CN114284497A - Water-based self-healing adhesive and preparation method thereof - Google Patents
Water-based self-healing adhesive and preparation method thereof Download PDFInfo
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- CN114284497A CN114284497A CN202111365542.5A CN202111365542A CN114284497A CN 114284497 A CN114284497 A CN 114284497A CN 202111365542 A CN202111365542 A CN 202111365542A CN 114284497 A CN114284497 A CN 114284497A
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- polyacrylic acid
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 54
- 239000000853 adhesive Substances 0.000 title claims abstract description 53
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- 238000002360 preparation method Methods 0.000 title abstract description 19
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- -1 acryloyl glycinamide hydrochloride Chemical compound 0.000 claims description 8
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
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- 230000009471 action Effects 0.000 claims description 3
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 claims description 2
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- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 26
- 229910052710 silicon Inorganic materials 0.000 abstract description 26
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
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- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a water-based self-healing adhesive and a preparation method thereof. The adhesive can be used as a polymer adhesive for assembling a silicon negative electrode of a battery to relieve huge volume change in the using process of the adhesive. In the curing process, the high reactivity of the amino group and the epoxy group reacts under a mild condition to generate covalent crosslinking, and the covalent crosslinking is coated around the silicon particles to inhibit the expansion of the silicon particles. Meanwhile, the silicon composite material has good flexibility and elasticity, can adapt to volume change in an electrical cycle process through elasticity change of a molecular chain, can reversibly stretch and contract in a silicon volume expansion process, and can provide an elastic constraint effect for silicon expansion.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a water-based self-healing adhesive and a preparation method thereof.
Background
With the increasing demand for high energy density energy storage devices, lithium ion batteries have attracted renewed interest in researchers by virtue of their excellent specific capacities. Compared with other materials, the silicon has excellent specific mass capacity and lower lithiation/delithiation voltage, and is a high-efficiency negative electrode material for improving the energy density of the lithium ion battery. However, silicon undergoes a very large change in volume during cycling, resulting in different degrees of pulverization of active materials and repeated growth of solid electrolyte interface films (SEI), which largely limits its wide application.
In order to solve the above problems and to facilitate commercial application of silicon-based negative electrode lithium ion batteries, various polymer binders have been explored. The water-based polyacrylic acid binder of the silicon negative electrode is firstly researched by Magasinski and colleagues, and the silicon-based negative electrode containing the polyacrylic acid binder is found to show relatively stable performance. The adhesive is a synthetic linear polymer formed by homopolymerizing acrylic acid, and is soluble in water and ethanol.
With the development of the technology, the single polyacrylic acid adhesive can not meet the requirements of the silicon-based negative electrode. The pure polyacrylic acid adhesive has high modulus, poor toughness, lacks multiple action sites with active materials, is easy to generate irreversible slippage, and has failure of a silicon-based negative electrode. To further expand the applicability of polyacrylic acid binders to silicon-based anodes, it is an important construction strategy to develop three-dimensionally crosslinked polyacrylic acid-based binders with self-healing properties to provide strong interactions with silicon particles. In the invention, a chemical crosslinking technology is adopted to construct a polyacrylic acid-based three-dimensional network. The adhesive consists of a mixed solution of epoxidized rubber emulsion and aminated polyacrylic acid, and belongs to one of water-soluble adhesives.
Disclosure of Invention
The invention aims to overcome the defects of the prior charge-discharge cycle stability technology of a lithium ion battery and provide a water-based self-healing adhesive and a preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows: an aqueous self-healing adhesive, characterized in that: the adhesive comprises a mixed solution of an epoxidized rubber emulsion and an aminated polyacrylic acid solution.
Further, the method comprises the following steps of; the epoxidation degree of the epoxidized rubber in the epoxidized rubber emulsion is 5-90 mol%, the mass percent concentration of the epoxidized rubber emulsion is 5-65%, and the mass percent concentration of the aminated polyacrylic acid solution is 0.1-10%.
Further, the method comprises the following steps of; the epoxidized rubber in the epoxidized rubber emulsion is selected from one or more of epoxidized natural rubber latex, epoxidized nitrile rubber latex, epoxidized hydrogenated nitrile rubber latex, epoxidized styrene-butadiene rubber latex, epoxidized polyisoprene latex, epoxidized isoprene rubber latex, epoxidized butadiene rubber latex and epoxidized polyurethane latex.
