WO2018068745A1 - Method for preparing lithium ion battery separator with high temperature resistance and low electrical resistivity - Google Patents

Method for preparing lithium ion battery separator with high temperature resistance and low electrical resistivity Download PDF

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Publication number
WO2018068745A1
WO2018068745A1 PCT/CN2017/105853 CN2017105853W WO2018068745A1 WO 2018068745 A1 WO2018068745 A1 WO 2018068745A1 CN 2017105853 W CN2017105853 W CN 2017105853W WO 2018068745 A1 WO2018068745 A1 WO 2018068745A1
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Prior art keywords
coating
slurry
graphene
mixed slurry
battery separator
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PCT/CN2017/105853
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French (fr)
Chinese (zh)
Inventor
徐锋
袁海朝
邓云飞
马文献
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河北金力新能源科技股份有限公司
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Publication of WO2018068745A1 publication Critical patent/WO2018068745A1/en

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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
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the technical field of battery separators, and in particular relates to a preparation method of a high temperature and low resistivity lithium ion battery separator.
  • the basic function of the battery separator in the lithium battery is to separate the positive and negative electrodes, and the adsorption of the electrolyte allows lithium ions to pass.
  • 3C products including Computer, Communication, and Consumer Electronics, are the main areas of lithium battery applications.
  • PP separators and PE separators can be used to obtain performance. Better satisfaction.
  • the performance of lithium batteries must be further improved to meet the requirements of electric vehicles. For example, in terms of safety, charge and discharge performance, cycle performance and rate, lithium batteries for electric vehicles are more suitable than 3C products. Lithium batteries have more stringent requirements.
  • the main research direction is the membrane coating treatment, that is, coating a ceramic slurry on the surface of the membrane.
  • ceramic coated separator is the most effective way to improve the safety of lithium batteries. After coating the ceramic slurry, the separator can effectively improve the heat shrinkage, safety, thermal stability and mechanical strength of the separator. To extend the life of the diaphragm.
  • the preparation method of the new lithium battery separator such as adding a graphene or the like to modify the coated diaphragm, has received more and more attention.
  • Graphene has been researched and applied more frequently in batteries due to its excellent mechanical properties and heat resistance and the ability to significantly increase the specific energy of the battery in batteries.
  • the high temperature resistance and heat shrinkage of ceramic coated separators cannot meet the requirements under certain temperature conditions, and the use of graphene modified ceramic coated separators can make lithium battery separators heat resistant and heat resistant.
  • the present invention provides a method for preparing a high temperature and low resistivity lithium ion battery separator, which is a mature and stable preparation process, and the produced battery separator has a coating slurry.
  • the dense, uniform, strong adhesion and low heat shrinkage of the material layer significantly improve the safety performance and service life of the battery.
  • a method for preparing a high temperature and low resistivity lithium ion battery separator wherein the battery separator comprises a base film and a coating slurry layer coated on one end surface or both end surfaces thereof, and the coating slurry layer material is
  • the ceramic slurry or the graphene-modified ceramic slurry has a coating slurry layer having at least one end surface on both end faces of the base film as a graphene-modified ceramic slurry, and the method for preparing the battery separator of the above structure comprises the following steps:
  • Deionized water and ceramic powder having a particle size of 0.05-1 ⁇ m are added to the planetary mixer at a weight ratio of (5-30): (95-70), and the planetary stirrer is equipped with an input ultrasonic vibration plate, followed by stirring at the same time. And ultrasonic vibration, the stirring speed is not less than 1000r / min, continuous for 0.5-2h, forming a first-stage mixed slurry;
  • N-methylpyrrolidone Adding N-methylpyrrolidone, alcohol, propylene carbonate, and sweet to the secondary mixed slurry
  • At least one of oil, dimethyl sulfoxide, polyoxyethylene alkyl phenol ether, polyoxyethylene fatty alcohol ether, and polyvinyl alcohol is added in an amount of 0.5-10% of the secondary mixed slurry while stirring and Ultrasonic vibration, stirring speed is not less than 1000r/min, continuous for 0.5-2h, forming a three-stage mixed slurry;
  • a 50% aqueous acrylic latex emulsion and a 2% sodium carboxymethylcellulose solution are added, and the aqueous acrylic latex emulsion and the sodium carboxymethylcellulose solution are respectively added.
  • 0.5-10% and 0.3-5% of the four-stage mixed slurry while stirring and ultrasonic vibration, the stirring speed is not less than 1000r/min, and the continuous mixing is performed for 0.5-2h to form a five-stage mixed slurry;
  • Ozone air leaching or corona treatment on the surface of the base film Ozone air leaching or corona treatment on the surface of the base film, ozone flow rate is 0.5-5L/min, and air shower time is 5-120 s;
  • the pretreated base film is placed on a micro gravure coater, and the graphene-modified ceramic slurry is placed in a liquid storage tank of a micro gravure coater to start a coating machine for coating work, and the coating speed is applied.
  • the coating thickness is maintained at 1-5 ⁇ m for 5-20 m/min. After coating, drying and winding are performed to obtain a high temperature resistant low resistivity lithium ion battery separator.
  • the invention has the beneficial effects that the preparation method of the invention provides a stable and high-efficiency process for producing a high temperature resistant low-resistivity lithium ion battery separator, and the method can improve the microstructure and properties of the slurry by adding a dispersant, so as to add components later.
  • the distribution is more uniform, and the prepared graphene-modified ceramic slurry is moderate in viscosity and suitable for coating, and the slurry has both low shrinkage rate at high temperature of the ceramic slurry and High safety, and high conductivity of graphene material at normal temperature and low electrical conductivity at high temperature.
  • it can not only further improve the low shrinkage rate and safety of the lithium ion battery at high temperatures.
  • the heat resistance stability and the heat shrinkage rate are greatly improved, and the charging speed of the lithium ion battery can be greatly improved, the specific energy of the battery can be improved, and the closed hole at a high temperature state can be realized to prevent the battery from further reacting.
  • the battery charge and discharge function is automatically restored at normal temperature, which greatly enhances the market competitiveness, so that when it is applied in the field of electric vehicles, it solves the shortcomings of charging time of electric vehicles, and is a clean energy vehicle.
  • Development provides technical support.
  • the invention provides a preparation method of a high temperature resistant low resistivity lithium ion battery separator, wherein the battery separator comprises a base film and a coating slurry layer coated on one end surface or both end surfaces thereof, and the coating slurry
  • the material of the material layer is ceramic slurry or graphene modified ceramic slurry
  • the coating slurry layer having at least one end surface on both end faces of the base film is made of graphene modified ceramic slurry.
  • Deionized water and ceramic powder having a particle size of 0.05-1 ⁇ m are added to the planetary mixer at a weight ratio of (5-30): (95-70), and the planetary stirrer is equipped with an input ultrasonic vibration plate, followed by stirring at the same time. And ultrasonic vibration, the stirring speed is not less than 1000r / min, continuous for 0.5-2h, forming a first-stage mixed slurry;
  • N-methylpyrrolidone Adding N-methylpyrrolidone, alcohol, propylene carbonate, and sweet to the secondary mixed slurry
  • At least one of oil, dimethyl sulfoxide, polyoxyethylene alkyl phenol ether, polyoxyethylene fatty alcohol ether, and polyvinyl alcohol (for convenience of description, the present invention also collectively refers to the aforementioned substances as "stabilizers")
  • the amount of addition is 0.5-10% of the secondary mixed slurry, while stirring and ultrasonic vibration, the stirring speed is not less than 1000r/min, and the continuous stirring is performed for 0.5-2h to form a three-stage mixed slurry;
  • a 50% aqueous acrylic latex emulsion and a 2% sodium carboxymethylcellulose solution are added, and the aqueous acrylic latex emulsion and the sodium carboxymethylcellulose solution are respectively added.
  • 0.5-10% and 0.3-5% of the four-stage mixed slurry while stirring and ultrasonic vibration, the stirring speed is not less than 1000r/min, and the continuous mixing is performed for 0.5-2h to form a five-stage mixed slurry;
  • Ozone air leaching or corona treatment on the surface of the base film Ozone air leaching or corona treatment on the surface of the base film, ozone flow rate is 0.5-5L/min, and air shower time is 5-120 s;
  • the pretreated base film is placed on a micro gravure coater, and the graphene-modified ceramic slurry is placed in a liquid storage tank of a micro gravure coater to start a coating machine for coating work, and the coating speed is applied.
  • the coating thickness is maintained at 1-5 ⁇ m for 5-20 m/min. After coating, drying and winding are performed to obtain a high temperature resistant low resistivity lithium ion battery separator.
  • the base film is a single layer, a double layer or a plurality of layers of PP, PE, a nonwoven fabric or a fiber material, and the base film has a thickness of 6 to 30 ⁇ m.
  • the ceramic powder is aluminum oxide, zirconium oxide, silicon oxide, or oxidation. At least one of magnesium, zinc oxide, and titanium dioxide.
  • the planetary mixer has a multi-blade agitating paddle, and the agitating paddle can realize the rotation while revolving, so that the material can flow up and down and around, so that the mixing can be achieved in a short time.
  • the inner wall of the tank is finished by a large vertical car, and then automatically polished by a large polishing machine, thereby ensuring that the movable scraper on the planet carrier completely scrapes off the material on the inner wall when rotating.
  • the input ultrasonic vibration plate can be position-selected and fixedly installed according to the spatial structure of the planetary mixer.
  • the upper cover of the planetary mixer In order to reduce the interference with the blade and facilitate the connection, it is preferably fixed at the bottom of the upper cover of the planetary mixer, when the planetary mixer is working, The upper cover lowers the sealing port, so that the input ultrasonic plate is immersed in the slurry to function as an ultrasonic vibration.
  • the dispersing agent is at least one of sodium polyacrylate, sodium polymetaphosphate, sodium silicate, and sodium lauryl sulfate, and a pH adjuster is further added to the dispersing agent.
  • the conditioning agent is selected from the group consisting of sodium orthophosphate, aqueous ammonia or a mixture of the two, adjusted to a pH between 7.5 and 8.5, more preferably adjusted to a pH of 8.
  • the dispersing agent not only has a dispersing effect, but also the sodium polyacrylate has the effects of thickening, stabilizing, water retaining and fresh keeping; the polymetaphosphate can prevent discoloration, increase viscosity, increase viscosity, improve expansion capacity, and enhance Emulsification, prevention of gel precipitation, prevention of turbidity, protection of food color, improvement of corrosion resistance and pH adjustment; sodium lauryl sulfate has good emulsification, foaming, penetrating and decontaminating properties.
  • the dispersing agent has a good dispersing effect at a pH of between 7.5 and 8.5, so that sodium orthophosphate, ammonia or a mixture of the two may be added to the dispersing agent depending on the actual situation.
  • ammonia can play the role of dissolving and adjusting the pH.
  • the sodium orthophosphate is almost completely decomposed into disodium hydrogen phosphate and sodium hydroxide in water, and can also be used to adjust the pH.
  • ammonia water is used to adjust the pH, and when the ammonia water is used in combination with the dispersant, the dispersion effect of the slurry can be further improved and the slurry can be more stable.
  • N-methylpyrrolidone also has a solvent or a dispersing agent;
  • alcohol is a solvent capable of dissolving various organic and inorganic substances;
  • propylene carbonate It has a dispersing action;
  • glycerin has a solvent and a thickener; dimethyl sulfoxide is used as a solvent;
  • polyoxyethylene alkyl phenol ether is a surfactant;
  • polyoxyethylene fatty alcohol ether is a defoaming agent;
  • Vinyl alcohol is a kind of coating adhesive, and the above substances can all stabilize, avoid reaction inside the slurry and facilitate storage of the slurry.
  • the sieve used is 200 mesh.
