CN107698713B - Metal surface primer of electric energy storage equipment and conductive coating composition thereof - Google Patents
Metal surface primer of electric energy storage equipment and conductive coating composition thereof Download PDFInfo
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- CN107698713B CN107698713B CN201710938312.0A CN201710938312A CN107698713B CN 107698713 B CN107698713 B CN 107698713B CN 201710938312 A CN201710938312 A CN 201710938312A CN 107698713 B CN107698713 B CN 107698713B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
Abstract
A metal surface primer of an electric energy storage device is obtained by emulsion polymerization of a prepolymer, an oil-soluble monomer, a water-soluble monomer, an initiator and a surfactant, wherein the prepolymer is prepared by reacting isocyanate, polyol and an acrylate monomer with hydroxyl at the temperature of 20-150 ℃ through a catalyst, the obtained metal surface primer has excellent adhesion with positive and negative active substances, and a battery pole piece is not swelled and fallen after being soaked in an electrolyte solution and can maintain the size stability of the pole piece for a long time. The lithium ion battery prepared by using the metal surface primer of the current collector provided by the invention has the characteristics of small internal resistance, low polarization, high battery capacity and the like.
Description
Technical Field
The invention relates to a primer for a metal surface of a current collector of an electric energy storage device and a conductive coating composition thereof, in particular to a primer with excellent adhesive force and a conductive coating composition prepared by using the primer.
Background
As an electric energy storage device, the lithium ion battery has the characteristics of high energy density, high output voltage, high output power, small self-discharge, wide working temperature, no memory effect and the like, and is widely applied to portable electronic devices such as mobile phones and notebook computers. At present, lithium ion batteries are widely applied to hybrid electric vehicles, plug-in hybrid electric vehicles and pure electric vehicles as power batteries.
The lithium ion battery mainly comprises a positive electrode, a negative electrode, a diaphragm, electrolyte and the like, wherein the positive electrode and the negative electrode generally comprise powdery active materials, namely a lithium transition metal oxide positive electrode material or a carbon negative electrode material, primer, a conductive additive and a current collector. The preparation method generally comprises the steps of mixing and grinding the active material, the conductive additive and the primer solution uniformly to prepare slurry, coating the slurry on copper foil and aluminum foil serving as current collectors, and carrying out drying, rolling and other processes. The most widely used primers are fluoropolymer primers such as polyvinylidene fluoride based primers.
However, polyvinylidene fluoride base glue has a plurality of defects in use: such as weak bonding strength; fluorine-containing elements can react with lithium intercalation graphite to cause thermal runaway and irreversible reaction of active substances; is sensitive to moisture; the price is high, which is not beneficial to reducing the cost; volatilization of the solvent both pollutes the environment and harms the health of operators.
In order to solve the problems, people research and develop the aqueous primer of the lithium ion battery, such as sodium carboxymethyl cellulose, polystyrene butadiene copolymer and the like, but the sodium carboxymethyl cellulose and the polystyrene butadiene copolymer aqueous primer have the phenomena of weaker bonding property, pole piece powder falling and the like, and are not favorable for the electrochemical performance of the battery.
Disclosure of Invention
The invention aims to provide a metal surface primer of electric energy storage equipment and a conductive coating composition thereof, which can solve the technical problems that the battery pole piece is swollen and falls off when being soaked in an electrolyte solution, the size of the pole piece cannot be kept stable, the internal resistance of the battery is large, the polarization is high and the battery capacity is low due to weak bonding force and pole piece powder falling of the conventional primer.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the metal surface primer of the electric energy storage device is synthesized from the following raw materials in parts by weight:
prepolymer: 1-70.5 parts;
oil-soluble monomers: 20-95 parts;
water-soluble monomer: 2.5-20 parts;
initiator: 0.3-10 parts;
surfactant (b): 0.3-3 parts;
deionized water: 150 parts;
proper amount of ammonia water;
the prepolymer is prepared from isocyanate: 20-60 parts of polyol: 35-70 parts of an acrylate monomer having a hydroxyl group: 4.5-10 parts and catalyst: 0.001-0.5 part of the compound is prepared by reaction at 20-150 ℃;
the polyhydric alcohol is at least one of polyethylene glycol adipate glycol, polyethylene glycol-propylene glycol adipate glycol, polyethylene glycol-diethylene glycol adipate glycol, polypropylene oxide glycol, polytetrahydrofuran glycol, tetrahydrofuran-propylene oxide copolymer glycol, polyethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, glycerol, trimethylolpropane, neopentyl glycol and sorbitol;
the water-soluble monomer is an acrylic monomer, and simultaneously contains a carbon-carbon double bond capable of carrying out free radical polymerization and a group with hydrophilicity;
the initiator comprises a peroxide initiator used for emulsion polymerization and a redox polymerization initiator formed by combining the peroxide initiator and a reducing agent.
