CN114597582B - Insulating adhesive film for side plate of battery cell module of power battery and preparation method of insulating adhesive film - Google Patents
Insulating adhesive film for side plate of battery cell module of power battery and preparation method of insulating adhesive film Download PDFInfo
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- CN114597582B CN114597582B CN202210257735.7A CN202210257735A CN114597582B CN 114597582 B CN114597582 B CN 114597582B CN 202210257735 A CN202210257735 A CN 202210257735A CN 114597582 B CN114597582 B CN 114597582B
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- 239000002313 adhesive film Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title abstract description 83
- 239000002245 particle Substances 0.000 claims abstract description 86
- 239000003822 epoxy resin Substances 0.000 claims abstract description 70
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 70
- 239000002274 desiccant Substances 0.000 claims abstract description 62
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 238000009413 insulation Methods 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 230000001681 protective effect Effects 0.000 claims abstract description 10
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000012545 processing Methods 0.000 claims abstract description 6
- 239000010440 gypsum Substances 0.000 claims description 33
- 229910052602 gypsum Inorganic materials 0.000 claims description 33
- 229920005610 lignin Polymers 0.000 claims description 26
- 238000003763 carbonization Methods 0.000 claims description 25
- 239000003292 glue Substances 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000197 pyrolysis Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 229920000459 Nitrile rubber Polymers 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 229920002379 silicone rubber Polymers 0.000 claims description 8
- 239000004254 Ammonium phosphate Substances 0.000 claims description 7
- 229920002799 BoPET Polymers 0.000 claims description 7
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 7
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 7
- 239000011324 bead Substances 0.000 claims description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000011707 mineral Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000004945 silicone rubber Substances 0.000 claims description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 239000003063 flame retardant Substances 0.000 claims description 5
- 238000007731 hot pressing Methods 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 4
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000467 phytic acid Substances 0.000 claims description 4
- 235000002949 phytic acid Nutrition 0.000 claims description 4
- 229940068041 phytic acid Drugs 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 19
- 230000000694 effects Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000003463 adsorbent Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 239000000306 component Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 229940095564 anhydrous calcium sulfate Drugs 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 150000004683 dihydrates Chemical group 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229920006335 epoxy glue Polymers 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical group CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229940095672 calcium sulfate Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- FCZCIXQGZOUIDN-UHFFFAOYSA-N ethyl 2-diethoxyphosphinothioyloxyacetate Chemical compound CCOC(=O)COP(=S)(OCC)OCC FCZCIXQGZOUIDN-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- -1 polydimethylsiloxane Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007847 structural defect Effects 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- 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
The application relates to the technical field of adhesive film processing, and particularly discloses an insulating adhesive film for a side plate of a battery cell module of a power battery and a preparation method of the insulating adhesive film. The insulating adhesive film comprises a PET adhesive film, an epoxy resin film and a PE protective film which are sequentially attached along the thickness direction, wherein the formula of the epoxy resin film comprises the following raw materials in parts by weight: 120-140 parts of epoxy resin, 30-40 parts of desiccant particles, 16-24 parts of curing agent, 2-4 parts of accelerator and 4-6 parts of auxiliary agent, wherein the desiccant particles are anhydrous gypsum particles coated with porous carbonized films on the surfaces, and the desiccant particles are subjected to dipping treatment of an insulating treatment agent. The desiccant particles absorb and solidify the moisture permeated into the epoxy resin film, so that the humidity of the epoxy resin film is reduced, the overall resistance of the adhesive film is improved, and the insulation performance of the adhesive film is improved.
Description
Technical Field
The application relates to the technical field of adhesive film processing, in particular to an insulating adhesive film for a side plate of a battery cell module of a power battery and a preparation method of the insulating adhesive film.
