CN111192996A - Organic coating/polyethylene composite diaphragm, preparation method thereof and lithium ion battery - Google Patents
Organic coating/polyethylene composite diaphragm, preparation method thereof and lithium ion battery Download PDFInfo
- Publication number
- CN111192996A CN111192996A CN201911304164.2A CN201911304164A CN111192996A CN 111192996 A CN111192996 A CN 111192996A CN 201911304164 A CN201911304164 A CN 201911304164A CN 111192996 A CN111192996 A CN 111192996A
- Authority
- CN
- China
- Prior art keywords
- polyethylene
- coating
- polyethylene wax
- diaphragm
- base film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- 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
- H01M50/431—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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention provides a polyethylene composite diaphragm, which comprises a polyethylene base film; and the polyethylene wax coating is compounded on at least one surface of the polyethylene base film. The polyethylene wax coating is adopted, the organic coating has good compatibility with the PE base membrane, the pore-closing temperature of the membrane is effectively reduced, the pore-closing performance of the polyethylene membrane is improved, the safety performance of the battery is improved, when the thin polyethylene base membrane is dealt with, the defects of pinholes, microcracks and the like of the polyethylene base membrane can be reduced through the organic coating structure, the pore tortuosity is increased, the self-discharge of the battery is reduced, the thickness of the thin membrane is realized on the premise that the comprehensive performance of the membrane is not influenced and even better. The polyethylene wax slurry provided by the invention has high purity and good stability, is easy to realize large-scale production, has low cost, is easy to be compounded with other functional coatings, is suitable for industrial production, and provides a feasible scheme for solving the problem of thinning of the PE diaphragm by a wet method.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery diaphragm materials, relates to a polyethylene composite diaphragm and a preparation method thereof, and a lithium ion battery, and particularly relates to an organic coating/polyethylene composite diaphragm and a preparation method thereof, and a lithium ion battery.
Background
The lithium ion battery is used as a core component of a pure electric new energy automobile, and the safety problem of the lithium ion battery becomes one of key indexes limiting further development of the lithium ion battery. The reasons for the safety accidents of lithium ion batteries are mainly related to the composition, design and manufacturing process of single batteries, except for design defects of the batteries, abuse in the using process and external environmental impact, wherein the battery pack is particularly critical to the influence of safety performance. The diaphragm is used as one of four main materials of the lithium ion battery, has important influence on the comprehensive performance of the lithium ion battery, and particularly plays a role in preventing the short circuit of the battery and providing an electrolyte ion channel in the aspect of safety performance because the diaphragm is positioned between a positive electrode and a negative electrode. The research on the thermal runaway reaction kinetic mechanism of the lithium ion battery shows that the whole process can be divided into three stages: (1) in the thermal runaway stage inside the battery, the internal temperature of the battery rises to about 100 ℃ due to heating, short circuit and the like, the SEI film of the anode starts to decompose, and the lithium intercalated into the graphite reacts with the electrolyte to further increase the internal temperature of the battery. (2) And in the battery swelling process, when the temperature of the battery rises to 200 ℃, the cathode material is decomposed to release a large amount of heat and gas, and the lithium-embedded anode starts to react with the electrolyte at the temperature of 250-350 ℃. (3) The whole thermal runaway of the battery is caused by the fact that the external package of the battery is broken as the internal pressure of the lithium ion battery is increased violently at the stage, and the external oxygen, electrolyte steam and combustible smoke/combustible smoke generated by various reactions are subjected to combustion reaction and then are combusted to fire, so that the whole thermal runaway of the lithium ion battery is caused. In the thermal runaway process of the lithium ion battery, the diaphragm mainly acts in the first stage, the polyolefin diaphragm is melted, the pore structure is closed, the lithium ion transmission is prevented, and the battery is disconnected, so that the further thermal runaway of the lithium ion battery is limited.
Thus, the importance of separators in lithium battery modules is increasing, and the impact thereof on lithium batteries is also becoming more and more important. Key indicators affecting membrane performance include thickness, air permeability, porosity, pore closing temperature, thermal stability, wettability, tensile strength, puncture strength, and the like. At present, the main material of the commercial lithium ion battery diaphragm is polyolefin, and the commercial lithium ion battery diaphragm can be divided into a wet diaphragm and a dry diaphragm according to different preparation processes. Under the influence of the trend of lithium ion batteries towards high energy density, the polyethylene diaphragm (PE film) prepared by a wet process has increasingly outstanding advantages in the aspect of controlling the thickness. However, as the thickness of the separator is reduced, the other properties of the separator are inevitably greatly affected, and the thermal stability, the electrolyte wettability and other properties of the separator are generally improved by coating inorganic ceramic materials such as alumina and boehmite. Although the ceramic coating can make up for the defect caused by the thinning of the diaphragm thickness to a certain extent, the problems of poor closed pore performance, more pinhole/microcrack defects and the like are still difficult to solve.
Therefore, how to find a suitable method, which can solve the above problems in the existing diaphragm, and have a thinner diaphragm thickness on the premise of ensuring that the comprehensive performance of the product is not affected, has become one of the key technical problems to be solved urgently in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a polyethylene composite separator, a preparation method thereof, and a lithium ion battery, in particular, an organic coating/polyethylene composite separator. On the basis of realizing the thinning of the PE diaphragm, the organic coating/polyethylene composite diaphragm provided by the invention has good compatibility with the PE base film, and can reduce the hole closing temperature of the diaphragm, improve the hole closing performance of the polyethylene diaphragm and improve the safety performance of a battery.
The invention provides a polyethylene composite diaphragm, which comprises a polyethylene base film;
and the polyethylene wax coating is compounded on at least one surface of the polyethylene base film.
Preferably, the polyethylene wax coating has a microscopic morphology of one or more of lobate, petaloid and spheroidal polyethylene wax particles in an overlapping arrangement;
the thickness of the polyethylene wax coating is 0.3-3 mu m;
the polyethylene-based film is a microporous film.
Preferably, the molecular weight of the polyethylene wax is 1000-10000;
the median particle size of the polyethylene wax particles is 0.1-3 mu m;
the polyethylene wax coating is compounded on the polyethylene base film by polyethylene wax slurry.
Preferably, the median pore diameter of the polyethylene-based film is 20-100 nm;
the thickness of the polyethylene base film is 3-20 mu m;
the polyethylene base film is prepared by a wet process.
