CN112625555A - Wear-resistant coating for surface of battery jar shell and preparation method thereof - Google Patents

Abstract

The invention discloses a wear-resistant coating for the surface of a battery jar shell and a preparation method thereof, wherein the wear-resistant coating comprises the following raw materials in parts by weight: 55-70 parts of composite matrix, 10-20 parts of rigid filler, 0.5-0.8 part of dimethyl silicone oil, 3-5 parts of dioctyl phthalate, 0.1-0.5 part of KH560, 10-15 parts of polyvinyl alcohol and 50-60 parts of water; adding the composite matrix and polyvinyl alcohol into water, heating and stirring at a constant speed to prepare a mixed solution; transferring the mixed solution into a reaction kettle, heating, stirring at a constant speed, adding dimethyl silicone oil, continuously stirring for 30min, cooling, adding dioctyl phthalate, adding rigid filler and KH560 after ultrasonic treatment is finished for 1.5h, and stirring at a constant speed to obtain the wear-resistant coating for the surface of the battery shell; the composite matrix is polyester modified epoxy acrylate, the toughness of the composite matrix can be improved by introducing diester, and the adhesion performance of the formed film layer to a base material is improved.

Description

Wear-resistant coating for surface of battery jar shell and preparation method thereof

Technical Field

The invention belongs to the technical field of paint preparation, and particularly relates to a wear-resistant paint for the surface of a battery shell and a preparation method thereof.

Background

The crosslinked network presented after the epoxy resin is cured is easy to cause crazing defects which are particularly sensitive to stress due to too high crosslinking density, and after the thermoplastic resin is added, the toughened thermoplastic resin is continuously penetrated in the epoxy resin network in the system, and as a result of the series connection, when a matrix is impacted, firstly the matrix is brittle failure, and then the thermoplastic resin is ductile deformation to absorb failure energy, so that the toughness of the epoxy resin is improved. The thermoplastic resins not only have better toughness, but also have higher modulus and heat resistance, and have obvious toughening and modifying effects on the epoxy resin when being used as a toughening agent.

Chinese patent CN105925143A wear-resistant epoxy paint, a preparation method thereof and a high wear-resistant epoxy coating. The invention provides a high wear-resistant epoxy coating, which is characterized by comprising the following components in percentage by weight: (1) the component A comprises the following components in percentage by mass: 45-55% of epoxy resin; 3-5% of a toughening agent; 3-5% of a diluent; 5-10% of an accelerant; 2-5% of a silane coupling agent; 20-25% of wear-resistant aggregate; 5-10% of filler; pigment: proper amount; (2) the component B comprises the following components in percentage by mass: 15-20% of m-xylylenediamine (MXDA); 15-20% of isophorone diamine (IPDA); 3-5% of 1, 3-cyclohexyldimethylamine (1, 3-BAC); polyether amine D23025-35%; 25-30% of styrenated phenol; 5-10% of trimethylolpropane triacrylate (TMPTA); the component A and the component B are mixed in a ratio of 1: 5.

Disclosure of Invention

In order to overcome the technical problems, the invention provides an abrasion-resistant coating for the surface of a battery shell and a preparation method thereof.

The technical problems to be solved by the invention are as follows:

the crosslinked network presented after the epoxy resin is cured is easy to cause crazing defects due to too high crosslinking density, the defects are particularly sensitive to stress, and the epoxy acrylate prepared in the prior art has high brittleness, so that the adhesive force of the formed film as a coating to a base material is low.

The purpose of the invention can be realized by the following technical scheme:

the wear-resistant coating for the surface of the battery jar shell comprises the following raw materials in parts by weight: 55-70 parts of composite matrix, 10-20 parts of rigid filler, 0.5-0.8 part of dimethyl silicone oil, 3-5 parts of dioctyl phthalate, 0.1-0.5 part of KH560, 10-15 parts of polyvinyl alcohol and 50-60 parts of water;

the wear-resistant coating for the surface of the battery jar shell is prepared by the following method:

firstly, adding a composite matrix and polyvinyl alcohol into water, heating to 90-110 ℃, and uniformly stirring for 10-15min at the temperature to obtain a mixed solution;

and secondly, transferring the mixed solution into a reaction kettle, heating to 65-70 ℃, uniformly stirring at a rotating speed of 100-150r/min, adding dimethyl silicone oil, continuously stirring for 30min, then cooling to 30-35 ℃, adding dioctyl phthalate, continuously stirring for 1h, performing ultrasonic treatment for 1.5h, controlling the power of the ultrasonic treatment to be 50-60W, adding rigid filler and KH560 after the ultrasonic treatment is finished, and uniformly stirring for 2h to obtain the wear-resistant coating for the surface of the battery shell.