Background
Currently, fossil energy is still dominant in energy structures in countries around the world. The massive use of fossil fuels in internal combustion engines can cause significant environmental damage, and thus new energy systems for replacing fossil fuel-internal combustion engine systems are being vigorously developed throughout the world. Among the new energy systems of the already-established scale, the battery-motor system powered by clean energy such as wind power, hydropower, etc. is most promising to replace the existing fossil fuel-internal combustion engine system. Whether the motor can completely replace the internal combustion engine depends on whether a power battery which is convenient for wide application can be developed. The battery cell is a core component of the power battery, and when a power battery manufacturer processes a cell module of the power battery, a resin adhesive film is often required to be adhered to the surface of an aluminum plate of a side plate of the cell module. The working environment of the power battery is generally located outdoors, so that the situation of high environmental humidity is unavoidable, and under the situation of high humidity, in order to prevent the power battery from electric leakage, the Chinese patent publication No. CN111040670B, which is a film adhered to the surface of the aluminum plate, needs to have good insulating effect, discloses an adhesive and a preparation method thereof, and a PET insulating film containing the adhesive, wherein the adhesive comprises the following components in parts by weight: 100 parts of epoxy resin, 20-100 parts of rubber, 5-30 parts of curing agent and 50-150 parts of flame retardant, wherein the curing agent comprises a mixture of anhydride epoxy resin flexible curing agent and polymer epoxy resin flexible curing agent. In the related art, an adhesive film is prepared by using an adhesive, and the insulation performance of the adhesive film is improved by using the high resistance of the rubber.
Regarding the above related art, the inventors believe that the excessive addition of the flame retardant in the adhesive film in the related art may affect the curing of the epoxy resin, resulting in poor water blocking performance of the adhesive film. In the environment with higher humidity, the adhesive film is easy to absorb moisture in the air, so that the resistance of the adhesive film is reduced, and the insulating performance of the adhesive film is influenced.
Disclosure of Invention
In the related art, the adhesive film is easy to absorb moisture when being used in an environment with high humidity, and the insulation performance of the adhesive film is affected. To improve this defect, the application provides an insulating adhesive film for a side plate of a battery cell module of a power battery and a preparation method thereof.
In a first aspect, the present application provides an insulating film for a side plate of a battery cell module of a power battery, which adopts the following technical scheme:
an insulating adhesive film for a side plate of a battery cell module of a power battery, wherein the insulating adhesive film comprises a PET adhesive film, an epoxy resin film and a PE protective film which are sequentially attached along the thickness direction, and the formula of the epoxy resin film comprises the following raw materials in parts by weight: 120-140 parts of epoxy resin, 30-40 parts of desiccant particles, 16-24 parts of curing agent, 2-4 parts of accelerator and 4-6 parts of auxiliary agent, wherein the desiccant particles are anhydrous gypsum particles coated with porous carbonized films on the surfaces, and the desiccant particles are subjected to dipping treatment of an insulation treatment agent.
Through adopting above-mentioned technical scheme, in the glued membrane of this application preparation, on the one hand, through adjusting raw materials quantity and raw materials kind, increased the epoxy's in epoxy resin membrane formula system the ratio, improved the density of cross-linking each other between the chain segment of epoxy, improved holistic water blocking ability and the adhesive property of glued membrane. On the other hand, in the practical application of the adhesive film, when the ambient humidity is high, the desiccant particles absorb the moisture permeated into the epoxy resin film, and then the anhydrous calcium sulfate in the desiccant particles is combined with the moisture and converted into hydrated calcium sulfate crystals. The anhydrous calcium sulfate cures the moisture absorbed by the epoxy resin film, thereby improving the resistance of the epoxy resin film and being beneficial to improving the insulating performance of the insulating adhesive film. In addition, the desiccant particles obtained through the impregnation treatment of the insulation treatment agent can release free insulation treatment agent to the periphery, the insulation treatment agent increases the resistance of the surface of the porous carbonized film on one hand, and increases the resistance around the desiccant particles on the other hand, so that the possibility of reducing the local resistance of the epoxy resin film after moisture is concentrated around the desiccant particles is reduced, and the insulation performance of the whole adhesive film is improved.
Preferably, the formula of the epoxy resin film comprises the following raw materials in parts by weight: 125-135 parts of epoxy resin, 33-37 parts of desiccant particles, 18-22 parts of curing agent, 2.5-3.5 parts of accelerator and 4.5-5.5 parts of auxiliary agent.
By adopting the technical scheme, the raw material ratio of the epoxy resin film is optimized, and the insulating property of the adhesive film is improved.
