breaking strength of 4.2 to 14.7 MPa, a porosity of 90 to 99%, and a liquid absorption rate of 240 to 320%.
  • the present invention has the following beneficial technical effects:
  • the invention adopts the electrospinning method to process the film into a film, and the process is simple and easy, and the prepared para-aramid polymer lithium ion battery separator forms a porous structure with ceramic particles.
  • the structure is beneficial to increase the porosity and liquid absorption rate of the separator, and the ceramic particles can adsorb a small amount of H 2 O and HF generated by decomposition of the electrolyte during the cycle of the battery, thereby improving the charging and discharging efficiency of the battery and prolonging the cycle life of the battery.
  • the prepared para-aramid polymer lithium ion battery separator has small film thickness and easy control, and has low heat shrinkage rate, good electrochemical stability, high porosity and liquid absorption rate, and mechanical mechanism. The strength can meet the requirements of the battery assembly process.
  • the solvent used in the invention is not corrosive, greatly prolongs the service life of the equipment, and imparts good fluidity on the basis of maintaining the physical and chemical properties of the para-aramid.
  • a preparation method of a para-aramid polymer separator which can be used for a lithium ion battery prepared by an electrospinning method comprising the following steps:
  • the co-solvent A is one or two of potassium sec-butoxide and potassium t-butoxide; the cosolvent B is one or two of methanol and ethanol; and the amount of the co-solvent A added is
  • the amount of the nitrogen element in the aramid polymer or the para-aramid fiber is doubled; the amount of the co-solvent B is four times the equivalent of the nitrogen element in the para-aramid polymer or the para-aramid fiber; the organic solvent N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), acetone, N-methylpyrrolidone (NMP), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) One or both of them; and the quality of the para-aramid polymer or the para-aramid fiber is the quality of the para-aramid polymer or the para-aramid fiber and the organic solvent and the co-solvent A and the co-solvent B.
  • the nano-scale inorganic ceramic particles are one or two of zirconium dioxide, aluminum oxide, titanium dioxide, silicon dioxide, magnesium oxide, zinc oxide, and nano-scale inorganic ceramics
  • the particle size of the particles is 10 to 130 nm, preferably 20 to 98 nm, and the mass ratio of the para-aramid polymer or the para-aramid fiber to the nano-scale inorganic ceramic particles (0.75 to 0.85): (0.15 to 0.25);
  • Electrospinning is carried out by using the dispersion, and a nascent inorganic/organic composite film is obtained on the receiving device, the spinning rate is 0.5 to 1.6 mL/h, and the distance between the spinning port and the receiving device is 10 to 16 cm. Wire voltage is 10 ⁇ 18kV;
  • the para-aramid polymer separator has a thickness of 22 to 48 ⁇ m, a tensile breaking strength of 4.2 to 14.7 MPa, a porosity of 90 to 99%, and a liquid absorption rate of 240 ⁇ . 320%.
  • co-solvent A potassium sec-butoxide
  • cosolvent B methanol
  • the dry para-aramid polymer/fiber and nano-ZrO 2 were then weighed, and the mass ratio of the aramid mass to the inorganic nanoparticles was 0.75:0.25.
  • the para-aramid polymer/fiber was first added to the above solvent, and after dissolution, a stock solution having a mass fraction of 0.6% based on the content of the para-aramid was obtained.
  • Nano ZrO 2 was then added thereto and mechanically stirred for 1 h to initially disperse the nanoparticles. After ultrasonic treatment for 15 min, the nanoparticles were further uniformly dispersed to prepare a dispersion.
  • the above dispersion was electrospun at a spinning rate of 0.5 mL/h at a temperature of 25 ° C and a humidity of 30%: the applied voltage was 10 kV, and the distance between the needle and the receiver was 10 cm.
  • the nascent ZrO 2 /para-aramid composite film obtained was removed from the receiver, and dried at 160 ° C for 1 h to obtain a para-aramid polymer separator which can be used for a lithium ion battery.
  • the separator was treated at 130 ° C for 1.5 h, the shrinkage was 0.5%, the thickness of the separator was 48 ⁇ m, the porosity was 97.2%, and the tensile strength at break was 5.2 MPa.
  • the separator was immersed in 1 mol/L of lithium hexafluorophosphate/ In the electrolytic solution of dimethyl carbonate/diethyl carbonate (mass ratio: 1:1), the obtained liquid absorption rate was 371.2%, the ionic conductivity was 1.93 mS/cm, and the electrochemical stability window was 5.63 V.
  • cosolvent A potassium sec-butoxide
  • cosolvent B ethanol
  • the dry para-aramid polymer/fiber and nano-Al 2 O 3 were then weighed, and the mass ratio of the aramid mass to the inorganic nanoparticles was 0.75:0.25.
  • the para-aramid polymer/fiber was first added to the above solvent, and after dissolution, a stock solution having a mass fraction of 2.44% based on the content of the para-aramid was obtained.