Further, the composite matrix is made by the following method:

step S1, adding bisphenol A into a three-neck flask, adding epichlorohydrin, introducing nitrogen, heating in a water bath at 35-50 ℃, stirring at a constant speed of 120r/min at 100-, reacting for 2 hours at the temperature, washing for 3 times by using deionized water, standing for layering, collecting an organic phase, distilling under reduced pressure until no fraction appears, preparing a resin matrix, controlling the weight ratio of bisphenol A to epichlorohydrin to be 1:5, the weight ratio of bisphenol A to 1, 6-hexamethylene diisocyanate to be 3: 1, and the weight ratio of bisphenol A to 20% sodium hydroxide solution to be 3: 1.5-2;

step S2, adding succinic anhydride into a three-neck flask, uniformly stirring at a rotation speed of 100-; transferring the resin matrix prepared in the step S1 to a reaction kettle, heating to 50-70 ℃, uniformly stirring at a rotating speed of 150 plus 200r/min, dropwise adding the product A, adding N, N-dimethylbenzylamine after dropwise adding, reacting at the temperature until the acid value is zero to prepare a reaction liquid, adding hydroquinone into the reaction liquid, dropwise adding a second mixed liquid, controlling the dropwise adding time to be 10min, uniformly stirring after dropwise adding, sampling every 30min to measure the acid value, stopping the reaction until the acid value is lower than 5mgKOH/g, discharging to prepare a composite matrix, controlling the dosage of succinic anhydride to be one third of the weight of the first mixed liquid, and controlling the weight ratio of the product A, the resin matrix, the N, N-dimethylbenzylamine and the hydroquinone to be 3: 10: 0.003-0.005: 0.001.

Further, in step S2, the first mixed solution is formed by mixing polyglycol and triethylamine in a medium weight ratio of 1: 1, and the second mixed solution is formed by mixing methyl methacrylate and N, N-dimethylbenzylamine in a weight ratio of 1000: 1.

The brittleness of the epoxy acrylate prepared in the prior art is large, so that the adhesion force of the epoxy acrylate as a coating film to a substrate is low, bisphenol A and 1, 6-hexamethylene diisocyanate are mixed in epoxy chloropropane in step S1, the bisphenol A and the 1, 6-hexamethylene diisocyanate react to generate an intermediate, then the intermediate reacts with the epoxy chloropropane under the action of sodium hydroxide to generate a resin matrix, wherein one part of the epoxy chloropropane is used as a solvent, the other part of the epoxy chloropropane can be used as a reactant, succinic anhydride is mixed with polydiol in step S2, the polydiol is capped by the succinic anhydride to prepare a product A, the product A is diester and is used as a chain extender, then the resin matrix is mixed with the product A, N-dimethylbenzylamine is added as a catalyst, the diester is introduced into the resin matrix to prepare a reaction liquid, and then hydroquinone is added as a polymerization inhibitor, and adding methyl methacrylate to terminate the residual epoxy groups to prepare a composite matrix, wherein the composite matrix is polyester modified epoxy acrylate, and the toughness of the composite matrix can be improved by introducing diester, so that the adhesion performance of the formed film layer to the base material is improved.

Further, the rigid filler is made by the following method:

step S11, adding glucose into deionized water, adding sodium carboxymethylcellulose, heating in a water bath at 40-45 ℃ and magnetically stirring for 20min to obtain a mixed solution A, transferring the mixed solution A into a reaction kettle, heating to 180 ℃ and 200 ℃ at a heating rate of 5 ℃/min, reacting for 20h at the temperature, filtering, washing with absolute ethyl alcohol for three times to obtain carbon microspheres, and controlling the weight ratio of the glucose to the sodium carboxymethylcellulose to the deionized water to be 1: 100: 0.02;

step S12, uniformly mixing the carbon microspheres and the silicon powder according to the weight ratio of 1.8-2: 1 to prepare a mixture, then adding ammonium bicarbonate powder, uniformly mixing, heating to 750 ℃ at the heating rate of 15 ℃/min under the argon atmosphere, preserving heat for 4h at the temperature, heating to 1100-1200 ℃ at the heating rate of 10 ℃/min, preserving heat for 2h, cooling to prepare the filler, and controlling the weight ratio of the ammonium bicarbonate powder to the mixture to be 1.5-1.8: 2.

Adding glucose into deionized water, adding sodium carboxymethylcellulose, heating in water bath to obtain carbon microsphere, the grain size of the prepared carbon microspheres can be controlled by controlling the time and the temperature of water bath heating, then the carbon microspheres and silicon powder are mixed according to the weight ratio of 1.8-2: 1 in the second step, then pore-forming agent is added to continue to be calcined in sections, sodium carboxymethyl cellulose can be coated on the surfaces of the carbon microspheres and the silicon powder and can be used as a lubricant, thereby reducing the friction force among the particles formed by the rigid filler SiC, further leading the prepared rigid filler SiC to have higher density, and in the process of continuously heating, the sodium carboxymethylcellulose is decomposed to generate a large number of pores, so that the formed rigid filler SiC generates pores, and the specific surface area of the rigid filler SiC can be further increased by adding ammonium bicarbonate as a pore-forming agent.