Preferably, the insulating treatment agent is amino-terminated liquid nitrile rubber or mineral insulating oil.
By adopting the technical scheme, the amino-terminated liquid nitrile rubber or the mineral insulating oil has good insulating performance, and when the mineral insulating oil is used as an insulating treatment agent, the mineral insulating oil has strong hydrophobicity and can prevent the absorbent particles from absorbing moisture although the electric resistance of the absorbent particles can be improved, so that the insulating performance of the adhesive film is improved only to a limited extent. When the amino-terminated liquid nitrile rubber is selected as an insulating treatment agent, on one hand, the electric resistance of the surface of the porous carbonized film can be improved, and on the other hand, active groups such as carboxyl, hydroxyl, amino, epoxy and the like on the amino-terminated liquid nitrile rubber can also enhance the hydrophilicity of the adsorbent particles, limit the penetration of moisture in the epoxy resin film by forming hydrogen bonds, and are favorable for improving the absorption effect of the adsorbent particles on the moisture, reduce the integral wetting degree of the epoxy resin film and improve the insulating property of the adhesive film.
Preferably, the desiccant particles are prepared as follows:
(1) Crushing gypsum materials to obtain gypsum particles;
(2) Uniformly mixing gypsum particles and lignin slurry, then drying the slurry obtained by mixing, and crushing the dried product to obtain precursor particles; in the step, the components of lignin slurry comprise an organic solvent and lignin;
(3) And (3) carrying out pyrolysis carbonization on the precursor particles, and then impregnating a carbonized solid product at room temperature by using an insulating treatment agent to obtain the drying agent particles.
Through adopting above-mentioned technical scheme, this application uses the gypsum material as the raw materials, smashes earlier and obtains gypsum granule, then uses organic polymer thick liquids as the carrier to lignin in the thick liquids is as the carbon source, has obtained the carbomorphism membrane that adheres to gypsum granule surface through pyrolysis carbomorphism. Then, the preparation of the desiccant particles is completed through the impregnation treatment of the insulating treatment agent.
Preferably, the lignin slurry comprises the following components in parts by weight: 40-60 parts of lignin, 80-100 parts of an organic solvent, 4-8 parts of a carbonization auxiliary agent and 8-12 parts of a binder, wherein the boiling point of the organic solvent is not higher than the boiling point of water.
By adopting the technical scheme, the raw material proportion of the organic polymer slurry is optimized, so that the effects of absorbing and solidifying moisture by the desiccant particles are improved, and the insulating property of the adhesive film is improved.
Preferably, the gypsum in the gypsum material is present in the form of hydrate crystals.
By adopting the technical scheme, because gypsum materials need pyrolysis treatment when preparing the drying agent particles, no matter gypsum in the gypsum materials exists in the form of hydrate crystals or in the form of anhydrous gypsum, and the anhydrous gypsum is contained in the adsorbent particles after the operation according to the preparation method of the application. When gypsum in the gypsum material exists in the form of hydrate crystals, the storage stability of the gypsum material is better, and the water vapor generated when the gypsum material loses moisture can also increase the number of pores in the porous carbonized film, so that the water absorption effect of the desiccant particles is improved, and the insulating property of the adhesive film is improved.
Preferably, the carbonization aid is phytic acid or ammonium phosphate.
By adopting the technical scheme, the phytic acid or the ammonium phosphate can be decomposed to generate phosphoric acid during pyrolysis carbonization, and the phosphoric acid can promote lignin carbonization on the surface of gypsum particles, so that the formation of a porous carbonized film is accelerated. Meanwhile, phosphoric acid can also permeate to the surface of the gypsum particles and is combined with calcium ions on the surface of the gypsum particles to form calcium phosphate, and the calcium phosphate reinforces the drying agent particles, so that the possibility of disintegration of the drying agent particles in the processing process is reduced. In addition, when ammonium phosphate is decomposed, the generated ammonia gas can also increase the number of air holes in the porous carbonized film, so that the adsorption effect of the desiccant particles is better when the ammonium phosphate is selected as a carbonization auxiliary agent, and the insulation performance of the adhesive film is improved.