  • the weight ratio of deionized water to the ceramic powder is (10-30): (90-70), and the first-stage mixed slurry is added with a substance (ie, a dispersant).
  • the ratio is 2-4%
  • the proportion of the added substance (ie, stabilizer) in the secondary mixed slurry is 5-10%
  • the proportion of graphene added in the tertiary mixed slurry is 0.5-1.5. %
  • the aqueous acrylic latex emulsion and the sodium carboxymethylcellulose solution in the four-stage mixed slurry are added in an amount of 3-8% and 1-5%, respectively.
  • the weight ratio of deionized water to the ceramic powder is 1:4 (ie, 20:80), and the proportion of the added material in the first-stage mixed slurry is 3%, in the secondary mixed slurry.
  • the proportion of the added material is 6%
  • the proportion of graphene added in the three-stage mixed slurry is 1%
  • the amount of the aqueous acrylic latex emulsion and the sodium carboxymethylcellulose solution in the fourth-stage mixed slurry are respectively increased.
  • the proportion is 6% and 3%.
  • an ozone generator can be used to generate ozone, and then the surface of the base film is subjected to air leaching.
  • the ozone is a strong oxidant, which oxidizes the surface of the plastic to generate a chemical reaction such as a hydroxy compound or a peroxy compound.
  • the adhesion of the membrane surface can be significantly improved, which is a chemical method to improve the adhesion of the base film surface.
  • the function of the step B is mainly to enhance the adhesion of the surface of the base film. Therefore, the base film can be treated by a corona method or the like, and the corona method is to physically improve the adhesion of the surface of the diaphragm. Applying high-frequency high-voltage electricity to the processing device to corona discharge, producing a small dense purple-blue spark, and various plasmas generated after air ionization are in a strong electric field. The surface of the base film in the impact treatment device is accelerated. The energy of the plasma particles is generally several to several tens of electron volts, which is close to the chemical bond energy of the plastic molecules. Therefore, the chemical bond cleavage of the molecules on the surface of the base film can be optimized to degrade. Increase the surface roughness to improve the adhesion of the base film surface.
  • the flow rate of the ozone is 1-4 L/min, and the air rinsing time is 30-100 s; more preferably, the flow rate of the ozone is 3 L/min, and the treatment time is 80 s.
  • the coater has a coating speed of 10 to 15 m/min and a coating thickness of 2 to 4 ⁇ m.
  • the coater has a coating speed of 12 m/min and a coating thickness of 3 ⁇ m. More preferably, in step C, the coating machine has a coating thickness of 2 ⁇ m.
  • the coating thickness means dry thickness.
  • the coating thickness is preferably monitored online by using a ray thickness gauge
  • the coating machine is provided with a control unit
  • the information output end of the ray thickness gauge is connected to the information input end of the control unit, the control
  • the information output end of the unit is connected to the control end of the coating machine power mechanism, and the ray thickness gauge transmits the collected coating thickness information to the control unit; when the coating thickness is normal, the control unit does not send an instruction to the coating machine;
  • the control unit sends a command to the coating maneuver, the speed of the coating machine power mechanism is increased, and the coating thickness is reduced to a normal range; when the coating thickness is too small, the control unit sends a command to the coater to apply
  • the machine power mechanism reduces the rotational speed and increases the coating thickness to the normal range.
  • the base film when applying the coating slurry layer, may be selected to be coated on one side, double-coated, or coated in a combined form, and in addition, The base film after the multi-layer coating is composited.
  • the graphene-modified ceramic slurry may be coated on one side or both sides of the base film, or the ceramic slurry may be coated on one end surface and the other end surface coated.
  • the graphene-modified ceramic slurry may be coated with a ceramic slurry on one end surface of the base film, and then the graphene-modified ceramic slurry may be further coated on the same side end surface.
  • the coating process on the coater includes base film unwinding, base film coating, and baking styling.
  • the coating process comprises:
  • base film unwinding the base film release reel releases the base film, and moves the base film toward the take-up reel, wherein the unwinding tension of the base film reel to the base film is 15-30N;
  • Base film coating the base film passes through the anilox rolls on both sides, and the anilox roll is pressed against the corresponding end surface of the base film, and the slurry (graphene modified ceramic slurry and/or ceramic slurry) Adhering to the corresponding one end surface of the base film to form a coated separator;
  • the coating membrane enters the heating and drying mechanism and is dried to obtain a battery separator
  • the heating and drying mechanism may be an oven, the heating mode of the oven is infrared heating, the heating temperature is between 50-70 ° C, and the time for conveying the coating membrane through the oven is 0.6-1.8 min, the coating The tension of the diaphragm in the heating and drying mechanism is maintained at 7-15N;
  • the reel is used to wind up the battery separator, and the tension of the winding is 4-12N.
  • the battery separator produced by the preparation method of the present invention generally has the following properties, and has an areal density of 10 to 50 g/m 2 , a thickness of 10 to 30 ⁇ m, an average pore diameter of 0.02 to 0.1 ⁇ m, and a porosity of 50 to 70%, and the battery of the present invention.
  • the separator material can also be used as a nickel-hydrogen battery separator and a filter material.
  • the battery separator has the characteristics of compactness, uniformity, firm adhesion, and small heat shrinkage of the diaphragm, and improves the safety performance of the lithium ion battery. Extending battery life has a significant effect.
  • the lithium battery made of the battery separator coated with the graphene-modified ceramic slurry has a small size and weight, and the energy storage density is increased by several tens of times, and more importantly, lithium.
  • the separator in the battery is in contact with the electrode through the electrolyte.
  • the graphene in the coating on the surface of the diaphragm can greatly improve the performance of the interface, such as increasing the contact area and improving the resistance of lithium ions to shuttle through the diaphragm, reducing the internal resistance and making the lithium ion pass through.
  • the battery charging time is calculated from the previous hours, changed to minutes or even seconds, the charging speed is greatly improved, applied to electric vehicles In the charging, it can almost match the speed of the refueling of traditional cars, and even faster.
  • An electric car consumes 10 minutes on a single charge, and the cruising range that can be reached is 1000 kilometers.
  • the gas permeability of the battery separator was tested in accordance with GB/T 458-2008, the tensile properties were measured in accordance with GB 13022-91, and the heat shrinkage rate was tested in accordance with GB/T 12027-2004.
  • the acupuncture strength was as follows. Measured: Using a tip hemispherical needle with a diameter of 1 mm, select the extrusion test on a mechanical tensile tester, pierce the diaphragm vertically, and record the maximum load (test conditions: test speed: 250 mm/min, maximum displacement between clamps: 10- 20mm).
  • the inner tank of the planetary mixer used is a multi-blade mixing paddle.
  • the inner wall of the tank is finished by a large vertical car, and then automatically polished by a large polishing machine.
  • the planetary mixer is equipped with an input ultrasonic vibration plate and fixed on the planetary mixer. At the bottom of the cover, when the mixer is working, the upper cover lowers the sealing port, and the input type ultrasonic vibration plate is immersed in the slurry.
  • the coating machine used is provided with a control unit, and the information output end of the ray thickness gauge is connected with the information input end of the control unit, and the information output end of the control unit is connected with the control end of the coating machine power mechanism, and the ray thickness gauge will collect
  • the coating thickness information is transmitted to the control unit.
  • the control unit does not send an instruction to the coating machine.
  • the control unit sends an instruction to the coating maneuver, and the coating machine power mechanism is accelerated.
  • the rotation speed reduces the coating thickness to the normal range.
  • the control unit sends a command to the coater, the coating machine power mechanism reduces the rotation speed, increases the coating thickness to the normal range, and is controlled by the control unit and the radiation.
  • This preparation example is for explaining the preparation method of the ordinary ceramic slurry used in the following examples and comparative examples.
  • Deionized water and alumina powder having a particle size of 0.5 ⁇ m were added to the planetary mixer at a weight ratio of 1:4.
  • the planetary mixer was started, and the input ultrasonic plate was immersed in the slurry while stirring and ultrasonically oscillating. Work, stirring speed is 1200r/min, continuous for 1h, forming First stage mixed slurry;
  • Sodium polyacrylate was added to the first-stage mixed slurry, and then the pH was adjusted to 8 by adding ammonia water, and the sodium polyacrylate was added in an amount of 3% by weight of the first-stage mixed slurry, followed by stirring and ultrasonic vibration, and the stirring speed was 1200 r/ Min, continued for 1 h to form a secondary mixed slurry;
  • a 50% aqueous acrylic latex emulsion and a 2% sodium carboxymethylcellulose solution were added to the tertiary mixed slurry, and the aqueous acrylic latex emulsion and the sodium carboxymethylcellulose solution were respectively added to the fourth grade.
  • Sodium polyacrylate was added to the first-stage mixed slurry, and then the pH was adjusted to 8 by adding ammonia water, and the sodium polyacrylate was added in an amount of 3% by weight of the first-stage mixed slurry, followed by stirring and ultrasonic vibration, and the stirring speed was 1200 r/ Min, continued for 1 h to form a secondary mixed slurry;
  • a 50% aqueous acrylic latex emulsion and a 2% sodium carboxymethylcellulose solution were added to the four-stage mixed slurry, and the aqueous acrylic latex emulsion and the sodium carboxymethylcellulose solution were respectively added to the fourth grade.
  • the ozone generator is used to generate ozone to carry out ozone air shower on the surface of the base film, the flow rate of ozone is 3L/min, the air shower time is 80s, and the base film is made of a single layer of PP material;
  • the pre-treated base film is placed on a micro-gravure coating machine, and the graphene-modified ceramic slurry is placed in a liquid storage tank of the micro-gravure coating machine by a diaphragm pump, and the coating machine is started to perform coating work, and the radiation is measured.
  • the thickness of the coating is monitored on-line to maintain the coating speed of the coating machine at 12 m/min and the coating thickness is maintained at 2 ⁇ m.
  • the coating process specifically includes:
  • Base film coating the base film passes through the anilox rolls on both sides, and the anilox roll is pressed against the corresponding end surface of the base film, and the graphene-modified ceramic slurry is adhered to the corresponding one of the base film.
  • the side end face On the side end face;
  • a common ceramic slurry is coated on the other end surface of the base film to form a modified coated separator
  • the modified coating diaphragm enters the oven.
  • the heating method in the oven is infrared heating, the heating temperature is 60 °C, the time of conveying the diaphragm through the oven is 1.2 min, and the tension of the modified coating diaphragm in the oven is 10N. After baking and setting, the battery separator is obtained;
  • the reel is used to wind up the finished product of the battery separator, and the tension of the winding is 8N.
  • the thickness of the common ceramic coating and the graphene-modified coating formed on the separator are respectively about 2 ⁇ m
  • the thickness of the base film is about 16 ⁇ m
  • the battery separator is recorded as 16B+2+2G, the properties of the membrane. See Table 1.
  • a battery separator was prepared according to the method of Example 1, except that the sodium polyacrylate of Example 1 was replaced with an equal weight of sodium polymetaphosphate, and aqueous ammonia was added to adjust the pH to 8, while the same weight of polyethylene was used for the alcohol. Alcohol replacement, thereby producing a battery separator in which the thickness of the common ceramic coating and the graphene-modified coating formed on the separator are respectively about 2 ⁇ m, and the thickness of the base film is about 16 ⁇ m, and the battery separator is recorded as 16B+2+2G', the properties of the film are shown in Table 1.
  • a battery separator was prepared according to the method of Example 1, except that the amount of sodium polyacrylate of Example 1 was adjusted to 2% of the first-stage mixed slurry, and the amount of alcohol added was adjusted to 9% of the secondary mixed slurry.
  • a battery separator is obtained, wherein the thickness of the common ceramic coating and the graphene-modified coating formed on the separator is about 2 ⁇ m, and the thickness of the base film is about 16 ⁇ m, which is recorded as 16B+2+2G.