Further, the method comprises the following steps of; the aminated polyacrylic acid in the aminated polyacrylic acid solution is generated by the reaction of an amination reagent and polyacrylic acid under the action of an initiator;
the number average relative molecular weight of the polyacrylic acid is 20000-450000 g/mol;
the amination reagent is selected from one or more of glycinamide hydrochloride, acryloyl glycinamide hydrochloride, glutamine hydrochloride, acetylglutamide hydrochloride and aminosilane coupling agent, the molar ratio of the amination reagent to polyacrylic acid is 0.2-1:1, and the molar ratio of the polyacrylic acid to the initiator is 1: 0.1-1.
Further, the method comprises the following steps of; the polyacrylic acid has a number average relative molecular weight of 25000 g/mol.
Further, the method comprises the following steps of; the initiator is prepared from carbodiimide hydrochloride and N-hydroxysuccinimide according to a molar ratio of 1:1 are mixed.
Further, the method comprises the following steps of; the mass ratio of the epoxidized rubber in the epoxidized rubber emulsion to the aminated polyacrylic acid in the aminated polyacrylic acid solution is 0.1-1: 0.1-1.
The other technical scheme of the invention is as follows: the preparation method of the water-based self-healing adhesive is characterized by comprising the following steps:
1) preparing an epoxidized rubber emulsion, namely mixing and stirring rubber latex, deionized water and an emulsifier, then adding an epoxidation reagent into the emulsion, carrying out epoxidation reaction for 1-12h at 40-60 ℃, and dialyzing the product for 24h by using the deionized water to obtain the epoxidized rubber emulsion;
2) preparing aminated polyacrylic acid, namely dissolving polyacrylic acid in deionized water to form polyacrylic acid solution, wherein the mass concentration of the polyacrylic acid solution is 0.5-3%, adding an alkali solution into the polyacrylic acid solution to adjust the pH value to 5-6, adding an initiator carbodiimide hydrochloride and N-hydroxysuccinimide into the polyacrylic acid solution, uniformly stirring, adding an amination reagent into the mixed solution, continuously stirring at room temperature for reaction for 12-36 hours, dialyzing the obtained product with deionized water, and freeze-drying to obtain the aminated polyacrylic acid;
3) dissolving the prepared aminated polyacrylic acid in water, adding the epoxidized rubber emulsion prepared in the step 1) into the aminated polyacrylic acid solution, and uniformly stirring at normal temperature to obtain the water-based self-healing adhesive, wherein the mass ratio of the aminated polyacrylic acid to the epoxidized rubber in the epoxidized rubber emulsion is 0.1-1: 0.1-1.
Further, the method comprises the following steps of; the rubber latex is selected from one or more of natural rubber latex, nitrile rubber latex, hydrogenated nitrile rubber latex, styrene-butadiene rubber latex, polyisoprene latex, isoprene rubber latex, butadiene rubber latex and polyurethane latex.
Further, the method comprises the following steps of; diluting the rubber latex in the step 1) to 30 wt% by deionized water, and adding 10g of emulsifier into 1mol of raw rubber, wherein the molar ratio of the rubber latex to the epoxidizing agent is 1: 1-5.
The epoxidation reagent is a mixed solution of formic acid and hydrogen peroxide, and the molar ratio of the formic acid to the hydrogen peroxide is 1: 1-10.
The invention has the beneficial effects that:
1) the adhesive can be used as a polymer adhesive for assembling a silicon negative electrode of a battery to relieve huge volume change in the using process of the adhesive. In the curing process, the high reactivity of the amino group and the epoxy group reacts under a mild condition to generate covalent crosslinking, and the covalent crosslinking is coated around the silicon particles to inhibit the expansion of the silicon particles. Meanwhile, the silicon composite material has good flexibility and elasticity, can adapt to volume change in an electrical cycle process through elasticity change of a molecular chain, can reversibly stretch and contract in a silicon volume expansion process, and can provide an elastic constraint effect for silicon expansion.
