CN111253704A - Plastic shell of anti-corrosion high-toughness lead storage battery - Google Patents
Plastic shell of anti-corrosion high-toughness lead storage battery Download PDFInfo
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- CN111253704A CN111253704A CN201911274103.6A CN201911274103A CN111253704A CN 111253704 A CN111253704 A CN 111253704A CN 201911274103 A CN201911274103 A CN 201911274103A CN 111253704 A CN111253704 A CN 111253704A
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- plastic shell
- inorganic composite
- storage battery
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- 229920003023 plastic Polymers 0.000 title claims abstract description 83
- 239000004033 plastic Substances 0.000 title claims abstract description 83
- 238000005260 corrosion Methods 0.000 title claims abstract description 38
- 238000003860 storage Methods 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 67
- 239000011248 coating agent Substances 0.000 claims abstract description 57
- 238000000576 coating method Methods 0.000 claims abstract description 57
- 239000000835 fiber Substances 0.000 claims abstract description 50
- 239000011521 glass Substances 0.000 claims abstract description 46
- 239000003822 epoxy resin Substances 0.000 claims abstract description 34
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 34
- 229910052582 BN Inorganic materials 0.000 claims abstract description 24
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 239000005341 toughened glass Substances 0.000 claims abstract description 23
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 14
- 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 10
- 239000003063 flame retardant Substances 0.000 claims abstract description 10
- 239000004709 Chlorinated polyethylene Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000000314 lubricant Substances 0.000 claims abstract description 5
- 238000001723 curing Methods 0.000 claims description 34
- 229910052731 fluorine Inorganic materials 0.000 claims description 34
- 239000011737 fluorine Substances 0.000 claims description 34
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 21
- 238000005245 sintering Methods 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 230000006835 compression Effects 0.000 claims description 15
- 238000007906 compression Methods 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical group O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 14
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000006229 carbon black Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 9
- 238000005286 illumination Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- 238000000016 photochemical curing Methods 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 5
- 238000011085 pressure filtration Methods 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004113 Sepiolite Substances 0.000 claims description 3
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 17
- 230000007547 defect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 4
- 235000017491 Bambusa tulda Nutrition 0.000 description 4
- 241001330002 Bambuseae Species 0.000 description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 4
- 239000011425 bamboo Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- YVTGSCBLHWQBJX-UHFFFAOYSA-N diethoxy-methyl-(3-methyloxiran-2-yl)oxysilane Chemical compound C(C)O[Si](C)(OC1C(C)O1)OCC YVTGSCBLHWQBJX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical group O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000003075 superhydrophobic effect Effects 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- -1 methacryloxypropyl Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B30/00—Compositions for artificial stone, not containing binders
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/48—Macromolecular compounds
- C04B41/4853—Epoxides
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/62—Coating or impregnation with organic materials
- C04B41/63—Macromolecular compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00844—Uses not provided for elsewhere in C04B2111/00 for electronic applications
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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- 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
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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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of lead storage battery plastic cases, in particular to an anti-corrosion high-toughness lead storage battery plastic case. The organic-inorganic composite board is composed of an organic-inorganic composite board on the inner side of a plastic shell and the plastic shell body coated on the outer side of the organic-inorganic composite board. The plastic shell comprises the following components in parts by weight: 80-100 parts of ABS resin, 10-25 parts of organic resin toughened glass fiber, 3-10 parts of chlorinated polyethylene, 10-15 parts of flame retardant, 1-5 parts of flame retardant synergist, 1-3 parts of compatilizer and 0.1-0.5 part of lubricant; the organic-inorganic composite board comprises the following components in parts by weight: 100 parts of glass microchip, 35-50 parts of flaky cubic boron nitride, 15-30 parts of epoxy resin and 0.05-0.1 part of curing agent. The invention overcomes the defect that the mechanical property of the lead storage battery in the prior art is continuously reduced along with the prolonging of the service time because the lead storage battery is not corrosion-resistant, and has good toughness and impact resistance; meanwhile, the coating has good corrosion resistance; the use safety of the plastic shell can be ensured for a long time.
Description
Technical Field
The invention relates to the field of lead storage battery plastic cases, in particular to an anti-corrosion high-toughness lead storage battery plastic case.
Background
A lead-acid battery (VRLA) is a battery whose electrodes are made mainly of lead and its oxides and whose electrolyte is a sulfuric acid solution. In the discharge state of the lead-acid battery, the main component of the positive electrode is lead dioxide, and the main component of the negative electrode is lead; in a charged state, the main components of the positive electrode and the negative electrode are lead sulfate.
Lead acid batteries generally consist of five major parts, which are: positive electrode, negative electrode, separator, electrolyte and battery case. The battery shell has the functions of protecting internal elements of the battery from being broken due to external collision, electrolyte leakage and the like, however, the material in the existing lithium battery shell is usually made of ABS material with good impact resistance effect, but the performance of the existing lithium battery shell cannot be completely relieved.
