CN115416377B - Protective material for new energy automobile power battery and preparation method thereof - Google Patents
Protective material for new energy automobile power battery and preparation method thereof Download PDFInfo
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- CN115416377B CN115416377B CN202211023759.2A CN202211023759A CN115416377B CN 115416377 B CN115416377 B CN 115416377B CN 202211023759 A CN202211023759 A CN 202211023759A CN 115416377 B CN115416377 B CN 115416377B
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- 239000000463 material Substances 0.000 title claims abstract description 69
- 230000001681 protective effect Effects 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims description 30
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 73
- 239000004917 carbon fiber Substances 0.000 claims abstract description 73
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 73
- 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 abstract description 45
- 239000003063 flame retardant Substances 0.000 claims abstract description 45
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 39
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 39
- -1 polysiloxane Polymers 0.000 claims abstract description 37
- 229920001155 polypropylene Polymers 0.000 claims abstract description 26
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 24
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 24
- 239000004945 silicone rubber Substances 0.000 claims abstract description 24
- 239000000945 filler Substances 0.000 claims abstract description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 22
- 239000003822 epoxy resin Substances 0.000 claims abstract description 20
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 20
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 18
- 239000007822 coupling agent Substances 0.000 claims abstract description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 42
- 239000004744 fabric Substances 0.000 claims description 35
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- XJFZOSUFGSANIF-UHFFFAOYSA-N 3-chloro-2-(chloromethyl)prop-1-ene Chemical group ClCC(=C)CCl XJFZOSUFGSANIF-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000000748 compression moulding Methods 0.000 claims description 15
- 229920001971 elastomer Polymers 0.000 claims description 15
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 14
- 239000000919 ceramic Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- RFSCGDQQLKVJEJ-UHFFFAOYSA-N 2-methylbutan-2-yl benzenecarboperoxoate Chemical compound CCC(C)(C)OOC(=O)C1=CC=CC=C1 RFSCGDQQLKVJEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 238000004513 sizing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 5
- 229920002748 Basalt fiber Polymers 0.000 claims description 4
- 229920000271 Kevlar® Polymers 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000004761 kevlar Substances 0.000 claims description 4
- 239000010456 wollastonite Substances 0.000 claims description 4
- 229910052882 wollastonite Inorganic materials 0.000 claims description 4
- 230000007613 environmental effect Effects 0.000 claims description 2
- QFXZANXYUCUTQH-UHFFFAOYSA-N ethynol Chemical group OC#C QFXZANXYUCUTQH-UHFFFAOYSA-N 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000009413 insulation Methods 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 80
- 239000004593 Epoxy Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000000622 chloryl group Chemical group O=Cl(=O)[*] 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions 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; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- 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
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
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- 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
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/249—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders specially adapted for aircraft or vehicles, e.g. cars or trains
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- 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
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/289—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs
- H01M50/293—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs characterised by the material
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2205/16—Fibres; Fibrils
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- 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 invention discloses a protective material for a power battery of a new energy automobile, which sequentially comprises a supporting layer, a flame-retardant fireproof layer and a carbon fiber/epoxy resin prepreg layer from top to bottom; the flame-retardant fireproof layer is prepared from the following raw materials in parts by weight: 25-35 parts of hyperbranched polysiloxane containing phosphaphenanthrene structure and vinyl, 60-70 parts of methyl vinyl silicone rubber, 8-12 parts of hydroxy fluorosilicone oil, 4-8 parts of 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer, 3-5 parts of coupling agent, 5-8 parts of reinforcing fiber, 20-30 parts of porcelain-forming filler, 4-6 parts of vulcanizing agent and 3-5 parts of 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane. The protective material for the new energy automobile power battery disclosed by the invention has the advantages of good flame retardance and fireproof performance, sufficient high temperature resistance, weather resistance and mechanical properties, good heat preservation and insulation performance and convenience in use.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a protective material for a new energy automobile power battery and a preparation method thereof.
Background
In recent years, with the development of society, global energy crisis is continuously increased, petroleum resources are gradually exhausted, atmospheric pollution and global air temperature are increasingly serious, and new energy automobiles are generated in the period of updating automobiles as main means for people to travel. As a new automobile, people have very high attention to normal working stability and driving safety, and a new energy device-power battery with stability and safety is a key point for determining the performances of the new energy automobile.
The new energy automobile has the characteristics of high-speed movement, severe vibration, high-temperature work and quick charge when running, so that potential hazards such as impact, stabbing, falling, burning, short connection and the like exist in the power battery during use, and the personal safety of a driver and the normal work stability of the power battery are seriously influenced. Particularly, when the battery pack of the new energy automobile is out of control, active particles in the battery cells are sprayed out from the explosion-proof valve ports in a spark manner, directly impact the battery module or the cover body of the battery pack, are melted or decomposed in a short time, and the fire is diffused to other single batteries in the battery pack or other battery modules and even the inside of the vehicle, so that the safety of the whole vehicle and the personal safety of personnel in the vehicle are endangered.
