KR101686475B1 - Binder compositoin for use of a secondary battery, binders, electrode composition comprising the same, and manufacturing method thereof - Google Patents
Binder compositoin for use of a secondary battery, binders, electrode composition comprising the same, and manufacturing method thereof Download PDFInfo
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- KR101686475B1 KR101686475B1 KR1020160022302A KR20160022302A KR101686475B1 KR 101686475 B1 KR101686475 B1 KR 101686475B1 KR 1020160022302 A KR1020160022302 A KR 1020160022302A KR 20160022302 A KR20160022302 A KR 20160022302A KR 101686475 B1 KR101686475 B1 KR 101686475B1
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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
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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
- 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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
Abstract
Description
The present invention relates to a binder composition for a starch-grafting secondary cell and a binder for a starch-grafting secondary cell. The present invention also relates to an electrode composition or a secondary battery comprising the binder for the starch-grafted secondary battery.
With the development of IT technology and the increase in demand for laptops and mobile phones, demand for lithium-ion batteries has also increased due to the expansion of electric vehicles and hybrid vehicles as an alternative to environmental problems and energy shortages. Long-life, high- , High density, stability, and the like have been studied.
In a typical lithium ion secondary battery, graphite is used as an anode active material. In recent years, graphite-silicon based active materials have been increasingly used. However, as the process of inserting lithium ions into the negative electrode active material during charging and desorbing at the time of discharging is repeated, the volume of the negative electrode active material expands and a volume change in which the voltage is reduced appears, so that the negative active material is separated from the electrode, The capacity of the battery is reduced and the battery life is reduced.
This phenomenon is remarkably increased in materials such as silicon and tin having a high discharge capacity, and the initial charge / discharge capacity is high, but the discharge capacity tends to decrease sharply as the cycle progresses.
Korean Patent Application No. 2013-0106143 relates to a negative electrode active material for a lithium secondary battery and a lithium secondary battery, which is an invention related to a negative electrode active material for a lithium secondary battery manufactured using graphite and silicon. In this typical lithium ion secondary battery, And graphite-silicon based active materials have been increasingly used in recent years. However, as the process of inserting lithium ions into the active material at the time of charging and discharging at the time of discharging is repeated, the volume of the active material is expanded, and the volume of the active material is changed. As a result, the active material is separated from the electrode, And the battery life is reduced.
In order to prevent this phenomenon, efforts have been made to improve the stability of the electrode and the performance of the battery by reducing the size of the active material to a nano size or deforming the shape of the active material and increasing the adhesive strength of the binder and suppressing the volume expansion with a binder ought.
Meanwhile, attempts have been made to form a binder composite part or to control the binder material, and in particular, there has been described that starch can be used as one of various binder materials (Korean Patent Application No. 2016-0010181, Korean Patent Application No. 2013-0082433), a method of preparing a binder by a method such as a copolymerization reaction of a starch and a specific compound or controlling a production process of a starch, and as a result, the battery characteristics can be improved There was no literature.
Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above-mentioned problems occurring in the prior art, and it is an object of the present invention to provide a binder composition for a secondary battery comprising a starch grafting copolymer containing starch and an unsaturated hydrocarbon monomer, It is an object of the present invention to provide a lithium ion secondary battery in which the charge / discharge cycle is improved by improving the adhesion between the base material and / or the active material and improving the dispersibility of the slurry and the stability in the electrolyte solution.
The inventors of the present invention have found that when the binder containing the starch grafting copolymer is applied to a lithium ion secondary battery, the adhesion between the active material and the metal base and / or the active material is improved and the lifetime characteristics of the battery are improved. It was confirmed that the binder containing the starch grafting copolymer was excellent in compatibility with carboxymethyl cellulose (CMC) used as a thickener and a dispersing agent.
In addition, the binder containing the starch-grafted copolymer improves the water retention value (WRV) of the electrode slurry as compared with the case of using a binder not containing the starch-grafted copolymer, thereby uniformly distributing the binder in the electrode It was confirmed that the adhesion and the electrochemical characteristics between the active material and the metal base and / or the active material can be improved.
Therefore, the inventors of the present invention have found that by applying a binder containing a starch-grafted copolymer to a lithium ion secondary battery to utilize the above-mentioned advantages, the adhesion between the active material and the metal base material and / Disclosed is a binder composition for a lithium ion secondary battery having a high initial dispersibility and a high charge / discharge cycle characteristics, a binder, an electrode composition containing the binder composition, and a lithium ion secondary battery comprising the binder composition.
One embodiment of the present invention is a binder composition for a secondary battery comprising a starch grafting copolymer comprising starch and an unsaturated hydrocarbon monomer, wherein the starch is a dextrose equivalent (%) Is 1 to 50, and the starch is contained in an amount of 1 to 30 parts by weight based on 100 parts by weight of the starch grafting copolymer, and the unsaturated hydrocarbon monomer is a vinyl monomer, a conjugated diene series A method for producing a starch-grafted secondary (A) grafted secondary particle according to any one of
Another embodiment of the present invention is a binder for a secondary battery emulsion-polymerized from a starch-grafted copolymer comprising starch and an unsaturated hydrocarbon monomer, wherein the binder is a mixture of 100 parts by weight of the starch-grafted copolymer Wherein the unsaturated hydrocarbon monomer is selected from the group consisting of a vinyl monomer, a conjugated diene monomer, an acrylate monomer, a nitrile monomer, a (meth) acrylate monomer, a (meth) acrylate monomer, Acrylic acid-based monomer, and (meth) acrylamide-based monomer. The present invention also provides a binder for a starch-grafting secondary battery.