In addition, although ABS plastics have certain corrosion resistance, the practical use of the ABS plastics shows that the pipe made of the ABS plastics is not resistant to sulfuric acid corrosion and can be cracked in a crushing manner when meeting sulfuric acid for a long time. This is particularly true in battery housings, which are usually sulfuric acid solution inside lead-acid batteries, so that the battery housings are usually slowly decomposed from inside to outside with the increase of service time, and the impact resistance is greatly reduced. Meanwhile, the lead storage battery can release a large amount of heat in the charging and discharging processes and release the heat periodically to a certain extent, so that the heat can accelerate the corrosion of sulfuric acid on a plastic shell of the lead storage battery.
In the prior art, for example, a corrosion-resistant lead storage battery plastic shell with application number CN201811057971.4 and a preparation method thereof, the corrosion-resistant lead storage battery plastic shell comprises the following components in parts by weight: 70-90 parts of ABS resin, 15-20 parts of epoxy resin, 10-15 parts of hydrogenated nitrile rubber, 10-20 parts of modified bamboo fiber, 10-20 parts of white carbon black, 6-10 parts of chlorinated polyethylene, 5-8 parts of stearic acid, 3-5 parts of antioxidant and 4-9 parts of stabilizer. According to the method, the graphene oxide reinforced and modified bamboo fiber and the white carbon black are used as the filler to prepare the lead storage battery plastic shell, the white carbon black, the modified bamboo fiber and the epoxy resin can form a complex three-dimensional network structure, and the prepared lead storage battery plastic shell has good corrosion resistance and strength, is simple in preparation process and is suitable for large-scale production. However, the corrosion resistance of the battery plastic shell is improved by the graphene oxide reinforced and modified bamboo fiber and white carbon black, but the ABS resin serving as the main material of the battery plastic shell is still in direct contact with sulfuric acid during use, so that the inside of the plastic shell is still slowly corroded and crushed, and the performance is greatly reduced with time.
Disclosure of Invention
The invention provides an anti-corrosion high-toughness lead storage battery plastic shell which has good corrosion resistance and can not be greatly reduced due to the fact that the mechanical property of a lead storage battery is continuously reduced along with the prolonging of the service time in order to overcome the defect that the lead storage battery in the prior art is not corrosion-resistant.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a corrosion-resistant high-toughness lead storage battery plastic shell is composed of an organic-inorganic composite plate on the inner side of the plastic shell and a plastic shell body coated on the outer side of the organic-inorganic composite plate;
wherein: the plastic shell comprises the following components in parts by weight: 80-100 parts of ABS resin, 10-25 parts of organic resin toughened glass fiber, 3-10 parts of chlorinated polyethylene, 10-15 parts of flame retardant, 1-5 parts of flame retardant synergist, 1-3 parts of compatilizer and 0.1-0.5 part of lubricant;
the organic-inorganic composite board comprises the following components in parts by weight: 100 parts of glass microchip, 35-50 parts of flaky cubic boron nitride, 15-30 parts of epoxy resin and 0.05-0.1 part of curing agent;
the organic-inorganic composite board is prepared by dispersing and compressing glass micro-sheets and flaky cubic boron nitride, sintering the glass micro-sheets and the flaky cubic boron nitride into flaky boards, impregnating the flaky boards with epoxy resin in a vacuum environment, taking out the flaky boards and curing the epoxy resin;
the surface of the organic-inorganic composite board on the inner side of the plastic shell is also coated with a layer of fluorine-containing coating.
The lead storage battery plastic shell is mainly composed of two layers, wherein the plastic shell body provides a forming buffer effect for the whole battery plastic shell and provides first-step protection for the lead storage battery.
The organic-inorganic composite board on the inner layer of the battery plastic shell consists of the acid corrosion resistant glass microchip and the flaky cubic boron nitride, can effectively prevent sulfuric acid from corroding the plastic shell, and meanwhile, the epoxy resin is filled in the organic-inorganic composite board, so that the mechanical strength of the glass microchip and the flaky cubic boron nitride after sintering can be effectively ensured, and the organic-inorganic composite effect is achieved. When the impact force is transmitted to the internal organic-inorganic composite board, the glass micro-sheets and the flaky cubic boron nitride can crack, but the epoxy resin filled between the glass micro-sheets and the flaky cubic boron nitride can consume part of external impact force due to good plastic deformation, and meanwhile, the epoxy resin can be filled in the middle of the crack, so that the crack is prevented from further growing.
In addition, the surface of the organic-inorganic composite plate is coated with a fluorine-containing coating which has super-hydrophobic performance, so that sulfuric acid solution in the plastic shell is isolated by the fluorine-containing coating, and the corrosion of the sulfuric acid solution on the plastic shell of the battery is prevented.
Preferably, the preparation method of the organic resin toughened glass fiber comprises the following steps:
(1) pore-forming: soaking the glass long fiber in a hydrogen peroxide solution containing 0.01-0.05 mol/L hydrofluoric acid and 0.1-0.15 mol/L hydrogen peroxide for 5-10 minutes, taking out, cleaning and drying to obtain the pore-forming glass long fiber;
(2) surface modification: and uniformly spraying an alcohol solution containing 10-20 mass percent of silane coupling agent on the surface of the pore-forming glass long fiber, vacuumizing to remove alcohol, and curing at 100-130 ℃ to obtain the organic resin toughened glass fiber.