Preferably, the polyethylene wax slurry comprises, by mass percent:
preferably, other functional coatings can be compounded on the polyethylene wax coating;
the other functional coating comprises a ceramic coating;
the ceramic powder in the ceramic coating comprises one or more of alumina, boehmite, magnesia, silica, zirconia, barium sulfate and calcium sulfate;
the median particle size of the ceramic powder is 0.1-2 mu m;
the specific surface area of the ceramic powder is 0.5-10 m2/g。
Preferably, the adhesive comprises one or more of styrene acrylic acid, polyacrylamide, polyvinyl alcohol, polyethylene oxide, modified paraffin resin, polyacrylic acid, polyurethane acrylate and polyacrylate copolymer emulsion;
the wetting agent comprises one or more of polyethylene glycol, polyvinylpyrrolidone, linear alkyl benzene sodium sulfonate, alkyl polyoxyethylene ether, sodium lauryl sulfate and alkyl sulfonate;
the stabilizer preferably comprises one or more of fatty amine polyoxyethylene ether, sodium carboxymethylcellulose, methylcellulose, hydroxypropyl methylcellulose, hydroxyethyl cellulose, gelatin, sodium alginate, fatty alcohol polyoxyethylene ether and polyether amine.
The invention provides a preparation method of a polyethylene composite diaphragm, which comprises the following steps:
1) mixing polyethylene wax emulsion and/or powder, water, adhesive, wetting agent and stabilizing agent at a high speed to obtain polyethylene wax slurry;
2) and coating the polyethylene wax slurry on the polyethylene base film, and drying to obtain the polyethylene composite diaphragm.
Preferably, the coating comprises one or more of spray coating, gravure coating, slot coating and wet-out coating;
the high-speed mixing time is 30-120 min;
the rotating speed of the high-speed mixing is 200-2000 r/min;
the drying time is 0.5-10 min;
the drying temperature is 30-80 ℃;
the method also comprises a step of drying the composite ceramic slurry.
The invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte;
the diaphragm comprises the polyethylene composite diaphragm or the polyethylene composite diaphragm prepared by the preparation method in any one of the above technical schemes.
The invention provides a polyethylene composite diaphragm, which comprises a polyethylene base film; and the polyethylene wax coating is compounded on at least one surface of the polyethylene base film. Compared with the prior art, the invention aims at the problem that the thickness of the conventional PE diaphragm of the lithium ion battery is reduced, and the negative influence of other performances of the diaphragm is increased, so that the thinning is difficult to realize. Currently, the thickness of the lithium ion battery separator which is the thinnest in commercial application is controlled to be 9 μm. In addition, the composite film disclosed in the industry has the advantages of high temperature resistance and low pore closing temperature if a multi-layer structure diaphragm is prepared by adopting a micro-nano lamination technology, or a ceramic layer and a high-density polyolefin layer are sequentially coated on a base film, so that the thermal stability of the diaphragm is improved, the pore closing temperature is reduced and the like, the base film is a multi-layer polypropylene diaphragm formed by the micro-nano lamination technology, or a technical scheme that organic slurry and ceramic slurry are coated on two sides of the multi-layer polypropylene diaphragm, the thickness of the lithium ion battery diaphragm is difficult to effectively reduce, the process for improving the pore closing mechanism of the diaphragm is complex, the large-scale realizability is low.
The invention provides an organic coating/polyethylene composite diaphragm, which creatively adopts a polyethylene wax coating, the organic coating has good compatibility with a PE base film, the closed pore temperature of the diaphragm is effectively reduced, the closed pore performance of the polyethylene diaphragm is improved, the safety performance of a battery is improved, when a thinner polyethylene base film is dealt with, the defects of pinholes, microcracks and the like of the polyethylene base film can be reduced through an organic coating structure, the porosity tortuosity is increased, and the self-discharge of the battery is reduced, so that the thinner diaphragm thickness can be realized on the premise that the comprehensive performance of the diaphragm is not influenced and is even better, and the thinning of the PE diaphragm is realized.
The polyethylene wax slurry provided by the invention has high purity and good stability, is easy to realize large-scale production, has low cost, is easy to be compounded with other coatings such as ceramic coatings, is suitable for industrial production, and provides a feasible scheme for solving the thinning problem of the wet-process PE diaphragm.
Experimental results show that the organic coating/polyethylene composite diaphragm provided by the invention has the advantages that on the premise of reducing the overall thickness, the performances of air permeability, thermal stability, heat storage and the like completely meet the production requirements of lithium ion batteries, the closed pore temperature of the diaphragm can be effectively reduced, and the safety performance of the battery is improved.
Drawings
FIG. 1 is an SEM electron micrograph of an organic coating composite membrane prepared in example 1 of the present invention;
FIG. 2 is an SEM micrograph of a commercial polyethylene-based film provided in comparative example 1 of the present invention;
FIG. 3 is an SEM micrograph of a disassembled diaphragm of example 1 of the present invention after thermal shock testing;
FIG. 4 is an SEM micrograph of a disassembled inventive comparative example 1 membrane after thermal shock testing;
FIG. 5 is an SEM electron micrograph of an organic coating composite membrane prepared in example 6 of the present invention;
fig. 6 is an SEM electron micrograph of the organic coating composite separator prepared in example 7 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the invention are not particularly limited in purity, and the invention preferably adopts analytically pure or conventional purity used in the field of lithium ion battery separator preparation.
The invention provides a polyethylene composite diaphragm, which comprises a polyethylene base film;
and the polyethylene wax coating is compounded on at least one surface of the polyethylene base film.
The polyethylene composite membrane comprises a polyethylene base membrane.
The invention has no special restriction on the selection of the polyethylene base film in principle, and a person skilled in the art can select and adjust the polyethylene base film according to the actual application condition, the product requirement and the quality requirement. Furthermore, the median pore diameter of the polyethylene-based film is preferably 20-100 nm, more preferably 20-80 nm, more preferably 25-60 μm, and more preferably 30-50 μm.
The specific parameters and types of the polyethylene base film are not particularly limited in principle, and a person skilled in the art can select and adjust the polyethylene base film according to the actual application condition, the product requirement and the quality requirement, in order to better ensure the compatibility with the polyethylene wax coating, improve the low-temperature hole closing effect and ensure the comprehensive performance, and simultaneously match with the composite coating structure, reduce the self defect and further reduce the thickness, the thickness of the polyethylene base film is preferably 3-20 μm, more preferably 5-18 μm, more preferably 8-15 μm, and more preferably 10-12 μm. The polyethylene-based film is preferably prepared by a wet process, namely a wet polyethylene film.
The polyethylene composite membrane comprises a polyethylene wax coating compounded on at least one surface of a polyethylene base membrane. The polyethylene wax coating is compounded on the polyethylene base film, and specifically can be compounded on one side of the polyethylene base film and also can be compounded on two sides of the polyethylene base film.
The structure of the polyethylene wax coating is not particularly limited in principle, and a person skilled in the art can select and adjust the structure according to the actual application condition, the product requirement and the quality requirement. More specifically, the median particle diameter of the polyethylene wax particles is preferably 0.1 to 3 μm, more preferably 0.3 to 2.8 μm, more preferably 0.5 to 2.5 μm, more preferably 0.8 to 2.2 μm, more preferably 1 to 2 μm, more preferably 1.3 to 1.8 μm.