The best solution at present is to adopt a protective material to isolate and protect the power cells in the battery pack. However, existing protective materials mainly include mica boards or aerogels. Because the mica plate has high density and is made of rigid materials, the mica plate is difficult to be fully attached to the battery; aerogels are expensive and do not withstand the high temperature flame of a battery explosion in thermal runaway.
In order to solve the above problems, chinese patent document CN201810963837.4 discloses a protective material for lithium battery pack of new energy automobile and a preparation method thereof, comprising the following steps: the invention also discloses a protective material of the lithium battery pack of the new energy automobile, which is prepared by the preparation method, and has the advantages of good mechanical property, high and low temperature resistance, excellent flame retardance, fireproof performance and weather resistance.
Therefore, the field still needs a protective material for the power battery of the new energy automobile with good flame retardance and fireproof performance, sufficient high temperature resistance, weather resistance and mechanical properties and convenient use and a preparation method thereof.
Disclosure of Invention
The invention mainly aims to provide a protective material for a new energy automobile power battery, which has good flame retardance and fireproof performance, sufficient high temperature resistance, weather resistance and mechanical properties and is convenient to use, and a preparation method thereof.
In order to achieve the above purpose, the invention provides a protective material for a power battery of a new energy automobile, which sequentially comprises a supporting layer, a flame-retardant fireproof layer and a carbon fiber/epoxy resin prepreg layer from top to bottom; the flame-retardant fireproof layer is prepared from the following raw materials in parts by weight: 25-35 parts of hyperbranched polysiloxane containing phosphaphenanthrene structure and vinyl, 60-70 parts of methyl vinyl silicone rubber, 8-12 parts of hydroxy fluorosilicone oil, 4-8 parts of 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer, 3-5 parts of coupling agent, 5-8 parts of reinforcing fiber, 20-30 parts of porcelain-forming filler, 4-6 parts of vulcanizing agent and 3-5 parts of 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane.
Preferably, the vulcanizing agent is a mixture formed by mixing tert-butyl peroxybenzoate, tert-butyl peroxy3, 5-trimethylhexanoate, tert-amyl peroxybenzoate and 1, 1-di-tert-butyl peroxy-3, 5-trimethylcyclohexane according to the mass ratio of 1:1 (0.8-1.2) to (1-3).
Preferably, the ceramic-forming filler is at least one of fly ash, talcum powder and wollastonite powder; the granularity of the ceramic filler is 1000-1500 meshes.
Preferably, the reinforcing fiber is any one of carbon fiber, kevlar fiber and basalt fiber; the reinforcing fiber has an average diameter of 3-5 μm and a length of 1-3mm.
Preferably, the coupling agent is at least one of a silane coupling agent KH550 and a silane coupling agent KH 570.
Preferably, the preparation method of the 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer comprises the following steps: adding 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole and 3-chloro-2-chloromethyl propylene into dimethyl sulfoxide, stirring at 30-50 ℃ for reaction for 8-10 hours, precipitating in water, washing the precipitated crude product with diethyl ether for 3-6 times, and finally removing diethyl ether by rotary evaporation to obtain the 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer.
Preferably, the molar ratio of the 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole, 3-chloro-2-chloromethyl propylene and dimethyl sulfoxide is 1:1 (6-10).
Preferably, the hydroxyl fluorosilicone oil is DX-8011 hydroxyl fluorosilicone oil of Guangzhou large-size Xe company; the methyl vinyl silicone rubber is methyl vinyl silicone rubber 110-2.
Preferably, the source of the hyperbranched polysiloxane containing phosphaphenanthrene structure and vinyl is not particularly required, and in one embodiment of the invention, the hyperbranched polysiloxane containing phosphaphenanthrene structure and vinyl is prepared according to the method in example 1 of chinese patent document CN 102219906B.
Preferably, the carbon fiber/epoxy prepreg layer is made of carbon fiber/epoxy prepreg made according to the method of CN105061995B example 1.
Preferably, the supporting layer is made of T700 carbon fiber cloth with surface modified by vinyl.
Preferably, the preparation method of the T700 carbon fiber cloth with the surface modified by vinyl comprises the following steps: adding a silane coupling agent KH570 into ethanol, uniformly mixing, coating on the T700 carbon fiber cloth, and drying at 60-80 ℃ to constant weight to obtain the T700 carbon fiber cloth with the surface modified by vinyl.
Preferably, the mass ratio of the silane coupling agent KH570, ethanol and the T700 carbon fiber cloth is 1 (8-10): 15.
The invention also provides a preparation method of the protective material for the new energy automobile power battery, which comprises the following steps:
step S1, mixing other raw materials except a vulcanizing agent in the flame-retardant fireproof layer according to parts by weight to obtain flame-retardant fireproof rubber compound without the vulcanizing agent;
S2, carrying out open mill on the mixed rubber at room temperature and adding a vulcanizing agent;
And S3, sequentially overlapping the support layer, the obtained sizing material, the carbon fiber/epoxy resin prepreg layer from top to bottom, and finally placing the material into a mould for compression molding to obtain the protective material for the power battery of the new energy automobile.