In order to enable the plastic shell to have good toughness, organic resin toughened glass fibers are added into the plastic shell. Generally speaking, pore formation on the surface of the fiber has a certain influence on the mechanical properties of the fiber. However, in the application document, pores are formed on the surface of the glass fiber, the pores formed on the surface of the glass fiber can provide attachment points for the toughened resin, and when the glass fiber is filled with a silane coupling agent and cured, the glass fiber can be effectively formed, so that the toughness of the originally easily-broken glass fiber is greatly improved, and the glass fiber is not easily broken.
Preferably, the silane coupling agent is one of gamma-glycidoxypropyltrimethoxysilane or methyl (gamma-glycidoxy) diethoxysilane.
Preferably, the flame retardant is a composition with a mass ratio of aluminum hydroxide to tetrabromobisphenol A of 4 (5-10).
Preferably, the flame-retardant synergist is a composition with the mass ratio of antimony trioxide to lanthanum oxide being (5-10): 1.
Preferably, the compatilizer is one of calcium carbonate, sepiolite, quartz powder or mica powder.
Preferably, the lubricant is one of stearic acid amide, ethylene bis stearamide or pentaerythritol stearate.
Preferably, the specific preparation process of the organic-inorganic composite board is as follows:
(S.1) settling and forming: placing the glass microchip and the flaky cubic boron nitride in water, stirring and dispersing at a high speed for 30-60 min, then carrying out reduced pressure filtration to obtain a filter cake, and drying the filter cake to obtain a plate blank;
(S.2) mechanical compression: performing uniaxial compression on the plate blank under the pressure of 20-30 MPa to obtain a pre-sintered material;
(S.3) sintering: sintering the pre-sintered material at 600-800 ℃ for 3-5 h, and naturally cooling to room temperature to obtain a porous plate;
(S.4) vacuum impregnation: placing the porous plate in a container, vacuumizing to 50-100 Pa, adding epoxy resin into the container, and soaking for 30-120 min;
(S.5) curing: and curing the porous plate impregnated with the epoxy resin at 110-125 ℃ to obtain the organic-inorganic composite plate.
In the first step of preparing the organic-inorganic composite board, the glass micro-sheets and the flaky cubic boron nitride are firstly placed in water, then are stirred and dispersed at a high speed, and then are naturally settled and then form a dense highly ordered structure through a suction filtration mode, so that the structure of each part of the board blank is uniform and stable. In addition, the density of the slab can be increased by mechanical compression, thereby ensuring the sintering rate during sintering. Meanwhile, glass can be melted to a certain extent in the sintering process, so that the flaky powder is adhered to form a whole with a porous structure inside. When the air in the gap is pumped out after the epoxy resin is vacuumized, the epoxy resin can smoothly enter the gap, the cured epoxy resin has good toughness, and the integral crack expansion resistance can be effectively improved.
Preferably, the preparation method of the fluorine-containing coating comprises the following steps:
a: thirteen-fluorine octyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane, hydroxyethyl acrylate and white carbon black are mixed according to the mass ratio of 100: (30-50): (10-20): (5-10) hydrolyzing the mixture to obtain a prepolymer;
b: preparing a solution from the prepolymer and petroleum ether according to a mass ratio of 1:1, adding 1-5% by mass of 2-hydroxy-2-methyl-1-phenyl-1-acetone into the solution, and uniformly mixing to obtain a photocuring coating;
c: uniformly coating the photocureable coating on the surface of the organic-inorganic composite board, standing to remove the solvent to obtain a coating with the thickness of 0.1-0.5 mm, and then reacting for a certain time under the illumination condition of an ultraviolet lamp to obtain the fluorine-containing coating.
The fluorine-containing coating is obtained by hydrolyzing tridecafluorooctyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane and hydroxyethyl acrylate to form a fluorine-silicon copolymer, and the fluorine-silicon copolymer contains tridecafluorooctyl, so that the fluorine-containing coating has low surface energy and good super-hydrophobic property, and can effectively separate corrosion of acid liquid in the plastic shell to the plastic shell.
Preferably, the illumination conditions of the ultraviolet lamp are as follows: the light intensity of the ultraviolet lamp is 365-405 nm, and the ultraviolet light is irradiated for 25-45 min.
The gamma-methacryloxypropyl trimethoxysilane has good photosensitivity because of containing methacryloxypropyl, can be cured spontaneously after being irradiated by ultraviolet light to form a curing film, and has the characteristics of short curing time, high curing efficiency and convenience in curing.
Therefore, the invention has the following beneficial effects:
(1) the material has good toughness and impact resistance;
(2) the corrosion resistance is good;
(3) the use safety of the plastic shell can be ensured for a long time.