The specific parameters of the polyethylene wax coating are not particularly limited in principle, and a person skilled in the art can select and adjust the polyethylene wax coating according to the actual application condition, the product requirement and the quality requirement, so that the compatibility with the polyethylene base film is better ensured, the low-temperature hole closing effect is improved, the comprehensive performance is ensured, the defects of the polyethylene base film can be reduced, the thickness is further reduced, and the molecular weight of the polyethylene wax in the polyethylene wax coating is preferably 1000-10000, more preferably 2000-9000, more preferably 3000-8000, more preferably 4000-7000 and more preferably 5000-6000. The thickness of the polyethylene wax coating is preferably 0.3-3 μm, more preferably 0.8-2.5 μm, more preferably 1.3-2 μm, and more preferably 1.5-1.8 μm.
The specific composition and source of the polyethylene wax coating are not particularly limited in principle, and a person skilled in the art can select and adjust the polyethylene wax coating according to the actual application condition, the product requirement and the quality requirement. In a still further aspect of the present invention,
the polyethylene wax slurry preferably comprises the following components in percentage by mass:
specifically, the addition amount of the polyethylene wax is preferably 10 to 35 parts by weight, more preferably 15 to 30 parts by weight, and still more preferably 20 to 25 parts by weight. The addition amount of the water is preferably 45 to 65 parts by weight, and more preferably 50 to 60 parts by weight. The addition amount of the adhesive is preferably 2 to 7 parts by weight, more preferably 3 to 6 parts by weight, and still more preferably 4 to 5 parts by weight. The addition amount of the wetting agent is preferably 0.5 to 4.5 parts by weight, more preferably 1 to 4 parts by weight, more preferably 1.5 to 3.5 parts by weight, and more preferably 2 to 3 parts by weight. The addition amount of the stabilizer is preferably 1.5 to 9 parts by weight, more preferably 2.5 to 8 parts by weight, and still more preferably 4.5 to 6 parts by weight.
The invention has no special restriction on the specific selection of the adhesive in the polyethylene wax slurry in principle, and the technicians in the field can select and adjust the adhesive according to the actual application condition, the product requirement and the quality requirement, in order to better ensure the compatibility with the polyethylene base film, improve the low-temperature hole closing effect and ensure the comprehensive performance, and meanwhile, the defects of the polyethylene base film can be reduced, the thickness is further reduced, the adhesive in the polyethylene wax slurry preferably comprises one or more of acrylic acid, polyvinyl amide, polyvinyl alcohol, polyethylene oxide, modified paraffin resin, polyvinyl acid, polyurethane acrylate and polyacrylate copolymer emulsion, and more preferably comprises acrylic acid, polyvinyl amide, polyvinyl alcohol, polyethylene oxide, modified paraffin resin, polyvinyl acid, polyurethane acrylate or polyacrylate copolymer emulsion.
The wetting agent in the polyethylene wax slurry preferably comprises one or more of polyethylene glycol, polyvinylpyrrolidone, linear alkyl benzene sulfonate, alkyl polyoxyethylene ether, sodium lauryl sulfate and alkyl sulfonate, and more preferably polyethylene glycol, polyvinylpyrrolidone, linear alkyl benzene sulfonate, alkyl polyoxyethylene ether, sodium lauryl sulfate and alkyl sulfonate.
The invention has no special restriction on the specific selection of the stabilizer in the polyethylene wax slurry in principle, and the technicians in the field can select and adjust the stabilizer according to the actual application condition, the product requirement and the quality requirement, in order to better ensure the compatibility with the polyethylene base film, improve the low-temperature hole closing effect and ensure the comprehensive performance, and meanwhile, the defects of the polyethylene-based film can be reduced, the thickness is further reduced, the stabilizer in the polyethylene wax slurry preferably comprises one or more of sodium carboxymethylcellulose, methylcellulose, hydroxypropyl methylcellulose, hydroxyethyl cellulose, gelatin, sodium alginate, fatty alcohol-polyoxyethylene ether and polyether amine, and more preferably comprises sodium carboxymethylcellulose, methylcellulose, hydroxypropyl methylcellulose, hydroxyethyl cellulose, gelatin, sodium alginate, fatty alcohol-polyoxyethylene ether or polyether amine.
The polyethylene composite diaphragm is complete and refined, the compatibility with a polyethylene base film is better ensured, the low-temperature hole closing effect is improved, the comprehensive performance is ensured, the defects of the polyethylene base film can be reduced, the thickness is further reduced, and the other side of the polyethylene base film can be compounded with a polyethylene wax coating, namely a second polyethylene wax coating.
The structure, composition and parameters of the second polyethylene wax coating and the corresponding preferred principles can be corresponded to the structure, composition and parameters of the polyethylene wax coating and the corresponding preferred principles, and are not described in detail herein.
The polyethylene composite diaphragm is complete and refined, the compatibility of the polyethylene base film is ensured, the low-temperature obturator effect is improved, the comprehensive performance is ensured, the defects of the polyethylene base film can be reduced, the practicability and the functionality of the polyethylene base film are improved on the basis of further reducing the thickness, and other functional coatings can be compounded on the polyethylene wax coating.
The specific choice of the other functional coating is not particularly limited by the present invention, and may be any functional coating known to those skilled in the art for use in conventional separators of this type, which may be selected and adjusted by those skilled in the art according to the actual application, product requirements and quality requirements, and preferably comprises a ceramic coating. Specifically, the specific components of the ceramic powder in the ceramic layer are not particularly limited in principle, and those skilled in the art can select and adjust the ceramic powder according to the actual application situation, the product requirements and the quality requirements, in order to better ensure the compatibility with the polyethylene-based film, improve the low-temperature pore-closing effect, ensure the comprehensive performance, reduce the defects of the polyethylene-based film and further reduce the thickness, the ceramic powder in the ceramic coating preferably comprises one or more of alumina, boehmite, magnesia, silica, zirconia, barium sulfate and calcium sulfate, and more preferably comprises alumina, boehmite, magnesia, silica, zirconia, barium sulfate or calcium sulfate.
The specific parameters of the ceramic powder are not particularly limited in principle, and a person skilled in the art can select and adjust the ceramic powder according to the actual application condition, the product requirement and the quality requirement, in order to better ensure the compatibility with the polyethylene base film, improve the low-temperature hole closing effect, ensure the comprehensive performance, reduce the defects of the polyethylene base film and further reduce the thickness, the median particle size of the ceramic powder is preferably 0.1-2 μm, more preferably 0.3-1.8 μm, more preferably 0.5-1.5 μm, and more preferably 0.8-1.2 μm. The specific surface area of the ceramic powder is preferably 0.5-10 m2(ii)/g, more preferably 1 to 8m2(ii)/g, more preferably 3 to 6m2A concentration of 4 to 5m2/g。
The preparation process of the ceramic coating is not particularly limited in principle, and a person skilled in the art can select and adjust the ceramic coating according to the actual application condition, the product requirement and the quality requirement. More specifically, the ceramic slurry of the present invention comprises a ceramic powder, water, a binder, a wetting agent and a stabilizer. The specific composition of the ceramic slurry is not particularly limited, and the ceramic slurry can be prepared according to the conventional ceramic slurry formula commonly used for the diaphragm, which is well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual application situation, the product requirement and the quality requirement.
