CN112072173A - Molecular brush polymer membrane based on cellulose network structure and preparation method and application thereof - Google Patents

Molecular brush polymer membrane based on cellulose network structure and preparation method and application thereof Download PDF

Info

Publication number
CN112072173A
CN112072173A CN202010893903.2A CN202010893903A CN112072173A CN 112072173 A CN112072173 A CN 112072173A CN 202010893903 A CN202010893903 A CN 202010893903A CN 112072173 A CN112072173 A CN 112072173A
Authority
CN
China
Prior art keywords
cellulose
network structure
dimethylformamide
battery
bacterial cellulose
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010893903.2A
Other languages
Chinese (zh)
Other versions
CN112072173B (en
Inventor
吴丁财
贾丹阳
刘如亮
周铭洪
刘绍鸿
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sun Yat Sen University
National Sun Yat Sen University
Original Assignee
National Sun Yat Sen University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by National Sun Yat Sen University filed Critical National Sun Yat Sen University
Priority to CN202010893903.2A priority Critical patent/CN112072173B/en
Publication of CN112072173A publication Critical patent/CN112072173A/en
Application granted granted Critical
Publication of CN112072173B publication Critical patent/CN112072173B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The invention provides a molecular brush polymer film based on a cellulose network structure, and a preparation method and application thereof. The three-dimensional network structure is formed by grafting functional polymers on cellulose through a surface grafting technology, and preparing a film through suction filtration or heating volatilization to serve as a gel polymer electrolyte part in a lithium battery. The network structure is a novel three-dimensional network structure constructed by taking natural polymer cellulose as a framework and grafting functional molecular brushes, so that the liquid absorption rate of the material can be obviously improved, and the moving speed of lithium ions can be effectively improved. In addition, on one hand, the transference number of lithium ions can be obviously improved by grafting the functional molecular brush with the lithium salt group. On the other hand, the functional molecular brush containing alkoxy groups can improve the ionic conductivity of lithium ions and effectively improve the electrochemical performance of the lithium battery. In the process of assembling the battery, the interfacial impedance between the internal electrode and the electrolyte of the lithium metal battery is effectively reduced by using an in-situ thermal polymerization method.

Description

Molecular brush polymer membrane based on cellulose network structure and preparation method and application thereof
Technical Field
The invention relates to a preparation method of a molecular brush gel polymer electrolyte with a cellulose function, and the electrolyte can be applied to a high-performance lithium battery. The invention relates to the field of preparation technology of high-performance gel polymer electrolyte and lithium batteries.
Background
Liquid electrolytes all have problems such as leakage, volume expansion, electrode corrosion, self-discharge, poor low temperature performance, and difficulty in designing different shapes. The gel polymer electrolyte has unique advantages, such as excellent thermal stability, and can greatly improve the safety performance of the battery, and in addition, the gel polymer electrolyte can simultaneously replace two parts, namely electrolyte and a diaphragm of the battery, so that the volume and the quality of a battery finished product are reduced, and the energy density is obviously improved. Meanwhile, the excellent flexibility of the polymer makes the polymer more likely to be used for batteries of wearable devices. Based on the comprehensive consideration of safety performance, wide working temperature range, flexible battery design and the like, the gel electrolyte having the advantages of both liquid electrolyte and solid electrolyte is the optimal choice.
The gel polymer electrolyte introduces a plasticizer on the basis of the solid polymer electrolyte, so that the ionic conductivity of the electrolyte is effectively improved, but the traditional gel electrolyte is usually prepared separately and then assembled into a battery together with a positive electrode and a negative electrode, so that the interface contact between the electrode and the electrolyte is poor, the internal resistance of the battery is increased due to poor interface contact, and the electrode and the electrolyte are separated when the bending strength is high, so that the exploration of an in-situ polymerization technology has very important significance for reducing the impedance of the battery. Meanwhile, the gel polymer electrolyte contains partial liquid phase components, and the safety problem caused by liquid electrolyte cannot be completely solved. In addition, the gel polymer electrolyte has a relatively low mechanical strength compared to a solid polymer electrolyte, and it is difficult to suppress penetration of lithium dendrites during charge and discharge cycles of a lithium metal battery.
The above gel polymer electrolyte cannot solve the problems of excessive internal resistance of the battery, safety problems due to liquid phase components, and insufficient mechanical strength to inhibit penetration of lithium dendrites. Therefore, it is of great importance to find a gel electrolyte having low battery resistance, strong mechanical strength and high safety performance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a gel polymer electrolyte of a cellulose grafted functional molecular brush with a three-dimensional network structure, a preparation method thereof and application thereof in a lithium battery. Firstly, the interface impedance between the internal electrode and the electrolyte of the lithium metal battery can be reduced by utilizing an in-situ thermal polymerization method; secondly, the movement speed of lithium ions can be effectively improved based on rich pores of a three-dimensional network structure; and thirdly, the concentration polarization of lithium ions in the circulation process can be reduced through uniform functional molecule brush grafting, the growth of lithium dendrites is effectively inhibited, and the possibility of short circuit of the battery is reduced. In addition, the cellulose has excellent mechanical properties and thermal stability, and provides effective guarantee for the safety of the battery.
In order to achieve the purpose, the technical scheme adopted by the application is as follows:
according to the first aspect, the invention provides a molecular brush material with functional groups grafted on cellulose, wherein the material is prepared by grafting functional polymers on a cellulose chain segment through a surface grafting technology, performing suction filtration or heating volatilization to prepare a macroscopic membrane, and then preparing a gel polymer electrolyte through in-situ thermal polymerization for a lithium battery.
Preferably, the functional polymer comprises one or more of poly-2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester, poly-methoxyethyl methacrylate, poly-glycidyl methacrylate, poly-isobutyl methacrylate, sodium poly-styrene sulfonate, poly-3-propyl methacrylate potassium, and poly-2-acrylamido-2-methyl-1-propane sulfonic acid.
Preferably, the present invention provides one or both of lignocellulose having a diameter of 4 to 10nm and a length of 1 to 3 μm and bacterial cellulose having a diameter of 50 to 100nm and a length of 20 μm.
Preferably, the present invention provides one or both of surface initiated-reversible addition-fragmentation chain transfer radical polymerization (SI-RAFT) and surface initiated-atom transfer radical polymerization (SI-ATRP).
