CN111785896A - Elastomer composite dot matrix coating composite diaphragm and lithium battery adopting same - Google Patents
Elastomer composite dot matrix coating composite diaphragm and lithium battery adopting same Download PDFInfo
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- CN111785896A CN111785896A CN201910269875.4A CN201910269875A CN111785896A CN 111785896 A CN111785896 A CN 111785896A CN 201910269875 A CN201910269875 A CN 201910269875A CN 111785896 A CN111785896 A CN 111785896A
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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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The composite diaphragm at least comprises a microporous PE base film and an elastomer composite dot matrix coating coated on the surface of the microporous PE base film, wherein the dot matrix coating adopts a microstructure formed by filling a three-dimensional rubber solid network framework, a high-viscosity liquid organic matter and a liquid/solid composition of nano-scale ceramic powder in the lattice coating; the three-dimensional rubber solid network framework provides compressible deformation and elastic recovery functions, and the high-viscosity liquid/solid composition which is dispersed and distributed in the framework plays roles in communicating, diffusing and transferring with external electrolyte; the three-dimensional rubber solid network framework main body material is prepared by taking an addition type liquid silica gel raw material as a rubber component and taking hydrophobic fumed silica nano powder as a reinforcing agent of silica gel through thermochemical crosslinking and curing at 85-125 ℃; the composite diaphragm has excellent liquid absorption and retention performances when used in the battery, and can improve the cycle life and safety of the lithium battery.
Description
Technical Field
The invention belongs to the technical field of diaphragm materials for lithium ion batteries and lithium ion batteries.
Technical Field
The diaphragm is used for isolating the positive pole piece and the negative pole piece in a lithium ion battery (the industry is called as the lithium battery for short) and has the functions of preventing physical short circuit and electronic insulation, and the micropores of the diaphragm are soaked with electrolyte and then have the function of an ion conductor.
Along with the improvement of the requirement of the power battery on the cycle life, the existing base film and ceramic coating composite diaphragm lack corresponding elastic following function and stress absorption function for the shrinkage of a negative pole piece during charge expansion and discharge of the negative pole piece and the existing diaphragm material due to the lack of a stress absorption mechanism of elastic deformation; in addition, the surface of the traditional polyolefin diaphragm is smooth, the friction force between the traditional polyolefin diaphragm and a pole piece is small, after the battery is kept for a long time at the temperature of 40-60 ℃ or at a higher temperature, the internal stress of the base film can cause shrinkage, the electrolyte holding capacity and uniformity between pole groups of the battery can be influenced, after charge and discharge circulation, the phenomenon that the pole piece is partially wrinkled or the pole piece and the diaphragm are in virtual contact in a local space often occurs in a high-capacity power lithium battery, and the service life of the power lithium battery pack is greatly shortened.
Therefore, the development of the composite diaphragm with the elastic following function and the internal stress reduction function of the lithium battery has important practical significance for prolonging the cycle life and improving the safety of the lithium ion battery.
At present, a physical gel lattice coating technology which forms a liquid absorption swelling function by rotationally spraying PVDF-HFP emulsion slurry on the surface of a diaphragm is adopted, and the problems of large particles and uneven coating often occur because the uniformity of rotational spraying is limited, and the uniformity of mass-produced products is difficult to control. In addition, after the PVDF-HFP copolymer is contacted with the electrolyte at a high temperature of 45-60 ℃ for a long time, besides the fact that the PVDF-HFP copolymer absorbs normal liquid and swells to form a physically crosslinked gel-state polymer and swells to be a certain elastomer, the PVDF-HFP copolymer can also have the problem that part of low-molecular polymer is dissolved in the electrolyte, and therefore subsequent quick charging and the like can be influenced, and even unsafe phenomena such as lithium precipitation and the like can occur due to the fact that the dissolved product blocks micropores of a base membrane.
In order to overcome the defects of the prior diaphragm technology and improve the service life and the safety of a battery, the invention designs a chemically crosslinked elastomer composite material dot matrix coating composite diaphragm and a lithium battery adopting the diaphragm, and particularly provides the invention.