2) The system has strong double hydrogen bond function and self-healing performance. The binding power between the battery binder and the active chemical substance and the current collector is enhanced, the conductivity of the electrode tube of the lithium ion battery and the stability of the network are ensured, the problems that an SEI film is continuously generated and is continuously damaged in the charging and discharging process of the battery are improved, and the long-cycle performance of the battery is excellent.
3) In addition, the self-repairing water-based adhesive is suitable for preparing electric conduction heat conduction materials, and has important application value in the fields of electronic skin, artificial muscles, coatings and the like. Compared with the market water-based adhesive, the adhesive has more excellent mechanical property, self-healing property under high deformation, modulus which is easy to regulate and control, and excellent aging resistance and adhesive property, and is an environment-friendly self-healing adhesive with practical value.
Drawings
FIG. 1 is SEM images of fracture surfaces of a polyacrylic acid binder electrode of comparative example 1 and a binder electrode of example 2 before and after 50 charge-discharge cycles.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the scope of protection is not limited thereto.
Example 1:
preparation of epoxidized natural rubber emulsion: 5667g of natural rubber latex was mixed with 5667g of deionized water and 500g of an emulsifier alkylphenol polyoxyethylene (OP-10) at 50 ℃ with stirring, then the pH of the mixed emulsion was neutralized to 7 with 10% by volume of an aqueous formic acid solution, and finally 3162mL of 30% by volume of an aqueous formic acid solution and 8500g H were added dropwise2O2And keeping the mixture at 50 ℃ for stirring and reacting for 5 hours to obtain emulsion with the epoxidation degree of 30 mol%, dialyzing the product by a dialysis bag (MWCO 7000) for 24 hours to remove small molecular impurities, and finally obtaining the epoxidized natural rubber emulsion with the mass fraction of 15%.
Preparation of aminated polyacrylic acid: 300g of polyacrylic acid (PAA) was dissolved in 9700g of deionized water, and then the solution pH was adjusted to 6 using 1mol/L of sodium hydroxide, and then 30g of carbodiimide hydrochloride (EDC) and 18g N-hydroxysuccinimide (NHS) were added to the solution and stirred at normal temperature. Finally, 23g of glycylamine hydrochloride was added to the mixed solution, and the reaction was continued with stirring at room temperature for 24 hours. Dialyzing the product with dialysis bag (MWCO 7000) for 24h to remove small molecule impurities, and freeze-drying to obtain aminated polyacrylic acid.
Preparing an adhesive: dissolving 1g of aminated polyacrylic acid in 25.6667g of deionized water, adding 6.6667g of epoxidized natural rubber emulsion into the aminated polyacrylic acid solution, and uniformly stirring at normal temperature to obtain the aminated polyacrylic acid/epoxidized natural rubber adhesive.
Example 2:
preparation of epoxidized natural rubber emulsion: 5667g of natural rubber latex was mixed with 5667g of deionized water and 500g of emulsifier OP-10 at 50 ℃ with stirring, the pH of the mixed emulsion was then neutralized to 7 with 10% by volume aqueous formic acid, and finally 3162mL of 30% by volume aqueous formic acid and 8500g H were added dropwise2O2And keeping the mixture at 50 ℃ for stirring and reacting for 5 hours to obtain emulsion with the epoxidation degree of 30%, dialyzing the product by using a dialysis bag (MWCO 7000) for 24 hours to remove small molecular impurities, and finally obtaining the epoxidized natural rubber emulsion with the mass fraction of 15%.
Preparation of aminated polyacrylic acid: 300g of PAA was dissolved in 9700g of deionized water, and then the solution pH was adjusted to 6 using 1mol/L sodium hydroxide, and then 30g of EDC and 18g of NHS were added to the solution and stirred at normal temperature. Finally, 23g of glycylamine hydrochloride was added to the mixed solution, and the reaction was continued with stirring at room temperature for 24 hours. Dialyzing the product with dialysis bag (MWCO 7000) for 24h to remove small molecule impurities, and freeze-drying to obtain aminated polyacrylic acid.