In a second aspect, the present invention provides a method for preparing a molecular brush polymer film based on a cellulose network structure, comprising the following steps:
(1) modifying cellulose and grafting bromine group to obtain the cellulose containing bromine functional group;
(2) uniformly mixing the bromine functional group-containing cellulose prepared in the step (1) with a high molecular monomer, a ligand, a catalyst and a solvent I, reacting for 20-40min under the protection of inert gas, adding a reducing agent, introducing inert gas for 20-40min, and reacting at 50-90 ℃ to obtain an intermediate product I; the polymer monomer is a sulfonic acid lithium-conducting monomer;
(3) adding a solvent II into the intermediate product I prepared in the step (2), centrifuging and washing for a plurality of times by using a hydrochloric acid solution, dispersing the centrifuged product in a LiOH solution, stirring for 6-24h, centrifuging again and washing the centrifuged product for a plurality of times by using water and/or ethanol to obtain an intermediate product II;
(4) dispersing the intermediate product II prepared in the step (3) in a solvent III, and performing suction filtration or heating volatilization to form a film;
and (3) when the high molecular monomer is an alkoxy lithium-conducting monomer, directly dispersing the intermediate product in a solvent III, and filtering or heating to volatilize the intermediate product to form the film.
Preferably, the polymer monomer in step (2) comprises one or more of 2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester, methoxyethyl methacrylate, glycidyl methacrylate, isobutyl methacrylate, sodium p-styrene sulfonate, potassium 3-propyl methacrylate, and 2-acrylamido-2-methyl-1-propane sulfonic acid.
Preferably, the ligand in step (2) comprises one or more of 1,1,4,7,10, 10-hexamethyl triethylene tetramine, N, N, N' -pentamethyl diethylene triamine and tris (2-dimethylaminoethyl) amine.
Preferably, the catalyst is one or two of cuprous bromide and cuprous chloride.
Preferably, the reducing agent is ascorbic acid.
Preferably, the molar ratio of the high molecular monomer to the cellulose containing a bromine functional group in step (2) is 50 to 300: 1, preferably 120: 1; the molar ratio of the high molecular monomer to the ligand is 25-150: 1, preferably 50: 1; the volume ratio of the high molecular monomer to the solvent I is 1-4: 1; the molar ratio of the high molecular monomer to the catalyst is 100-700: 1, preferably 500: 1; the molar ratio of the high molecular monomer to the reducing agent is 50-150: 1.
Preferably, the solvent I is N, N-dimethylformamide, and the solvent II is one or two of water and N, N-dimethylformamide; the solvent III is one or more of water, ethanol and N, N-dimethylformamide.
Preferably, the reaction time in step (2) is 12-72 h.
Preferably, the cellulose in step (1) is treated as follows: firstly, centrifuging an aqueous dispersion containing 500mg of cellulose for 30min to remove most of water solvent, then uniformly dispersing the aqueous dispersion in a mixed solution of 100-300mLN, N-dimethylformamide and 50-150mL of cyclohexane, heating and distilling the mixture in an oil bath kettle at 105 ℃ for 5-10h under the protection of inert gas, reducing the temperature of the oil bath to 90 ℃ after anhydrous distillation, evaporating the cyclohexane, completely replacing water with N, N-dimethylformamide, and modifying the treated cellulose.
Preferably, the step of modifying the cellulose with bromine groups in step (1) is: adding 4-dimethylaminopyridine and triethylamine into N, N-dimethylformamide dispersion liquid containing cellulose under the protection of ice water bath and inert gas, slowly dropwise adding 2-bromo-isobutyryl bromide, stirring at normal temperature for 12-48h, and performing post-treatment to obtain the cellulose containing bromine functional groups.
Preferably, the step of modifying the cellulose with bromine groups in step (1) is: adding 0.30-0.60g of 4-dimethylaminopyridine and 6.5-8.5mL of triethylamine into 100mL of N, N-dimethylformamide dispersion containing 500mg of cellulose under the protection of ice-water bath and inert gas, slowly dropwise adding 5.7mL of 2-bromo-isobutyryl bromide into a reaction device within 2.0-3.0h, stirring at normal temperature for 12-48h, and carrying out aftertreatment by using a mixed solution of ethanol and water in a certain proportion.
Specifically, the step of modifying the cellulose to be grafted with bromine groups in the step (1) is as follows: adding 0.5g of 4-dimethylaminopyridine and 7.5mL of triethylamine to 200mL of N, N-dimethylformamide dispersion containing 500mg of cellulose, slowly dropwise adding 5.7mL of 2-bromo-isobutyryl bromide to a reaction device in an ice-water bath and under a nitrogen atmosphere within 3h, stirring at normal temperature for 24h, centrifuging, and adding ethanol: 1 part of water: 1 and N, N-dimethylformamide for several times to obtain the cellulose containing bromine functional groups.
In a third aspect, the invention provides an application of a molecular brush polymer film based on a cellulose network structure in the preparation of a lithium metal battery, which comprises the following steps:
(a) uniformly mixing electrolyte, 2, 2-azobisisobutyronitrile and polyethylene glycol diacrylate in a glove box to prepare a precursor solution;
(b) cutting the molecular brush polymer film into the size of a diaphragm;
(c) using the precursor solution and the membrane-sized thin film in step (a) and step (b) for assembling a lithium metal battery;
(d) and (c) placing the battery in the step (c) in an oven at 50-80 ℃ for 3-6h to obtain the gelled lithium metal battery.
Preferably, the mass ratio of the electrolyte and the 2, 2-azobisisobutyronitrile in the step (a) is 80-300: 1, preferably 100: 1; the mass ratio of the polyethylene glycol diacrylate to the electrolyte is 1: 2 to 9, preferably 3 to 6.
Preferably, the inert gas in step (2) comprises one or two of nitrogen and argon.
Preferably, the step of centrifuging and washing with a hydrochloric acid solution several times as described in step (3) comprises: the centrifuged and separated product was dispersed in 1mol/L hydrochloric acid solution, centrifuged again and the centrifuged product was washed 4 to 6 times with the same concentration of hydrochloric acid solution.
Preferably, the concentration of the LiOH solution in the step (3) is 10-30 mg/mL.
The principle of the invention is as follows: firstly, functional polymers are grafted on cellulose by utilizing atom transfer radical polymerization reaction, then the cellulose @ functional polymer molecular brush is prepared into a macroscopic material by utilizing modes of suction filtration film forming or natural volatilization film forming and the like, and then the macroscopic material is gelatinized for a lithium metal battery through in-situ thermal polymerization. It is worth pointing out that cellulose is used as a natural polymer with rich pores, which provides guarantee for constructing a three-dimensional network structure, and in addition, the cellulose has excellent mechanical toughness and thermodynamic stability, and can inhibit the growth of lithium dendrite to a certain extent in the charge and discharge cycle process, thereby prolonging the service life of the battery and improving the safety of the battery. Meanwhile, functional polymers with lithium sulfonate or rich alkoxy chain segments are introduced, so that the ion transference number and the lithium ion conductivity can be obviously improved. In the process of assembling the battery, the interfacial impedance between the internal electrode and the electrolyte of the lithium metal battery is effectively reduced by using an in-situ thermal polymerization method.
In a fourth aspect, the invention provides a method for preparing the molecular brush polymer material with the cellulose network structure according to the second aspect, and the method is applied to lithium metal batteries.
