CN108832126B - Polycarboxylic acid aqueous binder containing coupling amido bond, preparation method and application thereof in lithium ion battery - Google Patents

Polycarboxylic acid aqueous binder containing coupling amido bond, preparation method and application thereof in lithium ion battery Download PDF

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CN108832126B
CN108832126B CN201810377949.1A CN201810377949A CN108832126B CN 108832126 B CN108832126 B CN 108832126B CN 201810377949 A CN201810377949 A CN 201810377949A CN 108832126 B CN108832126 B CN 108832126B
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coupling
polycarboxylic acid
solution
amido bond
aqueous binder
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CN108832126A (en
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王朝阳
李娟娟
张光照
杨宇
邓永红
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South China University of Technology SCUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention discloses a polycarboxylic acid aqueous binder containing a coupling amido bond, a preparation method and application thereof in a lithium ion battery. Dispersing macromolecular polymer containing carboxyl or carboxylate radical, micromolecule containing amino radical with reaction activity and coupling agent in water solution or buffer solution, and preparing polycarboxylic acid binder containing coupling amido bond by adopting a coupling method. The introduction of the coupling amido bond improves the performance of the polycarboxylic acid binder and the electrochemical performance of the lithium ion battery silicon negative electrode material under the long-term circulation condition. The method disclosed by the invention has the advantages of cheap and easily-obtained raw materials, simplicity in operation, easiness in implementation, no toxic substance from the raw materials to the target product, environment friendliness and the like. The method has the advantages of simple process, low operation and equipment cost, economy and environmental protection, is expected to realize industrial production through simple adjustment, and has great market application potential.

Description

Polycarboxylic acid aqueous binder containing coupling amido bond, preparation method and application thereof in lithium ion battery
Technical Field
The invention relates to the field of energy high polymer materials, in particular to a polycarboxylic acid aqueous binder containing coupling amido bonds, a preparation method and application thereof in a lithium ion battery.
Background
Although some lithium ion batteries for portable electronic devices have been successfully commercialized in the 21 st century, the rapid development of more and more portable electronic devices, electric vehicles and renewable energy storage materials, particularly lithium ion batteries, in hybrid electric vehicles and pure electric vehicles makes the demand for lithium ion batteries with high energy density and high power density more and more urgent. The graphite negative electrode material is the most widely commercialized negative electrode material for lithium ion batteries at present, but the theoretical specific capacity of the material is only 372mAh/g, and the urgent need of people for high-energy-density lithium ion batteries cannot be met; and the lithium intercalation potential of the graphite material is very close to the deposition potential of lithium, so that the lithium ion battery exists in the using processHuge potential safety hazard. Over the past decade, silicon-based materials have been successfully attractive to a number of researchers, with silicon negative electrode materials having a theoretical specific mass capacity (4200mAh/g, Li) 10 times that of conventional graphite materials22Si5vs 372mAh/g，LiC6) And a suitable working voltage (0.4-0.5V vs Li/Li)+) Moreover, silicon materials are abundant in the earth crust and widely available, so that silicon-based negative electrode materials are recognized as the most promising anode materials capable of satisfying the development of rechargeable lithium ion batteries with high energy density. However, silicon undergoes a large volume expansion of about 300% during the continuous lithium intercalation/deintercalation process, resulting in the destruction of the conductive network of the battery and the pulverization of the silicon particles, resulting in rapid degradation of the battery capacity and a great reduction in the battery life. The polymer binder plays a key role in keeping the integrity and the cycling stability of the battery, and the silicon electrode assembled by the traditional polyvinylidene fluoride binder is subjected to heating treatment at the temperature of 150-350 ℃ by the Journal of the electrochemical society,2008,155(3) A234-A238, and researches show that the cycling performance of the battery is improved along with the increase of the heat treatment temperature, particularly, after the silicon electrode is subjected to treatment at the temperature of 300 ℃, the silicon electrode still keeps the specific mass capacity of 600mAh/g after being cycled for 50 circles, and the cycling performance of the silicon electrode is obviously improved compared with that of the silicon electrode which is not subjected to treatment; researches of Chanhoon Kim et al (RSC Advances,2014,4(6):3070-3074) prove