Disclosure of Invention
The composite diaphragm is characterized by at least comprising a microporous PE base film and an elastomer composite dot matrix coating coated on the surface of the microporous PE base film, wherein the elastomer composite dot matrix coating adopts a microstructure formed by filling a three-dimensional Rubber solid network framework (Rubber-Net) and a high-viscosity liquid organic matter and a liquid/solid composition (L/S) of nano-scale ceramic powder in the composite diaphragm; the three-dimensional Rubber solid network framework (Rubber-Net) provides the elastomer functions of compressible deformation and elastic recovery, and the liquid/solid composition (L/S) dispersed and distributed in the three-dimensional Rubber solid network framework plays a role of communicating with external electrolyte for mass transfer; the three-dimensional Rubber solid network framework (Rubber-Net) main body material is prepared by taking an addition type liquid silica gel raw material as a Rubber component and taking hydrophobic fumed silica nano powder as a reinforcing agent of silica gel and performing thermochemical crosslinking and curing at 85-125 ℃; the high-viscosity liquid organic matter (L) dispersed and distributed among three-dimensional Rubber solid network frameworks (Rubber-Net) mainly comprises: ester solvent L1 with flash point above 125 ℃ and interdiffusion dissoluble with lithium battery electrolyte: one or a combination of Ethylene Carbonate (EC), Propylene Carbonate (PC) and dioctyl sebacate (DOS); viscosity modifier L2: one or the combination of highly active polyisobutylene with the kinematic viscosity of 800-10000cst, hydrogen-containing silicone oil and long-chain alkyl silicone oil; wetting and interface conditioner L3: 16 alkyl trimethoxy silane, 18 alkyl trimethoxy silane, vinyl tri (beta-methoxy ethoxy) silane, 2- (3, 4-epoxy cyclohexyl) ethyl triethoxy silane, 3- (2, 3 epoxy propoxy) propyl methyl diethoxy silane, polyether modified polysiloxane; nano-ceramic powder (S) which is dispersed and distributed among three-dimensional Rubber solid network frameworks (Rubber-Net) and hydrophobic fumed silica used in liquid silica gel raw materials, wherein the average particle size of aggregates of the nano-ceramic powder (S) is between 20 and 200 nanometers; the raw material composition of the addition type liquid silica gel mainly comprises: the liquid silica gel material composition is prepared by uniformly mixing double-end vinyl silicone oil and/or methyl vinyl silicone oil with vinyl contained in a side chain, wherein a cross-linking agent adopts hydrogen-containing silicone oil, the hydrogen-containing silicone oil comprises methyl-end side hydrogen silicone oil and/or double-end hydrogen silicone oil, a catalyst adopts a complex of VIII group transition metal in the periodic table of elements, the catalyst comprises a platinum complex formed by chloroplatinic acid and alkene, cycloparaffin, alcohol, ether and the like, a reinforcing agent adopts hydrophobic gas phase method white carbon black, and after the liquid silica gel material composition is uniformly mixed at a temperature range of 40-50 ℃, the kinematic viscosity (V-RN) of the liquid silica gel material composition is between 500 and 3000; uniformly mixing liquid organic matters and nano ceramic powder liquid/solid composition raw materials (L/S) which are dispersedly distributed among three-dimensional rubber solid network frameworks at a temperature range of 40-50 ℃, and then obtaining a composition with kinematic viscosity (V-LS) ═ V-RN) + (50-500) cst; the microporous PE-based membrane has a thickness of 5-23 microns, a porosity of 40-60%, an average pore size of 30-200 nm, a length a1 and a width b1 or diameter of the elastomer composite lattice coating of 30-200 microns, a2 transverse spacing between the elastomer composite lattice coating of (0.5-5) a1, and a b2 longitudinal spacing between the elastomer composite lattice coating of (0.5-5) b 1; the thickness T02 of the elastomer composite lattice coating is tested to be between 3 and 10 micrometers under the nominal pressure of 0.15 to 0.20MPa, the thickness T08 of the elastomer composite lattice coating is tested to be (0.4 to 0.6) T02 micrometers under the nominal pressure of 0.75 to 0.80MPa, and the ratio of the conductivity of the composite diaphragm after being soaked in the electrolyte to the conductivity of the pure electrolyte is 1: 2 to 9.
