CN112201845A - Ultra-stable interface semi-solid electrolyte battery composite diaphragm and preparation process thereof - Google Patents
Ultra-stable interface semi-solid electrolyte battery composite diaphragm and preparation process thereof Download PDFInfo
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- CN112201845A CN112201845A CN202011134366.XA CN202011134366A CN112201845A CN 112201845 A CN112201845 A CN 112201845A CN 202011134366 A CN202011134366 A CN 202011134366A CN 112201845 A CN112201845 A CN 112201845A
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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
- 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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- 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
Abstract
The invention discloses a composite diaphragm of a super-stable interface semi-solid electrolyte battery and a preparation process thereof. According to the invention, the solid electrolyte is coated on the surface of the base film, so that an ultra-stable interface of the battery is realized, and the solid electrolyte has high stability, so that a stable interface which is insensitive to the environment is formed between the solid electrolyte and the surface of the negative electrode, the stability of the battery can be ensured when the external temperature changes, and the decomposition and repair strength of the SEI film is reduced, so that the battery is ensured to have long service life, and the battery is suitable for wide popularization and use.
Description
Technical Field
The invention relates to the technical field of battery diaphragms, in particular to a composite diaphragm of a super-stable interface semi-solid electrolyte battery and a preparation process thereof.
Background
A battery that operates by moving lithium ions between a positive electrode and a negative electrode is called a lithium battery, and the lithium ion battery is composed of a positive electrode, a negative electrode, an electrolyte and a separator, and the separator plays an important role in the composition of the lithium ion battery. The conventional diaphragm usually has high molecular porous membranes such as polyethylene, polypropylene and the like, the surface of the high molecular porous membrane is coated with coating films of functional coatings such as ceramics, binders and the like, the conventional diaphragms are mainly used for improving the safety of the battery, providing lithium ion channels and isolating electrons, but a layer of SEI film is arranged on the surface of the negative electrode of the battery, and the stability of the SEI film in the battery is influenced by various factors such as temperature, voltage and the like to generate fluctuation. Therefore, the composite diaphragm of the ultra-stable interface semi-solid electrolyte battery and the preparation process thereof are provided.
Disclosure of Invention
The invention aims to provide a composite diaphragm of a super-stable interface semi-solid electrolyte battery and a preparation process thereof, which aim to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the composite diaphragm of the ultra-stable interface semi-solid electrolyte battery comprises a base film and a coating, wherein the coating is a solid electrolyte coating, and the coating comprises an inorganic solid electrolyte, a dispersing agent, a thickening agent, a binder, a wetting agent and water.
Furthermore, the mass ratio of the inorganic solid electrolyte, the dispersant, the thickener, the binder, the wetting agent and the purified water is 1 (0.003-0.008): (0.03-0.09): 0.03-0.1): 0.004-0.012): 1.0-8.0.
Further, the inorganic solid electrolyte is an oxide solid electrolyte or a sulfide solid electrolyte,
the oxide solid electrolyte is any one of LLZO, ABZ3, LISICON, NASICON and LIPON type ion fast conductors, and the sulfide solid electrolyte is amorphous sulfide solid electrolyte or crystalline sulfide solid electrolyte.
In the technical scheme, the coating is formed by the solid electrolyte, the dispersing agent, the thickening agent, the binder, the wetting agent and the water, so that the solid electrolyte is arranged on the surface of the base film through the coating, the solid electrolyte has higher stability, the stability between the solid point mechanism and the negative electrode is improved, a stable interface is formed, when the battery is charged, the stable interface is less influenced by the environment, the stability of the battery interface in the face of external temperature change can be ensured, the decomposition and repair strength of an SEI film is reduced, and the battery is ensured to have longer service life.