Preferably, the binder is silicone rubber powder or polyethylene glycol.
By adopting the technical scheme, the organic chain segments and the polyethylene glycol in the silicone rubber powder can form a carbonization structure under the pyrolysis carbonization condition, the carbonization structure is bonded with the porous carbonization film through combination of the porous carbonization film, the bonding of structural defects of the porous carbonization film is realized, and the possibility of cracking of the porous carbonization film in the pyrolysis process is reduced. When the binder is silicon rubber powder, the silicon-containing chain segment in the silicon rubber powder can also form a ceramic structure combined with the carbonization structure after pyrolysis, and the ceramic structure can be combined with gypsum particles, so that the bonding effect between the porous carbonization film and the gypsum particles is enhanced, and the possibility of disintegration of the drying agent particles during pyrolysis treatment is reduced.
Preferably, the component of the organic solvent is one of acetone or absolute ethyl alcohol.
By adopting the technical scheme, the boiling point of the acetone or the absolute ethyl alcohol is not higher than that of water, and the acetone or the absolute ethyl alcohol can be used for preparing lignin slurry. The ethanol can form hydrogen bonds with lignin molecules, so that lignin is easier to disperse in the ethanol, and convenience in preparing lignin slurry is improved.
In a second aspect, the present application provides a method for preparing an insulating film for a side plate of a battery cell module of a power battery, which adopts the following technical scheme.
The preparation method of the insulating adhesive film for the side plate of the battery cell module of the power battery comprises the following steps:
(1) Heating epoxy resin to a molten state under the condition of water bath heating, adding desiccant particles, a curing agent, an accelerator and an auxiliary agent into the molten epoxy resin, and uniformly stirring to obtain epoxy resin glue solution;
(2) Coating epoxy resin glue solution on a PET film, and then standing the PET film coated with the epoxy resin glue solution until the epoxy resin glue solution loses fluidity, so as to obtain an epoxy resin film;
(3) And covering a PE protective film on the surface of the epoxy resin glue film, and then carrying out hot pressing processing on the PE protective film, the epoxy resin film and the PET glue film to obtain the flame-retardant insulating glue film for the side plate of the battery cell module.
Through adopting above-mentioned technical scheme, this application is mixed epoxy with drier granule, curing agent, accelerator and auxiliary agent with molten state and is got epoxy glue solution to utilize epoxy glue solution to prepare the epoxy film, finally obtain the insulating glued membrane that is used for power battery electric core module curb plate through hot pressing.
In summary, the present application has the following beneficial effects:
1. in the adhesive film of the application, the desiccant particles absorb and solidify the moisture permeated into the epoxy resin film, so that the humidity of the epoxy resin film is reduced, the overall resistance of the adhesive film is improved, and the insulating property of the adhesive film is improved. In addition, the desiccant particles are subjected to the impregnation treatment of the insulating treatment agent, so that the possibility of reducing the local resistance of the epoxy resin film is reduced, and the insulating performance of the whole adhesive film is improved.
2. The amino-terminated liquid nitrile rubber or mineral insulating oil is preferably used as an insulating treatment agent, wherein the amino-terminated liquid nitrile rubber not only can improve the resistance of the surface of the porous carbonized film, but also can enhance the hydrophilicity of the desiccant particles, limit the penetration of moisture in the epoxy resin film, reduce the wetting degree of the epoxy resin film and improve the insulating property of the adhesive film.
3. According to the method, epoxy resin, desiccant particles, a curing agent, an accelerator and an auxiliary agent are manufactured into an epoxy resin film, and then the epoxy resin film, a PET film and a PE protective film are compounded through hot pressing, so that an insulating adhesive film for a power battery cell module side plate is obtained.
Detailed Description
The present application is further described in detail below with reference to examples and preparations.
The starting materials used in the preparation examples of the present application are all commercially available.
Preparation of desiccant particles
The following is an example of preparation 1.
