CN113328206A - Diaphragm and electrochemical device containing same - Google Patents

Diaphragm and electrochemical device containing same Download PDF

Info

Publication number
CN113328206A
CN113328206A CN202110594613.2A CN202110594613A CN113328206A CN 113328206 A CN113328206 A CN 113328206A CN 202110594613 A CN202110594613 A CN 202110594613A CN 113328206 A CN113328206 A CN 113328206A
Authority
CN
China
Prior art keywords
diaphragm
diaphragm according
coating
fibers
inorganic fiber
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
Application number
CN202110594613.2A
Other languages
Chinese (zh)
Inventor
蒋学鑫
张轲轲
王韶晖
汪志全
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anhui Yishitong New Energy Materials Co ltd
Original Assignee
Anhui Yishitong New Energy Materials Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Anhui Yishitong New Energy Materials Co ltd filed Critical Anhui Yishitong New Energy Materials Co ltd
Priority to CN202110594613.2A priority Critical patent/CN113328206A/en
Publication of CN113328206A publication Critical patent/CN113328206A/en
Pending legal-status Critical Current

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
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—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
    • H01M50/454—Separators, membranes or diaphragms characterised by the material having a layered structure comprising a non-fibrous layer and a fibrous layer superimposed on one another
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Cell Separators (AREA)

Abstract

The invention discloses a diaphragm and an electrochemical device containing the diaphragm, and relates to the technical field of batteries. Because the invention contains inorganic fiber, in the coating, the fibers are mutually overlapped to form a mutually supported structure, and can resist the shrinkage of the base film when being heated, thereby improving the heat shrinkage performance of the diaphragm; and because the bonding agent is not required to be completely filled among the fibers, the lapping among the fibers can be realized, compared with the prior art, the using amount of the bonding agent is relatively reduced, the content of organic substances in the coating is further reduced, and the thermal stability of the diaphragm coating is improved.