The solid electrolyte can be inorganic solid electrolyte, polymer solid electrolyte and composite solid electrolyte, wherein the inorganic solid electrolyte comprises oxide solid electrolyte and sulfide solid electrolyte, the oxide solid electrolyte is LLTO, ABZ3, LISICON, NASICON, LLZO, LIPON type ion fast conductor and the like, and the sulfide solid electrolyte is amorphous sulfide solid electrolyte and crystalline sulfide solid electrolyte;
the polymer solid electrolyte comprises a solid polymer electrolyte and a gel solid polymer electrolyte, wherein the main components of the gel solid polymer electrolyte are a polymer crystal group, a swollen amorphous phase and a liquid phase communicated in a pore channel, the polymer crystal group mainly comprises PMMA, PVDF-HFP, PEO, PVDF and PAN, and DMC, DEC, DMF, EC, PC and the like can be added into the gel solid polymer electrolyte to serve as a plasticizer;
the composite solid electrolyte is formed by adding inorganic filler into polymer electrolyte; the filler types mainly comprise inorganic inert filler, inorganic active filler and organic porous filler, wherein the inorganic inert filler is AL2O3、TIO2、SIO2MOF, graphene, etc., inorganic active fillers LATP, LAGP, LLTO, LLZO, LGPS, LPOS, etc., organic porous fillers PEO, PAN, etc.
Further, the thickening agent is sodium carboxymethyl cellulose or a mixed thickening agent taking sodium carboxymethyl cellulose as a main component, the dispersing agent is an anionic dispersing agent, the binder is an acrylic binder, and the wetting agent is a silicon ether surfactant.
Further, the base membrane is a polymer porous membrane or a polymer porous membrane coated with a coating layer on the surface, and the polymer porous membrane is one or more of polyethylene, polypropylene, polyimide and polyethylene terephthalate.
Further, the coating layer of the coating film comprises ceramic, a binder and nanocellulose, wherein the ceramic is one or more of alumina, boehmite, magnesium hydroxide, barium sulfate and aluminum hydroxide, and the binder is one or more of polyvinylidene fluoride and polymethyl methacrylate.
In the technical scheme, the binder is one or more of polyvinylidene fluoride, polymethyl methacrylate and AFL, the AFL is mainly a composite product of the polymethyl methacrylate and an acrylic binder, and the acrylic binder is coated on the surface of the polymethyl methacrylate to form a core-shell structure.
Further, the particle size distribution of the inorganic solid electrolyte is 0.1-5.0 microns, the thickness of the coating is 0.2-20 microns, and the thickness of the composite diaphragm is 2-100 microns.
A preparation process of a composite diaphragm of a super-stable interface semi-solid electrolyte battery comprises the following steps:
1) preparing slurry:
adding a dispersing agent into purified water, fully stirring for 10-30 min, adding an inorganic solid electrolyte, and stirring for 20-50 min to prepare an aqueous solution;
diluting a thickening agent, adding an aqueous solution, stirring for 30-60 min, adding a binder, stirring for 30-60 min, adding a wetting agent, and uniformly stirring to obtain a slurry;
2) preparing a coating:
and coating the slurry on the surface of the base film, baking to form a coating, and rolling to obtain the composite diaphragm.
Further, when the base film is a polymer porous film coated with a coating film on the surface, the specific preparation steps include:
a) preparing coating layer slurry:
taking aluminum oxide, magnesium oxide, copper oxide and barium sulfate powder, blending, placing at the temperature of 1000-1200 ℃, preserving heat for 30-60 min, heating to the temperature of 1500-1600 ℃, preserving heat for 2-3 h, cooling in a furnace, adding boehmite, magnesium hydroxide and aluminum hydroxide powder, blending, sintering again to prepare ceramic powder, blending with a coupling agent, and adding a solvent to prepare a dispersion liquid;
blending terephthalic acid and ethylene glycol, adding a catalyst, uniformly mixing, and adding isophthalic acid and butanediol to react to prepare polyester;
taking polyester glycol and isocyanate, adding a catalyst, heating for reaction, cooling, adding triethylamine hydrochloride and deionized water, and shearing and emulsifying to obtain an emulsion;
taking dimethyl siloxane, PEG-30 dipolyhydroxystearate and a thickening agent, slowly adding deionized water at the temperature of 0-20 ℃ and under the pressure of 0.03-0.05 MPa, simultaneously stirring at a high speed for 90-120 min, respectively adding emulsion and nano-cellulose, stirring uniformly at a low speed, respectively adding dispersion liquid, polyester and a binder, stirring at a low speed, and mixing uniformly to prepare coating layer slurry;
b) preparing a base film:
and (3) depositing the coating layer slurry on the surface of the polymer porous membrane at the flow rate of 5-10 mL/h for 6-14 times, heating the surface of the polymer porous membrane to 80-120 ℃ after deposition, preserving heat for 0.5-3 s, performing ultrasonic treatment, drying and cleaning to form a coating layer, and thus obtaining the base membrane. .