The invention also provides application of the preparation method of the molecular brush gel polymer electrolyte with the cellulose network structure in lithium metal batteries.
Compared with the prior art, the invention has the following beneficial effects:
(1) the problem of poor interface contact caused by independently preparing the gel electrolyte and assembling the gel electrolyte with the positive and negative electrodes into the battery can be effectively solved by utilizing the in-situ thermal polymerization reaction, and the separation between the electrodes and the electrolyte can be effectively avoided when the bending strength of the battery is higher.
(2) Lithium sulfonate is introduced through a functional polymer chain, and the single-ion conductor polymer electrolyte can obviously improve the transference number of lithium ions, reduce polarization and inhibit the growth of lithium dendrites by fixing anions on a polymer main chain; and the introduction of alkoxy groups on the functional polymer chain can coordinate lithium ions with ether oxygen atoms on the chain segment, promote the transmission of the lithium ions on the chain segment through the motion of the chain segment, and improve the ionic conductivity of the lithium ions.
(3) The cellulose is used as a matrix material, so that the pore structure of the material can be improved, the liquid absorption rate of the material is improved, the ionic conductivity of a target high polymer material is enhanced, and excellent thermodynamic stability is kept.
Drawings
To more clearly and clearly explain the objects, technical solutions and advantages of the present application, the present invention will be described in further detail below with reference to the accompanying drawings, which are used for describing embodiments and prior arts. It should be understood that the drawings in the following description are only a few embodiments of the present invention, are only used for explaining the present invention, and are not limited to the present invention, and those skilled in the art can also obtain other drawings based on the drawings under the premise of inventive work. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Fig. 1 (a) and (B) are scanning electron micrographs of bacterial cellulose and a first molecular brush polymer material with a bacterial cellulose network structure before grafting provided in example 1 of the present invention, and (C) is a scanning electron micrograph of a first molecular brush polymer material with a bacterial cellulose network structure provided in example 1 of the present invention; (D) a photo of a first molecular brush polymer material with a bacterial cellulose network structure provided in embodiment 1 of the present invention.
FIG. 2 is a thermogravimetric analysis chart of bacterial cellulose, a polymer of monomer 2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester and a molecular brush polymer material I with a bacterial cellulose network structure before grafting, which is provided by the embodiment 1 of the invention.
Fig. 3 is a digital photograph of a molecular brush polymer material with a bacterial cellulose network structure provided in example 1 of the present invention before (left) and after (right) gelation in a precursor solution.
Fig. 4 (a) and (B) are impedance test curves of the molecular brush polymer material having a bacterial cellulose network structure and the mechanical mixed material of bacterial cellulose and polymer provided in example 1 of the present invention, respectively.
Fig. 5 (a) is a linear sweep voltammogram of the molecular brush polymer material with a bacterial cellulose network structure and the mechanical mixed material of bacterial cellulose and polymer provided in example 1 of the present invention, (B) is a plot of ionic conductivity versus temperature of the molecular brush polymer material with a bacterial cellulose network structure provided in example 1 of the present invention, (C) is a rate capability of the molecular brush polymer material with a bacterial cellulose network structure and the mechanical mixed material of bacterial cellulose and polymer provided in example 1 of the present invention assembled into an LFP | GPE | Li gelation battery, and (D) is a plot of Li | GPE | Li gelation battery assembled from the molecular brush polymer material with a bacterial cellulose network structure and the mechanical mixed material of bacterial cellulose and polymer provided in example 1 of the present invention assembled into a Li | GPE | Li gelation battery at 1mA cm-2，1mAh cm-2Cycling performance under the conditions.
Detailed Description
The present invention will be described in further detail with reference to the following examples, and it should be understood that the described examples are only a part of the examples of the present invention, but not all examples, and the embodiments of the present invention are not limited thereto.
Example 1
The embodiment of the invention provides a preparation method of a cellulose functional molecular brush gel polymer material with a three-dimensional network structure and an application of the cellulose functional molecular brush gel polymer material in the preparation of a lithium metal battery, and the preparation method comprises the following steps:
(1) removing water from the bacterial cellulose dispersion liquid and replacing the water with N, N-dimethylformamide: firstly, centrifuging an aqueous dispersion containing 500mg of bacterial cellulose for 30min to remove most of water solvent, then uniformly dispersing the aqueous dispersion in a mixed solution of 200mL of N, N-dimethylformamide and 100mL of cyclohexane, heating and distilling the mixture in an oil bath kettle at 105 ℃ for 8h under the protection of nitrogen, reducing the temperature of the oil bath to 90 ℃ after anhydrous distillation, evaporating cyclohexane, and completely replacing water with N, N-dimethylformamide.
(2) Modifying the Bacterial Cellulose (BC) obtained in the step (1) and grafting a bromine group to obtain bacterial cellulose (BC-Br) containing bromine functional groups: adding 0.5g of 4-dimethylaminopyridine and 7.5mL of triethylamine to 200mL of N, N-dimethylformamide dispersion containing 500mg of bacterial cellulose, slowly dropwise adding 5.7mL of 2-bromo-isobutyryl bromide into a reaction device in an ice-water bath and nitrogen atmosphere within 2h, stirring for 24h at normal temperature, centrifuging, and then adding ethanol: 1 part of water: 1 and N, N-dimethylformamide for several times to obtain bacterial cellulose (BC-Br) containing bromine functional groups.
(3) 150mg (0.833mmol) of bacterial cellulose (BC-Br) containing bromine functional groups prepared in step (2), 18mL (97.5mmol) of 2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester, 400. mu.L (1.91mmol) of N, N, N' -pentamethyldiethylenetriamine, 43.2mg (0.193mmol) of CuBr2Uniformly mixing the mixture with 5mL of N, N-dimethylformamide, reacting for 30min under the protection of nitrogen, then adding 198mg (1.12mmol) of ascorbic acid, introducing nitrogen for 30min, reacting for 24h at 60 ℃, centrifuging, and then centrifuging and washing for several times by using N, N-dimethylformamide and deionized water to obtain an intermediate product I;
(4) dispersing the intermediate product I prepared in the step (3) in water, heating and volatilizing the intermediate product I on a polytetrafluoroethylene plate at 40 ℃ to form a film, and obtaining a molecular brush polymer material I with a bacterial cellulose network structure;
(5) preparing a precursor solution: 2g of electrolyte, 20mg of 2, 2-azobisisobutyronitrile and 353mg of polyethylene glycol diacrylate are uniformly mixed in a glove box;
(6) assembling the lithium metal gel polymer battery: cutting the material I into the size of a diaphragm, taking 50 mu L of precursor solution, assembling the precursor solution into a lithium metal battery in a glove box, and then placing the lithium metal battery in a 60 ℃ drying oven for reaction for 4 hours to obtain the gelled lithium metal battery.