Preparing an adhesive: dissolving 1g of aminated polyacrylic acid in 25.6667g of deionized water, adding 6.6667g of epoxidized natural rubber emulsion into the aminated polyacrylic acid solution, and uniformly stirring at normal temperature to obtain the aminated polyacrylic acid/epoxidized natural rubber adhesive.
Example 3:
preparation of epoxidized natural rubber emulsion: 5667g of natural rubber latex was mixed with 5667g of deionized water and 500g of emulsifier OP-10 at 50 ℃ with stirring, the pH of the mixed emulsion was then neutralized to 7 with 10% by volume aqueous formic acid, and finally 3162mL of 30% by volume aqueous formic acid and 8500g H were added dropwise2O2And keeping the mixture at 50 ℃ for stirring and reacting for 5 hours to obtain emulsion with the epoxidation degree of 30%, dialyzing the product by using a dialysis bag (MWCO 7000) for 24 hours to remove small molecular impurities, and finally obtaining the epoxidized natural rubber emulsion with the mass fraction of 15%.
Preparation of aminated polyacrylic acid: 300g of PAA was dissolved in 9700g of deionized water, and then the solution pH was adjusted to 6 using 1mol/L sodium hydroxide, and then 30g of EDC and 18g of NHS were added to the solution and stirred at normal temperature. Finally, 23g of glycylamine hydrochloride was added to the mixed solution, and the reaction was continued with stirring at room temperature for 24 hours. Dialyzing the product with dialysis bag (MWCO 7000) for 24h to remove small molecule impurities, and freeze-drying to obtain aminated polyacrylic acid.
Preparing an adhesive: dissolving 1g of aminated polyacrylic acid in 25.6667g of deionized water, adding 6.6667g of epoxidized natural rubber emulsion into the aminated polyacrylic acid solution, and uniformly stirring at normal temperature to obtain the aminated polyacrylic acid/epoxidized natural rubber adhesive.
Example 4:
preparation of epoxidized polyisoprene emulsion: mixing and stirring 5667g of polyisoprene latex, 5667g of deionized water and 500g of emulsifier OP-10 at 50 ℃, then neutralizing the pH value of the mixed emulsion to 7 by using 10 volume percent of formic acid aqueous solution, and finally dropwise adding 3162mL of 30 volume percent formic acid aqueous solution and 8500g H2O2And keeping the temperature at 50 ℃ for stirring and reacting for 5 hours to obtain emulsion with the epoxidation degree of 30%, dialyzing the product by a dialysis bag (MWCO 7000) for 24 hours to remove small molecular impurities, and finally obtaining the epoxidized polyisoprene emulsion with the mass fraction of 15%.
Preparation of aminated polyacrylic acid: 300g of PAA was dissolved in 9700g of deionized water, and then the solution pH was adjusted to 6 using 1mol/L sodium hydroxide, and then 30g of EDC and 18g of NHS were added to the solution and stirred at normal temperature. Finally, 23g of glycylamine hydrochloride was added to the mixed solution, and the reaction was continued with stirring at room temperature for 24 hours. Dialyzing the product with dialysis bag (MWCO 7000) for 24h to remove small molecule impurities, and freeze-drying to obtain aminated polyacrylic acid.
Preparing an adhesive: dissolving 1g of aminated polyacrylic acid in 25.6667g of deionized water, adding 6.6667g of epoxidized polyisoprene emulsion into the aminated polyacrylic acid solution, and uniformly stirring at normal temperature to obtain the aminated polyacrylic acid/epoxidized polyisoprene adhesive.
Example 5:
preparation of epoxidized polyisoprene emulsion: mixing and stirring 5667g of polyisoprene latex, 5667g of deionized water and 500g of emulsifier OP-10 at 50 ℃, then neutralizing the pH value of the mixed emulsion to 7 by using 10 volume percent of formic acid aqueous solution, and finally dropwise adding 3162mL of 30 volume percent formic acid aqueous solution and 8500g H2O2And keeping the temperature at 50 ℃ for stirring and reacting for 5 hours to obtain emulsion with the epoxidation degree of 30%, dialyzing the product by a dialysis bag (MWCO 7000) for 24 hours to remove small molecular impurities, and finally obtaining the epoxidized polyisoprene emulsion with the mass fraction of 15%.
