CN115440984A - Composite adhesive, preparation method and application thereof, lithium ion battery negative electrode slurry and lithium ion battery negative electrode - Google Patents

Composite adhesive, preparation method and application thereof, lithium ion battery negative electrode slurry and lithium ion battery negative electrode Download PDF

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CN115440984A
CN115440984A CN202211293778.7A CN202211293778A CN115440984A CN 115440984 A CN115440984 A CN 115440984A CN 202211293778 A CN202211293778 A CN 202211293778A CN 115440984 A CN115440984 A CN 115440984A
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lithium ion
negative electrode
ion battery
natural plant
plant polysaccharide
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田萌
葛鹏
虎琳琳
宁静
王路晗
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Western Metal Material Co ltd
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon

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Abstract

The invention provides a natural plant polysaccharide composite adhesive, a preparation method and application thereof, lithium ion battery negative electrode slurry and a lithium ion battery negative electrode, and relates to the technical field of lithium ion batteries. The natural plant polysaccharide composite adhesive provided by the invention comprises carboxymethyl tamarind gum and polyacrylic acid; the carboxymethyl tamarind gum and the polyacrylic acid are crosslinked through hydrogen bonds. The natural plant polysaccharide composite adhesive provided by the invention can relieve the internal stress generated by the expansion of the silicon particles, effectively inhibit the collapse of an electrode structure caused by the fragmentation of the silicon particles, maintain the integrity of the electrode structure and improve the electrochemical stability of a lithium ion battery.

Description

Composite adhesive, preparation method and application thereof, lithium ion battery negative electrode slurry and lithium ion battery negative electrode
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a natural plant polysaccharide composite adhesive, a preparation method and application thereof, lithium ion battery negative electrode slurry and a lithium ion battery negative electrode.
Background
The lithium ion battery is used as a main power battery of a new energy automobile, and the energy density of the lithium ion battery can meet the requirements of mileage anxiety and charging anxiety of people only when the energy density of the lithium ion battery reaches higher requirements, so that the development of a lithium ion battery cathode material with higher energy density, excellent rate capability and stable cycle performance becomes significant. Silicon has received much attention as a negative electrode material for lithium ion batteries because of its ultra-high theoretical capacity (about 4200 mAh/g), low intercalation potential, and abundant natural resources. In the research on silicon-based negative electrode materials of high-energy-density lithium ion batteries (Liu Hao, research on silicon-based negative electrode materials of high-energy-density lithium ion batteries [ D ]. University of academy of china (physical institute of academy of china), 2019.), it is pointed out that if a lithium-rich positive electrode is not used, a silicon-based negative electrode must be used when the energy density of a battery cell is over 280 Wh/kg.
The commercialization progress of the silicon-based negative electrode with high energy density lags behind that of the graphite negative electrode is that the silicon-based negative electrode material has large volume change in the charging and discharging processes, so that active particle pulverization, electric contact loss and side reaction continue to occur, and the service life of the silicon-based negative electrode is further shortened.
Disclosure of Invention
The invention aims to provide a natural plant polysaccharide composite adhesive, a preparation method and application thereof, lithium ion battery negative electrode slurry and a lithium ion battery negative electrode.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a natural plant polysaccharide type composite adhesive, which comprises carboxymethyl tamarind gum and polyacrylic acid; the carboxymethyl tamarind gum and the polyacrylic acid are crosslinked through hydrogen bonds.
Preferably, the mass ratio of the carboxymethyl tamarind gum to the polyacrylic acid is 5-10: 1 to 4.
Preferably, the preparation method of the carboxymethyl tamarind gum comprises the following steps: mixing tamarind gum, sodium hydroxide, methanol water solution and chloroacetic acid, and performing carboxymethylation treatment to obtain carboxymethyl tamarind gum.
The invention provides a preparation method of the natural plant polysaccharide composite adhesive in the technical scheme, which comprises the following steps:
mixing the carboxymethyl tamarind gum and the polyacrylic acid aqueous solution to obtain the natural plant polysaccharide type composite adhesive.
Preferably, the mixing is performed under stirring conditions; the stirring speed is 100-1000 r/min; the stirring time is 0.5-24 h.
The invention provides the application of the natural plant polysaccharide type composite adhesive in the technical scheme or the natural plant polysaccharide type composite adhesive prepared by the preparation method in the technical scheme in a lithium ion battery negative electrode material.