Description

Diaphragm and electrochemical device containing same
The technical field is as follows:
the invention belongs to the technical field of batteries, and particularly relates to a diaphragm and an electrochemical device containing the diaphragm.
Background art:
in a lithium ion battery, a separator mainly plays a role in preventing contact between a positive electrode and a negative electrode and allowing lithium ions to conduct, and is an important component of the lithium ion battery. At present, polyolefin diaphragm materials with a microporous structure, such as single-layer or multi-layer films of Polyethylene (PE) and Polypropylene (PP), are mainly used in commercial lithium ion batteries. The polyolefin separator may provide sufficient mechanical strength and chemical stability for a lithium ion battery, but exhibits greater thermal shrinkage under high temperature conditions. The thermal contraction causes the contact and short circuit of the positive electrode and the negative electrode, and a large amount of heat is rapidly accumulated, so that safety accidents such as fire, combustion and even explosion are caused.
In order to solve the problem, technicians use a polyolefin diaphragm as a base film and coat an inorganic ceramic material to improve the performance of the diaphragm, but in order to ensure that inorganic particles can be well bonded, a coating layer adopts more organic substances such as a bonding agent, a cross-linking agent and the like, the amount of the bonding agent is not less than 5% of the weight of the coating layer, and the organic substances are gradually aged and the strength of the coating layer is gradually lost in the use process of the battery due to poor thermal stability of the organic substances.
The invention content is as follows:
the invention aims to provide a diaphragm, wherein a fiber component is contained in a coating layer of the diaphragm, so that the problem of large thermal shrinkage of the conventional diaphragm can be solved. The coating has low organic matter content, and can improve the thermal stability of the coating.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a separator includes a microporous base film, inorganic fibers, and a binder.
The inorganic fiber is not particularly limited, and may be maintained in the battery without being oxidized or reduced.
The microporous base membrane is at least one of a polyolefin membrane, a fiber membrane and a composite membrane.
The shape of the inorganic fiber is at least one of needle shape, strip shape or rod shape,
the median particle size of the inorganic fibers is 1 to 10 μm, preferably 1 to 5 μm.
The inorganic fibers have an aspect ratio greater than 5.
The inorganic fiber includes a mixture of one or more of titanium dioxide, aluminum oxide hydrate, silicon carbide, silicon nitride, magnesium oxide, but is not limited thereto.
Preferably, the inorganic fibers comprise at least one of alumina, alumina hydrate.
Preferably, the alumina hydrate is boehmite.
The binder is at least one of polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-trichloroethylene, polyvinylidene fluoride-chlorotrifluoroethylene, polymethyl methacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinyl acetate, ethylene vinyl acetate copolymer, polyethylene oxide, cellulose acetate butyrate, cellulose acetate propionate, cyanoethyl pullulan (pullulan), cyanoethyl polyvinyl alcohol, cyanoethyl cellulose, cyanoethyl sucrose, pullulan, carboxymethyl cellulose, sodium carboxymethyl cellulose, acrylonitrile-butadiene-styrene copolymer, ethylene propylene diene monomer, sulfonated ethylene propylene diene monomer, Styrene Butadiene Rubber (SBR), fluororubber and polyimide.
The content of the binder is 0.2% -20%, preferably 0.2% -10%, and more preferably 0.5% -2% of the inorganic fiber.
The thickness of the separator is 2 to 30 μm, preferably 2 to 10 μm.
Use of the separator in an electrochemical device.
Since the separator is used for ion conduction, the separator prepared from the composition of the present invention can be used for lithium ion batteries, and also can be used for other electrochemical devices that function by ion conduction, such as sodium ions, potassium ions, magnesium ions, and aluminum ions.
The invention has the beneficial effects that:
1. because of the inorganic fiber, in the coating layer, the fibers are mutually overlapped to form a mutually supported structure, and the heat shrinkage of the base film can be resisted when the heat is applied, so that the heat shrinkage performance of the diaphragm is improved.
2. As the bonding agent is not required to be completely filled among the fibers, the lapping among the fibers can be realized, and compared with the prior art, the using amount of the bonding agent is relatively reduced, the content of organic substances in the coating is further reduced, and the thermal stability of the diaphragm coating is improved.
Description of the drawings:
fig. 1 is an SEM image of fibrous boehmite coated on the surface of a microporous base film.
The specific implementation mode is as follows:
in order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easy to understand, the invention is further explained by combining the specific embodiments and the drawings.
The sources of the raw materials in the following examples:
sodium carboxymethylcellulose is supplied by Japan paper making company under the model number MAC350HC
Microporous membrane substrate is available from shanghai, inc, model ND 18.
Electrolyte solution: supplied by Shenzhen New aegiu corporation, model number LBC3045M46
Example 1
Adding sodium carboxymethylcellulose and boehmite fibers with median particle size of 4 mu m and length-diameter ratio of 6 into water according to a mass ratio of 0.2:100, mixing to obtain slurry with solid content of 25%, uniformly coating the slurry on the surface of a microporous base film, drying to obtain a diaphragm with the thickness of 8 mu m boehmite coating, assembling a negative electrode plate (copper foil coated with graphite), the diaphragm, NMP (N-methylpyrrolidone), electrolyte and a positive electrode (aluminum foil coated with lithium cobaltate) into a soft package battery with the temperature resistance of 1 ampere hour, and testing the high temperature resistance of the soft package battery with the temperature resistance of 1 ampere hour.