Yet another embodiment of the present invention is a process for preparing a starch hydrolyzate, comprising: preparing a starch hydrolyzate having a D.E., Dextrose Equivalent (%) of 1 to 50; And 1 to 30 parts by weight of the starch per 100 parts by weight of the starch grafting copolymer, wherein the starch grafting copolymer is prepared by emulsifying the starch hydrolyzate and the unsaturated hydrocarbon monomer to prepare a starch grafting copolymer, The unsaturated hydrocarbon monomer may be a copolymer of a vinyl monomer, a conjugated diene monomer, an acrylate monomer, a nitrile monomer, a (meth) acrylate monomer, a (meth) acrylic acid monomer, and (meth) Wherein the binder is selected from the group consisting of one or more selected from the group consisting of:
Another embodiment of the present invention relates to a binder for the starch-grafting secondary battery; And an active material particle fixed by a binder for the starch grafting secondary battery, wherein the active material particles are capable of intercalating and deintercalating lithium ions, wherein the electrode for a starch grafting secondary battery Lt; / RTI >
Another embodiment of the present invention provides an electrode for a starch-grafted secondary battery, wherein the electrode composition for the starch-grafted secondary battery is formed on an electrode current collector.
Another embodiment of the present invention provides a lithium ion secondary battery comprising the electrode for the starch grafting secondary battery.
The binder composition for a starch-grafted secondary battery according to an embodiment of the present invention has high compatibility with carboxymethyl cellulose (CMC), and the stability and adhesion of the electrode composition including the binder for the starch-grafting secondary battery are improved , It is possible to reduce the defective electrode ratio according to the electrode manufacturing process and to provide a uniform adhesive force irrespective of the position of the electrode, thereby improving stability in the manufacturing process of the battery. In addition, the binder for the starch-grafted secondary battery in the electrode is uniformly distributed to reduce the resistance in the electrode, so that a battery exhibiting a high initial discharge capacity and having excellent charge-discharge cycle characteristics can be manufactured.
In addition, the binder for a starch-grafting secondary battery according to an embodiment of the present invention can control the physical properties by controlling the molecular weight and content of the starch and the kind of the grafting monomer. Therefore, the binder for the starch-grafted secondary battery can be applied to various kinds of active materials such as graphite, hard carbon, soft carbon, silicon or tin, and can easily be modified by applying the conditions of the electrode. It is possible to design a lithium ion secondary battery binder for developing optimal battery characteristics according to application fields such as tool and automobile battery.
FIG. 1 is a graph showing the results of measurement of the capacity maintenance rate according to the discharge cycle measured by charging a full cell manufactured according to Example 1, Comparative Example 1 and Comparative Example 2 of the present invention at 45 DEG C at 0.1 DEG C and discharging at 0.1 DEG C. FIG. Fig.
FIG. 2 is a graph showing the results of charging a half cell manufactured according to Example 1, Comparative Example 1 and Comparative Example 2 of the present invention at 0.5 C and discharging at 1 C, 2 C, 3 C and 5 C FIG. 3 is a graph showing a voltage according to discharge capacity. FIG.
Hereinafter, the present invention will be described in more detail. Those skilled in the art will appreciate that various modifications, additions, and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
The binder composition for a starch-grafted secondary battery according to the present invention comprises starch and an unsaturated hydrocarbon monomer, wherein the starch has a dextrose equivalent (DE) of 1 to 50 1 to 30 parts by weight of the starch is added to 100 parts by weight of the starch grafting copolymer, and the unsaturated hydrocarbon monomer is selected from the group consisting of a vinyl monomer, a conjugated diene monomer, an acrylate monomer, a nitrile monomer (Meth) acrylate monomer, (meth) acrylate monomer, and (meth) acrylamide monomer. The monomer may be one or more selected from the group consisting of monomers, (meth) acrylate monomers,
The kind of the starch is not particularly limited and may be unmodified starch or modified starch. Specifically, the starch may be selected from the group consisting of etherified, esterified, oxidized, acid treated, oxidized starch such as corn starch, waxy corn starch, tapioca starch, potato starch, sweet potato starch, rice starch, wheat starch, Etherification, and oxidative esterification. These modified starches may be used alone or in combination of two or more.
However, when the starch itself is used as a binder, the viscosity and the particle diameter of the binder composition and / or the electrode composition are excessively increased, so that the emulsion polymerization reaction does not proceed easily. Even if the binder is used to control the conditions, Swelling degree and / or water retention value (WRV) may be excessively increased.
On the other hand, the starch may be used in the form of a starch hydrolyzate, and the starch hydrolyzate may be formed by treating starch with a starch hydrolyzate commonly used for polymer starch chain cleavage. The kind of the starch hydrolyzing enzyme is not particularly limited and may be an alpha-amylase, a beta-amylase, a gluco-amylase, an iso-amylase and the like, preferably an alpha-amylase, Or heat-resistant alpha-amylase.
The process for producing the starch hydrolyzate may include a method in which a starch hydrolyzing enzyme is added to a starch slurry in which the starch and water are mixed to proceed a starch hydrolysis reaction, followed by cooling to produce a starch hydrolysis reaction mixture.
Specifically, the pH of the starch slurry mixed with the starch and water is adjusted to 2 to 12, preferably 4 to 10, such as 5 to 8, and the starch degrading enzyme is added in an amount of 0.001 to 10 Preferably 0.01 to 8 parts by weight, for example, 0.05 to 8 parts by weight, and more specifically 0.1 to 5 parts by weight may be added. The starch decomposition reaction temperature is controlled to be 20 to 150 캜, preferably 50 to 120 캜, for example, 70 to 100 캜, and the reaction is carried out for 30 minutes to 300 minutes, preferably 60 minutes to 200 minutes Lt; / RTI >
Further, the step of cooling may be carried out at a temperature of from 10 캜 to 90 캜, preferably from 20 캜 to 80 캜, for example, from 30 캜 to 65 캜, of the starch decomposition reaction mixture. If the cooling temperature is lower than 10 ° C or higher than 90 ° C, an unexpected change may occur in the viscosity of the prepared starch hydrolyzate, or unnecessary energy may be consumed for controlling the temperature for conducting the polymerization reaction. Therefore, And a cooling process is preferably performed at 10 ° C to 90 ° C so that the copolymerization reaction can be continuously performed after the starch decomposition step with the starch degrading enzyme.
The amount of the starch may be 1 part by weight to 30 parts by weight, preferably 5 to 25 parts by weight, for example, 7 parts by weight to 20 parts by weight, based on 100 parts by weight of the starch grafting copolymer. When the content of the starch is less than 1 part by weight, the compatibility with the carboxymethyl cellulose (CMC) contained in the electrode composition is reduced, and the stability and the adhesive strength of the electrode composition are not improved. , The flexibility of the starch grafting copolymer is reduced, and cracks may be generated in the electrode during the rolling and / or winding process for manufacturing the electrode for a secondary battery, particularly, the negative electrode.
