CN111697234B - Water-based crosslinking binder for lithium ion battery and preparation method and application thereof - Google Patents

Water-based crosslinking binder for lithium ion battery and preparation method and application thereof Download PDF

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CN111697234B
CN111697234B CN202010565233.1A CN202010565233A CN111697234B CN 111697234 B CN111697234 B CN 111697234B CN 202010565233 A CN202010565233 A CN 202010565233A CN 111697234 B CN111697234 B CN 111697234B
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lithium ion
water
maleic anhydride
binder
polyethylene maleic
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CN111697234A (en
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曾丹黎
葛明娇
张舜
毛万强
游钖霖
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China University of Geosciences
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China University of Geosciences
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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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • 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

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Abstract

The invention belongs to the field of lithium ion battery materials, and particularly relates to a water-based cross-linking type binder for a lithium ion battery, and a preparation method and application thereof. The water-based crosslinking type binder is formed by the ring-opening reaction of hydroxyl or amino and anhydride between natural high-molecular polysaccharide and polyethylene maleic anhydride, and has the characteristics of high binding power, simple and convenient preparation method, economy, environmental protection and the like. The water-based cross-linked binder contains hydroxyl, carboxyl, lithium carboxylate and other functional groups, so that the bonding strength among electrode components can be improved, the diffusion rate of lithium ions in the battery can be increased, and an electrode system with a more stable structure is formed. The lithium ion battery prepared by the binder has good battery rate performance, can still ensure stable long circulation and high specific capacity under the high rate of 20C, has quick charging performance and wide application prospect.

Description

Water-based crosslinking binder for lithium ion battery and preparation method and application thereof
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to a water-based crosslinking binder for a lithium ion battery, and a preparation method and application thereof.
Background
The rapid development of lithium ion batteries has led to the popularization of portable electronic devices, however, the high frequency use of electronic products poses a challenge to the quick charging performance of batteries, and this challenge also extends to other fields such as electric vehicles. In the long term, lithium ion batteries will become one of the main power supply methods. The binder is usually omitted because of its small proportion of components. Researches show that the function of the binder is important in maintaining the stability of the electrode material, and the rate performance and the cycle life of the battery can be effectively improved and the problem of capacity fading can be improved by using the proper binder. The most widely used positive electrode binder at present is polyvinylidene fluoride (PVDF), and the solvent used for dissolving the material is high-boiling oil solvent N-methyl pyrrolidone (NMP), so that the environment is not protected, and the cost is high. In addition, the PVDF has low bonding performance and tends to migrate to the surface in long circulation, so that the pole piece is cracked, and the performance of the battery is degraded. Compared with an oil-based binder, the water-based binder has the advantages of economy and environmental protection. At present, the use of the water-based binder in the whole lithium battery industry is more common in the novel cathode material, but the development of the water-based binder with higher binding power for improving the multiplying power and the cycle performance of the battery is still needed, so that the development of the water-based binder is a simple and low-cost method, the water-based binder is more suitable for the aim of the current green chemical industry, and the water-based binder has very important significance.
Disclosure of Invention
In view of this, the invention provides a water-based cross-linking type binder and a preparation method thereof, which are mainly applied to a lithium ion battery anode material.
The invention provides a water-based crosslinking type binder for a lithium ion battery, which is formed by the ring-opening esterification or amidation reaction of hydroxyl or amino and anhydride of natural high molecular polysaccharide and polyethylene maleic anhydride.
Further, the natural high molecular polysaccharide is selected from one or more of acacia, xanthan gum, pectin, carrageenan, agar, curdlan, sodium alginate and chitosan.
Further, the polyethylene maleic anhydride is one or a mixture of homopolymerization alternating type polyethylene maleic anhydride and mixed copolymerization type polyethylene maleic anhydride, and the number average molecular weight M of the polyethylene maleic anhydride is n 10 to 200 ten thousand.
Further, the mass ratio of the natural high-molecular polysaccharide to the polyethylene maleic anhydride is 5: 1-1: 5. Preferably, the mass ratio of the natural high molecular polysaccharide to the polyethylene maleic anhydride is 1: 1.