The organic coating/polyethylene composite diaphragm provided by the steps of the invention is a polyethylene diaphragm compounded by an organic coating, the target base film is a polyethylene base film, and the problem in the thin wet method PE diaphragm industrialization is solved through the polyethylene wax organic coating. Further, the solid particles in the polyethylene wax slurry can be single or multiple polyethylene wax particles with different forms; and the main component of the polyethylene wax slurry stabilizer is fatty amine polyoxyethylene ether, so that the problem of dispersion of polyethylene wax in a water phase is effectively solved. Meanwhile, the polyethylene wax coating also has proper binding capacity, and other functional coatings such as ceramic coatings can be compounded outside the polyethylene wax coating, so that the practicability and functionality of the organic coating/polyethylene composite diaphragm are greatly enhanced.
The invention also provides a preparation method of the polyethylene composite diaphragm, which comprises the following steps:
1) mixing polyethylene wax emulsion and/or powder, water, adhesive, wetting agent and stabilizing agent at a high speed to obtain polyethylene wax slurry;
2) and coating the polyethylene wax slurry on the polyethylene base film, and drying to obtain the polyethylene composite diaphragm.
The structure, composition and parameters of the raw materials and the corresponding preferred principles of the preparation method can be corresponding to the structure, composition and parameters of the materials in the polyethylene composite diaphragm and the corresponding preferred principles, and are not described in detail herein.
The polyethylene wax slurry is prepared by mixing polyethylene wax emulsion and/or powder, water, adhesive, wetting agent and stabilizer at a high speed.
The specific parameters of the high-speed mixing are not particularly limited in principle, and a person skilled in the art can select and adjust the parameters according to the actual application condition, the product requirements and the quality requirements, so that the compatibility with the polyethylene base film is better ensured, the low-temperature hole closing effect is improved, the comprehensive performance is ensured, the defects of the polyethylene base film can be reduced, the thickness is further reduced, and the high-speed mixing time is preferably 30-120 min, more preferably 50-100 min, and more preferably 70-80 min. The rotation speed of the high-speed mixing is preferably 200-2000 r/min, more preferably 400-1800 r/min, more preferably 600-1600 r/min, more preferably 800-1400 r/min, more preferably 1000-1200 r/min.
The polyethylene wax slurry is coated on the polyethylene base film and dried to obtain the polyethylene composite diaphragm.
The specific way of coating is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to the actual application, product requirements and quality requirements, and the invention is to better ensure compatibility with the polyethylene base film, improve low-temperature closed-cell effect, ensure comprehensive performance, and simultaneously reduce defects of the polyethylene base film and further reduce thickness, wherein the coating preferably comprises one or more of spray coating, gravure coating, narrow-slit coating and wet coating, and more preferably spray coating, gravure coating, narrow-slit coating or wet coating.
The specific parameters of the drying are not particularly limited in principle, and a person skilled in the art can select and adjust the parameters according to the actual application condition, the product requirement and the quality requirement. The drying time is preferably 0.5-10 min, more preferably 1-8 min, more preferably 3-6 min, and more preferably 4-5 min. The drying temperature is preferably 30-80 ℃, more preferably 40-70 ℃, and more preferably 50-60 ℃.
The invention is a complete and refined polyethylene composite diaphragm, which can ensure the compatibility of the polyethylene base film, improve the low-temperature hole closing effect, ensure the comprehensive performance, reduce the defects of the polyethylene base film, increase the practicability and functionality of the polyethylene base film on the basis of further reducing the thickness, and preferably further comprises the step of composite ceramic slurry after drying.
The concrete process of the composite ceramic slurry is not particularly limited in principle, and a person skilled in the art can select and adjust the composite ceramic slurry according to the actual application condition, the product requirement and the quality requirement.
The preparation process of the Polyethylene (PE) composite diaphragm provided by the steps of the invention has the advantages of simple process, low cost, easy large-scale production and wide practical value.
The invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte;
the separator comprises the polyethylene composite separator according to any one of the above technical schemes or the polyethylene composite separator prepared by the preparation method according to any one of the above technical schemes.
The definition and the type of the lithium ion battery are not particularly limited in principle, and the lithium ion battery can be selected and adjusted by the person skilled in the art according to the practical application situation, the product requirement and the quality requirement, and the lithium ion battery of the present invention preferably comprises a lithium ion power battery.
The invention provides an organic coating/polyethylene composite diaphragm, a preparation method thereof and a lithium ion battery. The invention adopts the polyethylene wax coating, the main effective component of the organic coating is polyethylene wax, the compatibility with the PE base membrane is good, the pore-closing temperature of the membrane is effectively reduced, the pore-closing performance of the polyethylene membrane is improved, the safety performance of the battery is improved, when the thin polyethylene base membrane is dealt with, the defects of pinholes, microcracks and the like of the polyethylene base membrane can be reduced through the organic coating structure, the pore tortuosity is increased, the short-circuit rate and the self-discharge of the battery are reduced, therefore, the thin membrane thickness is realized on the premise of ensuring that the comprehensive performance of the membrane is not influenced and even better. And the polyethylene wax slurry uses fatty amine polyoxyethylene ether as a stabilizer, the slurry has high purity and good stability, and is easy for large-scale production, and meanwhile, the polyethylene wax coating also has suitable combining capacity, and can be compounded with other functional coatings outside the polyethylene wax coating, such as a ceramic coating, and the organic polyethylene wax coating and the inorganic ceramic powder coating are compounded to be a multifunctional coating, and have the advantages of low-temperature hole closing and good high-temperature thermal stability, and the thickness of the finished diaphragm is reduced to the maximum extent, so that the practicability and functionality of the organic coating/polyethylene composite diaphragm are greatly enhanced.
The polyethylene wax slurry provided by the invention has high purity and good stability, is easy to realize large-scale production, has low cost, is easy to be compounded with other functional coatings such as ceramic coatings, is suitable for industrial production, and provides a feasible scheme for solving the thinning problem of the wet-process PE diaphragm.
Experimental results show that the organic coating/polyethylene composite diaphragm provided by the invention has the advantages that on the premise of reducing the overall thickness, the performances of air permeability, thermal stability, heat storage and the like completely meet the production requirements of lithium ion batteries, the closed pore temperature of the diaphragm can be effectively reduced, and the safety performance of the battery is improved.
