CN116462971A - Preparation method of heat-conducting insulating silicon gel composite material for lithium battery - Google Patents
Preparation method of heat-conducting insulating silicon gel composite material for lithium battery Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 12
- 239000010703 silicon Substances 0.000 title claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 8
- 239000000945 filler Substances 0.000 claims abstract description 42
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004005 microsphere Substances 0.000 claims abstract description 24
- 239000011258 core-shell material Substances 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000000741 silica gel Substances 0.000 claims abstract description 20
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 20
- 239000000499 gel Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000007790 scraping Methods 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 5
- 239000011521 glass Substances 0.000 claims abstract description 4
- 238000011049 filling Methods 0.000 claims description 20
- 229910003460 diamond Inorganic materials 0.000 claims description 12
- 239000010432 diamond Substances 0.000 claims description 12
- 229920001169 thermoplastic Polymers 0.000 claims description 11
- 239000004416 thermosoftening plastic Substances 0.000 claims description 11
- 239000011231 conductive filler Substances 0.000 claims description 9
- 229910052582 BN Inorganic materials 0.000 claims description 7
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004636 vulcanized rubber Substances 0.000 claims description 6
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 239000000806 elastomer Substances 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 229920006132 styrene block copolymer Polymers 0.000 claims description 2
- 229920006344 thermoplastic copolyester Polymers 0.000 claims description 2
- 229920002397 thermoplastic olefin Polymers 0.000 claims description 2
- 229920006345 thermoplastic polyamide Polymers 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- 239000011248 coating agent Substances 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 10
- 238000010345 tape casting Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 229920001296 polysiloxane Polymers 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 208000019901 Anxiety disease Diseases 0.000 description 2
- 230000036506 anxiety Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000006244 Medium Thermal Substances 0.000 description 1
- 238000000441 X-ray spectroscopy Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000011853 conductive carbon based material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/183—Sealing members
- H01M50/19—Sealing members characterised by the material
- H01M50/195—Composite material consisting of a mixture of organic and inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/183—Sealing members
- H01M50/19—Sealing members characterised by the material
- H01M50/198—Sealing members characterised by the material characterised by physical properties, e.g. adhesiveness or hardness
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- 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
Abstract
A preparation method of a heat-conducting insulating silicon gel composite material for a lithium battery comprises the following steps: uniformly mixing polycrystalline or monocrystalline micro/nano-scale heat-conducting filler and thermoplastic elastomer powder or particles, and preparing the heat-conducting filler/thermoplastic elastomer microsphere with a core-shell structure through high-temperature mechanical vibration; uniformly mixing the heat-conducting filler/thermoplastic elastomer microspheres and the silica gel according to a certain proportion, defoaming in vacuum at room temperature, and scraping the mixed colloidal slurry on the surface of a glass plate die to form a sheet, wherein the scraping thickness is 10-1000 mu m; and (3) curing at room temperature, and taking the cured composite material off the surface of the die to obtain the heat-conducting filler/silica gel composite material with the three-dimensional structure. The preparation method adopts core-shell coating, knife coating and other continuous operation methods, has simple process and easy operation, ensures the mechanical property and molding processability of the composite material, reduces the cost and is beneficial to industrialized popularization and application.
Description
Technical Field
The invention belongs to the technical field of polymer-based heat-conducting and insulating composite materials, and relates to a preparation method of a heat-conducting and insulating silicon gel composite material for a lithium battery.
Background
Nowadays, with the acceleration of the electric progress of automobiles and the continuous improvement of the requirements for cruising ability, the power battery cells of the electric automobiles are continuously developed towards the directions of high integration, high energy and light weight, the safety problems of electric automobile ignition, explosion and the like caused by thermal runaway of the batteries are increasingly outstanding, and the main challenges of global automobile manufacturers are changed from mileage anxiety to safety anxiety.