The invention also provides a preparation method of the water-based crosslinking type binder for the lithium ion battery, which comprises the following steps:
s1, adding water into the natural high-molecular polysaccharide, stirring and dissolving to obtain a natural high-molecular polysaccharide solution;
s2, adding an organic solvent into the polyethylene maleic anhydride, and stirring for dissolving to obtain a polyethylene maleic anhydride solution;
s3, dropwise adding a polyethylene maleic anhydride solution into a natural high-molecular polysaccharide solution, then adding an alkali solution, stirring for reaction to obtain a mixed system, adding an acid solution into the mixed system to adjust the pH value to be neutral so as to realize partial lithiation, then concentrating to obtain a concentrated solution, adding the concentrated solution into a settling agent for settling to obtain a white solid, and drying to obtain the aqueous cross-linking type binder.
Further, the mass ratio of the natural high-molecular polysaccharide to the polyethylene maleic anhydride is 5: 1-1: 5. Preferably, the mass ratio of the natural high molecular polysaccharide to the polyethylene maleic anhydride is 1: 1.
Further, the natural high molecular polysaccharide is selected from one or more of acacia, xanthan gum, pectin, carrageenan, agar, curdlan, sodium alginate and chitosan.
Further, the polyethylene maleic anhydride is one or a mixture of homopolymerization alternating type polyethylene maleic anhydride and mixed copolymerization type polyethylene maleic anhydride, and the number average molecular weight M of the polyethylene maleic anhydride is n 10 to 200 ten thousand.
Further, the organic solvent is N, N-dimethylformamide.
Further, lithium hydroxide is selected as the alkali solution.
Further, hydrochloric acid is selected as the acid solution.
Further, the settling agent is methanol or ethanol.
Further, the stirring reaction can be carried out at room temperature or under heating, and the stirring time is 0.2-48 h. Preferably, microwave radiation is carried out in the stirring reaction process, and the temperature of the microwave radiation is 20-120 ℃.
The invention also provides application of the water-based crosslinking adhesive in preparation of a positive pole piece.
The invention also provides a lithium ion secondary battery positive pole piece which is prepared from a current collector and positive pole slurry loaded on the current collector, wherein the positive pole slurry is formed by mixing a positive pole active material, a conductive additive and the water-based crosslinking type binder, and the mass ratio of the positive pole active material to the conductive additive to the water-based crosslinking type binder is (70-85) to (10-20) to (3-10).
Further, the positive active material is a lithium iron phosphate (LFP) positive material.
Further, the conductive additive is one or more of acetylene black, ketjen black, Super P, carbon nano tube and graphene.
The invention also provides a lithium ion secondary battery, which comprises a negative pole piece, an isolating membrane, electrolyte and a positive pole piece of the lithium ion secondary battery.
The water system crosslinking type binder provided by the invention is a crosslinking high molecular polymer formed by the ring-opening esterification or amidation reaction of hydroxyl or amino and anhydride between high molecular polysaccharide and polyethylene maleic anhydride, the preparation process is simple, and the mechanical property of the binder is enhanced by introducing a polyethylene maleic anhydride chain and reacting with polysaccharide to form a crosslinking structure. In addition, a large amount of hydroxyl, carboxylic acid and lithium carboxylate still exist on the molecular structure of the water-based crosslinking type adhesive, so that the adhesive strength of the adhesive is improved, a large amount of inter-chain hydrogen bond acting force and lithium ion conduction sites can be provided due to the existence of the carboxylic acid structure, the stability of the pole piece is enhanced, the lithium ion migration can be promoted, and the multiplying power and the cycle performance of the battery can be obviously improved when the water-based crosslinking type adhesive is applied to the pole piece.