As can be seen from FIG. 1, the prepared molecular brush polymer material with the bacterial cellulose network structure has the advantages that compared with the bacterial cellulose before grafting, the diameter of a fiber segment is increased from about 75nm to about 200nm, and the molecular brush polymer material can be macroscopically filmed.
As can be seen from FIG. 2, the grafting ratio of the prepared molecular brush polymer material I with the bacterial cellulose network structure is 125%.
Fig. 3 demonstrates that under this experimental condition, the electrolyte can be transformed from liquid to gel.
As can be seen from fig. 4, the impedance of the battery assembled from the molecularly brushed gel polymer having the bacterial cellulose network structure is significantly lower than that of the battery assembled from the bacterial cellulose and the polymer simply by mechanical mixing.
As can be seen from fig. 5, it is obviously different from simple mechanical mixing of bacterial cellulose and a polymer, and grafting of the polymer on the bacterial cellulose can obviously improve the rate capability of the lithium ion battery under high current density, and highlight the advantages of the molecular brush. The in-situ thermal polymerization of the present invention, i.e., the gelation reaction after the battery is mounted, is advantageous in that the internal resistance of the battery is significantly reduced (see fig. 5B for details).
In the sample of the molecular brush polymer material with the bacterial cellulose network structure provided in embodiment 1, the BC @ functional polymer brush is volatilized to form a film, and a scan and a physical image show that, macroscopically, the sample of the molecular brush polymer material with the bacterial cellulose network structure is a structure of a macroscopic film; microscopically, the fibers are intertwined with each other to form a three-dimensional network structure.
Example 2
The embodiment of the invention provides a preparation method of a cellulose functional molecular brush gel polymer material with a three-dimensional network structure and an application of the cellulose functional molecular brush gel polymer material in the preparation of a lithium metal battery, and the preparation method comprises the following steps:
(1) removing water from the bacterial cellulose dispersion liquid and replacing the water with N, N-dimethylformamide: firstly, centrifuging an aqueous dispersion containing 500mg of bacterial cellulose for 30min to remove most of water solvent, then uniformly dispersing the aqueous dispersion in a mixed solution of 200mL of N, N-dimethylformamide and 100mL of cyclohexane, heating and distilling the mixture in an oil bath kettle at 105 ℃ for 8h under the protection of nitrogen, reducing the temperature of the oil bath to 90 ℃ after anhydrous distillation, evaporating cyclohexane, and completely replacing water with N, N-dimethylformamide.
(2) Modifying the Bacterial Cellulose (BC) obtained in the step (1) and grafting a bromine group to obtain bacterial cellulose (BC-Br) containing bromine functional groups: adding 0.6g of 4-dimethylaminopyridine and 8.0mL of triethylamine into 200mL of N, N-dimethylformamide dispersion liquid containing 500mg of bacterial cellulose, slowly dropwise adding 5.7mL of 2-bromo-isobutyryl bromide into a reaction device in ice-water bath and nitrogen atmosphere within 2h, stirring at normal temperature for 12h, centrifuging, and then adding ethanol: 1 part of water: 1 and N, N-dimethylformamide for several times to obtain bacterial cellulose (BC-Br) containing bromine functional groups.
(3) 150mg (0.833mmol) of bacterial cellulose (BC-Br) containing bromine functional groups prepared in step (2), 18mL (97.5mmol) of 2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester, 300. mu.L (1.43mmol) of N, N, N' -pentamethyldiethylenetriamine, 32.2mg (0.144mmol) of CuBr2Uniformly mixing the mixture with 5mL of N, N-dimethylformamide, reacting for 30min under the protection of nitrogen, adding 148mg (0.84mmol) of ascorbic acid, introducing nitrogen for 30min, reacting for 48h at 60 ℃, centrifuging, and centrifugally washing with N, N-dimethylformamide and deionized water for several times to obtain an intermediate product I;
(4) dispersing the intermediate product I prepared in the step (3) in water, heating and volatilizing the intermediate product I on a polytetrafluoroethylene plate at 40 ℃ to form a film, and obtaining a molecular brush polymer material II with a bacterial cellulose network structure;
(5) preparing a precursor solution: 2g of electrolyte, 20mg of 2, 2-azobisisobutyronitrile and 353mg of polyethylene glycol diacrylate are uniformly mixed in a glove box;
(6) assembling the lithium metal gel polymer battery: and cutting the material II into the size of a diaphragm, taking 50 mu L of precursor solution, assembling the precursor solution into a lithium metal battery in a glove box, and then placing the lithium metal battery in a 60 ℃ drying oven for reaction for 4 hours to obtain the gelled lithium metal battery.
Example 3
The embodiment of the invention provides a preparation method of a cellulose functional molecular brush gel polymer material with a three-dimensional network structure and an application of the cellulose functional molecular brush gel polymer material in the preparation of a lithium metal battery, and the preparation method comprises the following steps:
(1) removing water from the bacterial cellulose dispersion liquid and replacing the water with N, N-dimethylformamide: firstly, centrifuging an aqueous dispersion containing 500mg of bacterial cellulose for 30min to remove most of water solvent, then uniformly dispersing the aqueous dispersion in a mixed solution of 200mL of N, N-dimethylformamide and 100mL of cyclohexane, heating and distilling the mixture in an oil bath kettle at 105 ℃ for 8h under the protection of nitrogen, reducing the temperature of the oil bath to 90 ℃ after anhydrous distillation, evaporating cyclohexane, and completely replacing water with N, N-dimethylformamide.
(2) Modifying the Bacterial Cellulose (BC) obtained in the step (1) and grafting a bromine group to obtain bacterial cellulose (BC-Br) containing bromine functional groups: adding 0.25g of 4-dimethylaminopyridine and 6.5mL of triethylamine to 200mL of N, N-dimethylformamide dispersion containing 500mg of bacterial cellulose, slowly dropwise adding 2.8mL of 2-bromo-isobutyryl bromide to a reaction device in an ice-water bath and nitrogen atmosphere within 1.5h, stirring at normal temperature for 48h, centrifuging, and then adding ethanol: 1 part of water: 1 and N, N-dimethylformamide for several times to obtain bacterial cellulose (BC-Br) containing bromine functional groups.
(3) 150mg (0.833mmol) of bacterial cellulose (BC-Br) containing bromine functional groups prepared in step (2), 18mL (97.5mmol) of 2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester, 300. mu.L (1.43mmol) of N, N, N' -pentamethyldiethylenetriamine, 32.2mg (0.144mmol) of CuBr2Uniformly mixing the mixture with 5mL of N, N-dimethylformamide, reacting for 30min under the protection of nitrogen, adding 148mg (0.84mmol) of ascorbic acid, introducing nitrogen for 30min, reacting for 24h at 70 ℃, centrifuging, and centrifugally washing with N, N-dimethylformamide and deionized water for several times to obtain an intermediate product I;
(4) dispersing the intermediate product I prepared in the step (3) in water, heating and volatilizing the intermediate product I on a polytetrafluoroethylene plate at 40 ℃ to form a film, and obtaining a molecular brush polymer material III with a bacterial cellulose network structure;
(5) preparing a precursor solution: 2g of electrolyte, 20mg of 2, 2-azobisisobutyronitrile and 353mg of polyethylene glycol diacrylate are uniformly mixed in a glove box;
(6) assembling the lithium metal gel polymer battery: and cutting the material III into the size of a diaphragm, assembling 50 mu L of precursor solution into a lithium metal battery in a glove box, and then placing the lithium metal battery in a 60 ℃ drying oven for reaction for 4h to obtain the gelled lithium metal battery.