Preferably, the lithium ion battery negative electrode material is a silicon-based negative electrode material.
The invention provides a lithium ion battery cathode slurry, which comprises an active material, a conductive additive and a binder; the adhesive is the natural plant polysaccharide composite adhesive or the natural plant polysaccharide composite adhesive prepared by the preparation method in the technical scheme.
Preferably, the mass ratio of the active material, the conductive additive and the binder is 80-95: 5 to 10:5 to 10.
The invention provides a lithium ion battery cathode, which comprises a current collector and a lithium ion battery cathode material attached to the current collector; the lithium ion battery negative electrode material is obtained by coating the lithium ion battery negative electrode slurry on a current collector and drying.
The invention provides a natural plant polysaccharide type composite adhesive, which comprises carboxymethyl tamarind gum and polyacrylic acid; the carboxymethyl tamarind gum and the polyacrylic acid are crosslinked through hydrogen bonds. In the invention, the natural tamarind gum is a neutral polysaccharide extracted from tamarind seeds, and the water solubility of the tamarind gum is increased after carboxymethylation treatment, so that the tamarind gum can be dissolved in cold water; hydroxyl on the side chain of the carboxymethyl tamarind gum in the adhesive and carboxyl on polyacrylic acid form hydrogen bond action, so that excellent mechanical property is provided, and the excellent adhesive strength is provided by abundant polar functional groups. The natural plant polysaccharide composite adhesive provided by the invention has good stability and adhesive force at high temperature, and when the natural plant polysaccharide composite adhesive is applied to a silicon-based negative electrode material, the excellent mechanical property and the excellent adhesive capacity of the adhesive can ensure the stability of an electrode structure and the integrity of a conductive network when the silicon volume expands, and the electrochemical stability of a battery is improved.
The invention also provides a preparation method of the natural plant polysaccharide type composite adhesive, the preparation method provided by the invention is green, environment-friendly, simple and feasible, and the obtained composite adhesive has good stability and strong adhesive force and is suitable for large-scale preparation.
The invention also provides the application of the natural plant polysaccharide composite binder in the lithium ion battery cathode material, the binding force of each component in the lithium ion battery cathode using the binder is strong, the binder can effectively relieve the stress generated among silicon-based material particles in the circulation process through excellent mechanical property and binding capacity, and the circulation stability of the lithium ion battery is obviously improved. The results of the examples show that the capacity retention rate of the lithium ion button half cell using the adhesive of the invention is still above 80% after 200 weeks of cycling.
Drawings
FIG. 1 is a graph showing a comparison of the peel strength of negative electrode plates of lithium ion batteries using binders of example 1 and comparative example 1;
fig. 2 is a graph comparing the cycle performance of lithium ion half cells using binders of example 1 and comparative example 1.
Detailed Description
The invention provides a natural plant polysaccharide type composite adhesive, which comprises carboxymethyl tamarind gum and polyacrylic acid; the carboxymethyl tamarind gum and polyacrylic acid are cross-linked through hydrogen bonds.
In the present invention, the mass ratio of the carboxymethyl tamarind gum to the polyacrylic acid is preferably 5 to 10:1 to 4. In the invention, the carboxymethyl tamarind gum can increase the viscosity and adhesiveness of the adhesive, and the polyacrylic acid can provide mechanical properties.
The natural plant polysaccharide composite adhesive provided by the invention comprises carboxymethyl tamarind gum. In the present invention, the carboxymethyl tamarind gum is preferably a product of carboxymethylation of tamarind gum. In the invention, the tamarind gum is natural polysaccharide. In the invention, the structural formula of the tamarind gum is shown as formula I:
Figure BDA0003902411520000041
in the present invention, the method for preparing the carboxymethyl tamarind gum preferably comprises: mixing tamarind gum, sodium hydroxide, methanol water solution and chloroacetic acid, and performing carboxymethylation treatment to obtain carboxymethyl tamarind gum. In the present invention, the concentration of tamarind gum in aqueous methanol solution is preferably 8 to 12wt.%, more preferably 10wt.%; the concentration of the sodium hydroxide in the methanol aqueous solution is preferably 8-10 wt.%; the concentration of chloroacetic acid in aqueous methanol solution is preferably 5 to 8wt.%. In the present invention, the mass ratio of methanol to water in the methanol aqueous solution is preferably (60 to 80): (20 to 40). In the present invention, the temperature of the carboxymethylation treatment is preferably 45 to 85 ℃, more preferably 80 ℃; the time of the carboxymethylation treatment is preferably 30 to 90min.
