CN115101886A - Preparation method of isolating film coating material and isolating film - Google Patents
Preparation method of isolating film coating material and isolating film Download PDFInfo
- Publication number
- CN115101886A CN115101886A CN202210597569.5A CN202210597569A CN115101886A CN 115101886 A CN115101886 A CN 115101886A CN 202210597569 A CN202210597569 A CN 202210597569A CN 115101886 A CN115101886 A CN 115101886A
- Authority
- CN
- China
- Prior art keywords
- complex
- mixing
- paraffin oil
- drying
- providing
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007888 film coating Substances 0.000 title claims abstract description 11
- 238000009501 film coating Methods 0.000 title claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 85
- 239000005662 Paraffin oil Substances 0.000 claims abstract description 74
- 238000002156 mixing Methods 0.000 claims abstract description 72
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000498 ball milling Methods 0.000 claims abstract description 39
- 239000011248 coating agent Substances 0.000 claims abstract description 34
- 238000000576 coating method Methods 0.000 claims abstract description 34
- 239000011259 mixed solution Substances 0.000 claims abstract description 29
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005507 spraying Methods 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 28
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 19
- 230000004888 barrier function Effects 0.000 claims description 9
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 235000010338 boric acid Nutrition 0.000 claims description 3
- 239000011148 porous material Substances 0.000 abstract description 15
- 239000003792 electrolyte Substances 0.000 abstract description 12
- 238000002955 isolation Methods 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 238000009718 spray deposition Methods 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 description 33
- 239000000843 powder Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 238000007873 sieving Methods 0.000 description 8
- 238000000875 high-speed ball milling Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000009776 industrial production Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- YDVNLQGCLLPHAH-UHFFFAOYSA-N dichloromethane;hydrate Chemical compound O.ClCCl YDVNLQGCLLPHAH-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
-
- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
Abstract
The embodiment of the application provides a preparation method of an isolation film coating material and an isolation film. The preparation method of the isolating film coating material comprises the following steps: providing an aluminum oxide material, deionized water and a pore-forming agent, and mixing to obtain a first complex; providing paraffin oil, mixing the first complex with the paraffin oil, and performing ball milling and embedding to obtain a second complex; mixing the aluminum oxide material and paraffin oil to obtain a third complex; ball-milling the second complex and the third complex to enable the third complex to wrap the second complex to obtain a fourth complex; and providing dichloromethane and deionized water, mixing to obtain a mixed solution, mixing the fourth complex with the mixed solution in a spraying manner, washing and drying. Through multi-stage mixing ball milling and spray forming, the coating material can contain a large number of pore structures to form a three-dimensional space layer structure, so that the wettability, the specific surface area and the dispersibility of the obtained coating material are effectively improved, and the absorption rate of the coating material to electrolyte can be improved.
Description
Technical Field
The application belongs to the technical field of isolation films, and particularly relates to a preparation method of an isolation film coating material and an isolation film.
Background
In recent years, electric devices powered by secondary batteries are widely applied and popularized in industries such as various electronic products and new energy automobiles. Higher demands are made on the cycle performance of the battery.
The separator is one of the key inner layer components of the secondary battery. The isolating membrane is arranged between the positive pole piece and the negative pole piece, mainly plays a role in preventing the short circuit of the positive pole and the negative pole, and can enable ions to pass through. Improving the performance of the separator is critical to improving the wettability of the battery.
Disclosure of Invention
The embodiment of the application provides a preparation method of an isolating membrane coating material and an isolating membrane, wherein the isolating membrane has a better pore structure, and the infiltration capacity of a secondary battery is effectively improved.
In a first aspect of embodiments of the present application, a method for preparing a barrier film coating material is provided, which includes the following steps:
providing an aluminum oxide material, deionized water and a pore-forming agent, and mixing to obtain a first complex;
providing paraffin oil, mixing the first complex with the paraffin oil, and performing ball milling and embedding to obtain a second complex;
mixing the alumina material and paraffin oil to obtain a third complex;
ball-milling the second complex and the third complex to enable the third complex to wrap the second complex to obtain a fourth complex;
and providing dichloromethane and deionized water, mixing to obtain a mixed solution, mixing the fourth complex with the mixed solution in a spraying mode, washing and drying to obtain the coating material.
By adopting the scheme, through multi-stage mixing ball milling and spray forming, the coating material can contain a large number of pore structures, a three-dimensional space layer structure is formed, the wettability, the specific surface area and the dispersibility of the obtained coating material are effectively improved, the absorption rate of the coating material to electrolyte can be improved, the thermal stability of the coated pole piece is improved, the stability of an electrochemical window of the battery is further ensured, secondly, the aluminum oxide material can be conveniently infiltrated by adopting paraffin oil, and thirdly, the process in the preparation method is easy to realize, and the industrial production is facilitated.
In some optional embodiments of the present application, in the step of providing and mixing the alumina material and the pore-forming agent to obtain the first composite body, the pore-forming agent is one of oxalic acid, boric acid and ammonium bicarbonate.
