CN112142917B - Modified chitosan water-based binder and preparation method thereof - Google Patents

Modified chitosan water-based binder and preparation method thereof Download PDF

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CN112142917B
CN112142917B CN202011217428.3A CN202011217428A CN112142917B CN 112142917 B CN112142917 B CN 112142917B CN 202011217428 A CN202011217428 A CN 202011217428A CN 112142917 B CN112142917 B CN 112142917B
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chitosan
modified chitosan
aqueous binder
alcohol
stirring
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CN112142917A (en
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陈华进
王卫霞
汪洋
钟爱民
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Yangzhou Polytechnic Institute
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
    • 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
    • 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
    • H01M4/623—Binders being polymers fluorinated polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Adding chitosan and sodium hydroxide solution into perfluoroalkyl glycidyl ether, and obtaining modified chitosan through acylation reaction; and adding trifluoroethyl acrylate, acrylic acid, ammonium persulfate, an emulsifier and water into the aqueous chitosan solution for emulsion polymerization to obtain the modified chitosan aqueous binder. The invention introduces fluorine element into the structure of chitosan to carry out chemical modification, thus improving the dispersibility and adhesiveness of chitosan; the surface of the chitosan contains a large amount of hydroxyl, so that on one hand, the copolymer formed on the surface of the chitosan by acrylic acid and fluorine-containing acrylate is facilitated; on the other hand, the polymer is wrapped outside the chitosan, so that the hydrogen bond acting force of hydroxyl and water is effectively reduced, and the lithium battery pole piece manufactured by using the aqueous binder can effectively inhibit the expansion of the pole piece in the charging and discharging processes; the aqueous binder does not release volatile organic solvent during preparation and use, is environment-friendly, and is safe and convenient to use.