Preparation example 1
In this application, desiccant particles are prepared according to the following method:
(1) Crushing gypsum materials to an average particle size of 350 mu m, and screening by using a 75 mu m square-hole screen, wherein the screened residues are gypsum particles; in the step, gypsum paste is anhydrous gypsum;
(2) Uniformly mixing gypsum particles and lignin slurry according to a weight ratio of 1:3, then drying the slurry obtained by mixing at 105 ℃, and crushing the dried product to obtain precursor particles; in the step, the components of lignin slurry comprise an organic solvent and lignin; the lignin slurry is obtained by mixing 40kg of lignin, 80kg of organic solvent, 4kg of carbonization auxiliary agent and 8kg of binder, stirring in a stirring pot at a rotating speed of 50rpm for 10min, wherein the organic solvent is acetone, the carbonization auxiliary agent is phytic acid, and the binder is polyethylene glycol
(3) Carrying out pyrolysis carbonization on precursor particles under the anaerobic condition of 700 ℃, continuously maintaining the temperature for 2 hours after reaching 700 ℃, cooling a solid product obtained by pyrolysis carbonization to room temperature, soaking for 2 hours by using an insulating treatment agent, grafting, and drying at 105 ℃ to obtain drying agent particles; in this step, the insulating treatment agent is mineral insulating oil.
As shown in Table 1, the preparation examples 1 to 5 were different in the raw material ratios of lignin slurry.
TABLE 1
| Sample of | Lignin/kg | Organic solvent/kg | Carbonization aid/kg | Adhesive/kg |
| Preparation example 1 | 40 | 80 | 4 | 8 |
| Preparation example 2 | 45 | 85 | 5 | 9 |
| Preparation example 3 | 50 | 90 | 6 | 10 |
| Preparation example 4 | 55 | 95 | 7 | 11 |
| Preparation example 5 | 60 | 100 | 8 | 12 |
Preparation example 6
This preparation differs from preparation 3 in that in step (3) of preparing the desiccant beads, the insulation treating agent is an amino-terminated liquid nitrile rubber.
Preparation example 7
This preparation differs from preparation 6 in that in step (1) of preparing the desiccant particles, the gypsum is dihydrate gypsum.
Preparation example 8
This preparation differs from preparation 7 in that in step (2) of preparing the desiccant particles, the carbonization aid is ammonium phosphate.
Preparation example 9
This preparation differs from preparation 8 in that in step (2) of preparing the desiccant particles, the binder is silicone rubber powder.
Preparation example 10
The difference between this preparation example and preparation example 9 is that in the step (2) of preparing the desiccant particles, the organic solvent is absolute ethanol, and the stirring rate in preparing lignin slurry is 5min.
PREPARATION EXAMPLE 11
The present preparation example differs from preparation example 1 in that in step (3) of preparing the desiccant particles, the solid product obtained by pyrolysis carbonization is directly used as the desiccant particles without the impregnation treatment of the insulating treatment agent.
Preparation example 12
This preparation differs from preparation 1 in that the raw material of the lignin slurry does not include a binder.
Examples
The starting materials used in the examples herein are all commercially available.
Examples 1 to 5
The following description will take example 1 as an example.
Example 1
In this embodiment, an insulating film for a side plate of a battery cell module of a power battery is prepared according to the following steps:
(1) Heating 120kg of epoxy resin to a molten state under the water bath heating condition of 90 ℃, adding 30kg of desiccant particles of preparation example 1, 16kg of curing agent, 2kg of accelerator and 4kg of auxiliary agent into the molten epoxy resin, and uniformly stirring to obtain epoxy resin glue solution; in the step, the curing agent is diethylenetriamine, the accelerator is 2,4, 6-tris (dimethylaminomethyl) phenol, and the auxiliary agent is prepared according to the ratio of 1:1:1, a leveling agent, a wetting agent and a defoaming agent are mixed according to the weight ratio, wherein the leveling agent is polyether polyester modified organic siloxane with average molecular weight of 10000, the wetting agent is 1,4 butanediol, and the defoaming agent is polydimethylsiloxane with average molecular weight of 120000;
(2) Coating epoxy resin glue solution on a PET film, and then standing the PET film coated with the epoxy resin glue solution until the epoxy resin glue solution loses fluidity, so as to obtain an epoxy resin film;
(3) And covering a PE protective film on the surface of the epoxy resin glue film, and then carrying out hot pressing processing on the PE protective film, the epoxy resin film and the PET glue film to obtain the flame-retardant insulating glue film for the side plate of the battery cell module.