In the technical scheme, the plasticity of the prepared ceramic powder is improved by sintering the powdery aluminum oxide and the powdery magnesium oxide at high temperature, the copper oxide and the barium sulfate are mixed, the melting temperature is reduced, the powdery aluminum oxide and the powdery magnesium oxide are melted at high temperature and filled in pores formed by thermal expansion of the aluminum oxide and the magnesium oxide, the sintering and mixing of the copper oxide and the barium sulfate in the ceramic powder are promoted, the dispersity is improved, the prepared ceramic powder is enhanced, the heat conductivity of the prepared ceramic powder is improved, the prepared diaphragm is abnormally heated, the heat can be rapidly transferred to the surface of the base film when the temperature is raised, the base film is promoted to close the pores, the barrier reaction is carried out, the time delay caused by heat transfer is reduced, and the safety performance of the prepared battery is improved; then, the powder is blended with boehmite, magnesium hydroxide and aluminum hydroxide powder and sintered again, so that the chemical and electrochemical corrosion resistance of the prepared ceramic powder can be improved, the leveling property of the prepared coating layer slurry is improved, and the strength and the corrosion resistance of the prepared coating layer are improved;
mixing dimethyl siloxane, PEG-30 dipolyhydroxystearate and a thickening agent, shearing to prepare emulsion droplets, mixing the emulsion droplets with polyurethane emulsion to increase the number of emulsion particles, mixing the emulsion droplets with polyester, a binder and the like to obtain an organic carrier of ceramic powder, promoting the dispersion degree of the ceramic powder in the organic carrier to prepare coating layer slurry, depositing the coating layer slurry on the surface of a polymer porous membrane, forming a porous coating layer with a thinner thickness through a deposition position, performing heat and ultrasonic treatment to break the emulsion particles to form pores, increasing the porosity of a prepared base membrane, avoiding the obstruction of the pores in the polymer porous membrane and promoting the passage of lithium ions, and when the ceramic powder in the coating layer slurry is mixed with the organic carrier, the ceramic powder is positioned at the outer side of the emulsion particles to form the coating layer, avoiding the ceramic powder from being filled in the pores of the base membrane, the ceramic powder is prevented from falling to influence the internal environment of the battery;
the dimethyl siloxane can react with the nano-cellulose to inhibit the swelling of the nano-cellulose, so that the size stability of the prepared coating layer is prevented from being influenced, and the strength of the prepared base film is improved; the melting point of the prepared polyester is reduced by adding the isophthalic acid and the butanediol into the terephthalic acid and the ethylene glycol, a skeleton structure with low melting point is formed when the emulsion particles are wrapped by the polyester, the pore structure of the prepared base film is stabilized, and when the battery is heated abnormally, the pore melting and closing are accelerated, so that the safe use of the battery is ensured.