The technical scheme provided by the invention has the beneficial effects that:
1. the preparation method provided by the invention is simple, only two reactant solutions are required to be stirred for reaction, and no by-product polluting the environment is generated in the reaction process; one of the reactants is natural high molecular polymer, the source is wide, the storage capacity is rich, the selling price is low, and the cost for preparing the battery is greatly reduced; when the water-based crosslinking type binder prepared by the invention is used, the prepared binder can be completely dissolved and dispersed only by taking a proper amount of the prepared binder into a beaker, adding a small amount of deionized water and stirring for 5 minutes at normal temperature, so that the real environmental protection, energy conservation, high efficiency, low cost and no pollution are realized; in the aspect of bonding strength, on the premise of ensuring the same dosage, the bonding strength of the water-based crosslinking type bonding agent is superior to that of a commercial bonding agent PVDF, the bonding force is obviously improved on the basis of raw materials, and the obvious bonding advantage is determined; in addition, if the PVDF is used for replacing, the battery preparation process flow can be reserved, and equipment does not need to be updated;
2. the aqueous cross-linking type binder prepared by the invention contains polar groups such as ester groups, carboxyl groups, hydroxyl groups and the like, and also has a lithium carboxylate structure through partial lithiation, and a large number of hydrogen bonds existing among molecules can better maintain the stability of an electrode, so that the synthesized material has good binding capacity; the prepared water-based crosslinking type binder has good thermal stability, and can not generate the condition of binder structure decomposition when being applied to the LFP electrode system at the use temperature;
3. under the same laboratory preparation process, compared with a battery prepared by using a commercial binder PVDF, the rate performance and the battery cycle performance under a large rate of the battery prepared by using the water-based crosslinking binder of the invention are both kept superior, and the theoretical specific capacity of the battery after 20C cycles of 1000 cycles still reaches 108mAh g -1 The coulombic efficiency in the circulating process is kept between 97 and 99 percent, and the excellent circulating and multiplying power performance shows that the water-based crosslinking adhesive has higher commercial value.
Drawings
Fig. 1 is a graph showing the peel strength of a positive electrode sheet prepared using an aqueous cross-linking type adhesive GAE in example 1 of the present invention, PVDF as an adhesive in comparative example 1, and acacia in comparative example 2.
Fig. 2 is a graph showing the battery cycle performance at a high current density of 20C for lithium ion batteries manufactured using different binders according to example 1 of the present invention and comparative example 1.
Fig. 3 is a graph showing the rate performance of the lithium ion battery produced in example 1 of the present invention and the lithium ion battery produced in comparative example 1.
Fig. 4 is a graph of long cycle performance of the lithium ion battery fabricated in example 4 of the present invention and the lithium ion battery fabricated in comparative example 1, tested at a high current density of 20C.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be further described with reference to the following examples and accompanying drawings.
Example 1:
example 1 provides an aqueous crosslinking binder for a positive electrode of a lithium ion battery, a method for preparing the same, and a lithium ion secondary battery including the same.
The preparation process of the water-based crosslinking binder comprises the following steps:
respectively weighing 0.75g of Arabic gum and 0.75g of polyethylene maleic anhydride in a 200mL beaker, adding 50mL of deionized water into the Arabic gum, and stirring and dissolving at room temperature on a magnetic stirrer to obtain Arabic gum solution; adding 50mL of N, N-Dimethylformamide (DMF) into a beaker containing polyethylene maleic anhydride, and heating, stirring and dissolving at 80 ℃ on a magnetic stirrer to obtain a polyethylene maleic anhydride solution; after gum arabic and polyethylene maleic anhydride are completely dissolved, dropwise adding a polyethylene maleic anhydride solution into a gum arabic solution under a normal-temperature stirring state, dropwise adding a lithium hydroxide solution with the concentration of 0.5M until the pH value is 8-10, then placing a reaction beaker into a microwave radiation reactor, setting the power to 800 watts, stirring and reacting at 80 ℃ for 12min, obtaining a mixed system after the reaction is finished, adding a hydrochloric acid solution with the concentration of 0.5M into the mixed system, adjusting the pH value to be neutral, concentrating by using a rotary evaporator to obtain a concentrated solution, settling the concentrated solution in 200mL of an ethanol solution to obtain a white solid, drying the white solid in a blast oven at 60 ℃, and then placing in a vacuum oven at 80 ℃ for drying for 24h to obtain the water-based cross-linking type binder GAE.
The polyethylene maleic anhydride used in this example 1 was homopolymerized alternating polyethylene maleic anhydride, i.e., polyethylene-Alt-maleic anhydride, molecular weight M n Is 100,000 to 500,000D.
The preparation process of the positive electrode plate of the lithium ion battery in this embodiment 1 is as follows: 0.2105g of lithium iron phosphate (LiFePO) 4 ) 0.0602g of acetylene black and 0.0301g of the synthesized water-based cross-linking type adhesive GAE are prepared into anode slurry according to the proportion of 70 wt%, 20 wt% and 10 wt%, the anode slurry is evenly coated on a current collector aluminum foil by a scraper, the current collector aluminum foil is dried for 6 hours in a common air-blast oven at 60 ℃ after the coating is finished, and then the current collector aluminum foil is placed at 80 DEG CAnd (3) drying for 24 hours in a vacuum oven, completely removing residual moisture in the pole piece, and cutting into a circular positive pole piece with the diameter of 15mm by using a slicing machine after drying.