that the agarose with a cross-linked structure can effectively cover porous silicon particles, the high reversible capacity of 2350mAh/g is realized under the multiplying power of 10Ah/g, and the coulombic efficiency is 89.8%. Myung-Hyun Ryou et al (Advanced Materials,2013,25(11):1571-1576) introduce catechol into sodium alginate and polyacrylic acid, the modified binder shows significantly improved adhesion and cycle performance compared to pure sodium alginate and pure polyacrylic acid, the cycling of a cell based on silicon and catechol modified sodium alginate at 3C has almost no capacity fade compared to 0.1C, 3% fluoroethylene carbonate is used as the electrolyte additive, when the surface density of the active substance is 0.2-0.3mg/cm2At both current densities, a specific capacity of about 2500mAh/g was obtained. The polycarboxylic acids contain a large number of carboxyl groups or carboxylate groups in the molecular chain, and some of them also containThe active material silicon-based negative electrode material has a large number of hydroxyl groups, can generate hydrogen bonds or covalent bonds with active material silicon particles, remarkably enhances the interaction force among the active material, the binder and the copper foil, and is greatly beneficial to improving the electrochemical performance and the mechanical performance of the lithium ion battery silicon-based negative electrode material.
Disclosure of Invention
So far, the literature reports on lithium ion battery binders are inexhaustible, and many reported novel binders, such as carboxymethyl cellulose, styrene-butadiene rubber, polyacrylic acid, polyvinyl alcohol, sodium alginate, numerous natural gums and the like, have greatly improved performance compared with the traditional binder polyvinylidene fluoride, but when the binder is used for a silicon-based negative electrode material with extremely high theoretical specific capacity, the capacity exertion level of an active substance still cannot meet the urgent requirements of people on lithium ion batteries with high energy density, high power density, long cycle life and high capacity retention rate, and the specific capacity of a silicon negative electrode has a great improvement possibility. In view of the problems of the silicon electrode such as the damage of the integrity of the electrode, the pulverization of the active material and the like in the circulation, the invention aims to improve the binding capacity of a binder, so that the active substance, the copper foil and the binder form a firmer whole, the pulverization of silicon particles in the circulation process is relieved, the integrity of the electrode is improved, thereby improving the long cycle stability, rate capability and capacity retention rate of the silicon-based cathode and other electrodes with higher capacity, meanwhile, the specific capacity of the electrode and the capacity of active substances are improved, and in order to achieve the aim, the invention prepares the polycarboxylic acid aqueous binder containing the coupling amido bond, the electrochemical performance of the binder is obviously improved by modifying the original polymer, and the long-period cycle performance and the charge and discharge performance of a silicon electrode assembled by using the modified polycarboxylic acid binder under high current density are improved.
Under the action of a coupling agent, micromolecules containing reactive amino groups and macromolecular polymers containing reactive carboxyl groups or carboxylate groups are subjected to coupling reaction, and coupling amido bonds are introduced to polymer chain segments.
When the prepared polycarboxylic acid aqueous binder containing the coupling amido bond is applied to a silicon cathode electrode, the electrochemical properties such as the cycle performance, the multiplying power performance and the like of the silicon electrode can be improved, but the application of the prepared binder is not limited to the silicon electrode, and the binder can also be applied to other lithium ion battery electrode materials, and comprises the following steps: silicon-based negative electrode materials, graphite negative electrode materials, lithium cobaltate, lithium iron phosphate positive electrode materials, nickel cobalt lithium manganate ternary positive electrode materials and the like, and the application range is extremely wide.
In order to overcome the defects of the prior art, the invention aims to provide a polycarboxylic acid aqueous binder containing coupling amido bonds, a preparation method and application thereof in a lithium ion battery.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a polycarboxylic acid aqueous binder containing coupling amido bonds comprises the following steps:
(1) adding the polymer into deionized water or a buffer solution, and stirring to dissolve the polymer;
(2) after the step (1) is finished, adding a coupling agent into the solution in the step (1), and continuously stirring;
(3) after the step (2) is finished, adding small molecules containing reactive amino groups into the reaction solution in the step (2) to obtain viscous solution;
(4) and (4) dialyzing the viscous solution obtained in the step (3), freezing, and drying in a freeze dryer to obtain the polycarboxylic acid aqueous binder containing the coupling amido bond.