Compared with the prior art, the invention has the following beneficial effects:
according to the composite diaphragm of the ultra-stable interface semi-solid electrolyte battery and the preparation process thereof, the ultra-stable interface of the battery is realized by coating the solid electrolyte on the surface of the base film, and the solid electrolyte has higher stability, so that a stable interface which is insensitive to the environment is formed between the solid electrolyte and the surface of a negative electrode, the stability of the battery can be ensured when the external temperature changes, the decomposition and repair strength of an SEI film is reduced, and the long service life of the battery is ensured.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1) Preparing slurry:
adding dispersant into purified water, stirring for 100min, adding inorganic solid electrolyte, stirring for 20min to obtain water solution;
diluting the thickening agent, adding the aqueous solution, stirring for 30min, adding the binder, stirring for 30min, adding the wetting agent, and uniformly stirring to obtain slurry;
wherein the inorganic solid electrolyte is LLZO, the particle size distribution of the inorganic solid electrolyte is 0.5 mu m, and the mass ratio of the inorganic solid electrolyte, the dispersant, the thickening agent, the binder, the wetting agent and the purified water is 1:0.003:0.03:0.03:0.004: 1.0;
2) preparing a coating:
and coating the slurry on the surface of a base film, wherein the thickness of the coating is 3 mu m, the base film is a polyethylene porous isolating film prepared by a wet method, and the coating is formed after baking and is rolled to prepare the composite diaphragm.
Example 2
1) Preparing slurry:
adding dispersant into purified water, stirring for 20min, adding inorganic solid electrolyte, stirring for 35min to obtain water solution;
diluting the thickening agent, adding the aqueous solution, stirring for 45min, adding the binder, stirring for 45min, adding the wetting agent, and uniformly stirring to obtain slurry;
wherein the inorganic solid electrolyte is LLZO, the particle size distribution of the inorganic solid electrolyte is 2.5 mu m, and the mass ratio of the inorganic solid electrolyte to the dispersing agent to the thickening agent to the binding agent to the wetting agent to the purified water is 1:0.005:0.06:0.06:0.008: 4.5;
2) preparing a coating:
coating the slurry on the surface of a base film, wherein the thickness of the coating is 10 mu m, the base film is a polyethylene porous isolating film prepared by a wet method, forming a coating after baking, and rolling to obtain the composite diaphragm.
Example 3
1) Preparing slurry:
adding dispersant into purified water, stirring for 30min, adding inorganic solid electrolyte, stirring for 50min to obtain water solution;
diluting the thickening agent, adding the aqueous solution, stirring for 60min, adding the binder, stirring for 60min, adding the wetting agent, and uniformly stirring to obtain slurry;
wherein the inorganic solid electrolyte is LLZO, the particle size distribution of the inorganic solid electrolyte is 0.5 mu m, and the mass ratio of the inorganic solid electrolyte, the dispersant, the thickening agent, the binder, the wetting agent and the purified water is 1:0.008:0.09:0.1:0.012: 8.0;
2) preparing a coating:
coating the slurry on the surface of a base film, wherein the thickness of the coating is 20 microns, the base film is a polyethylene porous isolating film prepared by a wet method, baking to form a coating, and rolling to obtain the composite diaphragm.
Example 4
1) Preparing slurry:
adding dispersant into purified water, stirring for 20min, adding inorganic solid electrolyte, stirring for 35min to obtain water solution;
diluting the thickening agent, adding the aqueous solution, stirring for 45min, adding the binder, stirring for 45min, adding the wetting agent, and uniformly stirring to obtain slurry;
wherein the inorganic solid electrolyte is ABZ3, the particle size distribution of the inorganic solid electrolyte is 2.5 mu m, and the mass ratio of the inorganic solid electrolyte, the dispersant, the thickening agent, the binder, the wetting agent and the purified water is 1:0.005:0.06:0.06:0.008: 4.5;
2) preparing a coating:
coating the slurry on the surface of a base film, wherein the thickness of the coating is 10 mu m, the base film is a polypropylene porous isolating film prepared by a wet method, forming a coating after baking, and rolling to prepare the composite diaphragm.
Example 5
1) Preparing slurry:
adding dispersant into purified water, stirring for 20min, adding inorganic solid electrolyte, stirring for 35min to obtain water solution;
diluting the thickening agent, adding the aqueous solution, stirring for 45min, adding the binder, stirring for 45min, adding the wetting agent, and uniformly stirring to obtain slurry;
wherein the inorganic solid electrolyte is LISICON, the particle size distribution of the inorganic solid electrolyte is 2.5 mu m, and the mass ratio of the inorganic solid electrolyte, the dispersant, the thickening agent, the binder, the wetting agent and the purified water is 1:0.005:0.06:0.06:0.008: 4.5;
2) preparing a coating:
and coating the slurry on the surface of a base film, wherein the thickness of the coating is 10 microns, the base film is a polyimide porous isolating film prepared by a wet method, baking to form a coating, and rolling to obtain the composite diaphragm.