Detailed Description
The following description of the embodiments is provided to enable any person skilled in the art to make and use the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the following embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Example 1
The anti-corrosion high-toughness lead storage battery plastic shell is composed of an organic-inorganic composite plate on the inner side of the plastic shell and a plastic shell body wrapping the outer side of the organic-inorganic composite plate, and the surface of the organic-inorganic composite plate is further coated with a layer of fluorine-containing coating.
The plastic shell comprises the following components in parts by weight: 80 parts of ABS resin, 10 parts of organic resin toughened glass fiber, 3 parts of chlorinated polyethylene, 10 parts of a composition with the mass ratio of aluminum hydroxide to tetrabromobisphenol A being 4: 5, 1 part of a composition with the mass ratio of antimony trioxide to lanthanum oxide being 5:1, 1 part of calcium carbonate and 0.1 part of stearic acid amide.
The preparation method of the organic resin toughened glass fiber comprises the following steps:
(1) pore-forming: soaking the glass long fiber in a hydrogen peroxide solution containing 0.01mol/L hydrofluoric acid and 0.1mol/L hydrogen peroxide for 5 minutes, taking out, cleaning and drying to obtain the pore-forming glass long fiber;
(2) surface modification: and uniformly spraying an alcohol solution containing 10 mass percent of gamma-glycidoxypropyltrimethoxysilane on the surface of the pore-forming glass long fiber, vacuumizing to remove alcohol, and curing at 100 ℃ to obtain the organic resin toughened glass fiber.
The organic-inorganic composite board comprises the following components in parts by weight: 100 parts of glass microchip, 35 parts of flaky cubic boron nitride, 15 parts of epoxy resin and 0.05 part of curing agent.
The specific preparation process of the organic-inorganic composite board comprises the following steps:
(S.1) settling and forming: placing the glass microchip and the flaky cubic boron nitride in water, stirring at a high speed for dispersing for 30min, then filtering under reduced pressure to obtain a filter cake, and drying the filter cake to obtain a plate blank;
(S.2) mechanical compression: performing uniaxial compression on the plate blank under the pressure of 20MPa to obtain a pre-sintered material;
(S.3) sintering: sintering the pre-sintered material at 600 ℃ for 3h, and naturally cooling to room temperature to obtain a porous plate;
(S.4) vacuum impregnation: placing the porous plate in a container, vacuumizing to 50Pa, adding epoxy resin into the container, and soaking for 300 min;
(S.5) curing: and curing the porous plate impregnated with the epoxy resin at 110 ℃ to obtain the organic-inorganic composite plate.
The preparation method of the fluorine-containing coating comprises the following steps:
a: thirteen-fluorine octyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane, hydroxyethyl acrylate and white carbon black are mixed according to the mass ratio of 100: 30: 10: 5 the prepolymer obtained after hydrolysis of the mixture;
b: preparing a solution from the prepolymer and petroleum ether according to a mass ratio of 1:1, adding 1-5% by mass of 2-hydroxy-2-methyl-1-phenyl-1-acetone into the solution, and uniformly mixing to obtain a photocuring coating;
c: uniformly coating the photocureable coating on the surface of the organic-inorganic composite board, standing to remove the solvent to obtain a coating with the thickness of 0.1mm, and then reacting for 25min under the illumination condition of an ultraviolet lamp with the wavelength of 365nm to obtain the fluorine-containing coating.
Example 2
The anti-corrosion high-toughness lead storage battery plastic shell is composed of an organic-inorganic composite plate on the inner side of the plastic shell and a plastic shell body wrapping the outer side of the organic-inorganic composite plate, and the surface of the organic-inorganic composite plate is further coated with a layer of fluorine-containing coating.
The plastic shell comprises the following components in parts by weight: 100 parts of ABS resin, 25 parts of organic resin toughened glass fiber, 10 parts of chlorinated polyethylene, 15 parts of a composition with the mass ratio of aluminum hydroxide to tetrabromobisphenol A being 4: 10, 5 parts of a composition with the mass ratio of antimony trioxide to lanthanum oxide being 10:1, 3 parts of sepiolite and 0.5 part of ethylene bis stearamide.
The preparation method of the organic resin toughened glass fiber comprises the following steps:
(1) pore-forming: soaking the glass long fiber in a hydrogen peroxide solution containing 0.05mol/L hydrofluoric acid and 0.15mol/L hydrogen peroxide for 10 minutes, taking out, cleaning and drying to obtain the pore-forming glass long fiber;
(2) surface modification: and uniformly spraying an alcohol solution containing 20 mass percent of methyl (gamma-epoxy propoxy) diethoxysilane on the surface of the pore-forming glass long fiber, vacuumizing to remove alcohol, and curing at 130 ℃ to obtain the organic resin toughened glass fiber.
The organic-inorganic composite board comprises the following components in parts by weight: 100 parts of glass microchip, 50 parts of flaky cubic boron nitride, 30 parts of epoxy resin and 0.1 part of curing agent.