Preferably, the specific process parameters of the compression molding in step S3 are: the temperature of the upper die is 140 ℃; the temperature of the lower die is 130 ℃; a first pressurizing of 31bar and a dwell time of 10s; the second stage was pressurized at 111bar and dwell time 300s.
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) The preparation method of the protective material for the power battery of the new energy automobile disclosed by the invention can be completed by adopting conventional equipment and operation steps, has the advantages of low investment, low energy consumption and high preparation efficiency, is suitable for continuous large-scale production, and has higher cost performance and market popularization and application values.
(2) The invention discloses a protective material for a new energy automobile power battery, which sequentially comprises a supporting layer, a flame-retardant fireproof layer and a carbon fiber/epoxy resin prepreg layer from top to bottom; through the arrangement of the multilayer structure, the prepared material can combine the advantages of each layer of material, the arrangement of the supporting layer can provide excellent mechanical properties for the protective material, and through arranging the supporting layer on the surface layer, the influence of the supporting layer on the adhesive properties of the flame-retardant fireproof layer and the carbon fiber/epoxy resin prepreg layer is avoided, the mechanical properties are improved, and the flame-retardant fireproof layer is protected; through surface modification, vinyl exists on the surface of the supporting layer, and copolymerization reaction can be carried out between the vinyl-containing components of the flame-retardant fireproof layer and the supporting layer, so that covalent bond connection is formed between the two layers, the adhesion between the flame-retardant fireproof layer and the supporting layer is improved, and delamination is effectively avoided.
(3) The invention discloses a protective material for a new energy automobile power battery, which is prepared from the following raw materials in parts by weight: 25-35 parts of hyperbranched polysiloxane containing phosphaphenanthrene structure and vinyl, 60-70 parts of methyl vinyl silicone rubber, 8-12 parts of hydroxy fluorosilicone oil, 4-8 parts of 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer, 3-5 parts of coupling agent, 5-8 parts of reinforcing fiber, 20-30 parts of porcelain-forming filler, 4-6 parts of vulcanizing agent and 3-5 parts of 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane. Through the interaction among the raw materials, the prepared material has good flame retardant and fireproof performance and low risk of high-temperature delamination. By simultaneously introducing phosphaphenanthrene, hyperbranched siloxane, fluorosilicone oil, oxazole, quaternary ammonium salt (2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer) and phenoxy phenyl, hexafluoropropane and other structures, the structures have multiple functions of electronic effect, steric effect and conjugation effect, so that the prepared material has good flame retardance and fire resistance, sufficient high temperature resistance, weather resistance and mechanical properties, good heat preservation and insulation and long service life. Wherein, the raw material containing unsaturated olefinic bond can be vulcanized under the action of vulcanizing agent, and the raw material containing amino and hydroxyl can generate epoxy ring-opening reaction with epoxy groups in the prepreg layer, so that the two layers form an integrated structure and an interpenetrating network structure, thereby further improving the performance.
(4) The protective material for the new energy automobile power battery disclosed by the invention adopts a one-step molding process, so that the complexity of a separate curing process of each layer is avoided, the adhesion between each layer is enhanced, and the risk of high Wen Tuoceng is reduced; through the selection of compression molding process parameters and vulcanizing agents, the two are mutually matched, so that the prepared protective material has good comprehensive performance and performance stability, and is particularly better in flame retardance and fireproof performance, more sufficient in high temperature resistance, weather resistance and mechanical properties and longer in service life.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the invention. The preferred embodiments in the following description are by way of example only and other obvious variations will occur to those skilled in the art.
The thickness of the flame-retardant fireproof layer in each embodiment of the invention is 0.8mm; the thickness of the supporting layer is 0.35mm; the thickness of the carbon fiber/epoxy resin prepreg layer was 1.2mm.
Example 1
The protective material for the new energy automobile power battery sequentially comprises a supporting layer, a flame-retardant fireproof layer and a carbon fiber/epoxy resin prepreg layer from top to bottom; the flame-retardant fireproof layer is prepared from the following raw materials in parts by weight: 25 parts of hyperbranched polysiloxane containing phosphaphenanthrene structure and vinyl, 60 parts of methyl vinyl silicone rubber, 8 parts of hydroxyl fluorosilicone oil, 4 parts of 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer, 3 parts of coupling agent, 5 parts of reinforcing fiber, 20 parts of porcelain forming filler, 4 parts of vulcanizing agent and 3 parts of 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane.
The vulcanizing agent is a mixture formed by mixing tert-butyl peroxybenzoate, tert-butyl peroxy3, 5-trimethylhexanoate, tert-amyl peroxybenzoate and 1, 1-di-tert-butyl peroxy-3, 5-trimethylcyclohexane according to a mass ratio of 1:1:0.8:1; the ceramic filler is double fly powder; the granularity of the ceramic filler is 1000 meshes; the reinforcing fiber is carbon fiber; the average diameter of the reinforcing fiber is 3 mu m, and the length is 1mm; the coupling agent is a silane coupling agent KH550.