Description

Modified chitosan aqueous binder and preparation method thereof
Technical Field
The invention relates to the technical field of binders, in particular to a modified chitosan water-based binder and a preparation method thereof.
Background
Lithium is the lightest metal element and has the smallest ionic radius, and the standard electrode potential is low, so that the lithium battery has higher volume capacity density and mass capacity density and higher voltage, and therefore, the lithium battery is gradually the mainstream energy storage device at present. The electrode in the lithium ion battery consists of three parts, namely an active substance, a conductive agent and a binder, wherein the binder is best in use amount, but plays a similar role of a neural network for connecting each part of an electrode system, and has great influence on the stability and the cycle performance of the battery.
With the development of science and technology, people tend to develop water-based environment-friendly materials, and water-based adhesives taking water as a solvent are concerned. The currently reported aqueous binders mainly comprise sodium carboxymethylcellulose, sodium alginate, natural polysaccharides and the like, the materials contain more hydroxyl groups, and a large number of hydrogen bonds can be generated among the binders, electrode materials and current collectors, so that the battery has better electrochemical performance, but the currently marketed aqueous binders have limited binding power and effect of inhibiting the expansion of pole pieces.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to prepare the aqueous environment-friendly adhesive through chemical modification of chitosan, and simultaneously has better adhesive property and property of inhibiting the expansion of a pole piece.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a modified chitosan aqueous binder comprises the following steps:
1) Adding perfluoroalkyl alcohol and epichlorohydrin into a reaction bottle, adding sodium ethoxide, stirring at room temperature, and reacting for 24h to obtain perfluoroalkyl glycidyl ether;
2) Adding chitosan and a sodium hydroxide solution into the perfluoroalkyl glycidyl ether, stirring for 1h at room temperature, then heating to 60 ℃, and continuing stirring for 3h to obtain modified chitosan;
3) Adding trifluoroethyl acrylate, acrylic acid, ammonium persulfate, an emulsifier and water into the modified chitosan emulsion, stirring at 60-70 ℃ for reaction for 3-5 h, and discharging to obtain the modified chitosan aqueous binder.
Further, the perfluoroalkyl alcohol is one of perfluorooctyl alcohol, perfluorobutyl alcohol and perfluorohexyl alcohol.
Further, the molar ratio of the perfluoroalkyl alcohol to the epichlorohydrin is 1.
Further, the emulsifier is polyvinyl alcohol having a molecular weight of 5000-15000.
Further, the molar ratio of the trifluoroethyl acrylate to the acrylic acid to the ammonium persulfate to the emulsifier is 1 to 5.
The modified chitosan aqueous binder prepared by the preparation method.
The polysaccharide adhesive often has performance defects of low peeling strength with a current collector, insufficient electronic conductivity and the like; in addition, the structural modification has the defects of low solubility of an organic solvent, harsh structural optimization conditions and the like. Therefore, compounding with other polymers is often required to achieve better adhesion properties. In the invention, chitosan is selected as a starting material, the chitosan is widely existed in the nature, and the molecule contains amino and hydroxyl, so that the chitosan has unique biological activity and physicochemical property. As shown in formula 1, the chitosan modified by acylation reaction is modified, and fluorine is introduced into a molecular structure, so that the dispersibility of chitosan in a solution system can be effectively improved. Wherein n is in the range of 2-8, preferably 2, 4 or 6.
Figure BDA0002760874580000021
Compared with the prior art, the invention has the beneficial effects that: the invention introduces fluorine element into the structure of chitosan to carry out chemical modification, thus improving the dispersibility and adhesiveness of chitosan; the surface of the chitosan contains a large amount of hydroxyl, so that on one hand, the copolymer formed on the surface of the chitosan by the acrylate and the fluorine-containing acrylate is facilitated; on the other hand, the polymer is wrapped outside the chitosan, so that the hydrogen bond acting force between hydroxyl and water is effectively reduced, the dispersibility is improved, and the fluorine-containing polymer chain is fully contacted with the active substance and the electrode material, so that the conductivity is improved; the lithium battery pole piece manufactured by the aqueous binder can effectively inhibit the expansion of the pole piece in the charging and discharging processes; the aqueous binder does not release volatile organic solvent during preparation and use, is environment-friendly, and is safe and convenient to use.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1:
1) Adding 1mol of perfluorooctyl ethanol and 1mol of epoxy chloropropane into a reaction bottle, adding 0.1g of sodium ethoxide, and stirring at room temperature for reaction for 24 hours to obtain perfluoroalkyl glycidyl ether;
2) Adding 5g of chitosan and sodium hydroxide solution into the perfluoroalkyl glycidyl ether, stirring for 1h at room temperature, then heating to 60 ℃, and continuing stirring for 3h to obtain modified chitosan;
3) Adding 1mol of trifluoroethyl acrylate, 1mol of acrylic acid, 0.01mol of ammonium persulfate, 2.0mmol of polyvinyl alcohol (Mn =5000 g/mol) and 50ml of water into the modified chitosan emulsion, stirring and reacting at 60-70 ℃ for 3h, and discharging to obtain the modified chitosan aqueous binder.
Example 2:
1) Adding 1mol of perfluorooctyl ethanol and 1mol of epoxy chloropropane into a reaction bottle, adding 0.1g of sodium ethoxide, and stirring at room temperature for reaction for 24 hours to obtain perfluoroalkyl glycidyl ether;
2) Adding 5g of chitosan and sodium hydroxide solution into the perfluoroalkyl glycidyl ether, stirring for 1h at room temperature, then heating to 60 ℃, and continuing stirring for 3h to obtain modified chitosan;
3) Adding 2mol of trifluoroethyl acrylate, 1mol of acrylic acid, 0.01mol of ammonium persulfate, 1.5mmol of polyvinyl alcohol (Mn =6000 g/mol) and 50ml of water into the modified chitosan emulsion, stirring at 60-70 ℃ for reaction for 4h, and discharging to obtain the modified chitosan aqueous binder.
Example 3:
1) Adding 1mol of perfluorohexylethanol and 1mol of epichlorohydrin into a reaction bottle, adding 0.1g of sodium ethoxide, stirring and reacting for 24 hours at room temperature to obtain perfluoroalkyl glycidyl ether;
2) Adding 5g of chitosan and sodium hydroxide solution into the perfluoroalkyl glycidyl ether, stirring for 1h at room temperature, then heating to 60 ℃, and continuing stirring for 3h to obtain modified chitosan;
3) Adding 3mol of trifluoroethyl acrylate, 1mol of acrylic acid, 0.01mol of ammonium persulfate, 1mmol of polyvinyl alcohol (Mn =8000 g/mol) and 50ml of water into the modified chitosan emulsion, stirring at 60-70 ℃ for reaction for 5h, and discharging to obtain the modified chitosan aqueous binder.
Example 4:
1) Adding 1mol of perfluorobutyl ethanol and 1mol of epoxy chloropropane into a reaction bottle, adding 0.1g of sodium ethoxide, and stirring at room temperature for reaction for 24 hours to obtain perfluoroalkyl glycidyl ether;
2) Adding 5g of chitosan and sodium hydroxide solution into the perfluoroalkyl glycidyl ether, stirring for 1h at room temperature, then heating to 60 ℃, and continuing stirring for 3h to obtain modified chitosan;
3) Adding 5mol of trifluoroethyl acrylate, 1mol of acrylic acid, 0.01mol of ammonium persulfate, 1mmol of polyvinyl alcohol (Mn =10000 g/mol) and 50ml of water into the modified chitosan emulsion, stirring at 60-70 ℃ for reaction for 5h, and discharging to obtain the modified chitosan aqueous binder.
According to the proportion of graphite: conductive carbon black: the modified chitosan aqueous binder =8, adding a trace amount of cellulose emulsion and water to mix into uniform slurry, uniformly blade-coating the slurry on a copper foil, vacuum-drying, and punching into 6mm round pieces by using a tablet press to obtain the positive pole piece. And (3) assembling the positive pole piece, the polypropylene microporous diaphragm and the negative pole lithium piece into a battery in sequence, and dropwise adding a proper amount of electrolyte to obtain the lithium battery of application examples 1-4.
Comparative example: the modified chitosan aqueous binder is replaced by a CMC/SBR aqueous binder sold in the market, and the modified chitosan aqueous binder, a polypropylene microporous diaphragm, a lithium sheet and electrolyte are assembled into a lithium battery.
The peel strength of the pole pieces and the expansion of the 4.2V fully charged pole pieces for examples 1-4 and the comparative battery, as well as the conductivity results for the binder are shown in table 1.
TABLE 1
Peel strength N/cm The swelling ratio% Conductivity omega/cm
Example 1 0.39 12.3 1.71×10 -5
Example 2 0.43 11.5 1.08×10 -5
Example 3 0.41 11.2 1.01×10 -5
Example 4 0.38 12.0 1.68×10 -5
Comparative example 0.21 20.2 ---
The modified chitosan aqueous binder provided by the embodiment of the invention can effectively inhibit the expansion of a pole piece in a lithium battery, and simultaneously improves the adhesive force and peel strength of the aqueous binder.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.