A preparation method of a wear-resistant coating for the surface of a battery jar shell comprises the following steps:

firstly, adding a composite matrix and polyvinyl alcohol into water, heating to 90-110 ℃, and uniformly stirring for 10-15min at the temperature to obtain a mixed solution;

and secondly, transferring the mixed solution into a reaction kettle, heating to 65-70 ℃, uniformly stirring at a rotating speed of 100-150r/min, adding dimethyl silicone oil, continuously stirring for 30min, then cooling to 30-35 ℃, adding dioctyl phthalate, continuously stirring for 1h, performing ultrasonic treatment for 1.5h, controlling the power of the ultrasonic treatment to be 50-60W, adding rigid filler and KH560 after the ultrasonic treatment is finished, and uniformly stirring for 2h to obtain the wear-resistant coating for the surface of the battery shell.

The invention has the beneficial effects that:

(1) the invention relates to a wear-resistant coating for the surface of a battery jar shell, which is prepared from a composite matrix, a rigid filler and other raw materials, wherein in the preparation process of the composite matrix, in step S1, bisphenol A and 1, 6-hexamethylene diisocyanate are mixed in epoxy chloropropane, the bisphenol A and the 1, 6-hexamethylene diisocyanate react to generate an intermediate, then the intermediate reacts with the epoxy chloropropane under the action of sodium hydroxide to generate a resin matrix, one part of the epoxy chloropropane is used as a solvent, the other part of the epoxy chloropropane can be used as a reactant, in step S2, succinic anhydride is mixed with polydiol, the polydiol is capped by the succinic anhydride to prepare a product A, the product A is diester and is used as a chain extender, then the resin matrix is mixed with the product A, N-dimethylbenzylamine is added as a catalyst, and the diester is introduced into the resin matrix, preparing a reaction solution, adding hydroquinone serving as a polymerization inhibitor, adding methyl methacrylate to terminate the residual epoxy groups, and preparing a composite matrix, wherein the composite matrix is polyester modified epoxy acrylate, and the toughness of the composite matrix can be improved by introducing diester, so that the adhesion performance of the formed film layer to a base material is improved.

(2) Glucose is added into deionized water in the preparation process of the rigid filler, then sodium carboxymethyl cellulose is added, a carbon microsphere is prepared by water bath heating, the particle size of the prepared carbon microsphere can be controlled by controlling the time and temperature of the water bath heating, then the carbon microsphere and silicon powder are mixed according to the weight ratio of 1.8-2: 1 in the second step, then a pore-forming agent is added for continuous sectional calcination, the sodium carboxymethyl cellulose can be coated on the surfaces of the carbon microsphere and the silicon powder and can serve as a lubricant, so that the friction force between particles formed by the rigid filler SiC is reduced, the prepared rigid filler SiC has high density, the sodium carboxymethyl cellulose is decomposed by itself in the continuous heating process to generate a large amount of pores, the formed rigid filler SiC generates pores by itself, and the ammonium bicarbonate is added as the pore-forming agent, so that the specific surface area of the rigid filler SiC can be further increased, the stability of the prepared coating is improved, and the prepared coating is endowed with excellent wear resistance.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The wear-resistant coating for the surface of the battery jar shell comprises the following raw materials in parts by weight: 55 parts of a composite matrix, 10 parts of rigid filler, 0.5 part of dimethyl silicone oil, 3 parts of dioctyl phthalate, 0.1 part of KH560, 10 parts of polyvinyl alcohol and 50 parts of water;

the wear-resistant coating for the surface of the battery jar shell is prepared by the following method:

firstly, adding a composite matrix and polyvinyl alcohol into water, heating to 90 ℃, and uniformly stirring for 10min at the temperature to obtain a mixed solution;

and secondly, transferring the mixed solution into a reaction kettle, heating to 65 ℃, uniformly stirring at a rotating speed of 100r/min, adding simethicone, continuously stirring for 30min, then cooling to 30 ℃, adding dioctyl phthalate, continuously stirring for 1h, performing ultrasonic treatment for 1.5h, controlling the ultrasonic power to be 50W, adding rigid filler and KH560 after the ultrasonic treatment is finished, and uniformly stirring for 2h to obtain the wear-resistant coating for the surface of the battery shell.