Example 4
The embodiment of the invention provides a preparation method of a cellulose functional molecular brush gel polymer material with a three-dimensional network structure and an application of the cellulose functional molecular brush gel polymer material in the preparation of a lithium metal battery, and the preparation method comprises the following steps:
(1) removing water from the bacterial cellulose dispersion liquid and replacing the water with N, N-dimethylformamide: firstly, centrifuging an aqueous dispersion containing 500mg of bacterial cellulose for 30min to remove most of water solvent, then uniformly dispersing the aqueous dispersion in a mixed solution of 200mL of N, N-dimethylformamide and 100mL of cyclohexane, heating and distilling the mixture in an oil bath kettle at 105 ℃ for 8h under the protection of nitrogen, reducing the temperature of the oil bath to 90 ℃ after anhydrous distillation, evaporating cyclohexane, and completely replacing water with N, N-dimethylformamide.
(2) Modifying the Bacterial Cellulose (BC) obtained in the step (1) and grafting a bromine group to obtain bacterial cellulose (BC-Br) containing bromine functional groups: adding 0.25g of 4-dimethylaminopyridine and 6.5mL of triethylamine to 200mL of N, N-dimethylformamide dispersion containing 500mg of bacterial cellulose, slowly dropwise adding 2.8mL of 2-bromo-isobutyryl bromide to a reaction device in an ice-water bath and nitrogen atmosphere within 1.5h, stirring at normal temperature for 48h, centrifuging, and then adding ethanol: 1 part of water: 1 and N, N-dimethylformamide for several times to obtain bacterial cellulose (BC-Br) containing bromine functional groups.
(3) 150mg (0.833mmol) of bacterial cellulose (BC-Br) containing bromine functional groups prepared in the step (2) and 10mL (54.2mmol) of 2-methyl-2-propyl2- (2-methoxyethoxy) ethyl enoate, 220. mu.L (1.05mmol) of N, N, N' -pentamethyldiethylenetriamine, 24mg (0.107mmol) of CuBr2Uniformly mixing the mixture with 5mL of N, N-dimethylformamide, reacting for 30min under the protection of nitrogen, adding 110mg (0.62mmol) of ascorbic acid, introducing nitrogen for 30min, reacting for 48h at 70 ℃, centrifuging, and centrifugally washing with N, N-dimethylformamide and deionized water for several times to obtain an intermediate product I;
(4) dispersing the intermediate product I prepared in the step (3) in water, heating and volatilizing the intermediate product I on a polytetrafluoroethylene plate at 40 ℃ to form a film, and obtaining a molecular brush polymer material IV with a bacterial cellulose network structure;
(5) preparing a precursor solution: 2g of electrolyte, 20mg of 2, 2-azobisisobutyronitrile and 353mg of polyethylene glycol diacrylate are uniformly mixed in a glove box;
(6) assembling the lithium metal gel polymer battery: cutting the material IV into the size of a diaphragm, taking 50 mu L of precursor solution, assembling the precursor solution into a lithium metal battery in a glove box, and then placing the lithium metal battery in a 60 ℃ drying oven for reaction for 4 hours to obtain the gelled lithium metal battery.
TABLE 1 Room temperature Ionic conductivity and Ionic transport number of molecular Brush gel Polymer electrolytes having a cellulose network Structure
Figure BDA0002657797320000081
Figure BDA0002657797320000091
Example 5
The embodiment of the invention provides a preparation method of a cellulose functional molecular brush gel polymer material with a three-dimensional network structure and an application of the cellulose functional molecular brush gel polymer material in the preparation of a lithium metal battery, and the preparation method comprises the following steps:
(1) removing water from the bacterial cellulose dispersion liquid and replacing the water with N, N-dimethylformamide: firstly, centrifuging an aqueous dispersion containing 500mg of bacterial cellulose for 30min to remove most of water solvent, then uniformly dispersing the aqueous dispersion in a mixed solution of 200mL of N, N-dimethylformamide and 100mL of cyclohexane, heating and distilling the mixture in an oil bath kettle at 105 ℃ for 8h under the protection of nitrogen, reducing the temperature of the oil bath to 90 ℃ after anhydrous distillation, evaporating cyclohexane, and completely replacing water with N, N-dimethylformamide.
(2) Modifying the Bacterial Cellulose (BC) obtained in the step (1) and grafting a bromine group to obtain bacterial cellulose (BC-Br) containing bromine functional groups: adding 0.25g of 4-dimethylaminopyridine and 6.5mL of triethylamine to 200mL of N, N-dimethylformamide dispersion containing 500mg of bacterial cellulose, slowly dropwise adding 2.8mL of 2-bromo-isobutyryl bromide to a reaction device in an ice-water bath and nitrogen atmosphere within 1.5h, stirring at normal temperature for 48h, centrifuging, and then adding ethanol: 1 part of water: 1 and N, N-dimethylformamide for several times to obtain bacterial cellulose (BC-Br) containing bromine functional groups.
(3) 150mg (0.833mmol) of bacterial cellulose (BC-Br) containing bromine functional groups prepared in step (2), 6.45mL (48.8mmol) of glycidyl methacrylate, 204. mu.L (0.976mmol) of N, N, N' -pentamethyldiethylenetriamine, 21.9mg (0.098mmol) of CuBr2Uniformly mixing the mixture with 5mL of N, N-dimethylformamide, reacting for 30min under the protection of nitrogen, adding 75.2mg (0.569mmol) of ascorbic acid, introducing nitrogen for 30min, reacting for 24h at 80 ℃, centrifuging, and centrifugally washing for several times by using N, N-dimethylformamide and deionized water to obtain an intermediate product I;
(4) dispersing the intermediate product I prepared in the step (3) in water, heating and volatilizing the intermediate product I on a polytetrafluoroethylene plate at 40 ℃ to form a film, and obtaining a molecular brush polymer material V with a bacterial cellulose network structure;
(5) preparing a precursor solution: 2g of electrolyte, 20mg of 2, 2-azobisisobutyronitrile and 353mg of polyethylene glycol diacrylate are uniformly mixed in a glove box;
(6) assembling the lithium metal gel polymer battery: and cutting the material III into the size of a diaphragm, assembling 50 mu L of precursor solution into a lithium metal battery in a glove box, and then placing the lithium metal battery in a 60 ℃ drying oven for reaction for 4h to obtain the gelled lithium metal battery.