In order to further illustrate the present invention, the following detailed description of a polyethylene composite separator, a preparation method thereof, and a lithium ion battery provided by the present invention is provided in conjunction with examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and specific operation procedures are given, only for further illustrating the features and advantages of the present invention, but not for limiting the claims of the present invention, and the scope of the present invention is not limited to the following examples.
Example 1
(1) Preparation of polyethylene wax slurry: adding a wetting agent, a binder and deionized water with a certain mass into a polyethylene wax emulsion containing fatty amine polyoxyethylene ether (the molecular weight of the polyethylene wax is 3000, and the median particle size is 0.4 mu m), and stirring at a high speed to obtain uniformly mixed polyethylene wax slurry, wherein the mass ratio of the polyethylene wax to the deionized water to the binder to the wetting agent to the stabilizer is 30: 60: 2.8: 0.2: 7;
(2) preparing an organic coating composite diaphragm: and (2) coating the polyethylene wax slurry prepared in the step (1) on one side of a polyethylene base film with the thickness of 6 microns in a gravure coating mode, and drying to obtain the polyethylene wax-coated PE diaphragm with the thickness of 2 microns.
The organic coating composite membrane prepared in example 1 of the present invention was characterized.
Referring to fig. 1, fig. 1 is an SEM electron micrograph of the organic coating composite separator prepared in example 1 of the present invention.
As can be seen from FIG. 1, the polyethylene wax on the surface of the coating of the polyethylene diaphragm prepared in example 1 of the invention is uniformly distributed, the particles are in a blade shape, and the particle size range is 0.5-1.5 μm.
Example 2
The preparation process of the specific polyethylene slurry and organic coating composite separator is the same as that of example 1, except that single-sided coating is changed into double-sided coating.
Example 3
(1) Preparation of polyethylene wax slurry: adding alumina ceramic powder, a wetting agent, a binder and deionized water with certain mass into polyethylene wax emulsion containing fatty amine polyoxyethylene ether (the molecular weight of the polyethylene wax is 3000, the median particle size is 0.4 mu m), and stirring at high speed to obtain uniformly mixed polyethylene wax slurry, wherein the mass ratio of the polyethylene wax, the deionized water, the binder, the wetting agent and the stabilizer is 15: 15: 60: 2.8: 0.2: 7;
(2) preparing an organic coating composite diaphragm: and (2) coating the polyethylene wax slurry prepared in the step (1) on one side of a polyethylene base film with the thickness of 6 microns in a gravure coating mode, and drying to obtain the polyethylene wax-coated PE diaphragm with the thickness of 2 microns.
Example 4
(1) Preparation of polyethylene wax slurry: adding a wetting agent, a binder and deionized water with a certain mass into a polyethylene wax emulsion containing fatty amine polyoxyethylene ether (the molecular weight of the polyethylene wax is 3000, and the median particle size is 0.4 mu m), and stirring at a high speed to obtain uniformly mixed polyethylene wax slurry, wherein the mass ratio of the polyethylene wax to the deionized water to the binder to the wetting agent to the stabilizer is 30: 60: 2.8: 0.2: 7;
(2) preparing an organic coating composite diaphragm: and (2) coating the polyethylene wax slurry prepared in the step (1) on one side of a polyethylene base film with the thickness of 6 microns in a gravure coating mode, and drying to obtain the polyethylene wax-coated PE diaphragm with the thickness of 2 microns.
(3) Preparing ceramic slurry: adding alumina powder (with median particle size of 0.5 μm) into sodium carboxymethylcellulose solution, stirring at high speed for dispersion, adding wetting agent, binder and deionized water, and stirring at high speed to obtain uniformly mixed ceramic slurry, wherein the mass ratio of alumina to deionized water to binder to wetting agent to stabilizer is 35: 57: 2.8: 0.2: 5;
(4) preparation of a double-layer coated separator: and (3) coating the ceramic slurry prepared in the step (3) on one side of the organic coating of the diaphragm prepared in the step (2) in a thickness manner by adopting a gravure coating mode, and drying to obtain the double-layer coated PE diaphragm, wherein the thickness of the ceramic coating is 2 microns.
Comparative example 1
Commercial 9 μm polyethylene-based films without any coating were selected.
The organic coating composite separator prepared in comparative example 1 of the present invention was characterized.
Referring to fig. 2, fig. 2 is an SEM electron micrograph of a commercial polyethylene-based film provided in comparative example 1 of the present invention.
Comparative example 2
And (3) selecting a 6-micron polyethylene base film, and performing single-side ceramic coating, wherein the specific implementation process is the same as the steps (3) and (4) in the example 4, and the thickness of the ceramic coating is changed to be 3 microns, so that the ceramic coating diaphragm is obtained.
Comparative example 3
Selecting a 9-micron polyethylene base film, and carrying out single-side ceramic coating, wherein the specific implementation process is the same as the step (3) and the step (4) in the example 4, the thickness of the ceramic coating is changed into 3 microns, and the ceramic coating diaphragm obtained in the comparative example is the thinnest ceramic coating diaphragm in the current commercial use.
Example 5
The lithium ion battery separators prepared in examples 1 to 4 and comparative examples 1 to 2 of the present invention were subjected to a performance test.
Referring to table 1, table 1 shows test data of lithium ion battery separators prepared in examples 1 to 4 of the present invention and comparative examples 1 to 2.
TABLE 1
The test data in table 1 show that compared with comparative example 1, the air permeability values and the thermal stability of the diaphragms obtained in the embodiments 1 to 4 and the comparative examples 2 to 3 of the present invention are significantly improved (the thermal shrinkage rate is reduced). Compared with comparative examples 1 to 3, the thermal closed-pore temperatures of the diaphragms obtained in examples 1 to 4 of the present invention were all reduced to different degrees.
In order to further verify the beneficial effects of the inorganic coating composite polyethylene diaphragm provided by the invention, the 2Ah soft package battery is assembled and tested, wherein the positive electrode is lithium cobaltate, the negative electrode is graphite, and the diaphragm is the diaphragm prepared in the examples 1-4 and the comparative examples 1-2.
The prepared cell was tested as follows:
(1) thermal storage test: firstly, testing the 1C discharge capacity of the battery at 25 ℃, recording A, and charging to a full state of the battery; secondly, placing the battery at 60 ℃ for 7 days, taking out the battery and cooling, testing the 1C discharge capacity of the battery at 25 ℃, and recording B; and thirdly, at the temperature of 25 ℃, discharging the battery again at 1C after the battery is fully charged, and recording the discharge capacity C. The storage capacity retention rate (B/A100%) and the recovery capacity retention rate (C/A100%) were calculated, and the self-discharge performance of the battery was evaluated, with the higher the retention rate, the better the storage performance of the battery.