Preparation of aminated polyacrylic acid: 300g of PAA was dissolved in 9700g of deionized water, and then the solution pH was adjusted to 6 using 1mol/L sodium hydroxide, and then 30g of EDC and 18g of NHS were added to the solution and stirred at normal temperature. Finally, 23g of glycylamine hydrochloride was added to the mixed solution, and the reaction was continued with stirring at room temperature for 24 hours. Dialyzing the product with dialysis bag (MWCO 7000) for 24h to remove small molecule impurities, and freeze-drying to obtain aminated polyacrylic acid.
Preparing an adhesive: dissolving 1g of aminated polyacrylic acid in 25.6667g of deionized water, adding 6.6667g of epoxidized polyisoprene emulsion into the aminated polyacrylic acid solution, and uniformly stirring at normal temperature to obtain the aminated polyacrylic acid/epoxidized polyisoprene adhesive.
Example 6:
epoxidized polyisoprenePreparation of the olefin emulsion: mixing and stirring 5667g of polyisoprene latex, 5667g of deionized water and 500g of emulsifier OP-10 at 50 ℃, then neutralizing the pH value of the mixed emulsion to 7 by using 10 volume percent of formic acid aqueous solution, and finally dropwise adding 3162mL of 30 volume percent formic acid aqueous solution and 8500g H2O2And keeping the temperature at 50 ℃ for stirring and reacting for 5 hours to obtain emulsion with the epoxidation degree of 30%, dialyzing the product by a dialysis bag (MWCO 7000) for 24 hours to remove small molecular impurities, and finally obtaining the epoxidized polyisoprene emulsion with the mass fraction of 15%.
Preparation of aminated polyacrylic acid: 300g of PAA was dissolved in 9700g of deionized water, and then the solution pH was adjusted to 6 using 1mol/L sodium hydroxide, and then 30g of EDC and 18g of NHS were added to the solution and stirred at normal temperature. Finally, 23g of glycylamine hydrochloride was added to the mixed solution, and the reaction was continued with stirring at room temperature for 24 hours. Dialyzing the product with dialysis bag (MWCO 7000) for 24h to remove small molecule impurities, and freeze-drying to obtain aminated polyacrylic acid.
Preparing an adhesive: dissolving 1g of aminated polyacrylic acid in 25.6667g of deionized water, adding 6.6667g of epoxidized polyisoprene emulsion into the aminated polyacrylic acid solution, and uniformly stirring at normal temperature to obtain the aminated polyacrylic acid/epoxidized polyisoprene adhesive.
Test experiments:
the adhesives prepared in examples 1-6 were each prepared as polymer films for tensile testing, see table 1, by the method of: pouring the adhesive into a tetrafluoroethylene mold, and drying for 12h in a vacuum oven at 80 ℃ to obtain the crosslinked polymer film.
The binders prepared in examples 1 to 6 were used to prepare silicon anodes and lithium ion half cell assemblies, respectively:
the preparation method of the lithium ion half-cell silicon anode comprises the following steps: uniformly mixing silicon, an adhesive and a Super P conductive agent according to a mass ratio of 6:2:2, diluting the mixture by using deionized water as a solvent, fully grinding the mixture to obtain uniform slurry, wherein the mass concentration of the slurry is 6%, uniformly scraping the slurry on a copper current collector by using a doctor blade, and uniformly scraping the silicon on the copper current collectorThe loading capacity is 0.8-0.9mg/cm2. After drying at 80 ℃ for 12 hours in an oven, the electrodes were cut into small 12mm diameter disks using a die cutter, weighed and dried further in a vacuum oven at 80 ℃ for 12 hours to give silicon anodes. 1mol of lithium hexafluorophosphate was dissolved in an electrolyte solvent of ethylene carbonate/diethyl carbonate/ethyl methyl carbonate (volume ratio 1:1:1) to prepare an electrolyte solution having a lithium hexafluorophosphate concentration of 1mol/L, and 10 wt% of fluoroethylene carbonate (FEC) was added to the electrolyte solution, while a lithium metal sheet was used as a counter electrode, polypropylene PP-2500 was used as a separator, and the resultant was placed in a glove box (H) filled with argon gas2O，O2Content less than or equal to 0.01), assembling the CR2032 coin-type battery, standing the obtained battery for 48h, and then carrying out electrochemical test, wherein the test results are shown in Table 1.