Example 6
The embodiment of the invention provides a molecular brush polymer material with a bacterial cellulose network structure and a preparation method of a molecular brush gel polymer electrolyte with the bacterial cellulose network structure, which comprise the following steps:
(1) removing water from the bacterial cellulose dispersion liquid and replacing the water with N, N-dimethylformamide: firstly, centrifuging an aqueous dispersion containing 500mg of bacterial cellulose for 30min to remove most of water solvent, then uniformly dispersing the aqueous dispersion in a mixed solution of 200mL of N, N-dimethylformamide and 100mL of cyclohexane, heating and distilling the mixture in an oil bath kettle at 105 ℃ for 8h under the protection of nitrogen, reducing the temperature of the oil bath to 90 ℃ after anhydrous distillation, evaporating cyclohexane, and completely replacing water with N, N-dimethylformamide.
(2) Modifying the Bacterial Cellulose (BC) obtained in the step (1) and grafting a bromine group to obtain bacterial cellulose (BC-Br) containing bromine functional groups: adding 0.25g of 4-dimethylaminopyridine and 6.5mL of triethylamine to 200mL of N, N-dimethylformamide dispersion containing 500mg of bacterial cellulose, slowly dropwise adding 2.8mL of 2-bromo-isobutyryl bromide to a reaction device in an ice-water bath and nitrogen atmosphere within 1.5h, stirring at normal temperature for 48h, centrifuging, and then adding ethanol: 1 part of water: 1 and N, N-dimethylformamide for several times to obtain bacterial cellulose (BC-Br) containing bromine functional groups.
(3) 150mg (0.833mmol) of bacterial cellulose (BC-Br) containing bromine functional groups prepared in step (2), 8.60mL (65mmol) of glycidyl methacrylate, 272. mu.L (1.3mmol) of N, N, N' -pentamethyldiethylenetriamine, and 29.1mg (0.13mmol) of CuBr2Uniformly mixing the mixture with 5mL of N, N-dimethylformamide, reacting for 30min under the protection of nitrogen, then adding 133mg (0.754mmol) of ascorbic acid, introducing nitrogen for 30min, reacting for 36h at 70 ℃, centrifuging, and then centrifuging and washing for several times by using N, N-dimethylformamide and deionized water to obtain an intermediate product I;
(4) dispersing the intermediate product I prepared in the step (3) in water, heating and volatilizing the intermediate product I on a polytetrafluoroethylene plate at 40 ℃ to form a film, and obtaining a molecular brush polymer material VI with a bacterial cellulose network structure;
(5) preparing a precursor solution: 2g of electrolyte, 20mg of 2, 2-azobisisobutyronitrile and 353mg of polyethylene glycol diacrylate are uniformly mixed in a glove box;
(6) assembling the lithium metal gel polymer battery: cutting the material IV into the size of a diaphragm, taking 50 mu L of precursor solution, assembling the precursor solution into a lithium metal battery in a glove box, and then placing the lithium metal battery in a 60 ℃ drying oven for reaction for 4 hours to obtain the gelled lithium metal battery.
TABLE 2 Room temperature Ionic conductivity and Ionic transport number of molecular Brush gel Polymer electrolytes having a cellulose network Structure
Figure BDA0002657797320000101
Example 7
The embodiment of the invention provides a preparation method of a cellulose functional molecular brush gel polymer material with a three-dimensional network structure and an application of the cellulose functional molecular brush gel polymer material in the preparation of a lithium metal battery, and the preparation method comprises the following steps:
(1) removing water from the bacterial cellulose dispersion liquid and replacing the water with N, N-dimethylformamide: firstly, centrifuging an aqueous dispersion containing 500mg of bacterial cellulose for 30min to remove most of water solvent, then uniformly dispersing the aqueous dispersion in a mixed solution of 200mL of N, N-dimethylformamide and 100mL of cyclohexane, heating and distilling the mixture in an oil bath kettle at 105 ℃ for 8h under the protection of nitrogen, reducing the temperature of the oil bath to 90 ℃ after anhydrous distillation, evaporating cyclohexane, and completely replacing water with N, N-dimethylformamide.
(2) Modifying the Bacterial Cellulose (BC) obtained in the step (1) and grafting a bromine group to obtain bacterial cellulose (BC-Br) containing bromine functional groups: adding 0.5g of 4-dimethylaminopyridine and 7.5mL of triethylamine to 200mL of N, N-dimethylformamide dispersion containing 500mg of bacterial cellulose, slowly dropwise adding 5.7mL of 2-bromo-isobutyryl bromide into a reaction device in an ice-water bath and nitrogen atmosphere within 2h, stirring for 24h at normal temperature, centrifuging, and then adding ethanol: 1 part of water: 1 and N, N-dimethylformamide for several times to obtain bacterial cellulose (BC-Br) containing bromine functional groups.
(3) 150mg (0.833mmol) of the bromohydrin prepared in step (2)Energetic bacterial cellulose (BC-Br), 20.1g (97.5mmol) of sodium p-styrenesulfonate, 400. mu.L (1.91mmol) of N, N, N' -pentamethyldiethylenetriamine, 43.2mg (0.193mmol) of CuBr2Uniformly mixing 5mL of N, N-dimethylformamide and 5mL of deionized water, reacting for 30min under the protection of nitrogen, adding 198mg (1.12mmol) of ascorbic acid, introducing nitrogen for 30min, reacting for 36h at 90 ℃, centrifuging, and centrifugally washing for several times by using N, N-dimethylformamide and deionized water to obtain an intermediate product I;
(4) adding 200mL of deionized water into the intermediate product I prepared in the step (3), centrifuging and using 1.0moL of L-1Washing with a hydrochloric acid solution for several times, dispersing the centrifugal product in 200mL of 23mg/mL LiOH solution, stirring for 12h, centrifuging again, and washing the centrifugal product with deionized water for several times to obtain an intermediate product II;
(5) dispersing the intermediate product I prepared in the step (3) in water, heating and volatilizing the intermediate product I on a polytetrafluoroethylene plate at 40 ℃ to form a film, and obtaining a molecular brush polymer material VII with a bacterial cellulose network structure;
(6) preparing a precursor solution: 2g of electrolyte, 20mg of 2, 2-azobisisobutyronitrile and 353mg of polyethylene glycol diacrylate are uniformly mixed in a glove box;
(7) assembling the lithium metal gel polymer battery: and cutting the material V into the size of a diaphragm, taking 50 mu L of precursor solution, assembling the precursor solution into a lithium metal battery in a glove box, and then placing the lithium metal battery in a 60 ℃ drying oven for reaction for 4 hours to obtain the gelled lithium metal battery.