The circular positive electrode sheet made in example 1 was assembled into a button half cell model CR2025 in which the negative and counter electrodes used were lithium metal sheets, the separator used a commercial polypropylene (PP) membrane and the electrolyte was 1M LiPF 6 EC/DMC (1:1, vol%).
Comparative example 1:
comparative example 1 was a button cell assembled by making a positive electrode sheet using PVDF as a commercial binder.
The preparation steps of the positive electrode plate of the lithium ion battery of the comparative example 1 are as follows:
0.2102g of lithium iron phosphate (LiFePO) 4 ) 0.0602g of acetylene black and 0.0304g of PVDF are prepared into anode slurry according to the proportion of 70 wt%, 20 wt% and 10 wt% for coating, the current collector is aluminum foil, after the coating is finished, the anode slurry is placed in a common oven to be dried for 6 hours at 60 ℃, then the anode slurry is dried for 24 hours at 100 ℃ in a vacuum oven, and after the drying is finished, the anode slurry is cut into a circular anode plate with the diameter of 15 mm.
Assembling the prepared positive pole piece into a CR2025 button cell, wherein the used negative pole is a metal lithium piece, the used isolating membrane is a polypropylene membrane (PP membrane), and the electrolyte is 1M LiPF 6 EC/DMC (1:1, vol%).
Comparative example 2:
comparative example 2 was a button cell assembled by using a positive electrode sheet made of gum arabic as a raw material, and the electrochemical behavior was examined.
The preparation of the positive electrode plate of the lithium ion battery of comparative example 2 was as follows:
0.2102g of lithium iron phosphate (LiFePO) 4 ) 0.0602g of acetylene black and 0.0304g of Arabic gum are prepared into positive electrode slurry according to the proportion of 70 wt%, 20 wt% and 10 wt% for coating, the current collector is an aluminum foil, the positive electrode slurry is placed in a common oven to be dried for 6 hours at 60 ℃ after the coating is finished, then the positive electrode slurry is dried in a vacuum oven for 24 hours at 100 ℃, and the positive electrode slurry is cut into a circular positive electrode plate with the diameter of 15mm after the drying is finished.
Subjecting the above-obtained extract to a reactionThe pole piece is assembled into a CR2025 button cell, wherein the used negative electrode is a metal lithium piece, the isolating membrane is a polypropylene membrane (PP membrane), and the electrolyte is 1M LiPF 6 EC/DMC (1:1, vol%).
FIG. 1 is a graph showing the peel strength of a positive electrode sheet prepared using an aqueous cross-linking type binder GAE in example 1, a binder PVDF in comparative example 1, and gum arabic in comparative example 2, and it can be seen from FIG. 1 that the peel strengths of the binders GAE, PVDF, and GA (gum arabic) are 0.38kN/m, 0.24kN/m, and 0.20kN/m, respectively. It can be seen that the bonding strength of the bonding agent GAE prepared in example 1 is significantly better than that of the commercial bonding agent PVDF and the raw material gum arabic, and the battery system is better stabilized in terms of improving the bonding strength, which further illustrates that the use of the bonding agent prepared in example 1 can better improve the cycle and rate performance of the lithium ion battery.
FIG. 2 is a graph showing the cycle performance at a high current density of 20C of the lithium ion batteries manufactured in example 1 and comparative example 1 using different binders, and it can be seen from FIG. 2 that the lithium ion battery manufactured in example 1 has a first discharge specific capacity of up to 108mAh g at a high current density of 20C -1 And in the subsequent cycle process of 1000 cycles, the coulombic efficiency is close to 100%, and after the battery is cycled for 1000 cycles, the discharge specific capacity of the battery is still basically consistent with the initial specific capacity, and the battery is basically free from attenuation. The binder GAE of example 1 has a clear advantage over the commercial binder PVDF, both in terms of specific discharge capacity and cycling stability. The use of the binder GAE is proved to well promote the migration of ions, improve the diffusion rate, ensure that the lithium ion battery still has ultrahigh specific discharge capacity under high current density, and remarkably improve the advantages of the lithium ion battery in quick charge and quick discharge performance.