Preferably, the isocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and hydrogenated diphenylmethane diisocyanate.
Preferably, the acrylate monomer having a hydroxyl group is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate and hydroxyethyl methacrylate.
Preferably, the catalyst is at least one of bismuth neodecanoate, bismuth laurate, bismuth isooctanoate, bismuth naphthenate, dibutyltin dilaurate, bis-dimethylaminoethyl ether, pentamethyldiethylenetriamine and dimethylcyclohexylamine.
Preferably, the oil-soluble monomer is at least one of methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, n-propyl methacrylate, n-propyl acrylate, isopropyl methacrylate, isopropyl acrylate, n-butyl methacrylate, n-butyl acrylate, isobutyl methacrylate, isobutyl acrylate, t-butyl methacrylate, t-butyl acrylate, n-hexyl methacrylate, n-hexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, lauryl methacrylate, lauryl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, isononyl methacrylate, isononyl acrylate, isobornyl methacrylate and isobornyl acrylate. Preferably, the water-soluble monomer is at least one of acrylic acid, methacrylic acid, acrylonitrile, acrylamide, methylolacrylamide, itaconic acid, hydroxyethyl acrylate, and hydroxypropyl acrylate.
Preferably, the initiator is at least one of ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, and t-butyl peroxide.
In addition, the invention also provides a conductive coating composition containing the metal surface primer of the electric energy storage device, which further comprises a positive electrode active material and a negative electrode active material, wherein the positive electrode active material and the negative electrode active material are uniformly mixed with the primer in a certain proportion to prepare slurry, and the slurry is uniformly coated on the metal surface through coating equipment, and the positive electrode active material is selected from Ni-Mn-L i lithium composite oxide, Ni-Co-L i lithium composite oxide, lithium cobaltate, Ni-Co-Mn oxide and spinel type lithium manganateOlive type lithium iron phosphate, TiS2、MnO2、Mn03And V2O5At least one of; the negative active material is at least one selected from polyacetylene, polypyrrole, coke, acetylene black, carbon nanotubes, artificial graphite, natural graphite, lithium titanate and silicon.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
1. the invention uses isocyanate, polyol and acrylate monomer with hydroxyl to react at 20-150 ℃ to prepare a prepolymer.
2. The metal surface primer of the current collector used in the electric energy storage device is obtained by emulsion polymerization of an oil-soluble monomer, a water-soluble monomer, a prepolymer and an initiator in the presence of a surfactant.
3. According to the invention, the anode active material, the cathode active material and a certain proportion of primer are uniformly mixed to prepare slurry, and the slurry is uniformly coated on the metal surface through coating equipment, so that the conductive coating of the primer on the metal surface of the electric energy storage equipment is further prepared. The metal surface primer has excellent adhesiveness with positive and negative active materials, and the battery pole piece does not swell or fall off after being soaked in an electrolyte solution, and can keep the size stability of the pole piece for a long time.
4. The lithium ion battery prepared by using the metal surface primer of the current collector provided by the invention has the characteristics of small internal resistance, low polarization, high battery capacity and the like.
Detailed Description
In order to make the technical means, innovative features, objectives and functions realized by the present invention easy to understand, the present invention is further described below.
The examples described herein are specific embodiments of the present invention, are intended to be illustrative and exemplary in nature, and are not to be construed as limiting the scope of the invention. In addition to the embodiments described herein, those skilled in the art will be able to employ other technical solutions which are obvious based on the disclosure of the claims and the specification of the present application, and these technical solutions include technical solutions which make any obvious replacement or modification for the embodiments described herein.
The prepolymer of the embodiment of the invention is obtained by the catalytic reaction of isocyanate, polyol and acrylate monomer with hydroxyl at 20-150 ℃.