The term dextrose equivalent used in the present invention is used as an index (%) indicating the degree of hydrolysis of starch and can be measured by KS H ISO 5377 and expressed as a ratio of reducing sugar directly to the total amount of starch solids .
The dextrose equivalent of the starch may be 1 to 50, preferably 5 to 45, more preferably 8 to 40, such as 10 to 35, specifically 15 to 30. When the dextrose equivalent is less than 1, the viscosity and the particle diameter of the particles may be excessively increased during the preparation of the starch grafting copolymer, so that the emulsion polymerization reaction may not proceed easily. If the dextrose equivalent is more than 50, emulsion polymerization reactivity may be improved The molecular weight of the produced binder is excessively reduced, and the adhesive force of the binder can be remarkably reduced.
The vinyl monomer may be styrene,
The nitrile monomer may be any one or two or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and fumaronitrile (Meth) acrylate monomer is at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) (Meth) acrylate, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, (Meth) acrylate, isopropyl (meth) acrylate, isopropyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate and isobutyl (meth) acrylate.
On the other hand, the (meth) acrylic acid-based monomer may be used in a group consisting of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, citraconic acid, metaconic acid, clutaronic acid, tetralidophthalic acid, crotonic acid and isocrotonic acid And the (meth) acrylamide monomer may be any one selected from the group consisting of acrylamide, methacrylamide, n-methylol acrylamide, and n-butoxymethyl acrylamide, or 2 or more.
The binder composition for a starch-grafted secondary battery according to the present invention may further comprise 0.1 to 10 parts by weight, preferably 0.3 to 8 parts by weight, of a carboxylic acid monomer per 100 parts by weight of the binder composition for the starch-grafting secondary battery, To 0.8 part by weight to 7 parts by weight, so that the particle stability of the prepared binder for a starch-grafting secondary battery can be improved.
If the content of the carboxylic acid monomer is less than 0.1 part by weight, the prepared starch grafting secondary battery may have a problem of lowering the particle stability of the binder. If the content of the carboxylic acid monomer is more than 10 parts by weight, And the adhesive force may be poor.
The kind of the carboxylic acid monomer is not particularly limited, but acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, citraconic acid, metaconic acid, clutaronic acid, tetralidophthalic acid, crotonic acid and isocrotonic acid May be used alone or in combination of two or more.
The binder for a starch-grafted secondary battery according to the present invention is a binder for a secondary battery emulsion-polymerized from a starch-grafted copolymer containing starch and an unsaturated hydrocarbon monomer, wherein the starch has a dextrose equivalent ( DE, Dextrose Equivalent (%) may be from 1 to 50, and 1 part by weight to 30 parts by weight of the starch is contained with respect to 100 parts by weight of the starch grafting copolymer, and the unsaturated hydrocarbon monomer is a vinyl monomer, (Meth) acrylate monomer, a (meth) acrylamide monomer, a (meth) acrylamide monomer, a (meth) acrylate monomer, an acrylate monomer, a nitrile monomer, Or more.
The starch may have a DE (Dextrose Equivalent) (%) of 1 to 50, preferably 5 to 45, more preferably 8 to 40, such as 10 to 35, 30, and the significance of the amount of the dextrose equivalent, the type of the starch, and the manufacturing method are the same as those described above for the binder composition for the starch-grafted secondary battery.
And 0.1 to 10 parts by weight of a carboxylic acid monomer per 100 parts by weight of the binder for the starch grafting secondary battery. The limitations of the numerical values are as described for the binder composition for the starch-grafted secondary battery.
Also, the type of the unsaturated hydrocarbon monomer is as described for the binder composition for the starch-grafted secondary battery.
The binder for a starch-grafted secondary battery according to the present invention may have an average particle diameter of 50 nm to 500 nm, preferably 80 nm to 300 nm, for example, 100 nm to 200 nm, and the particle diameter may be an amount of initiator added, , Reaction temperature, stirring speed, and the like.
The method for preparing a binder for a starch-grafted secondary battery according to the present invention comprises the steps of: preparing a starch hydrolyzate having a dextrose equivalent of 1 to 50; And 1 to 30 parts by weight of the starch per 100 parts by weight of the starch grafting copolymer, wherein the starch grafting copolymer is prepared by emulsifying the starch hydrolyzate and the unsaturated hydrocarbon monomer to prepare a starch grafting copolymer, The unsaturated hydrocarbon monomer may be a copolymer of a vinyl monomer, a conjugated diene monomer, an acrylate monomer, a nitrile monomer, a (meth) acrylate monomer, a (meth) acrylic acid monomer, and (meth) Or a combination of two or more members selected from the group consisting of
The step of preparing the starch hydrolyzate comprises the steps of: preparing a starch slurry by adding 0.001 part by weight to 10 parts by weight of a starch hydrolyzing enzyme to a mixed slurry of an aqueous solution having a pH of 2 to 12 and 100 parts by weight of the starch; Performing a starch decomposition reaction at 20 ° C to 150 ° C for 30 minutes to 300 minutes; And cooling at 10 캜 to 90 캜, and specific conditions and significance of the numerical limitation are as described for the binder composition for the starch-grafted secondary battery.
The step of preparing the starch grafting copolymer may include 1 to 10 parts by weight of an emulsifier per 100 parts by weight of the starch grafting copolymer and may be performed at 20 to 100 ° C for 30 to 600 minutes.
As the method of forming the polymer copolymer, emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, ion polymerization, radical polymerization, or living radical polymerization can be used. However, the polymerisation is obtained in a state of being dispersed in water, Emulsion polymerization which is unnecessary and excellent in efficiency in the production process is preferable.
The above-mentioned emulsion polymerization method is not particularly limited, and may be carried out by adding water to an airtight container equipped with a stirrer and a heating device; Additives such as dispersants, emulsifiers, and crosslinking agents; A polymerization initiator; And monomers are added to the mixture in such a manner that the content thereof is controlled, and then the mixture in the closed vessel is stirred to raise the temperature to initiate polymerization.