Example 8
The embodiment of the invention provides a preparation method of a cellulose functional molecular brush gel polymer material with a three-dimensional network structure and an application of the cellulose functional molecular brush gel polymer material in the preparation of a lithium metal battery, and the preparation method comprises the following steps:
(1) removing water from the bacterial cellulose dispersion liquid and replacing the water with N, N-dimethylformamide: firstly, centrifuging an aqueous dispersion containing 500mg of bacterial cellulose for 30min to remove most of water solvent, then uniformly dispersing the aqueous dispersion in a mixed solution of 200mL of N, N-dimethylformamide and 100mL of cyclohexane, heating and distilling the mixture in an oil bath kettle at 105 ℃ for 8h under the protection of nitrogen, reducing the temperature of the oil bath to 90 ℃ after anhydrous distillation, evaporating cyclohexane, and completely replacing water with N, N-dimethylformamide.
(2) Modifying the Bacterial Cellulose (BC) obtained in the step (1) and grafting a bromine group to obtain bacterial cellulose (BC-Br) containing bromine functional groups: adding 0.5g of 4-dimethylaminopyridine and 7.5mL of triethylamine to 200mL of N, N-dimethylformamide dispersion containing 500mg of bacterial cellulose, slowly dropwise adding 5.7mL of 2-bromo-isobutyryl bromide into a reaction device in an ice-water bath and nitrogen atmosphere within 2h, stirring for 24h at normal temperature, centrifuging, and then adding ethanol: 1 part of water: 1 and N, N-dimethylformamide for several times to obtain bacterial cellulose (BC-Br) containing bromine functional groups.
(3) 150mg (0.833mmol) of bacterial cellulose (BC-Br) containing bromine functional groups prepared in the step (2), 10.0g (48.5mmol) of sodium p-styrenesulfonate, 200. mu.L (0.96mmol) of N, N, N' -pentamethyldiethylenetriamine, 21.7mg (0.097mmol) of CuBr2Uniformly mixing 5mL of N, N-dimethylformamide and 5mL of deionized water, reacting for 30min under the protection of nitrogen, adding 99mg (0.56mmol) of ascorbic acid, introducing nitrogen for 30min, reacting for 48h at 90 ℃, centrifuging, and centrifugally washing for several times by using N, N-dimethylformamide and deionized water to obtain an intermediate product I;
(4) adding 200mL of deionized water into the intermediate product I prepared in the step (3), centrifuging and using 1.0moL of L-1Washing with a hydrochloric acid solution for several times, dispersing the centrifugal product in 100mL of 23mg/mL LiOH solution, stirring for 12h, centrifuging again, and washing the centrifugal product with deionized water for several times to obtain an intermediate product II;
(5) dispersing the intermediate product I prepared in the step (3) in water, heating and volatilizing the intermediate product I on a polytetrafluoroethylene plate at 40 ℃ to form a film, and obtaining a molecular brush polymer material eight with a bacterial cellulose network structure;
(6) preparing a precursor solution: 2g of electrolyte, 20mg of 2, 2-azobisisobutyronitrile and 353mg of polyethylene glycol diacrylate are uniformly mixed in a glove box;
(7) assembling the lithium metal gel polymer battery: and cutting the material six into the size of a diaphragm, assembling 50 mu L of precursor solution into a lithium metal battery in a glove box, and then placing the lithium metal battery in a 60 ℃ drying oven for reaction for 4h to obtain the gelled lithium metal battery.
Example 9
The embodiment of the invention provides a preparation method of a cellulose functional molecular brush gel polymer material with a three-dimensional network structure and an application of the cellulose functional molecular brush gel polymer material in the preparation of a lithium metal battery, and the preparation method comprises the following steps:
(1) removing water from the bacterial cellulose dispersion liquid and replacing the water with N, N-dimethylformamide: firstly, centrifuging an aqueous dispersion containing 500mg of bacterial cellulose for 30min to remove most of water solvent, then uniformly dispersing the aqueous dispersion in a mixed solution of 200mL of N, N-dimethylformamide and 100mL of cyclohexane, heating and distilling the mixture in an oil bath kettle at 105 ℃ for 8h under the protection of nitrogen, reducing the temperature of the oil bath to 90 ℃ after anhydrous distillation, evaporating cyclohexane, and completely replacing water with N, N-dimethylformamide.
(2) Modifying the Bacterial Cellulose (BC) obtained in the step (1) and grafting a bromine group to obtain bacterial cellulose (BC-Br) containing bromine functional groups: adding 0.5g of 4-dimethylaminopyridine and 7.5mL of triethylamine to 200mL of N, N-dimethylformamide dispersion containing 500mg of bacterial cellulose, slowly dropwise adding 5.7mL of 2-bromo-isobutyryl bromide into a reaction device in an ice-water bath and nitrogen atmosphere within 2h, stirring for 24h at normal temperature, centrifuging, and then adding ethanol: 1 part of water: 1 and N, N-dimethylformamide for several times to obtain bacterial cellulose (BC-Br) containing bromine functional groups.
(3) 150mg (0.833mmol) of bacterial cellulose (BC-Br) containing bromine functional groups prepared in the step (2), 10.0g (48.5mmol) of sodium p-styrenesulfonate, 200. mu.L (0.96mmol) of N, N, N' -pentamethyldiethylenetriamine, 21.7mg (0.097mmol) of CuBr2Uniformly mixing 5mL of N, N-dimethylformamide and 5mL of deionized water, reacting for 30min under the protection of nitrogen, adding 99mg (0.56mmol) of ascorbic acid, introducing nitrogen for 30min, reacting for 72h at 80 ℃, centrifuging, and centrifugally washing for several times by using N, N-dimethylformamide and deionized water to obtain an intermediate product I;
(4) adding 200mL of deionized water into the intermediate product I prepared in the step (3), centrifuging and using 1.0moL of L-1Washing with a hydrochloric acid solution for several times, dispersing the centrifugal product in 200mL of 23mg/mL LiOH solution, stirring for 12h, centrifuging again, and washing the centrifugal product with deionized water for several times to obtain an intermediate product II;
(5) dispersing the intermediate product I prepared in the step (3) in water, heating and volatilizing the intermediate product I on a polytetrafluoroethylene plate at 40 ℃ to form a film, and obtaining a molecular brush polymer material with a bacterial cellulose network structure;
(6) preparing a precursor solution: 2g of electrolyte, 20mg of 2, 2-azobisisobutyronitrile and 353mg of polyethylene glycol diacrylate are uniformly mixed in a glove box;
(7) assembling the lithium metal gel polymer battery: and cutting the material V into the size of a diaphragm, taking 50 mu L of precursor solution, assembling the precursor solution into a lithium metal battery in a glove box, and then placing the lithium metal battery in a 60 ℃ drying oven for reaction for 4 hours to obtain the gelled lithium metal battery.