Example 6
1) Preparing slurry:
adding dispersant into purified water, stirring for 20min, adding inorganic solid electrolyte, stirring for 35min to obtain water solution;
diluting the thickening agent, adding the aqueous solution, stirring for 45min, adding the binder, stirring for 45min, adding the wetting agent, and uniformly stirring to obtain slurry;
wherein the inorganic solid electrolyte is NASICON, the particle size distribution of the inorganic solid electrolyte is 2.5 mu m, and the mass ratio of the inorganic solid electrolyte, the dispersant, the thickening agent, the binder, the wetting agent and the purified water is 1:0.005:0.06:0.06:0.008: 4.5;
2) preparing a coating:
coating the slurry on the surface of a base film, wherein the thickness of the coating is 10 mu m, the base film is a polyethylene glycol terephthalate porous isolating film prepared by a wet method, forming a coating after baking, and rolling to prepare the composite diaphragm.
Example 7
1) Preparing slurry:
adding dispersant into purified water, stirring for 20min, adding inorganic solid electrolyte, stirring for 35min to obtain water solution;
diluting the thickening agent, adding the aqueous solution, stirring for 45min, adding the binder, stirring for 45min, adding the wetting agent, and uniformly stirring to obtain slurry;
wherein the inorganic solid electrolyte is LLZO, the particle size distribution of the inorganic solid electrolyte is 2.5 mu m, and the mass ratio of the inorganic solid electrolyte to the dispersing agent to the thickening agent to the binding agent to the wetting agent to the purified water is 1:0.005:0.06:0.06:0.008: 4.5;
a) preparing coating layer slurry:
mixing aluminum oxide, magnesium oxide, copper oxide and barium sulfate powder, keeping the mixture at 1000 ℃ for 30min, heating to 1500 ℃, keeping the temperature for 2h, cooling in a furnace, adding boehmite, magnesium hydroxide and aluminum hydroxide powder, mixing, sintering again to obtain ceramic powder, mixing with a coupling agent, and adding a solvent to obtain a dispersion liquid;
blending terephthalic acid and ethylene glycol, adding a catalyst, uniformly mixing, and adding isophthalic acid and butanediol to react to prepare polyester;
taking polyester glycol and isocyanate, adding a catalyst, heating for reaction, cooling, adding triethylamine hydrochloride and deionized water, and shearing and emulsifying to obtain an emulsion;
taking dimethyl siloxane, PEG-30 dipolyhydroxystearate and a thickening agent, slowly adding deionized water at the temperature of 0 ℃ and under the pressure of 0.03MPa, simultaneously stirring at a high speed for 90min, respectively adding emulsion and nano-cellulose, stirring uniformly at a low speed, respectively adding dispersion liquid, polyester and a binder, stirring at a low speed, and mixing uniformly to prepare coating layer slurry;
b) preparing a base film:
depositing the coating slurry on the surface of a high polymer porous membrane at the flow rate of 5mL/h, wherein the deposition frequency of a polyethylene porous isolating membrane prepared by the high polymer porous membrane through a wet method is 6, heating the surface of the polyethylene porous isolating membrane to 80 ℃ after deposition, preserving heat for 0.5s, simultaneously performing ultrasonic treatment, drying and cleaning to form a coating layer, and preparing a base membrane;
2) preparing a coating:
coating the slurry on the surface of the base film, wherein the thickness of the coating is 10 mu m, baking to form a coating, and rolling to obtain the composite diaphragm.