By adopting the scheme, the oxalic acid, the ammonium bicarbonate and the boric acid are used, so that the pore-forming agent can be decomposed in the low-temperature heating process, carbon dioxide is generated to escape, and then micro-pore pores are generated on the composite body.
In some optional embodiments of the present application, in the step of providing and mixing an aluminum oxide material and a pore-forming agent to obtain a first composite, a particle size of the aluminum oxide material and the pore-forming agent is 50nm to 100nm, and a ratio of the aluminum oxide material, deionized water and the pore-forming agent is 4-5: 0.5-1.0: 4.5-5 by weight.
In some optional embodiments of the present application, in the step of providing and mixing the alumina material and the pore-forming agent to obtain the first composite body, the drying step further includes drying to remove water, wherein the drying temperature is 60 ℃ to 80 ℃, and the drying time is 5h to 10 h.
In some optional embodiments of the present application, paraffin oil is provided, the first complex is mixed with paraffin oil, and the mixture is subjected to ball milling and embedding to obtain the second complex, wherein the ratio of the first complex to the paraffin oil is 3-5: 5-7 by weight.
In some optional embodiments of the present application, paraffin oil is provided, the first complex is mixed with paraffin oil, and the mixture is subjected to ball milling to obtain a second complex, and the ball milling is performed at a high speed by using a ball mill to enable the first complex and the paraffin oil to be mutually embedded.
By adopting the scheme, the paraffin oil and the first complex are mutually embedded, so that the embedded structure is firmer, and the problem of loose delamination is not easy to occur, wherein the embedding refers to the cross-linking combination of different object pieces.
In some alternative embodiments of the present application, paraffin oil is provided, the first complex is mixed with paraffin oil, and the second complex is obtained by ball milling, wherein the second complex has a particle size of 150nm to 500 nm.
In some optional embodiments of the present application, in the step of providing paraffin oil, mixing the first complex with paraffin oil, and performing ball milling and embedding to obtain the second complex, the step further includes drying to remove moisture, wherein the drying temperature is 60 ℃ to 80 ℃, and the drying time is 5h to 10 h.
In some optional embodiments of the present application, in the step of providing paraffin oil, mixing the first complex with paraffin oil, and performing ball milling and embedding to obtain the second complex, the method further comprises filtering with a filter screen to obtain the second complex with uniform particle size.
In some alternative embodiments of the present application, the alumina material and the paraffin oil are mixed to obtain the third composite, and the alumina material has a particle size of 200nm to 600 nm.
In some optional embodiments of the present application, in the step of mixing the aluminum oxide material and the paraffin oil to obtain the third composite, a ratio of the aluminum oxide material to the paraffin oil is 3-5: 5-7 by weight.
In some optional embodiments of the present application, the step of mixing the aluminum oxide material and the paraffin oil to obtain the third composite further comprises drying to remove moisture, wherein the drying temperature is 60 ℃ to 80 ℃, and the drying time is 5h to 10 h.
In some optional embodiments of the present application, the step of mixing the aluminum oxide material and the paraffin oil to obtain the third composite further comprises filtering with a filter screen to obtain the third composite with a uniform particle size.
In some optional embodiments of the present application, the step of ball milling the second complex and the third complex to wrap the third complex around the second complex to obtain the fourth complex further includes drying to remove moisture, wherein the drying temperature is 60 ℃ to 80 ℃, and the drying time is 5h to 10 h.
In some optional embodiments of the present application, in the step of ball-milling the second complex and the third complex to wrap the third complex around the second complex, the fourth complex is obtained, and the fourth complex is obtained by filtering with a filter screen.
By adopting the scheme, the third composite is formed by mixing paraffin oil and alumina, and the second composite is formed by mixing pore-forming agent, alumina and paraffin oil, so that after the two composites are fully extracted, the density and specific surface area of the third composite are higher than those of the second composite, and the composite with high specific surface area is wrapped on the composite with low specific surface area to form a gradient hierarchical structure with a small inside and a large outside, which is more favorable for improving the passing quantity and efficiency of ions in the electrochemical process.
In some optional embodiments of the present application, the second complex and the third complex are ball-milled, and the third complex wraps the second complex to obtain a fourth complex, wherein the ratio of the second complex to the third complex is 1-4: 6-9 by weight.
In some optional embodiments of the application, dichloromethane and deionized water are provided and mixed to obtain a mixed solution, a fourth complex and the mixed solution are mixed in a spraying mode, and in the step of washing and drying, the ratio of the dichloromethane to the deionized water is 3-4: 6-7 by volume.
In some optional embodiments of the present application, dichloromethane and deionized water are provided and mixed to obtain a mixed solution, the fourth complex is mixed with the mixed solution by using a spraying manner, and in the washing and drying step, the fourth complex is sprayed into the mixed solution by using a vacuum sprayer in a spraying manner, wherein the spraying pressure is 0.1MPa to 0.3 MPa.
By adopting the above mode, the jetting impact force of the fourth complex in the mixed solution can be utilized in a spraying mode, so that the paraffin oil is uniformly extracted by the dichloromethane, and the pore-forming agent is decomposed when meeting deionized water.