The reaction mechanism of the prepolymer can be explained as follows: the isocyanate can react with active hydrogen of hydroxyl-containing compounds such as alcohol, polyol, polyether, polyester, etc. to generate carbamate. In the reaction process, isocyanate and polyalcohol react alternately to continuously increase the molecular weight of the prepolymer, when the isocyanate reacts with the acrylate monomer with hydroxyl, the reaction is terminated, and meanwhile, double bonds are introduced into a molecular chain, so that the subsequent polymerization with the oil-soluble monomer and the water-soluble monomer is facilitated.
The isocyanate in the prepolymer used in the invention is at least one selected from toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate.
The polyol in the prepolymer used in the present invention is at least one selected from the group consisting of polyethylene glycol adipate diol, polyethylene glycol-propylene glycol adipate diol, polyethylene glycol-diethylene glycol adipate diol, polypropylene oxide diol, polytetrahydrofuran diol, tetrahydrofuran-propylene oxide copolymer diol, polyethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, glycerin, trimethylolpropane, neopentyl glycol, sorbitol, and the like.
The acrylic ester monomer with hydroxyl in the prepolymer used in the invention is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate and hydroxyethyl methacrylate.
The catalyst in the prepolymer used in the invention is selected from at least one of bismuth neodecanoate, bismuth laurate, bismuth isooctanoate, bismuth naphthenate, dibutyltin dilaurate, bis-dimethylamino ethyl ether, pentamethyl diethylenetriamine and dimethyl cyclohexylamine.
The invention provides a metal surface primer of an electric energy storage device prepared by utilizing the prepolymer, which comprises the following raw materials in parts by weight:
prepolymer: 1-70.5 parts;
oil-soluble monomers: 20-95 parts;
water-soluble monomer: 2.5-20 parts;
initiator: 0.3-10 parts;
surfactant (b): 0.3-3 parts;
deionized water: 150 parts;
proper amount of ammonia water.
The reaction mechanism of the primer can be explained as follows: the double bonds in molecules of the water-soluble monomer, the oil-soluble monomer and the prepolymer with unsaturated double bonds are opened under the action of an initiator to form free radicals, and the monomer with the free radicals and the prepolymer carry out repeated addition reaction among the molecules to connect a plurality of monomer molecules and the prepolymer to form macromolecules.
The prepolymer used in the invention is 1 to 70.5 parts, preferably 3 to 45 parts. By setting the content of the prepolymer within the above range, the adhesion between the active materials of the primer and the current collector is significantly improved, and the current collector can obtain sufficient flexibility.
The oil-soluble monomers used in the present invention are ethylenically unsaturated monomers such as methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, n-propyl methacrylate, n-propyl acrylate, isopropyl methacrylate, isopropyl acrylate, n-butyl methacrylate, n-butyl acrylate, isobutyl methacrylate, isobutyl acrylate, t-butyl methacrylate, t-butyl acrylate, n-hexyl methacrylate, n-hexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, lauryl methacrylate, lauryl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, isononyl methacrylate, isononyl acrylate, isobornyl methacrylate and isobornyl acrylate, and like methacrylates, acrylates, methacrylates, acrylates, methacrylates, one or more of styrene, vinyl acetate, and the like. At least one of n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, lauryl methacrylate, lauryl acrylate, styrene, isobornyl methacrylate and isobornyl acrylate is preferable.
The oil-soluble monomer used in the present invention is 20 to 95 parts, preferably 25 to 90 parts, more preferably 28 to 85 parts. When the content of the oil-soluble monomer is in the above range, the adhesion between the active materials of the primer and the adhesion between the active materials and the current collector are improved.
The water-soluble monomer used in the invention is a water-soluble acrylic monomer, and contains a carbon-carbon double bond capable of free radical polymerization and a monomer with hydrophilic carboxyl, amido, cyano, hydroxyl and other groups, such as one or more of acrylic acid, methacrylic acid, acrylonitrile, acrylamide, hydroxymethyl acrylamide, itaconic acid, hydroxyethyl acrylate and hydroxypropyl acrylate. One or more of acrylic acid, acrylonitrile, acrylamide, and methylol acrylamide are preferred.
The water-soluble monomer used in the present invention is preferably 3 to 18 parts, more preferably 3 to 15 parts. When the content of the water-soluble monomer is in the above range, emulsion polymerization stability or mechanical stability is improved, and adhesiveness between active materials of the primer and between the active materials and the current collector is improved.