Further, the polymer contains carboxyl groups or carboxylate groups, including polyacrylic acid, sodium polyacrylate, polymethacrylic acid, sodium polymethacrylate, alginic acid and sodium alginate; the mass fraction of the polymer is 1-10%, the specific size depends on the viscosity of the polymer, and the higher the mass fraction is, the higher the viscosity is.
Further, the stirring in the step (1) is mechanical stirring or magnetic stirring, the stirring aims at accelerating dissolution and well dispersing reactants in the solvent, the stirring dissolution time of the polymer is adjusted according to different reaction times, the polymer can be completely dissolved in 2-3 hours at room temperature, and the dissolution time can be shortened by increasing the temperature; the stirring temperature can be adjusted according to the actual production efficiency and the energy supply mode.
Further, the pH value of the deionized water or the buffer solution is 4.5-6.5, and the pH value of the buffer solution is adjusted by a phosphate buffer solution and a cacodylic acid buffer solution; the pH value of the deionized water is adjusted by a sodium hydroxide solution, an ammonia water solution and a hydrochloric acid solution.
Further, the coupling agent is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride EDC, N-hydroxysuccinimide NHS or a mixture of the two; the ratio of the amount of the coupling agent to the amount of the carboxyl group or carboxylate group-containing substance in the polymer is 0.1 to 0.6, preferably 0.2 to 0.4; the coupling agent activates carboxyl groups or carboxylate groups on the polymer and amino groups in the small molecules containing the reactive amino groups, and the activated carboxyl groups or carboxylate groups are coupled with the activated amino groups to obtain coupled amide bonds.
Further, the small molecules containing the reactive amino groups comprise glycinamide hydrochloride and semicarbazide hydrochloride, and the small molecules are directly added into the solid or dissolved and then added into the solid; the ratio of the amount of the reactive amino group substance to the amount of the carboxyl group or carboxylate group substance is 3 to 20%, preferably 5 to 10%.
Further, the temperature used in the reaction in the step (3) can be adjusted according to the production efficiency and the energy supply mode; the reaction time is adjusted according to different reaction temperatures, the reaction can be fully carried out for 12 to 24 hours at room temperature, the temperature is increased, and the reaction time is shortened.
Further, the dialysis is deionized water dialysis, the dialysis treatment time is 2-3 days according to the standard that the dialysis bag is not broken by expansion, and the deionized water is required to be replaced during the dialysis; the cut-off molecular weight of the dialysis bag is 3.5-10 KDa.
Further, the freezing comprises refrigerator freezing layer freezing and liquid nitrogen freezing; the freeze drying time is determined by the amount of deionized water in the solution; the number of dialysis times depends on the amount of EDC or NHS or the like and glycine amide hydrochloride or semicarbazide hydrochloride or the like, and is generally 2 to 4.
The invention also provides the polycarboxylic acid aqueous binder containing the coupling amido bond prepared by the preparation method.
The invention discloses an application of a polycarboxylic acid aqueous binder containing coupling amido bond in a lithium ion battery, which comprises the following steps:
(1) adding a polycarboxylic acid aqueous binder containing a coupling amido bond into deionized water, and continuously stirring to obtain a polycarboxylic acid aqueous solution containing the coupling amido bond;
(2) uniformly mixing the polycarboxylic acid aqueous solution containing the coupling amido bond obtained in the step (1) with an active material and a conductive agent, coating the mixture on a current collector by using a scraper on a coating machine, and then airing at room temperature;
(3) punching the finished product dried in the step (2) into an electrode plate by using a punching machine;
(4) and (4) transferring the moisture on the dried surface of the electrode pole piece obtained in the step (3) into a glove box, weighing, and assembling the battery to obtain the lithium ion battery.