As shown in Table 2, examples 1 to 5 are different in mainly the raw material ratio of the epoxy resin film
TABLE 2
| Sample of | Epoxy resin/kg | Desiccant granule/kg | Curing agent/kg | Accelerator/kg | Auxiliary agent/kg |
| Example 1 | 120 | 30 | 16 | 2 | 4 |
| Example 2 | 125 | 33 | 18 | 2.5 | 4.5 |
| Example 3 | 130 | 35 | 20 | 3 | 5 |
| Example 4 | 135 | 37 | 22 | 3.5 | 5.5 |
| Example 5 | 140 | 40 | 24 | 4 | 6 |
Example 6
This example differs from example 3 in that the desiccant beads are those of preparation example 2.
Examples 6-14 differ from example 3 in the preparation of desiccant beads as shown in Table 3.
| Sample of | Preparation of desiccant particles | Sample of | Preparation of desiccant particles |
| Example 3 | Preparation example 1 | Example 10 | Preparation example 6 |
| Example 6 | Preparation example 2 | Example 11 | Preparation example 7 |
| Example 7 | Preparation example 3 | Example 12 | Preparation example 8 |
| Example 8 | Preparation example 4 | Example 13 | Preparation example 9 |
| Example 9 | Preparation example 5 | Example 14 | Preparation example 10 |
Comparative example
Comparative example 1
The adhesive film prepared in example 1 of chinese patent publication No. CN 111040670B.
Comparative example 2
This comparative example differs from example 3 in that the desiccant beads of preparation 1 were replaced with activated carbon beads.
Comparative example 3
This comparative example differs from example 3 in that the desiccant particles of preparation 1 are replaced by silica particles.
Comparative example 4
This comparative example differs from example 3 in that the desiccant beads are those of preparation 11.
Performance detection test method
1. The adhesive film was cured at 150℃for 30min, and after the adhesive film was completely cooled, the adhesive film was tested for volume resistivity by referring to GB/T15662-1995, the humidity of the test environment was 85%, and the test results are shown in Table 4.
TABLE 4 Table 4
2. The adhesive film and the aluminum plate were combined into one body by using a hot press, and then the adhesive film adhered to the surface of the aluminum plate was subjected to peel strength detection by referring to GB/T2792-2014, and the results are shown in Table 5.
TABLE 5
| Sample of | Peel strength/(N/cm) |
| Example 1 | 15.5 |
| Example 2 | 15.6 |
| Example 3 | 15.7 |
| Example 4 | 15.6 |
| Example 5 | 15.6 |
| Comparative example 1 | 12.9 |
3. In the desiccant particles prepared in preparation examples 1 to 10, 1000g of each sample was randomly selected for screening test, the test sieve selected for screening test was 75 μm square hole sieve, the test method of screening test was referred to GB/T14684-2001, and the calculation result of the screen residue ratio of screening test is shown in Table 6.
| Sample of | Screen surplus rate/% | Sample of | Screen surplus rate/% |
| Preparation example 1 | 96.4 | Preparation example 7 | 96.4 |
| Preparation example 2 | 96.5 | Preparation example 8 | 96.7 |
| Preparation example 3 | 96.4 | Preparation example 9 | 98.9 |
| Preparation example 4 | 96.7 | Preparation example 10 | 98.9 |
| Preparation example 5 | 96.5 | PREPARATION EXAMPLE 11 | 90.7 |
| Preparation example 6 | 96.6 | Preparation example 12 | 92.4 |
As can be seen from the combination of examples 1 to 5 and comparative example 1 and table 4, the volume resistivity measured in examples 1 to 5 is higher than that in comparative example 1, indicating that the formulation system of the present application increases the water blocking performance of the adhesive film by adsorbing moisture in the epoxy resin film using the desiccant particles and increases the water blocking performance of the adhesive film by increasing the ratio of the epoxy resin to the epoxy resin film, thereby increasing the electrical resistance of the epoxy resin film and improving the insulation performance of the adhesive film as a whole. As can be seen from a combination of examples 1-5 and comparative example 1 in combination with table 5, examples 1-5 all measured higher peel strengths than comparative example 1, demonstrating that the formulation of the present application also improved the adhesive properties of the adhesive film by increasing the epoxy resin to epoxy resin film ratio.