The preparation method of the 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer comprises the following steps: adding 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole and 3-chloro-2-chloromethyl propylene into dimethyl sulfoxide, stirring at 30 ℃ for reaction for 8 hours, precipitating in water, washing the precipitated crude product with diethyl ether for 3 times, and finally removing diethyl ether by rotary evaporation to obtain 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer; the molar ratio of the 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole to the 3-chloro-2-chloromethyl propylene to the dimethyl sulfoxide is 1:1:6; mn= 10570g/mol, M W/Mn =1.137 of the polymer by GPC testing; the polymer is added into an aqueous solution of silver nitrate with the mass percentage concentration of 10%, white precipitation of the silver nitrate can occur, and existence of chloride ions is proved, wherein the quaternary ammonium reaction of end-to-end connection between tertiary amino groups on 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole and chloryl groups on 3-chloro-2-chloromethyl propylene occurs, and a quaternary ammonium salt structure exists in the molecular structure; the polymer can be dissolved in dimethyl sulfoxide, and the polymer is proved to have no crosslinking reaction; through EDX elemental analysis and calculation, the molar ratio of structural units respectively introduced by 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole and 3-chloro-2-chloromethyl propylene in the polymer is about 1:1;
The hydroxyl fluorosilicone oil is DX-8011 hydroxyl fluorosilicone oil of Guangzhou large-longevity company; the methyl vinyl silicone rubber is methyl vinyl silicone rubber 110-2; the hyperbranched polysiloxane containing the phosphaphenanthrene structure and the vinyl is prepared according to the method in the example 1 of the Chinese patent document CN 102219906B; the carbon fiber/epoxy prepreg layer was made of carbon fiber/epoxy prepreg made according to the method of CN105061995B example 1.
The supporting layer is made of T700 carbon fiber cloth with surface modified by vinyl; the preparation method of the T700 carbon fiber cloth with the surface modified by vinyl comprises the following steps: adding a silane coupling agent KH570 into ethanol, uniformly mixing, coating on the T700 carbon fiber cloth, and drying at 60 ℃ to constant weight to obtain the T700 carbon fiber cloth with the surface modified by vinyl; the mass ratio of the silane coupling agent KH570 to the ethanol to the T700 carbon fiber cloth is 1:8:15.
The preparation method of the protective material for the new energy automobile power battery comprises the following steps:
step S1, mixing other raw materials except a vulcanizing agent in the flame-retardant fireproof layer according to parts by weight to obtain flame-retardant fireproof rubber compound without the vulcanizing agent;
S2, carrying out open mill on the mixed rubber at room temperature and adding a vulcanizing agent;
Step S3, sequentially overlapping the support layer, the obtained sizing material and the carbon fiber/epoxy resin prepreg layer from top to bottom, and finally placing the mixture into a mould for compression molding to obtain the protective material for the power battery of the new energy automobile; the specific process parameters of the compression molding are as follows: the temperature of the upper die is 140 ℃; the temperature of the lower die is 130 ℃; a first pressurizing of 31bar and a dwell time of 10s; the second stage was pressurized at 111bar and dwell time 300s.
Example 2
The protective material for the new energy automobile power battery sequentially comprises a supporting layer, a flame-retardant fireproof layer and a carbon fiber/epoxy resin prepreg layer from top to bottom; the flame-retardant fireproof layer is prepared from the following raw materials in parts by weight: 27 parts of hyperbranched polysiloxane containing phosphaphenanthrene structure and vinyl, 63 parts of methyl vinyl silicone rubber, 9 parts of hydroxy fluorosilicone oil, 5 parts of 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer, 3.5 parts of coupling agent, 6 parts of reinforcing fiber, 23 parts of porcelain filler, 4.5 parts of vulcanizing agent and 3.5 parts of 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane.
The vulcanizing agent is a mixture formed by mixing tert-butyl peroxybenzoate, tert-butyl peroxy3, 5-trimethylhexanoate, tert-amyl peroxybenzoate and 1, 1-di-tert-butyl peroxy-3, 5-trimethylcyclohexane according to a mass ratio of 1:1:0.9:1.5; the ceramic filler is talcum powder; the granularity of the ceramic filler is 1100 meshes; the reinforcing fiber is a Kevlar fiber; the reinforcing fiber has an average diameter of 3.5 μm and a length of 1.5mm; the coupling agent is a silane coupling agent KH570.
The preparation method of the 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer comprises the following steps: adding 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole and 3-chloro-2-chloromethyl propylene into dimethyl sulfoxide, stirring at 35 ℃ for reaction for 8.5 hours, precipitating in water, washing the precipitated crude product with diethyl ether for 4 times, and finally removing diethyl ether by rotary evaporation to obtain 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer; the molar ratio of the 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole to the 3-chloro-2-chloromethyl propylene to the dimethyl sulfoxide is 1:1:7.