Further, the mass fraction of the binder is 5-40%, the mass fraction of the conductive agent is 5-40%, and the mass fraction of the active material is 20-90%; the active material comprises a nanoscale silicon negative electrode material, a micron-sized silicon negative electrode material, a silicon-based material, artificial graphite, natural graphite, lithium iron phosphate and a nickel cobalt lithium manganate ternary positive electrode material; the conductive agent is a substance capable of increasing conductivity and comprises acetylene black, conductive graphite, Super P, Ketjen black and carbon nano tubes; the current collector comprises copper foil, aluminum foil, foam copper, non-woven fabric plated with copper, foam nickel and non-woven fabric plated with nickel.
Further, the pole piece is dried to remove moisture contained in the electrode material, and the used method comprises a vacuum drying method; the temperature for drying the pole piece is determined according to the physical and chemical properties of the battery material, and is not too high or too low.
Electrochemical performance test results show that the initial discharge specific capacity of the nano-silicon lithium ion battery assembled by using the sodium polyacrylate binder is only 2867mAh/g under the current density of 840mA/g, after circulation for 100 weeks, the mass specific capacity is only 2051mAh/g, the capacity retention rate is 71.54%, after the sodium polyacrylate is modified by using glycinamide hydrochloride, the nano-silicon lithium ion battery assembled by using the sodium polyacrylate binder has the initial discharge specific capacity of 3559mAh/g under the same conditions, after circulation for 100 weeks, the mass specific capacity is still up to 2629mAh/g, the capacity retention rate is 73.87%, the electrochemical performance is obviously improved, and meanwhile, the multiplying power performance of the lithium ion battery using the modified sodium polyacrylate aqueous binder is also improved.
Compared with the prior art, the invention has the following advantages and technical effects:
the lithium ion battery prepared by mixing the polycarboxylic acid aqueous binder containing the coupling amido bond, the active substance and the conductive agent has good electrochemical performance, and compared with some binders reported in the prior art, the cycle performance and the high-rate charge and discharge performance of the lithium ion battery are greatly improved.
The method disclosed by the invention has the advantages of low-cost and easily-obtained raw materials, simplicity in operation, easiness in implementation, capability of operating at room temperature, energy conservation, no toxic substance generation and environmental friendliness.
The method has the advantages of simple process, low operation and equipment cost, economy and environmental protection, is expected to realize industrial production through simple adjustment, and has great market application potential.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. Other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principles of the invention are intended to be included within the scope of the invention.
Example 1
A preparation method of a glycyl amine hydrochloride modified sodium polyacrylate water-based binder comprises the following steps:
(1) under the action of magnetic stirring, 1g of polyacrylic acid is dissolved in 100mL of deionized water;
(2) adjusting the pH value of the solution in the step (1) to 5.7 by using a sodium hydroxide solution and a hydrochloric acid solution;
(3) adding 0.40g of EDC into 5mL of deionized water, dissolving completely, adding the EDC solution into the polymer solution in the step (2), and stirring for 20 minutes at room temperature;
(4) adding 0.08g of glycylamine hydrochloride into the reaction solution in the step (3), and stirring at room temperature for 12 hours to obtain a colorless and transparent viscous solution;
(5) and (3) dialyzing the viscous solution obtained in the step (4) for 2 times, then placing the viscous solution in a refrigerator for freezing, and after the viscous solution is completely frozen, placing the viscous solution in a freeze dryer for drying to obtain the glycinamide hydrochloride modified sodium polyacrylate (polycarboxylic acid containing coupling amido bond) aqueous binder.
Example 2
A preparation method of a glycyl amine hydrochloride modified sodium alginate aqueous binder comprises the following steps:
(1) under magnetic stirring, 1g of sodium alginate was dissolved in 100mL of phosphate buffered solution (pH 6.5);
(2) dissolving 0.27g of EDC and 0.40g of NHS by using a small amount of the solvent in the step (1), adding the two coupling agent solutions into the polymer solution in the step (1) after the dissolution is completed, and stirring for 30 minutes at room temperature;
(3) adding 0.15g of glycylamine hydrochloride into the reaction solution in the step (2), and stirring for 16 hours at room temperature to obtain a colorless and transparent viscous solution;
(4) and (3) dialyzing the viscous solution obtained in the step (3) for 3 times, then placing the viscous solution in a refrigerator for freezing, and after the viscous solution is completely frozen, placing the viscous solution in a freeze dryer for drying to obtain the glycinamide hydrochloride modified sodium alginate (polycarboxylic acid containing coupling amido bond) aqueous binder.