Example 8
1) Preparing slurry:
adding dispersant into purified water, stirring for 20min, adding inorganic solid electrolyte, stirring for 35min to obtain water solution;
diluting the thickening agent, adding the aqueous solution, stirring for 45min, adding the binder, stirring for 45min, adding the wetting agent, and uniformly stirring to obtain slurry;
wherein the inorganic solid electrolyte is LLZO, the particle size distribution of the inorganic solid electrolyte is 2.5 mu m, and the mass ratio of the inorganic solid electrolyte to the dispersing agent to the thickening agent to the binding agent to the wetting agent to the purified water is 1:0.005:0.06:0.06:0.008: 4.5;
a) preparing coating layer slurry:
taking and mixing aluminum oxide, magnesium oxide, copper oxide and barium sulfate powder, keeping the temperature at 1100 ℃ for 45min, heating to 1550 ℃ and keeping the temperature for 2.5h, cooling in a furnace, adding boehmite, magnesium hydroxide and aluminum hydroxide powder for mixing, sintering again to prepare ceramic powder, mixing with a coupling agent, and adding a solvent to prepare a dispersion liquid;
blending terephthalic acid and ethylene glycol, adding a catalyst, uniformly mixing, and adding isophthalic acid and butanediol to react to prepare polyester;
taking polyester glycol and isocyanate, adding a catalyst, heating for reaction, cooling, adding triethylamine hydrochloride and deionized water, and shearing and emulsifying to obtain an emulsion;
taking dimethyl siloxane, PEG-30 dipolyhydroxystearate and a thickening agent, slowly adding deionized water at the temperature of 10 ℃ and under the pressure of 0.04MPa, simultaneously stirring at a high speed for 105min, respectively adding emulsion and nano-cellulose, stirring uniformly at a low speed, respectively adding dispersion liquid, polyester and a binder, stirring at a low speed, and mixing uniformly to prepare coating layer slurry;
b) preparing a base film:
depositing the coating slurry on the surface of a high polymer porous membrane at a flow rate of 7mL/h, wherein the deposition frequency of a polyethylene porous isolating membrane prepared by the high polymer porous membrane through a wet method is 10 times, heating the surface of the high polymer porous membrane to 100 ℃ after deposition, preserving heat for 1.7s, simultaneously performing ultrasonic treatment, drying and cleaning to form a coating layer, and preparing a base membrane;
2) preparing a coating:
coating the slurry on the surface of the base film, wherein the thickness of the coating is 10 mu m, baking to form a coating, and rolling to obtain the composite diaphragm.
Example 9
1) Preparing slurry:
adding dispersant into purified water, stirring for 20min, adding inorganic solid electrolyte, stirring for 35min to obtain water solution;
diluting the thickening agent, adding the aqueous solution, stirring for 45min, adding the binder, stirring for 45min, adding the wetting agent, and uniformly stirring to obtain slurry;
wherein the inorganic solid electrolyte is LLZO, the particle size distribution of the inorganic solid electrolyte is 2.5 mu m, and the mass ratio of the inorganic solid electrolyte to the dispersing agent to the thickening agent to the binding agent to the wetting agent to the purified water is 1:0.005:0.06:0.06:0.008: 4.5;
a) preparing coating layer slurry:
taking and mixing aluminum oxide, magnesium oxide, copper oxide and barium sulfate powder, keeping the mixture at 1200 ℃ for 60min, heating the mixture to 1600 ℃, keeping the temperature for 3h, cooling the furnace, adding boehmite, magnesium hydroxide and aluminum hydroxide powder, mixing, sintering again to prepare ceramic powder, mixing with a coupling agent, and adding a solvent to prepare a dispersion liquid;
blending terephthalic acid and ethylene glycol, adding a catalyst, uniformly mixing, and adding isophthalic acid and butanediol to react to prepare polyester;
taking polyester glycol and isocyanate, adding a catalyst, heating for reaction, cooling, adding triethylamine hydrochloride and deionized water, and shearing and emulsifying to obtain an emulsion;
taking dimethyl siloxane, PEG-30 dipolyhydroxystearate and a thickening agent, slowly adding deionized water at the temperature of 20 ℃ and under the pressure of 0.05MPa, simultaneously stirring at a high speed for 120min, respectively adding emulsion and nano-cellulose, stirring uniformly at a low speed, respectively adding dispersion liquid, polyester and a binder, stirring at a low speed, and mixing uniformly to prepare coating layer slurry;
b) preparing a base film:
depositing coating slurry on the surface of a high polymer porous membrane at the flow rate of 10mL/h, wherein the deposition frequency of a polyethylene porous isolating membrane prepared by the high polymer porous membrane through a wet method is 14, heating the surface of the polyethylene porous isolating membrane to 120 ℃ after deposition, preserving heat for 3s, simultaneously carrying out ultrasonic treatment, drying and cleaning to form a coating layer, and preparing a base membrane;
2) preparing a coating:
coating the slurry on the surface of the base film, wherein the thickness of the coating is 10 mu m, baking to form a coating, and rolling to obtain the composite diaphragm.