The silica gel is a thermosetting resin with good elasticity and chemical corrosion resistance, and is a main matrix material adopted in the thermal management of the battery pack of the new energy automobile. The heat generated by the battery cell is conducted to the battery plate through the heat conduction organic silicon pouring sealant filled around the battery cell, and the functions of fixing, damping and bonding are also achieved, and the heat is conducted to the air through the battery plate. However, the thermal conductivity of the organic silicon resin applied in engineering is about 0.1-0.2W/mK, and the organic silicon resin is not suitable to be directly used as a high polymer thermal management material. The main method for improving the heat conductivity is to perform organic/inorganic compounding, i.e. adding a filling material with high heat conductivity into the material. Currently, insulating fillers comprise medium thermal conductive ceramic materials (thermal conductivity in the range of 200-500W/mK), such as alumina, boron nitride and aluminum nitride, and high thermal conductive carbon-based materials (thermal conductivity in the range of 1000-2000W/mK), such as single-crystal or polycrystalline micron-sized diamond. Generally, 50% -90% of the filling volume fraction is required to meet the requirement of heat conductivity (such as CN202210433872.1 and CN 202211647373.9), however, the content of the heat conductive filler in this range can greatly reduce the mechanical properties and processing properties of the polymer composite material, so finding a solution to make the filler form a three-dimensional continuous heat conductive network under low filling content is the most effective solution. At present, the mainstream is to construct a three-dimensional continuous heat conduction network by using an ice template, but the method has high requirements on processing conditions on one hand and preparation conditions on the other hand, and cannot be effectively suitable for the current industrial production and application.
In order to realize the preparation of the high-performance heat-conducting filler/silica gel heat-conducting composite material, a proper method is selected to ensure that the heat-conducting filler has a three-dimensional structure in the composite material. How to control the three-dimensional assembly of the heat conducting filler in the silica gel matrix is needed to be solved in the field of the preparation of the thermal interface material.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a heat-conducting insulating silicon gel composite material for a lithium battery, which adopts core-shell cladding, knife coating and other simple and easy-to-operate methods to prepare a heat-conducting filler/silicon gel composite material with a three-dimensional structure, the prepared composite material has controllable structural performance and obvious three-dimensional assembly effect, and simultaneously, the cost is greatly reduced, and the volume content of the heat-conducting filler can be reduced.
The technical scheme adopted for solving the technical problems is as follows: the preparation method of the heat-conducting insulating silicon gel composite material for the lithium battery is characterized by comprising the following steps of:
1) Preparing a thermally conductive filler/thermoplastic elastomer microsphere with a 'core-shell structure':
the preparation method comprises the steps of selecting polycrystalline or monocrystalline micro/nano-scale heat conduction filling bodies and thermoplastic elastomer powder or particles as raw materials, uniformly mixing 80-50 parts by mass of the heat conduction filling bodies and 20-50 parts by mass of the thermoplastic elastomer powder or particles, and preparing the heat conduction filling bodies/thermoplastic elastomer with a core-shell structure through heating mechanical vibrationBody microsphere with temperature of 50-200deg.C and vibration frequency of 50-150H Z The vibration time is 5-30 minutes;
2) Preparing a heat-conducting filler/silica gel composite material with a three-dimensional structure:
uniformly mixing the prepared heat-conducting filler/thermoplastic elastomer microsphere and silica gel according to a certain proportion, defoaming for 3-15 minutes in vacuum at room temperature, and scraping the mixed colloidal slurry on the surface of a glass plate die through a coater to form a sheet, wherein the scraping thickness is 10-1000 mu m; and then curing at room temperature, and finally removing the cured composite material from the surface of the mold to obtain the heat-conducting filler/silica gel composite material with the three-dimensional structure.
Preferably, the heat conducting filler in the step 1) is one or more of diamond, boron nitride, aluminum oxide, zinc oxide, silicon carbide or silicon dioxide, and the average grain diameter is 0.01-200 μm.
The thermoplastic elastomer in the step 1) is one or more of thermoplastic styrene block copolymer, thermoplastic polyolefin elastomer, thermoplastic vulcanized rubber, thermoplastic polyurethane, thermoplastic copolyester, thermoplastic polyamide or thermoplastic organosilicon elastomer, and the average particle size is 10 mu m-1mm.