The specific preparation process of the organic-inorganic composite board comprises the following steps:
(S.1) settling and forming: placing glass micro-sheets and flaky cubic boron nitride in water, stirring at a high speed for dispersing for 60min, then carrying out reduced pressure filtration to obtain a filter cake, and drying the filter cake to obtain a plate blank;
(S.2) mechanical compression: performing uniaxial compression on the plate blank under the pressure of 30MPa to obtain a pre-sintered material;
(S.3) sintering: sintering the pre-sintered material at 800 ℃ for 5 hours, and naturally cooling to room temperature to obtain a porous plate;
(S.4) vacuum impregnation: placing the porous plate in a container, vacuumizing to 100Pa, adding epoxy resin into the container, and soaking for 120 min;
(S.5) curing: and curing the porous plate impregnated with the epoxy resin at 125 ℃ to obtain the organic-inorganic composite plate.
The preparation method of the fluorine-containing coating comprises the following steps:
a: thirteen-fluorine octyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane, hydroxyethyl acrylate and white carbon black are mixed according to the mass ratio of 100: 50: 20: 10 hydrolysis of the mixture to obtain a prepolymer;
b: preparing the prepolymer and petroleum ether into a solution according to the mass ratio of 1:1, adding 2-hydroxy-2-methyl-1-phenyl-1-acetone accounting for 5% of the mass of the whole solution, and uniformly mixing to obtain a photocuring coating;
c: uniformly coating the photocureable coating on the surface of the organic-inorganic composite board, standing to remove the solvent to obtain a coating with the thickness of 0.5mm, and then reacting for 45min under the illumination condition of an ultraviolet lamp with the wavelength of 405nm to obtain the fluorine-containing coating.
Example 3
The anti-corrosion high-toughness lead storage battery plastic shell is composed of an organic-inorganic composite plate on the inner side of the plastic shell and a plastic shell body wrapping the outer side of the organic-inorganic composite plate, and the surface of the organic-inorganic composite plate is further coated with a layer of fluorine-containing coating.
The plastic shell comprises the following components in parts by weight: 85 parts of ABS resin, 15 parts of organic resin toughened glass fiber, 5 parts of chlorinated polyethylene, 12 parts of a composition with a mass ratio of aluminum hydroxide to tetrabromobisphenol A being 4:6, 3 parts of a composition with a mass ratio of antimony trioxide to lanthanum oxide being 6:1, 2 parts of quartz powder and 0.3 part of ethylene bis stearamide.
The preparation method of the organic resin toughened glass fiber comprises the following steps:
(1) pore-forming: soaking the glass long fiber in a hydrogen peroxide solution containing 0.03mol/L hydrofluoric acid and 0.12mol/L hydrogen peroxide for 8 minutes, taking out, cleaning and drying to obtain the pore-forming glass long fiber;
(2) surface modification: and uniformly spraying an alcohol solution containing 15 mass percent of gamma-glycidoxypropyltrimethoxysilane on the surface of the pore-forming glass long fiber, vacuumizing to remove alcohol, and curing at 115 ℃ to obtain the organic resin toughened glass fiber.
The organic-inorganic composite board comprises the following components in parts by weight: 100 parts of glass microchip, 40 parts of flaky cubic boron nitride, 20 parts of epoxy resin and 0.08 part of curing agent.
The specific preparation process of the organic-inorganic composite board comprises the following steps:
(S.1) settling and forming: placing the glass microchip and the flaky cubic boron nitride in water, stirring and dispersing for 45min at a high speed, then filtering under reduced pressure to obtain a filter cake, and drying the filter cake to obtain a plate blank;
(S.2) mechanical compression: performing uniaxial compression on the plate blank under the pressure of 25MPa to obtain a pre-sintered material;
(S.3) sintering: sintering the pre-sintered material at 650 ℃ for 4h, and naturally cooling to room temperature to obtain a porous plate;
(S.4) vacuum impregnation: placing the porous plate in a container, vacuumizing to 80Pa, adding epoxy resin into the container, and soaking for 50 min;
(S.5) curing: and curing the porous plate impregnated with the epoxy resin at 115 ℃ to obtain the organic-inorganic composite plate.
The preparation method of the fluorine-containing coating comprises the following steps:
a: thirteen-fluorine octyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane, hydroxyethyl acrylate and white carbon black are mixed according to the mass ratio of 100: 35: 15: 5 the prepolymer obtained after hydrolysis of the mixture;
b: preparing the prepolymer and petroleum ether into a solution according to the mass ratio of 1:1, adding 2-hydroxy-2-methyl-1-phenyl-1-acetone accounting for 2% of the mass of the whole solution, and uniformly mixing to obtain a photocuring coating;
c: uniformly coating the photocureable coating on the surface of the organic-inorganic composite board, standing to remove the solvent to obtain a coating with the thickness of 0.4mm, and then reacting for 30min under the illumination condition of an ultraviolet lamp with the wavelength of 405nm to obtain the fluorine-containing coating.
Example 4
The anti-corrosion high-toughness lead storage battery plastic shell is composed of an organic-inorganic composite plate on the inner side of the plastic shell and a plastic shell body wrapping the outer side of the organic-inorganic composite plate, and the surface of the organic-inorganic composite plate is further coated with a layer of fluorine-containing coating.