In some optional embodiments of the present application, dichloromethane and deionized water are provided and mixed to obtain a mixed solution, the fourth complex is mixed with the mixed solution in a spraying manner, and in the washing and drying step, the drying temperature is 180 ℃ to 300 ℃, and the drying time is 5h to 10 h.
By adopting the mode, the pore-forming agent can be decomposed at the drying temperature.
In a second aspect of the embodiments of the present application, there is provided a separator including the above coating material.
In some alternative embodiments of the present application, the separator has a porosity of 53% to 55%, a wettability of 101% to 105%, and a shrinkage of 1.1% to 1.2%
Compared with the prior art, in the preparation method of the isolating membrane coating material and the isolating membrane, the coating material can contain a large number of pore structures through multi-stage mixed ball milling and spray forming, a three-dimensional space layer structure is formed, the wettability, the specific surface area and the dispersibility of the obtained coating material are effectively improved, the absorption rate of the coating material to electrolyte can be improved, the thermal stability of a coated pole piece is improved, the stability of an electrochemical window of a battery is further ensured, and secondly, the process in the preparation method is easy to realize and is convenient for industrial production.
Detailed Description
In order to make the purpose, technical solution and advantageous technical effects of the present invention clearer, the present invention is further described in detail with reference to the following embodiments. It should be understood that the embodiments described in this specification are only for explaining the present application and are not intended to limit the present application.
For the sake of brevity, only some numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and similarly any upper limit may be combined with any other upper limit to form a range not explicitly recited. Also, although not explicitly recited, each point or individual numerical value between the endpoints of a range is encompassed within that range. Thus, each point or individual value may form a range not explicitly recited as its own lower or upper limit combined with any other point or individual value or combined with other lower or upper limits.
In the description herein, when a composition is described as containing, comprising or including a particular component, or when a process is described as containing, comprising or including a particular process step, it is contemplated that the composition of the present application also consists essentially of or consists of that component, and that the process of the present application also consists essentially of or consists of that process step.
The use of the terms "comprising," "including," "containing," and "having" are generally to be construed as open-ended and non-limiting unless otherwise expressly specified.
In the description herein, it is to be noted that, unless otherwise specified, "above" and "below" are inclusive, and "a plurality" of "one or more" means two or more.
The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. At various points throughout this application, guidance is provided through lists of examples, which examples can be used in various combinations. In each instance, the list is merely a representative group and should not be construed as exhaustive.
The performance of the isolating membrane, which is one of the key inner layer components in the structure of the secondary battery, directly affects the capacity, rate, service life, safety and other performances of the battery. The interface compatibility between the isolating membrane material and the electrode and the retentivity of the isolating membrane to the electrolyte have important influences on the charge and discharge performance, the cycle performance and the service life of the secondary battery.
The inventor of the application discovers through research that the traditional isolating membrane generally uses irregular-shaped solid alumina ceramic to coat the polyolefin isolating membrane to form a ceramic composite coating isolating membrane for solving the temperature resistance and safety performance of the polyolefin isolating membrane of the lithium ion battery, and can effectively avoid the shrinkage deformation of the polyolefin isolating membrane when the internal temperature of the battery is too high, thereby avoiding the short circuit of the battery. However, the alumina material has the defects of poor wettability, low specific surface area, poor dispersibility and the like, so that the conductive ion penetration resistance of the internal reaction of the battery is increased, and the electrochemical performance of the battery is reduced. In view of this, the embodiments of the present application provide a barrier film coating material, a method for preparing the barrier film coating material, and a barrier film.
In a first aspect of embodiments of the present application, there is provided a method for preparing a barrier film coating material, including the steps of
S01, providing an aluminum oxide material and a pore-forming agent and mixing to obtain a first complex;
s02, providing paraffin oil, mixing the first complex with the paraffin oil, and performing ball milling and embedding to obtain a second complex;
s03, mixing the alumina material and the paraffin oil to obtain a third complex;
s04, ball-milling the second complex and the third complex to enable the third complex to wrap the second complex to obtain a fourth complex;
and S05, providing dichloromethane and deionized water, mixing to obtain a mixed solution, mixing the fourth complex with the mixed solution in a spraying mode, washing and drying.
Through multistage mixing ball-milling and spray forming, can make coating material contain a large amount of pore structures, form three-dimensional space layer structure, effectively improve infiltration nature, specific surface area and the dispersibility of gained coating material, can also improve the absorptivity of coating material to electrolyte, improve the thermal stability of pole piece after the coating, and then guarantee that the electrochemistry window of battery is stable, secondly, technology among the preparation method realizes easily, the industrial production of being convenient for.
In some optional embodiments of the present application, in the step of providing and mixing S01 the alumina material and the pore former to obtain the first composite, the pore former uses one of oxalic acid, boric acid and ammonium bicarbonate.
In some optional embodiments of the present application, in the step of S01, providing and mixing the aluminum oxide material and the pore-forming agent to obtain the first composite, the particle size of the aluminum oxide material and the pore-forming agent is 50nm to 100nm, and the ratio of the aluminum oxide material to the pore-forming agent is 4 to 5: 5 to 6 by weight.