The hydroxyl fluorosilicone oil is DX-8011 hydroxyl fluorosilicone oil of Guangzhou large-longevity company; the methyl vinyl silicone rubber is methyl vinyl silicone rubber 110-2; the hyperbranched polysiloxane containing the phosphaphenanthrene structure and the vinyl is prepared according to the method in the example 1 of the Chinese patent document CN 102219906B; the carbon fiber/epoxy prepreg layer was made of carbon fiber/epoxy prepreg made according to the method of CN105061995B example 1.
The supporting layer is made of T700 carbon fiber cloth with surface modified by vinyl; the preparation method of the T700 carbon fiber cloth with the surface modified by vinyl comprises the following steps: adding a silane coupling agent KH570 into ethanol, uniformly mixing, coating on the T700 carbon fiber cloth, and drying at 65 ℃ to constant weight to obtain the T700 carbon fiber cloth with the surface modified by vinyl; the mass ratio of the silane coupling agent KH570 to the ethanol to the T700 carbon fiber cloth is 1:8.5:15.
The preparation method of the protective material for the new energy automobile power battery comprises the following steps:
step S1, mixing other raw materials except a vulcanizing agent in the flame-retardant fireproof layer according to parts by weight to obtain flame-retardant fireproof rubber compound without the vulcanizing agent;
S2, carrying out open mill on the mixed rubber at room temperature and adding a vulcanizing agent;
Step S3, sequentially overlapping the support layer, the obtained sizing material and the carbon fiber/epoxy resin prepreg layer from top to bottom, and finally placing the mixture into a mould for compression molding to obtain the protective material for the power battery of the new energy automobile; the specific process parameters of the compression molding are as follows: the temperature of the upper die is 140 ℃; the temperature of the lower die is 130 ℃; a first pressurizing of 31bar and a dwell time of 10s; the second stage was pressurized at 111bar and dwell time 300s.
Example 3
The protective material for the new energy automobile power battery sequentially comprises a supporting layer, a flame-retardant fireproof layer and a carbon fiber/epoxy resin prepreg layer from top to bottom; the flame-retardant fireproof layer is prepared from the following raw materials in parts by weight: 30 parts of hyperbranched polysiloxane containing phosphaphenanthrene structure and vinyl, 65 parts of methyl vinyl silicone rubber, 10 parts of hydroxyl fluorosilicone oil, 6 parts of 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer, 4 parts of coupling agent, 6.5 parts of reinforcing fiber, 25 parts of porcelain filler, 5 parts of vulcanizing agent and 4 parts of 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane.
The vulcanizing agent is a mixture formed by mixing tert-butyl peroxybenzoate, tert-butyl peroxy3, 5-trimethylhexanoate, tert-amyl peroxybenzoate and 1, 1-di-tert-butyl peroxy-3, 5-trimethylcyclohexane according to a mass ratio of 1:1:1:2; the ceramic filler is wollastonite powder; the granularity of the ceramic filler is 1300 meshes; the reinforcing fiber is basalt fiber; the average diameter of the reinforcing fiber is 4 mu m, and the length is 2mm; the coupling agent is a silane coupling agent KH550.
The preparation method of the 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer comprises the following steps: adding 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole and 3-chloro-2-chloromethyl propylene into dimethyl sulfoxide, stirring at 40 ℃ for reacting for 9 hours, precipitating in water, washing the precipitated crude product with diethyl ether for 5 times, and finally removing diethyl ether by rotary evaporation to obtain 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer; the molar ratio of the 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole to the 3-chloro-2-chloromethyl propylene to the dimethyl sulfoxide is 1:1:8.
The hydroxyl fluorosilicone oil is DX-8011 hydroxyl fluorosilicone oil of Guangzhou large-longevity company; the methyl vinyl silicone rubber is methyl vinyl silicone rubber 110-2; the hyperbranched polysiloxane containing the phosphaphenanthrene structure and the vinyl is prepared according to the method in the example 1 of the Chinese patent document CN 102219906B; the carbon fiber/epoxy prepreg layer was made of carbon fiber/epoxy prepreg made according to the method of CN105061995B example 1.
The supporting layer is made of T700 carbon fiber cloth with surface modified by vinyl; the preparation method of the T700 carbon fiber cloth with the surface modified by vinyl comprises the following steps: adding a silane coupling agent KH570 into ethanol, uniformly mixing, coating on the T700 carbon fiber cloth, and drying at 70 ℃ to constant weight to obtain the T700 carbon fiber cloth with the surface modified by vinyl; the mass ratio of the silane coupling agent KH570 to the ethanol to the T700 carbon fiber cloth is 1:9:15.
The preparation method of the protective material for the new energy automobile power battery comprises the following steps:
step S1, mixing other raw materials except a vulcanizing agent in the flame-retardant fireproof layer according to parts by weight to obtain flame-retardant fireproof rubber compound without the vulcanizing agent;
S2, carrying out open mill on the mixed rubber at room temperature and adding a vulcanizing agent;
Step S3, sequentially overlapping the support layer, the obtained sizing material and the carbon fiber/epoxy resin prepreg layer from top to bottom, and finally placing the mixture into a mould for compression molding to obtain the protective material for the power battery of the new energy automobile; the specific process parameters of the compression molding are as follows: the temperature of the upper die is 140 ℃; the temperature of the lower die is 130 ℃; a first pressurizing of 31bar and a dwell time of 10s; the second stage was pressurized at 111bar and dwell time 300s.