Further, the heat-conducting filler in step 1) needs to be pretreated before mixing: screening out the required size range by using screening screens with different apertures, sequentially ultrasonically cleaning with acetone, ethanol and deionized water for 5+/-1 min, and drying in an oven.
Further, the mass ratio of the heat-conducting filler/thermoplastic elastomer microsphere to the silica gel in the step 2) is 1: 0.09-5.
Preferably, the curing time at room temperature in step 2) is 5 to 24 hours. The temperature in the step 1) is 0.75 to 0.85 times (preferably 0.8 times) the softening point of the thermoplastic elastomer powder or particles.
Finally, the volume content of the heat conduction filling body/silica gel composite material with the three-dimensional structure is 5% -45%.
Compared with the prior art, the invention has the advantages that:
1. coating an organic and inorganic core shell by adopting a thermo-mechanical vibration method to finish the preparation of the heat conduction filling body/thermoplastic elastomer microsphere, wherein the size, the structure and the heat conductivity of the microsphere are controllable;
2. the three-dimensional distribution structure of the heat conduction filling body is realized in the silica gel by utilizing a method combining a 'core-shell structure' and blade coating, the three-dimensional distribution situation of the 'core-shell structure' and the heat conduction filling body in the silica gel is characterized, the three-dimensional assembly effect is obvious, and the heat conductivity of the composite material sheet in the out-of-plane direction is improved;
3. the volume content of the heat-conducting filling body can be effectively reduced, so that the composite material keeps good flexibility.
The invention adopts core-shell coating, knife coating and other continuous operation methods to prepare the polymer composite material with the three-dimensional heat conduction network structure, the process is simple and easy to operate, the structure performance of the prepared composite material is controllable, the filling amount of the required heat conduction filling body is less, on one hand, the mechanical property and the molding processability of the composite material are ensured, on the other hand, the cost is greatly reduced, and the invention is beneficial to industrialized popularization and application.
Drawings
FIG. 1 is a flow chart of the preparation of a sheet of thermally conductive composite material having a three-dimensional structure provided in example 1 of the present invention;
FIGS. 2 (a) and (b) are surface topography diagrams of a core-shell structure of organic-inorganic microspheres with different diamond sizes; ((a) core 300 microns, shell 20 microns corresponds to example 1 (b) core 300 microns, shell 10 microns)
Fig. 3 is a surface topography of a three-dimensional assembly of a thermally conductive filler provided in embodiment 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the embodiments of the drawings.
Example 1
The preparation method of the heat-conducting insulating silicon gel composite material for the lithium battery is shown in a figure 1, and the preparation process comprises the following specific steps:
1. pretreatment of thermally conductive filler particles
The heat conducting filler is monocrystalline micron-sized heat conducting filler diamond particles, the monocrystalline micron-sized heat conducting filler diamond particles are screened out to be in a required size range by using screens with different apertures, and are sequentially cleaned by acetone, ethanol and deionized water in an ultrasonic manner for 5 minutes, and then are dried in an oven.
2. Preparation of thermally conductive filler/thermoplastic elastomer microspheres with core-shell structure
The single crystal heat conducting filler diamond particles with the average particle diameter of 20 mu m and the thermoplastic polyurethane elastomer particles with the average particle diameter of 300 mu m are mixed according to the weight ratio of 3.3:1, mixing, placing into a high temperature mechanical vibration device, vibrating and coating for 30min at 100deg.C with vibration frequency of 50H Z The heat-conducting filler/thermoplastic elastomer microsphere with a core-shell structure is obtained.
3. Preparation of heat-conducting filler/silica gel composite material with three-dimensional structure
The heat conduction filling body/thermoplastic elastomer microsphere with the 'core-shell structure' prepared in the second step and the silica gel AB component are mixed according to the mass ratio of 1:0.095, vacuum defoamating for 5-10 min at room temperature, pouring the mixed colloidal slurry on the surface of a glass plate die, scraping and coating the slurry into a sheet by a coater, scraping and coating the sheet to a thickness of 450 mu m, and solidifying at room temperature for 24 hours. And tearing off the solidified composite material from the surface of the die to obtain the diamond/silica gel composite material with the three-dimensional structure.