Preparing raw materials of an elastomer composite dot matrix at 40-50 ℃ in advance, stirring and uniformly dispersing the raw material mixture under vacuum to form composite glue solution, dipping the raw materials by adopting a dot-matrix gravure roll, transferring and coating the mixture to the surface of a PE microporous base film, arranging a negative pressure adsorption roll at an inlet of a coating oven for isolating front and rear process tension, and applying an additional force pressing the non-crosslinked glue solution dot matrix into the base film through a negative pressure effect, so that the permeation effect and the bonding strength of the glue solution on the PE microporous base film are improved, and heating a composite diaphragm coated with the dot-matrix glue solution to 95-125 ℃ in the coating oven for thermal cross-linking curing for 20-300 seconds; and (3) isolating the process tension of the composite diaphragm before and after the composite diaphragm is isolated by a negative pressure adsorption roller at the outlet of the coating oven, cooling the composite diaphragm to 25-40 ℃ by a water cooling roller or a cooling air blowing, and then rolling to obtain the composite diaphragm coated by the elastomer composite dot matrix.
When the elastomer composite material lattice single-side coated composite diaphragm is used in a lithium battery, one side of the lattice coating correspondingly contacts with the negative pole piece.
When the elastomer composite material lattice single-side coated composite diaphragm is used in a lithium battery, one side of the lattice coating correspondingly contacts with the positive pole piece.
The two sides of the microporous PE base film are respectively coated with an elastomer composite dot matrix coating, the thickness of the microporous PE base film is between 9 and 16 micrometers, the porosity is between 43 and 55 percent, the average pore diameter is between 40 and 120 nanometers, the Gurley value is between 40 and 130s/100cc, the length a1 and the width b1 of the elastomer composite dot matrix are between 80 and 130 micrometers, the transverse interval a2 between the dot matrixes is between (1.0 and 1.5) a1, and the longitudinal interval b2 between the dot matrixes is between (1.0 and 1.5) b 1; the raw material composition of the addition type liquid silica gel is uniformly mixed at the temperature of 40-50 ℃, and the kinematic viscosity (V-RN) is between 800-1800st, and the main raw materials comprise: 100 parts of double-end vinyl silicone oil with the vinyl content of 0.30-0.36 percent, 230 parts of terminal methyl side hydrogen silicone oil with the hydrogen content of 0.17-0.20 percent, 80-110 parts of hydrophobic fumed silica serving as a reinforcing agent, and 20-200 nanometers of the average particle size of a white carbon black aggregate; after the liquid/solid composition raw materials (L/S) of the liquid organic matter and the nano ceramic powder filled between the three-dimensional rubber solid network frameworks are uniformly mixed at the temperature of between 40 and 50 ℃, the kinematic viscosity (V-LS) of the liquid/solid composition raw materials is between 1000-2000st, and the main raw materials comprise: 230-280 parts by weight of Ethylene Carbonate (EC), 70-130 parts by weight of a viscosity regulator R2: high-activity polyisobutene or/and long-chain alkyl silicone oil with the kinematic viscosity of 3000-8000cst, 3-6 parts by weight of wetting agent R3: polyether modified polysiloxane; 80-150 parts of nano ceramic powder, hydrophobic fumed silica is adopted, and the average particle size of the white silica aggregate is 20-200 nm; uniformly mixing liquid/solid composition raw materials (L/S), continuously uniformly mixing the liquid/solid composition raw materials with a composition of a liquid silica gel raw material to prepare a composite material glue solution, respectively coating composite material dot matrix coatings on two surfaces of a PE microporous base film by adopting a dot matrix gravure process, heating at 95-125 ℃, performing thermochemical crosslinking treatment on a composite material slurry coating to prepare a composite diaphragm with an elastomer composite material dot matrix coating on two surfaces, testing the sum total thickness of the two surface coatings of the elastomer composite material dot matrix coating by adopting 0.2MPa nominal pressure to be 8-10 micrometers, testing the sum total thickness of the two surface coatings of the elastomer composite material dot matrix coating by adopting 0.8MPa nominal pressure to be 4-6 micrometers, and testing the ratio of the conductivity of the composite diaphragm after soaking electrolyte to the conductivity of pure electrolyte to be 1: 4-8, the battery pole group made by the composite diaphragm clamped between the positive pole piece and the negative pole piece of the lithium battery can still keep electronic insulation at 150 ℃/30min