Comparative example 1
Assembly of silicon anodes and lithium ion half cells was prepared using polyacrylic acid with a molecular weight of 250000g/mol as binder:
the preparation method of the lithium ion half-cell silicon anode comprises the following steps: uniformly mixing silicon, polyacrylic acid and Super P conductive agent according to the mass ratio of 6:2:2, diluting with deionized water as a solvent, fully grinding to obtain uniform slurry, wherein the mass concentration of the slurry is 6%, uniformly scraping and covering the slurry on a copper current collector by using a doctor blade, and the loading capacity of the silicon is 0.8-0.9mg/cm2. After drying at 80 ℃ for 12 hours in an oven, the electrodes were cut into small 12mm diameter disks using a die cutter, weighed and dried further in a vacuum oven at 80 ℃ for 12 hours to give silicon anodes. 1mol of lithium hexafluorophosphate was dissolved in an electrolyte solvent of ethylene carbonate/diethyl carbonate/ethyl methyl carbonate (volume ratio 1:1:1, concentration: 1mol/L), and 10 wt% of FEC was added to the electrolyte solution while using a metallic lithium plate as a counter electrode and polypropylene PP-2500 as a separator, in a glove box (H) filled with argon gas2O，O2Content less than or equal to 0.01), assembling the CR2032 coin-type battery, standing the obtained battery for 48h, and then carrying out electrochemical test, wherein the test results are shown in Table 1.
TABLE 1
According to experimental data, the adhesive prepared by the invention has a unique hydrogen bond and chemical bond double-cross-linking structure, and has self-healing performance and proper strength and elongation, so that the battery can keep high peel strength, first coulombic efficiency and electrode specific capacity after circulation in the continuous working process. In particular, the adhesive prepared in example 2 exhibited the most excellent properties.
SEM characterizations are carried out on the fracture surfaces of the polyacrylic acid binder electrode of the comparative example 1 and the binder electrode of the example 2 before and after 50 charge-discharge cycles, and as shown in FIG. 1, (a) and (b) are SEM images of the thickness of the polyacrylic acid binder electrode of the comparative example 1 before and after 50 charge-discharge cycles; (c) and (d) SEM images of the thickness of the binder electrode of example 2 before and after 50 charge-discharge cycles.
The thickness of the polyacrylic acid binder electrode of comparative example 1 before cycling was 13.8 μm and the binder electrode of example 2 was 13.54 μm. After 50 charge-discharge cycles, the thickness of the polyacrylic acid binder electrode of comparative example 1 rose to 18.75 μm, whereas the thickness of the binder electrode of example 2 was only 16.69 μm. Comparative example 1 the polyacrylic acid binder electrode thickness is significantly increased is the result of repeated generation and breakage of the SEI film, increasing the chance of contact of silicon particles with the electrolyte, further increasing the loss of the electrolyte, and eventually leading to the deactivation of the electrode due to the broken pulverization of the active material, which indicates that the binder of example 2 can reduce the loss of the electrolyte, avoid the pulverization of the active material, and improve the cycling stability.
Constant current charge and discharge and rate performance of the battery were tested using the LAND battery test system (CT2001A, China): (1) the test voltage range is 0.005-1.5v, and (2) the test temperature is 30 ℃. The cell was subjected to Cyclic Voltammetry (CV) and Electrochemical Impedance (EIS) tests using a Bio-Logic VMP3 electrochemical workstation, wherein the CV tests were performed at a scan rate of 0.1mV S-1 over a voltage range of 0.005-1.5V at an ambient temperature of 30 ℃. The EIS test was carried out at an AC amplitude of 5mV in the frequency range of 100mHZ-2MHz at an ambient temperature of 30 ℃.
The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.
Claims (9)
1. An aqueous self-healing adhesive, characterized in that: the adhesive comprises a mixed solution of an epoxidized rubber emulsion and an aminated polyacrylic acid solution.