As can be seen from the combination of example 3 and comparative example 2 and the combination of table 4, the volume resistivity measured in example 3 is higher than that in comparative example 2, indicating that the insulation performance of the adhesive film is poor due to the lower resistance of the activated carbon after the activated carbon is used instead of the desiccant particles.
As can be seen in combination with example 3 and comparative example 3 and with table 4, the volume resistivity measured in example 3 is higher than that in comparative example 3, indicating that the improvement in the insulation properties of the adhesive film by the adsorbent particles is not due to the filling effect of the adsorbent particles.
As can be seen from the combination of example 3 and comparative example 4 and the combination of table 4, the volume resistivity measured in example 3 is higher than that in comparative example 4, indicating that it is difficult to achieve a good insulation effect of the adhesive film because the porous carbonized film itself has a low resistance when the adsorbent particles are not impregnated with the insulation treating agent in the preparation stage.
As can be seen in combination with examples 3 and examples 6-9 and table 4, wherein the relatively high volume resistivity is example 7, it is demonstrated that the desiccant particles prepared according to the raw material formulation of preparation example 3 are more conducive to improving the insulation properties of the adhesive film.
As can be seen by combining examples 7 and 10 with table 4, the volume resistivity measured in example 10 is higher than that in example 7, which shows that when the amino-terminated liquid nitrile rubber is selected as the insulation treating agent, the amino-terminated liquid nitrile rubber not only increases the surface resistance of the porous carbonized film, but also enhances the hydrophilicity of the adsorbent particles through the active groups such as carboxyl, hydroxyl, amino, epoxy groups and the like, limits the penetration of moisture in the epoxy resin film, improves the absorption effect of the adsorbent particles on moisture, further reduces the overall wetting degree of the epoxy resin film compared with example 7, and improves the insulation performance of the adhesive film.
As can be seen from the combination of examples 10 and 11 and table 4, the volume resistivity measured in example 11 is higher than that in example 10, which means that the crystal water released by the dihydrate gypsum is converted into steam during pyrolysis and carbonization, and the diffusion of steam increases the number of pores in the porous carbonized film, thereby improving the water absorption effect of the desiccant particles and the insulation performance of the adhesive film.
As can be seen from the combination of example 12 and example 11 and the combination of table 5, the volume resistivity measured in example 12 is higher than that in example 11, which shows that ammonia gas generated by decomposition of ammonium phosphate increases the number of pores in the porous carbonized film and improves the insulation performance of the adhesive film.
As can be seen from the combination of examples 13 to 14 and example 12 and Table 4, the insulation properties of examples 13 to 14 are not greatly different from those of example 12, indicating that the replacement of polyethylene glycol with silicone rubber powder has little effect on the insulation properties of the adhesive film. And after the acetone is replaced by the absolute ethyl alcohol, the insulating property of the adhesive film is not obviously reduced under the condition of shortening the stirring time, which indicates that the preparation speed of lignin slurry can be accelerated by adopting the absolute ethyl alcohol as an organic solvent.