Fig. 3 is a performance graph of the rate of the lithium ion battery manufactured in example 1 and the lithium ion battery manufactured in comparative example 1, and it can be seen from fig. 3 that, in the case of current densities of 5C, 10C, 15C and 20C, the discharge specific capacity of the battery manufactured by the binder GAE is significantly improved compared with the battery manufactured by the commercial binder PVDF, and it is further shown that the binder GAE helps to ensure the integrity of the battery pole piece at high current density and promote the transmission of lithium ions.
Example 2:
example 2 provides an aqueous crosslinking binder for a positive electrode of a lithium ion battery, a method for preparing the same, and a lithium ion secondary battery including the same.
The preparation process of the water-based crosslinking binder comprises the following steps:
respectively weighing 1.5g of pectin and 0.75g of polyethylene maleic anhydride in a 200mL beaker, adding 50mL of deionized water into the pectin, and stirring and dissolving at room temperature on a magnetic stirrer to obtain a pectin solution; adding 50mL of N, N-Dimethylformamide (DMF) into a beaker containing polyethylene maleic anhydride, and heating, stirring and dissolving at 80 ℃ on a magnetic stirrer to obtain a polyethylene maleic anhydride solution; after completely dissolving pectin and polyethylene maleic anhydride, dropwise adding a polyethylene maleic anhydride solution into the pectin solution under the state of stirring at normal temperature, dropwise adding a lithium hydroxide solution with the concentration of 0.5M until the pH value is 8-10, then placing a reaction beaker in a microwave radiation reactor, setting the power to 800 watts, stirring and reacting at 80 ℃ for 12min to obtain a mixed system after the reaction is finished, adding a hydrochloric acid solution with the concentration of 0.5M into the mixed system, adjusting the pH value to be neutral, concentrating by using a rotary evaporator to obtain a concentrated solution, settling the concentrated solution in 200mL of ethanol solution to obtain a white solid, drying the white solid in a blast oven at 60 ℃, and then placing in a vacuum oven at 80 ℃ for drying for 24h to obtain the water-based crosslinking type binder GAE-1.
The preparation process of the positive electrode plate of the lithium ion battery in the embodiment 2 is as follows: 0.2251g of lithium iron phosphate (LiFePO) 4 ) 0.0601g of acetylene black and 0.0150g of the synthesized aqueous cross-linking type binder GAE-1 are prepared into positive electrode slurry according to the proportion of 75 wt%, 20 wt% and 5 wt%, the positive electrode slurry is uniformly coated on a current collector aluminum foil by using a scraper, after the coating is finished, the current collector aluminum foil is placed in a common air-blowing oven at 60 ℃ for drying for 6 hours, then the current collector aluminum foil is placed in a vacuum oven at 80 ℃ for drying for 24 hours, residual moisture in the pole piece is completely removed, and the circular positive pole piece with the diameter of 15mm is cut by using a slicing machine after the drying is finished.
The circular positive electrode manufactured in example 2 was usedThe sheets were assembled into a CR2025 model button half cell in which the negative and counter electrodes used were lithium metal sheets, the separator used a commercial polypropylene (PP) membrane and the electrolyte was 1M LiPF 6 EC/DMC (1:1, vol%).
Example 3:
example 3 provides an aqueous crosslinking binder for a positive electrode of a lithium ion battery, a method for preparing the same, and a lithium ion secondary battery including the same.
The preparation process of the water-based crosslinking binder comprises the following steps:
respectively weighing 3g of agar and 0.75g of polyethylene maleic anhydride in a 200mL beaker, adding 50mL of deionized water into the agar, and stirring and dissolving at room temperature on a magnetic stirrer to obtain an agar solution; adding 50mL of N, N-Dimethylformamide (DMF) into a beaker containing polyethylene maleic anhydride, and heating, stirring and dissolving the mixture on a magnetic stirrer at 80 ℃ to obtain a polyethylene maleic anhydride solution; after agar and polyethylene maleic anhydride are completely dissolved, dropwise adding a polyethylene maleic anhydride solution into the agar solution under the condition of stirring at normal temperature, dropwise adding a lithium hydroxide solution with the concentration of 0.5M until the pH value is 8-10, then placing a reaction beaker in a microwave radiation reactor, setting the power to 800 watts, stirring and reacting at 80 ℃ for 12min to obtain a mixed system after the reaction is finished, adding a hydrochloric acid solution with the concentration of 0.5M into the mixed system, adjusting the pH value to be neutral, concentrating by using a rotary evaporator to obtain a concentrated solution, settling the concentrated solution in 200mL of ethanol solution to obtain a white solid, drying the white solid in a blast oven at 60 ℃, and then placing in a vacuum oven at 80 ℃ for drying for 24h to obtain the water-based crosslinking type binder GAE-2.