Experiment of
Samples were prepared from the composite separators obtained in examples 1 to 9 and conventional battery separators, and the porosity, air permeability, closed cell temperature, thermal stability and battery capacity retention rate of the prepared batteries were measured and recorded:
the method for testing the capacity retention rate of the battery comprises the following steps: the prepared battery is charged to 4.2V at constant current and constant voltage with the current of 0.5C, then charged at constant voltage until the current is reduced to 0.05C and cut off, then discharged to 3.0V at the current of 1.0C, the discharge capacity is recorded, the discharge capacity under 0.2C is 100 percent, and the corresponding battery capacity retention rate is calculated, wherein the battery capacity retention rate is (the discharge capacity under the rate discharge/the discharge capacity under 0.2C) multiplied by 100 percent
Testing the porosity of the prepared diaphragm by taking GB/T33052-2016 as a test standard;
testing the air permeability of the prepared diaphragm by taking GB/T36363-2018 as a test standard;
testing the thermal shrinkage rate of the prepared diaphragm by taking GB/T34848-2017 as a test standard;
from the data in the table above, it is clear that the following conclusions can be drawn:
the composite diaphragm obtained in the examples 1 to 9 is compared with a conventional battery diaphragm and a battery manufactured by the conventional battery diaphragm, and the detection result shows that the porosity and the air permeability of the composite diaphragm and the conventional battery diaphragm in the examples 1 to 3 are improved, the battery capacity retention rate of the battery manufactured by the conventional battery diaphragm is improved, the thermal shrinkage rate is reduced, and the closed pore temperature is not obviously changed, which fully indicates that the invention improves the thermal stability of the composite diaphragm and improves the mobility of lithium ions in the diaphragm; in addition, compared with the examples 4 to 6, the inorganic electrolyte and the base film materials of the examples 1 to 3 are different, and the porosity, the air permeability, the closed pore temperature and the thermal stability are correspondingly changed, so that the combination of different materials can affect the performance of the prepared composite diaphragm;
compared with the embodiment 2, the base film materials of the embodiments 7 to 9 are different, and comprise the polymer porous film and the coating layer, the porosity and the battery capacity retention rate of the manufactured battery are improved, the thermal shrinkage rate and the closed pore temperature are reduced, and the change of the air permeability is not obvious.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A composite diaphragm of a super-stable interface semi-solid electrolyte battery is characterized in that: the composite diaphragm comprises a base film and a coating, wherein the coating is a solid electrolyte coating, and the coating comprises an inorganic solid electrolyte, a dispersing agent, a thickening agent, a binder, a wetting agent and water.
2. The ultra-stable interface semi-solid electrolyte battery composite separator membrane of claim 1, wherein: the mass ratio of the inorganic solid electrolyte, the dispersant, the thickener, the binder, the wetting agent and the purified water is 1 (0.003-0.008): 0.03-0.09): 0.03-0.1): 0.004-0.012): 1.0-8.0.
3. The ultra-stable interface semi-solid electrolyte battery composite separator membrane of claim 1, wherein: the inorganic solid electrolyte is an oxide solid electrolyte or a sulfide solid electrolyte,
the oxide solid electrolyte is any one of LLZO, ABZ3, LISICON, NASICON and LIPON type ion fast conductors, and the sulfide solid electrolyte is amorphous sulfide solid electrolyte or crystalline sulfide solid electrolyte.