Claims (6)

1. The preparation method of the modified chitosan water-based binder is characterized by comprising the following steps:
1) Adding perfluoroalkyl alcohol and epichlorohydrin into a reaction bottle, adding sodium ethoxide, stirring at room temperature, and reacting for 24h to obtain perfluoroalkyl glycidyl ether;
2) Adding chitosan and a sodium hydroxide solution into the perfluoroalkyl glycidyl ether, stirring for 1h at room temperature, then heating to 60 ℃, and continuing stirring for 3h to obtain modified chitosan;
3) Adding trifluoroethyl acrylate, acrylic acid, ammonium persulfate, an emulsifier and water into the modified chitosan, stirring and reacting at 60-70 ℃ for 3-5 h, and discharging to obtain the modified chitosan aqueous binder.
2. The method for preparing the modified chitosan aqueous binder as claimed in claim 1, wherein the perfluoroalkyl alcohol is one of perfluorooctyl alcohol, perfluorobutyl alcohol and perfluorohexyl alcohol.
3. The process for preparing a modified chitosan aqueous binder as claimed in claim 1, wherein the molar ratio of the perfluoroalkyl alcohol to the epichlorohydrin is 1.
4. The method for preparing the modified chitosan aqueous binder as claimed in claim 1, wherein the emulsifier is polyvinyl alcohol having a molecular weight of 5000-15000.
5. The preparation method of the modified chitosan aqueous binder as claimed in claim 1, wherein the molar ratio of the trifluoroethyl acrylate, the acrylic acid, the ammonium persulfate and the emulsifier is 1 to 5.
6. An aqueous binder of modified chitosan prepared by the method of any one of claims 1 to 5.
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Publication number Priority date Publication date Assignee Title
JP2015005474A (en) * 2013-06-24 2015-01-08 株式会社ダイセル Binding agent, electrode material slurry, electrode, manufacturing method thereof, and secondary battery
CN106279706A (en) * 2016-08-09 2017-01-04 武汉工程大学 A kind of preparation method of polyether grafting chitosan derivatives crude oil desalting demulsifier
CN107858028A (en) * 2017-12-06 2018-03-30 苏州铂邦胶业有限公司 Anti-corrosive antibacterial water paint

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015005474A (en) * 2013-06-24 2015-01-08 株式会社ダイセル Binding agent, electrode material slurry, electrode, manufacturing method thereof, and secondary battery
CN106279706A (en) * 2016-08-09 2017-01-04 武汉工程大学 A kind of preparation method of polyether grafting chitosan derivatives crude oil desalting demulsifier
CN107858028A (en) * 2017-12-06 2018-03-30 苏州铂邦胶业有限公司 Anti-corrosive antibacterial water paint

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