The preparation process of the lithium ion battery cathode material of the embodiment 3 is as follows: 0.2105g of lithium iron phosphate (LiFePO) 4 ) 0.0602g of Super P, 0.0301g of the synthesized water-based cross-linking type adhesive GAE-2 is prepared into anode slurry according to the proportion of 70 wt%, 20 wt% and 10 wt%, the anode slurry is evenly coated on a current collector aluminum foil by using a scraper, after the coating is finished, the current collector aluminum foil is placed in a common air-blast oven at 60 ℃ for drying for 6h, then the current collector aluminum foil is placed in a vacuum oven at 80 ℃ for drying for 24h, and the anode is completely removedAnd (4) cutting residual moisture in the sheet into a circular positive pole piece with the diameter of 15mm by using a slicing machine after drying.
The circular positive electrode sheet made in example 3 was assembled into a button half cell model CR2025 in which the negative and counter electrodes used were lithium metal sheets, the separator used a commercial polypropylene (PP) membrane and the electrolyte was 1M LiPF 6 EC/DMC (1:1, vol%).
Example 4:
example 4 provides an aqueous crosslinking binder for a positive electrode of a lithium ion battery, a method for preparing the same, and a lithium ion secondary battery including the same.
The preparation process of the water-based crosslinking binder comprises the following steps:
respectively weighing 0.75g of Arabic gum and 0.75g of polyethylene maleic anhydride in a 200mL beaker, adding 50mL of deionized water into the Arabic gum, and stirring and dissolving at room temperature on a magnetic stirrer to obtain Arabic gum solution; adding 50mL of N, N-Dimethylformamide (DMF) into a beaker containing polyethylene maleic anhydride, and heating, stirring and dissolving at 80 ℃ on a magnetic stirrer to obtain a polyethylene maleic anhydride solution; after gum arabic and polyethylene maleic anhydride are completely dissolved, dropwise adding a polyethylene maleic anhydride solution into the gum arabic solution under a normal-temperature stirring state, dropwise adding a lithium hydroxide solution with the concentration of 0.5M until the pH value is 8-10, heating and stirring at 60 ℃ for reaction for 48 hours, obtaining a mixed system after the reaction is finished, adding a hydrochloric acid solution with the concentration of 0.5M into the mixed system, adjusting the pH value to be neutral, concentrating by using a rotary evaporator to obtain a concentrated solution, settling the concentrated solution in 200mL of ethanol solution to obtain a white solid, drying the white solid in a blast oven at 60 ℃, and drying in a vacuum oven at 80 ℃ for 24 hours to obtain the water-based cross-linked binder GAE.
The polyethylene maleic anhydride used in this example 4 is alternating polyethylene maleic anhydride, i.e. polyethylene-Alt-maleic anhydride, molecular weight M n Is 100,000 to 500,000D.
The preparation processes of the lithium ion battery positive electrode plate and the lithium ion battery in the embodiment 4 are the same as those in the embodiment 1.
Fig. 4 is a graph of long cycle performance of the lithium ion battery fabricated in example 4 and the lithium ion battery fabricated in comparative example 1, tested at a high current density of 20C. As can be seen from fig. 4, the battery prepared from the binder GAE of example 4 had better data stability in the 20C rate test than the corresponding battery prepared using the binder PVDF with a specific capacity decay of less than 2.7 units during 1000 cycles of cycling test. It can be further demonstrated that the lithium ion battery prepared by using the binder GAE of this example has better electrode stability.
Example 5:
example 5 provides an aqueous crosslinking binder for a positive electrode of a lithium ion battery, a method for preparing the same, and a lithium ion secondary battery including the same.