  • the properties of the membrane are shown in Table 1.
  • a battery separator was prepared according to the method of Example 1, except that the amount of sodium polyacrylate of Example 1 was adjusted to 5% of the first-stage mixed slurry, and the amount of alcohol added was adjusted to 10% of the secondary mixed slurry.
  • a battery separator is obtained, wherein the thickness of the common ceramic coating and the graphene-modified coating formed on the separator is about 2 ⁇ m, and the thickness of the base film is about 16 ⁇ m, which is recorded as 16B+2+2G. ', the properties of the membrane are shown in Table 1.
  • a battery separator was prepared by the method of Example 1, except that a common ceramic slurry was coated on both end faces of the base film to prepare a battery separator in which the two end faces of the separator were formed.
  • the thickness of the ceramic coating is about 2 ⁇ m
  • the thickness of the base film is about 16 ⁇ m, which is recorded as 16B+2+2.
  • the properties of the film are shown in Table 1.
  • 16B means a base film of about 16 ⁇ m thick used in the above embodiment, which has a porosity of 45%, an average pore diameter of 0.08 ⁇ m, and a closed cell temperature of about 134 °C.

Abstract

The present invention belongs to the technical field of battery separators, and relates to a method for preparing a lithium ion battery separator with a high temperature resistance and low electrical resistivity. The battery separator comprises a base film and a coating slurry layer coated on one or both of the end surfaces of the base film, wherein the material of the coating slurry layer is a ceramic slurry or a graphene-modified ceramic slurry, and the material of the coating slurry layer on at least one of the two end surfaces of the base film is a graphene-modified ceramic slurry. The steps for the preparation of the separator comprise preparing the graphene-modified ceramic slurry, pre-treating the base film, and coating and drying, wherein in the preparation of the graphene-modified ceramic slurry, a dispersant, a stabilizer, graphene, an aqueous acrylic latex and a sodium carboxymethylcellulose solution are sequentially added, the resulting slurry has a stable performance, and further has the advantages of ceramic slurries and graphene materials. The battery separator formed by coating the base film with the slurry has a low shrinkage rate at high temperature and a high safety, allows for a high battery charging rate, and is suitable for high-temperature operations for electromobiles, etc. and industries requiring fast-charging batteries, etc.

Description

一种耐高温低电阻率锂离子电池隔膜的制备方法Method for preparing high temperature and low resistivity lithium ion battery separator 技术领域Technical field
本发明属于电池隔膜技术领域，具体涉及一种耐高温低电阻率锂离子电池隔膜的制备方法。The invention belongs to the technical field of battery separators, and in particular relates to a preparation method of a high temperature and low resistivity lithium ion battery separator.
背景技术Background technique
电池隔膜在锂电池中的基本作用为隔开正负极，并且吸附电解液允许锂离子通过。3C产品包括计算机(Computer)、通信(Communication)和消费类电子产品(Consumer Electronics)，是锂电池应用的主要领域，对于3C产品的锂电池，仅使用PP隔膜和PE隔膜，其性能就能得到较好的满足。但是随着电动汽车的不断发展，锂电池的性能必须进一步提升才能满足电动汽车的要求，比如在安全性、充放电性能、循环性能及倍率性等方面，电动汽车用锂电池就比3C产品用锂电池有更加严格的要求。目前，在提高锂电池隔膜性能方面的发展研究以改善隔膜表面性质和调整隔膜基体材料为主。在改善隔膜表面性质方面，主要的研究方向是隔膜涂布处理，即在隔膜表面涂覆一层陶瓷浆料。就目前情况来看，陶瓷涂布隔膜是提高锂电池安全性最有效的方式，隔膜涂布陶瓷浆料后可有效提高隔膜的耐热收缩性、安全性、热稳定性并改善隔膜的机械强度，从而延长隔膜的使用寿命。The basic function of the battery separator in the lithium battery is to separate the positive and negative electrodes, and the adsorption of the electrolyte allows lithium ions to pass. 3C products, including Computer, Communication, and Consumer Electronics, are the main areas of lithium battery applications. For lithium batteries of 3C products, only PP separators and PE separators can be used to obtain performance. Better satisfaction. However, with the continuous development of electric vehicles, the performance of lithium batteries must be further improved to meet the requirements of electric vehicles. For example, in terms of safety, charge and discharge performance, cycle performance and rate, lithium batteries for electric vehicles are more suitable than 3C products. Lithium batteries have more stringent requirements. At present, research on improving the performance of lithium battery separators is mainly to improve the surface properties of the separator and to adjust the substrate of the diaphragm. In the improvement of the surface properties of the membrane, the main research direction is the membrane coating treatment, that is, coating a ceramic slurry on the surface of the membrane. As far as the current situation is concerned, ceramic coated separator is the most effective way to improve the safety of lithium batteries. After coating the ceramic slurry, the separator can effectively improve the heat shrinkage, safety, thermal stability and mechanical strength of the separator. To extend the life of the diaphragm.
为了进一步使电池隔膜的性能满足动力锂电池的要求，新型锂电池隔膜的制备方法，如以添加石墨烯等材料来改性涂布隔膜得到越来越多的关注。石墨烯以其优异的机械性能和耐热性能及在电池中能大幅提高电池比能量等优势在电池中的研究和应用越来越频繁。就目前来说，陶瓷涂布隔膜的耐高温性以及耐热收缩率在一定温度条件下不能够满足要求，而采用石墨烯改性陶瓷涂布隔膜能使锂电池隔膜耐热稳定性和耐热收缩率得到较大的 提高，并能大幅提高电池的充放电速度，提高电池的比能量，且经过特殊工艺制备的石墨烯改性隔膜电池可实现高温闭孔，防止电池进一步反应进而防止电池过热产生的一系列危害，常温时自动恢复电池的充放电功能，大幅提升市场竞争力；但现有技术中还没有较为成熟的制备该石墨烯改性涂层隔膜的方法。In order to further make the performance of the battery separator meet the requirements of the power lithium battery, the preparation method of the new lithium battery separator, such as adding a graphene or the like to modify the coated diaphragm, has received more and more attention. Graphene has been researched and applied more frequently in batteries due to its excellent mechanical properties and heat resistance and the ability to significantly increase the specific energy of the battery in batteries. At present, the high temperature resistance and heat shrinkage of ceramic coated separators cannot meet the requirements under certain temperature conditions, and the use of graphene modified ceramic coated separators can make lithium battery separators heat resistant and heat resistant. Shrinkage is getting bigger Improve, and can greatly improve the battery charge and discharge speed, improve the specific energy of the battery, and the graphene modified diaphragm battery prepared by a special process can achieve high temperature closed cells, prevent the battery from further reaction and prevent the battery from overheating. The battery charge and discharge function is automatically restored at normal temperature, which greatly enhances the market competitiveness; however, there is no mature method for preparing the graphene modified coated separator in the prior art.
发明内容Summary of the invention
为了弥补现有技术的不足，本发明提供了一种耐高温低电阻率锂离子电池隔膜的制备方法，该方法是一种具有成熟、稳定特点的制备工艺，所生产的电池隔膜具有涂布浆料层致密、均匀、粘接牢固以及热收缩小的优点，显著提高了电池的安全性能和使用寿命。In order to make up for the deficiencies of the prior art, the present invention provides a method for preparing a high temperature and low resistivity lithium ion battery separator, which is a mature and stable preparation process, and the produced battery separator has a coating slurry. The dense, uniform, strong adhesion and low heat shrinkage of the material layer significantly improve the safety performance and service life of the battery.
本发明的具体技术方案是：The specific technical solution of the present invention is:
一种耐高温低电阻率锂离子电池隔膜的制备方法，其中，该电池隔膜包括基膜及涂布在其一侧端面或者两侧端面上的涂布浆料层，涂布浆料层材质为陶瓷浆料或者石墨烯改性陶瓷浆料，基膜两侧端面上至少有一侧端面的涂布浆料层材质为石墨烯改性陶瓷浆料，制备上述结构电池隔膜的方法包括以下步骤：A method for preparing a high temperature and low resistivity lithium ion battery separator, wherein the battery separator comprises a base film and a coating slurry layer coated on one end surface or both end surfaces thereof, and the coating slurry layer material is The ceramic slurry or the graphene-modified ceramic slurry has a coating slurry layer having at least one end surface on both end faces of the base film as a graphene-modified ceramic slurry, and the method for preparing the battery separator of the above structure comprises the following steps:
A、制备石墨烯改性陶瓷浆料A. Preparation of graphene modified ceramic slurry
向行星搅拌机中加入去离子水和粒度为0.05-1μm的陶瓷粉末，重量比为(5～30)：(95～70)，所述行星搅拌机中安装有投入式超声波震板，随后同时进行搅拌和超声波震荡，搅拌速度不小于1000r/min，持续进行0.5-2h，形成一级混合浆料；Deionized water and ceramic powder having a particle size of 0.05-1 μm are added to the planetary mixer at a weight ratio of (5-30): (95-70), and the planetary stirrer is equipped with an input ultrasonic vibration plate, followed by stirring at the same time. And ultrasonic vibration, the stirring speed is not less than 1000r / min, continuous for 0.5-2h, forming a first-stage mixed slurry;
向所述一级混合浆料中加入分散剂，加入量为一级混合浆料的0.5-5％，同时进行搅拌和超声波震荡，搅拌速度不小于1000r/min，持续进行0.5-2h，形成二级混合浆料；Adding a dispersing agent to the first-stage mixed slurry, the amount of which is 0.5-5% of the first-stage mixed slurry, while stirring and ultrasonic vibration, the stirring speed is not less than 1000r/min, and the continuous stirring is performed for 0.5-2h, forming two Grade mixed slurry;
向所述二级混合浆料中加入N-甲基吡咯烷酮、酒精、丙烯碳酸酯、甘 油、二甲基亚砜、聚氧乙烯烷基酚醚、聚氧乙烯脂肪醇醚和聚乙烯醇中的至少一种，加入量为二级混合浆料的0.5-10％，同时进行搅拌和超声波震荡，搅拌速度不小于1000r/min，持续进行0.5-2h，形成三级混合浆料；Adding N-methylpyrrolidone, alcohol, propylene carbonate, and sweet to the secondary mixed slurry At least one of oil, dimethyl sulfoxide, polyoxyethylene alkyl phenol ether, polyoxyethylene fatty alcohol ether, and polyvinyl alcohol is added in an amount of 0.5-10% of the secondary mixed slurry while stirring and Ultrasonic vibration, stirring speed is not less than 1000r/min, continuous for 0.5-2h, forming a three-stage mixed slurry;
向所述三级混合浆料中加入石墨烯，加入量为三级混合浆料的0.5-2％，同时进行搅拌和超声波震荡，搅拌速度不小于1000r/min，持续进行0.5-2h，形成四级混合浆料；Adding graphene to the three-stage mixed slurry, adding 0.5-2% of the three-stage mixed slurry, stirring and ultrasonic vibration, stirring speed not less than 1000r/min, continuing for 0.5-2h, forming four Grade mixed slurry;
向所述四级混合浆料中加入含量为50％的水性丙烯酸胶乳液和含量为2％的羧甲基纤维素钠溶液，水性丙烯酸胶乳液和羧甲基纤维素钠溶液的加入量分别为四级混合浆料的0.5-10％和0.3-5％，同时进行搅拌和超声波震荡，搅拌速度不小于1000r/min，持续进行0.5-2h，形成五级混合浆料；To the fourth-stage mixed slurry, a 50% aqueous acrylic latex emulsion and a 2% sodium carboxymethylcellulose solution are added, and the aqueous acrylic latex emulsion and the sodium carboxymethylcellulose solution are respectively added. 0.5-10% and 0.3-5% of the four-stage mixed slurry, while stirring and ultrasonic vibration, the stirring speed is not less than 1000r/min, and the continuous mixing is performed for 0.5-2h to form a five-stage mixed slurry;
关闭超声波震荡，开启真空，将设备转速降低至500r/min以下，搅拌0.5-1h后关闭真空，平衡设备大气压后打开设备，形成初级石墨烯改性陶瓷浆料，然后经过150-250目筛网进行较大颗粒的筛除，剩余物质形成所述石墨烯改性陶瓷浆料；Turn off the ultrasonic vibration, turn on the vacuum, reduce the equipment speed to below 500r/min, close the vacuum after stirring for 0.5-1h, balance the equipment atmospheric pressure, open the equipment, form the primary graphene modified ceramic slurry, and then pass the 150-250 mesh screen. Performing screening of larger particles, and the remaining material forms the graphene-modified ceramic slurry;
B、基膜预处理B, base film pretreatment
对基膜表面进行臭氧风淋或者电晕处理，臭氧风淋时，臭氧的流量为0.5-5L/min，风淋时间为5-120s；Ozone air leaching or corona treatment on the surface of the base film, ozone flow rate is 0.5-5L/min, and air shower time is 5-120 s;
C、涂布烘干C, coating drying
将预处理后的基膜置于微凹版涂布机上，将所述石墨烯改性陶瓷浆料置于微凹版涂布机的储液槽中，启动涂布机进行涂布工作，涂布速度为5-20m/min，涂布厚度保持在1-5μm，涂布后烘干、收卷即得到耐高温低电阻率锂离子电池隔膜。The pretreated base film is placed on a micro gravure coater, and the graphene-modified ceramic slurry is placed in a liquid storage tank of a micro gravure coater to start a coating machine for coating work, and the coating speed is applied. The coating thickness is maintained at 1-5 μm for 5-20 m/min. After coating, drying and winding are performed to obtain a high temperature resistant low resistivity lithium ion battery separator.