The present disclosure and technical schemes are further explained as follows:
the thickness of the microporous PE base film is controlled to be between 5 and 23 micrometers, the porosity is controlled to be between 40 and 60 percent, the average pore diameter is controlled to be between 30 and 200 nanometers, the thickness of the PE base film is higher than 23 micrometers, the porosity is lower than 40 percent, and the average pore diameter is smaller than 30 nanometers. The length a1 and width b1 of the elastomeric composite lattices are controlled to be between 30 and 200 microns, the transverse spacing a2 between the lattices is between (0.5 and 5) a1, the longitudinal spacing b2 between the lattices is between (0.5 and 5) b1, the configuration is convenient for the electrolyte to form a capillary action between the elastomer composite lattice and the pole pieces contacted with the elastomer composite lattice, the composite diaphragm can expand and contract along with the pole pieces and still ensure that the electrolyte between the pole pieces is fully distributed and kept wet without the occurrence of local barren solution, the elastomer composite lattice has compression and elastic recovery performance, nominal pressure of 0.15-0.20MPa is adopted, a flat head precision thickness gauge is adopted to test the thickness T02 of a lattice coating to be between 3 and 10 micrometers, when the lattice coating is measured by using a nominal pressure test of 0.75-0.80MPa, the lattice coating can be deformed by compression, and the thickness is reduced by T08-T02 times.
The raw material composition of the addition type liquid silica gel mainly comprises: the invention specially controls the kinematic viscosity (V-RN) of the liquid silica gel raw material composition to be between 500 and 3000cst, is convenient for proper transfer during coating and controls the fluidity of a glue solution lattice, and an addition reaction can be carried out between the glue solution of the liquid silica gel and partial high-activity polyisobutylene in a coating oven under the action of high temperature of 85-125 ℃, the invention effectively controls the components and physical states of the organic liquid composition and the nano ceramic powder among the rubber networks, and the organic liquid composition maintains slightly higher viscosity, so when the liquid silica gel is subjected to thermochemical crosslinking, the composition of the liquid organic matter dispersed and distributed in the liquid organic matter has proper viscosity and steric effect of the nano powder, can effectively prevent the liquid silicon rubber from forming a closed-pore network during curing, can obtain an open three-dimensional rubber solid network skeleton form, when the composite diaphragm is applied to a lithium battery later, after the battery is injected with liquid, organic solvents DMC, EC, PC, DEC, EMC and lithium salt in electrolyte can be diffused and dissolved with liquid organic matters in an elastomer composite material lattice, namely the elastomer composite material lattice has ion conduction and mass transfer capacity in the lithium battery; the nano ceramic powder distributed in the three-dimensional rubber solid network framework and the crosslinked rubber network can form a capillary action, namely, the electrolyte can be partially separated out after the elastic composite material lattice coating is compressed, and the electrolyte can be sucked into the three-dimensional rubber solid network framework through the capillary action after the lattice elasticity is recovered. The composite separator structure of the present invention has excellent electrolyte retaining and distributing capabilities.
After the two surfaces of the diaphragm are coated with the dot matrix coating of the elastomer composite material, the interface friction coefficient and the friction force of the pole group and the composite diaphragm in the lithium battery are improved, so that the contraction of the polyolefin base film is prevented, the electronic insulation holding capacity of the pole group at high temperature is ensured, and the safety of the lithium battery can be improved.
Drawings
Description figure 1 is a schematic diagram of the lattice coating composite membrane of the invention, wherein a1 is the length of the lattice coating, a2 is the spacing distance between the transverse directions of the lattice coating, b1 is the width of the lattice coating, b2 is the spacing distance between the longitudinal directions of the lattice coating, t1 is the thickness of the PE microporous base membrane, and t2 is the thickness of the lattice coating.