In some optional embodiments of the present application, in the step of providing and mixing the alumina material and the pore-forming agent to obtain the first composite, drying to remove water is further performed, wherein the drying temperature is 60 ℃ to 80 ℃, and the drying time is 5h to 10 h.
In some optional embodiments of the present application, S02, paraffin oil is provided, the first complex is mixed with the paraffin oil, and the mixture is subjected to ball milling and embedding to obtain the second complex, wherein the ratio of the first complex to the paraffin oil is 3-5: 5-7 by weight.
In some optional embodiments of the present application, in the step of providing S02 paraffin oil, mixing the first complex with paraffin oil, and performing ball milling to obtain the second complex, the ball milling is performed at high speed by using a ball mill to perform ball milling to make the first complex and paraffin oil to be engaged with each other.
In some alternative embodiments of the present application, S02, paraffin oil is provided, the first complex is mixed with the paraffin oil, and the first complex is ball-milled and embedded, and in the step of obtaining the second complex, the particle size of the second complex is 150nm to 500 nm.
In some optional embodiments of the present application, in the step S02 of providing paraffin oil, mixing the first composite with paraffin oil, and performing ball milling to obtain the second composite, the step further includes drying to remove water, wherein the drying temperature is 60 ℃ to 80 ℃, and the drying time is 5h to 10 h.
In some optional embodiments of the present application, in the step of providing S02 paraffin oil, mixing the first complex with the paraffin oil, and performing ball milling and embedding to obtain the second complex, the method further comprises filtering with a filter screen to obtain the second complex with uniform particle size.
In some optional embodiments of the present application, in the step of mixing S03 the alumina material and the paraffin oil to obtain the third composite, the alumina material has a particle size of 200nm to 600 nm.
In some optional embodiments of the present application, in the step of S03, the aluminum oxide material and the paraffin oil are mixed to obtain the third composite, and a ratio of the aluminum oxide material to the paraffin oil is 3-5: 5-7 by weight.
In some optional embodiments of the present application, the step of mixing the alumina material and the paraffin oil to obtain the third composite further comprises drying to remove moisture, wherein the drying temperature is 60 ℃ to 80 ℃, and the drying time is 5h to 10 h.
In some optional embodiments of the present application, in the step of S03, mixing the aluminum oxide material and the paraffin oil to obtain the third composite, the step of filtering with a filter screen to obtain the third composite with a uniform particle size is further included.
In some optional embodiments of the present application, in the step S04, ball milling the second complex and the third complex, and wrapping the second complex with the third complex to obtain a fourth complex, drying to remove moisture at a temperature of 60 ℃ to 80 ℃ for 5h to 10 h.
In some optional embodiments of the present application, in the step S04, ball milling the second complex and the third complex, and wrapping the second complex with the third complex to obtain a fourth complex, filtering with a filter screen to obtain a fourth complex with a uniform particle size.
In some optional embodiments of the application, S05, providing dichloromethane and deionized water and mixing to obtain a mixed solution, mixing the fourth complex with the mixed solution in a spraying manner, and in the washing and drying step, the ratio of dichloromethane to deionized water is 3-4: 6-7 by volume.
In some optional embodiments of the present application, S05, providing dichloromethane and deionized water, and mixing to obtain a mixed solution, mixing the fourth complex with the mixed solution by using a spraying manner, wherein in the washing and drying step, the spraying manner uses a vacuum sprayer to spray the fourth complex into the mixed solution, and the spraying pressure is 0.1MPa to 0.3 MPa.
The jetting impact force of the fourth composite body in the mixed solution can be utilized in a spraying mode, so that the paraffin oil is uniformly extracted by dichloromethane, and the pore-forming agent is decomposed when meeting deionized water.
In some optional embodiments of the present application, S05, providing dichloromethane and deionized water, and mixing to obtain a mixed solution, mixing the fourth complex with the mixed solution by spraying, wherein in the washing and drying step, the drying temperature is 180 ℃ to 300 ℃, and the drying time is 5h to 10 h.
The pore-forming agent can be decomposed by the drying temperature.
In a second aspect of the embodiments of the present application, there is provided a separator including the above coating material.
In some alternative embodiments of the present application, the separator has a porosity of 53% to 55%, a wettability of 101% to 105%, and a shrinkage of 1.1% to 1.2%
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrative only since numerous modifications and variations within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are on a weight basis, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further treatment, and the equipment used in the examples is commercially available.
Example 1
Preparing an isolating membrane:
uniformly mixing 40g of alumina powder with the grain size of 50nm, 10g of deionized water and 50g of oxalic acid, drying in a drying box at the low temperature of 60 ℃ for 10h, and removing water to obtain a first complex. And mixing 90g of the first complex with 210g of paraffin oil, carrying out high-speed ball milling by using a ball mill to form a second complex which is mutually embedded, wherein the grain diameter of the second complex is 150nm, drying the second complex in a drying box at the low temperature of 60 ℃ for 10h, and filtering by using a filter screen with the pore diameter of 200nm to obtain the second complex with uniform grain diameter. Mixing 40g of alumina powder with the particle size of 200nm and 50g of paraffin oil uniformly, drying at the low temperature of 60 ℃ for 10h in a drying oven, removing water, and filtering by using a filter screen with the pore size of 200nm to obtain a third complex with uniform particle size. And (3) performing composite ball milling on 50g of the second complex and 60g of the third complex by using a ball mill to enable the third complex to wrap the second complex to obtain a fourth complex, drying the fourth complex in a drying box at the low temperature of 60 ℃ for 10 hours, removing water, and filtering by using a filter screen with the aperture of 200 nm. Spraying 35% dichloromethane water solution by volume fraction to the fourth complex with vacuum sprayer at 0.1MPa, and washing insoluble substance to obtain coating material.