According to the invention, preferably, after the carboxymethylation treatment, the obtained system is subjected to solid-liquid separation, and then the solid substance obtained by the solid-liquid separation is dried to obtain the carboxymethyl tamarind gum. In the present invention, the method of solid-liquid separation is preferably filtration.
The natural plant polysaccharide composite adhesive provided by the invention comprises polyacrylic acid. In the present invention, the structural formula of the polyacrylic acid is represented by formula II:
Figure BDA0003902411520000042
in the present invention, the polyacrylic acid preferably has a weight average molecular weight of 10 to 1000 ten thousand.
The invention provides a preparation method of the natural plant polysaccharide type composite adhesive in the technical scheme, which comprises the following steps:
mixing the carboxymethyl tamarind gum with the polyacrylic acid aqueous solution to obtain the natural plant polysaccharide type composite adhesive.
In the present invention, the method for preparing the aqueous polyacrylic acid solution preferably includes: and (3) mixing an acrylic acid monomer, water and an initiator under a protective atmosphere, and carrying out polymerization reaction to obtain a polyacrylic acid aqueous solution. In the present invention, the acrylic monomer, water and initiator mixture preferably includes: the acrylic monomer is dissolved in water and the initiator is added. In the present invention, the concentration of the acrylic monomer in water is preferably 15 to 20wt.%. In the present invention, the water is preferably deionized water. In the present invention, the mass of the initiator is preferably 0.05 to 0.2%, more preferably 0.10 to 0.125% of the mass of the acrylic monomer. In the present invention, the initiator is preferably one of azobisisobutyronitrile, ammonium persulfate, and potassium persulfate. In the present invention, the temperature of the polymerization reaction is preferably 60 to 80 ℃, and the time of the polymerization reaction is preferably 1 to 2 hours, more preferably 1.5 hours. In the present invention, the protective atmosphere is preferably an argon atmosphere or a nitrogen atmosphere. The invention can prevent the inhibition of oxygen to the polymerization reaction by carrying out the polymerization reaction in a protective atmosphere.
In the present invention, the mixing is preferably performed under stirring conditions; the stirring speed is preferably 100-1000 r/min, and more preferably 300-500 r/min; the stirring time is preferably 0.5 to 24 hours, more preferably 8 hours.
The invention provides an application of the natural plant polysaccharide type composite adhesive in the technical scheme or the natural plant polysaccharide type composite adhesive prepared by the preparation method in the technical scheme in a lithium ion battery anode material, and the natural plant polysaccharide type composite adhesive is preferably applied to a silicon-based anode material. The natural plant polysaccharide composite adhesive provided by the invention enables a silicon-based negative electrode material to still keep good stability and adhesive force under high loading, and shows excellent electrochemical performance when a button-type half cell is assembled by using a silicon negative electrode of the composite adhesive.
The invention provides a lithium ion battery cathode slurry, which comprises an active material, a conductive additive and a binder; the adhesive is the natural plant polysaccharide composite adhesive or the natural plant polysaccharide composite adhesive prepared by the preparation method in the technical scheme.
In the present invention, the mass ratio of the active material, the conductive additive and the binder is preferably 80 to 95:5 to 10:5 to 10. In the present invention, the active material preferably includes one of a silicon material, a silicon carbon material, and a silicon oxygen material; the conductive additive preferably includes one of SuperP, acetylene black, and Ketjen black.
In the present invention, the preparation method of the lithium ion battery negative electrode slurry preferably includes: mixing the active material, the conductive additive and the adhesive, and dispersing the mixture in water by ball milling to obtain the lithium ion battery cathode slurry. In the present invention, the water is preferably deionized water. In the present invention, the solid content of the lithium ion battery negative electrode slurry is preferably 30 to 55wt.%, and more preferably 45wt.%.