The composite matrix is prepared by the following method:

step S1, adding bisphenol A into a three-neck flask, adding epichlorohydrin, introducing nitrogen, heating in a water bath at 50 ℃, uniformly stirring and dropwise adding 1, 6-hexamethylene diisocyanate at a rotating speed of 100r/min, controlling the dropwise adding time to be 10min, uniformly stirring and reacting for 2h, then heating to 60 ℃, slowly dropwise adding a sodium hydroxide solution with the mass fraction of 20%, controlling the dropwise adding time to be 15min, reacting for 2h at the temperature, washing for 3 times with deionized water, standing and layering, collecting an organic phase, and carrying out reduced pressure distillation until no fraction appears to prepare a resin matrix, wherein the weight ratio of bisphenol A to epichlorohydrin is controlled to be 1:5, the weight ratio of bisphenol A to 1, 6-hexamethylene diisocyanate is 3: 1, and the weight ratio of bisphenol A to 20% of the sodium hydroxide solution is 3: 1.5;

step S2, adding succinic anhydride into a three-neck flask, uniformly stirring at a rotation speed of 100r/min for 10min, heating to 60 ℃, adding the first mixed solution, uniformly stirring, and reacting for 2h to obtain a product A; transferring the resin matrix prepared in the step S1 into a reaction kettle, heating to 50 ℃, uniformly stirring at a rotating speed of 150r/min, dropwise adding the product A, adding N, N-dimethylbenzylamine after dropwise adding, reacting at the temperature until the acid value is zero to prepare a reaction liquid, adding hydroquinone into the reaction liquid, dropwise adding a second mixed liquid, controlling the dropwise adding time to be 10min, uniformly stirring after dropwise adding, sampling every 30min, measuring the acid value, stopping the reaction until the acid value is lower than 5mgKOH/g, discharging, and preparing a composite matrix, wherein the dosage of succinic anhydride is controlled to be one third of the weight of the first mixed liquid, and the weight ratio of the product A, the resin matrix, the N, N-dimethylbenzylamine and the hydroquinone is 3: 10: 0.003: 0.001.

The first mixed solution is formed by mixing polyglycol and triethylamine according to a medium weight ratio of 1: 1, and the second mixed solution is formed by mixing methyl methacrylate and N, N-dimethylbenzylamine according to a weight ratio of 1000: 1.

The rigid filler is prepared by the following method:

step S11, adding glucose into deionized water, adding sodium carboxymethylcellulose, heating in a water bath at 40 ℃ and magnetically stirring for 20min to obtain a mixed solution A, transferring the mixed solution A into a reaction kettle, heating to 180 ℃ at a heating rate of 5 ℃/min, reacting for 20h at the temperature, filtering, washing with absolute ethyl alcohol for three times to obtain carbon microspheres, and controlling the weight ratio of the glucose, the sodium carboxymethylcellulose and the deionized water to be 1: 100: 0.02;

step S12, uniformly mixing the carbon microspheres and the silicon powder according to the weight ratio of 1.8: 1 to prepare a mixture, then adding ammonium bicarbonate powder, uniformly mixing, heating to 750 ℃ at the heating rate of 15 ℃/min under the argon atmosphere, preserving heat for 4h at the temperature, then heating to 1100 ℃ at the heating rate of 10 ℃/min, preserving heat for 2h, cooling to prepare the filler, and controlling the weight ratio of the ammonium bicarbonate powder to the mixture to be 1.5: 2.

Example 2

The wear-resistant coating for the surface of the battery jar shell comprises the following raw materials in parts by weight: 60 parts of a composite matrix, 14 parts of rigid filler, 0.6 part of dimethyl silicone oil, 4 parts of dioctyl phthalate, 0.2 part of KH560, 12 parts of polyvinyl alcohol and 54 parts of water;

the wear-resistant coating for the surface of the battery jar shell is prepared by the following method:

firstly, adding a composite matrix and polyvinyl alcohol into water, heating to 90 ℃, and uniformly stirring for 10min at the temperature to obtain a mixed solution;

and secondly, transferring the mixed solution into a reaction kettle, heating to 65 ℃, uniformly stirring at a rotating speed of 100r/min, adding simethicone, continuously stirring for 30min, then cooling to 30 ℃, adding dioctyl phthalate, continuously stirring for 1h, performing ultrasonic treatment for 1.5h, controlling the ultrasonic power to be 50W, adding rigid filler and KH560 after the ultrasonic treatment is finished, and uniformly stirring for 2h to obtain the wear-resistant coating for the surface of the battery shell.