Example 2
Adding sodium carboxymethylcellulose and boehmite fibers with the median particle size of 4 micrometers and the length-diameter ratio of 6 into water according to the mass ratio of 20:100, mixing to obtain slurry with the solid content of 25%, uniformly coating the slurry on the surface of a microporous base film, drying to obtain a diaphragm with the thickness of boehmite coating of 8 micrometers, assembling a negative electrode plate (copper foil coated with graphite), the diaphragm, NMP, electrolyte (lithium hexafluorophosphate) and a positive electrode (aluminum foil coated with lithium cobaltate) into a soft package battery at 1 ampere hour, and testing the high temperature resistance of the soft package battery at 1 ampere hour.
Example 3
Adding sodium carboxymethylcellulose and boehmite fibers with the median particle size of 4 micrometers and the length-diameter ratio of 6 into water according to the mass ratio of 10:100, mixing to obtain slurry with the solid content of 25%, uniformly coating the slurry on the surface of a microporous base film, drying to obtain a diaphragm with the thickness of boehmite coating of 8 micrometers, assembling a negative electrode plate (copper foil coated with graphite), the diaphragm, NMP, electrolyte (lithium hexafluorophosphate) and a positive electrode (aluminum foil coated with lithium cobaltate) into a soft package battery at 1 ampere hour, and testing the high temperature resistance of the soft package battery at 1 ampere hour.
Example 4
Adding sodium carboxymethylcellulose and boehmite fibers with the median particle size of 4 micrometers and the length-diameter ratio of 6 into water according to the mass ratio of 2:100, mixing to obtain slurry with the solid content of 25%, uniformly coating the slurry on the surface of a microporous base film, drying to obtain a diaphragm with the thickness of boehmite coating of 8 micrometers, assembling a negative electrode plate (copper foil coated with graphite), the diaphragm, NMP, electrolyte (lithium hexafluorophosphate) and a positive electrode (aluminum foil coated with lithium cobaltate) into a soft package battery with the volume of 1 ampere hour, and testing the high temperature resistance of the soft package battery with the volume of 1 ampere hour.
Example 5
Adding sodium carboxymethylcellulose and boehmite fibers with the median particle size of 1 mu m and the length-diameter ratio of 6 into water according to the mass ratio of 2:100, mixing to obtain slurry with the solid content of 25%, uniformly coating the slurry on the surface of a microporous base film, drying to obtain a coating with the thickness of 8 microns, stripping the coating to serve as a diaphragm, assembling a negative electrode plate (copper foil coated with graphite), the diaphragm, NMP, electrolyte (lithium hexafluorophosphate) and a positive electrode (aluminum foil coated with lithium cobaltate) into a soft-package battery with the temperature resistance of 1 ampere hour, and testing the high-temperature resistance of the soft-package battery with the temperature of 1 ampere hour.
Example 6
Adding sodium carboxymethylcellulose and boehmite fibers with the median particle size of 10 microns and the length-diameter ratio of 6 into water according to the mass ratio of 2:100, mixing to obtain slurry with the solid content of 25%, uniformly coating the slurry on the surface of a microporous base film, drying to obtain a diaphragm with the thickness of boehmite coating of 8 microns, assembling a negative electrode plate (copper foil coated with graphite), the diaphragm, NMP, electrolyte (lithium hexafluorophosphate) and a positive electrode (aluminum foil coated with lithium cobaltate) into a soft package battery with the volume of 1 ampere hour, and testing the high temperature resistance of the soft package battery with the volume of 1 ampere hour.
Example 7
Adding sodium carboxymethylcellulose and boehmite fibers with median particle size of 4 mu m and length-diameter ratio of 10 into water according to a mass ratio of 2:100, mixing to obtain slurry with solid content of 25%, uniformly coating the slurry on the surface of a microporous base film, drying to obtain a diaphragm with the thickness of 8um boehmite coating, assembling a negative electrode plate (copper foil coated with graphite), the diaphragm, a sodium sulfate solution and a positive electrode (aluminum foil coated with sodium iron phosphate) into a soft-package battery with the temperature resistance of 1 ampere hour, and testing the high-temperature resistance of the soft-package battery with the temperature resistance of 1 ampere hour.
Example 8
Adding sodium carboxymethylcellulose and boehmite fibers with the median particle size of 4 micrometers and the length-diameter ratio of 4 into water according to the mass ratio of 2:100, mixing to obtain slurry with the solid content of 25%, uniformly coating the slurry on the surface of a microporous base film, drying to obtain a diaphragm with the thickness of boehmite coating of 8 micrometers, assembling a negative electrode plate (aluminum foil coated with graphite), the diaphragm, NMP (NMP), electrolyte (lithium hexafluorophosphate) and a positive electrode (aluminum foil coated with lithium cobaltate) into a soft package battery with the temperature resistance of 1 ampere hour, and testing the high temperature resistance of the soft package battery with the temperature resistance of 1 ampere hour.
Example 9