The initiator used in the present invention includes peroxide initiators used for emulsion polymerization such as ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, and t-butyl peroxide, and redox polymerization initiators obtained by combining these initiators with reducing agents such as sodium bisulfite, rongalite, and ascorbic acid. One or more of potassium persulfate, potassium persulfate and sodium bisulfite are preferred.
The emulsion polymerization method can comprise the method of carrying out emulsion polymerization, seed emulsion polymerization by one-time feeding and carrying out emulsion polymerization by continuously dripping monomers, wherein the polymerization temperature is between 30 and 100 ℃.
The surfactant used in the present invention includes anionic surfactants and nonionic surfactants. The anionic surfactant includes alkylbenzene sulfonate, alkyl sulfate, polyoxyethylene ether sulfate, fatty acid salt, etc., the nonionic surfactant includes polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polycyclic phenyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, alkylphenol ethoxylates, etc., and the surfactants may be used alone or in combination of 2 or more.
The amount of the surfactant to be used is preferably 0.3 to 3 parts relative to 100 parts of the total monomers. By setting the surfactant content in the above range, the obtained primer emulsion has high mechanical stability, a small particle diameter, and is less likely to cause particle sedimentation.
After the primer emulsion is prepared by emulsion polymerization, an alkaline substance can be added to adjust the pH value of the primer to be 5-10, preferably 6-9, so as to improve the polymerization stability, mechanical stability and chemical stability of the primer emulsion. These basic substances may include ammonia, triethylamine, sodium hydroxide, lithium hydroxide and the like, and these basic substances may be used alone or in combination of 2 or more.
The invention also provides a conductive coating composition for the electric energy storage device, which is prepared by mixing the primer on the metal surface of the electric energy storage device with the positive and negative electrode active substances to prepare homogenate and coating the homogenate on the metal surface.
The positive electrode active material to which the present invention is applied includes a nickel-containing lithium composite oxide such as lithium cobaltate, a Ni-Co-Mn-based oxide, a Ni-Mn-L i-based lithium composite oxide, and a Ni-Co-L i-based lithium composite oxide, or spinel-type lithium manganate, olive-type lithium iron phosphate, TiS2、MnO2、Mn03、V2O5One or more of an isochalcogen compound.
The negative active material suitable for the invention comprises polyacetylene, polypyrrole, coke, acetylene black, carbon nano tube, artificial graphite, natural graphite, lithium titanate, silicon and the like.
The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the scope of the invention.
The following description is given by way of several specific examples to further understanding the invention.
Example 1
Synthesis of prepolymer
In a reactor, heating 25 parts of isophorone diisocyanate and 70 parts of polyethylene glycol adipate glycol to 60 ℃ for reaction for 0.5h, adding 0.001 part of dibutyltin dilaurate, slowly heating to 75 ℃ for reaction for 3h, adding 5 parts of hydroxyethyl acrylate into a reaction system, reacting for 2h at 75 ℃, and slowly cooling to room temperature to obtain the prepolymer.
Synthesis of primer
Adding 40 parts of styrene, 40 parts of n-butyl acrylate, 10.5 parts of prepolymer, 5 parts of hydroxymethyl acrylamide, 4 parts of acrylic acid, 0.2 part of sodium dodecyl sulfate, 0.1 part of octyl phenol-10 and 138 parts of deionized water into a four-mouth flask, stirring at the rotating speed of 800r/min for 30min for pre-emulsification to obtain pre-emulsion, transferring the pre-emulsion into a dropping funnel, dissolving 0.5 part of ammonium persulfate into 2 parts of deionized water and adding into the dropping funnel, adding 10 parts of deionized water into the four-mouth flask, starting stirring, slowly heating to 80 ℃, beginning to simultaneously dropwise add the pre-emulsion and the ammonium persulfate solution, dropwise adding for 3h, heating to 90 ℃, keeping the temperature for 1h, slowly cooling to 25 ℃, adding a certain amount of ammonia water and adjusting the pH value to 7.
Example 2
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that the oil-soluble monomers were 40 parts of styrene and 40 parts of lauryl acrylate.
Example 3
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that the oil-soluble monomers were 10 parts of styrene and 10 parts of n-butyl acrylate, and 70.5 parts of a prepolymer.
Example 4
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that the oil-soluble monomers were 50 parts of styrene and 45 parts of n-butyl acrylate, and 0.5 part of methylolacrylamide.