The emulsifier may be used in an amount of 1 to 10 parts by weight based on 100 parts by weight of the starch grafting copolymer. A surfactant may be used as the emulsifier. The surfactant may be an anionic surfactant, a cationic surfactant, Anionic surfactant or nonionic surfactant can be used, and an anionic surfactant can be preferably used. Specific examples of the anionic surfactant include higher fatty acid alkali salts, N-acrylamino acid salts, alkyl ether carboxylic acid salts, acylated peptides, alkyl sulfonates, alkylbenzenes, alkyl amino acid salts, alkyl naphthalene sulfonates, sulfosuccinates, Alkyl ether sulfates, alkyl aryl ether sulfates, alkyl amide sulfates, alkyl phosphates, alkyltriphosphates or alkylaryl ether ginseng salts, and preferably sodium dodecylbenzene sulfonate ) Can be used.
The additive may include a chelating agent, and the chelating agent may be any one or more selected from the group consisting of ethylenediaminetetraacetic acid, hydroxyethyldiatetraacetic acid, and propanediamine tetraacetic acid.
The initiator may be a decomposition initiator and a redox initiator, preferably a decomposition initiator. The decomposition initiator may be any one or more selected from the group consisting of potassium persulfate, ammonium persulfate, sodium hydrosulfite, potassium sulfite, sodium persulfate, and sodium viper sulfate.
The emulsion polymerization may be carried out at a temperature of from 20 to 100 캜, preferably from 30 to 90 캜, for example, from 35 to 80 캜, for a period of from 30 minutes to 600 minutes, preferably from 60 minutes to 400 minutes, For 120 to 300 minutes.
The method for manufacturing a binder for a starch-grafted secondary battery according to the present invention may include a method for producing a binder that is a core-shell structure. Specifically, a method for producing a binder for a starch- The starch grafting may be performed by Seed Polymerization. More specifically, starch grafting may be performed by adding starch selectively to the core and the cell of the binder for the starch grafting secondary battery.
Specifically, the seed polymerization is a method in which a seed latex is first prepared, and then a polymerization reaction is started using the seed latex. The seed latex is not controlled by the amount of the emulsifier used but the size of the seed latex It is easy to control the particle diameter and the reaction control is advantageous.
The method for producing a binder for a starch-grafted secondary battery according to the present invention may further include a step of removing by-products generated during the copolymerization reaction of the unreacted unsaturated hydrocarbon monomer and / or starch, , A high-temperature steam method, a heat-reduced distillation method, or the like.
However, a chemical method in which an oxidizing agent such as t-butyl hydroperoxide, cumene hydroperoxide and the like and a reducing agent such as sodium hydrosulfite and sodium metabisulfite are added and reacted Is preferably a high-temperature steam method or a heat-reduced-pressure distillation method in that it can cause a side reaction during charging and discharging of the battery.
In the high-temperature steam method, heating is performed at 50 to 200 ° C, preferably 60 to 180 ° C, in order to prevent the productivity from being deteriorated because it takes too much time to remove unreacted monomers and / The unreacted monomers can be completely removed. In the above-mentioned heating and vacuum distillation method, the mixture is heated to 60 to 100 DEG C, preferably 70 to 90 DEG C and reduced in pressure from 300 mmHg to 400 mmHg A step of removing unreacted monomers and / or grafting by-products can be performed.
Meanwhile, the step of preparing the starch hydrolyzate is as described for the binder composition for the starch grafting secondary battery.
In addition, 1 part by weight to 30 parts by weight of the starch may be added to 100 parts by weight of the starch grafting copolymer formed by emulsion polymerization in the step of emulsion-polymerizing the starch hydrolyzate and the unsaturated hydrocarbon monomer, The binder composition for the starch grafting secondary battery is as described above.
The step of emulsion-polymerizing the starch hydrolyzate and the unsaturated hydrocarbon monomer may further include the step of adding 0.1 to 10 parts by weight of a carboxylic acid monomer. The numerical limitation is that the binder composition for the starch grafting secondary battery As described.
The electrode composition for a starch-grafted secondary battery according to the present invention comprises active material particles fixed by a binder for the starch-grafting secondary battery and a binder for the starch-grafting secondary battery according to an embodiment of the present invention, Intercalation and deintercalation of lithium ions may be possible.
The binder for the starch grafting secondary battery may be 0.1 part by weight to 10 parts by weight per 100 parts by weight of the electrode composition for the starch grafting secondary battery. When the amount is less than 0.1 parts by weight, the adhesive strength is poor. Can be reduced.
The electrode composition for the starch-grafted secondary battery may further include carboxymethyl cellulose (CMC). The carboxymethyl cellulose may serve as a dispersing agent and thickener for the electrode composition for the starch grafting secondary battery, and preferably by mixing with styrene butadiene rubber (SBR) to form the starch grafting secondary battery, It is possible to minimize the binder content and improve the bonding ability at the same time.
The carboxymethyl cellulose may have a substitution degree of hydroxy (-OH) group of 0.7 to 1.2 with a carboxymethyl group (-CH 2 CO 2 H) and a pH of 5.5 to 9.0. The pH of the carboxymethyl cellulose can be controlled according to the substitution degree of hydroxy, and when carboxymethyl cellulose having the degree of substitution and pH is used, the effect as a dispersant and thickener of the electrode composition is excellent.
The molecular weight of the carboxymethylcellulose may be 500,000 g / mol to 900,000 g / mol. When the molecular weight is less than 500,000 g / mol, the adhesive strength of the prepared binder may be poor. When the molecular weight exceeds 900,000 g / mol, the viscosity of the electrode composition may be too high, Lt; / RTI >
Accordingly, the starch grafting electrode composition according to an embodiment of the present invention repeatedly expands and contracts as the electrode active material for a lithium ion secondary battery, particularly, a negative electrode, is charged and discharged, By limiting the acidity and the molecular weight of the carboxymethyl cellulose, the binder for the starch grafting secondary battery can be flexibly deformed according to the expansion and contraction of the active material, and the surface of the electrode active material can be coated with a high covering ratio, So that the binder for the secondary battery can bind the electrode active material particles with high strength.