Adding sodium carboxymethylcellulose and alumina fiber with a median particle size of 4 micrometers and a length-diameter ratio of 8 into water according to a mass ratio of 1.5:100, mixing to obtain slurry with a solid content of 25%, uniformly coating the slurry on the surface of a microporous base film, drying to obtain a diaphragm with a boehmite coating thickness of 8 micrometers, assembling a negative pole piece (copper foil coated with graphite), the diaphragm, NMP, electrolyte (lithium hexafluorophosphate) and a positive pole (aluminum foil coated with lithium cobaltate) into a soft package battery with a volume of 1 ampere hour, and testing the high temperature resistance of the soft package battery with the volume of 1 ampere hour.
Comparative example 1
The preparation method comprises the steps of adding sodium carboxymethylcellulose and boehmite powder with the median particle size of 4 microns into water according to the mass ratio of 2:100, mixing to obtain slurry with the solid content of 25%, uniformly coating the slurry on the surface of a microporous base film, and drying to obtain the diaphragm with the thickness of 8-micron boehmite coating, wherein the powder is easy to peel off due to less binder. The problem of flaking is eliminated by gradually increasing the ratio of sodium carboxymethylcellulose to 5: 100. And assembling a negative pole piece (copper foil coated with graphite), a diaphragm, NMP (N-methyl pyrrolidone), electrolyte (lithium hexafluorophosphate) and a positive pole (aluminum foil coated with lithium cobaltate) into a 1 ampere-hour soft package battery, and testing the high temperature resistance of the 1 ampere-hour soft package battery.
Comparative example 2
Adding sodium carboxymethylcellulose and boehmite powder with the median particle size of 4 mu m into water according to the mass ratio of 5:100, mixing to obtain slurry with the solid content of 25%, uniformly coating the slurry on the surface of a microporous base film, drying to obtain a diaphragm with the thickness of 8 mu m boehmite coating, assembling a negative electrode plate (aluminum foil coated with hard carbon), the diaphragm, a sodium sulfate solution and a positive electrode (aluminum foil coated with sodium iron phosphate) into a soft package battery with the temperature resistance of 1 ampere hour, and testing the high-temperature resistance of the soft package battery with the temperature resistance of 1 ampere hour.
TABLE 1 Heat shrinkage and puncture Strength of separators after coating of examples and comparative examples
Figure BDA0003090459700000051
Figure BDA0003090459700000061
And (4) testing standard: according to GB/T36363-2018 polyolefin diaphragm for lithium ion battery
And (3) testing conditions are as follows: heat shrinkage ratio: 105 ℃ for 1 hour.
TABLE 2 examples and comparative examples 1 ampere-hour pouch battery heat-resistant temperature, and first specific capacity
Heat-resistant temperature (. degree. C.) of battery First specific capacity (mA. h/g)
Example 1 210 145
Example 2 204 142
Example 3 207 144
Example 4 206 144
Example 5 207 143
Example 6 208 145
Example 7 208 108
Example 8 208 145
Example 9 203 145
Comparative example 1 170 142
Comparative example 2 172 105
The heat-resisting temperature test method of the battery comprises the steps of placing a soft package battery (in a full-charge state) with the 1 ampere hour in an oven with a set temperature, keeping the temperature for 30min, and testing the temperature when fire or explosion occurs.
The first specific capacity test condition is as follows: GB/T36276-: 2.75-4.2V
As can be seen from table 1, the thermal shrinkage of the separator coated with boehmite fibers is significantly reduced, and the puncture strength is also improved to some extent.
As can be seen from table 2, the heat-resistant temperature of the battery using the boehmite fiber-coated separator was significantly increased.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. A separator, characterized by: comprises a microporous base film, inorganic fibers and a binder.
2. A diaphragm according to claim 1, wherein: the microporous base membrane is at least one of a polyolefin membrane, a fiber membrane and a composite membrane.
3. A diaphragm according to claim 1, wherein: the shape of the inorganic fiber is at least one of needle shape, strip shape or rod shape, the median particle size is 1-10 mu m, and the length-diameter ratio is more than 5.
4. A diaphragm according to claim 1, wherein: the inorganic fiber comprises one or more of titanium dioxide, aluminum oxide hydrate, silicon carbide, silicon nitride and magnesium oxide.
5. A diaphragm according to claim 4, wherein: the inorganic fiber comprises at least one of alumina and alumina hydrate.
6. A diaphragm according to claim 4, wherein: the alumina hydrate is boehmite.
7. A diaphragm according to claim 1, wherein: the binder is at least one of polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-trichloroethylene, polyvinylidene fluoride-chlorotrifluoroethylene, polymethyl methacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinyl acetate, ethylene vinyl acetate copolymer, polyethylene oxide, cellulose acetate butyrate, cellulose acetate propionate, cyanoethyl pullulan (pullulan), cyanoethyl polyvinyl alcohol, cyanoethyl cellulose, cyanoethyl sucrose, pullulan, carboxymethyl cellulose, sodium carboxymethyl cellulose, acrylonitrile-butadiene-styrene copolymer, ethylene propylene diene monomer, sulfonated ethylene propylene diene monomer, Styrene Butadiene Rubber (SBR), fluororubber and polyimide.
8. A diaphragm according to claim 1, wherein: the content of the binder is 0.2-20% of the inorganic fiber.
9. A diaphragm according to claim 1, wherein: the thickness of the diaphragm is 2-30 μm.
10. Use of the separator of any of claims 1-9 in an electrochemical device.
CN202110594613.2A 2021-05-28 2021-05-28 Diaphragm and electrochemical device containing same Pending CN113328206A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110594613.2A CN113328206A (en) 2021-05-28 2021-05-28 Diaphragm and electrochemical device containing same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110594613.2A CN113328206A (en) 2021-05-28 2021-05-28 Diaphragm and electrochemical device containing same