Example 3
A preparation method of semicarbazide hydrochloride modified polymethacrylic acid aqueous binder comprises the following steps:
(1) under the action of magnetic stirring, 5g of polymethacrylic acid is dissolved in 50mL of deionized water;
(2) adjusting the pH value of the solution in the step (1) to 4.5 by using a sodium hydroxide solution and a hydrochloric acid solution;
(3) adding 2.5g of EDC into 5mL of deionized water, dissolving completely, adding the EDC solution into the polymer solution in the step (2), and stirring for 40 minutes at room temperature;
(4) dissolving 1.5g of semicarbazide hydrochloride by using 5mL of deionized water, adding the solution into the reaction solution in the step (3) after complete dissolution, and stirring the solution for 16 hours at room temperature to obtain a colorless and transparent viscous solution;
(5) dialyzing the viscous solution obtained in the step (4) for 3 times, freezing the viscous solution by using liquid nitrogen, and drying the viscous solution in a freeze dryer to obtain the semicarbazide hydrochloride modified polymethacrylic acid (polycarboxylic acid containing coupling amido bond) aqueous binder.
Example 4
A preparation method of a glycylamine hydrochloride modified sodium polymethacrylate aqueous binder comprises the following steps:
(1) 2g of sodium polymethacrylate were dissolved in 50mL of phosphate buffer solution (pH 5.4) with magnetic stirring;
(2) adding 0.5g of EDC and 1.0g of NHS into 5mL of phosphate buffer solution, after completely dissolving, adding the EDC solution into the polymer solution of (1), and stirring for 20 minutes at room temperature;
(3) adding 0.6g of semicarbazide hydrochloride into the reaction solution in the step (2), and stirring for 12 hours at room temperature to obtain a colorless and transparent viscous solution;
(4) and (3) dialyzing the viscous solution obtained in the step (3) for 4 times, then placing the viscous solution in a refrigerator for freezing, and after the viscous solution is completely frozen, placing the viscous solution in a freeze dryer for drying to obtain the glycinamide hydrochloride modified sodium polymethacrylate (polycarboxylic acid containing coupling amide bonds) aqueous binder.
Example 5
A preparation method of semicarbazide hydrochloride modified sodium alginate aqueous binder comprises the following steps:
(1) under the action of magnetic stirring, 1g of sodium alginate is dissolved in 80mL of deionized water;
(2) 0.6g of NHS was added to the polymer solution of (1) and stirred at room temperature for 35 minutes;
(3) dissolving 0.6g of semicarbazide hydrochloride by using a small amount of deionized water, adding the solution into the reaction solution in the step (2), and stirring the solution for 20 hours at room temperature to obtain a colorless and transparent viscous solution;
(4) dialyzing the viscous solution obtained in the step (3) for 3 times, freezing the viscous solution by using liquid nitrogen, and putting the frozen viscous solution into a freeze dryer to obtain the semicarbazide hydrochloride modified sodium alginate (polycarboxylic acid containing coupling amido bonds) aqueous binder.
Example 6
An application of a sodium polyacrylate water-based binder in a lithium ion battery comprises the following specific processes:
(1) dissolving 0.1g of sodium polyacrylate solid in 2mL of deionized water;
(2) uniformly mixing the sodium polyacrylate solution in the step (1) with 0.3g of silicon powder and 0.1g of conductive agent Super P to obtain electrode slurry, adjusting the viscosity of the slurry by adding deionized water, coating the slurry on a copper foil on a coating machine, and airing at room temperature to obtain a silicon negative electrode;
(3) punching the silicon negative electrode obtained in the step (2) into a pole piece with a certain diameter by using a punching machine, and drying the pole piece in a vacuum drying oven at 120 ℃ for 12 hours;
(4) and transferring the dried pole pieces into a glove box filled with argon, weighing the pole pieces one by one, recording the weight, and assembling the pole pieces into a battery in the glove box to obtain the lithium ion battery.