4. And (3) characterizing and testing the prepared composite material, and further characterizing the assembly quality of a core-shell structure in the heat-conducting filler/thermoplastic elastomer microsphere, the three-dimensional assembly quality of the heat-conducting filler in the composite material and the heat-conducting property of the composite material. Characterizing the assembly condition of a core-shell structure in the heat-conducting filler/thermoplastic elastomer microsphere by using a scanning electron microscope and a metallographic microscope; characterizing the three-dimensional distribution of the thermally conductive filler in the composite material using a scanning electron microscope or energy scattering X-ray spectroscopy (EDS); a laser thermal conductivity analyzer was used to characterize the thermal conductivity of the thermally conductive filler/silicone gel composite material having a three-dimensional structure.
When the diamond volume content in this example was measured to be 40%, the thermal conductivity of the sample was 2W/mK, and its Shore hardness was 40. FIGS. 2 (a) and (b) are surface topography diagrams of the "core-shell structure" of organic-inorganic microspheres of different diamond sizes; fig. 3 is a surface topography of a three-dimensional assembly of thermally conductive fillers.
Example 2
The difference from example 1 is that: the heat-conducting filler is hexagonal boron nitride micron sheets with the average diameter of 1 mu m, the average particle diameter of the thermoplastic elastomer is 60 mu m, and the weight ratio of the hexagonal boron nitride micron sheets to the thermoplastic elastomer is 1:1, mixing the heat-conducting filler/thermoplastic elastomer microsphere with a core-shell structure and the silicone gel AB component according to the mass ratio of 1:0.49, mixing uniformly; the blade coating thickness was 100. Mu.m, and the thermal conductivity of the sample was 0.24W/mK. The other steps are the same as in example 1.
Example 3
The difference from example 1 is that: the heat conducting filler is aluminum nitride micron sheets, and the average grain diameter of the heat conducting filler is 1 mu m; the thermoplastic elastomer is thermoplastic organosilicon elastomer, the average grain diameter is 30 mu m, and the weight ratio of the aluminum nitride micron sheet to the thermoplastic elastomer is 3:1, mixing; the temperature of the high-temperature mechanical vibration is 150 ℃; the heat-conducting filler/thermoplastic elastomer microsphere with the 'core-shell structure' and the silicone gel AB component are mixed according to the mass ratio of 1:0.7, the thickness of the blade coating is 35 μm, and the thermal conductivity of the sample is 0.28W/mK. The other steps are the same as in example 1.
Example 4
The difference from example 1 is that: the heat conducting filler is hexagonal boron nitride micron sheet with average diameter of 1 μm, the thermoplastic elastomer is thermoplastic vulcanized rubber powder with average particle diameter of 40 μm, and the weight ratio of hexagonal boron nitride micron sheet to thermoplastic elastomer is 4:1, mixing, wherein the temperature of high-temperature mechanical vibration is 120 ℃; the heat-conducting filler/thermoplastic elastomer microsphere with the 'core-shell structure' and the silicone gel AB component are mixed according to the mass ratio of 1:0.32, the blade coating thickness was 50 μm and the thermal conductivity of the sample was 1.6W/mK. The other steps are the same as in example 1.
Example 5
The difference from example 1 is that: the vibration frequency of high-temperature mechanical vibration is 100H Z The core-shell vibration coating time is 10min, and the sample performance is unchanged. The other steps are the same as in example 1.
Example 6
The difference from example 1 is that: the heat conducting filler is silicon dioxide, and the average grain diameter of the heat conducting filler is 0.2 mu m; the thermoplastic elastomer is thermoplastic vulcanized rubber powder, the average particle diameter of the thermoplastic vulcanized rubber powder is 10 mu m, and the mass ratio of the thermoplastic elastomer to the thermoplastic vulcanized rubber powder is 4:1, mixing; the temperature of high-temperature mechanical vibration is 100 ℃, and the vibration time is 15 minutes; the heat-conducting filler/thermoplastic elastomer microsphere with the 'core-shell structure' and the silicone gel AB component are mixed according to the mass ratio of 1:0.2, the thickness of the knife coating is 800 μm, and the thermal conductivity of the sample is 0.26W/mK. The other steps are the same as in example 1.