Mixing the coating material with PVDF (polyvinylidene fluoride) to prepare slurry, and drying and shaping the slurry on two sides of a polyolefin isolating membrane with the thickness of 9 mu m, the porosity of 40% and the pore diameter of 100nm to obtain the isolating membrane.
Example 2
Preparing an isolating membrane:
this embodiment is substantially the same as embodiment 1 except that: uniformly mixing 45g of alumina powder with the grain size of 70nm, 10g of deionized water and 45g of oxalic acid, drying in a drying box at the low temperature of 60 ℃ for 10 hours, and removing water to obtain a first complex. And mixing 100g of the first complex with 200g of paraffin oil, carrying out high-speed ball milling by using a ball mill to form a second complex which is mutually embedded, wherein the particle size of the second complex is 300nm, drying the second complex in a drying box at the low temperature of 60 ℃ for 10h, and sieving to obtain the second complex with uniform particle size. Mixing 50g of alumina powder with the particle size of 200nm and 70g of paraffin oil uniformly, drying at the low temperature of 60 ℃ for 10h in a drying oven, removing water, and sieving to obtain a third complex with uniform particle size. And (3) performing composite ball milling on 40g of the second complex and 80g of the third complex by using a ball mill to enable the third complex to wrap the second complex to obtain a fourth complex, drying the fourth complex in a drying box at the low temperature of 60 ℃ for 10 hours, and removing water. Spraying the fourth complex to the dichloromethane aqueous solution with the volume fraction of 40% by using a vacuum sprayer at the pressure of 0.2MPa in a spraying manner, and washing insoluble substances to obtain the coating material.
Example 3
Preparing an isolating membrane:
this embodiment is substantially the same as embodiment 1 except that: and (3) uniformly mixing 50g of alumina powder with the particle size of 100nm, 8g of deionized water and 50g of oxalic acid, drying in a drying box at the low temperature of 60 ℃ for 10 hours, and removing water to obtain a first complex. And mixing 120g of the first complex with 180g of paraffin oil, carrying out high-speed ball milling by using a ball mill to form a second complex which is mutually embedded, wherein the particle size of the second complex is 600nm, drying the second complex in a drying box at the low temperature of 60 ℃ for 10h, and sieving to obtain the second complex with uniform particle size. Mixing 50g of aluminum oxide powder with the particle size of 600nm and 50g of paraffin oil uniformly, drying at the low temperature of 60 ℃ for 10h in a drying oven, removing water, and sieving to obtain a third complex with uniform particle size. And (3) performing composite ball milling on 40g of the second complex and 60g of the third complex by using a ball mill to enable the third complex to wrap the second complex to obtain a fourth complex, drying the fourth complex in a drying box at the low temperature of 60 ℃ for 10 hours, and removing water. Spraying a dichloromethane aqueous solution with the volume fraction of 30% to the fourth complex through a vacuum sprayer at the pressure of 0.3MPa by adopting a spraying mode, and washing insoluble substances to obtain the coating material.
Example 4
Preparing an isolating membrane:
this embodiment is substantially the same as embodiment 1 except that: and (3) uniformly mixing 50g of alumina powder with the particle size of 100nm, 10g of deionized water and 50g of oxalic acid, drying in a drying box at the low temperature of 60 ℃ for 10 hours, and removing water to obtain a first complex. And mixing 100g of the first complex with 200g of paraffin oil, carrying out high-speed ball milling by using a ball mill to form a second complex which is mutually embedded, wherein the particle size of the second complex is 400nm, drying the second complex in a drying box at the low temperature of 60 ℃ for 10h, and sieving to obtain the second complex with uniform particle size. Mixing 50g of alumina powder with the particle size of 400nm and 60g of paraffin oil uniformly, drying at the low temperature of 60 ℃ for 10h in a drying oven, removing water, and sieving to obtain a third complex with uniform particle size. And (3) performing composite ball milling on 40g of the second complex and 60g of the third complex by using a ball mill to enable the third complex to wrap the second complex to obtain a fourth complex, drying the fourth complex in a drying box at the low temperature of 60 ℃ for 10 hours, and removing water. Spraying 35% dichloromethane water solution by volume fraction to the fourth complex with a vacuum sprayer at 0.2MPa, and washing insoluble substances to obtain the coating material.