本发明的有益效果是：本发明的制备方法为生产耐高温低电阻率锂离子电池隔膜提供了稳定、高效的工艺，该方法通过添加分散剂能够改善浆料的组织性能，使后续添加成分的分布更加均匀，所制备的石墨烯改性陶瓷浆料粘度适中，适于涂布，该浆料既具有陶瓷浆料的高温下低收缩率和 高安全性，又具备石墨烯材料常温下高导电率及高温下低导电率的特性，利用其作为隔膜的涂布材料，不仅可以进一步提高锂离子电池在高温下的低收缩率和安全性，使耐热稳定性和耐热收缩率得到较大的提高，而且还能够大幅提高锂离子电池的充电速度，提高电池的比能量，此外还可实现高温状态下的闭孔，防止电池进一步反应，进而避免电池过热产生的一系列危害，常温时自动恢复电池的充放电功能，大幅提升市场竞争力，使得其应用在电动汽车领域时，解决了电动汽车充电耗时的缺点，为清洁能源汽车的发展提供了技术支撑。The invention has the beneficial effects that the preparation method of the invention provides a stable and high-efficiency process for producing a high temperature resistant low-resistivity lithium ion battery separator, and the method can improve the microstructure and properties of the slurry by adding a dispersant, so as to add components later. The distribution is more uniform, and the prepared graphene-modified ceramic slurry is moderate in viscosity and suitable for coating, and the slurry has both low shrinkage rate at high temperature of the ceramic slurry and High safety, and high conductivity of graphene material at normal temperature and low electrical conductivity at high temperature. By using it as a coating material for the separator, it can not only further improve the low shrinkage rate and safety of the lithium ion battery at high temperatures. The heat resistance stability and the heat shrinkage rate are greatly improved, and the charging speed of the lithium ion battery can be greatly improved, the specific energy of the battery can be improved, and the closed hole at a high temperature state can be realized to prevent the battery from further reacting. In order to avoid a series of hazards caused by battery overheating, the battery charge and discharge function is automatically restored at normal temperature, which greatly enhances the market competitiveness, so that when it is applied in the field of electric vehicles, it solves the shortcomings of charging time of electric vehicles, and is a clean energy vehicle. Development provides technical support.
具体实施方式detailed description
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Specific embodiments of the present invention will be described in detail below. It is to be understood that the specific embodiments described herein are merely illustrative and not restrictive.
本发明提供了一种耐高温低电阻率锂离子电池隔膜的制备方法，其中，该电池隔膜包括基膜及涂布在其一侧端面或者两侧端面上的涂布浆料层，涂布浆料层材质为陶瓷浆料或者石墨烯改性陶瓷浆料，基膜两侧端面上至少有一侧端面的涂布浆料层材质为石墨烯改性陶瓷浆料。制备上述结构电池隔膜的方法包括以下步骤：The invention provides a preparation method of a high temperature resistant low resistivity lithium ion battery separator, wherein the battery separator comprises a base film and a coating slurry layer coated on one end surface or both end surfaces thereof, and the coating slurry The material of the material layer is ceramic slurry or graphene modified ceramic slurry, and the coating slurry layer having at least one end surface on both end faces of the base film is made of graphene modified ceramic slurry. The method of preparing the above-described structural battery separator includes the following steps:
A、制备石墨烯改性陶瓷浆料A. Preparation of graphene modified ceramic slurry
向行星搅拌机中加入去离子水和粒度为0.05-1μm的陶瓷粉末，重量比为(5～30)：(95～70)，所述行星搅拌机中安装有投入式超声波震板，随后同时进行搅拌和超声波震荡，搅拌速度不小于1000r/min，持续进行0.5-2h，形成一级混合浆料；Deionized water and ceramic powder having a particle size of 0.05-1 μm are added to the planetary mixer at a weight ratio of (5-30): (95-70), and the planetary stirrer is equipped with an input ultrasonic vibration plate, followed by stirring at the same time. And ultrasonic vibration, the stirring speed is not less than 1000r / min, continuous for 0.5-2h, forming a first-stage mixed slurry;
向所述一级混合浆料中加入分散剂，加入量为一级混合浆料的0.5-5％，同时进行搅拌和超声波震荡，搅拌速度不小于1000r/min，持续进行0.5-2h，形成二级混合浆料；Adding a dispersing agent to the first-stage mixed slurry, the amount of which is 0.5-5% of the first-stage mixed slurry, while stirring and ultrasonic vibration, the stirring speed is not less than 1000r/min, and the continuous stirring is performed for 0.5-2h, forming two Grade mixed slurry;
向所述二级混合浆料中加入N-甲基吡咯烷酮、酒精、丙烯碳酸酯、甘 油、二甲基亚砜、聚氧乙烯烷基酚醚、聚氧乙烯脂肪醇醚和聚乙烯醇中的至少一种(为了便于描述，本发明也将前述物质统称为“稳定剂”)，加入量为二级混合浆料的0.5-10％，同时进行搅拌和超声波震荡，搅拌速度不小于1000r/min，持续进行0.5-2h，形成三级混合浆料；Adding N-methylpyrrolidone, alcohol, propylene carbonate, and sweet to the secondary mixed slurry At least one of oil, dimethyl sulfoxide, polyoxyethylene alkyl phenol ether, polyoxyethylene fatty alcohol ether, and polyvinyl alcohol (for convenience of description, the present invention also collectively refers to the aforementioned substances as "stabilizers"), The amount of addition is 0.5-10% of the secondary mixed slurry, while stirring and ultrasonic vibration, the stirring speed is not less than 1000r/min, and the continuous stirring is performed for 0.5-2h to form a three-stage mixed slurry;
向所述三级混合浆料中加入石墨烯，加入量为三级混合浆料的0.5-2％，同时进行搅拌和超声波震荡，搅拌速度不小于1000r/min，持续进行0.5-2h，形成四级混合浆料；Adding graphene to the three-stage mixed slurry, adding 0.5-2% of the three-stage mixed slurry, stirring and ultrasonic vibration, stirring speed not less than 1000r/min, continuing for 0.5-2h, forming four Grade mixed slurry;
向所述四级混合浆料中加入含量为50％的水性丙烯酸胶乳液和含量为2％的羧甲基纤维素钠溶液，水性丙烯酸胶乳液和羧甲基纤维素钠溶液的加入量分别为四级混合浆料的0.5-10％和0.3-5％，同时进行搅拌和超声波震荡，搅拌速度不小于1000r/min，持续进行0.5-2h，形成五级混合浆料；To the fourth-stage mixed slurry, a 50% aqueous acrylic latex emulsion and a 2% sodium carboxymethylcellulose solution are added, and the aqueous acrylic latex emulsion and the sodium carboxymethylcellulose solution are respectively added. 0.5-10% and 0.3-5% of the four-stage mixed slurry, while stirring and ultrasonic vibration, the stirring speed is not less than 1000r/min, and the continuous mixing is performed for 0.5-2h to form a five-stage mixed slurry;
关闭超声波震荡，开启真空，将设备转速降低至500r/min以下，搅拌0.5-1h后关闭真空，平衡设备大气压后打开设备，形成初级石墨烯改性陶瓷浆料，然后经过150-250目筛网进行较大颗粒的筛除，剩余物质形成所述石墨烯改性陶瓷浆料；Turn off the ultrasonic vibration, turn on the vacuum, reduce the equipment speed to below 500r/min, close the vacuum after stirring for 0.5-1h, balance the equipment atmospheric pressure, open the equipment, form the primary graphene modified ceramic slurry, and then pass the 150-250 mesh screen. Performing screening of larger particles, and the remaining material forms the graphene-modified ceramic slurry;
B、基膜预处理B, base film pretreatment
对基膜表面进行臭氧风淋或者电晕处理，臭氧风淋时，臭氧的流量为0.5-5L/min，风淋时间为5-120s；Ozone air leaching or corona treatment on the surface of the base film, ozone flow rate is 0.5-5L/min, and air shower time is 5-120 s;
C、涂布烘干C, coating drying
将预处理后的基膜置于微凹版涂布机上，将所述石墨烯改性陶瓷浆料置于微凹版涂布机的储液槽中，启动涂布机进行涂布工作，涂布速度为5-20m/min，涂布厚度保持在1-5μm，涂布后烘干、收卷即得到耐高温低电阻率锂离子电池隔膜。The pretreated base film is placed on a micro gravure coater, and the graphene-modified ceramic slurry is placed in a liquid storage tank of a micro gravure coater to start a coating machine for coating work, and the coating speed is applied. The coating thickness is maintained at 1-5 μm for 5-20 m/min. After coating, drying and winding are performed to obtain a high temperature resistant low resistivity lithium ion battery separator.
本发明中，优选所述基膜为PP、PE、无纺布或者纤维材质的单层、双层或者多层，所述基膜的厚度为6-30μm。In the present invention, it is preferable that the base film is a single layer, a double layer or a plurality of layers of PP, PE, a nonwoven fabric or a fiber material, and the base film has a thickness of 6 to 30 μm.
本发明中，优选所述陶瓷粉末为三氧化二铝、氧化锆、氧化硅、氧化 镁、氧化锌和二氧化钛中的至少一种。In the present invention, it is preferred that the ceramic powder is aluminum oxide, zirconium oxide, silicon oxide, or oxidation. At least one of magnesium, zinc oxide, and titanium dioxide.