Example 5
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that the prepolymer was used in an amount of 35 parts, and the oil-soluble monomer was 40 parts of styrene and 15.5 parts of n-butyl acrylate.
Example 6
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that 5 parts of a prepolymer was used, 40 parts of styrene was used as an oil-soluble monomer, and 45.5 parts of n-butyl acrylate was used as an oil-soluble monomer.
Example 7
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that the amount of the prepolymer was 2.2 parts, and the oil-soluble monomer was 40 parts of styrene and 48.3 parts of n-butyl acrylate.
Example 8
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that the prepolymer was used in an amount of 50 parts, and the oil-soluble monomer was 25 parts of styrene and 15.5 parts of n-butyl acrylate.
Example 9
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that the oil-soluble monomer was 40 parts of styrene and 46 parts of n-butyl acrylate, and the water-soluble monomer was 3 parts of acrylic acid.
Example 10
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that the oily monomer was 34 parts of styrene and 40 parts of n-butyl acrylate, and the water-soluble monomer was 10 parts of methylolacrylamide.
Example 11
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that the water-soluble monomers were 5 parts of methylolacrylamide and 4 parts of acrylonitrile.
Example 12
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that the water-soluble monomers were 1.5 parts of methylolacrylamide and 1 part of acrylonitrile, the oil-soluble monomers were 46.5 parts of styrene, and 40 parts of n-butyl acrylate.
Example 13
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that the water-soluble monomers were 5 parts of methylolacrylamide and 15 parts of acrylonitrile. The oil-soluble monomer is styrene 35 and n-butyl acrylate 34 parts.
Example 14
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that the prepolymer was used in an amount of 8 parts and the initiator was used in an amount of 3 parts.
Example 15
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that the prepolymer was used in an amount of 1 part and the initiator was used in an amount of 10 parts.
Example 16
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that the initiators were 0.3 part of potassium persulfate and 0.2 part of sodium bisulfite.
Example 17
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that the prepolymer was used in an amount of 10.7 parts and the initiator was used in an amount of 0.3 part.
Example 18
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that the initiator was 0.5 part of potassium persulfate.
Example 19
A prepolymer was synthesized in the same manner as in example 1, except that 40 parts of isocyanate and 55 parts of polyol were used.
A primer was synthesized in the same manner as in example 1.
Example 20
A prepolymer was synthesized in the same manner as in example 1, except that the isocyanate was used in an amount of 60 parts and the polyol was used in an amount of 35 parts.
A primer was synthesized in the same manner as in example 1.
Example 21
A prepolymer was synthesized in the same manner as in example 1, except that 20 parts of isocyanate and 10 parts of an acrylate monomer having a hydroxyl group were used.
A primer was synthesized in the same manner as in example 1.
Example 22
A prepolymer was synthesized in the same manner as in example 1, except that the isocyanate was 25 parts of tolylene diisocyanate.
A primer was synthesized in the same manner as in example 1.
Example 23
A prepolymer was synthesized in the same manner as in example 1, except that the polyol was 70 parts of polyethylene glycol.
A primer was synthesized in the same manner as in example 1.
Example 24
A prepolymer was synthesized in the same manner as in example 1, except that the acrylate monomer having a hydroxyl group was 5 parts of hydroxypropyl acrylate.
A primer was synthesized in the same manner as in example 1.
Example 25
A prepolymer was synthesized in the same manner as in example 1, except that 0.25 part of dibutyltin dilaurate and 4.8 parts of hydroxyethyl acrylate were used.
A primer was synthesized in the same manner as in example 1.
Example 26
A prepolymer was synthesized in the same manner as in example 1, except that 0.5 part of dibutyltin dilaurate and 4.5 parts of hydroxyethyl acrylate were used.
A primer was synthesized in the same manner as in example 1.
Example 27
A prepolymer was synthesized in the same manner as in example 1, except that the synthesis temperature was 20 ℃.
A primer was synthesized in the same manner as in example 1.
Example 28
A prepolymer was synthesized in the same manner as in example 1, except that the synthesis temperature was 150 ℃.
A primer was synthesized in the same manner as in example 1.
Example 29
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that the amount of the prepolymer was 7.8 parts, the amount of the surfactant sodium lauryl sulfate was 2 parts, and the amount of the octylphenol-10 was 1 part.