Example 5
Preparing an isolating membrane:
this embodiment is substantially the same as embodiment 1 except that: and (3) uniformly mixing 40g of alumina powder with the grain size of 80nm, 10g of deionized water and 50g of oxalic acid, drying for 10 hours at the low temperature of 60 ℃ in a drying box, and removing water to obtain a first complex. And mixing 100g of the first complex with 100g of paraffin oil, carrying out high-speed ball milling by using a ball mill to form a second complex which is mutually embedded, wherein the particle size of the second complex is 400nm, drying the second complex in a drying box at the low temperature of 60 ℃ for 10h, and sieving to obtain the second complex with uniform particle size. And (3) uniformly mixing 40g of aluminum oxide powder with the particle size of 400nm and 60g of paraffin oil, drying at the low temperature of 60 ℃ for 10h in a drying oven, removing water, and sieving to obtain a third complex with uniform particle size. And (3) performing composite ball milling on 40g of the second complex and 60g of the third complex by using a ball mill to enable the third complex to wrap the second complex to obtain a fourth complex, drying the fourth complex in a drying box at the low temperature of 60 ℃ for 10 hours, and removing water. Spraying 35% dichloromethane aqueous solution by vacuum sprayer at 0.2MPa, and washing insoluble substances to obtain coating material.
Comparative example 1
Preparation of the Release film
Coating a polyethylene film surface with the thickness of 9 mu m, the porosity of 40 percent and the pore diameter of 100nm with a mixed coating material of alumina ceramic particles and polyvinylidene fluoride, and uniformly coating the two surfaces of the polyethylene isolating film, wherein the average particle diameter D50 of the alumina ceramic particles is 300 nm.
Test method
Temperature resistance test
And (3) placing a plurality of groups of same isolating membranes in a drying box, taking out the isolating membranes at different temperatures respectively, measuring the air permeability of the isolating membranes, and when the air permeability of the isolating membranes is reduced to 0, indicating that the isolating membranes are completely closed at the temperature value and have a complete blocking function, wherein the highest temperature resistance value is the temperature value.
Porosity test
1) Cutting 5 isolating membranes with the thickness of 100mm multiplied by 100 mm;
2) measuring the length, width and thickness of the sample;
3) weighing the mass of the sample by using an analytical balance, and converting the mass into gram weight;
4) the porosity was calculated according to the following formulas 1 and 2.
Wherein
ρ 1 Gram weight of sample in grams per square meter (g/m) 2 )；
m-mass of the sample in grams (g);
l-the length of the sample in meters (m);
b-width of the sample in meters (m);
p-porosity of the sample, expressed in%;
d-thickness of the sample in micrometers (um);
ρ 0 the density of the raw material is given in grams per cubic centimeter (g/cm) 3 )。
Shrinkage test
1) Cutting 5 isolating membranes with the thickness of 100mm multiplied by 100 mm;
2) measuring the width of the test sample, and recording as L1;
3) placing the isolation film sample in an oven, and placing for 10min at 105 ℃;
4) taking out the isolation film after high-temperature baking, and measuring the width of the isolation film, wherein the width is marked as L2;
5) the shrinkage was calculated according to the following formula
(L1-L2)/L1*100％。
Wettability test
The wettability of the isolating membrane is characterized by the liquid absorption rate of the isolating membrane, and the liquid absorption rate of the isolating membrane is measured by electrolyte. A sample of the separator was cut into a 2cm by 2cm square, and M1 was weighed using LiPF6 as an electrolyte in lmol/L. The electrolyte system is that Ethylene Carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (EMC) are 1: 1(V/V), then the sample membrane is soaked in the electrolyte for 30min and taken out, the electrolyte on the membrane surface is lightly absorbed by filter paper, and M2 is weighed.
Calculated according to the formula
P＝(M2-M1)/M1×100％ (3)
Ml-mass after soaking (g);
m2-isolation film mass (g).
Specific capacity test
Mixing a positive active substance LiFePO4, a conductive agent and a binder into slurry according to the mass ratio of 8: 1, coating the slurry on an aluminum foil, airing, and drying in vacuum (133Pa) at 105 ℃ for 10 hours to prepare an electrode wafer (the content of the active substance is 3mg) with the diameter of 12 mm. LiPF6 was dissolved in a mixed solvent of ethylene carbonate, diethyl carbonate and dimethyl carbonate at a volume ratio of 1: 1 to prepare an electrolyte solution having a concentration of 1 mol/L. And assembling the CR2032 button cell by taking a metal lithium sheet as a negative electrode in a dry glove box filled with argon. Electrochemical performance tests were performed using the CT2001A battery test system. The method of constant current charging and discharging is adopted, the voltage is 2.0V to 4.2V when the test is carried out at 25 ℃, and the specific capacity value is measured.
The specific test results are shown in table 1.
TABLE 1 preparation parameters and test results for examples 1 to 5 and comparative example 1
As can be seen from table 1, compared with comparative example 1, in examples 1 to 5, the performances of the obtained barrier film in terms of temperature resistance, porosity, wettability, shrinkage rate and specific capacity are greatly improved, and by adopting the porous material with multi-level gradients, an excellent three-dimensional spatial layer structure can be formed, so that wettability, specific surface area and dispersibility are improved, the absorption rate of the electrolyte is improved, thermal stability is improved, and the stability of an electrochemical window of the battery is ensured.