Example 7
The application of the glycylamine hydrochloride modified sodium polyacrylate water-based binder in the lithium ion battery comprises the following specific processes:
(1) dissolving 0.1g of the glycylamine hydrochloride modified sodium polyacrylate aqueous binder obtained in example 1 in 2mL of deionized water;
(2) uniformly mixing the glycylamine hydrochloride modified sodium polyacrylate solution obtained in the step (1) with 0.3g of silicon powder and 0.1g of conductive agent Super P to obtain electrode slurry, adjusting the viscosity of the slurry by adding deionized water, coating the slurry on a copper foil on a coating machine, and airing at room temperature to obtain a silicon negative electrode;
(3) punching the silicon negative electrode obtained in the step (2) into a pole piece with a certain diameter by using a punching machine, and drying the pole piece in a vacuum drying oven at 120 ℃ for 12 hours;
(4) and transferring the dried pole pieces into a glove box filled with argon, weighing the pole pieces one by one, recording the weight, and assembling the pole pieces into a battery in the glove box to obtain the lithium ion battery.
Example 8
An application of semicarbazide hydrochloride modified polymethacrylic acid aqueous binder in a lithium ion battery is disclosed, which comprises the following steps:
(1) dissolving 0.8g of semicarbazide hydrochloride modified polymethacrylic acid aqueous binder in 2mL of deionized water;
(2) uniformly mixing the glycylamine hydrochloride modified sodium polyacrylate solution obtained in the step (1) with 0.4g of silicon powder and 0.8g of conductive agent Super P to obtain electrode slurry, adjusting the viscosity of the slurry by adding deionized water, coating the slurry on a copper foil on a coating machine, and airing at room temperature to obtain a silicon negative electrode;
(3) punching the silicon negative electrode obtained in the step (2) into a pole piece with a certain diameter by using a punching machine, and drying the pole piece in a vacuum drying oven at 120 ℃ for 12 hours;
(4) and transferring the dried pole pieces into a glove box filled with argon, weighing the pole pieces one by one, recording the weight, and assembling the pole pieces into a battery in the glove box to obtain the lithium ion battery.
Example 9
An application of a glycylamine hydrochloride modified sodium alginate aqueous binder in a lithium ion battery comprises the following specific processes:
(1) 1g of glycinamide hydrochloride modified sodium alginate aqueous binder is dissolved in 5mL of deionized water;
(2) uniformly mixing the glycylamine hydrochloride modified sodium polyacrylate solution obtained in the step (1) with 3g of silicon powder and 1g of conductive agent Super P to obtain electrode slurry, adjusting the viscosity of the slurry by adding deionized water, coating the slurry on a copper foil on a coating machine, and airing at room temperature to obtain a silicon negative electrode;
(3) punching the silicon negative electrode obtained in the step (2) into a pole piece with a certain diameter by using a punching machine, and drying the pole piece in a vacuum drying oven at 120 ℃ for 12 hours;
(4) and transferring the dried pole pieces into a glove box filled with argon, weighing the pole pieces one by one, recording the weight, and assembling the pole pieces into a battery in the glove box to obtain the lithium ion battery.
For the nano silicon negative electrode lithium ion battery assembled by the sodium polyacrylate aqueous binder in the embodiment 6, after the battery is cycled for 100 weeks under the current density of 840mA/g, the specific mass capacity is only 2051mAh/g, and the capacity retention rate is 71.54%, while for the nano silicon lithium ion battery assembled by the glycinamide hydrochloride modified sodium polyacrylate aqueous binder in the embodiment 7, after the battery is cycled for 100 weeks under the same condition, the specific mass capacity is still up to 2629mAh/g, the capacity retention rate is 73.87%, and the charge and discharge performance of the battery is remarkably improved.