Example 4
The protective material for the new energy automobile power battery sequentially comprises a supporting layer, a flame-retardant fireproof layer and a carbon fiber/epoxy resin prepreg layer from top to bottom; the flame-retardant fireproof layer is prepared from the following raw materials in parts by weight: 33 parts of hyperbranched polysiloxane containing phosphaphenanthrene structure and vinyl, 68 parts of methyl vinyl silicone rubber, 11 parts of hydroxyl fluorosilicone oil, 7 parts of 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer, 4.5 parts of coupling agent, 7.5 parts of reinforcing fiber, 28 parts of porcelain filler, 5.5 parts of vulcanizing agent and 4.5 parts of 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane.
The vulcanizing agent is a mixture formed by mixing tert-butyl peroxybenzoate, tert-butyl peroxy3, 5-trimethylhexanoate, tert-amyl peroxybenzoate and 1, 1-di-tert-butyl peroxy-3, 5-trimethylcyclohexane according to a mass ratio of 1:1:1.1:2.5; the ceramic filler is a mixture formed by mixing double fly powder, talcum powder and wollastonite powder according to the mass ratio of 1:2:1; the granularity of the ceramic filler is 1400 meshes; the reinforcing fiber is a mixture formed by mixing carbon fiber, kevlar fiber and basalt fiber according to the mass ratio of 1:3:2; the reinforcing fiber has an average diameter of 4.5 mu m and a length of 2.5mm; the coupling agent is a mixture formed by mixing a silane coupling agent KH550 and a silane coupling agent KH570 according to a mass ratio of 3:5.
The preparation method of the 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer comprises the following steps: adding 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole and 3-chloro-2-chloromethyl propylene into dimethyl sulfoxide, stirring at 45 ℃ for reacting for 9.5 hours, precipitating in water, washing the precipitated crude product with diethyl ether for 5 times, and finally removing diethyl ether by rotary evaporation to obtain 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer; the molar ratio of the 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole to the 3-chloro-2-chloromethyl propylene to the dimethyl sulfoxide is 1:1:9.5.
The hydroxyl fluorosilicone oil is DX-8011 hydroxyl fluorosilicone oil of Guangzhou large-longevity company; the methyl vinyl silicone rubber is methyl vinyl silicone rubber 110-2; the hyperbranched polysiloxane containing the phosphaphenanthrene structure and the vinyl is prepared according to the method in the example 1 of the Chinese patent document CN 102219906B; the carbon fiber/epoxy prepreg layer was made of carbon fiber/epoxy prepreg made according to the method of CN105061995B example 1.
The supporting layer is made of T700 carbon fiber cloth with surface modified by vinyl; the preparation method of the T700 carbon fiber cloth with the surface modified by vinyl comprises the following steps: adding a silane coupling agent KH570 into ethanol, uniformly mixing, coating on the T700 carbon fiber cloth, and drying at 75 ℃ to constant weight to obtain the T700 carbon fiber cloth with the surface modified by vinyl; the mass ratio of the silane coupling agent KH570 to the ethanol to the T700 carbon fiber cloth is 1:9.5:15.
The preparation method of the protective material for the new energy automobile power battery comprises the following steps:
step S1, mixing other raw materials except a vulcanizing agent in the flame-retardant fireproof layer according to parts by weight to obtain flame-retardant fireproof rubber compound without the vulcanizing agent;
S2, carrying out open mill on the mixed rubber at room temperature and adding a vulcanizing agent;
Step S3, sequentially overlapping the support layer, the obtained sizing material and the carbon fiber/epoxy resin prepreg layer from top to bottom, and finally placing the mixture into a mould for compression molding to obtain the protective material for the power battery of the new energy automobile; the specific process parameters of the compression molding are as follows: the temperature of the upper die is 140 ℃; the temperature of the lower die is 130 ℃; a first pressurizing of 31bar and a dwell time of 10s; the second stage was pressurized at 111bar and dwell time 300s.
Example 5
The protective material for the new energy automobile power battery sequentially comprises a supporting layer, a flame-retardant fireproof layer and a carbon fiber/epoxy resin prepreg layer from top to bottom; the flame-retardant fireproof layer is prepared from the following raw materials in parts by weight: 35 parts of hyperbranched polysiloxane containing phosphaphenanthrene structure and vinyl, 70 parts of methyl vinyl silicone rubber, 12 parts of hydroxyl fluorosilicone oil, 8 parts of 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer, 5 parts of coupling agent, 8 parts of reinforcing fiber, 30 parts of porcelain forming filler, 6 parts of vulcanizing agent and 5 parts of 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane.