The invention provides a lithium ion battery cathode, which comprises a current collector and a lithium ion battery cathode material attached to the current collector; the lithium ion battery negative electrode material is obtained by coating the lithium ion battery negative electrode slurry on a current collector and drying. In the present invention, the coating thickness of the lithium ion battery negative electrode slurry on the current collector is preferably 120 μm. In the present invention, the current collector preferably includes a copper foil. In the present invention, the thickness of the current collector is preferably 12 μm. In the present invention, the coating is preferably performed using an automatic coating machine.
In the invention, the lithium ion battery negative electrode is preferably a negative electrode pole piece with the diameter of 12 mm.
The invention also provides a lithium ion battery, which comprises the lithium ion battery cathode in the technical scheme.
In a specific embodiment of the invention, the lithium ion battery cathode in the technical scheme is assembled into a 2016 button type half cell to test the performance of the cathode. In the present invention, the method for preparing the 2016 button type half cell preferably comprises the following steps: placing the negative electrode of the lithium ion battery in a glove box filled with argon to assemble a 2016 button type half battery; a pure lithium sheet was used as the counter electrode and Celgard2300 was used as the separator; the electrolyte solution contains 1mol/L lithium hexafluorophosphate (LiPF) 6 ) And mixing the Ethylene Carbonate (EC) and diethyl carbonate (DEC) (the volume ratio is 1:1), and adding 5% volume fraction of fluoroethylene carbonate (FEC) to obtain the lithium ion battery.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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
(1) Dissolving 2.0g of acrylic acid in 12mL of deionized water, and fully and uniformly stirring; 2.5mg of ammonium persulfate is added into the solution, nitrogen is introduced for 40 minutes to remove oxygen, the system is heated to 60 ℃, and a polymerization reaction is carried out for 1.5 hours to obtain a polyacrylic acid aqueous solution.
(2) Dispersing 10.0g of tamarind gum into 100mL of methanol aqueous solution, wherein the methanol content in the methanol aqueous solution is 80wt.%, adding 8g of sodium hydroxide and 5g of chloroacetic acid, heating to 85 ℃ for reaction for 90min, and filtering and drying the reacted system to obtain the carboxymethyl tamarind gum.
(3) And adding 10g of the carboxymethyl tamarind gum into the polyacrylic acid aqueous solution, and stirring for 8 hours to obtain a clear natural plant polysaccharide type composite adhesive, which is marked as carboxymethyl tamarind gum-polyacrylic acid.
Comparative example 1
Polyacrylic acid was used as comparative example 1.
Test example
(1) Mixing a negative active material silicon powder (with the particle size of 100-1000 nm), a conductive additive SuperP and a binder according to the weight ratio of 8:1:1, and uniformly dispersing the mixture in deionized water by ball milling to obtain uniformly mixed lithium ion battery cathode slurry.
(2) Uniformly coating the lithium ion battery negative electrode slurry in the step (1) on copper foil with the thickness of 12 microns by using an automatic coating machine, wherein the coating thickness is 120 microns, and then placing the copper foil in a vacuum drying oven to dry and remove a solvent; after drying, the obtained product was cut into a negative electrode sheet having a diameter of 12 mm.
(3) Transferring the negative pole piece prepared in the step (2) into a glove box filled with argon to assemble a 2016 button type half cell; a pure lithium sheet was used as the counter electrode and Celgard2300 was used as the separator; the electrolyte adopts lithium hexafluorophosphate (LiPF) containing 1mol/L 6 ) Ethylene Carbonate (EC) and diethyl carbonate (DEC) (1:1 by volume) were mixed, and 5% volume fraction fluoroethylene carbonate (FEC) was added.
(4) And (3) standing the assembled button half cell in the step (3) for 6 hours, and then cycling at a multiplying power of 0.1C for one week in a voltage range of 0.01-2.00V and then performing charge-discharge cycling at a multiplying power of 0.3C.