As can be seen from the combination of preparation examples 1 to 12 and Table 6, the screen surplus ratio measured in preparation examples 1 to 8 was close, indicating that the disintegration ratio of the desiccant particles during the preparation of preparation examples 1 to 8 was close. The higher screen residue ratio measured in preparation examples 9-10 than in preparation examples 1-8 shows that the use of silicone rubber powder as binder in preparation examples 9 and 10 enhances the degree of bonding between the porous carbonized film and gypsum particles, thus reducing the likelihood of disintegration of the desiccant particles. The disintegration rates measured for preparation examples 11-12 were lower than for examples 1-10, indicating that desiccant particles that have not been impregnated with an insulating treatment agent or desiccant without binder are more prone to disintegrate.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (7)
1. The insulating adhesive film for the side plate of the battery cell module of the power battery is characterized by comprising a PET adhesive film, an epoxy resin film and a PE protective film which are sequentially attached along the thickness direction, wherein the formula of the epoxy resin film comprises the following raw materials in parts by weight: 125-135 parts of epoxy resin, 33-37 parts of desiccant particles, 18-22 parts of curing agent, 2.5-3.5 parts of accelerator and 4.5-5.5 parts of auxiliary agent, wherein the desiccant particles are anhydrous gypsum particles coated with porous carbonized films on the surfaces, and the desiccant particles are subjected to impregnation treatment of an insulation treatment agent; the insulating treatment agent is amino-terminated liquid nitrile rubber or mineral insulating oil; the desiccant beads were prepared as follows:
(1) Crushing gypsum materials to obtain gypsum particles;
(2) Uniformly mixing gypsum particles and lignin slurry, then drying the slurry obtained by mixing, and crushing the dried product to obtain precursor particles; in the step, the components of lignin slurry comprise an organic solvent and lignin;
(3) And (3) carrying out pyrolysis carbonization on the precursor particles, and then impregnating a carbonized solid product at room temperature by using an insulating treatment agent to obtain the drying agent particles.
2. The insulating film for a power cell module side panel of claim 1, wherein the lignin slurry comprises the following components in parts by weight: 40-60 parts of lignin, 80-100 parts of an organic solvent, 4-8 parts of a carbonization auxiliary agent and 8-12 parts of a binder, wherein the boiling point of the organic solvent is not higher than the boiling point of water.
3. An insulating film for a side plate of a battery cell module according to claim 2, wherein gypsum in the gypsum is present in the form of hydrate crystals.
4. The insulating film for a side plate of a battery cell module of claim 3, wherein the charring aid is phytic acid or ammonium phosphate.
5. The insulating film for a side plate of a battery cell module of claim 2, wherein the adhesive is silicone rubber powder or polyethylene glycol.
6. The insulating film for a side plate of a battery cell module according to claim 2, wherein the organic solvent is one of acetone or absolute ethyl alcohol.
7. The method for preparing an insulating film for a side plate of a battery cell module of a power battery according to any one of claims 1 to 6, comprising the steps of: (1) Heating epoxy resin to a molten state under the condition of water bath heating, adding desiccant particles, a curing agent, an accelerator and an auxiliary agent into the molten epoxy resin, and uniformly stirring to obtain epoxy resin glue solution;
(2) Coating epoxy resin glue solution on a PET film, and then standing the PET film coated with the epoxy resin glue solution until the epoxy resin glue solution loses fluidity, so as to obtain an epoxy resin film;
(3) And covering a PE protective film on the surface of the epoxy resin glue film, and then carrying out hot pressing processing on the PE protective film, the epoxy resin film and the PET glue film to obtain the flame-retardant insulating glue film for the side plate of the battery cell module.
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| CN202210257735.7A CN114597582B (en) | 2022-03-16 | 2022-03-16 | Insulating adhesive film for side plate of battery cell module of power battery and preparation method of insulating adhesive film |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108940182A (en) * | 2018-07-12 | 2018-12-07 | 杭州家爽包装材料有限公司 | A kind of method preparing calcium oxide desiccant and product |
| CN111040670A (en) * | 2019-12-24 | 2020-04-21 | 苏州赛伍应用技术股份有限公司 | Adhesive, preparation method thereof and PET (polyethylene terephthalate) insulating adhesive film containing adhesive |
| CN114181652A (en) * | 2021-12-28 | 2022-03-15 | 深圳市纽菲斯新材料科技有限公司 | Low-dielectric-loss insulating adhesive film and preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108940182A (en) * | 2018-07-12 | 2018-12-07 | 杭州家爽包装材料有限公司 | A kind of method preparing calcium oxide desiccant and product |
| CN111040670A (en) * | 2019-12-24 | 2020-04-21 | 苏州赛伍应用技术股份有限公司 | Adhesive, preparation method thereof and PET (polyethylene terephthalate) insulating adhesive film containing adhesive |
| CN114181652A (en) * | 2021-12-28 | 2022-03-15 | 深圳市纽菲斯新材料科技有限公司 | Low-dielectric-loss insulating adhesive film and preparation method and application thereof |
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