根据一种实施方式，所述行星搅拌机的罐内设有多浆叶式搅拌桨，该搅拌桨能在公转的同时实现自转，能使物料上下及四周流动，从而可在很短时间内达到混合效果；罐体的内壁经过大型立车精加工，之后经过大型抛光机自动抛光，因而能确保行星架上的活动刮刀在旋转时将内壁上的物料完全刮掉。另外，所述投入式超声波震板可根据行星搅拌机空间结构进行位置选择和固定安装，为了减少与桨叶的干涉并方便连接，优选将其固定在行星搅拌机上盖底部，在行星搅拌机工作时，所述上盖会下降密封端口，使投入式超声波震板浸入到浆料中，起到超声波震荡的功能。According to an embodiment, the planetary mixer has a multi-blade agitating paddle, and the agitating paddle can realize the rotation while revolving, so that the material can flow up and down and around, so that the mixing can be achieved in a short time. The effect; the inner wall of the tank is finished by a large vertical car, and then automatically polished by a large polishing machine, thereby ensuring that the movable scraper on the planet carrier completely scrapes off the material on the inner wall when rotating. In addition, the input ultrasonic vibration plate can be position-selected and fixedly installed according to the spatial structure of the planetary mixer. In order to reduce the interference with the blade and facilitate the connection, it is preferably fixed at the bottom of the upper cover of the planetary mixer, when the planetary mixer is working, The upper cover lowers the sealing port, so that the input ultrasonic plate is immersed in the slurry to function as an ultrasonic vibration.
步骤A中，优选所述分散剂为聚丙烯酸钠、多偏磷酸钠、硅酸钠和十二烷基硫酸钠中的至少一种，所述分散剂中还添加有pH调节剂，所述pH调节剂选自正磷酸钠、氨水或两者的混合物，调节pH在7.5-8.5之间，更优选调节pH为8。In the step A, preferably, the dispersing agent is at least one of sodium polyacrylate, sodium polymetaphosphate, sodium silicate, and sodium lauryl sulfate, and a pH adjuster is further added to the dispersing agent. The conditioning agent is selected from the group consisting of sodium orthophosphate, aqueous ammonia or a mixture of the two, adjusted to a pH between 7.5 and 8.5, more preferably adjusted to a pH of 8.
所述分散剂除了均具备分散作用外，其中的聚丙烯酸钠还具有增稠、稳定、保水、保鲜等效果；多偏磷酸钠能防止变色、增加粘稠性、增高粘度、提高膨胀能力、增强乳化作用、防止凝胶沉淀、防止浑浊、保护食品色泽、提高防腐性能及pH调节等作用；十二烷基硫酸钠具有良好的乳化、发泡、渗透和去污性能。The dispersing agent not only has a dispersing effect, but also the sodium polyacrylate has the effects of thickening, stabilizing, water retaining and fresh keeping; the polymetaphosphate can prevent discoloration, increase viscosity, increase viscosity, improve expansion capacity, and enhance Emulsification, prevention of gel precipitation, prevention of turbidity, protection of food color, improvement of corrosion resistance and pH adjustment; sodium lauryl sulfate has good emulsification, foaming, penetrating and decontaminating properties.
所述分散剂在pH为7.5-8.5之间时的分散效果较好，因此根据实际情况可以在分散剂中添加正磷酸钠、氨水或者两者的混合物。其中，氨水可起到溶解和调整酸碱度的作用，正磷酸钠在水中几乎完全分解为磷酸氢二钠和氢氧化钠，也可用于调节酸碱度。优选情况下，使用氨水来调节酸碱度，氨水与所述分散剂配合使用时，能进一步提高浆料的分散效果并使浆料更稳定。The dispersing agent has a good dispersing effect at a pH of between 7.5 and 8.5, so that sodium orthophosphate, ammonia or a mixture of the two may be added to the dispersing agent depending on the actual situation. Among them, ammonia can play the role of dissolving and adjusting the pH. The sodium orthophosphate is almost completely decomposed into disodium hydrogen phosphate and sodium hydroxide in water, and can also be used to adjust the pH. Preferably, ammonia water is used to adjust the pH, and when the ammonia water is used in combination with the dispersant, the dispersion effect of the slurry can be further improved and the slurry can be more stable.
在所述二级混合浆料添加的物质中，N-甲基吡咯烷酮还具有溶剂或者分散剂作用；酒精是一种溶剂，能溶解多种有机物和无机物；丙烯碳酸酯 具有分散剂作用；甘油具有溶剂和增稠剂的作用；二甲基亚砜用作溶剂；聚氧乙烯烷基酚醚是一种表面活性剂；聚氧乙烯脂肪醇醚为消泡剂；聚乙烯醇是一种涂料胶黏剂，上述物质均可起到稳定作用，避免浆料内部发生反应，便于浆料的存放。Among the substances added in the secondary mixed slurry, N-methylpyrrolidone also has a solvent or a dispersing agent; alcohol is a solvent capable of dissolving various organic and inorganic substances; propylene carbonate It has a dispersing action; glycerin has a solvent and a thickener; dimethyl sulfoxide is used as a solvent; polyoxyethylene alkyl phenol ether is a surfactant; polyoxyethylene fatty alcohol ether is a defoaming agent; Vinyl alcohol is a kind of coating adhesive, and the above substances can all stabilize, avoid reaction inside the slurry and facilitate storage of the slurry.
步骤A中，对所述初级石墨烯改性陶瓷浆料进行筛网筛除时，优选所用筛网为200目。In the step A, when the primary graphene-modified ceramic slurry is sieved, it is preferred that the sieve used is 200 mesh.
按照一种优选的实施方式，步骤A中，去离子水与所述陶瓷粉末的重量比为(10～30)：(90～70)，所述一级混合浆料中加入物质(即分散剂)占比为2-4％，所述二级混合浆料中加入物质(即稳定剂)占比为5-10％，所述三级混合浆料中加入的石墨烯占比为0.5-1.5％，所述四级混合浆料中水性丙烯酸胶乳液和羧甲基纤维素钠溶液的加入量分别占比为3-8％和1-5％。According to a preferred embodiment, in step A, the weight ratio of deionized water to the ceramic powder is (10-30): (90-70), and the first-stage mixed slurry is added with a substance (ie, a dispersant). The ratio is 2-4%, the proportion of the added substance (ie, stabilizer) in the secondary mixed slurry is 5-10%, and the proportion of graphene added in the tertiary mixed slurry is 0.5-1.5. %, the aqueous acrylic latex emulsion and the sodium carboxymethylcellulose solution in the four-stage mixed slurry are added in an amount of 3-8% and 1-5%, respectively.
更优选地，去离子水与所述陶瓷粉末的重量比为1：4(即20：80)，所述一级混合浆料中加入物质占比为3％，所述二级混合浆料中加入物质占比为6％，所述三级混合浆料中加入的石墨烯占比为1％，所述四级混合浆料中水性丙烯酸胶乳液和羧甲基纤维素钠溶液的加入量分别占比为6％和3％。More preferably, the weight ratio of deionized water to the ceramic powder is 1:4 (ie, 20:80), and the proportion of the added material in the first-stage mixed slurry is 3%, in the secondary mixed slurry. The proportion of the added material is 6%, the proportion of graphene added in the three-stage mixed slurry is 1%, and the amount of the aqueous acrylic latex emulsion and the sodium carboxymethylcellulose solution in the fourth-stage mixed slurry are respectively increased. The proportion is 6% and 3%.
在本发明中，所提到的百分数均指重量百分数。In the present invention, the percentages mentioned are all by weight.
步骤B中，具体可采用臭氧发生器产生臭氧，然后对基膜表面进行风淋，臭氧是一种强氧化剂，使塑料表面分子氧化，产生羟基化合物、过氧化合物等化学反应，经过处理后的隔膜表面附着力能明显提高，这种方式为化学方法改善基膜表面附着力。In step B, an ozone generator can be used to generate ozone, and then the surface of the base film is subjected to air leaching. The ozone is a strong oxidant, which oxidizes the surface of the plastic to generate a chemical reaction such as a hydroxy compound or a peroxy compound. The adhesion of the membrane surface can be significantly improved, which is a chemical method to improve the adhesion of the base film surface.
另外，步骤B的作用主要是为了增强基膜表面的附着力，因此，还可利用电晕方式等对基膜进行处理，电晕方式是通过物理方式提高隔膜表面附着力，该方式工作原理为在处理装置上施加高频高压电，使其电晕放电，产生细小密集的紫蓝色火花，空气电离后产生的各种等离子在强电场的作 用下，加速冲击处理装置内的基膜表面，这些等离子粒子的能量一般在几至几十电子伏特，与塑料分子的化学键能相接近，因此，能优化基膜表面分子的化学键断裂而降解，增大表面粗糙度，从而改善基膜表面附着力。In addition, the function of the step B is mainly to enhance the adhesion of the surface of the base film. Therefore, the base film can be treated by a corona method or the like, and the corona method is to physically improve the adhesion of the surface of the diaphragm. Applying high-frequency high-voltage electricity to the processing device to corona discharge, producing a small dense purple-blue spark, and various plasmas generated after air ionization are in a strong electric field. The surface of the base film in the impact treatment device is accelerated. The energy of the plasma particles is generally several to several tens of electron volts, which is close to the chemical bond energy of the plastic molecules. Therefore, the chemical bond cleavage of the molecules on the surface of the base film can be optimized to degrade. Increase the surface roughness to improve the adhesion of the base film surface.
步骤B中，优选进行臭氧风淋时，臭氧的流量为1-4L/min，风淋时间为30-100s；更优选臭氧的流量为3L/min，处理时间为80s。In the step B, it is preferred that when the ozone is blasted, the flow rate of the ozone is 1-4 L/min, and the air rinsing time is 30-100 s; more preferably, the flow rate of the ozone is 3 L/min, and the treatment time is 80 s.
步骤C中，优选所述涂布机的涂布速度为10-15m/min，涂布厚度为2-4μm。In the step C, it is preferred that the coater has a coating speed of 10 to 15 m/min and a coating thickness of 2 to 4 μm.
例如，所述涂布机的涂布速度为12m/min，涂布厚度为3μm。更优选地，步骤C中，所述涂布机的涂布厚度为2μm。For example, the coater has a coating speed of 12 m/min and a coating thickness of 3 μm. More preferably, in step C, the coating machine has a coating thickness of 2 μm.
本发明中，涂布厚度均是指干厚。In the present invention, the coating thickness means dry thickness.
步骤C中，优选利用射线测厚仪对涂布厚度进行在线监测，所述涂布机设置有控制单元，射线测厚仪的信息输出端与所述控制单元的信息输入端相连，所述控制单元的信息输出端与涂布机动力机构控制端相连，射线测厚仪将采集的涂布厚度信息传送至控制单元；当涂布厚度正常时，控制单元不向涂布机发送指令；当涂布厚度过大时，控制单元向涂布机动发送指令，涂布机动力机构加快转速，减小涂布厚度至正常范围；当涂布厚度过小时，控制单元向涂布机发送指令，涂布机动力机构降低转速，增大涂布厚度至正常范围。In step C, the coating thickness is preferably monitored online by using a ray thickness gauge, the coating machine is provided with a control unit, and the information output end of the ray thickness gauge is connected to the information input end of the control unit, the control The information output end of the unit is connected to the control end of the coating machine power mechanism, and the ray thickness gauge transmits the collected coating thickness information to the control unit; when the coating thickness is normal, the control unit does not send an instruction to the coating machine; When the thickness of the cloth is too large, the control unit sends a command to the coating maneuver, the speed of the coating machine power mechanism is increased, and the coating thickness is reduced to a normal range; when the coating thickness is too small, the control unit sends a command to the coater to apply The machine power mechanism reduces the rotational speed and increases the coating thickness to the normal range.
本发明中，在进行涂布浆料层的涂布时，可以选择对基膜进行单面涂布、双面涂布或者将不同涂布浆料以组合的形式涂布，此外，还可以对多层涂布后的基膜进行复合，例如可以在基膜的单面或者双面涂布所述石墨烯改性陶瓷浆料，也可以一侧端面涂布陶瓷浆料，另一侧端面涂布所述石墨烯改性陶瓷浆料，还可以在基膜的一侧端面先涂布陶瓷浆料，然后在同一侧端面上再涂布所述石墨烯改性陶瓷浆料。In the present invention, when applying the coating slurry layer, the base film may be selected to be coated on one side, double-coated, or coated in a combined form, and in addition, The base film after the multi-layer coating is composited. For example, the graphene-modified ceramic slurry may be coated on one side or both sides of the base film, or the ceramic slurry may be coated on one end surface and the other end surface coated. The graphene-modified ceramic slurry may be coated with a ceramic slurry on one end surface of the base film, and then the graphene-modified ceramic slurry may be further coated on the same side end surface.