The plastic shell comprises the following components in parts by weight: 90 parts of ABS resin, 18 parts of organic resin toughened glass fiber, 6 parts of chlorinated polyethylene, 13 parts of a composition with the mass ratio of aluminum hydroxide to tetrabromobisphenol A being 4:6, 3 parts of a composition with the mass ratio of antimony trioxide to lanthanum oxide being 8:1, 2 parts of mica powder and 0.4 part of pentaerythritol stearate.
The preparation method of the organic resin toughened glass fiber comprises the following steps:
(1) pore-forming: soaking the glass long fiber in a hydrogen peroxide solution containing 0.04mol/L hydrofluoric acid and 0.13mol/L hydrogen peroxide for 8 minutes, taking out, cleaning and drying to obtain the pore-forming glass long fiber;
(2) surface modification: and uniformly spraying an alcohol solution containing 16 mass percent of methyl (gamma-epoxy propoxy) diethoxysilane on the surface of the pore-forming glass long fiber, vacuumizing to remove alcohol, and curing at 120 ℃ to obtain the organic resin toughened glass fiber.
The organic-inorganic composite board comprises the following components in parts by weight: 100 parts of glass microchip, 35-50 parts of flaky cubic boron nitride, 25 parts of epoxy resin and 0.08 part of curing agent.
The specific preparation process of the organic-inorganic composite board comprises the following steps:
(S.1) settling and forming: placing glass micro-sheets and flaky cubic boron nitride in water, stirring at a high speed for dispersing for 50min, then carrying out reduced pressure filtration to obtain a filter cake, and drying the filter cake to obtain a plate blank;
(S.2) mechanical compression: performing uniaxial compression on the plate blank under the pressure of 25MPa to obtain a pre-sintered material;
(S.3) sintering: sintering the pre-sintered material at 750 ℃ for 4h, and naturally cooling to room temperature to obtain a porous plate;
(S.4) vacuum impregnation: placing the porous plate in a container, vacuumizing to 80Pa, adding epoxy resin into the container, and soaking for 100 min;
(S.5) curing: and curing the porous plate impregnated with the epoxy resin at 120 ℃ to obtain the organic-inorganic composite plate.
The preparation method of the fluorine-containing coating comprises the following steps:
a: thirteen-fluorine octyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane, hydroxyethyl acrylate and white carbon black are mixed according to the mass ratio of 100: 40: 15: 8, hydrolyzing the mixture to obtain a prepolymer;
b: preparing the prepolymer and petroleum ether into a solution according to the mass ratio of 1:1, adding 2-hydroxy-2-methyl-1-phenyl-1-acetone accounting for 2% of the mass of the whole solution, and uniformly mixing to obtain a photocuring coating;
c: uniformly coating the photocureable coating on the surface of the organic-inorganic composite board, standing to remove the solvent to obtain a coating with the thickness of 0.2mm, and then reacting for 45min under the illumination condition of an ultraviolet lamp with the wavelength of 405nm to obtain the fluorine-containing coating.
Example 5
The anti-corrosion high-toughness lead storage battery plastic shell is composed of an organic-inorganic composite plate on the inner side of the plastic shell and a plastic shell body wrapping the outer side of the organic-inorganic composite plate, and the surface of the organic-inorganic composite plate is further coated with a layer of fluorine-containing coating.
The plastic shell comprises the following components in parts by weight: 95 parts of ABS resin, 20 parts of organic resin toughened glass fiber, 6 parts of chlorinated polyethylene, 12 parts of a composition with the mass ratio of aluminum hydroxide to tetrabromobisphenol A being 4:8, 4 parts of a composition with the mass ratio of antimony trioxide to lanthanum oxide being 8:1, 1.5 parts of mica powder and 0.25 part of ethylene bis stearamide.
The preparation method of the organic resin toughened glass fiber comprises the following steps:
(1) pore-forming: soaking the glass long fiber in a hydrogen peroxide solution containing 0.03mol/L hydrofluoric acid and 0.14mol/L hydrogen peroxide for 8 minutes, taking out, cleaning and drying to obtain the pore-forming glass long fiber;
(2) surface modification: and uniformly spraying an alcohol solution containing 10-20 mass percent of methyl (gamma-epoxypropoxy) diethoxysilane on the surface of the pore-forming glass long fiber, vacuumizing to remove alcohol, and curing at 105 ℃ to obtain the organic resin toughened glass fiber.
The organic-inorganic composite board comprises the following components in parts by weight: 100 parts of glass microchip, 40 parts of flaky cubic boron nitride, 20 parts of epoxy resin and 0.08 part of curing agent.