The composite matrix is prepared by the following method:

step S1, adding bisphenol A into a three-neck flask, adding epichlorohydrin, introducing nitrogen, heating in a water bath at 50 ℃, uniformly stirring and dropwise adding 1, 6-hexamethylene diisocyanate at a rotating speed of 100r/min, controlling the dropwise adding time to be 10min, uniformly stirring and reacting for 2h, then heating to 60 ℃, slowly dropwise adding a sodium hydroxide solution with the mass fraction of 20%, controlling the dropwise adding time to be 15min, reacting for 2h at the temperature, washing for 3 times with deionized water, standing and layering, collecting an organic phase, and carrying out reduced pressure distillation until no fraction appears to prepare a resin matrix, wherein the weight ratio of bisphenol A to epichlorohydrin is controlled to be 1:5, the weight ratio of bisphenol A to 1, 6-hexamethylene diisocyanate is 3: 1, and the weight ratio of bisphenol A to 20% of the sodium hydroxide solution is 3: 1.5;

step S2, adding succinic anhydride into a three-neck flask, uniformly stirring at a rotation speed of 100r/min for 10min, heating to 60 ℃, adding the first mixed solution, uniformly stirring, and reacting for 2h to obtain a product A; transferring the resin matrix prepared in the step S1 into a reaction kettle, heating to 50 ℃, uniformly stirring at a rotating speed of 150r/min, dropwise adding the product A, adding N, N-dimethylbenzylamine after dropwise adding, reacting at the temperature until the acid value is zero to prepare a reaction liquid, adding hydroquinone into the reaction liquid, dropwise adding a second mixed liquid, controlling the dropwise adding time to be 10min, uniformly stirring after dropwise adding, sampling every 30min, measuring the acid value, stopping the reaction until the acid value is lower than 5mgKOH/g, discharging, and preparing a composite matrix, wherein the dosage of succinic anhydride is controlled to be one third of the weight of the first mixed liquid, and the weight ratio of the product A, the resin matrix, the N, N-dimethylbenzylamine and the hydroquinone is 3: 10: 0.003: 0.001.

The first mixed solution is formed by mixing polyglycol and triethylamine according to a medium weight ratio of 1: 1, and the second mixed solution is formed by mixing methyl methacrylate and N, N-dimethylbenzylamine according to a weight ratio of 1000: 1.

The rigid filler is prepared by the following method:

step S11, adding glucose into deionized water, adding sodium carboxymethylcellulose, heating in a water bath at 40 ℃ and magnetically stirring for 20min to obtain a mixed solution A, transferring the mixed solution A into a reaction kettle, heating to 180 ℃ at a heating rate of 5 ℃/min, reacting for 20h at the temperature, filtering, washing with absolute ethyl alcohol for three times to obtain carbon microspheres, and controlling the weight ratio of the glucose, the sodium carboxymethylcellulose and the deionized water to be 1: 100: 0.02;

step S12, uniformly mixing the carbon microspheres and the silicon powder according to the weight ratio of 1.8: 1 to prepare a mixture, then adding ammonium bicarbonate powder, uniformly mixing, heating to 750 ℃ at the heating rate of 15 ℃/min under the argon atmosphere, preserving heat for 4h at the temperature, then heating to 1100 ℃ at the heating rate of 10 ℃/min, preserving heat for 2h, cooling to prepare the filler, and controlling the weight ratio of the ammonium bicarbonate powder to the mixture to be 1.5: 2.

Example 3

The wear-resistant coating for the surface of the battery jar shell comprises the following raw materials in parts by weight: 65 parts of a composite matrix, 18 parts of rigid filler, 0.6 part of dimethyl silicone oil, 4 parts of dioctyl phthalate, 0.4 part of KH560, 14 parts of polyvinyl alcohol and 58 parts of water;

the wear-resistant coating for the surface of the battery jar shell is prepared by the following method:

firstly, adding a composite matrix and polyvinyl alcohol into water, heating to 90 ℃, and uniformly stirring for 10min at the temperature to obtain a mixed solution;

and secondly, transferring the mixed solution into a reaction kettle, heating to 65 ℃, uniformly stirring at a rotating speed of 100r/min, adding simethicone, continuously stirring for 30min, then cooling to 30 ℃, adding dioctyl phthalate, continuously stirring for 1h, performing ultrasonic treatment for 1.5h, controlling the ultrasonic power to be 50W, adding rigid filler and KH560 after the ultrasonic treatment is finished, and uniformly stirring for 2h to obtain the wear-resistant coating for the surface of the battery shell.