2. An aqueous self-healing type adhesive according to claim 1, characterized in that: the epoxidation degree of the epoxidized rubber in the epoxidized rubber emulsion is 5-90 mol%, the mass percent concentration of the epoxidized rubber emulsion is 5-65%, and the mass percent concentration of the aminated polyacrylic acid solution is 0.1-10%.
3. An aqueous self-healing type adhesive according to claim 1, characterized in that: the epoxidized rubber in the epoxidized rubber emulsion is selected from one or more of epoxidized natural rubber latex, epoxidized nitrile rubber latex, epoxidized hydrogenated nitrile rubber latex, epoxidized styrene-butadiene rubber latex, epoxidized polyisoprene latex, epoxidized isoprene rubber latex, epoxidized butadiene rubber latex and epoxidized polyurethane latex.
4. An aqueous self-healing type adhesive according to claim 1, characterized in that: the aminated polyacrylic acid in the aminated polyacrylic acid solution is generated by the reaction of an amination reagent and polyacrylic acid under the action of an initiator;
the number average relative molecular weight of the polyacrylic acid is 20000-450000 g/mol;
the amination reagent is selected from one or more of glycinamide hydrochloride, acryloyl glycinamide hydrochloride, glutamine hydrochloride, acetylglutamide hydrochloride and aminosilane coupling agent, the molar ratio of the amination reagent to polyacrylic acid is 0.2-1:1, and the molar ratio of the polyacrylic acid to the initiator is 1: 0.1-1.
5. An aqueous self-healing adhesive according to claim 4, characterized in that: the polyacrylic acid has a number average relative molecular weight of 25000 g/mol.
6. An aqueous self-healing type adhesive according to claim 1, characterized in that: the mass ratio of the epoxidized rubber in the epoxidized rubber emulsion to the aminated polyacrylic acid in the aminated polyacrylic acid solution is 0.1-1: 0.1-1.
7. A method for preparing the aqueous self-healing adhesive according to any one of claims 1 to 6, comprising the steps of:
1) preparing an epoxidized rubber emulsion, namely mixing and stirring rubber latex, deionized water and an emulsifier, then adding an epoxidation reagent into the emulsion, carrying out epoxidation reaction for 1-12h at 40-60 ℃, and dialyzing the product for 24h by using the deionized water to obtain the epoxidized rubber emulsion;
2) preparing aminated polyacrylic acid, namely dissolving polyacrylic acid in deionized water to form polyacrylic acid solution, wherein the mass concentration of the polyacrylic acid solution is 0.5-3%, adding an alkali solution into the polyacrylic acid solution to adjust the pH value to 5-6, adding an initiator carbodiimide hydrochloride and N-hydroxysuccinimide into the polyacrylic acid solution, uniformly stirring, adding an amination reagent into the mixed solution, continuously stirring at room temperature for reaction for 12-36 hours, dialyzing the obtained product with deionized water, and freeze-drying to obtain the aminated polyacrylic acid;
3) dissolving the prepared aminated polyacrylic acid in water, adding the epoxidized rubber emulsion prepared in the step 1) into the aminated polyacrylic acid solution, and uniformly stirring at normal temperature to obtain the water-based self-healing adhesive, wherein the mass ratio of the aminated polyacrylic acid to the epoxidized rubber in the epoxidized rubber emulsion is 0.1-1: 0.1-1.
8. The method for preparing an aqueous self-healing type adhesive according to claim 7, wherein: the rubber latex is selected from one or more of natural rubber latex, nitrile rubber latex, hydrogenated nitrile rubber latex, styrene-butadiene rubber latex, polyisoprene latex, isoprene rubber latex, butadiene rubber latex and polyurethane latex.
9. The method for preparing an aqueous self-healing type adhesive according to claim 7, wherein: diluting the rubber latex in the step 1) to 30 wt% by deionized water, and adding 10g of emulsifier into 1mol of raw rubber, wherein the molar ratio of the rubber latex to the epoxidizing agent is 1: 1-5;
the epoxidation reagent is a mixed solution of formic acid and hydrogen peroxide, and the molar ratio of the formic acid to the hydrogen peroxide is 1: 1-10.
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| CN115322739A (en) * | 2022-09-15 | 2022-11-11 | 广州市白云化工实业有限公司 | Self-healing condensed type silicone sealant and preparation method thereof |
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