The preparation process of the water-based crosslinking binder comprises the following steps:
respectively weighing 0.75g of sodium alginate and 0.75g of polyethylene maleic anhydride in a 200mL beaker, adding 50mL of deionized water into the sodium alginate, and stirring and dissolving at room temperature on a magnetic stirrer to obtain a sodium alginate solution; adding 50mL of N, N-Dimethylformamide (DMF) into a beaker containing polyethylene maleic anhydride, and heating, stirring and dissolving at 80 ℃ on a magnetic stirrer to obtain a polyethylene maleic anhydride solution; after completely dissolving sodium alginate and polyethylene maleic anhydride, dropwise adding a polyethylene maleic anhydride solution into a sodium alginate solution under the state of stirring at normal temperature, dropwise adding a lithium hydroxide solution with the concentration of 0.5M until the pH value is between 8 and 10, then placing a reaction beaker into a microwave radiation reactor, setting the power to 800 watts, stirring and reacting at 80 ℃ for 12min, obtaining a mixed system after the reaction is finished, adding a hydrochloric acid solution with the concentration of 0.5M into the mixed system, adjusting the pH value to be neutral, concentrating by using a rotary evaporator to obtain a concentrated solution, settling the concentrated solution in 200mL of an ethanol solution to obtain a white solid, drying the white solid in a blast oven at 60 ℃, and then placing in a vacuum oven at 80 ℃ for drying for 24h to obtain the water-based crosslinking type binder GAE-3.
The preparation processes of the positive electrode plate of the lithium ion battery and the lithium ion battery in the embodiment 5 are the same as those in the embodiment 1.
Example 6:
example 6 provides an aqueous crosslinking binder for a positive electrode of a lithium ion battery, a method for preparing the same, and a lithium ion secondary battery including the same.
Example 6 the procedure for preparing the aqueous crosslinking type adhesive GAE-3 was the same as in example 5.
The preparation process of the lithium ion battery positive electrode piece of the embodiment 6 is as follows: 0.2251g of lithium iron phosphate (LiFePO) 4 ) 0.0601g of acetylene black and 0.0150g of synthesized aqueous cross-linking type binder GAE-3 are prepared according to the proportion of 75 wt%, 20 wt% and 5 wt% to obtain positive electrode slurry, the positive electrode slurry is uniformly coated on a current collector aluminum foil by using a scraper, after the coating is finished, the positive electrode slurry is placed in a common air-blowing oven at 60 ℃ for drying for 6 hours, then the positive electrode slurry is placed in a vacuum oven at 80 ℃ for drying for 24 hours, residual moisture in the electrode piece is completely removed, and after the drying is finished, the positive electrode piece is cut into a circular positive electrode piece with the diameter of 15mm by using a slicing machine.
The circular positive electrode sheet made in example 6 was assembled into a button half cell model CR2025 in which the negative and counter electrodes used were lithium metal sheets, the separator used a commercial polypropylene (PP) membrane and the electrolyte was 1M LiPF 6 EC/DMC (1:1, vol%).
Example 7:
example 7 provides an aqueous crosslinked binder for a positive electrode of a lithium ion battery, a method for preparing the same, and a lithium ion secondary battery including the same.
The preparation process of the water-based crosslinking binder comprises the following steps:
respectively weighing 0.75g of carrageenan and 1.5g of polyethylene maleic anhydride in a 200mL beaker, adding 50mL of deionized water into the carrageenan, and stirring and dissolving the carrageenan on a magnetic stirrer at room temperature to obtain a carrageenan solution; adding 50mL of N, N-Dimethylformamide (DMF) into a beaker containing polyethylene maleic anhydride, and heating, stirring and dissolving the mixture on a magnetic stirrer at 80 ℃ to obtain a polyethylene maleic anhydride solution; after carrageenin and polyethylene maleic anhydride are completely dissolved, dropwise adding a polyethylene maleic anhydride solution into the carrageenin solution under the condition of stirring at normal temperature, dropwise adding a lithium hydroxide solution with the concentration of 0.5M until the pH value is between 8 and 10, then placing a reaction beaker into a microwave radiation reactor, setting the power to 800 watts, stirring and reacting for 12min at 80 ℃, obtaining a mixed system after the reaction is finished, adding a hydrochloric acid solution with the concentration of 0.5M into the mixed system, adjusting the pH value to be neutral, concentrating by using a rotary evaporator to obtain a concentrated solution, settling the concentrated solution in 200mL of ethanol solution to obtain a white solid, drying the white solid in a blast oven at 60 ℃, and then placing in a vacuum oven at 80 ℃ for drying for 24h to obtain the water-based crosslinking type binder GAE-4.
The preparation processes of the positive electrode plate of the lithium ion battery and the lithium ion battery in this example 7 are the same as those in example 1.
Example 8:
example 8 provides an aqueous crosslinking binder for a positive electrode of a lithium ion battery, a method for preparing the same, and a lithium ion secondary battery including the same.