The composite matrix is prepared by the following method:

step S1, adding bisphenol A into a three-neck flask, adding epichlorohydrin, introducing nitrogen, heating in a water bath at 50 ℃, uniformly stirring and dropwise adding 1, 6-hexamethylene diisocyanate at a rotating speed of 100r/min, controlling the dropwise adding time to be 10min, uniformly stirring and reacting for 2h, then heating to 60 ℃, slowly dropwise adding a sodium hydroxide solution with the mass fraction of 20%, controlling the dropwise adding time to be 15min, reacting for 2h at the temperature, washing for 3 times with deionized water, standing and layering, collecting an organic phase, and carrying out reduced pressure distillation until no fraction appears to prepare a resin matrix, wherein the weight ratio of bisphenol A to epichlorohydrin is controlled to be 1:5, the weight ratio of bisphenol A to 1, 6-hexamethylene diisocyanate is 3: 1, and the weight ratio of bisphenol A to 20% of the sodium hydroxide solution is 3: 1.5;

step S2, adding succinic anhydride into a three-neck flask, uniformly stirring at a rotation speed of 100r/min for 10min, heating to 60 ℃, adding the first mixed solution, uniformly stirring, and reacting for 2h to obtain a product A; transferring the resin matrix prepared in the step S1 into a reaction kettle, heating to 50 ℃, uniformly stirring at a rotating speed of 150r/min, dropwise adding the product A, adding N, N-dimethylbenzylamine after dropwise adding, reacting at the temperature until the acid value is zero to prepare a reaction liquid, adding hydroquinone into the reaction liquid, dropwise adding a second mixed liquid, controlling the dropwise adding time to be 10min, uniformly stirring after dropwise adding, sampling every 30min, measuring the acid value, stopping the reaction until the acid value is lower than 5mgKOH/g, discharging, and preparing a composite matrix, wherein the dosage of succinic anhydride is controlled to be one third of the weight of the first mixed liquid, and the weight ratio of the product A, the resin matrix, the N, N-dimethylbenzylamine and the hydroquinone is 3: 10: 0.003: 0.001.

The first mixed solution is formed by mixing polyglycol and triethylamine according to a medium weight ratio of 1: 1, and the second mixed solution is formed by mixing methyl methacrylate and N, N-dimethylbenzylamine according to a weight ratio of 1000: 1.

The rigid filler is prepared by the following method:

step S11, adding glucose into deionized water, adding sodium carboxymethylcellulose, heating in a water bath at 40 ℃ and magnetically stirring for 20min to obtain a mixed solution A, transferring the mixed solution A into a reaction kettle, heating to 180 ℃ at a heating rate of 5 ℃/min, reacting for 20h at the temperature, filtering, washing with absolute ethyl alcohol for three times to obtain carbon microspheres, and controlling the weight ratio of the glucose, the sodium carboxymethylcellulose and the deionized water to be 1: 100: 0.02;

step S12, uniformly mixing the carbon microspheres and the silicon powder according to the weight ratio of 1.8: 1 to prepare a mixture, then adding ammonium bicarbonate powder, uniformly mixing, heating to 750 ℃ at the heating rate of 15 ℃/min under the argon atmosphere, preserving heat for 4h at the temperature, then heating to 1100 ℃ at the heating rate of 10 ℃/min, preserving heat for 2h, cooling to prepare the filler, and controlling the weight ratio of the ammonium bicarbonate powder to the mixture to be 1.5: 2.

Example 4

The wear-resistant coating for the surface of the battery jar shell comprises the following raw materials in parts by weight: 70 parts of composite matrix, 20 parts of rigid filler, 0.8 part of dimethyl silicone oil, 5 parts of dioctyl phthalate, 0.5 part of KH560, 15 parts of polyvinyl alcohol and 60 parts of water;

the wear-resistant coating for the surface of the battery jar shell is prepared by the following method:

firstly, adding a composite matrix and polyvinyl alcohol into water, heating to 90 ℃, and uniformly stirring for 10min at the temperature to obtain a mixed solution;

and secondly, transferring the mixed solution into a reaction kettle, heating to 65 ℃, uniformly stirring at a rotating speed of 100r/min, adding simethicone, continuously stirring for 30min, then cooling to 30 ℃, adding dioctyl phthalate, continuously stirring for 1h, performing ultrasonic treatment for 1.5h, controlling the ultrasonic power to be 50W, adding rigid filler and KH560 after the ultrasonic treatment is finished, and uniformly stirring for 2h to obtain the wear-resistant coating for the surface of the battery shell.