Examples
Example one
The two sides of the microporous PE base film are respectively coated with an elastomer composite dot matrix coating, the thickness of the microporous PE base film is between 9 and 16 micrometers, the porosity is between 43 and 55 percent, the average pore diameter is between 40 and 120 nanometers, the Gurley value is between 40 and 130s/100cc, the length a1 and the width b1 of the elastomer composite dot matrix are between 80 and 130 micrometers, the transverse interval a2 between the dot matrixes is between (1.0 and 1.5) a1, and the longitudinal interval b2 between the dot matrixes is between (1.0 and 1.5) b 1; the raw material composition of the addition type liquid silica gel is uniformly mixed at the temperature of 40-50 ℃, the kinematic viscosity (V-RN) is between 900 and 1100cst, and the main raw materials comprise: 100 parts of double-end vinyl silicone oil with the vinyl content of 0.30-0.36 percent, 230 parts of terminal methyl side hydrogen silicone oil with the hydrogen content of 0.17-0.20 percent, 80-110 parts of hydrophobic fumed silica serving as a reinforcing agent, and 20-200 nanometers of the average particle size of a white carbon black aggregate; after the liquid organic matter filled between the three-dimensional rubber solid network frameworks and the liquid/solid composition raw material (L/S) of the nano ceramic powder are uniformly mixed at the temperature of between 40 and 50 ℃, the kinematic viscosity (V-LS) of the liquid/solid composition raw material is between 1200 and 1500cst, and the main raw materials comprise: 260-280 parts by weight of Ethylene Carbonate (EC), 90-110 parts by weight of viscosity regulator R2: high-activity polyisobutylene or/and long-chain alkyl silicone oil with the kinematic viscosity of 4000-5000cst, 3-5 parts by weight of wetting agent R3: polyether modified polysiloxane; 100-120 parts by weight of nano ceramic powder and hydrophobic fumed silica, wherein the average particle size of the white carbon black aggregate is 50-120 nm; uniformly mixing liquid/solid composition raw materials (L/S), continuously uniformly mixing the liquid/solid composition raw materials with a composition of a liquid silica gel raw material to prepare a composite material glue solution, respectively coating composite material dot matrix coatings on two surfaces of a PE microporous base film by adopting a dot matrix gravure process, heating at 95-125 ℃, performing thermochemical crosslinking treatment on a composite material slurry coating to prepare a composite diaphragm with an elastomer composite material dot matrix coating on two surfaces, testing the sum total thickness of the two surface coatings of the elastomer composite material dot matrix coating by adopting 0.2MPa nominal pressure to be 8-10 micrometers, testing the sum total thickness of the two surface coatings of the elastomer composite material dot matrix coating by adopting 0.8MPa nominal pressure to be 4-6 micrometers, wherein the ratio of the conductivity of the composite diaphragm after soaking electrolyte to the conductivity of pure electrolyte is 1: 5-8, the composite diaphragm is clamped between the positive pole piece and the negative pole piece of the lithium battery to form a battery pole group which can still keep electronic insulation at the temperature of 180 ℃/30min with the temperature of 150-.
Claims (5)
1. The composite diaphragm is characterized by at least comprising a microporous PE base film and an elastomer composite dot matrix coating coated on the surface of the microporous PE base film, wherein the elastomer composite dot matrix coating adopts a microstructure formed by filling a three-dimensional Rubber solid network framework (Rubber-Net) and a high-viscosity liquid organic matter and a liquid/solid composition (L/S) of nano-scale ceramic powder in the composite diaphragm; the three-dimensional Rubber solid network framework (Rubber-Net) provides the elastomer functions of compressible deformation and elastic recovery, and the liquid/solid composition (L/S) dispersed and distributed in the three-dimensional Rubber solid network framework plays a role of communicating with external electrolyte for mass transfer; the three-dimensional Rubber solid network framework (Rubber-Net) main body material is prepared by taking an addition type liquid silica gel raw material as a Rubber component and taking hydrophobic fumed silica nano powder as a reinforcing agent of silica gel and performing thermochemical crosslinking and curing at 85-125 ℃; the high-viscosity liquid organic matter (L) dispersed and distributed among three-dimensional Rubber solid network frameworks (Rubber-Net) mainly comprises: ester solvent L1 with flash point above 125 ℃ and interdiffusion dissoluble with lithium battery electrolyte: one or a combination of Ethylene Carbonate (EC), Propylene Carbonate (PC) and dioctyl sebacate (DOS); viscosity modifier L2: one or the combination of highly active polyisobutylene with the kinematic