The specific preparation process of the organic-inorganic composite board comprises the following steps:
(S.1) settling and forming: placing glass micro-sheets and flaky cubic boron nitride in water, stirring at a high speed for dispersing for 50min, then carrying out reduced pressure filtration to obtain a filter cake, and drying the filter cake to obtain a plate blank;
(S.2) mechanical compression: performing uniaxial compression on the plate blank under the pressure of 28MPa to obtain a pre-sintered material;
(S.3) sintering: sintering the pre-sintered material at 780 ℃ for 4h, and naturally cooling to room temperature to obtain a porous plate;
(S.4) vacuum impregnation: placing the porous plate in a container, vacuumizing to 100Pa, adding epoxy resin into the container, and soaking for 30 min;
(S.5) curing: and curing the porous plate impregnated with the epoxy resin at 125 ℃ to obtain the organic-inorganic composite plate.
The preparation method of the fluorine-containing coating comprises the following steps:
a: thirteen-fluorine octyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane, hydroxyethyl acrylate and white carbon black are mixed according to the mass ratio of 100: 30: 20: 5 the prepolymer obtained after hydrolysis of the mixture;
b: preparing the prepolymer and petroleum ether into a solution according to the mass ratio of 1:1, adding 2-hydroxy-2-methyl-1-phenyl-1-acetone accounting for 2.6 percent of the mass of the whole solution, and uniformly mixing to obtain a photocuring coating;
c: uniformly coating the photocureable coating on the surface of the organic-inorganic composite board, standing to remove the solvent to obtain a coating with the thickness of 0.3mm, and then reacting for 25min under the illumination condition of an ultraviolet lamp with the wavelength of 365nm to obtain the fluorine-containing coating.
The molding steps of the plastic case of the anti-corrosion high-toughness lead storage battery in the embodiments 1 to 5 are as follows:
(1) firstly, preparing an organic-inorganic composite board;
(2) installing the prepared organic-inorganic composite board inside a mold, and then injecting the material obtained by uniformly mixing all components in the plastic shell into the mold through injection molding, wherein during injection molding, the temperature of a main plastic barrel is 230 ℃, the temperature of a forming mold is 55 ℃, the pressure maintaining pressure is 62MPa, and the pressure maintaining time is 8s, so that the plastic shell body is wrapped on the outer side of the organic-inorganic composite board;
(3) and coating a layer of fluorine-containing coating on the surface of the organic-inorganic composite board, decompressing and pumping out the solvent petroleum ether, and then irradiating by an ultraviolet lamp to obtain the cured fluorine-containing coating.
Comparative example 1
The conditions in comparative example 1 were identical to those in example 5 except that no organic-inorganic composite panel was included in comparative example 1.
The lead storage battery plastic cases prepared in examples 1 to 5 and comparative example 1 and commercially available plastic cases were tested, and the test method was as follows:
(1) the bending strength was measured by a three-point bending method, and a rectangular test specimen having dimensions of 80mm (length) x 10mm (width) x 4mm (thickness) was prepared according to the GB/T9341-2000 plastic bending property test method.
(2) Tensile Strength Using a high and low temperature tensile tester (AI-7000M), dumbbell-type test specimens were prepared, having dimensions of 80mm (length) × 12mm (end width) × 4mm (middle width) × 4mm (thickness).
(3) The impact strength was measured by a liquid crystal display impact tester (XJ-50Z), and the test specimen size was also 80mm (length) x 10mm (width) x 4mm (thickness).
(4) The dielectric property test adopts a TH2826A model LCR digital bridge test of Changzhou Council electronic shares company, the test voltage is 0.5V, the test frequency is 1MHz, and an SMD fixture (modified double wafers are 12 mm) is used.
(5) The acid resistance test method is as follows: and (3) putting a sample to be detected into a sulfuric acid solution with the temperature of 60 ℃ and the concentration of 20%, and soaking for 5 days.
The test results were as follows:
as can be seen from the above table, the lead storage battery plastic shell prepared in the present invention has significantly improved tensile strength, impact strength, bending strength, dielectric constant and acid resistance compared to commercially available plastic shells. Meanwhile, in comparative example 5 and comparative example 1, it is found that the mechanical, electrical and corrosion resistance properties of the plastic shell can be effectively improved by adding the organic-inorganic composite board in the plastic shell under the same conditions of the plastic shell.
Claims (10)
1. The anti-corrosion high-toughness lead storage battery plastic shell is characterized by comprising an organic-inorganic composite plate on the inner side of the plastic shell and a plastic shell body coated on the outer side of the organic-inorganic composite plate;
wherein: the plastic shell comprises the following components in parts by weight: 80-100 parts of ABS resin, 10-25 parts of organic resin toughened glass fiber, 3-10 parts of chlorinated polyethylene, 10-15 parts of flame retardant, 1-5 parts of flame retardant synergist, 1-3 parts of compatilizer and 0.1-0.5 part of lubricant;
the organic-inorganic composite board comprises the following components in parts by weight: 100 parts of glass microchip, 35-50 parts of flaky cubic boron nitride, 15-30 parts of epoxy resin and 0.05-0.1 part of curing agent;
the organic-inorganic composite board is prepared by dispersing and compressing glass micro-sheets and flaky cubic boron nitride, sintering the glass micro-sheets and the flaky cubic boron nitride into flaky boards, impregnating the flaky boards with epoxy resin in a vacuum environment, taking out the flaky boards and curing the epoxy resin;
the surface of the organic-inorganic composite board on the inner side of the plastic shell is also coated with a layer of fluorine-containing coating.