The composite matrix is prepared by the following method:

step S1, adding bisphenol A into a three-neck flask, adding epichlorohydrin, introducing nitrogen, heating in a water bath at 50 ℃, uniformly stirring and dropwise adding 1, 6-hexamethylene diisocyanate at a rotating speed of 100r/min, controlling the dropwise adding time to be 10min, uniformly stirring and reacting for 2h, then heating to 60 ℃, slowly dropwise adding a sodium hydroxide solution with the mass fraction of 20%, controlling the dropwise adding time to be 15min, reacting for 2h at the temperature, washing for 3 times with deionized water, standing and layering, collecting an organic phase, and carrying out reduced pressure distillation until no fraction appears to prepare a resin matrix, wherein the weight ratio of bisphenol A to epichlorohydrin is controlled to be 1:5, the weight ratio of bisphenol A to 1, 6-hexamethylene diisocyanate is 3: 1, and the weight ratio of bisphenol A to 20% of the sodium hydroxide solution is 3: 1.5;

step S2, adding succinic anhydride into a three-neck flask, uniformly stirring at a rotation speed of 100r/min for 10min, heating to 60 ℃, adding the first mixed solution, uniformly stirring, and reacting for 2h to obtain a product A; transferring the resin matrix prepared in the step S1 into a reaction kettle, heating to 50 ℃, uniformly stirring at a rotating speed of 150r/min, dropwise adding the product A, adding N, N-dimethylbenzylamine after dropwise adding, reacting at the temperature until the acid value is zero to prepare a reaction liquid, adding hydroquinone into the reaction liquid, dropwise adding a second mixed liquid, controlling the dropwise adding time to be 10min, uniformly stirring after dropwise adding, sampling every 30min, measuring the acid value, stopping the reaction until the acid value is lower than 5mgKOH/g, discharging, and preparing a composite matrix, wherein the dosage of succinic anhydride is controlled to be one third of the weight of the first mixed liquid, and the weight ratio of the product A, the resin matrix, the N, N-dimethylbenzylamine and the hydroquinone is 3: 10: 0.003: 0.001.

The first mixed solution is formed by mixing polyglycol and triethylamine according to a medium weight ratio of 1: 1, and the second mixed solution is formed by mixing methyl methacrylate and N, N-dimethylbenzylamine according to a weight ratio of 1000: 1.

The rigid filler is prepared by the following method:

step S11, adding glucose into deionized water, adding sodium carboxymethylcellulose, heating in a water bath at 40 ℃ and magnetically stirring for 20min to obtain a mixed solution A, transferring the mixed solution A into a reaction kettle, heating to 180 ℃ at a heating rate of 5 ℃/min, reacting for 20h at the temperature, filtering, washing with absolute ethyl alcohol for three times to obtain carbon microspheres, and controlling the weight ratio of the glucose, the sodium carboxymethylcellulose and the deionized water to be 1: 100: 0.02;

step S12, uniformly mixing the carbon microspheres and the silicon powder according to the weight ratio of 1.8: 1 to prepare a mixture, then adding ammonium bicarbonate powder, uniformly mixing, heating to 750 ℃ at the heating rate of 15 ℃/min under the argon atmosphere, preserving heat for 4h at the temperature, then heating to 1100 ℃ at the heating rate of 10 ℃/min, preserving heat for 2h, cooling to prepare the filler, and controlling the weight ratio of the ammonium bicarbonate powder to the mixture to be 1.5: 2.

Comparative example 1

This comparative example compares to example 1 with an epoxy resin instead of the composite matrix.

Comparative example 2

This comparative example compares to example 1 with nano-silicon carbide replacing the rigid filler.

Comparative example 3

The comparative example is a wear-resistant coating in the market.

The abrasion resistance of examples 1 to 4 and comparative examples 1 to 3 was measured, and the results are shown in the following table:

an alcohol wear-resistance tester is used, a 500g weight is added, 99.7% alcohol is soaked in white cotton cloth, and the coating is rubbed back and forth, so that the frequency of the coating beginning to be damaged is increased.

	Example 1	Example 2	Example 3	Example 4	Comparative example 1	Comparative example 2	Comparative example 3
								Number of times	720	730	725	725	650	600	580

It can be seen from the above table that examples 1-4 exhibited failure at 720-; therefore, methyl methacrylate is added to seal the residual epoxy groups to prepare a composite matrix, the composite matrix is polyester modified epoxy acrylate, the toughness of the composite matrix can be improved by introducing diester, the adhesion performance of a formed film layer to a base material is improved, and ammonium bicarbonate is used as a pore-forming agent, so that the specific surface area of the rigid filler SiC can be further increased, the stability of the prepared coating is improved, and the prepared coating is endowed with excellent wear resistance.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.

Claims (5)

1. The wear-resistant coating for the surface of the battery jar shell is characterized by comprising the following raw materials in parts by weight: 55-70 parts of composite matrix, 10-20 parts of rigid filler, 0.5-0.8 part of dimethyl silicone oil, 3-5 parts of dioctyl phthalate, 0.1-0.5 part of KH560, 10-15 parts of polyvinyl alcohol and 50-60 parts of water;

the wear-resistant coating for the surface of the battery jar shell is prepared by the following method:

firstly, adding a composite matrix and polyvinyl alcohol into water, heating to 90-110 ℃, and uniformly stirring for 10-15min at the temperature to obtain a mixed solution;

and secondly, transferring the mixed solution into a reaction kettle, heating to 65-70 ℃, uniformly stirring at a rotating speed of 100-150r/min, adding dimethyl silicone oil, continuously stirring for 30min, then cooling to 30-35 ℃, adding dioctyl phthalate, continuously stirring for 1h, performing ultrasonic treatment for 1.5h, controlling the power of the ultrasonic treatment to be 50-60W, adding rigid filler and KH560 after the ultrasonic treatment is finished, and uniformly stirring for 2h to obtain the wear-resistant coating for the surface of the battery shell.