Example 30
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that 9.3 parts of a prepolymer was used, 1 part of a surfactant, sodium lauryl sulfate was used, and 0.5 part of octylphenol-10 was used.
Comparative example 1
A primer was synthesized in the same manner as in example 1, except that the prepolymer was used in an amount of 0 part, and the oil-soluble monomer was 45 parts of styrene and 45.5 parts of n-butyl acrylate.
Comparative example 2
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that the oil-soluble monomers were 44 parts of styrene and 45 parts of n-butyl acrylate, and the amount of the water-soluble monomer was 0 part.
Comparative example 3
A prepolymer was synthesized in the same manner as in example 1.
A primer was synthesized in the same manner as in example 1, except that the prepolymer was used in an amount of 90.5 parts and the oil-soluble monomer was used in an amount of 0 part.
In addition, comparative evaluation was performed by the following method.
(1) Viscosity: testing with a Bolifei rotary viscometer at a liquid temperature of 23 ℃ at a rotating speed of 60rpm and a 31# rotor;
(2) electrode peel strength: the coating weight after drying was 7mg/cm2The slurry was coated on a copper foil or an aluminum foil as a current collector, and dried by heating at 60 ℃ for 10min and further dried at 120 ℃ for 10min to obtain an electrode, the obtained electrode was left at 23 ℃ and 50% RH for 24 hours, the electrode slurry-coated surface was attached to a stainless steel plate using a double-sided tape, and the 180 ° peel strength (peel width 25mm, peel speed 100mm/min) was measured and was considered to be good when the peel strength was not less than 15 mN/mm.
(3) Amount of active material peeled: and (3) attaching a 3M adhesive tape to the coating surface of the electrode slurry, slowly tearing off the adhesive tape, observing the amount of the active substances remained on the adhesive tape, judging the level by 1-5, wherein 1 is no residual active substances, and 5 is a large amount of residual active substances.
(4) Charge-discharge cycle characteristics: constant current-constant voltage charging (charging at constant current 1C to upper limit voltage 4.2V and charging at constant voltage 4.2V to elapse of 1.5h, and constant current 1C discharging to lower limit voltage 2.75V) was repeated under the condition of 25 ℃. The charge-discharge high-temperature cycle characteristics of the battery were indicated by a capacity retention rate, that is, a ratio of the discharge capacity at the 300 th cycle to the discharge capacity at the 1 st cycle. A battery having a capacity retention rate of 85% or more was regarded as having good charge/discharge cycle characteristics.
The test results are shown in Table 1.
TABLE 1 Battery Performance test
As can be seen from table 1, examples 1 to 30 are remarkably improved in performances such as electrode peel strength, active material peel amount, and charge-discharge cycle characteristics, while the viscosity is kept in compliance with the use standard, as compared with comparative examples 1 to 3.
As shown in table 1, when the prepolymers were added in the primer synthesis in examples 1 to 30, the viscosity and the electrode peel strength of the primers obtained were superior to those of comparative example 1 in which no prepolymer was added, in terms of the electrode peel strength, the active material peel amount, and the charge-discharge cycle characteristics.
Compared with comparative example 2 in which no water-soluble monomer was added, the primer synthesized in examples 1 to 30, in which the water-soluble monomer was added, was superior in viscosity and electrode peel strength to those of comparative example 1 in terms of electrode peel strength, active material peel amount, charge-discharge cycle characteristics, and the like.
Compared with comparative example 3 in which no oil-soluble monomer was added, the primer synthesized in examples 1 to 30 in which the oil-soluble monomer was added had superior viscosity and electrode peel strength to those of comparative example 1 in terms of electrode peel strength, active material peel amount, charge-discharge cycle characteristics, and the like.