4. The ultra-stable interface semi-solid electrolyte battery composite separator membrane of claim 1, wherein: the thickening agent is sodium carboxymethyl cellulose or a mixed thickening agent taking sodium carboxymethyl cellulose as a main component, the dispersing agent is an anionic dispersing agent, the binder is an acrylic acid binder, and the wetting agent is a silicon ether surfactant.
5. The ultra-stable interface semi-solid electrolyte battery composite separator membrane of claim 1, wherein: the base membrane is a polymer porous membrane or a polymer porous membrane coated with a coating layer on the surface, and the polymer porous membrane is one or more of polyethylene, polypropylene, polyimide and polyethylene terephthalate.
6. The ultra-stable interface semi-solid electrolyte battery composite separator membrane of claim 5, wherein: the coating layer comprises ceramic, a binder and nanocellulose, the ceramic is one or more of alumina, boehmite, magnesium hydroxide, barium sulfate and aluminum hydroxide, and the binder is one or more of polyvinylidene fluoride and polymethyl methacrylate.
7. The ultra-stable interface semi-solid electrolyte battery composite separator membrane of claim 1, wherein: the particle size distribution of the inorganic solid electrolyte is 0.1-5.0 mu m, the thickness of the coating is 0.2-20 mu m, and the thickness of the composite diaphragm is 2-100 mu m.
8. A preparation process of a composite diaphragm of a super-stable interface semi-solid electrolyte battery is characterized by comprising the following steps:
1) preparing slurry:
adding a dispersing agent into purified water, fully stirring for 10-30 min, adding an inorganic solid electrolyte, and stirring for 20-50 min to prepare an aqueous solution;
diluting a thickening agent, adding an aqueous solution, stirring for 30-60 min, adding a binder, stirring for 30-60 min, adding a wetting agent, and uniformly stirring to obtain a slurry;
2) preparing a coating:
and coating the slurry on the surface of the base film, baking to form a coating, and rolling to obtain the composite diaphragm.
9. The preparation process of the ultra-stable interface semi-solid electrolyte battery composite diaphragm according to claim 8, characterized in that: when the base membrane is a polymer porous membrane with a coating membrane coated on the surface, the preparation method specifically comprises the following steps:
a) preparing coating layer slurry:
taking aluminum oxide, magnesium oxide, copper oxide and barium sulfate powder, blending, placing at the temperature of 1000-1200 ℃, preserving heat for 30-60 min, heating to the temperature of 1500-1600 ℃, preserving heat for 2-3 h, cooling in a furnace, adding boehmite, magnesium hydroxide and aluminum hydroxide powder, blending, sintering again to prepare ceramic powder, blending with a coupling agent, and adding a solvent to prepare a dispersion liquid;
blending terephthalic acid and ethylene glycol, adding a catalyst, uniformly mixing, and adding isophthalic acid and butanediol to react to prepare polyester;
taking polyester glycol and isocyanate, adding a catalyst, heating for reaction, cooling, adding triethylamine hydrochloride and deionized water, and shearing and emulsifying to obtain an emulsion;
taking dimethyl siloxane, PEG-30 dipolyhydroxystearate and a thickening agent, slowly adding deionized water at the temperature of 0-20 ℃ and under the pressure of 0.03-0.05 MPa, simultaneously stirring at a high speed for 90-120 min, respectively adding emulsion and nano-cellulose, stirring uniformly at a low speed, respectively adding dispersion liquid, polyester and a binder, stirring at a low speed, and mixing uniformly to prepare coating layer slurry;
b) preparing a base film:
and (3) depositing the coating layer slurry on the surface of the polymer porous membrane at the flow rate of 5-10 mL/h for 6-14 times, heating the surface of the polymer porous membrane to 80-120 ℃ after deposition, preserving heat for 0.5-3 s, performing ultrasonic treatment, drying and cleaning to form a coating layer, and thus obtaining the base membrane.
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