Compared with the prior art, the barrier film coating material preparation method and the barrier film of the embodiment of the application can enable the coating material to contain a large number of pore structures through multi-stage mixing ball milling and spray forming, so that a three-dimensional spatial layer structure is formed, the wettability, the specific surface area and the dispersibility of the obtained coating material are effectively improved, the absorption rate of the coating material to electrolyte can be improved, the thermal stability of a coated pole piece is improved, the stability of an electrochemical window of a battery is further ensured, secondly, the process in the preparation method is easy to realize, and the industrial production is facilitated.
While the invention has been described with reference to specific embodiments, the scope of the invention is not limited thereto, and those skilled in the art can easily conceive various equivalent modifications or substitutions within the technical scope of the invention. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (14)
1. A preparation method of a barrier film coating material is characterized by comprising the following steps:
providing an aluminum oxide material, deionized water and a pore-forming agent, and mixing to obtain a first complex;
providing paraffin oil, mixing the first complex with the paraffin oil, and performing ball milling and embedding to obtain a second complex;
mixing the aluminum oxide material and paraffin oil to obtain a third complex;
ball-milling the second complex and the third complex to enable the third complex to wrap the second complex to obtain a fourth complex;
and providing dichloromethane and deionized water, mixing to obtain a mixed solution, mixing the fourth complex with the mixed solution in a spraying mode, washing and drying to obtain the coating material.
2. The method according to claim 1, wherein in the step of providing and mixing the alumina material and the pore-forming agent to obtain the first composite, the pore-forming agent is one of oxalic acid, boric acid, and ammonium bicarbonate.
3. The preparation method of claim 2, wherein in the step of providing and mixing the aluminum oxide material and the pore-forming agent to obtain the first composite, the particle size of the aluminum oxide material and the pore-forming agent is 50nm to 100nm, and the ratio of the aluminum oxide material, the deionized water and the pore-forming agent is 4-5: 0.5-1.0: 4.5-5 by weight.
4. The preparation method according to claim 1, wherein paraffin oil is provided, the first complex and the paraffin oil are mixed and are subjected to ball milling and embedding to obtain the second complex, and the ratio of the first complex to the paraffin oil is 3-5: 5-7 by weight.
5. The method according to claim 4, wherein in the step of providing paraffin oil, mixing the first complex with paraffin oil, and performing ball milling and embedding to obtain the second complex, the ball milling is performed at high speed by using a ball mill to embed the first complex and the paraffin oil.
6. The method according to claim 5, wherein the step of providing paraffin oil, mixing the first composite with paraffin oil, and performing ball milling and embedding to obtain the second composite, wherein the second composite has a particle size of 150nm to 500 nm.
7. The method according to claim 6, wherein the third composite is obtained by providing paraffin oil and mixing the alumina material with the paraffin oil, wherein the alumina material has a particle size of 200nm to 600 nm.
8. The method according to any one of claims 1 to 7, wherein in the step of mixing the aluminum oxide material and the paraffin oil to obtain the third composite, the ratio of the aluminum oxide material to the paraffin oil is 3 to 5: 5 to 7 by weight.
9. The preparation method of claim 8, wherein the step of ball milling the second complex and the third complex to wrap the second complex with the third complex to obtain the fourth complex further comprises drying to remove moisture at a temperature of 60 ℃ to 80 ℃ for 5h to 10 h.
10. The preparation method according to claim 9, wherein the second complex and the third complex are ball-milled, and the third complex wraps the second complex to obtain a fourth complex, wherein the ratio of the second complex to the third complex is 1-4: 6-9 by weight.
11. The preparation method of claim 10, wherein dichloromethane and deionized water are provided and mixed to obtain a mixed solution, the fourth complex and the mixed solution are mixed in a spraying manner, and in the washing and drying step, the ratio of dichloromethane to deionized water is 3-4: 6-7 by volume.
12. The preparation method according to claim 11, wherein the dichloromethane and the deionized water are provided and mixed to obtain a mixed solution, the fourth complex is mixed with the mixed solution by a spraying manner, and in the washing and drying step, the fourth complex is sprayed into the mixed solution by a vacuum sprayer in a spraying manner, wherein the spraying pressure is 0.1 to 0.3 MPa.