The carboxymethyl tamarind gum-polyacrylic acid prepared in example 1 and the polyacrylic acid of comparative example 1 were used as binders to prepare a negative electrode plate of a lithium ion battery, and the adhesion strength of the electrode was tested using a 180 ° peel test, and the obtained peel strength comparison graph is shown in fig. 1. As can be seen from FIG. 1, with a polyacrylic acid binder (about 9 N.m) -1 ) Compared with the electrode using the carboxymethyl tamarind gum-polyacrylic acid composite adhesive, the electrode has stronger bonding strength of 12 N.m -1 。
The carboxymethyl tamarind gum-polyacrylic acid prepared in example 1 and the polyacrylic acid prepared in comparative example 1 were applied to the negative electrode as binders, respectively, and a 2016 coin-type half cell was assembled, and the cells were testedCell electrochemical performance, the results obtained are shown in table 1; the resulting cycle performance is plotted in figure 2. As can be seen from FIG. 2, when the electrode loading mass was 3.0mAh cm -2 The electrode using carboxymethyl tamarind gum-polyacrylic acid has a high capacity retention rate of 80.7% at a current density of 0.3C. By contrast, the natural plant polysaccharide-based composite binder prepared in this example has higher cycle stability than polyacrylic acid.
Example 2
(1) 2.0g of acrylic acid is dissolved in 12mL of deionized water and is fully and uniformly stirred; 2.5mg of ammonium persulfate is added into the solution, nitrogen is introduced for 40 minutes to remove oxygen, the temperature of the system is raised to 60 ℃, and the polymerization reaction is carried out for 1.5 hours to obtain the polyacrylic acid aqueous solution.
(2) Dispersing 8.0g of tamarind gum into 100mL of methanol aqueous solution, wherein the methanol content in the methanol aqueous solution is 80wt.%, adding 8g of sodium hydroxide and 5g of chloroacetic acid, heating to 85 ℃ for reaction for 90min, and filtering and drying the reacted system to obtain the carboxymethyl tamarind gum.
(3) And adding 8g of the carboxymethyl tamarind gum into the polyacrylic acid aqueous solution, and stirring for 8 hours to obtain the clear natural plant polysaccharide type composite adhesive.
The natural plant polysaccharide composite adhesive is applied to a negative electrode by adopting a method of a test example, a lithium ion battery is assembled, and electrochemical performance is tested, and the obtained result is shown in table 1.
Example 3
(1) Dissolving 2.0g of acrylic acid in 12mL of deionized water, and fully and uniformly stirring; 2.5mg of ammonium persulfate is added into the solution, nitrogen is introduced for 40 minutes to remove oxygen, the temperature of the system is raised to 60 ℃, and the polymerization reaction is carried out for 1.5 hours to obtain the polyacrylic acid aqueous solution.
(2) Dispersing 10.0g of tamarind gum into 100mL of methanol aqueous solution, wherein the methanol content in the methanol aqueous solution is 80wt.%, adding 10g of sodium hydroxide and 8g of chloroacetic acid, heating to 80 ℃, reacting for 90min, and filtering and drying the reacted system to obtain the carboxymethyl tamarind gum.
(3) And adding 7g of the carboxymethyl tamarind gum into the polyacrylic acid aqueous solution, and stirring for 8 hours to obtain the clear natural plant polysaccharide type composite adhesive.
The natural plant polysaccharide composite adhesive is applied to a negative electrode by adopting a method of a test example, a lithium ion battery is assembled, and electrochemical performance is tested, and the obtained result is shown in table 1.
Example 4
(1) Dissolving 2.0g of acrylic acid in 12mL of deionized water, and fully and uniformly stirring; 2mg of ammonium persulfate is added into the solution, nitrogen is introduced for 40 minutes to remove oxygen, the system is heated to 60 ℃, and polymerization reaction is carried out for 1.5 hours to obtain a polyacrylic acid aqueous solution.
(2) Dispersing 10.0g of tamarind gum into 100mL of methanol aqueous solution, wherein the methanol content in the methanol aqueous solution is 80wt.%, adding 8g of sodium hydroxide and 5g of chloroacetic acid, heating to 85 ℃ for reaction for 90min, and filtering and drying the reacted system to obtain the carboxymethyl tamarind gum.
(3) And adding 6g of the carboxymethyl tamarind gum into the polyacrylic acid aqueous solution, and stirring for 8 hours to obtain the clear natural plant polysaccharide type composite adhesive.
The natural plant polysaccharide composite adhesive is applied to a negative electrode by adopting a method of a test example, a lithium ion battery is assembled, and electrochemical performance is tested, and the obtained result is shown in table 1.
Example 5
(1) Dissolving 2.0g of acrylic acid in 12mL of deionized water, and fully and uniformly stirring; 2.5mg of ammonium persulfate is added into the solution, nitrogen is introduced for 40 minutes to remove oxygen, the temperature of the system is raised to 60 ℃, and the polymerization reaction is carried out for 1.5 hours to obtain the polyacrylic acid aqueous solution.