The vulcanizing agent is a mixture formed by mixing tert-butyl peroxybenzoate, tert-butyl peroxy3, 5-trimethylhexanoate, tert-amyl peroxybenzoate and 1, 1-di-tert-butyl peroxy-3, 5-trimethylcyclohexane according to a mass ratio of 1:1:1.2:3; the ceramic filler is talcum powder; the granularity of the ceramic filler is 1500 meshes; the reinforcing fiber is carbon fiber; the average diameter of the reinforcing fiber is 5 mu m, and the length of the reinforcing fiber is 3mm; the coupling agent is a silane coupling agent KH550.
The preparation method of the 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer comprises the following steps: adding 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole and 3-chloro-2-chloromethyl propylene into dimethyl sulfoxide, stirring at 50 ℃ for reaction for 10 hours, precipitating in water, washing the precipitated crude product with diethyl ether for 6 times, and finally removing diethyl ether by rotary evaporation to obtain 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer; the molar ratio of the 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole to the 3-chloro-2-chloromethyl propylene to the dimethyl sulfoxide is 1:1:10.
The hydroxyl fluorosilicone oil is DX-8011 hydroxyl fluorosilicone oil of Guangzhou large-longevity company; the methyl vinyl silicone rubber is methyl vinyl silicone rubber 110-2; the hyperbranched polysiloxane containing the phosphaphenanthrene structure and the vinyl is prepared according to the method in the example 1 of the Chinese patent document CN 102219906B; the carbon fiber/epoxy prepreg layer was made of carbon fiber/epoxy prepreg made according to the method of CN105061995B example 1.
The supporting layer is made of T700 carbon fiber cloth with surface modified by vinyl; the preparation method of the T700 carbon fiber cloth with the surface modified by vinyl comprises the following steps: adding a silane coupling agent KH570 into ethanol, uniformly mixing, coating on the T700 carbon fiber cloth, and drying at 80 ℃ to constant weight to obtain the T700 carbon fiber cloth with the surface modified by vinyl; the mass ratio of the silane coupling agent KH570 to the ethanol to the T700 carbon fiber cloth is 1:10:15.
The preparation method of the protective material for the new energy automobile power battery comprises the following steps:
step S1, mixing other raw materials except a vulcanizing agent in the flame-retardant fireproof layer according to parts by weight to obtain flame-retardant fireproof rubber compound without the vulcanizing agent;
S2, carrying out open mill on the mixed rubber at room temperature and adding a vulcanizing agent;
Step S3, sequentially overlapping the support layer, the obtained sizing material and the carbon fiber/epoxy resin prepreg layer from top to bottom, and finally placing the mixture into a mould for compression molding to obtain the protective material for the power battery of the new energy automobile; the specific process parameters of the compression molding are as follows: the temperature of the upper die is 140 ℃; the temperature of the lower die is 130 ℃; a first pressurizing of 31bar and a dwell time of 10s; the second stage was pressurized at 111bar and dwell time 300s.
Comparative example 1
The present invention provides a protective material for a power battery of a new energy automobile, which is similar to example 1 except that no 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer is added.
Comparative example 2
The invention provides a protective material for a power battery of a new energy automobile, which is similar to example 1, except that 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane is not added, and methyl vinyl silicone rubber is used for replacing hyperbranched polysiloxane containing a phosphaphenanthrene structure and vinyl.
The test results of the related performance tests of the protection material samples for the power battery of the new energy automobile prepared in the examples 1-5 and the comparative examples 1-2 are shown in the table 1, and the test methods are as follows:
(1) Peel strength: the material of 100mm×50mm size was cut, and peel strength test was performed in the 90 ° direction to test the peel strength between the flame retardant layer and the carbon fiber/epoxy prepreg layer.
(2) Flame retardancy: the test was performed according to UL-94.
(3) High temperature resistance: the flame is continuously burned by using oxyacetylene flame at 1300 ℃, the flame-retardant fireproof layer is used as a fire-facing surface, the time for the whole material to burn through is recorded, and the gas pressure is about 0.4MPa.
(4) Weather resistance: the products of each example were placed under an environmental condition of 85 ℃ x 85% rh for 1500 hours, taken out, cooled to room temperature, and the peel strength was measured according to the test method of (1) peel strength, and the retention of peel strength was calculated, with the greater the number, the better the weather resistance.
As can be seen from table 1, the protective material for a power battery of a new energy automobile disclosed in the example of the present invention has more excellent fire resistance, flame retardance and weather resistance and greater interlayer peel strength as compared with the comparative example product, which is a result of the synergistic effect of each formulation, structure and preparation steps. The addition of 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane, phosphaphenanthrene structure and vinyl-containing hyperbranched polysiloxane is beneficial for improving the above properties.