(2) And (3) thermal shock test: the method aims to detect the closed cell performance of the diaphragm under a battery system, the soft package battery is placed in an oven at 130 ℃ and kept for 10min, an SEM photo of the test diaphragm is disassembled, and the closed cell condition is observed.
The membrane of comparative example 1 of inventive example 1 was characterized after the thermal shock test.
Referring to fig. 3, fig. 3 is an SEM micrograph of a disassembled separator of example 1 of the present invention after a thermal shock test.
Referring to fig. 4, fig. 4 is an SEM electron micrograph of a disassembled separator of comparative example 1 of the present invention after a thermal shock test.
As shown by the electron microscope results of fig. 3 and 4, the polyethylene separator coated with polyethylene wax exhibited a significant closed cell effect compared to the commercial polyethylene-based film.
Referring to table 2, table 2 shows performance data of lithium ion batteries manufactured by the separators prepared in examples 1 to 4 of the present invention and comparative examples 1 to 2.
TABLE 2
| Item | Storage capacity retention (%) | Recovery capacity retention (%) | Closed cell condition |
| Example 1 | 94.8％ | 98.3％ | Closed cell |
| Example 2 | 95.9％ | 98.7％ | Closed cell |
| Example 3 | 95.2％ | 98.0％ | Closed cell |
| Example 4 | 96.5％ | 98.9％ | The ceramic layer is blocked and difficult to determine |
| Comparative example 1 | 89.5％ | 93.3％ | Obturator foramen |
| Comparative example 2 | 94.4％ | 97.8％ | The ceramic layer is blocked and difficult to determine |
| Comparative example 3 | 95.2％ | 98.1％ | The ceramic layer is blocked and difficult to determine |
The test data in table 2 show that, compared with comparative example 1, examples 1 to 4 of the present invention and comparative examples 2 to 3, the storage capacity retention rate and the recovery capacity retention rate of the battery are significantly improved, and it can be seen that the organic coating provided by the present invention and the conventional inorganic ceramic coating provided by the present invention have beneficial effects in solving the self-discharge problem of the battery. The thermal shock test structure of the battery shows that the organic coating composite diaphragm provided by the patent can still keep good low-temperature closed-pore performance under a battery system.
The organic coating composite polyethylene diaphragm disclosed by the invention has the advantages of excellent physical properties, low closed pore temperature and low self-discharge of the prepared battery, improves the performance of the diaphragm, and particularly has important practical value in the aspect of solving the thinning of the diaphragm.
Example 6
(1) Preparation of polyethylene wax slurry: and (3) mixing the following components in percentage by mass: 55: 5, passing the polyethylene wax powder (polyethylene wax molecular weight: 2700), deionized water and the stabilizer through a 50Mpa high-pressure homogenizer for 3 times to obtain the polyethylene wax emulsion, wherein the median particle size of the polyethylene wax particles is controlled to be 0.6-0.7 mu m.
(2) And (2) stirring the polyethylene wax emulsion prepared in the step (1) with a wetting agent, a binder and deionized water in a certain mass at a high speed to obtain the uniformly mixed polyethylene wax slurry. The total mass ratio of the polyethylene wax, the deionized water, the binder, the wetting agent and the stabilizer is 30: 60: 2.8: 0.2: 7.
(3) preparing an organic coating composite diaphragm: and (3) coating the polyethylene wax slurry prepared in the step (2) on one side of a polyethylene base film with the thickness of 6 microns in a gravure coating mode, and drying to obtain the polyethylene wax coated PE diaphragm with the thickness of 2 microns.
The organic coating composite membrane prepared in example 6 of the present invention was characterized.
Referring to fig. 5, fig. 5 is an SEM electron micrograph of the organic coating composite separator prepared in example 6 of the present invention.
As can be seen from fig. 5, the polyethylene wax on the surface of the coating of the polyethylene membrane prepared in example 6 of the present invention is uniformly distributed, and the particles are petal-shaped.
Example 7
According to the preparation method of the embodiment 6, the polyethylene wax powder raw material is changed, the molecular weight is 3400, the homogenizing pressure is changed to 30Mpa, the median particle size range of polyethylene wax particles is controlled to be 0.75-0.85 mu m, and other processes are kept unchanged, so that the organic coating composite membrane is obtained.
The organic coating composite membrane prepared in example 7 of the present invention was characterized.
Referring to fig. 6, fig. 6 is an SEM electron micrograph of the organic coating composite separator prepared in example 7 of the present invention.
As can be seen from FIG. 6, the polyethylene wax is uniformly distributed on the surface of the coating of the polyethylene membrane prepared in example 6 of the present invention, and the particles are in a sphere-like shape.
While the present invention has been described in detail with respect to an organic coating/polyethylene composite separator and a method for making the same, and a lithium ion battery, the principles and embodiments of the present invention are described herein using specific examples, which are provided only to facilitate an understanding of the methods and their core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A polyethylene composite diaphragm is characterized by comprising a polyethylene base film;
and the polyethylene wax coating is compounded on at least one surface of the polyethylene base film.
2. The polyethylene composite separator according to claim 1, wherein the polyethylene wax coating layer has a microscopic morphology of one or more of lobed, petal-like, and sphere-like polyethylene wax particles arranged in an overlapping arrangement;
the thickness of the polyethylene wax coating is 0.3-3 mu m;
the polyethylene-based film is a microporous film.
3. The polyethylene composite separator according to claim 1, wherein the polyethylene wax has a molecular weight of 1000 to 10000;
the median particle size of the polyethylene wax particles is 0.1-3 mu m;
the polyethylene wax coating is compounded on the polyethylene base film by polyethylene wax slurry.
4. The polyethylene composite separator according to claim 1, wherein the median pore diameter of the polyethylene-based film is 20 to 100 nm;
the thickness of the polyethylene base film is 3-20 mu m;
the polyethylene base film is prepared by a wet process.
5. The polyethylene composite separator according to claim 1, wherein the polyethylene wax slurry comprises, in mass percent:
6. the polyethylene composite membrane according to claim 5, wherein the polyethylene wax coating layer can be compounded with other functional coating layers;
the other functional coating comprises a ceramic coating;
the ceramic powder in the ceramic coating comprises one or more of alumina, boehmite, magnesia, silica, zirconia, barium sulfate and calcium sulfate;
the median particle size of the ceramic powder is 0.1-2 mu m;
the specific surface area of the ceramic powder is 0.5-10 m2/g。
7. The polyethylene composite separator according to claim 5, wherein the adhesive comprises one or more of acrylic acid, polyacrylamide, polyvinyl alcohol, polyethylene oxide, modified paraffin resin, polyacrylic acid, urethane acrylate and polyacrylate copolymer emulsion;
the wetting agent comprises one or more of polyethylene glycol, polyvinylpyrrolidone, linear alkyl benzene sodium sulfonate, alkyl polyoxyethylene ether, sodium lauryl sulfate and alkyl sulfonate;
the stabilizer preferably comprises one or more of fatty amine polyoxyethylene ether, sodium carboxymethylcellulose, methylcellulose, hydroxypropyl methylcellulose, hydroxyethyl cellulose, gelatin, sodium alginate, fatty alcohol polyoxyethylene ether and polyether amine.