通常地，所述涂布机上的涂布过程包括基膜放卷、基膜涂布以及烘烤定型。按照一种优选的实施方式，所述涂布过程包括： Typically, the coating process on the coater includes base film unwinding, base film coating, and baking styling. According to a preferred embodiment, the coating process comprises:
1)基膜放卷：基膜放卷轴释放所述基膜，使基膜向收卷轴方向移动，其中，基膜放卷轴对基膜的放卷张力为15-30N；1) base film unwinding: the base film release reel releases the base film, and moves the base film toward the take-up reel, wherein the unwinding tension of the base film reel to the base film is 15-30N;
2)基膜涂布：基膜经过两侧的网纹辊，网纹辊顶紧基膜中相对应一侧的端面，同时将浆料(石墨烯改性陶瓷浆料和/或陶瓷浆料)粘附在基膜的相对应一侧端面上，形成涂布隔膜；2) Base film coating: the base film passes through the anilox rolls on both sides, and the anilox roll is pressed against the corresponding end surface of the base film, and the slurry (graphene modified ceramic slurry and/or ceramic slurry) Adhering to the corresponding one end surface of the base film to form a coated separator;
3)烘烤定型：所述涂布隔膜进入加热烘干机构，进行烘干，从而制得电池隔膜；3) baking and setting: the coating membrane enters the heating and drying mechanism and is dried to obtain a battery separator;
所述加热烘干机构可以是烘箱，所述烘箱的加热方式为红外加热，加热温度在50-70℃之间，输送所述涂布隔膜经过烘箱的时间为0.6-1.8min，所述涂布隔膜在所述加热烘干机构中的张力保持在7-15N；The heating and drying mechanism may be an oven, the heating mode of the oven is infrared heating, the heating temperature is between 50-70 ° C, and the time for conveying the coating membrane through the oven is 0.6-1.8 min, the coating The tension of the diaphragm in the heating and drying mechanism is maintained at 7-15N;
4)成品收卷：收卷轴对电池隔膜进行收卷，收卷的张力为4-12N。4) Finished winding: The reel is used to wind up the battery separator, and the tension of the winding is 4-12N.
本发明制备方法生产的电池隔膜通常具有以下性能，其面密度为10-50g/m2，厚度为10-30μm，平均孔径为0.02-0.1μm，孔隙率为50-70％，本发明的电池隔膜材料除可以作为锂离子电池隔膜外，还可以用做镍氢电池隔膜和过滤材料，该电池隔膜具有致密、均匀、粘接牢固、隔膜热收缩小的特点，对提高锂离子电池安全性能、延长电池寿命具有明显效果。The battery separator produced by the preparation method of the present invention generally has the following properties, and has an areal density of 10 to 50 g/m 2 , a thickness of 10 to 30 μm, an average pore diameter of 0.02 to 0.1 μm, and a porosity of 50 to 70%, and the battery of the present invention. In addition to being used as a separator for lithium-ion batteries, the separator material can also be used as a nickel-hydrogen battery separator and a filter material. The battery separator has the characteristics of compactness, uniformity, firm adhesion, and small heat shrinkage of the diaphragm, and improves the safety performance of the lithium ion battery. Extending battery life has a significant effect.
使用所述石墨烯改性陶瓷浆料涂布后的电池隔膜制成的锂电池，其尺寸和重量均有所变小，而且能量储存密度得到了数十倍的提高，更重要地是，锂电池中隔膜通过电解液与电极接触，隔膜表面涂层中的石墨烯可大幅改善界面的性能，例如增大接触面积以及改善锂离子在隔膜当中穿梭的阻力，降低内阻，使锂离子通过更加顺畅，提升电池倍率充放电性能，其能大大缩短充电时间，电池的充电时间从以前的以小时为单位计算，变为以分钟甚至以秒为单位来计算，充电速度大大提高，应用到电动汽车的充电中，几乎可以与传统汽车的加油快捷性相媲美，甚至更快，一辆电动汽车一次充电消耗10分钟，可达到的续航里程为1000公里。The lithium battery made of the battery separator coated with the graphene-modified ceramic slurry has a small size and weight, and the energy storage density is increased by several tens of times, and more importantly, lithium. The separator in the battery is in contact with the electrode through the electrolyte. The graphene in the coating on the surface of the diaphragm can greatly improve the performance of the interface, such as increasing the contact area and improving the resistance of lithium ions to shuttle through the diaphragm, reducing the internal resistance and making the lithium ion pass through. Smooth, improve battery rate charge and discharge performance, which can greatly shorten the charging time, the battery charging time is calculated from the previous hours, changed to minutes or even seconds, the charging speed is greatly improved, applied to electric vehicles In the charging, it can almost match the speed of the refueling of traditional cars, and even faster. An electric car consumes 10 minutes on a single charge, and the cruising range that can be reached is 1000 kilometers.
下面的实施例对本发明的特点做进一步的说明，但本发明的内容并不 受实施例的限制。The following embodiments further illustrate the features of the present invention, but the contents of the present invention are not Limited by the examples.
以下实施例和对比例中，电池隔膜的透气度按照GB/T 458-2008测试，拉伸性能按照GB 13022-91测量，热收缩率按照GB/T 12027-2004测试，针刺强度按照以下方法测得：用直径1mm的顶端半球型针，在力学拉伸仪上选择挤压试验，垂直刺穿隔膜，记录最大负荷(试验条件为，试验速度：250mm/min，夹具间最大位移：10-20mm)。In the following examples and comparative examples, the gas permeability of the battery separator was tested in accordance with GB/T 458-2008, the tensile properties were measured in accordance with GB 13022-91, and the heat shrinkage rate was tested in accordance with GB/T 12027-2004. The acupuncture strength was as follows. Measured: Using a tip hemispherical needle with a diameter of 1 mm, select the extrusion test on a mechanical tensile tester, pierce the diaphragm vertically, and record the maximum load (test conditions: test speed: 250 mm/min, maximum displacement between clamps: 10- 20mm).
以下制备例、实施例和对比例中，In the following Preparation Examples, Examples and Comparative Examples,
所采用的行星搅拌机的罐内为多浆叶式搅拌桨，罐体内壁经过大型立车精加工，之后经过大型抛光机自动抛光，行星搅拌机中安装有投入式超声波震板，固定在行星搅拌机上盖底部，搅拌机工作时，上盖下降密封端口，投入式超声波震板浸入浆料中。The inner tank of the planetary mixer used is a multi-blade mixing paddle. The inner wall of the tank is finished by a large vertical car, and then automatically polished by a large polishing machine. The planetary mixer is equipped with an input ultrasonic vibration plate and fixed on the planetary mixer. At the bottom of the cover, when the mixer is working, the upper cover lowers the sealing port, and the input type ultrasonic vibration plate is immersed in the slurry.
所采用的涂布机设置有控制单元，射线测厚仪的信息输出端与控制单元的信息输入端相连，控制单元的信息输出端与涂布机动力机构控制端相连，射线测厚仪将采集的涂布厚度信息传送至控制单元，当涂布厚度正常时，控制单元不向涂布机发送指令，当涂布厚度过大时，控制单元向涂布机动发送指令，涂布机动力机构加快转速，减小涂布厚度至正常范围，当涂布厚度过小时，控制单元向涂布机发送指令，涂布机动力机构降低转速，增大涂布厚度至正常范围，借助控制单元和射线测厚仪的使用。The coating machine used is provided with a control unit, and the information output end of the ray thickness gauge is connected with the information input end of the control unit, and the information output end of the control unit is connected with the control end of the coating machine power mechanism, and the ray thickness gauge will collect The coating thickness information is transmitted to the control unit. When the coating thickness is normal, the control unit does not send an instruction to the coating machine. When the coating thickness is too large, the control unit sends an instruction to the coating maneuver, and the coating machine power mechanism is accelerated. The rotation speed reduces the coating thickness to the normal range. When the coating thickness is too small, the control unit sends a command to the coater, the coating machine power mechanism reduces the rotation speed, increases the coating thickness to the normal range, and is controlled by the control unit and the radiation. The use of thick gauges.
制备例Preparation example
本制备例用于说明以下实施例和对比例中所采用的普通陶瓷浆料的制备方法。This preparation example is for explaining the preparation method of the ordinary ceramic slurry used in the following examples and comparative examples.
向行星搅拌机中加入去离子水和粒度为0.5μm的三氧化二铝粉末，重量比为1：4，启动该行星搅拌机，将投入式超声波震板浸入浆料中，同时进行搅拌和超声波震荡的工作，搅拌速度为1200r/min，持续进行1h，形成 一级混合浆料；Deionized water and alumina powder having a particle size of 0.5 μm were added to the planetary mixer at a weight ratio of 1:4. The planetary mixer was started, and the input ultrasonic plate was immersed in the slurry while stirring and ultrasonically oscillating. Work, stirring speed is 1200r/min, continuous for 1h, forming First stage mixed slurry;
向一级混合浆料中加入聚丙烯酸钠，然后添加氨水将pH调节至8，聚丙烯酸钠加入量为一级混合浆料重量的3％，随后，同时进行搅拌和超声波震荡，搅拌速度1200r/min，持续进行1h，形成二级混合浆料；Sodium polyacrylate was added to the first-stage mixed slurry, and then the pH was adjusted to 8 by adding ammonia water, and the sodium polyacrylate was added in an amount of 3% by weight of the first-stage mixed slurry, followed by stirring and ultrasonic vibration, and the stirring speed was 1200 r/ Min, continued for 1 h to form a secondary mixed slurry;
向二级混合浆料中加入酒精，加入量为二级混合浆料的6％，同时进行搅拌和超声波震荡，搅拌速度1200r/min，持续进行1h，形成三级混合浆料；Adding alcohol to the secondary mixed slurry, adding 6% of the secondary mixed slurry, stirring and ultrasonic vibration, stirring speed 1200r/min, for 1h, forming a three-stage mixed slurry;
向三级混合浆料中加入含量为50％的水性丙烯酸胶乳液和含量为2％的羧甲基纤维素钠溶液，水性丙烯酸胶乳液和羧甲基纤维素钠溶液的加入量分别为四级混合浆料的6％和3％，同时进行搅拌和超声波震荡，搅拌速度1200r/min，持续进行1h，形成四级混合浆料；A 50% aqueous acrylic latex emulsion and a 2% sodium carboxymethylcellulose solution were added to the tertiary mixed slurry, and the aqueous acrylic latex emulsion and the sodium carboxymethylcellulose solution were respectively added to the fourth grade. 6% and 3% of the mixed slurry, while stirring and ultrasonic vibration, stirring speed 1200r / min, for 1h, forming a four-stage mixed slurry;
关闭超声波震荡，开启真空，将设备转速降低至400r/min，搅拌0.8h后关闭真空，平衡设备大气压后打开设备，形成初级陶瓷浆料，然后经过200目筛网进行较大颗粒的筛除，剩余物质形成所述普通陶瓷浆料。Turn off the ultrasonic vibration, turn on the vacuum, reduce the equipment speed to 400r/min, close the vacuum after stirring for 0.8h, balance the equipment atmospheric pressure, open the equipment, form the primary ceramic slurry, and then sieve the larger particles through the 200 mesh screen. The remaining material forms the common ceramic slurry.