2. The wear-resistant coating for the surface of the battery jar shell as claimed in claim 1, wherein the composite matrix is prepared by the following method:

step S1, adding bisphenol A into a three-neck flask, adding epichlorohydrin, introducing nitrogen, heating in a water bath at 35-50 ℃, stirring at a constant speed of 120r/min at 100-, reacting for 2 hours at the temperature, washing for 3 times by using deionized water, standing for layering, collecting an organic phase, distilling under reduced pressure until no fraction appears, preparing a resin matrix, controlling the weight ratio of bisphenol A to epichlorohydrin to be 1:5, the weight ratio of bisphenol A to 1, 6-hexamethylene diisocyanate to be 3: 1, and the weight ratio of bisphenol A to 20% sodium hydroxide solution to be 3: 1.5-2;

step S2, adding succinic anhydride into a three-neck flask, uniformly stirring at a rotation speed of 100-; transferring the resin matrix prepared in the step S1 to a reaction kettle, heating to 50-70 ℃, uniformly stirring at a rotating speed of 150 plus 200r/min, dropwise adding the product A, adding N, N-dimethylbenzylamine after dropwise adding, reacting at the temperature until the acid value is zero to prepare a reaction liquid, adding hydroquinone into the reaction liquid, dropwise adding a second mixed liquid, controlling the dropwise adding time to be 10min, uniformly stirring after dropwise adding, sampling every 30min to measure the acid value, stopping the reaction until the acid value is lower than 5mgKOH/g, discharging to prepare a composite matrix, controlling the dosage of succinic anhydride to be one third of the weight of the first mixed liquid, and controlling the weight ratio of the product A, the resin matrix, the N, N-dimethylbenzylamine and the hydroquinone to be 3: 10: 0.003-0.005: 0.001.

3. The wear-resistant coating for the surface of the battery jar shell as claimed in claim 2, wherein in the step S2, the first mixed solution is formed by mixing polyglycol and triethylamine according to a medium weight ratio of 1: 1, and the second mixed solution is formed by mixing methyl methacrylate and N, N-dimethylbenzylamine according to a weight ratio of 1000: 1.

4. The wear-resistant coating for the surface of the battery shell as claimed in claim 1, wherein the rigid filler is prepared by the following method:

step S11, adding glucose into deionized water, adding sodium carboxymethylcellulose, heating in a water bath at 40-45 ℃ and magnetically stirring for 20min to obtain a mixed solution A, transferring the mixed solution A into a reaction kettle, heating to 180 ℃ and 200 ℃ at a heating rate of 5 ℃/min, reacting for 20h at the temperature, filtering, washing with absolute ethyl alcohol for three times to obtain carbon microspheres, and controlling the weight ratio of the glucose to the sodium carboxymethylcellulose to the deionized water to be 1: 100: 0.02;

step S12, uniformly mixing the carbon microspheres and the silicon powder according to the weight ratio of 1.8-2: 1 to prepare a mixture, then adding ammonium bicarbonate powder, uniformly mixing, heating to 750 ℃ at the heating rate of 15 ℃/min under the argon atmosphere, preserving heat for 4h at the temperature, heating to 1100-1200 ℃ at the heating rate of 10 ℃/min, preserving heat for 2h, cooling to prepare the filler, and controlling the weight ratio of the ammonium bicarbonate powder to the mixture to be 1.5-1.8: 2.

5. The preparation method of the wear-resistant coating for the surface of the battery jar shell as claimed in claim 1, characterized by comprising the following steps:

firstly, adding a composite matrix and polyvinyl alcohol into water, heating to 90-110 ℃, and uniformly stirring for 10-15min at the temperature to obtain a mixed solution;

and secondly, transferring the mixed solution into a reaction kettle, heating to 65-70 ℃, uniformly stirring at a rotating speed of 100-150r/min, adding dimethyl silicone oil, continuously stirring for 30min, then cooling to 30-35 ℃, adding dioctyl phthalate, continuously stirring for 1h, performing ultrasonic treatment for 1.5h, controlling the power of the ultrasonic treatment to be 50-60W, adding rigid filler and KH560 after the ultrasonic treatment is finished, and uniformly stirring for 2h to obtain the wear-resistant coating for the surface of the battery shell.