13. A separator comprising the coating material obtained according to any one of claims 1 to 12.
14. The separator of claim 13, wherein the separator has a porosity of 53% to 55%, a wettability of 101% to 105%, and a shrinkage of 1.1% to 1.2%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210597569.5A CN115101886B (en) | 2022-05-30 | 2022-05-30 | Preparation method of isolating film coating material and isolating film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210597569.5A CN115101886B (en) | 2022-05-30 | 2022-05-30 | Preparation method of isolating film coating material and isolating film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115101886A true CN115101886A (en) | 2022-09-23 |
| CN115101886B CN115101886B (en) | 2024-09-17 |
Family
ID=83289557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210597569.5A Active CN115101886B (en) | 2022-05-30 | 2022-05-30 | Preparation method of isolating film coating material and isolating film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115101886B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1081098A (en) * | 1963-11-12 | 1967-08-31 | Pechiney Saint Gobain | Highly porous active alumina |
| GB1169497A (en) * | 1968-04-05 | 1969-11-05 | Mc Donnell Douglas Corp | Battery Separator and Battery Containing said Separator. |
| US20130171499A1 (en) * | 2011-04-05 | 2013-07-04 | Jae Won Yang | Porous membrane and method for manufacturing the same |
| KR20170019185A (en) * | 2015-08-11 | 2017-02-21 | 금오공과대학교 산학협력단 | Alumina graula by spray-drying and manufacturing method thereof |
| CN108178656A (en) * | 2018-01-11 | 2018-06-19 | 江西理工大学 | A kind of high porosity porous ceramics microballoon and preparation method thereof |
| US20190051906A1 (en) * | 2016-09-09 | 2019-02-14 | Sumitomo Chemical Company, Limited | Alumina powder, alumina slurry, alumina-containing coating layer, multilayer separation membrane and secondary battery |
| US20200067053A1 (en) * | 2016-03-23 | 2020-02-27 | Shanghai Energy New Materials Technology Co., Ltd. | Isolation membrane for electrochemical apparatus, and preparation method and application thereof |
-
2022
- 2022-05-30 CN CN202210597569.5A patent/CN115101886B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1081098A (en) * | 1963-11-12 | 1967-08-31 | Pechiney Saint Gobain | Highly porous active alumina |
| GB1169497A (en) * | 1968-04-05 | 1969-11-05 | Mc Donnell Douglas Corp | Battery Separator and Battery Containing said Separator. |
| US20130171499A1 (en) * | 2011-04-05 | 2013-07-04 | Jae Won Yang | Porous membrane and method for manufacturing the same |
| KR20170019185A (en) * | 2015-08-11 | 2017-02-21 | 금오공과대학교 산학협력단 | Alumina graula by spray-drying and manufacturing method thereof |
| US20200067053A1 (en) * | 2016-03-23 | 2020-02-27 | Shanghai Energy New Materials Technology Co., Ltd. | Isolation membrane for electrochemical apparatus, and preparation method and application thereof |
| US20190051906A1 (en) * | 2016-09-09 | 2019-02-14 | Sumitomo Chemical Company, Limited | Alumina powder, alumina slurry, alumina-containing coating layer, multilayer separation membrane and secondary battery |
| CN108178656A (en) * | 2018-01-11 | 2018-06-19 | 江西理工大学 | A kind of high porosity porous ceramics microballoon and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115101886B (en) | 2024-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2672545B1 (en) | Battery separator and preparation method thereof, and lithium ion battery | |
| EP2077594A1 (en) | Composite separator films for lithium-ion batteries | |
| CN105514328A (en) | Ceramic diaphragm for lithium ion battery and preparation method of ceramic diaphragm | |
| CN105161661A (en) | Composite diaphragm for lithium ion battery, preparation method of composite diaphragm, and lithium ion battery | |
| CN105938919A (en) | Electrolyte containing inorganic substance additive and lithium ion battery containing electrolyte | |
| CN113839005B (en) | Gel composite positive electrode for solid-state battery and preparation method thereof | |
| CN111180644A (en) | Lithium ion battery diaphragm with ultrathin coating layer | |
| CN110571393A (en) | slurry for lithium battery diaphragm, preparation method of slurry, lithium battery diaphragm and lithium battery | |
| WO2020107287A1 (en) | Porous composite separator, preparation method therefor and lithium ion battery containing same | |
| CN115799441A (en) | Lithium ion battery and power utilization device | |
| CN114171849B (en) | Composite diaphragm with core-shell structure and preparation method thereof | |
| CN111933922B (en) | Negative pole piece with coating layer, and preparation method and application thereof | |
| WO2015165762A1 (en) | Process for producing a monolithic body of a porous carbon material, monolithic bodies of special porous carbon materials and their use | |
| CN115101886B (en) | Preparation method of isolating film coating material and isolating film | |
| WO2023179550A1 (en) | Composite oil-based separator and preparation method therefor, and secondary battery | |
| CN111244361A (en) | Modified polyolefin diaphragm and preparation method and application thereof | |
| CN115148997B (en) | Composite positive electrode active material, method for preparing same, and electric device comprising same | |
| KR102496671B1 (en) | Manufacturing method of silicon negative active material with nano silicon mixture inserted into pores of coffee grounds | |
| Li et al. | A sandwich-structure composite membrane as separator with high wettability and thermal properties for advanced lithium-ion batteries | |
| CN107814964A (en) | A kind of water paste and preparation method, battery diaphragm and lithium ion battery | |
| CN114709377A (en) | High-nickel positive electrode material and preparation method and application thereof | |
| CN109167006B (en) | Lithium ion battery diaphragm and preparation method thereof | |
| Nahvi Bayani et al. | Aluminum hydroxide-based flame-retardant composite separator for lithium-ion batteries | |
| CN111900313A (en) | Diaphragm and application thereof | |
| CN115719795B (en) | Secondary battery |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |