CN115064697A - Application of modified polyacrylonitrile, binder, negative plate and lithium ion battery - Google Patents

Application of modified polyacrylonitrile, binder, negative plate and lithium ion battery Download PDF

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Publication number
CN115064697A
CN115064697A CN202210826356.5A CN202210826356A CN115064697A CN 115064697 A CN115064697 A CN 115064697A CN 202210826356 A CN202210826356 A CN 202210826356A CN 115064697 A CN115064697 A CN 115064697A
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binder
polyacrylonitrile
negative electrode
lithium ion
ion battery
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袁淑霞
李欣芷
吕春祥
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/027—Negative electrodes

Abstract

The invention relates to application of modified polyacrylonitrile, a binder, a negative plate and a lithium ion battery, and relates to the technical field of lithium batteries. The main technical scheme adopted is as follows: the invention provides application of modified polyacrylonitrile in preparation of a lithium battery negative electrode binder, wherein the modified polyacrylonitrile is a hydrolysis product of polyacrylonitrile. In addition, the invention also provides a lithium ion battery cathode binder which comprises 50-95% of modified polyacrylonitrile and 5-50% of thickening agent. The invention is mainly used for providing a new application of modified polyacrylonitrile in preparing a lithium battery cathode binder, under the synergistic action of various beneficial functional groups, the binder can form stronger interaction with an active substance and a current collector, has higher bonding strength and excellent mechanical properties, can effectively relieve volume expansion of a cathode plate in the charging and discharging processes, and improves the capacity retention rate and the cycle stability of a battery. In addition, the binder and the preparation method thereof have the advantages of low cost, simple process and environmental protection.

Description

Application of modified polyacrylonitrile, binder, negative plate and lithium ion battery
Technical Field
The invention relates to the technical field of lithium batteries, in particular to application of modified polyacrylonitrile, a binder, a negative plate and a lithium ion battery.
Background
The lithium ion battery has the advantages of high energy density and power density, low self-discharge rate, long cycle life and the like, and is widely applied to the fields of portable equipment, electric automobiles, aerospace and the like.
At present, graphite materials are generally adopted as negative electrode materials of commercial lithium ion batteries, but the theoretical specific capacity of the lithium ion batteries is only 372mAh/g, and lithium dendrites are easily formed, so that potential safety hazards are generated. Silicon has extremely high theoretical specific capacity (4200mAh/g), abundant reserves in the earth crust and low working voltage, and is expected to replace graphite to become one of the most promising negative electrode materials of the new-generation lithium ion battery. However, silicon generates a large volume change during charging and discharging, which causes active material to be broken, electrical contact to be lost, and a surface SEI film to be broken and regenerated continuously, which increases consumption of an electrolyte, and finally causes capacity attenuation and rate performance reduction. In order to solve the problems, most of the prior art focuses on the active material itself, and measures such as size and structure regulation or compounding with other materials are adopted, but the methods are complex in process, high in cost and difficult to realize industrialization.
Although the binder accounts for a small proportion in an electrode system, the binder is a source of the mechanical property of the whole electrode, and plays an important role in maintaining the structural integrity of the electrode, promoting lithium ion transmission, relieving the expansion of active substances, maintaining the stability of an SEI film and the like.
Currently, polyvinylidene fluoride (PVDF), styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC), polyacrylic acid (PAA), and the like are commonly used as binders for lithium ion batteries. Among them, PVDF is generally dissolved by an organic solvent N-methyl pyrrolidone (NMP), which causes serious environmental pollution, high swelling rate of the pole piece, poor mechanical properties, weak binding force with silicon-based active materials, and influences capacity exertion and cycling stability. CMC has poor cohesiveness and high brittleness, is often combined with SBR in industry, but SBR lacks beneficial functional groups, is not suitable for silicon-based active substances with large volume expansion, and cannot maintain the structural integrity of an electrode. Although the PAA binder has strong cohesiveness and can form strong connection with an active substance through a hydrogen bond effect, the PAA binder is easy to generate an agglomeration effect due to a large amount of carboxyl, so that the binder solution is gelatinous and has extremely poor fluidity, the difficulty of a coating process is increased, and the uniform distribution of each component in a pole piece is influenced. In addition, the PAAli is obtained by industrially neutralizing part of carboxyl groups with LiOH, and the binder is the best performance in the current commercial lithium battery negative electrode binder; but the high-expansion silicon-based negative electrode has poor mechanical properties, is cold, brittle and hot, and has limited interface strengthening effect of a single functional group in a binder molecule in a multi-interface electrode system, so that the high-expansion silicon-based negative electrode cannot meet the long-cycle use requirement of the high-expansion silicon-based negative electrode.
Therefore, in view of the above problems, it is necessary to provide a novel adhesive having excellent properties.
Disclosure of Invention
In view of the above, the invention provides an application of modified polyacrylonitrile, a binder, a negative plate and a lithium ion battery, and mainly aims to provide an application of modified polyacrylonitrile in a lithium battery negative binder; the binder prepared from the modified polyacrylonitrile has excellent performance, can effectively relieve volume expansion of a negative plate in the charge and discharge processes, and improves the capacity retention rate and the cycle stability of a battery.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
on one hand, the embodiment of the invention provides application of modified polyacrylonitrile, a binder, a negative plate and a lithium ion battery, wherein the modified polyacrylonitrile is a hydrolysis product of polyacrylonitrile.
Preferably, the modacrylic contains a cyano group, a carboxylate group, and an amide group.
Preferably, the modified polyacrylonitrile and the thickening agent are applied to the preparation of the lithium battery negative electrode binder; preferably, the modified polyacrylonitrile and the thickening agent are compounded to be used as a lithium battery negative electrode binder; preferably, in the lithium battery negative electrode binder: the mass fraction of the modified polyacrylonitrile is 50-95%, and the mass fraction of the thickening agent is 5-50%; preferably, the thickener is one or more of starch, chitosan, xanthan gum, guar gum, agar, alginate jelly, cyclodextrin, carboxymethyl cellulose and polyacrylic acid.
Preferably, the preparation method of the modified polyacrylonitrile comprises the following steps:
hydrolysis treatment: hydrolyzing polyacrylonitrile raw material under the set temperature and alkaline condition to obtain a product mixture after hydrolysis;
and (3) post-treatment: carrying out post-treatment on the product mixture after the hydrolysis treatment to obtain a polyacrylonitrile hydrolysate; wherein the polyacrylonitrile hydrolysis product is the modacrylic.
Preferably, in the step of the hydrolysis treatment: the set temperature is 70-200 ℃, preferably 100-170 ℃, and more preferably 120-150 ℃.
Preferably, in the step of the hydrolysis treatment: the time of the hydrolysis treatment is 1-8 h; preferably 2-4 h.
Preferably, in the step of the hydrolysis treatment: the alkaline condition is provided by one or more alkaline substances of sodium hydroxide, potassium hydroxide and lithium hydroxide.
Preferably, in the step of hydrolysis treatment, polyacrylonitrile raw material, alkaline substance and deionized water are uniformly mixed to obtain reaction liquid; heating the reaction solution to the set temperature, and carrying out hydrolysis treatment; further preferably, the pH value of the reaction solution is 8-14, preferably 10-14; more preferably, the mass concentration of the polyacrylonitrile raw material in the reaction solution is 1 to 50%, preferably 1 to 30%, and more preferably 5 to 30%.
Preferably, in the step of hydrolysis treatment, the polyacrylonitrile raw material has the molecular weight of 50000-300000g/mol, and further preferably 80000-250000 g/mol.
Preferably, in the step of post-processing: and the post-treatment comprises the steps of filtering, dialyzing, precipitating, cleaning and drying the product mixture after the hydrolysis treatment, and the obtained solid powder is the polyacrylonitrile hydrolysate.
In another aspect, the embodiment of the invention provides a lithium battery negative electrode binder, which comprises, by mass, 50-95% of modified polyacrylonitrile and 5-50% of a thickener; wherein the modified polyacrylonitrile is a hydrolysis product of polyacrylonitrile. Preferably, the modacrylic contains a cyano group, a carboxylate group, and an amide group. Preferably, the thickener is one or more of starch, chitosan, xanthan gum, guar gum, agar, alginate jelly, cyclodextrin, carboxymethyl cellulose and polyacrylic acid.
In another aspect, an embodiment of the present invention further provides a lithium ion battery negative electrode sheet, where the lithium ion battery negative electrode sheet includes the lithium ion battery negative electrode binder.
In another aspect, an embodiment of the present invention further provides a method for preparing a lithium ion battery negative electrode sheet, which includes the following steps:
preparing a binder solution: fully dissolving modified polyacrylonitrile and a thickening agent in a solvent to obtain a binder solution;
preparing anode slurry: adding a conductive agent and a negative electrode active material into the binder solution, and uniformly mixing to obtain negative electrode slurry;
preparing a negative plate: and coating the negative electrode slurry on a current collector, and drying to obtain the lithium ion battery negative electrode plate.
Preferably, in the preparation of the binder solution, the solvent is selected from water, preferably deionized water.
Preferably, deionized water is also added in the preparation of the negative electrode slurry.
Preferably, in the negative electrode slurry, the mass fraction of the binder is 5 to 20%.
Preferably, the conductive agent is one or more of Super P, acetylene black, carbon nanotubes, Ketjen black and graphene.
Preferably, the current collector is a conductive metal foil or mesh, more preferably a foil or mesh of copper, aluminum, nickel, stainless steel, and particularly preferably a copper foil.
Preferably, the negative active material is one or two of a silicon-based material and a carbon-based material.
Preferably, the silicon-based material is one or more of silicon, silicon oxide and a silicon-carbon composite material, preferably silicon, and further preferably nano silicon.
Preferably, the carbon material is one or more of graphite, soft carbon and hard carbon.
In another aspect, an embodiment of the present invention provides a lithium ion battery, where the lithium ion battery includes a lithium ion battery negative electrode sheet; the lithium ion battery negative plate is the lithium ion battery negative plate; or the lithium ion battery negative plate is prepared by the preparation method of the lithium ion battery negative plate.
Compared with the prior art, the application of the modified polyacrylonitrile, the binder, the negative plate and the lithium ion battery have at least the following beneficial effects:
on one hand, the embodiment of the invention provides a new application of modified polyacrylonitrile in preparation of a lithium ion battery cathode binder; wherein the modified polyacrylonitrile is a hydrolysis product of polyacrylonitrile. Here, the following description is required for this application: the polyacrylonitrile has high modulus and strength, excellent mechanical property, is beneficial to inhibiting the volume expansion of active substances, contains strong polar cyano functional groups, and is easy to form strong dipole-dipole interaction with surrounding substances, so that the polyacrylonitrile has strong cohesiveness to a current collector. The modified polyacrylonitrile (hydrolysis product of polyacrylonitrile) also has strong polar amide groups and carboxylate groups, and the functional groups can form a strong hydrogen bond action with hydroxyl on the surface of an active substance, and are particularly favorable for maintaining the structural integrity of an electrode and improving the circulation stability of a silicon-based negative electrode with large volume expansion. Therefore, the modified polyacrylonitrile for preparing the battery cathode binder has excellent mechanical property and binding property, can effectively relieve the volume expansion of the cathode sheet in the charging and discharging processes, improves the capacity retention rate and the cycle stability of the battery, and is particularly suitable for silicon cathodes with large volume expansion.
Further, the embodiment of the invention also provides a lithium ion battery cathode binder prepared by compounding modified polyacrylonitrile and a thickening agent; here, it should be noted that: hydroxyl groups, carboxylate groups, amide groups, cyano groups and the like widely existing in a system formed by compounding the modified polyacrylonitrile and the thickening agent can form a physically-crosslinked network structure, so that the improvement of mechanical properties is facilitated, the volume expansion of silicon is further relieved, and lithium ion transmission is facilitated, so that the rate capability is improved.
Further, the thickening agent adopted in the embodiment of the invention mainly comprises one or more of starch, chitosan, xanthan gum, guar gum, agar, seaweed gel, cyclodextrin, carboxymethyl cellulose and polyacrylic acid. Here, it should be noted that: the modified polyacrylonitrile contains three strong polar functional groups, and the thickening agents of the types contain a large number of strong polar functional groups, so that the modified polyacrylonitrile and the thickening agents can form strong intermolecular hydrogen bond action after being compounded to form a physical crosslinking network structure, on one hand, the viscosity of the modified polyacrylonitrile can be improved, and the stable slurry can be formed; on the other hand, the mechanical property of the modified polyacrylonitrile or the thickening agent which is independently used as the binder can be improved, and the volume expansion of silicon can be better buffered; moreover, the existence of the network structure is beneficial to the transmission of lithium ions and is beneficial to improving the rate capability.
In addition, the embodiment of the invention also provides a lithium ion battery cathode binder, a lithium ion battery cathode and a lithium battery, and the binder including the modified polyacrylonitrile (preferably, the modified polyacrylonitrile + the thickener) is adopted, so that the binder has the beneficial effects, and repeated description is omitted here. In addition, the preparation process of the binder provided by the embodiment of the invention has the advantages of simplicity, easiness in operation and low cost, and is easy to realize industrial production.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
Fig. 1 is a graph comparing the cycle performance curves of lithium batteries using the binders prepared in example 4 and comparative example 2.
Fig. 2 is a graph comparing rate performance curves of lithium batteries using the binders prepared in example 4 and comparative example 2.
Fig. 3 is a graph comparing cycle performance curves of lithium batteries using the binders prepared in example 4, comparative example 1, and comparative example 4.
Fig. 4 is a graph comparing the cycle performance curves of lithium batteries using the binders prepared in example 6 and comparative example 3.
Fig. 5 is a graph comparing the cycle performance curves of lithium batteries using binders prepared in examples 1, 2, 3, 5, 7, 8, 9, and 10.
Detailed Description
To further explain the technical means and effects of the present invention adopted to achieve the predetermined object, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
Based on the problems of the current commercial negative electrode binder, the invention mainly provides the application of modified polyacrylonitrile, the binder, a negative electrode plate and a lithium ion battery, and the specific scheme of the invention is as follows:
on one hand, the embodiment of the invention provides application of modified polyacrylonitrile in preparation of a lithium battery negative electrode binder, wherein the modified polyacrylonitrile is a hydrolysis product of polyacrylonitrile.
The invention firstly proposes that the modified polyacrylonitrile (namely, the hydrolysis product of the polyacrylonitrile) can be used for preparing the lithium battery cathode binder. It should be noted here that: on one hand, polyacrylonitrile has high modulus and strength, excellent mechanical property, is beneficial to inhibiting the volume expansion of active substances, contains strong polar cyano functional groups, and is easy to form strong dipole-dipole interaction with surrounding substances, so that the polyacrylonitrile has strong cohesiveness to a current collector. On the basis, polyacrylonitrile is hydrolyzed under the conditions of heating and alkalinity to obtain strong polar amide groups and carboxylate groups, the functional groups can form strong hydrogen bond action with hydroxyl on the surface of an active substance, and particularly for a silicon-based negative electrode with large volume expansion, the structural integrity of the electrode is favorably maintained, and the circulation stability is improved.
Preferably, the modified polyacrylonitrile contains a cyano group, a carboxylate group and an amide group. Here, it should be noted that: in the prior art, for hydrolysis of polyacrylonitrile, cyano groups are not reserved as much as possible (the cyano groups are hydrolyzed as much as possible and replaced by other groups), but the modified polyacrylonitrile disclosed by the invention contains three groups, namely the cyano groups, carboxylate groups and amide groups, so that the modified polyacrylonitrile has excellent mechanical properties and adhesive properties, can form a strong hydrogen bond effect with hydroxyl on the surface of an active substance, and is particularly favorable for maintaining the structural integrity of an electrode and improving the circulation stability of a silicon-based negative electrode with large volume expansion.
Preferably, the modified polyacrylonitrile and the thickening agent are applied to preparing the lithium battery negative electrode binder. The modified polyacrylonitrile and the thickening agent are compounded to be used as a lithium battery negative electrode binder; wherein, in the lithium battery negative electrode binder: the mass fraction of the modified polyacrylonitrile is 50-95%, and the mass fraction of the thickening agent is 5-50%. Wherein the thickener is selected from one or more of starch, chitosan, xanthan gum, guar gum, agar, alginate jelly, cyclodextrin, carboxymethyl cellulose, and polyacrylic acid. Here, it should be noted that: hydroxyl, carboxylate groups, amide groups, cyano groups and the like widely existing in a system after the modified polyacrylonitrile and the thickening agent are compounded can form a physically-crosslinked network structure, so that the improvement of mechanical properties is facilitated, the volume expansion of silicon is further relieved, and lithium ion transmission is facilitated, so that the rate capability is improved.
Preferably, the modified polyacrylonitrile is prepared by the following steps:
hydrolysis treatment: and (3) carrying out hydrolysis treatment on the polyacrylonitrile raw material under the set temperature and alkaline condition to obtain a product mixture after hydrolysis treatment. Wherein the set temperature is 70-200 ℃, preferably 100-170 ℃, and more preferably 120-150 ℃. The time of the hydrolysis treatment is 1-8 h; preferably 2-4 h. Wherein the alkaline condition is provided by one or more alkaline substances of sodium hydroxide, potassium hydroxide and lithium hydroxide. In the step of hydrolysis treatment, polyacrylonitrile raw materials, alkaline substances and deionized water are uniformly mixed to obtain reaction liquid, and the reaction liquid is heated to a set temperature for hydrolysis treatment; further preferably, the pH value of the reaction solution is 8-14, preferably 10-14; further preferably, the concentration of the polyacrylonitrile raw material in the reaction solution is 1 to 50%, preferably 1 to 30%, and further preferably 5 to 30%. Wherein the molecular weight of the polyacrylonitrile raw material is 50000-300000g/mol, and is more preferably 80000-250000 g/mol. Here, regarding the polyacrylonitrile raw material: the polyacrylonitrile raw material can be powder, solution or waste in the carbon fiber production process, such as waste silk and waste film.
And (3) post-treatment: carrying out post-treatment on the product mixture after the hydrolysis treatment to obtain a polyacrylonitrile hydrolysate; wherein the polyacrylonitrile hydrolysis product is the modacrylic. Wherein, in the step of post-processing: and the post-treatment comprises the steps of filtering, dialyzing, precipitating, cleaning and drying the product mixture after the hydrolysis treatment, and the obtained solid powder is the polyacrylonitrile hydrolysate.
In another aspect, the embodiment of the invention provides a lithium battery negative electrode binder, wherein the lithium battery negative electrode binder comprises, by mass, 50-95% of modacrylic and 5-50% of a thickening agent; wherein the modified polyacrylonitrile is a hydrolysis product of polyacrylonitrile. Preferably, the modacrylic contains a cyano group, a carboxylate group, and an amide group. Preferably, the thickener is one or more selected from starch, chitosan, xanthan gum, guar gum, agar, alginate jelly, cyclodextrin, carboxymethyl cellulose, and polyacrylic acid. In addition, for the preparation of the modacrylic, the preparation method is referred to, and the details are not repeated.
In another aspect, an embodiment of the present invention provides a lithium ion battery negative electrode sheet, where the lithium ion battery negative electrode sheet includes the lithium ion battery negative electrode binder.
The preparation method of the lithium ion battery negative plate comprises the following steps:
preparing a binder solution: and (3) fully dissolving the modified polyacrylonitrile and the thickening agent in a solvent to obtain a binder solution. Wherein, the solvent is selected from water (preferably deionized water).
Preparing anode slurry: and adding a conductive agent and a negative electrode active material into the binder solution, and mixing to obtain negative electrode slurry. Wherein, in the negative electrode slurry, the mass fraction of the binder is 5-20%. The conductive agent is one or more of Super P, acetylene black, carbon nano tubes, Ketjen black and graphene. Wherein, the negative active material is one or two of silicon-based material and carbon material. The silicon-based material is one or more of silicon, silicon oxide and a silicon-carbon composite material, preferably silicon, and further preferably nano silicon. Wherein the carbon material is one or more of graphite, soft carbon and hard carbon.
Preparing a negative plate: and coating the negative electrode slurry on a current collector, and drying to obtain the lithium ion battery negative electrode plate. The current collector is a conductive metal foil or mesh, more preferably a foil or mesh of copper, aluminum, nickel, stainless steel, and particularly preferably a copper foil.
In another aspect, an embodiment of the present invention further provides a lithium ion battery, where the lithium ion battery includes a lithium ion battery negative electrode sheet; the lithium ion battery negative plate is the lithium ion battery negative plate; or the lithium ion battery negative plate is prepared by the preparation method of the lithium ion battery negative plate.
The invention is further illustrated below by means of specific experimental examples as follows:
example 1
The preparation method of the lithium ion battery negative electrode binder solution mainly comprises the following steps:
1) putting 10g of polyacrylonitrile raw material (powder with the molecular weight of 85000g/mol) and 10g of NaOH powder into 100mL of deionized water to obtain reaction liquid; after being uniformly mixed, the mixture is placed in a three-neck flask and is mechanically stirred for 3 hours under the oil bath heating condition (the heating temperature is 130 ℃), and a product mixture after hydrolysis treatment is obtained.
2) And filtering, dialyzing, precipitating with ethanol, cleaning and drying the product mixture after hydrolysis treatment to obtain solid powder, namely the modified polyacrylonitrile.
The modified polyacrylonitrile obtained in the step is determined to contain a cyano group, a carboxylate group and an amide group.
3) Fully dissolving the modified polyacrylonitrile and the amylopectin in deionized water according to the mass ratio of 1:1, and uniformly stirring to prepare a binder solution with the solid content of 5 wt% for later use.
Example 2
The preparation method of the lithium ion battery negative electrode binder solution mainly comprises the following steps:
1) 10g of polyacrylonitrile raw material (powder, molecular weight is 85000g/mol) and 5g of NaOH powder are put into 100mL of deionized water, uniformly mixed and placed in a three-neck flask, and mechanically stirred for 4 hours under the oil bath heating condition (heating temperature is 130 ℃) to obtain a product mixture after hydrolysis treatment.
2) And filtering, dialyzing, precipitating with ethanol, cleaning and drying the product mixture after hydrolysis treatment to obtain solid powder, namely the modified polyacrylonitrile.
The modified polyacrylonitrile obtained in the step is determined to contain a cyano group, a carboxylate group and an amide group.
3) Fully dissolving the modified polyacrylonitrile and the seaweed gel in deionized water according to the mass ratio of 2:1, and uniformly stirring to prepare a binder solution with the solid content of 5 wt% for later use.
Example 3
The preparation method of the lithium ion battery negative electrode binder solution mainly comprises the following steps:
1) 10g of polyacrylonitrile raw material (powder, molecular weight is 85000g/mol) and 10g of NaOH powder are put into 100mL of deionized water, uniformly mixed and placed in a three-neck flask, and mechanically stirred for 3 hours under the oil bath heating condition (heating temperature is 145 ℃) to obtain a product mixture after hydrolysis treatment.
2) And filtering, dialyzing, precipitating with ethanol, cleaning and drying the product mixture after hydrolysis treatment to obtain solid powder, namely the modified polyacrylonitrile.
The modified polyacrylonitrile obtained in the step is determined to contain a cyano group, a carboxylate group and an amide group.
3) Fully dissolving the modified polyacrylonitrile and the carboxymethyl cellulose in deionized water according to the mass ratio of 3:1, and uniformly stirring to prepare a binder solution with the solid content of 5 wt% for later use.
Example 4
The preparation method of the lithium ion battery negative electrode binder solution mainly comprises the following steps:
1) 10g of polyacrylonitrile raw material (powder, molecular weight of 150000g/mol) and 10g of NaOH powder are put into 100mL of deionized water, uniformly mixed and placed into a three-neck flask, and mechanically stirred for 2 hours under the oil bath heating condition (heating temperature is 145 ℃) to obtain a product mixture after hydrolysis treatment.
2) And filtering, dialyzing, precipitating with ethanol, cleaning and drying the product mixture after hydrolysis treatment to obtain solid powder, namely the modified polyacrylonitrile.
The modified polyacrylonitrile obtained in the step is determined to contain a cyano group, a carboxylate group and an amide group.
3) Fully dissolving the modified polyacrylonitrile and the carboxymethyl cellulose in deionized water according to the mass ratio of 1:1, and uniformly stirring to prepare a binder solution with the solid content of 5 wt% for later use.
Example 5
The preparation method of the lithium ion battery negative electrode binder solution mainly comprises the following steps:
1) 10g of polyacrylonitrile raw material (powder, molecular weight of 150000g/mol) and 10g of NaOH powder are put into 100mL of deionized water, uniformly mixed and placed into a three-neck flask, and mechanically stirred for 2 hours under the oil bath heating condition (heating temperature is 145 ℃) to obtain a product mixture after hydrolysis treatment.
2) And filtering, dialyzing, precipitating with ethanol, cleaning and drying the product mixture after hydrolysis treatment to obtain solid powder, namely the modified polyacrylonitrile.
The modified polyacrylonitrile obtained in the step is determined to contain a cyano group, a carboxylate group and an amide group.
3) Fully dissolving the modified polyacrylonitrile and the xanthan gum in deionized water according to the mass ratio of 3:1, and uniformly stirring to prepare a binder solution with the solid content of 5 wt% for later use.
Example 6
The preparation method of the lithium ion battery negative electrode binder solution mainly comprises the following steps:
1) 10g of polyacrylonitrile raw material (powder, molecular weight of 150000g/mol) and 10g of NaOH powder are put into 100mL of deionized water, uniformly mixed and placed into a three-neck flask, and mechanically stirred for 3 hours under the oil bath heating condition (heating temperature is 145 ℃) to obtain a product mixture after hydrolysis treatment.
2) And filtering, dialyzing, precipitating with ethanol, cleaning and drying the product mixture after hydrolysis treatment to obtain solid powder, namely the modified polyacrylonitrile.
The modified polyacrylonitrile obtained in the step is determined to contain a cyano group, a carboxylate group and an amide group.
3) Fully dissolving the modified polyacrylonitrile and the polyacrylic acid in deionized water according to the mass ratio of 4:1, and uniformly stirring to prepare a binder solution with the solid content of 5 wt% for later use.
Example 7
The preparation method of the lithium ion battery negative electrode binder solution mainly comprises the following steps:
1) 10g of polyacrylonitrile raw material (powder, molecular weight of 150000g/mol) and 10g of NaOH powder are put into 100mL of deionized water, uniformly mixed and placed into a three-neck flask, and mechanically stirred for 4 hours under the condition of oil bath heating (heating temperature of 145 ℃) to obtain a product mixture after hydrolysis treatment.
2) And filtering, dialyzing, precipitating with ethanol, cleaning and drying the product mixture after hydrolysis treatment to obtain solid powder, namely the modified polyacrylonitrile.
The modified polyacrylonitrile obtained in the step is determined to contain a cyano group, a carboxylate group and an amide group.
3) Fully dissolving the modified polyacrylonitrile and the cyclodextrin in deionized water according to the mass ratio of 2:1, and uniformly stirring to prepare a binder solution with the solid content of 5 wt% for later use.
Example 8
The preparation method of the lithium ion battery negative electrode binder solution mainly comprises the following steps:
1) 20g of polyacrylonitrile raw material (powder, molecular weight of 150000g/mol) and 20g of NaOH powder are put into 100mL of deionized water, uniformly mixed and placed into a three-neck flask, and mechanically stirred for 3 hours under the oil bath heating condition (heating temperature of 120 ℃) to obtain a product mixture after hydrolysis treatment.
2) And filtering, dialyzing, precipitating with ethanol, cleaning and drying the product mixture after hydrolysis treatment to obtain solid powder, namely the modified polyacrylonitrile.
The modified polyacrylonitrile obtained in the step is determined to contain a cyano group, a carboxylate group and an amide group.
3) Fully dissolving the modified polyacrylonitrile and the guar gum in deionized water according to the mass ratio of 2:1, and uniformly stirring to prepare a binder solution with the solid content of 5 wt% for later use.
Example 9
The preparation method of the lithium ion battery negative electrode binder solution mainly comprises the following steps:
1) 10g of polyacrylonitrile raw material (powder, molecular weight of 150000g/mol) and 5g of NaOH powder are put into 100mL of deionized water, uniformly mixed and placed into a three-neck flask, and mechanically stirred for 3 hours under the oil bath heating condition (heating temperature of 130 ℃) to obtain a product mixture after hydrolysis treatment.
2) And filtering, dialyzing, precipitating with ethanol, cleaning and drying the product mixture after hydrolysis treatment to obtain solid powder, namely the modified polyacrylonitrile.
The modified polyacrylonitrile obtained in the step is determined to contain a cyano group, a carboxylate group and an amide group.
3) Fully dissolving the modified polyacrylonitrile and the agar in deionized water according to the mass ratio of 1:1, and uniformly stirring to prepare a binder solution with the solid content of 5 wt% for later use.
Example 10
The preparation method of the lithium ion battery negative electrode binder solution mainly comprises the following steps:
1) 10g of polyacrylonitrile raw material (powder, molecular weight of 150000g/mol) and 7g of NaOH powder are uniformly mixed in 100mL of deionized water, placed in a three-neck flask, and mechanically stirred for 4 hours under the oil bath heating condition (heating temperature of 130 ℃) to obtain a product mixture after hydrolysis treatment.
2) And filtering, dialyzing, precipitating with ethanol, cleaning and drying the product mixture after hydrolysis treatment to obtain solid powder, namely the modified polyacrylonitrile.
The modified polyacrylonitrile obtained in the step is determined to contain a cyano group, a carboxylate group and an amide group.
3) Fully dissolving the modified polyacrylonitrile and the chitosan in deionized water according to the mass ratio of 2:1, and uniformly stirring to prepare a binder solution with the solid content of 5 wt% for later use.
Comparative example 1
Comparative example 1 a lithium ion battery negative electrode binder solution was prepared, wherein comparative example 1 differs from example 4 in that: the lithium ion battery negative electrode binder solution prepared in comparative example 1 was not added with carboxymethyl cellulose as a thickener.
Here, it should be noted that: comparative example 1 is not prior art, but is merely a comparative experiment to highlight the synergistic effect of modacrylic and thickener.
Comparative example 2
Comparative example 2 a lithium ion battery negative binder solution was prepared, wherein the binder was lithium polyacrylate.
Comparative example 3
And (3) preparing the lithium ion battery cathode binder solution, wherein the binder is a mixture of polyacrylonitrile and polyacrylic acid, the mass ratio of the polyacrylonitrile to the polyacrylic acid is 4:1, and the solvent is dimethyl sulfoxide.
Comparative example 4
Comparative example 4 a lithium ion battery negative electrode binder solution was prepared, wherein comparative example 4 differs from example 4 in that: no modacrylic was added to the lithium ion battery negative binder solution prepared in comparative example 4.
The lithium ion battery negative electrode sheets are manufactured by adopting the binder solutions of the examples 1-10 and the comparative examples 1-4 and assembled into button cells, and the method comprises the following steps: weighing and uniformly mixing the active material nano-silicon, the conductive additive Keqin black and the binder according to the mass ratio of 7:1:2, adding deionized water (or dimethyl sulfoxide), and stirring at room temperature for 1h to prepare the battery pole piece slurry. The slurry was uniformly coated on a current collector copper foil with a doctor blade and dried in a vacuum oven at 80 ℃ for 12 h. And punching the dried pole piece into a small circular sheet with the diameter of 12 mm. Packaging the negative pole piece, the diaphragm, the electrolyte, the lithium piece, the elastic piece and the gasket by using a positive and negative electrode shell in a glove box filled with argon to obtain a 2032 button half-cell, wherein the electrolyte is 1M LiPF 6 In (3) Ethylene Carbonate (EC)/Ethyl Methyl Carbonate (EMC)/diethyl carbonate (DEC) (volume ratio 1:1:1, 10 wt% fluoroethylene carbonate (FEC) was added).
Test methods and conditions: the cycling stability and the multiplying power performance of the battery are tested by adopting a constant current method, and the potential window is 0.01-1.5V.
Wherein, the test results are shown in fig. 1-5, and can be seen from fig. 1-5:
(1) referring to fig. 1 and 2, it can be seen that: compared with the electrochemical performance of the lithium battery adopting the conventional binder lithium polyacrylate, the electrochemical performance of the lithium battery adopting the binder prepared by the embodiment of the invention is more excellent.
(2) As can be seen from fig. 3: carboxymethyl cellulose is independently adopted as a binder, and modified polyacrylonitrile is independently adopted as the binder, so that the electrochemical performance of the lithium battery is poor; and the modified polyacrylonitrile and the carboxymethyl cellulose are used as the binder, so that the electrochemical performance of the lithium battery is greatly improved. Therefore, the modified polyacrylonitrile and the thickening agent in the binder provided by the embodiment of the invention have obvious synergistic effect.
(3) As can be seen from fig. 4: compared with the scheme (see comparative example 3) that the thickener polyacrylonitrile and the polyacrylic acid are mixed to be used as the lithium battery negative electrode binder, the scheme that the modified polyacrylonitrile and the thickener are compounded to be used as the lithium battery negative electrode binder has remarkably excellent electrochemical performance.
Here, it should be noted that: the compounding principle of the comparative example 3 is that polyacrylic acid is used alone, the slurry is seriously settled, and stable lithium battery negative electrode slurry cannot be obtained, so that polyacrylonitrile is added to be used as a thickening agent, and the stability of the slurry is improved. While polyacrylonitrile alone does not work well with the active material silicon, polyacrylic acid is added to enhance the interaction with the active material.
The principle of the scheme of the embodiment of the invention is as follows: the modified polyacrylonitrile contains three strong polar functional groups (cyano, carboxylate groups and amide groups), and the thickening agent contains a large amount of strong polar carboxyl groups, so that the modified polyacrylonitrile and the thickening agent can form strong intermolecular hydrogen bonding after being compounded to form a physical crosslinking network structure, on one hand, the viscosity of the modified polyacrylonitrile can be improved, and the stable slurry can be formed; on the other hand, the mechanical property of the modified polyacrylonitrile or the thickening agent which is independently used as the binder can be improved, and the volume expansion of silicon can be better buffered; moreover, the existence of the network structure is beneficial to the transmission of lithium ions and is beneficial to improving the rate capability.
(4) As can be seen from fig. 5: lithium batteries using the binders prepared in the embodiments of the present invention all have excellent electrochemical properties. It should be noted that: the different viscosities of the different thickeners mentioned in the examples of the present invention result in different rheological behavior and stability of the slurry, which directly affects the dispersion of the active material and thus the electrochemical performance. In addition, different types and contents of the strong polar functional groups contained in different types of thickeners have different bond energies with modacrylic through hydrogen bond interaction, so that the buffering effect on the volume expansion of silicon is different, and finally, the difference of electrochemical properties is caused.
In addition, it should be noted that: when polyacrylonitrile is hydrolyzed, cyano groups are not retained, and only carboxyl/carboxylate groups and amide groups are present, the modified polyacrylonitrile obtained by the hydrolysis is not effective in use as a binder for a negative electrode of a lithium battery by combining a thickener with the modified polyacrylonitrile having cyano groups, carboxylate groups and amide groups.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.

Claims (10)

1. The application of the modified polyacrylonitrile in preparing the lithium battery cathode binder is disclosed, wherein the modified polyacrylonitrile is a hydrolysis product of polyacrylonitrile.
2. The use of modacrylic in the preparation of a lithium battery anode binder according to claim 1 wherein the modacrylic contains cyano groups, carboxylate groups, and amide groups.
3. The application of the modified polyacrylonitrile according to claim 1 in preparing a lithium battery negative electrode binder, wherein the modified polyacrylonitrile and the thickening agent are applied in preparing the lithium battery negative electrode binder;
preferably, the modified polyacrylonitrile and the thickening agent are compounded to be used as a lithium battery cathode binder;
preferably, in the lithium battery negative electrode binder: the mass fraction of the modified polyacrylonitrile is 50-95%, and the mass fraction of the thickening agent is 5-50%;
preferably, the thickener is one or more of starch, chitosan, xanthan gum, guar gum, agar, alginate jelly, cyclodextrin, carboxymethyl cellulose and polyacrylic acid.
4. The use of the modacrylic according to any one of claims 1 to 3 in the preparation of a binder for a negative electrode of a lithium battery, wherein the preparation method of the modacrylic comprises the following steps:
hydrolysis treatment: hydrolyzing polyacrylonitrile raw material under the set temperature and alkaline condition to obtain a product mixture after hydrolysis;
and (3) post-treatment: carrying out post-treatment on the product mixture after the hydrolysis treatment to obtain a polyacrylonitrile hydrolysate; wherein the polyacrylonitrile hydrolysis product is the modacrylic;
preferably, in the step of the hydrolysis treatment: the set temperature is 70-200 ℃, preferably 100-170 ℃, and further preferably 120-150 ℃;
preferably, in the step of the hydrolysis treatment: the time of the hydrolysis treatment is 1-8 h; preferably 2-4 h;
preferably, in the step of the hydrolysis treatment: the alkaline condition is provided by one or more alkaline substances of sodium hydroxide, potassium hydroxide and lithium hydroxide;
preferably, in the step of hydrolysis treatment, polyacrylonitrile raw material, alkaline substance and deionized water are uniformly mixed to obtain reaction liquid; heating the reaction solution to the set temperature, and carrying out hydrolysis treatment; further preferably, the pH value of the reaction solution is 8-14, preferably 10-14; further preferably, in the reaction solution, the mass concentration of the polyacrylonitrile raw material is 1 to 50%, preferably 1 to 30%, and further preferably 5 to 30%;
preferably, in the step of hydrolysis treatment, the molecular weight of the polyacrylonitrile raw material is 50000-300000g/mol, and more preferably 80000-250000 g/mol;
preferably, in the step of post-processing: and the post-treatment comprises the steps of filtering, dialyzing, precipitating, cleaning and drying the product mixture after the hydrolysis treatment, and the obtained solid powder is the polyacrylonitrile hydrolysate.
5. The lithium battery negative electrode binder is characterized by comprising 50-95% of modified polyacrylonitrile and 5-50% of a thickening agent in percentage by mass;
wherein the modified polyacrylonitrile is a hydrolysis product of polyacrylonitrile.
6. The negative electrode binder for lithium batteries according to claim 5,
the modified polyacrylonitrile contains cyano, carboxylate groups and amide groups; and/or
The thickener is one or more of starch, chitosan, xanthan gum, guar gum, agar, alginate jelly, cyclodextrin, carboxymethyl cellulose and polyacrylic acid.
7. A lithium ion battery negative electrode sheet, characterized in that the lithium ion battery negative electrode sheet comprises the lithium ion battery negative electrode binder of claim 5 or 6.
8. The preparation method of the lithium ion battery negative plate of claim 7, characterized by comprising the following steps:
preparing a binder solution: fully dissolving modified polyacrylonitrile and a thickening agent in a solvent to obtain a binder solution;
preparing anode slurry: adding a conductive agent and a negative electrode active material into the binder solution according to a dosage ratio, and uniformly mixing to obtain negative electrode slurry;
preparing a negative plate: coating the negative electrode slurry on a current collector, and drying to obtain a lithium ion battery negative electrode plate;
preferably, in the preparation of the binder solution, the solvent is selected from water, preferably deionized water;
preferably, deionized water is also added in the preparation of the cathode slurry;
preferably, in the negative electrode slurry, the mass fraction of the binder is 5-20%;
preferably, the conductive agent is one or more of Super P, acetylene black, carbon nanotubes, Ketjen black and graphene;
preferably, the current collector is a conductive metal foil or mesh, more preferably a foil or mesh of copper, aluminum, nickel, stainless steel, and particularly preferably a copper foil.
9. The preparation method of the lithium ion battery negative electrode sheet according to claim 8, wherein the negative electrode active material is one or two of a silicon-based material and a carbon material;
preferably, the silicon-based material is one or more of silicon, silicon oxide and a silicon-carbon composite material, preferably silicon, and further preferably nano silicon;
preferably, the carbon material is one or more of graphite, soft carbon and hard carbon.
10. The lithium ion battery is characterized by comprising a lithium ion battery negative plate; the lithium ion battery negative plate is the lithium ion battery negative plate of claim 7; or the lithium ion battery negative plate is prepared by the preparation method of the lithium ion battery negative plate of claim 8 or 9.
CN202210826356.5A 2022-07-14 2022-07-14 Application of modified polyacrylonitrile, binder, negative plate and lithium ion battery Pending CN115064697A (en)

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