Example 7
The difference from example 1 is that: the heat conducting filling body is diamond particles, and the average particle size of the heat conducting filling body is 10 mu m; the thermoplastic elastomer is thermoplastic polyurethane, the mass ratio is 2.2:1, and the average particle diameter is 300 mu m; the temperature of high-temperature mechanical vibration is 50 ℃, the vibration frequency is 120Hz, and the vibration time is 5 minutes; the heat-conducting filler/thermoplastic elastomer microsphere with the 'core-shell structure' and the silicone gel AB component are mixed according to the mass ratio of 1:1.44, the blade coating thickness was 500 μm and the thermal conductivity of the sample was 0.5W/mK at a diamond volume content of 10%. The other steps are the same as in example 1.
The foregoing embodiments are further illustrative of the technical solution of the present invention, but are not limited thereto, and modifications and equivalents of the technical solution of the present invention should be made without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. The preparation method of the heat-conducting insulating silicon gel composite material for the lithium battery is characterized by comprising the following steps of:
1) Preparing a thermally conductive filler/thermoplastic elastomer microsphere with a 'core-shell structure':
selecting polycrystalline or monocrystalline micro/nano-scale heat conducting filling body and thermoplastic elastomer powder or particles as raw materials, uniformly mixing 80-50 parts by mass of the heat conducting filling body and 20-50 parts by mass of the thermoplastic elastomer powder or particles, and preparing the core through heating mechanical vibrationShell structure heat conducting stuffing/thermoplastic elastomer microsphere at 50-200 deg.c and vibration frequency of 50-150H Z The vibration time is 5-30 minutes;
2) Preparing a heat-conducting filler/silica gel composite material with a three-dimensional structure:
uniformly mixing the prepared heat-conducting filler/thermoplastic elastomer microsphere and silica gel according to a certain proportion, defoaming for 3-15 minutes in vacuum at room temperature, and scraping the mixed colloidal slurry on the surface of a glass plate die through a coater to form a sheet, wherein the scraping thickness is 10-1000 mu m; and then curing at room temperature, and finally removing the cured composite material from the surface of the mold to obtain the heat-conducting filler/silica gel composite material with the three-dimensional structure.
2. The method of manufacturing according to claim 1, characterized in that: the heat conducting filling body in the step 1) is one or more of diamond, boron nitride, aluminum oxide, zinc oxide, silicon carbide or silicon dioxide, and the average grain diameter is 0.01-200 mu m.
3. The method of manufacturing according to claim 1, characterized in that: the thermoplastic elastomer in the step 1) is one or more of thermoplastic styrene block copolymer, thermoplastic polyolefin elastomer, thermoplastic vulcanized rubber, thermoplastic polyurethane, thermoplastic copolyester, thermoplastic polyamide or thermoplastic organosilicon elastomer, and the average particle size is 10 mu m-1mm.
4. The method of manufacturing according to claim 1, characterized in that: the heat-conducting filler of step 1) needs to be pretreated before mixing: screening out the required size range by using screening screens with different apertures, sequentially ultrasonically cleaning with acetone, ethanol and deionized water for 5+/-1 min, and drying in an oven.
5. The method of manufacturing according to claim 1, characterized in that: the mass ratio of the heat-conducting filler/thermoplastic elastomer microsphere to the silica gel in the step 2) is 1: 0.09-5.
6. The method of manufacturing according to claim 1, characterized in that: the curing time at room temperature in the step 2) is 5-24 hours.
7. The method of manufacturing according to claim 1, characterized in that: the temperature in the step 1) is 0.75 to 0.85 times of the softening point of the thermoplastic elastomer powder or particles.
8. The method of manufacturing according to claim 1, characterized in that: the volume content of the heat conduction filling body/silica gel composite material with the three-dimensional structure is 5% -45%.
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