viscosity of 800-10000cst, hydrogen-containing silicone oil and long-chain alkyl silicone oil; wetting and interface conditioner L3: 16 alkyl trimethoxy silane, 18 alkyl trimethoxy silane, vinyl tri (beta-methoxy ethoxy) silane, 2- (3, 4-epoxy cyclohexyl) ethyl triethoxy silane, 3- (2, 3 epoxy propoxy) propyl methyl diethoxy silane, polyether modified polysiloxane; nano-ceramic powder (S) which is dispersed and distributed among three-dimensional Rubber solid network frameworks (Rubber-Net) and hydrophobic fumed silica used in liquid silica gel raw materials, wherein the average particle size of aggregates of the nano-ceramic powder (S) is between 20 and 200 nanometers; the raw material composition of the addition type liquid silica gel mainly comprises: the liquid silica gel material composition is prepared by uniformly mixing double-end vinyl silicone oil and/or methyl vinyl silicone oil with vinyl contained in a side chain, wherein a cross-linking agent adopts hydrogen-containing silicone oil, the hydrogen-containing silicone oil comprises methyl-end side hydrogen silicone oil and/or double-end hydrogen silicone oil, a catalyst adopts a complex of VIII group transition metal in the periodic table of elements, the catalyst comprises a platinum complex formed by chloroplatinic acid and alkene, cycloparaffin, alcohol, ether and the like, a reinforcing agent adopts hydrophobic gas phase method white carbon black, and after the liquid silica gel material composition is uniformly mixed at a temperature range of 40-50 ℃, the kinematic viscosity (V-RN) of the liquid silica gel material composition is between 500 and 3000; uniformly mixing liquid organic matters and nano ceramic powder liquid/solid composition raw materials (L/S) which are dispersedly distributed among three-dimensional rubber solid network frameworks at a temperature range of 40-50 ℃, and then obtaining a composition with kinematic viscosity (V-LS) ═ V-RN) + (50-500) cst; the microporous PE-based membrane has a thickness of 5-23 microns, a porosity of 40-60%, an average pore size of 30-200 nm, a length a1 and a width b1 or diameter of the elastomer composite lattice coating of 30-200 microns, a2 transverse spacing between the elastomer composite lattice coating of (0.5-5) a1, and a b2 longitudinal spacing between the elastomer composite lattice coating of (0.5-5) b 1; the thickness T02 of the elastomer composite lattice coating is tested to be between 3 and 10 micrometers under the nominal pressure of 0.15 to 0.20MPa, the thickness T08 of the elastomer composite lattice coating is tested to be (0.4 to 0.6) T02 micrometers under the nominal pressure of 0.75 to 0.80MPa, and the ratio of the conductivity of the composite diaphragm after being soaked in the electrolyte to the conductivity of the pure electrolyte is 1: 2 to 9.
2. The composite diaphragm coated with the lattice of the elastomer composite material and the lithium battery adopting the diaphragm as claimed in claim 1, wherein the raw materials of the lattice of the elastomer composite material are prepared at 40-50 ℃ in advance, the raw material mixture is stirred and uniformly dispersed under vacuum to form a composite glue solution, then the composite glue solution is transferred and coated on the surface of the PE microporous base membrane after being subjected to the mesh point gum dipping of a lattice gravure roll, a negative pressure adsorption roll is arranged at the inlet of a coating oven for isolating the process tension before and after isolation, and an additional force for pressing the non-crosslinked glue solution lattice into the base membrane is applied to the non-crosslinked glue solution lattice through the negative pressure effect, so that the infiltration effect and the bonding strength of the heat-exchange glue solution on the PE microporous base membrane are improved, and the composite diaphragm coated with the lattice glue solution is heated to 95-125 ℃ in the coating oven for cross-; and (3) isolating the process tension of the composite diaphragm before and after the composite diaphragm is isolated by a negative pressure adsorption roller at the outlet of the coating oven, cooling the composite diaphragm to 25-40 ℃ by a water cooling roller or a cooling air blowing, and then rolling to obtain the composite diaphragm coated by the elastomer composite dot matrix.
3. The elastomer composite lattice coated composite separator as claimed in claim 1, wherein when the elastomer composite lattice single-side coated composite separator is used in a lithium battery, one side of the lattice coating layer is correspondingly contacted with the negative electrode plate.
4. The elastomer composite lattice coated composite diaphragm and the lithium battery adopting the diaphragm of claim 1, wherein when the elastomer composite lattice single-side coated composite diaphragm is used in the lithium battery, one side of the lattice coating layer is correspondingly contacted with the positive pole piece.