(2) Dispersing 10.0g of tamarind gum into 100mL of methanol aqueous solution, wherein the methanol content in the methanol aqueous solution is 80wt.%, adding 8g of sodium hydroxide and 5g of chloroacetic acid, heating to 85 ℃ for reaction for 90min, and filtering and drying the reacted system to obtain the carboxymethyl tamarind gum.
(3) And adding 5g of the carboxymethyl tamarind gum into the polyacrylic acid aqueous solution, and stirring for 8 hours to obtain the clear natural plant polysaccharide type composite adhesive.
The natural plant polysaccharide composite adhesive is applied to a negative electrode by adopting a method of a test example, a lithium ion battery is assembled, and electrochemical performance is tested, and the obtained result is shown in table 1.
TABLE 1 electrochemical cycling Performance data for examples 1-5 and comparative example 1
Figure BDA0003902411520000091
As can be seen from the results in Table 1, the natural plant polysaccharide-based composite binder of the present invention has a capacity of 3mAh cm -2 In the case, the first-cycle coulombic efficiency of the thick electrode is more than 87%, the capacity retention rate after 200-cycle cycles is more than 80%, but the capacity retention rate after 200-cycle cycles of the comparative adhesive polyacrylic acid is only 46.8%. Therefore, the natural plant polysaccharide composite adhesive provided by the invention obviously improves the cycling stability of the silicon-based negative electrode material.
The natural plant polysaccharide composite adhesive provided by the invention can effectively relieve stress generated among silicon-based material particles in a circulation process through excellent mechanical property and adhesive capacity, and remarkably improves the circulation stability of a lithium ion battery. The adhesive is water-soluble, green and environment-friendly, has an easily-regulated structure, and can well meet the preparation and production requirements of the silicon-based cathode.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A natural plant polysaccharide type composite adhesive is characterized by comprising carboxymethyl tamarind gum and polyacrylic acid; the carboxymethyl tamarind gum and the polyacrylic acid are crosslinked through hydrogen bonds.
2. The natural plant polysaccharide type composite adhesive according to claim 1, wherein the mass ratio of the carboxymethyl tamarind gum to the polyacrylic acid is 5-10: 1 to 4.
3. The natural plant polysaccharide based composite adhesive according to claim 1, wherein the carboxymethyl tamarind gum is prepared by a method comprising: mixing tamarind gum, sodium hydroxide, methanol water solution and chloroacetic acid, and performing carboxymethylation treatment to obtain carboxymethyl tamarind gum.
4. A method for preparing the natural plant polysaccharide-based composite binder of any one of claims 1 to 3, comprising the steps of:
mixing the carboxymethyl tamarind gum with the polyacrylic acid aqueous solution to obtain the natural plant polysaccharide type composite adhesive.
5. The production method according to claim 4, wherein the mixing is performed under stirring conditions; the stirring speed is 100-1000 r/min; the stirring time is 0.5-24 h.
6. Use of the natural plant polysaccharide-based composite binder according to any one of claims 1 to 3 or the natural plant polysaccharide-based composite binder prepared by the preparation method according to any one of claims 4 to 5 in a negative electrode material of a lithium ion battery.
7. The use of claim 6, wherein the lithium ion battery negative electrode material is a silicon-based negative electrode material.
8. The lithium ion battery negative electrode slurry is characterized by comprising an active material, a conductive additive and a binder; the adhesive is the natural plant polysaccharide type composite adhesive according to any one of claims 1 to 3 or the natural plant polysaccharide type composite adhesive produced by the production method according to any one of claims 4 to 5.
9. The lithium ion battery negative electrode slurry of claim 8, wherein the mass ratio of the active material, the conductive additive and the binder is 80-95: 5 to 10:5 to 10.
10. A lithium ion battery negative electrode comprises a current collector and a lithium ion battery negative electrode material attached to the current collector; the lithium ion battery negative electrode material is obtained by coating the lithium ion battery negative electrode slurry of any one of claims 8 to 9 on a current collector and drying.
CN202211293778.7A 2022-10-21 2022-10-21 Composite adhesive, preparation method and application thereof, lithium ion battery negative electrode slurry and lithium ion battery negative electrode Pending CN115440984A (en)

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