2. The anti-corrosion high-toughness lead storage battery plastic shell according to claim 1, wherein the preparation method of the organic resin toughened glass fiber comprises the following steps:
(1) pore-forming: soaking the glass long fiber in a hydrogen peroxide solution containing 0.01-0.05 mol/L hydrofluoric acid and 0.1-0.15 mol/L hydrogen peroxide for 5-10 minutes, taking out, cleaning and drying to obtain the pore-forming glass long fiber;
(2) surface modification: and uniformly spraying an alcohol solution containing 10-20 mass percent of silane coupling agent on the surface of the pore-forming glass long fiber, vacuumizing to remove alcohol, and curing at 100-130 ℃ to obtain the organic resin toughened glass fiber.
3. The plastic case for anti-corrosion high-toughness lead storage battery of claim 2, wherein the silane coupling agent is one of gamma-glycidoxypropyltrimethoxysilane or methyl (gamma-glycidoxypropyl) diethoxysilane.
4. The anti-corrosion high-toughness lead storage battery plastic shell as claimed in claim 1, wherein the flame retardant is a composition of aluminum hydroxide and tetrabromobisphenol A in a mass ratio of 4 (5-10).
5. The anti-corrosion high-toughness lead storage battery plastic shell according to claim 1, wherein the flame-retardant synergist is a composition of antimony trioxide and lanthanum oxide in a mass ratio of (5-10): 1.
6. The plastic case for anti-corrosion high-toughness lead-acid battery of claim 1, wherein the compatilizer is one of calcium carbonate, sepiolite, quartz powder or mica powder.
7. The plastic case for anti-corrosion high-toughness lead-acid battery of claim 1, wherein the lubricant is one of stearic acid amide, ethylene bis-stearamide or pentaerythritol stearate.
8. The anti-corrosion high-toughness lead storage battery plastic shell according to claim 1, wherein the organic-inorganic composite board is prepared by the following specific process:
(S.1) settling and forming: placing glass micro-sheets and flaky cubic boron nitride in water, stirring at a high speed for dispersing for 30-60 min, then carrying out reduced pressure filtration to obtain a filter cake, and drying the filter cake to obtain a plate blank;
(S.2) mechanical compression: performing uniaxial compression on the plate blank under the pressure of 20-30 MPa to obtain a pre-sintered material;
(S.3) sintering: sintering the pre-sintered material at 600-800 ℃ for 3-5 h, and naturally cooling to room temperature to obtain a porous plate;
(S.4) vacuum impregnation: placing the porous plate in a container, vacuumizing to 50-100 Pa, adding epoxy resin into the container, and soaking for 30-120 min;
(S.5) curing: and curing the porous plate impregnated with the epoxy resin at 110-125 ℃ to obtain the organic-inorganic composite plate.
9. The anti-corrosion high-toughness lead storage battery plastic shell according to claim 1, wherein the fluorine-containing coating is prepared by the following steps:
a: thirteen-fluorine octyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane, hydroxyethyl acrylate and white carbon black are mixed according to the mass ratio of 100: (30-50): (10-20): (5-10) hydrolyzing the mixture to obtain a prepolymer;
b: preparing a solution from the prepolymer and petroleum ether according to a mass ratio of 1:1, adding 1-5% by mass of 2-hydroxy-2-methyl-1-phenyl-1-acetone into the solution, and uniformly mixing to obtain a photocuring coating;
c: uniformly coating the photocureable coating on the surface of the organic-inorganic composite board, standing to remove the solvent to obtain a coating with the thickness of 0.1-0.5 mm, and then reacting for a certain time under the illumination condition of an ultraviolet lamp to obtain the fluorine-containing coating.
10. The plastic shell for the anti-corrosion high-toughness lead storage battery of claim 9, wherein the illumination conditions of the ultraviolet lamp are as follows: the light intensity of the ultraviolet lamp is 365-405 nm, and the ultraviolet light is irradiated for 25-45 min.
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| CN102220062A (en) * | 2011-05-13 | 2011-10-19 | 武汉大学 | Aqueous UV curing coating and preparation method thereof |
| CN109294152A (en) * | 2018-09-05 | 2019-02-01 | 浙江畅通科技有限公司 | A kind of high strength heat resistant lead-acid battery plastic housing and preparation method thereof |
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2019
- 2019-12-12 CN CN201911274103.6A patent/CN111253704A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102220062A (en) * | 2011-05-13 | 2011-10-19 | 武汉大学 | Aqueous UV curing coating and preparation method thereof |
| CN109294152A (en) * | 2018-09-05 | 2019-02-01 | 浙江畅通科技有限公司 | A kind of high strength heat resistant lead-acid battery plastic housing and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115093671A (en) * | 2022-07-06 | 2022-09-23 | 滨海长兴塑业有限公司 | Corrosion-resistant lead storage battery plastic shell and preparation method thereof |
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