The electrode composition for the starch-grafted secondary battery may have a water retention value (WRV) of 3000 mg or less as measured by AA-GWR (Kaltec Secientific Inc.). Therefore, the electrode composition for a starch-grafted secondary battery according to an embodiment of the present invention maintains a low degree of maintenance, so that the binder is uniformly dispersed, thereby improving the charge-discharge cycle characteristics.
The electrode composition for a starch-grafted secondary battery according to the present invention can be formed on an electrode current collector of the star-grafting secondary battery. Specifically, the electrode active material and the conductive material are mixed by the binder for the starch- And when the peel strength is measured at a rate of 100 mm / min using a UTM (20 kgf Load Cell), the adhesive force is 10 gf / mm to 30 gf / mm .
The electrode for the secondary battery may be an anode or a cathode. The anode is prepared, for example, by applying a mixture of a cathode active material, a conductive material, a binder for the starch-grafting secondary battery, and the like on a cathode current collector, and drying the anode current collector. The negative electrode slurry, which is a mixture of an active material, a conductive material, carboxymethyl cellulose, and a binder for the starch grafting secondary battery, is coated using a doctor blade, dipping, and brushing, and then dried at 80 to 150 ° C for 5 minutes to 60 minutes . The solid content of the slurry may be 20 wt% to 80 wt%, and the thickness of the negative electrode after drying may be 20 mu m to 150 mu m.
The current collector in the electrode is a portion where electrons move in the electrochemical reaction of the active material, and an anode current collector and a cathode current collector exist depending on the type of the electrode.
The negative electrode current collector may be manufactured to have a thickness of 5 to 30 탆. The negative electrode current collector is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery, and examples thereof include copper foil, nickel foil, stainless steel foil, titanium foil, nickel foil, Foams, polymeric substrates coated with a conductive metal, or a combination thereof.
The cathode current collector may be manufactured to have a thickness of 3 탆 to 500 탆. The positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery. Examples of the positive electrode current collector include copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver or the like, aluminum-cadmium alloy, or the like can be used.
The positive electrode current collector or the negative electrode current collector may be formed into various shapes such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric by forming minute irregularities on the surface to enhance the binding force of the electrode active material.
As the solvent for the electrode composition, an organic solvent such as carboxymethylcellulose, NMP (N-methylpyrrolidone), DMF (dimethylformamide), acetone, dimethylacetamide or the like, water or the like can be used, and preferably carboxymethylcellulose And the solvent for the electrode composition may be used alone or in admixture of two or more.
The substitution degree, molecular weight, and pH of the hydroxy (-OH) group of the carboxymethyl cellulose are as described above.
In the electrode for the starch grafting secondary battery, the electrode active material is a material capable of generating an electrochemical reaction, and is used for preparing a negative electrode and a positive electrode slurry. Depending on the type of the electrode, the negative electrode active material and the positive electrode active material exist.
Examples of the negative electrode active material used in the present invention include carbon and graphite materials capable of intercalation and deintercalation of lithium ions, Si-based materials, metals and compounds capable of being alloyed with lithium, metals and compounds thereof A composite of carbon and graphite materials, a lithium-containing nitride, and the like. As the carbon and graphite materials, natural graphite, artificial graphite, expanded graphite, carbon fiber, non-graphitizable carbon, carbon black, carbon nanotube, fullerene, activated carbon, hard carbon and soft carbon may be used. The Si-based material is at least one selected from the group consisting of Si, SiOx (0 <x <2), Si-Y alloy (Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, ), A Si-C composite, or a combination of these may be used. As the metal and the element which can be alloyed with lithium, Al, Si, Sn, Ag, Bi, Mg, Zn, In, Ge, Pb, Pd, Pt and Ti can be used. The amount of the negative electrode active material used for the negative electrode slurry may be 20 to 80 parts by weight based on 100 parts by weight of the negative electrode slurry.
The positive electrode active material is not particularly limited, but is preferably a positive electrode active material represented by the
The lithium transition metal oxide represented by
Examples of the other cathode active material include layered compounds such as lithium cobalt oxide (LiCoO 2 ) and lithium nickel oxide (LiNiO 2 ); Compounds substituted with one or more transition metals; Lithium manganese oxides such as Li 1 + y Mn 2 - y O 4 (y is 0 to 0.33), LiMnO 3 , LiMn 2 O 3 and LiMnO 2 ; Lithium copper oxide (Li 2 CuO 2 ); Vanadium oxides such as LiV 3 O 8 , LiFe 3 O 4 , V 2 O 5 and Cu 2 V 2 O 7 ; Formula LiNi 1 - y M y O 2 Ni site type lithium nickel oxide which is represented by (M = Co, and Mn, Al, Cu, Fe, Mg, B or Ga, y = 0.01 to 0.3); Formula LiMn 2 - y M y O 2 (M = Co, Ni, Fe, Cr, and Zn, or Ta, y = 0.01 to 0.1) or Li 2 Mn 3 MO 8 (M = Fe, Co, Ni, Cu or Zn A lithium manganese composite oxide represented by the following formula LiMn 2 O 4 in which a part of Li in the formula is substituted with an alkaline earth metal ion; Disulfide compounds; Fe 2 (MoO 4 ) 3 , and the like. However, the present invention is not limited to these.
In a preferred embodiment, the cathode active material may be included in addition to the lithium transition metal oxide, and further comprises a LiCoO 2, LiCoO 2 is 20% by weight to 80% by weight, based on the total weight of the positive electrode active material of the formula (I).
However, the lithium transition metal oxide represented by
The positive electrode is prepared, for example, by applying a positive electrode mixture containing the positive electrode active material on a positive electrode collector, followed by drying, and the positive electrode mixture may contain the above-described components, if necessary.
As the positive electrode binder, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), or the like may be used in addition to the binder for the starch grafting secondary battery according to an embodiment of the present invention.
The conductive material may be optionally added to impart insufficient conductivity to the electrode active material, and may be added in an amount of 1 to 30 wt% based on the total weight of the electrode material mixture. The conductive material is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery. For example, natural graphite, artificial graphite, carbon black, acetylene black, carbon nanotube, metal powder, , Metal powders such as nickel, aluminum, and silver, or metal fibers, and conductive materials such as polyphenylene derivatives may be mixed and used.