Publications (1)

Publication Number Publication Date
CN113328206A true CN113328206A (en) 2021-08-31

Family

ID=77422354

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110594613.2A Pending CN113328206A (en) 2021-05-28 2021-05-28 Diaphragm and electrochemical device containing same

Country Status (1)

Country Link
CN (1) CN113328206A (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016012548A (en) * 2014-06-30 2016-01-21 三菱製紙株式会社 Battery separator
US20160308184A1 (en) * 2013-12-04 2016-10-20 Cornell University Ceramic-polymer hybrid nanostructures, methods for producing and applications thereof
CN106684292A (en) * 2017-01-18 2017-05-17 清陶（昆山）能源发展有限公司 Ionic conductor ceramic fiber composite diaphragm and preparation method and application thereof
CN108695476A (en) * 2018-05-21 2018-10-23 湖南人文科技学院 Ceramic diaphragm and its preparation method and application
CN111509168A (en) * 2019-01-31 2020-08-07 青岛蓝科途膜材料有限公司 Lithium ion battery diaphragm with high-temperature-resistant coating and preparation method thereof
CN112042005A (en) * 2017-12-22 2020-12-04 新罗纳米技术有限公司 Separator having a separator layer comprising ceramic
CN112456528A (en) * 2020-11-30 2021-03-09 中国铝业股份有限公司 Boehmite and preparation method and application thereof
CN112521616A (en) * 2019-08-30 2021-03-19 比亚迪股份有限公司 Grafted ceramic powder and preparation method thereof, ceramic diaphragm and preparation method thereof, lithium ion battery, battery module and battery pack