The preparation process of the water-based crosslinking binder comprises the following steps:
respectively weighing 0.75g of xanthan gum and 3g of polyethylene maleic anhydride in a 200mL beaker, adding 50mL of deionized water into the xanthan gum, and stirring and dissolving at room temperature on a magnetic stirrer to obtain a xanthan gum solution; adding 50mL of N, N-Dimethylformamide (DMF) into a beaker containing polyethylene maleic anhydride, and heating, stirring and dissolving at 80 ℃ on a magnetic stirrer to obtain a polyethylene maleic anhydride solution; after completely dissolving xanthan gum and polyethylene maleic anhydride, dropwise adding a polyethylene maleic anhydride solution into a xanthan gum solution under a normal-temperature stirring state, dropwise adding a lithium hydroxide solution with the concentration of 0.5M until the pH value is 8-10, then placing a reaction beaker into a microwave radiation reactor, setting the power to 800 watts, stirring and reacting at 80 ℃ for 12min to obtain a mixed system after the reaction is finished, adding a hydrochloric acid solution with the concentration of 0.5M into the mixed system, adjusting the pH value to be neutral, concentrating by using a rotary evaporator to obtain a concentrated solution, settling the concentrated solution in 200mL of ethanol solution to obtain a white solid, drying the white solid in a blast oven at 60 ℃, and then placing in a vacuum oven at 80 ℃ for drying for 24h to obtain the water-based crosslinking type binder GAE-5.
The preparation processes of the positive electrode plate of the lithium ion battery and the lithium ion battery in this embodiment 8 are the same as those in embodiment 1.
In conclusion, the lithium ion battery assembled by the water-based crosslinking type binder prepared by the invention has excellent comprehensive performance, is green, cheap and easily available in raw materials, is efficient, environment-friendly, safe and pollution-free in use, has outstanding fast charge and fast discharge performance, and has wide application prospect.
The features of the embodiments and embodiments described herein above may be combined with each other without conflict.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (6)

1. A preparation method of a water-based crosslinking type binder for a lithium ion battery is characterized by comprising the following steps:
s1, adding water into the natural high molecular polysaccharide, stirring and dissolving to obtain a natural high molecular polysaccharide solution;
s2, adding an organic solvent into the polyethylene maleic anhydride, and stirring for dissolving to obtain a polyethylene maleic anhydride solution;
s3, dropwise adding a polyethylene maleic anhydride solution into a natural high-molecular polysaccharide solution, then adding lithium hydroxide, stirring for reaction, performing microwave radiation to obtain a mixed system, adding hydrochloric acid into the mixed system to adjust the pH value, then concentrating to obtain a concentrated solution, adding the concentrated solution into a settling agent for settling to obtain a white solid, and drying to obtain a water-based crosslinking binder;
the settling agent is methanol or ethanol;
the natural high molecular polysaccharide is selected from one or more of arabic gum, xanthan gum, pectin, carrageenan, agar, curdlan and sodium alginate; the polyethylene maleic anhydride is one or a mixture of homopolymerization alternating type polyethylene maleic anhydride and mixed copolymerization type polyethylene maleic anhydride.
2. The method for preparing an aqueous crosslinked binder for a lithium ion battery according to claim 1, wherein the mass ratio of the natural polymer polysaccharide to the polyethylene maleic anhydride is 5:1 to 1: 5.
3. The application of the water-based cross-linking adhesive prepared by the preparation method of any one of claims 1-2 in preparing a positive pole piece.
4. A positive pole piece of a lithium ion secondary battery is characterized by being prepared from a current collector and positive pole slurry loaded on the current collector, wherein the positive pole slurry is prepared by mixing a positive pole active material, a conductive additive and a water-based crosslinking type binder, and the water-based crosslinking type binder is prepared by the preparation method of any one of claims 1-2, wherein the mass ratio of the positive pole active material to the conductive additive to the water-based crosslinking type binder is (70-85): (10-20): (3-10).
5. The positive electrode plate of the lithium-ion secondary battery as claimed in claim 4, wherein the positive active material is a lithium iron phosphate positive electrode material; the conductive additive is one or more of acetylene black, Ketjen black, Super P, carbon nanotube and graphene.
6. A lithium ion secondary battery, characterized by comprising a negative electrode sheet, a separator, an electrolyte and the positive electrode sheet of the lithium ion secondary battery of claim 4 or 5.
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