5. The elastomer composite dot matrix coated composite separator and the lithium battery using the same as claimed in claim 1, wherein both sides of the microporous PE-based film are coated with the elastomer composite dot matrix coating layer, respectively, the microporous PE-based film has a thickness of 9-16 μm, a porosity of 43-55%, an average pore size of 40-120 nm, a Gurley value of 40-130s/100cc, a length a1 and a width b1 of the elastomer composite dot matrix of 80-130 μm, a2 of transverse intervals between the dots a1 of (1.0-1.5) a1, and a b2 of longitudinal intervals between the dots b 3838 of (1.0-1.5) b 1; the raw material composition of the addition type liquid silica gel is uniformly mixed at the temperature of 40-50 ℃, and the kinematic viscosity (V-RN) is between 800-1800st, and the main raw materials comprise: 100 parts of double-end vinyl silicone oil with the vinyl content of 0.30-0.36 percent, 230 parts of terminal methyl side hydrogen silicone oil with the hydrogen content of 0.17-0.20 percent, 80-110 parts of hydrophobic fumed silica serving as a reinforcing agent, and 20-200 nanometers of the average particle size of a white carbon black aggregate; after the liquid/solid composition raw materials (L/S) of the liquid organic matter and the nano ceramic powder filled between the three-dimensional rubber solid network frameworks are uniformly mixed at the temperature of between 40 and 50 ℃, the kinematic viscosity (V-LS) of the liquid/solid composition raw materials is between 1000-2000st, and the main raw materials comprise: 230-280 parts by weight of Ethylene Carbonate (EC), 70-130 parts by weight of a viscosity regulator R2: high-activity polyisobutene or/and long-chain alkyl silicone oil with the kinematic viscosity of 3000-8000cst, 3-6 parts by weight of wetting agent R3: polyether modified polysiloxane; 80-150 parts of nano ceramic powder, hydrophobic fumed silica is adopted, and the average particle size of the white silica aggregate is 20-200 nm; uniformly mixing liquid/solid composition raw materials (L/S), continuously uniformly mixing the liquid/solid composition raw materials with a composition of a liquid silica gel raw material to prepare a composite material glue solution, respectively coating composite material dot matrix coatings on two surfaces of a PE microporous base film by adopting a dot matrix gravure process, heating at 95-125 ℃, performing thermochemical crosslinking treatment on a composite material slurry coating to prepare a composite diaphragm with an elastomer composite material dot matrix coating on two surfaces, testing the sum total thickness of the two surface coatings of the elastomer composite material dot matrix coating by adopting 0.2MPa nominal pressure to be 8-10 micrometers, testing the sum total thickness of the two surface coatings of the elastomer composite material dot matrix coating by adopting 0.8MPa nominal pressure to be 4-6 micrometers, and testing the ratio of the conductivity of the composite diaphragm after soaking electrolyte to the conductivity of pure electrolyte to be 1: 4-8, the composite diaphragm is clamped between the positive pole piece and the negative pole piece of the lithium battery to form a battery pole group which can still keep electronic insulation at 150 ℃/30 min.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103035864A (en) * | 2011-09-30 | 2013-04-10 | 天津东皋膜技术有限公司 | High temperature resistant coating diaphragm with compression elasticity and thermal shutdown |
| US20180051137A1 (en) * | 2015-12-17 | 2018-02-22 | Lg Chem, Ltd. | Lithium secondary battery anode and lithium secondary battery including same |
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2019
- 2019-04-04 CN CN201910269875.4A patent/CN111785896A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103035864A (en) * | 2011-09-30 | 2013-04-10 | 天津东皋膜技术有限公司 | High temperature resistant coating diaphragm with compression elasticity and thermal shutdown |
| US20180051137A1 (en) * | 2015-12-17 | 2018-02-22 | Lg Chem, Ltd. | Lithium secondary battery anode and lithium secondary battery including same |
Non-Patent Citations (1)
| Title |
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| 钟国彬;王中会;梁鑫;项宏发;: "黏结剂对锂离子电池陶瓷涂敷隔膜的性能影响", 储能科学与技术, no. 06, 19 October 2018 (2018-10-19) * |
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