The present invention can provide a lithium secondary battery including the electrode for the starch-grafted secondary battery manufactured according to an embodiment of the present invention.
The lithium secondary battery may include a separator. The separator may be an insulating thin film having a high ion permeability and mechanical strength interposed between the anode and the cathode. The pore diameter of the separation membrane is generally 0.01 to 10 mu m and the thickness may be 5 to 300 mu m. Preferable examples of the separation membrane include olefin-based polymers such as polypropylene, which is chemically resistant and hydrophobic; A sheet or a nonwoven fabric made of glass fiber, polyethylene or the like can be used. When a solid electrolyte such as a polymer is used as the electrolyte, the solid electrolyte may also serve as a separation membrane.
The lithium salt-containing nonaqueous electrolyte solution may be composed of an electrolyte solution and a lithium salt, and the nonaqueous organic solvent, the organic solid electrolyte, and the inorganic solid electrolyte may be used as the electrolyte solution.
Examples of the non-aqueous organic solvent include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma -Butyrolactone, 1,2-dimethoxyethane, tetrahydroxyfuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane , Acetonitrile, nitromethane, methyl formate, methyl acetate, triester phosphate, trimethoxymethane, dioxolane derivatives, sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate Nonionic organic solvents such as tetrahydrofuran derivatives, ethers, methyl pyrophosphate, ethyl propionate and the like can be used.
Examples of the organic solid electrolyte include a polymer electrolyte such as a polyethylene derivative, a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, an agitation lysine, a polyester sulfide, a polyvinyl alcohol, a polyvinylidene fluoride, A polymer containing an ionic dissociation group and the like may be used.
Examples of the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Nitrides, halides and sulfates of Li such as Li 4 SiO 4 -LiI-LiOH and Li 3 PO 4 -Li 2 S-SiS 2 can be used.
The lithium salt is a substance that can be easily dissolved in the non-aqueous electrolyte. Examples of the lithium salt include LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, 4-phenyl-lithium borate, already And the like may be used.
For the purpose of improving the charge / discharge characteristics and the flame retardancy, the electrolytic solution is preferably mixed with an organic solvent such as pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylenediamine, glyme, Benzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrrole, 2-methoxyethanol, . In some cases, a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride may be further added in order to impart nonflammability. In order to improve the high-temperature storage characteristics, a carbon dioxide gas may be further added, and fluoro-ethylene carbonate (FEC), propylene sultone (PRS), fluoro-propylene carbonate (FPC), ethylene carbonate (EC), ethyl methyl carbonate, diethyl carbonate and the like .
The lithium secondary battery according to the present invention can be used not only in a battery cell used as a power source of a small device but also as a unit cell in a middle- or large-sized battery module including a plurality of battery cells used as a power source for a medium- have.
Preferred examples of the above medium to large devices include a power tool that is powered by an electric motor and moves; An electric vehicle including an electric vehicle (EV), a hybrid electric vehicle (HEV), a plug-in hybrid electric vehicle (PHEV), and the like; An electric motorcycle including an electric bike (E-bike) and an electric scooter (E-scooter); An electric golf cart, and the like, but the present invention is not limited thereto.
The present invention will be described in more detail with reference to specific examples. The described embodiments are illustrative only and the scope of the present invention is not limited thereto. The contents not described here will not be described in detail because those skilled in the art will be able to deduce technically sufficient information.
Example One
Starch Decomposition Produce ( Step 1 )
Ion exchange water was added to a high-pressure reactor equipped with a stirrer, a temperature controller, a pH meter, and a nitrogen gas inlet and equipped with a device capable of continuously feeding monomer, surfactant, and initiator, and starch (DS-SyncSTA S50, The pH of the starch slurry was adjusted to 6 by using hydrochloric acid and the pH was maintained by stirring for 20 minutes until the pH was stabilized.
Thereafter, the temperature of the high-pressure reactor was raised to 95 DEG C after adding alpha-amylase having excellent heat resistance (Liquozyme supra, Novozyme, Denmark), and the reaction was carried out with maintaining the temperature for 90 minutes to decompose the starch. The starch hydrolyzate was cooled to prepare a starch hydrolyzate, and the dextrose equivalent (DE) (%) of the starch hydrolyzate was measured to be 10.
Starch Grafting Preparation of Binder for Secondary Battery Step 2 )
Ion exchanged water, a chelating agent (ethylenediaminetetraacetic acid), and a surfactant (sodium dodecylbenzenesulfonate) are added to a solution containing the starch hydrolyzate, and after filling with nitrogen gas, an initiator dissolved in the ion exchange water Potassium persulfate) and an unsaturated hydrocarbon monomer mixture were continuously added at 70 캜 for 120 minutes and the reaction was carried out for 160 minutes to prepare binder particles for a starch grafting secondary battery cathode.
On the other hand, when the total weight of the starch hydrolyzate and the unsaturated hydrocarbon monolayer mixture is 100 parts by weight, 15 parts by weight of starch, 0.015 part by weight of alpha-amylase, 20 parts by weight of styrene, 60 parts by weight, and itaconic acid was controlled to be 5 parts by weight.
Starch Grafting Post-treatment of binder for secondary battery
After the solution containing the binder particles for the starch grafting secondary battery negative electrode was cooled to 30 ° C, sodium hydroxide was added thereto to adjust the pH to 6.5, and then the mixture was heated to 85 ° C and then reduced to 300 mmHg to 400 mmHg , And steam at 100 DEG C was supplied for 30 minutes to completely remove unreacted monomers and grafting by-products.
Cathode manufacturing
97 parts by weight of graphite as the negative electrode active material, 2 parts by weight of the binder for the starch grafting secondary battery negative electrode and 1 part by weight of carboxymethyl cellulose were mixed with distilled water to prepare a Cu thin film having a thickness of 10 탆, And coated and dried to prepare a negative electrode. At this time, the drying temperature and time were controlled at 100 ° C for 30 minutes.
Manufacture of batteries
Lithium nickel-manganese cobalt oxide as a cathode active material, acetylene black as a conductive material, and polyvinylidene fluoride (PVDF) as a positive electrode binder were mixed at a weight ratio of 92: 4: 4 and applied to an aluminum collector body.
The electrolyte solution was prepared by dissolving LiPF 6 in a concentration of 1M in a nonaqueous solvent containing ethylene carbonate (EC): ethyl methyl carbonate (EMC): diethyl carbonate (DEC) in a ratio of 1: 2: 1.
As a separator, a porous polyethylene film was used to prepare a full cell.
Example 2
In Example 1, the dextrose equivalent (DE) (%) was controlled to be 10, and when the total weight of the starch hydrolyzate and the unsaturated hydrocarbon monolith mixture was 100 weight parts, 15 weight parts of starch , 0.015 part by weight of alpha-amylase, 20 parts by weight of styrene, 25 parts by weight of 1,3-butadiene, 30 parts by weight of butyl acrylate, 5 parts by weight of acrylonitrile, 3 parts by weight of itaconic acid, 2 parts by weight based on 100 parts by weight of the total weight of the composition.
Example 3
In Example 1, the dextrose equivalent (DE) (%) was controlled to be 10, and when the weight sum of the starch hydrolyzate and the unsaturated hydrocarbon monolayer mixture was 100 weight parts, 10 weight parts of starch , 0.001 part by weight of alpha-amylase, 20 parts by weight of styrene, 30 parts by weight of 1,3-butadiene, 30 parts by weight of butyl acrylate, 5 parts by weight of acrylonitrile and 5 parts by weight of itaconic acid as the monomer mixture The procedure of Example 1 was repeated to prepare a full-cell.
Comparative Example One
Manufacture of Binder for Secondary Battery Cathode
(Ethylene diamine tetraacetic acid), a surfactant (sodium dodecyldithiocarbamate), and a surfactant in a high-pressure reactor equipped with a stirrer, a temperature controller, a pH meter, a nitrogen gas inlet and a monomer, (Potassium persulfate) and an unsaturated hydrocarbon monomer solution dissolved in ion-exchanged water were continuously fed at 70 ° C for 120 minutes, and the reaction was carried out for 160 minutes Binder.
On the other hand, when the total weight of the unsaturated hydrocarbon monolith mixture was 100 parts by weight, 30 parts by weight of styrene, 65 parts by weight of 1,3-butadiene and 5 parts by weight of itaconic acid were controlled.
Cathode manufacturing
97 parts by weight of graphite as an anode active material, 2 parts by weight of the binder for the secondary battery negative electrode and 1 part by weight of carboxymethylcellulose were mixed with distilled water to uniformly coat the negative electrode composition on a Cu thin film having a thickness of 10 탆 using an applicator Coated and dried to prepare a negative electrode. At this time, the drying temperature and time were controlled at 100 ° C for 30 minutes.
Manufacture of batteries
Lithium nickel-manganese cobalt oxide as a cathode active material, acetylene black as a conductive material, and polyvinylidene fluoride (PVDF) as a positive electrode binder were mixed at a weight ratio of 92: 4: 4 and applied to an aluminum collector body.
The electrolyte solution was prepared by dissolving LiPF 6 in a concentration of 1M in a nonaqueous solvent containing ethylene carbonate (EC): ethyl methyl carbonate (EMC): diethyl carbonate (DEC) in a ratio of 1: 2: 1.
As a separator, a porous polyethylene film was used to prepare a full cell.
Comparative Example 2
In Comparative Example 1, when the total weight of the unsaturated hydrocarbon monolith mixture was 100 parts by weight, 25 parts by weight of styrene, 35 parts by weight of 1,3-butadiene, 30 parts by weight of butyl acrylate, 5 parts by weight of acrylonitrile , And 5 parts by weight of itaconic acid was controlled to be added.
Experimental Example 1: Measurement of binder particle size and glass transition temperature
The particle size and glass transition temperature of each of the binders prepared according to the methods of Examples 1 to 3 and Comparative Examples 1 and 2 were measured and the results are shown in Table 3 below.
Experimental Example 2: Cathode adhesion measurement
Each of the negative electrodes prepared according to the methods of Examples 1 to 3 and Comparative Examples 1 and 2 was cut into a size of 25 mm in width and 100 mm in length. A double - sided tape having a width of 20 mm and a length of 40 mm was attached to an acryl plate having a width of 40 mm and a length of 100 mm. The prepared electrode was stuck on the double-sided tape and lightly pressed five times with a hand roller. Each negative electrode specimen prepared in accordance with the methods of Examples 1 to 3 and Comparative Examples 1 and 2 was mounted on a UTM (20 kgf Load cell) to peel off about 25 mm of one side of the negative electrode, The 180 ° peel strength was measured while a tape attached to one surface of the negative electrode was fixed to the lower clip and peeled at a rate of 100 mm / min on the clip. Five or more specimens were prepared per sample and the average value was calculated. The results are shown in Table 3 below.
Experimental Example 3: Measurement of the swelling degree of the negative electrode by the electrolyte
Each of the binders prepared according to the methods of Examples 1 to 3 and Comparative Examples 1 and 2 was dried at 70 ° C for 48 hours to prepare a film shape. The film was formed into a film having a width of 10 mm (W), a length of 45 mm, a height of 0.3 Mm. Three or more specimens were prepared per sample and each mass (A) was measured.
Each sample was then placed in a 20 ml vial and 18 ml of a mixed solution of ethylene carbonate and propylene carbonate in which 1 mol of LiPF 6 salt dissolved was mixed so as to have a weight ratio of 7: The vial containing the sample was stored in a dry oven at 70 DEG C for 72 hours.
After 4 hours, the mass (B) of the dried film was measured and the swelling degree was measured according to the following
Swelling degree (%) = (A-B) / (B)
Experimental Example 4: Measurement of maintenance of electrode composition
Absorbent paper was laid under the measuring cell of the AA-GWR (Kaltec Secientific Inc.), 2 cc of the electrode composition was added, and a pressure of 1.5 bar was applied for 30 seconds to measure the amount of water absorbed in the absorbent paper three times. Table 3 shows the results.
(Nm)
Glass transition temperature
()
Cathode adhesion
(gf / mm)
(%)
(Mg)
Experimental Example 5: Charging and discharging Cycle characteristic measurement
The batteries prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were charged at 45 ° C at 1 ° C, discharged at 1 ° C, and the discharge capacity per cycle was shown in Fig. 1, And discharge capacities of the respective batteries manufactured in Comparative Examples 1 and 2 are shown in FIG.
As shown in Table 3, it can be seen that the negative electrode comprising the binder for the starch-grafting secondary battery produced according to Examples 1 to 3 of the present invention shows a high adhesive force. 1 and 2, it is possible to prevent the electrode active material from easily separating and to prevent cracking due to bulk expansion of the electrode active material, as the adhesive force by the binder for the secondary battery is excellent. Therefore, It can be confirmed that the capacity of the secondary battery including the binder for the starch-grafted secondary battery according to the present invention is high in the charge-discharge cycle.
In particular, the binders for the starch-grafted secondary batteries prepared in Examples 1 to 3 of the present invention are excellent in compatibility with the carboxyl methyl cellulose and have excellent resistance to dispersion of the binder in the electrode and low resistance. Therefore, the battery can exhibit excellent performance even at high output, and the application range of the battery can be expanded. On the other hand, in Comparative Example 1, the negative electrode adhesion and the swelling degree of the negative electrode by the electrolyte were high. However, since the electrode composition had a high degree of repair, the binder dispersion became uneven and the resistance increased as the charge / discharge cycle progressed. There is a problem of a rapid decrease.
In this connection, it can be seen that the lithium ion secondary battery according to Examples 1 to 3 of the present invention has improved charge-discharge cycle characteristics and rate characteristics as shown in FIGS. 1 and 2. FIG.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that such detail is solved by the person skilled in the art without departing from the scope of the invention. will be. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.
Claims (27)
The starch has a dextrose equivalent (DE) (%) of 10 to 35,
10 parts by weight to 15 parts by weight of the starch is contained in 100 parts by weight of the starch grafting copolymer,
The unsaturated hydrocarbon monomer may be at least one monomer selected from the group consisting of a vinyl monomer, a conjugated diene monomer, an acrylate monomer, a nitrile monomer, a (meth) acrylate monomer, a (meth) acrylic acid monomer, , And one or more selected from the group consisting of < RTI ID = 0.0 >
Binder composition for starch grafting secondary batteries.
The starch has a dextrose equivalent (DE) (%) of 10 to 35,
Wherein the starch is contained in an amount of 10 parts by weight to 15 parts by weight with respect to 100 parts by weight of the starch grafting copolymer,
The unsaturated hydrocarbon monomer may be at least one monomer selected from the group consisting of a vinyl monomer, a conjugated diene monomer, an acrylate monomer, a nitrile monomer, a (meth) acrylate monomer, a (meth) acrylic acid monomer, , And one or more selected from the group consisting of < RTI ID = 0.0 >
Binder for starch grafting rechargeable batteries.
And emulsifying and polymerizing the starch hydrolyzate and the unsaturated hydrocarbon monomer to prepare a starch grafting copolymer,
Wherein the starch is contained in an amount of 10 parts by weight to 15 parts by weight per 100 parts by weight of the starch grafting copolymer,
The unsaturated hydrocarbon monomer may be at least one monomer selected from the group consisting of a vinyl monomer, a conjugated diene monomer, an acrylate monomer, a nitrile monomer, a (meth) acrylate monomer, a (meth) acrylic acid monomer, , And one or more selected from the group consisting of < RTI ID = 0.0 >
A method for manufacturing a binder for a starch grafting secondary cell.
preparing a starch slurry by adding 0.001 part by weight to 10 parts by weight of a starch hydrolyzate to a mixed slurry of an aqueous solution having a pH of 2 to 12 and starch per 100 parts by weight of the starch;
Performing a starch decomposition reaction at 20 ° C to 150 ° C for 30 minutes to 300 minutes; And
Lt; RTI ID = 0.0 > 10 C < / RTI > to 90 C,
A method for manufacturing a binder for a starch grafting secondary cell.
The active material particles being fixed by a binder for the starch grafting secondary battery,
Wherein the active material particles are capable of intercalating and deintercalating lithium ions,
Electrode composition for starch grafting secondary batteries.
The carboxymethylcellulose has a degree of substitution of hydroxy (-OH) group by carboxymethyl group (-CH 2 CO 2 H) of 0.7 to 1.2, a molecular weight of 500,000 g / mol to 900,000 g / mol and a pH of 5.5 to 9.0 By weight based on the weight of the starch grafted secondary battery.
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| CN109616638A (en) * | 2018-12-05 | 2019-04-12 | 中南大学 | Spherical core-shell structure mixed graphite @ hard carbon composite material and preparation method and application thereof |
| CN110120521A (en) * | 2018-02-07 | 2019-08-13 | 中山天贸电池有限公司 | It is a kind of for improving the negative electrode slurry and processing method of lithium ion battery cryogenic property |
| WO2021060737A1 (en) * | 2019-09-23 | 2021-04-01 | 주식회사 엘지화학 | Binder for lithium secondary battery negative electrode, and lithium secondary battery negative electrode including same |
| WO2021154039A1 (en) * | 2020-01-30 | 2021-08-05 | 주식회사 엘지화학 | Binder composition for negative electrode, negative electrode comprising same, and secondary lithium battery comprising same |
| WO2022086249A1 (en) * | 2020-10-23 | 2022-04-28 | 주식회사 엘지화학 | Anode mixture for secondary battery, and anode and secondary battery including same |
| KR20220160174A (en) * | 2021-05-27 | 2022-12-06 | 금호석유화학 주식회사 | A method for preparing latex composition for dip-forming |
| WO2023120880A1 (en) * | 2021-12-24 | 2023-06-29 | 주식회사 엘지에너지솔루션 | Negative electrode, and secondary battery comprising negative electrode |
| CN117384323A (en) * | 2023-12-12 | 2024-01-12 | 成都锂能科技有限公司 | Starch-based precursor material and preparation method and application thereof |
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