  • Nano Al 2 O 3 was then added thereto and mechanically stirred for 1 h to initially disperse the nanoparticles. After ultrasonic treatment for 20 min, the nanoparticles were further uniformly dispersed to prepare a dispersion.
  • the above dispersion was electrospun at a spinning rate of 0.5 mL/h at a temperature of 25 ° C and a humidity of 30%: the applied voltage was 11.6 kV, and the distance between the needle and the receiver was 11.2 cm.
  • the nascent Al 2 O 3 /para-aramid composite film was taken out from the receiver, and dried at 170 ° C for 1 h to obtain a para-aramid polymer separator which can be used for a lithium ion battery.
  • the separator was treated at 130 ° C for 1.5 h, the shrinkage was 0.6%, the separator thickness was 41 ⁇ m, the porosity was 96.7%, and the tensile rupture strength was 6.6 MPa.
  • the separator was immersed in 1 mol/L of lithium hexafluorophosphate/ethylene carbonate/ In the electrolytic solution of dimethyl carbonate/diethyl carbonate (mass ratio: 1:1), the obtained liquid absorption rate was 359.6%, the ionic conductivity was 2.14 mS/cm, and the electrochemical stability window was 5.58 V.
  • co-solvent A potassium t-butoxide
  • co-solvent B methanol
  • the para-aramid polymer/fiber was first added to the above solvent, and after dissolution, a stock solution having a mass fraction of 4.28% based on the content of the para-aramid was obtained.
  • Nano TiO 2 was added thereto and mechanically stirred for 1 hour to initially disperse the nanoparticles. After ultrasonic treatment for 25 min, the nanoparticles were further uniformly dispersed to prepare a dispersion.
  • the above dispersion was electrospun at a spinning rate of 0.5 mL/h at a temperature of 25 ° C and a humidity of 30%: the applied voltage was 13.2 kV, and the distance between the needle and the receiver was 12.4 cm.
  • the nascent TiO 2 para-aramid composite film obtained was removed from the receiver, and dried at 75 ° C for 1 h to obtain a para-aramid polymer separator which can be used for a lithium ion battery.
  • the separator was treated at 130 ° C for 1.5 h, the shrinkage was 0.3%, the separator thickness was 39 ⁇ m, the porosity was 97.2%, and the tensile rupture strength was 7.4 MPa.
  • the separator was immersed in 1 mol/L of lithium hexafluorophosphate/ethylene carbonate/ In the electrolytic solution of dimethyl carbonate/diethyl carbonate (mass ratio: 1:1), the obtained liquid absorption rate was 324.8%, the ionic conductivity was 2.37 mS/cm, and the electrochemical stability window was 5.64 V.
  • cosolvent A potassium tert-butoxide
  • cosolvent B ethanol
  • the dried para-aramid polymer/fiber and any molar ratio of nano-Al 2 O 3 and nano-SiO 2 were weighed, and the mass ratio of the aramid mass to the inorganic nanoparticles was 0.80:0.20.
  • the para-aramid polymer/fiber was first added to the above solvent, and after dissolution, a stock solution having a mass fraction of 6.12% based on the content of the para-aramid was obtained.
  • inorganic nano-Al 2 O 3 and nano-SiO 2 were added thereto, and mechanically stirred for 1 hour to initially disperse the nanoparticles. After ultrasonic treatment for 28 min, the nanoparticles were further uniformly dispersed to prepare a dispersion.
  • the above dispersion was electrospun at a spinning rate of 1.16 mL/h at a temperature of 25 ° C and a humidity of 30%: the applied voltage was 14.8 kV, and the distance between the needle and the receiver was 13.6 cm.
  • the nascent SiO 2 /para-aramid composite film obtained was removed from the receiver, and dried at 220 ° C for 1.4 h to obtain a para-aramid polymer separator which can be used for a lithium ion battery.
  • the separator was treated at 130 ° C for 1.5 h, the shrinkage was 0.6%, the separator thickness was 37 ⁇ m, the porosity was 94.9%, and the tensile rupture strength was 8.2 MPa.
  • the separator was immersed in 1 mol/L of lithium hexafluorophosphate/ethylene carbonate/ In the electrolytic solution of dimethyl carbonate/diethyl carbonate (mass ratio: 1:1), the obtained liquid absorption rate was 301.9%, the ionic conductivity was 2.51 mS/cm, and the electrochemical stability window was 5.59 V.
  • the cosolvent A any ratio of potassium sec-butoxide and potassium t-butoxide
  • the co-solvent B methanol
  • inorganic nano-MgO and nano-SiO 2 were added thereto, and mechanically stirred for 1 hour to initially disperse the nanoparticles. After ultrasonic treatment for 28 min, the nanoparticles were further uniformly dispersed to prepare a dispersion.
  • the above dispersion was electrospun at a spinning rate of 1.38 mL/h at a temperature of 25 ° C and a humidity of 30%: the applied voltage was 16.4 kV, and the distance between the needle and the receiver was 14.8 cm.