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160308184A1 (en) * 2013-12-04 2016-10-20 Cornell University Ceramic-polymer hybrid nanostructures, methods for producing and applications thereof
JP2016012548A (en) * 2014-06-30 2016-01-21 三菱製紙株式会社 Battery separator
CN106684292A (en) * 2017-01-18 2017-05-17 清陶（昆山）能源发展有限公司 Ionic conductor ceramic fiber composite diaphragm and preparation method and application thereof
CN112042005A (en) * 2017-12-22 2020-12-04 新罗纳米技术有限公司 Separator having a separator layer comprising ceramic
CN108695476A (en) * 2018-05-21 2018-10-23 湖南人文科技学院 Ceramic diaphragm and its preparation method and application
CN111509168A (en) * 2019-01-31 2020-08-07 青岛蓝科途膜材料有限公司 Lithium ion battery diaphragm with high-temperature-resistant coating and preparation method thereof
CN112521616A (en) * 2019-08-30 2021-03-19 比亚迪股份有限公司 Grafted ceramic powder and preparation method thereof, ceramic diaphragm and preparation method thereof, lithium ion battery, battery module and battery pack
CN112456528A (en) * 2020-11-30 2021-03-09 中国铝业股份有限公司 Boehmite and preparation method and application thereof

Similar Documents

Publication Publication Date Title
WO2018145666A1 (en) High temperature-resistant lithium ion battery separator having a variety of coatings and preparation method therefor
CN112467079A (en) Silicon-containing negative plate and lithium ion battery comprising same
CN111244365B (en) Composite coating diaphragm with consistent aperture and preparation method thereof
CN110416467B (en) Polymer diaphragm and preparation method and application thereof, and lithium ion battery and preparation method thereof
CN107611314B (en) Lithium ion battery and coating diaphragm thereof
CN112467308B (en) Diaphragm, preparation method thereof and lithium ion battery
CN110120485B (en) Polymer diaphragm and preparation method and application thereof, and lithium ion battery and preparation method thereof
CN114361717B (en) Composite separator and electrochemical device
CN108550764B (en) Superfine diamond coating isolating membrane and lithium ion battery applying same
CN108417762A (en) Lithium ion battery separator and preparation method thereof, lithium ion battery
CN112018326A (en) Negative plate and lithium ion battery comprising same
CN112968254A (en) Diaphragm for lithium ion battery, preparation method of diaphragm and lithium ion battery
CN114006024A (en) Diaphragm and battery containing same
CN112467309A (en) Diaphragm and electrochemical device
CN108448028B (en) Lithium ion battery diaphragm and preparation method thereof
CN109786629B (en) Polymer diaphragm and preparation method and application thereof, and lithium ion battery and preparation method thereof
CN111900317A (en) Composite diaphragm, preparation method thereof and lithium ion battery
CN113675374A (en) Negative electrode, preparation method thereof and lithium ion battery
WO2023098646A1 (en) Separator and battery comprising same
CN113328206A (en) Diaphragm and electrochemical device containing same
CN113328205A (en) Composition, electrode containing composition and application of composition
US20150162640A1 (en) Nonaqueous electrolyte secondary battery and method of manufacturing nonaqueous electrolyte secondary battery
CN114843482B (en) Core-shell type silicon-carbon composite material and preparation method and application thereof
TWI756982B (en) Secondary granulated silicon carbon base battery negative electrode material and preparation method thereof
CN114300808A (en) Diaphragm and battery comprising same

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

Application publication date: 20210831

RJ01 Rejection of invention patent application after publication