实施例1Example 1
A、制备石墨烯改性陶瓷浆料A. Preparation of graphene modified ceramic slurry
向行星搅拌机中加入去离子水和粒度为0.5μm的三氧化二铝粉末，重量比为1：4，启动行星搅拌机，同时进行搅拌和超声波震荡，搅拌速度为1200r/min，持续进行1h，形成一级混合浆料；Add deionized water and alumina powder with a particle size of 0.5 μm to the planetary mixer at a weight ratio of 1:4. Start the planetary mixer, stir and ultrasonically shake at a speed of 1200 r/min for 1 h. First stage mixed slurry;
向一级混合浆料中加入聚丙烯酸钠，然后添加氨水将pH调节至8，聚丙烯酸钠加入量为一级混合浆料重量的3％，随后，同时进行搅拌和超声波震荡，搅拌速度1200r/min，持续进行1h，形成二级混合浆料；Sodium polyacrylate was added to the first-stage mixed slurry, and then the pH was adjusted to 8 by adding ammonia water, and the sodium polyacrylate was added in an amount of 3% by weight of the first-stage mixed slurry, followed by stirring and ultrasonic vibration, and the stirring speed was 1200 r/ Min, continued for 1 h to form a secondary mixed slurry;
向二级混合浆料中加入酒精，加入量为二级混合浆料的6％，同时进行搅拌和超声波震荡，搅拌速度1200r/min，持续进行1h，形成三级混合浆料；Adding alcohol to the secondary mixed slurry, adding 6% of the secondary mixed slurry, stirring and ultrasonic vibration, stirring speed 1200r/min, for 1h, forming a three-stage mixed slurry;
向三级混合浆料中加入石墨烯，加入量为三级混合浆料的1％，同时进行搅拌和超声波震荡，搅拌速度1200r/min，持续进行1h，形成四级混合浆 料；Adding graphene to the three-stage mixed slurry, adding 1% of the three-stage mixed slurry, stirring and ultrasonic vibration, stirring speed 1200r/min, for 1h, forming a four-stage mixed slurry material;
向四级混合浆料中加入含量为50％的水性丙烯酸胶乳液和含量为2％的羧甲基纤维素钠溶液，水性丙烯酸胶乳液和羧甲基纤维素钠溶液的加入量分别为四级混合浆料的6％和3％，同时进行搅拌和超声波震荡，搅拌速度1200r/min，持续进行1h，形成五级混合浆料；A 50% aqueous acrylic latex emulsion and a 2% sodium carboxymethylcellulose solution were added to the four-stage mixed slurry, and the aqueous acrylic latex emulsion and the sodium carboxymethylcellulose solution were respectively added to the fourth grade. 6% and 3% of the mixed slurry, while stirring and ultrasonic vibration, stirring speed 1200r / min, for 1h, forming a five-stage mixed slurry;
关闭超声波震荡，开启真空，将设备转速降低至400r/min，搅拌0.8h后关闭真空，平衡设备大气压后打开设备，形成初级石墨烯改性陶瓷浆料，然后经过200目筛网进行较大颗粒的筛除，剩余物质形成石墨烯改性陶瓷浆料；Turn off the ultrasonic vibration, turn on the vacuum, reduce the equipment speed to 400r/min, close the vacuum after stirring for 0.8h, balance the equipment atmospheric pressure, open the equipment, form the primary graphene modified ceramic slurry, and then pass the 200 mesh screen for larger particles. Screening, the remaining material forms a graphene modified ceramic slurry;
B、基膜预处理B, base film pretreatment
利用臭氧发生器产生臭氧对基膜表面进行臭氧风淋，臭氧的流量为3L/min，风淋时间为80s，基膜选用单层的PP材质；The ozone generator is used to generate ozone to carry out ozone air shower on the surface of the base film, the flow rate of ozone is 3L/min, the air shower time is 80s, and the base film is made of a single layer of PP material;
C、涂布烘干C, coating drying
将预处理后的基膜置于微凹版涂布机上，利用隔膜泵将石墨烯改性陶瓷浆料置微凹版涂布机的储液槽中，启动涂布机进行涂布工作，利用射线测厚仪对涂布厚度进行在线监测，使涂布机的涂布速度保持在12m/min，涂布厚度保持在2μm；涂布过程具体包括：The pre-treated base film is placed on a micro-gravure coating machine, and the graphene-modified ceramic slurry is placed in a liquid storage tank of the micro-gravure coating machine by a diaphragm pump, and the coating machine is started to perform coating work, and the radiation is measured. The thickness of the coating is monitored on-line to maintain the coating speed of the coating machine at 12 m/min and the coating thickness is maintained at 2 μm. The coating process specifically includes:
1)基膜放卷：基膜放卷轴释放所述基膜，基膜向收卷轴方向移动，放卷张力为17N；1) base film unwinding: the base film release reel releases the base film, the base film moves toward the take-up reel, and the unwinding tension is 17N;
2)基膜涂布：基膜经过两侧的网纹辊，网纹辊顶紧基膜中相对应一侧的端面，同时将石墨烯改性陶瓷浆料粘附在基膜的相对应一侧端面上；2) Base film coating: the base film passes through the anilox rolls on both sides, and the anilox roll is pressed against the corresponding end surface of the base film, and the graphene-modified ceramic slurry is adhered to the corresponding one of the base film. On the side end face;
按照上述涂布过程，将普通陶瓷浆液涂覆在基膜另一侧的端面上，形成改性涂布隔膜；According to the above coating process, a common ceramic slurry is coated on the other end surface of the base film to form a modified coated separator;
3)烘烤定型：改性涂布隔膜进入烘箱，烘箱中加热方式为红外加热，加热温度在60℃，输送隔膜经过烘箱的时间为1.2min，改性涂布隔膜在烘箱中的张力为10N，经烘烤定型后，得到电池隔膜成品； 3) Baking stereotype: The modified coating diaphragm enters the oven. The heating method in the oven is infrared heating, the heating temperature is 60 °C, the time of conveying the diaphragm through the oven is 1.2 min, and the tension of the modified coating diaphragm in the oven is 10N. After baking and setting, the battery separator is obtained;
4)成品收卷：收卷轴对电池隔膜成品进行收卷，收卷的张力为8N。该电池隔膜中，隔膜上所形成的普通陶瓷涂层和石墨烯改性涂层的厚度分别约为2μm，基膜厚度约为16μm，将该电池隔膜记为16B+2+2G，膜的性质见表1。4) Finished product winding: The reel is used to wind up the finished product of the battery separator, and the tension of the winding is 8N. In the battery separator, the thickness of the common ceramic coating and the graphene-modified coating formed on the separator are respectively about 2 μm, the thickness of the base film is about 16 μm, and the battery separator is recorded as 16B+2+2G, the properties of the membrane. See Table 1.
实施例2Example 2
根据实施例1的方法制备电池隔膜，所不同的是，将实施例1的聚丙烯酸钠用等重量的多偏磷酸钠替换，并添加氨水调pH为8，同时将酒精用等重量的聚乙烯醇替换，从而制得电池隔膜，该电池隔膜中，隔膜上所形成的普通陶瓷涂层和石墨烯改性涂层的厚度分别约为2μm，基膜厚度约为16μm，将该电池隔膜记为16B+2+2G’，膜的性质见表1。A battery separator was prepared according to the method of Example 1, except that the sodium polyacrylate of Example 1 was replaced with an equal weight of sodium polymetaphosphate, and aqueous ammonia was added to adjust the pH to 8, while the same weight of polyethylene was used for the alcohol. Alcohol replacement, thereby producing a battery separator in which the thickness of the common ceramic coating and the graphene-modified coating formed on the separator are respectively about 2 μm, and the thickness of the base film is about 16 μm, and the battery separator is recorded as 16B+2+2G', the properties of the film are shown in Table 1.
实施例3Example 3
根据实施例1的方法制备电池隔膜，所不同的是，将实施例1的聚丙烯酸钠的用量调整为一级混合浆料的2％，将酒精加入量调整为二级混合浆料的9％，从而制得电池隔膜，该电池隔膜中，隔膜上所形成的普通陶瓷涂层和石墨烯改性涂层的厚度分别约为2μm，基膜厚度约为16μm，记为16B+2+2G”，膜的性质见表1。A battery separator was prepared according to the method of Example 1, except that the amount of sodium polyacrylate of Example 1 was adjusted to 2% of the first-stage mixed slurry, and the amount of alcohol added was adjusted to 9% of the secondary mixed slurry. Thus, a battery separator is obtained, wherein the thickness of the common ceramic coating and the graphene-modified coating formed on the separator is about 2 μm, and the thickness of the base film is about 16 μm, which is recorded as 16B+2+2G. The properties of the membrane are shown in Table 1.
实施例4Example 4
根据实施例1的方法制备电池隔膜，所不同的是，将实施例1的聚丙烯酸钠的用量调整为一级混合浆料的5％，将酒精加入量调整为二级混合浆料的10％，从而制得电池隔膜，该电池隔膜中，隔膜上所形成的普通陶瓷涂层和石墨烯改性涂层的厚度分别约为2μm，基膜厚度约为16μm，记为16B+2+2G”’，膜的性质见表1。 A battery separator was prepared according to the method of Example 1, except that the amount of sodium polyacrylate of Example 1 was adjusted to 5% of the first-stage mixed slurry, and the amount of alcohol added was adjusted to 10% of the secondary mixed slurry. Thus, a battery separator is obtained, wherein the thickness of the common ceramic coating and the graphene-modified coating formed on the separator is about 2 μm, and the thickness of the base film is about 16 μm, which is recorded as 16B+2+2G. ', the properties of the membrane are shown in Table 1.
对比例1Comparative example 1
参照实施例1的方法制备电池隔膜，所不同的是，在基膜的两侧端面均涂覆普通陶瓷浆料，从而制得电池隔膜，该电池隔膜中，隔膜上两侧端面所形成的普通陶瓷涂层的厚度分别约为2μm，基膜厚度约为16μm，记为16B+2+2，膜的性质见表1。A battery separator was prepared by the method of Example 1, except that a common ceramic slurry was coated on both end faces of the base film to prepare a battery separator in which the two end faces of the separator were formed. The thickness of the ceramic coating is about 2 μm, and the thickness of the base film is about 16 μm, which is recorded as 16B+2+2. The properties of the film are shown in Table 1.
表1隔膜性质Table 1 diaphragm properties
Figure PCTCN2017105853-appb-000001
Figure PCTCN2017105853-appb-000001
Figure PCTCN2017105853-appb-000002
Figure PCTCN2017105853-appb-000002
注：“16B”是指上述实施例采用的约16μm厚的基膜，其孔隙率为45％，平均孔径为0.08μm，闭孔温度约为134℃。Note: "16B" means a base film of about 16 μm thick used in the above embodiment, which has a porosity of 45%, an average pore diameter of 0.08 μm, and a closed cell temperature of about 134 °C.
由表1中数据可见，实施例中经石墨烯改性涂层隔膜的耐热性能明显好于基膜和普通陶瓷隔膜，收缩率相对更小，透气更小，即内阻更小，针刺强度有显著提高，安全性提高，充电速度加快。It can be seen from the data in Table 1 that the heat resistance of the graphene-modified coated separator in the examples is significantly better than that of the base film and the ordinary ceramic separator, the shrinkage ratio is relatively smaller, the gas permeability is smaller, that is, the internal resistance is smaller, and the needle punching is performed. The strength is significantly improved, the safety is improved, and the charging speed is increased.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solutions of the present invention within the scope of the technical idea of the present invention. These simple variants All fall within the scope of protection of the present invention.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。It should be further noted that the specific technical features described in the above specific embodiments may be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention has various possibilities. The combination method will not be described separately.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。 In addition, any combination of various embodiments of the invention may be made as long as it does not deviate from the idea of the invention, and it should be regarded as the disclosure of the invention.