8. The preparation method of the polyethylene composite diaphragm is characterized by comprising the following steps:
1) mixing polyethylene wax emulsion and/or powder, water, adhesive, wetting agent and stabilizing agent at a high speed to obtain polyethylene wax slurry;
2) and coating the polyethylene wax slurry on the polyethylene base film, and drying to obtain the polyethylene composite diaphragm.
9. The method of claim 8, wherein the coating comprises one or more of spray coating, gravure coating, slot coating, and wet-out coating;
the high-speed mixing time is 30-120 min;
the rotating speed of the high-speed mixing is 200-2000 r/min;
the drying time is 0.5-10 min;
the drying temperature is 30-80 ℃;
the method also comprises a step of drying the composite ceramic slurry.
10. A lithium ion battery is characterized by comprising a positive electrode, a negative electrode, a diaphragm and electrolyte;
the membrane comprises the polyethylene composite membrane as defined in any one of claims 1 to 7 or the polyethylene composite membrane prepared by the preparation method as defined in any one of claims 8 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911304164.2A CN111192996A (en) | 2019-12-17 | 2019-12-17 | Organic coating/polyethylene composite diaphragm, preparation method thereof and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911304164.2A CN111192996A (en) | 2019-12-17 | 2019-12-17 | Organic coating/polyethylene composite diaphragm, preparation method thereof and lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111192996A true CN111192996A (en) | 2020-05-22 |
Family
ID=70709594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911304164.2A Pending CN111192996A (en) | 2019-12-17 | 2019-12-17 | Organic coating/polyethylene composite diaphragm, preparation method thereof and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111192996A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111785894A (en) * | 2020-07-22 | 2020-10-16 | 河北金力新能源科技股份有限公司 | Preparation method of low-closed-pore-temperature diaphragm, prepared low-closed-pore-temperature diaphragm and application of diaphragm |
| CN112332027A (en) * | 2020-09-22 | 2021-02-05 | 河北金力新能源科技股份有限公司 | Lithium battery diaphragm slurry, diaphragm and lithium battery |
| CN112615111A (en) * | 2020-12-08 | 2021-04-06 | 惠州锂威电子科技有限公司 | High-liquid-retention self-repairing diaphragm, preparation method thereof and lithium ion battery |
| CN113690548A (en) * | 2021-08-03 | 2021-11-23 | 惠州锂威新能源科技有限公司 | Safety diaphragm, preparation method thereof and lithium ion battery |
| CN113690547A (en) * | 2021-08-03 | 2021-11-23 | 惠州锂威新能源科技有限公司 | Safety diaphragm, preparation method and lithium ion battery |
| CN114039166A (en) * | 2021-11-09 | 2022-02-11 | 深圳市旭然电子有限公司 | Diaphragm for lithium ion battery, preparation method of diaphragm and lithium ion battery |
| CN114374058A (en) * | 2021-12-06 | 2022-04-19 | 武汉中兴创新材料技术有限公司 | Coating diaphragm and preparation method and application thereof |
| CN114628852A (en) * | 2022-05-13 | 2022-06-14 | 宁德卓高新材料科技有限公司 | Cation selective diaphragm and preparation method and application thereof |
| CN114696038A (en) * | 2020-12-30 | 2022-07-01 | 山东海科创新研究院有限公司 | Polyolefin composite diaphragm coated with organic emulsion, preparation method of polyolefin composite diaphragm and lithium ion battery |
| CN114696039A (en) * | 2020-12-29 | 2022-07-01 | 山东海科创新研究院有限公司 | Polyolefin composite diaphragm with good thermal stability for lithium ion battery, preparation method of polyolefin composite diaphragm and lithium ion battery |
| CN117343375A (en) * | 2023-12-06 | 2024-01-05 | 新乡市中科膜材料科技有限公司 | Low-closed-pore high-safety composite diaphragm and preparation method and application thereof |
| CN117937051A (en) * | 2024-03-21 | 2024-04-26 | 宁德新能源科技有限公司 | Separator, secondary battery and electronic device |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532563A (en) * | 2012-02-21 | 2012-07-04 | 南京天诗新材料科技有限公司 | Method for preparing waterborne polymer wax dispersoid |
| CN103094517A (en) * | 2012-12-13 | 2013-05-08 | 深圳中兴创新材料技术有限公司 | Composite battery membrane and preparation method thereof |
| CN103247770A (en) * | 2013-04-25 | 2013-08-14 | 东莞新能源科技有限公司 | Lithium-ion battery separator and manufacturing method thereof |
| CN203386832U (en) * | 2013-06-20 | 2014-01-08 | 深圳中兴创新材料技术有限公司 | Three-layer membrane for lithium ion battery |
| CN103865186A (en) * | 2012-12-12 | 2014-06-18 | 上海雅运纺织助剂有限公司 | Oxidized polyethylene wax micro-emulsion composition and preparation method thereof |
| CN108550766A (en) * | 2018-04-26 | 2018-09-18 | 沧州明珠塑料股份有限公司 | A kind of Thermal shutdown high temperature resistant high safety coating modified diaphragm and preparation method thereof |
| CN109473602A (en) * | 2017-09-07 | 2019-03-15 | 比亚迪股份有限公司 | Battery diaphragm and preparation method thereof and lithium battery |
| CN109524597A (en) * | 2018-11-20 | 2019-03-26 | 哈尔滨理工大学 | A kind of preparation method of the polyethylene wax microballoon with automatic shutoff function/PVDF composite lithium ion cell diaphragm |
| CN109868651A (en) * | 2019-01-28 | 2019-06-11 | 上海矽联新材料科技有限公司 | A kind of graphene modified maleic anhydridization polythene wax emulsion and preparation method thereof |
-
2019
- 2019-12-17 CN CN201911304164.2A patent/CN111192996A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532563A (en) * | 2012-02-21 | 2012-07-04 | 南京天诗新材料科技有限公司 | Method for preparing waterborne polymer wax dispersoid |
| CN103865186A (en) * | 2012-12-12 | 2014-06-18 | 上海雅运纺织助剂有限公司 | Oxidized polyethylene wax micro-emulsion composition and preparation method thereof |
| CN103094517A (en) * | 2012-12-13 | 2013-05-08 | 深圳中兴创新材料技术有限公司 | Composite battery membrane and preparation method thereof |
| CN103247770A (en) * | 2013-04-25 | 2013-08-14 | 东莞新能源科技有限公司 | Lithium-ion battery separator and manufacturing method thereof |
| CN203386832U (en) * | 2013-06-20 | 2014-01-08 | 深圳中兴创新材料技术有限公司 | Three-layer membrane for lithium ion battery |
| CN109473602A (en) * | 2017-09-07 | 2019-03-15 | 比亚迪股份有限公司 | Battery diaphragm and preparation method thereof and lithium battery |