Claims (9)

1. A preparation method of a polycarboxylic acid aqueous binder containing coupling amido bonds is characterized by comprising the following steps:
(1) adding the polymer into deionized water or a buffer solution, and stirring to dissolve the polymer;
(2) after the step (1) is finished, adding a coupling agent into the solution in the step (1), and continuously stirring; the coupling agent is more than one of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride EDC and N-hydroxysuccinimide NHS; the ratio of the amount of the coupling agent to the amount of the substance containing carboxyl groups or carboxylate groups in the polymer is 0.1-0.6;
(3) after the step (2) is finished, adding small molecules containing reactive amino groups into the solution in the step (2) to obtain viscous solution; activating carboxyl groups or carboxylate groups on the polymer and amino groups in the micromolecules containing the reactive amino groups by using a coupling agent, and coupling the activated carboxyl groups or carboxylate groups with the activated amino groups to obtain a coupling amide bond;
(4) and (4) dialyzing the viscous solution obtained in the step (3), freezing, and drying in a freeze dryer to obtain the polycarboxylic acid aqueous binder containing the coupling amido bond.
2. The preparation method of the polycarboxylic acid aqueous binder containing the coupling amido bond, according to the claim 1, is characterized in that the polymer contains carboxyl group or carboxylate group, comprising polyacrylic acid, sodium polyacrylate, polymethacrylic acid, sodium polymethacrylate, alginic acid, sodium alginate; the mass fraction of the polymer is 1% -10%; the stirring is mechanical stirring or magnetic stirring.
3. The method for preparing the aqueous polycarboxylic acid binder containing the coupling amido bonds according to claim 1, wherein the pH value of deionized water or a buffer solution is 4.5-6.5, and the pH value of the buffer solution is adjusted by a phosphate buffer solution and a cacodylic acid buffer solution; the pH value of the deionized water is adjusted by sodium hydroxide solution, ammonia water solution and hydrochloric acid solution.
4. The method of claim 1, wherein the small molecules containing reactive amino groups comprise glycinamide hydrochloride and semicarbazide hydrochloride, either added directly to the solid or dissolved and then added; the ratio of the amount of the reactive amino group substance to the amount of the carboxyl group or carboxylate group substance is 3 to 20%.
5. The method for preparing the polycarboxylic acid aqueous binder containing the coupling amido bond according to claim 1, wherein the dialysis is deionized water dialysis, and the dialysis time is 2-4 times.
6. The method for preparing an aqueous binder of polycarboxylic acid containing coupled amide bonds according to claim 1, characterized in that said freezing comprises freezer frozen layer freezing and liquid nitrogen freezing.
7. An aqueous binder of polycarboxylic acid containing a coupling amide bond obtained by the method according to any one of claims 1 to 6.
8. The application of the polycarboxylic acid aqueous binder containing the coupling amido bond in the lithium ion battery is characterized by comprising the following steps:
(1) adding a polycarboxylic acid aqueous binder containing a coupling amido bond into deionized water, and continuously stirring to obtain a polycarboxylic acid aqueous solution containing the coupling amido bond;
(2) mixing the polycarboxylic acid aqueous solution containing the coupling amido bond obtained in the step (1) with an active material and a conductive agent, coating the mixture on a current collector by using a scraper on a coating machine, and then airing at room temperature;
(3) punching the finished product dried in the step (2) into an electrode plate by using a punching machine;
(4) and (4) transferring the moisture on the dried surface of the electrode pole piece obtained in the step (3) into a glove box, weighing, and assembling the battery to obtain the lithium ion battery.
9. The application of the polycarboxylic acid water-based binder containing the coupling amido bond in the lithium ion battery is characterized in that the mass fractions of the components in the binder, the conductive agent and the active material are 5-40%, 5-40% and 20-90% in sequence; the active material comprises a nanoscale silicon negative electrode material, a micron-sized silicon negative electrode material, a silicon-based material, artificial graphite, natural graphite, lithium iron phosphate and a nickel cobalt lithium manganate ternary positive electrode material; the conductive agent is a substance capable of increasing conductivity and comprises acetylene black, conductive graphite, Super P, Ketjen black or carbon nano tubes; the current collector comprises copper foil, aluminum foil, copper foam, non-woven fabric plated with copper, nickel foam or non-woven fabric plated with nickel.
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