Claims (10)

  1. 一种耐高温低电阻率锂离子电池隔膜的制备方法，其特征在于：该电池隔膜包括基膜及涂布在其一侧端面或者两侧端面上的涂布浆料层，涂布浆料层材质为陶瓷浆料或者石墨烯改性陶瓷浆料，基膜两侧端面上至少有一侧端面的涂布浆料层材质为石墨烯改性陶瓷浆料，制备上述结构电池隔膜的方法包括以下步骤：A method for preparing a high temperature resistant low resistivity lithium ion battery separator, characterized in that the battery separator comprises a base film and a coating slurry layer coated on one end surface or both end surfaces thereof, and the coating slurry layer is coated The material is ceramic slurry or graphene-modified ceramic slurry, and the coating slurry layer having at least one end surface on both end faces of the base film is made of graphene-modified ceramic slurry, and the method for preparing the battery separator of the above structure comprises the following steps :
    A、制备石墨烯改性陶瓷浆料A. Preparation of graphene modified ceramic slurry
    向行星搅拌机中加入去离子水和粒度为0.05-1μm的陶瓷粉末，重量比为(5～30)：(95～70)，所述行星搅拌机中安装有投入式超声波震板，随后同时进行搅拌和超声波震荡，搅拌速度不小于1000r/min，持续进行0.5-2h，形成一级混合浆料；Deionized water and ceramic powder having a particle size of 0.05-1 μm are added to the planetary mixer at a weight ratio of (5-30): (95-70), and the planetary stirrer is equipped with an input ultrasonic vibration plate, followed by stirring at the same time. And ultrasonic vibration, the stirring speed is not less than 1000r / min, continuous for 0.5-2h, forming a first-stage mixed slurry;
    向所述一级混合浆料中加入分散剂，加入量为一级混合浆料的0.5-5％，同时进行搅拌和超声波震荡，搅拌速度不小于1000r/min，持续进行0.5-2h，形成二级混合浆料；Adding a dispersing agent to the first-stage mixed slurry, the amount of which is 0.5-5% of the first-stage mixed slurry, while stirring and ultrasonic vibration, the stirring speed is not less than 1000r/min, and the continuous stirring is performed for 0.5-2h, forming two Grade mixed slurry;
    向所述二级混合浆料中加入N-甲基吡咯烷酮、酒精、丙烯碳酸酯、甘油、二甲基亚砜、聚氧乙烯烷基酚醚、聚氧乙烯脂肪醇醚和聚乙烯醇中的至少一种，加入量为二级混合浆料的0.5-10％，同时进行搅拌和超声波震荡，搅拌速度不小于1000r/min，持续进行0.5-2h，形成三级混合浆料；Adding N-methylpyrrolidone, alcohol, propylene carbonate, glycerin, dimethyl sulfoxide, polyoxyethylene alkyl phenol ether, polyoxyethylene fatty alcohol ether and polyvinyl alcohol to the secondary mixed slurry At least one, the amount of addition is 0.5-10% of the secondary mixed slurry, while stirring and ultrasonic vibration, the stirring speed is not less than 1000r / min, continuous for 0.5-2h, forming a three-stage mixed slurry;
    向所述三级混合浆料中加入石墨烯，加入量为三级混合浆料的0.5-2％，同时进行搅拌和超声波震荡，搅拌速度不小于1000r/min，持续进行0.5-2h，形成四级混合浆料；Adding graphene to the three-stage mixed slurry, adding 0.5-2% of the three-stage mixed slurry, stirring and ultrasonic vibration, stirring speed not less than 1000r/min, continuing for 0.5-2h, forming four Grade mixed slurry;
    向所述四级混合浆料中加入含量为50％的水性丙烯酸胶乳液和含量为2％的羧甲基纤维素钠溶液，水性丙烯酸胶乳液和羧甲基纤维素钠溶液的加入量分别为四级混合浆料的0.5-10％和0.3-5％，同时进行搅拌和超声波震荡，搅拌速度不小于1000r/min，持续进行0.5-2h，形成五级混合浆料； To the fourth-stage mixed slurry, a 50% aqueous acrylic latex emulsion and a 2% sodium carboxymethylcellulose solution are added, and the aqueous acrylic latex emulsion and the sodium carboxymethylcellulose solution are respectively added. 0.5-10% and 0.3-5% of the four-stage mixed slurry, while stirring and ultrasonic vibration, the stirring speed is not less than 1000r/min, and the continuous mixing is performed for 0.5-2h to form a five-stage mixed slurry;
    关闭超声波震荡，开启真空，将设备转速降低至500r/min以下，搅拌0.5-1h后关闭真空，平衡设备大气压后打开设备，形成初级石墨烯改性陶瓷浆料，然后经过150-250目筛网进行较大颗粒的筛除，剩余物质形成所述石墨烯改性陶瓷浆料；Turn off the ultrasonic vibration, turn on the vacuum, reduce the equipment speed to below 500r/min, close the vacuum after stirring for 0.5-1h, balance the equipment atmospheric pressure, open the equipment, form the primary graphene modified ceramic slurry, and then pass the 150-250 mesh screen. Performing screening of larger particles, and the remaining material forms the graphene-modified ceramic slurry;
    B、基膜预处理B, base film pretreatment
    对基膜表面进行臭氧风淋或者电晕处理，臭氧风淋时，臭氧的流量为0.5-5L/min，风淋时间为5-120s；Ozone air leaching or corona treatment on the surface of the base film, ozone flow rate is 0.5-5L/min, and air shower time is 5-120 s;
    C、涂布烘干C, coating drying
    将预处理后的基膜置于微凹版涂布机上，将所述石墨烯改性陶瓷浆料置于微凹版涂布机的储液槽中，启动涂布机进行涂布工作，涂布速度为5-20m/min，涂布厚度保持在1-5μm，涂布后烘干、收卷，即得到耐高温低电阻率锂离子电池隔膜。The pretreated base film is placed on a micro gravure coater, and the graphene-modified ceramic slurry is placed in a liquid storage tank of a micro gravure coater to start a coating machine for coating work, and the coating speed is applied. It is 5-20 m/min, the coating thickness is maintained at 1-5 μm, and after drying, winding and winding, a high-temperature low-resistance lithium ion battery separator is obtained.
  2. 根据权利要求1所述的耐高温低电阻率锂离子电池隔膜的制备方法，其中，步骤A中，所述分散剂为聚丙烯酸钠、多偏磷酸钠、硅酸钠和十二烷基硫酸钠中的至少一种，所述分散剂中还添加有pH调节剂，所述pH调节剂选自正磷酸钠、氨水或两者的混合物，调节pH在7.5-8.5之间。The method for preparing a high temperature resistant low-resistivity lithium ion battery separator according to claim 1, wherein in the step A, the dispersing agent is sodium polyacrylate, sodium polymetaphosphate, sodium silicate and sodium lauryl sulfate. At least one of the dispersing agents further comprising a pH adjusting agent selected from the group consisting of sodium orthophosphate, aqueous ammonia or a mixture of the two, and the pH is adjusted to be between 7.5 and 8.5.
  3. 根据权利要求1所述的耐高温低电阻率锂离子电池隔膜的制备方法，其中，所述基膜为PP、PE、无纺布或者纤维材质的单层、双层或者多层，所述基膜的厚度为6-30μm。The method for preparing a high temperature resistant low-resistivity lithium ion battery separator according to claim 1, wherein the base film is a single layer, a double layer or a plurality of layers of PP, PE, non-woven fabric or fiber material. The thickness of the film is 6-30 μm.
  4. 根据权利要求1所述的耐高温低电阻率锂离子电池隔膜的制备方法，其中，所述陶瓷粉末为三氧化二铝、氧化锆、氧化硅、氧化镁、氧化锌和二氧化钛中的至少一种。 The method for preparing a high temperature resistant low-resistivity lithium ion battery separator according to claim 1, wherein the ceramic powder is at least one of aluminum oxide, zirconium oxide, silicon oxide, magnesium oxide, zinc oxide, and titanium oxide. .
  5. 根据权利要求1所述的耐高温低电阻率锂离子电池隔膜的制备方法，其中，步骤A中，去离子水与所述陶瓷粉末的重量比为1：4，所述一级混合浆料中加入物质占比为3％，所述二级混合浆料中加入物质占比为6％，所述三级混合浆料中加入的石墨烯占比为1％，所述四级混合浆料中水性丙烯酸胶乳液和羧甲基纤维素钠溶液的加入量分别占比为6％和3％。The method for preparing a high temperature resistant low-resistivity lithium ion battery separator according to claim 1, wherein in step A, the weight ratio of deionized water to the ceramic powder is 1:4, in the first-stage mixed slurry. The proportion of the added substance is 3%, the proportion of the added substance in the secondary mixed slurry is 6%, and the proportion of graphene added in the three-stage mixed slurry is 1%, and the ratio of the graphene added in the three-stage mixed slurry is The aqueous acrylic latex emulsion and the sodium carboxymethylcellulose solution were added in an amount of 6% and 3%, respectively.
  6. 根据权利要求1所述的耐高温低电阻率锂离子电池隔膜的制备方法，其中，步骤A中，对所述初级石墨烯改性陶瓷浆料进行筛网筛除时，所用筛网为200目。The method for preparing a high temperature resistant low-resistivity lithium ion battery separator according to claim 1, wherein in the step A, when the primary graphene-modified ceramic slurry is sieved, the screen used is 200 mesh. .
  7. 根据权利要求1所述的耐高温低电阻率锂离子电池隔膜的制备方法，其中，步骤B中，臭氧的流量为3L/min，处理时间为80s。The method for preparing a high temperature resistant low-resistivity lithium ion battery separator according to claim 1, wherein in step B, the flow rate of ozone is 3 L/min, and the treatment time is 80 s.
  8. 根据权利要求1所述的耐高温低电阻率锂离子电池隔膜的制备方法，其中，步骤C中，所述涂布机的涂布速度为12m/min，涂布厚度为3μm。The method for producing a high temperature resistant low-resistivity lithium ion battery separator according to claim 1, wherein in the step C, the coater has a coating speed of 12 m/min and a coating thickness of 3 μm.
  9. 根据权利要求1所述的耐高温低电阻率锂离子电池隔膜的制备方法，其中，步骤C中，所述涂布机的涂布厚度为2μm。The method for producing a high temperature resistant low-resistivity lithium ion battery separator according to claim 1, wherein in the step C, the coater has a coating thickness of 2 μm.
  10. 根据权利要求1所述的耐高温低电阻率锂离子电池隔膜的制备方法，其中，步骤C中，利用射线测厚仪对涂布厚度进行在线监测，所述涂布机设置有控制单元，射线测厚仪的信息输出端与所述控制单元的信息输入端相连，所述控制单元的信息输出端与涂布机动力机构控制端相连，所述射线测厚仪将采集的涂布厚度信息传送至控制单元；当涂布厚度正常时，控制单元不向涂布机发送指令；当涂布厚度过大时，控制单元向涂布机动发送指令，涂布机动力机构加快转速，减小涂布厚度至正常范围；当涂布 厚度过小时，控制单元向涂布机发送指令，涂布机动力机构降低转速，增大涂布厚度至正常范围。 The method for preparing a high temperature resistant low-resistivity lithium ion battery separator according to claim 1, wherein in step C, the coating thickness is monitored online by using a ray thickness gauge, and the coating machine is provided with a control unit, the ray The information output end of the thickness gauge is connected to the information input end of the control unit, and the information output end of the control unit is connected to the control end of the coater power mechanism, and the ray thickness gauge transmits the collected coating thickness information. To the control unit; when the coating thickness is normal, the control unit does not send an instruction to the coater; when the coating thickness is too large, the control unit sends an instruction to the coating maneuver, the coater power mechanism speeds up the rotation, and reduces the coating Thickness to normal range; when coated When the thickness is too small, the control unit sends a command to the coater, and the coater power mechanism reduces the rotation speed to increase the coating thickness to a normal range.
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