| CN108550766A (en) * | 2018-04-26 | 2018-09-18 | 沧州明珠塑料股份有限公司 | A kind of Thermal shutdown high temperature resistant high safety coating modified diaphragm and preparation method thereof |
| CN109524597A (en) * | 2018-11-20 | 2019-03-26 | 哈尔滨理工大学 | A kind of preparation method of the polyethylene wax microballoon with automatic shutoff function/PVDF composite lithium ion cell diaphragm |
| CN109868651A (en) * | 2019-01-28 | 2019-06-11 | 上海矽联新材料科技有限公司 | A kind of graphene modified maleic anhydridization polythene wax emulsion and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张天胜: "《表面活性剂应用技术》", 30 September 2001 * |
| 赵明生、姚福生: "《实用机电节能技术手册》", 30 June 1997 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111785894A (en) * | 2020-07-22 | 2020-10-16 | 河北金力新能源科技股份有限公司 | Preparation method of low-closed-pore-temperature diaphragm, prepared low-closed-pore-temperature diaphragm and application of diaphragm |
| CN112332027A (en) * | 2020-09-22 | 2021-02-05 | 河北金力新能源科技股份有限公司 | Lithium battery diaphragm slurry, diaphragm and lithium battery |
| CN112615111A (en) * | 2020-12-08 | 2021-04-06 | 惠州锂威电子科技有限公司 | High-liquid-retention self-repairing diaphragm, preparation method thereof and lithium ion battery |
| CN114696039A (en) * | 2020-12-29 | 2022-07-01 | 山东海科创新研究院有限公司 | Polyolefin composite diaphragm with good thermal stability for lithium ion battery, preparation method of polyolefin composite diaphragm and lithium ion battery |
| CN114696038A (en) * | 2020-12-30 | 2022-07-01 | 山东海科创新研究院有限公司 | Polyolefin composite diaphragm coated with organic emulsion, preparation method of polyolefin composite diaphragm and lithium ion battery |
| CN113690547A (en) * | 2021-08-03 | 2021-11-23 | 惠州锂威新能源科技有限公司 | Safety diaphragm, preparation method and lithium ion battery |
| CN113690548A (en) * | 2021-08-03 | 2021-11-23 | 惠州锂威新能源科技有限公司 | Safety diaphragm, preparation method thereof and lithium ion battery |
| CN114039166A (en) * | 2021-11-09 | 2022-02-11 | 深圳市旭然电子有限公司 | Diaphragm for lithium ion battery, preparation method of diaphragm and lithium ion battery |
| CN114374058A (en) * | 2021-12-06 | 2022-04-19 | 武汉中兴创新材料技术有限公司 | Coating diaphragm and preparation method and application thereof |
| CN114374058B (en) * | 2021-12-06 | 2024-07-02 | 武汉中兴创新材料技术有限公司 | Coating diaphragm and preparation method and application thereof |
| CN114628852A (en) * | 2022-05-13 | 2022-06-14 | 宁德卓高新材料科技有限公司 | Cation selective diaphragm and preparation method and application thereof |
| CN114628852B (en) * | 2022-05-13 | 2022-09-09 | 宁德卓高新材料科技有限公司 | Cation selective membrane and preparation method and application thereof |
| CN117343375A (en) * | 2023-12-06 | 2024-01-05 | 新乡市中科膜材料科技有限公司 | Low-closed-pore high-safety composite diaphragm and preparation method and application thereof |
| CN117343375B (en) * | 2023-12-06 | 2024-03-01 | 新乡市中科膜材料科技有限公司 | Low-closed-pore high-safety composite diaphragm and preparation method and application thereof |
| CN117937051A (en) * | 2024-03-21 | 2024-04-26 | 宁德新能源科技有限公司 | Separator, secondary battery and electronic device |
| CN117937051B (en) * | 2024-03-21 | 2024-06-21 | 宁德新能源科技有限公司 | Separator, secondary battery and electronic device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111192996A (en) | Organic coating/polyethylene composite diaphragm, preparation method thereof and lithium ion battery | |
| CN111244362B (en) | Composite diaphragm, preparation method thereof and lithium ion battery | |
| CN110299496B (en) | Battery diaphragm, power battery and vehicle | |
| CN113078414A (en) | Polypropylene composite diaphragm with low-temperature thermal closed-cell mechanism, preparation method thereof and lithium ion battery | |
| CN112467308B (en) | Diaphragm, preparation method thereof and lithium ion battery | |
| CN108039439B (en) | Composite diaphragm and preparation method thereof | |
| CN111653717A (en) | Preparation method of composite diaphragm, composite diaphragm and lithium ion battery | |
| KR102536847B1 (en) | Separator, secondary battery and device including the same | |
| CN114361717B (en) | Composite separator and electrochemical device | |
| CN106450105B (en) | Porous composite material partition plate, preparation method thereof, composite structure battery cell and lithium ion battery | |
| CN109841785A (en) | A kind of battery diaphragm and preparation method thereof and the lithium ion battery comprising the diaphragm | |
| CN106450047A (en) | High-temperature lithium ion power battery and making method thereof | |
| CN111785893A (en) | Low-closed-pore-temperature coated polypropylene diaphragm and preparation method thereof | |
| CN113921986A (en) | Composite diaphragm and battery comprising same | |
| KR20220124821A (en) | Separator, its manufacturing method and related secondary batteries, battery modules, battery packs and devices | |
| CN113394516A (en) | Lithium ion battery diaphragm, preparation method thereof and lithium ion battery | |
| CN113078411A (en) | Organic coating/non-woven fabric composite diaphragm with low-temperature hole closing function, preparation method thereof and lithium ion battery | |
| CN115558471A (en) | Phase-change microcapsule, high-safety lithium battery composite positive electrode and preparation method thereof | |
| CN114335554A (en) | Lithium metal battery and application thereof | |
| CN106848225B (en) | Coating material for improving safety of lithium ion battery, preparation method thereof and battery application | |
| WO2023179550A1 (en) | Composite oil-based separator and preparation method therefor, and secondary battery | |
| WO2023179780A1 (en) | Isolation film and preparation method therefor, battery, and electrical apparatus | |
| Wang et al. | Novel ZrO2@ Polyimde nano-microspheres-coated polyethylene separators for high energy density and high safety Li-ion battery | |
| WO2023138287A1 (en) | Composite separator, electrochemical apparatus, and terminal device | |
| WO2022110226A1 (en) | Separator, preparation method therefor, and secondary battery, battery module, battery pack and device related thereto |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200522 |