TABLE 1
| Project | Peel strength (N/25 mm) | Flame retardancy (grade) | High temperature resistance (min) | Weather resistance (%) |
| Example 1 | 50 | V-0 | ＞58min | 99.1 |
| Example 2 | 52 | V-0 | ＞61min | 99.3 |
| Example 3 | 56 | V-0 | ＞65min | 99.6 |
| Example 4 | 58 | V-0 | ＞67min | 99.7 |
| Example 5 | 61 | V-0 | ＞70min | 99.9 |
| Comparative example 1 | 44 | V-2 | ＜40min | 96.5 |
| Comparative example 2 | 40 | V-2 | ＜45min | 95.3 |
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The protective material for the new energy automobile power battery is characterized by sequentially comprising a supporting layer, a flame-retardant fireproof layer and a carbon fiber/epoxy resin prepreg layer from top to bottom; the flame-retardant fireproof layer is prepared from the following raw materials in parts by weight: 25-35 parts of hyperbranched polysiloxane containing phosphaphenanthrene structure and vinyl, 60-70 parts of methyl vinyl silicone rubber, 8-12 parts of hydroxy fluorosilicone oil, 4-8 parts of 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer, 3-5 parts of coupling agent, 5-8 parts of reinforcing fiber, 20-30 parts of porcelain-forming filler, 4-6 parts of vulcanizing agent and 3-5 parts of 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane;
The preparation method of the 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer comprises the following steps: adding 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole and 3-chloro-2-chloromethyl propylene into dimethyl sulfoxide, stirring at 30-50 ℃ for reaction for 8-10 hours, precipitating in water, washing the precipitated crude product with diethyl ether for 3-6 times, and finally removing diethyl ether by rotary evaporation to obtain 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole/3-chloro-2-chloromethyl propylene polymer; the molar ratio of the 2, 5-bis (diethylamino) phenyl-1, 3, 4-diazole to the 3-chloro-2-chloromethyl propylene to the dimethyl sulfoxide is 1:1 (6-10).
2. The protective material for the power battery of the new energy automobile according to claim 1, wherein the vulcanizing agent is a mixture formed by mixing (0.8-1.2) and (1-3) of tert-butyl peroxybenzoate, tert-butyl peroxy3, 5-trimethylhexanoate, tert-amyl peroxybenzoate and 1, 1-di-tert-butyl peroxy-3, 5-trimethylcyclohexane according to a mass ratio of 1:1.
3. The protective material for a power battery of a new energy automobile according to claim 1, wherein the porcelain-forming filler is at least one of double fly powder, talcum powder and wollastonite powder; the granularity of the ceramic filler is 1000-1500 meshes; the reinforcing fiber is any one of carbon fiber, kevlar fiber and basalt fiber; the average diameter of the reinforcing fiber is 3-5 mu m, and the length is 1-3mm; the coupling agent is at least one of silane coupling agent KH550 and silane coupling agent KH 570.
4. The protective material for a power battery of a new energy automobile according to claim 1, wherein the hydroxyfluorosilicone oil is DX-8011 hydroxyfluorosilicone oil of guangzhou large-longevity company; the methyl vinyl silicone rubber is methyl vinyl silicone rubber 110-2.
5. The protective material for a power battery of a new energy automobile according to claim 1, wherein the supporting layer is made of T700 carbon fiber cloth with a vinyl-modified surface.
6. The protective material for a power battery of a new energy automobile according to claim 5, wherein the preparation method of the surface vinyl-modified T700 carbon fiber cloth comprises the following steps: adding a silane coupling agent KH570 into ethanol, uniformly mixing, coating on the T700 carbon fiber cloth, and drying at 60-80 ℃ to constant weight to obtain the T700 carbon fiber cloth with the surface modified by vinyl; the mass ratio of the silane coupling agent KH570 to the ethanol to the T700 carbon fiber cloth is 1 (8-10): 15.
7. The protective material for a power battery of a new energy automobile according to any one of claims 1 to 6, wherein the peel strength between the flame retardant and flame retardant layer of the protective material and the carbon fiber/epoxy resin prepreg layer in the 90 ° direction is not less than 50N/25mm, and the flame retardant UL-94 flame retardant rating is V-0 rating; continuously burning by using an oxyacetylene flame at 1300 ℃, taking the flame-retardant fireproof layer as a fire-facing surface, and enabling the whole material to be burnt for more than or equal to 58 minutes; after 1500 hours under the environmental condition of 85 ℃ multiplied by 85%RH, the retention rate of the peel strength between the material flame-retardant fireproof layer and the carbon fiber/epoxy resin prepreg layer is more than or equal to 99.1%.
8. A method for producing the protective material for a power battery of a new energy automobile according to any one of claims 1 to 6, comprising the steps of:
step S1, mixing other raw materials except a vulcanizing agent in the flame-retardant fireproof layer according to parts by weight to obtain flame-retardant fireproof rubber compound without the vulcanizing agent;
S2, carrying out open mill on the mixed rubber at room temperature and adding a vulcanizing agent to obtain a rubber material;
And S3, sequentially overlapping the support layer, the obtained sizing material, the carbon fiber/epoxy resin prepreg layer from top to bottom, and finally placing the material into a mould for compression molding to obtain the protective material for the power battery of the new energy automobile.
9. The method for preparing a protective material for a power battery of a new energy automobile according to claim 8, wherein specific process parameters of the compression molding in step S3 are as follows: the temperature of the upper die is 140 ℃; the temperature of the lower die is 130 ℃; a first pressurizing of 31bar and a dwell time of 10s; the second stage was pressurized at 111bar and dwell time 300s.
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