  • the obtained nascent MgO/para-aramid composite film was taken out from the receiver, and dried at 70 ° C for 1.2 h to obtain a para-aramid polymer separator which can be used for a lithium ion battery.
  • the separator was treated at 130 ° C for 1.5 h, the shrinkage was 0.5%, the separator thickness was 30 ⁇ m, the porosity was 96.4%, and the tensile rupture strength was 10.4 MPa.
  • the separator was immersed in 1 mol/L of lithium hexafluorophosphate/ethylene carbonate/ In the electrolytic solution of dimethyl carbonate/diethyl carbonate (mass ratio 1:1:1), the obtained liquid absorption rate was 289.1%, the ionic conductivity was 2.58 mS/cm, and the electrochemical stability window was 5.62 V.
  • co-solvent A potassium t-butoxide
  • cosolvent B any ratio of methanol and ethanol
  • the dry para-aramid polymer/fiber and the nanometer MgO and nano-ZnO in any molar ratio were weighed, and the mass ratio of the aramid mass to the inorganic nanoparticle was 0.85:0.15.
  • the para-aramid polymer/fiber was first added to the above solvent, and after dissolution, a stock solution having a mass fraction of 9.80% based on the content of the para-aramid was obtained.
  • Inorganic nano-MgO and nano-ZnO were added thereto, and mechanically stirred for 1 hour to initially disperse the nanoparticles. After ultrasonic treatment for 28 min, the nanoparticles were further uniformly dispersed to prepare a dispersion.
  • the dispersion was electrospun at a spinning rate of 1.6 mL/h at a temperature of 25 ° C and a humidity of 30%: the applied voltage was 18 kV, and the distance between the needle and the receiver was 16.0 cm.
  • the nascent ZnO/para-aramid composite film obtained was removed from the receiver, and dried at 220 ° C for 1.5 h to obtain a para-aramid polymer separator which can be used for a lithium ion battery.
  • the separator was treated at 130 ° C for 1.5 h, the shrinkage was 0.4%, the separator thickness was 36 ⁇ m, the porosity was 91.2%, and the tensile rupture strength was 12.9 MPa.
  • the separator was immersed in 1 mol/L of lithium hexafluorophosphate/ethylene carbonate/ In the electrolytic solution of dimethyl carbonate/diethyl carbonate (mass ratio: 1:1), the obtained liquid absorption rate was 274.7%, the ionic conductivity was 3.02 mS/cm, and the electrochemical stability window was 5.59 V.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
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Abstract

L'invention concerne un procédé de préparation d'un séparateur de polymère de para-aramide fabriqué par électrofilage et utilisé pour une batterie au lithium-ion, consistant à: dissoudre un polymère de para-aramide ou une fibre de para-aramide par ajout d'un cosolvant, puis ajouter des particules nanocéramiques inorganiques à celui-ci pour obtenir un mélange liquide; effectuer une agitation mécanique et une sonification pour disperser les particules céramiques inorganiques uniformément, de manière à obtenir une dispersion; et effectuer l'électrofilage à l'aide de la dispersion pour obtenir un film composite inorganique/organique primaire, puis effectuer le séchage de manière à obtenir un séparateur de polymère de para-aramide fabriqué par électrofilage et utilisé pour une batterie au lithium-ion. Un séparateur de batterie lithium-ion préparé selon la présente invention présente une porosité élevée et une résistance élevée au retrait thermique, ainsi qu'une conductivité ionique élevée et une bonne stabilité électrochimique, améliorant ainsi les performances de sécurité d'une batterie.
PCT/CN2018/115437 2018-04-26 2018-11-14 Procédé de préparation de séparateur de polymère de para-aramide fabriqué par électrofilage et utilisé pour une batterie au lithium-ion WO2019205589A1 (fr)

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CN201810385938.8A CN108666501A (zh) 2018-04-26 2018-04-26 一种以静电纺丝法制取的可用于锂离子电池的对位芳纶聚合物隔膜的制备方法
CN201810385938.8 2018-04-26

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CN114374054A (zh) * 2022-01-14 2022-04-19 惠州市赛能电池有限公司 含硅隔膜及其制备方法、锂电池
CN115275513A (zh) * 2022-07-05 2022-11-01 天津工业大学 一种锌离子电池用聚酰胺6无纺布电池隔膜及其制备方法
CN115341386A (zh) * 2022-08-15 2022-11-15 四川华造宏材科技有限公司 柔性导电复合纳米纤维薄膜及其制备方法
CN117977106A (zh) * 2024-01-10 2024-05-03 上海晨堡新材料科技有限公司 一种锂离子电池隔膜的制备方法
EP4322306A3 (fr) * 2023-07-06 2024-06-05 Yantai Tayho Advanced Materials Research Institute Co. ,Ltd Suspension composite, son procédé de préparation et son utilisation
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CN114725616A (zh) * 2022-04-15 2022-07-08 青岛科技大学 一种无机杂化芳纶纳米纤维隔膜、制备方法及其在锂电池中的应用
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