Claims (7)
1. The metal surface primer of the electric energy storage device is characterized in that the raw materials for synthesizing the metal surface primer of the electric energy storage device comprise the following components in parts by weight:
prepolymer: 1-70.5 parts;
oil-soluble monomers: 20-95 parts;
water-soluble monomer: 2.5-20 parts;
initiator: 0.3-10 parts;
surfactant (b): 0.3-3 parts;
deionized water: 150 parts;
proper amount of ammonia water;
the prepolymer is prepared from isocyanate: 20-60 parts of polyol: 35-70 parts of an acrylate monomer having a hydroxyl group: 4.5-10 parts and catalyst: 0.001-0.5 part of the compound is prepared by reaction at 20-150 ℃;
the polyhydric alcohol is at least one of polyethylene glycol adipate glycol, polyethylene glycol-propylene glycol adipate glycol, polyethylene glycol-diethylene glycol adipate glycol, polypropylene oxide glycol, polytetrahydrofuran glycol, tetrahydrofuran-propylene oxide copolymer glycol, polyethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, glycerol, trimethylolpropane, neopentyl glycol and sorbitol;
the water-soluble monomer is an acrylic monomer, and simultaneously contains a carbon-carbon double bond capable of carrying out free radical polymerization and a group with hydrophilicity;
the oil-soluble monomer is at least one of methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, n-propyl methacrylate, n-propyl acrylate, isopropyl methacrylate, isopropyl acrylate, n-butyl methacrylate, n-butyl acrylate, isobutyl methacrylate, isobutyl acrylate, tert-butyl methacrylate, tert-butyl acrylate, n-hexyl methacrylate, n-hexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, lauryl methacrylate, lauryl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, isononyl methacrylate, isononyl acrylate, isobornyl methacrylate and isobornyl acrylate.
2. The metal surface primer for an electrical energy storage device of claim 1, wherein: the isocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate.
3. The metal surface primer for an electrical energy storage device of claim 1, wherein: the acrylate monomer with hydroxyl is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate and hydroxyethyl methacrylate.
4. The metal surface primer for an electrical energy storage device of claim 1, wherein: the catalyst is at least one of bismuth neodecanoate, bismuth laurate, bismuth isooctanoate, bismuth naphthenate, dibutyltin dilaurate, bis-dimethylamino ethyl ether, pentamethyl diethylenetriamine and dimethyl cyclohexylamine.
5. The metal surface primer for an electrical energy storage device of claim 1, wherein: the water-soluble monomer is at least one of acrylic acid, methacrylic acid, acrylamide, itaconic acid, hydroxyethyl acrylate and hydroxypropyl acrylate.
6. The metal surface primer for an electrical energy storage device of claim 1, wherein: the initiator is at least one of ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, tert-butyl peroxide, sodium bisulfite, rongalite and ascorbic acid.
7. An electrically conductive coating composition comprising the metal surface primer of the electrical energy storage device of any of claims 1-6, wherein: further comprises a positive electrode active material, a negative electrode active material, a positive electrode active material and a negative electrode active materialThe positive active material is selected from Ni-Mn-L i series lithium composite oxide, Ni-Co-L i series lithium composite oxide, lithium cobaltate, Ni-Co-Mn series oxide, spinel type lithium manganate, TiS2、MnO2、MnO3And V2O5At least one of; the negative active material is at least one selected from polyacetylene, polypyrrole, coke, acetylene black, carbon nanotubes, artificial graphite, natural graphite, lithium titanate and silicon.
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|---|---|---|---|---|
| JPH111676A (en) * | 1997-06-11 | 1999-01-06 | Nippon Polyurethane Ind Co Ltd | Binder for battery electrode and its production |
| CN101007933A (en) * | 2006-01-27 | 2007-08-01 | 三星Sdi株式会社 | Polyurethane binder, electrodes containing the same and lithium battery employing the electrodes |
| CN102471449A (en) * | 2009-07-30 | 2012-05-23 | 旭硝子株式会社 | Unsaturated urethane oligomer, curable resin composition, transparent laminate, and process for producing same |
| CN105602497A (en) * | 2016-01-26 | 2016-05-25 | 浙江中科立德新材料有限公司 | Polyurethane-modified acrylic acid waterborne binder and preparing method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH111676A (en) * | 1997-06-11 | 1999-01-06 | Nippon Polyurethane Ind Co Ltd | Binder for battery electrode and its production |
| CN101007933A (en) * | 2006-01-27 | 2007-08-01 | 三星Sdi株式会社 | Polyurethane binder, electrodes containing the same and lithium battery employing the electrodes |
| CN102471449A (en) * | 2009-07-30 | 2012-05-23 | 旭硝子株式会社 | Unsaturated urethane oligomer, curable resin composition, transparent laminate, and process for producing same |
| CN105602497A (en) * | 2016-01-26 | 2016-05-25 | 浙江中科立德新材料有限公司 | Polyurethane-modified acrylic acid waterborne binder and preparing method and application thereof |
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