Example 10
The embodiment of the invention provides a preparation method of a cellulose functional molecular brush gel polymer material with a three-dimensional network structure and an application of the cellulose functional molecular brush gel polymer material in the preparation of a lithium metal battery, and the preparation method comprises the following steps:
(1) removing water from the bacterial cellulose dispersion liquid and replacing the water with N, N-dimethylformamide: firstly, centrifuging an aqueous dispersion containing 500mg of bacterial cellulose for 30min to remove most of water solvent, then uniformly dispersing the aqueous dispersion in a mixed solution of 200mL of N, N-dimethylformamide and 100mL of cyclohexane, heating and distilling the mixture in an oil bath kettle at 105 ℃ for 8h under the protection of nitrogen, reducing the temperature of the oil bath to 90 ℃ after anhydrous distillation, evaporating cyclohexane, and completely replacing water with N, N-dimethylformamide.
(2) Modifying the Bacterial Cellulose (BC) obtained in the step (1) and grafting a bromine group to obtain bacterial cellulose (BC-Br) containing bromine functional groups: adding 0.5g of 4-dimethylaminopyridine and 7.5mL of triethylamine to 200mL of N, N-dimethylformamide dispersion containing 500mg of bacterial cellulose, slowly dropwise adding 5.7mL of 2-bromo-isobutyryl bromide into a reaction device in an ice-water bath and nitrogen atmosphere within 2h, stirring for 24h at normal temperature, centrifuging, and then adding ethanol: 1 part of water: 1 and N, N-dimethylformamide for several times to obtain bacterial cellulose (BC-Br) containing bromine functional groups.
(3) 150mg (0.833mmol) of bacterial cellulose (BC-Br) containing bromine functional groups prepared in the step (2), 13.4g (65mmol) of sodium p-styrene sulfonate, 267 μ L (1.27mmol) of N, N, N' -pentamethyldiethylenetriamine, 28.8mg (0.129mmol) of CuBr2Uniformly mixing 5mL of N, N-dimethylformamide and 5mL of deionized water, reacting for 30min under the protection of nitrogen, adding 132mg (0.747mmol) of ascorbic acid, introducing nitrogen for 30min, reacting for 60h at 80 ℃, centrifuging, and centrifugally washing for several times by using N, N-dimethylformamide and deionized water to obtain an intermediate product I;
(4) adding 200mL of deionized water into the intermediate product I prepared in the step (3), centrifuging and using 1.0moL of L-1Washing with a hydrochloric acid solution for several times, dispersing the centrifugal product in 100mL of 23mg/mL LiOH solution, stirring for 12h, centrifuging again, and washing the centrifugal product with deionized water for several times to obtain an intermediate product II;
(5) dispersing the intermediate product I prepared in the step (3) in water, heating and volatilizing the intermediate product I on a polytetrafluoroethylene plate at 40 ℃ to form a film, and obtaining a molecular brush polymer material with a bacterial cellulose network structure;
(6) preparing a precursor solution: 2g of electrolyte, 20mg of 2, 2-azobisisobutyronitrile and 353mg of polyethylene glycol diacrylate are uniformly mixed in a glove box;
(7) assembling the lithium metal gel polymer battery: and cutting the material six into the size of a diaphragm, assembling 50 mu L of precursor solution into a lithium metal battery in a glove box, and then placing the lithium metal battery in a 60 ℃ drying oven for reaction for 4h to obtain the gelled lithium metal battery.
TABLE 3 Room temperature Ionic conductivity and Ionic transport number of molecular Brush gel Polymer electrolyte having cellulose network Structure
Figure BDA0002657797320000141
Finally, it should be noted that: the above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. It will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof, and it is intended that the present invention encompass such changes and modifications.

Claims (10)

1. A preparation method of a molecular brush polymer film based on a cellulose network structure is characterized by comprising the following steps:
(1) modifying cellulose and grafting bromine group to obtain the cellulose containing bromine functional group;
(2) uniformly mixing the bromine functional group-containing cellulose prepared in the step (1) with a high molecular monomer, a ligand, a catalyst and a solvent I, reacting for 20-40min under the protection of inert gas, adding a reducing agent, introducing inert gas for 20-40min, and reacting at 50-90 ℃ to obtain an intermediate product I; the polymer monomer is a sulfonic acid lithium-conducting monomer;
(3) adding a solvent II into the intermediate product I prepared in the step (2), centrifuging and washing for a plurality of times by using a hydrochloric acid solution, dispersing the centrifuged product in a LiOH solution, stirring for 6-24h, centrifuging again and washing the centrifuged product for a plurality of times by using water and/or ethanol to obtain an intermediate product II;
(4) dispersing the intermediate product II prepared in the step (3) in a solvent III, and performing suction filtration or heating volatilization to form a film;
and (3) when the high molecular monomer is an alkoxy lithium-conducting monomer, directly dispersing the intermediate product in a solvent III, and filtering or heating to volatilize the intermediate product to form the film.
2. The method according to claim 1, wherein the polymer monomer in step (2) comprises one or more of 2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester, methoxyethyl methacrylate, glycidyl methacrylate, isobutyl methacrylate, sodium p-styrenesulfonate, potassium propyl methacrylate-3-sulfonate, and 2-acrylamido-2-methyl-1-propanesulfonic acid.
3. The method according to claim 2, wherein the ligand in step (2) comprises one or more of 1,1,4,7,10, 10-hexamethyltriethylene tetramine, N, N, N' -pentamethyldiethylenetriamine and tris (2-dimethylaminoethyl) amine;
the catalyst is one or two of cuprous bromide and cuprous chloride;
the reducing agent is ascorbic acid.
4. The method according to claim 1, 2 or 3, wherein the molar ratio of the polymer monomer to the cellulose containing a bromine functional group in the step (2) is 50 to 300: 1, preferably 120: 1; the molar ratio of the high molecular monomer to the ligand is 25-150: 1, preferably 50: 1; the volume ratio of the high molecular monomer to the solvent I is 1-4: 1; the molar ratio of the high molecular monomer to the catalyst is 100-700: 1, preferably 500: 1; the molar ratio of the high molecular monomer to the reducing agent is 50-150: 1.
5. The preparation method according to claim 1, 2 or 3, wherein the solvent I is N, N-dimethylformamide, and the solvent II is one or two of water and N, N-dimethylformamide; the solvent III is one or more of water, ethanol and N, N-dimethylformamide.
6. The method according to claim 1, 2 or 3, wherein the reaction time in step (2) is 12 to 72 hours.
7. The method according to claim 1, 2 or 3, wherein the step of modifying the cellulose with a bromine group in the step (1) is: adding 4-dimethylaminopyridine and triethylamine into N, N-dimethylformamide dispersion liquid containing cellulose under the protection of ice water bath and inert gas, slowly dropwise adding 2-bromo-isobutyryl bromide, stirring at normal temperature for 12-48h, and performing post-treatment to obtain the cellulose containing bromine functional groups.
8. A molecular brush polymer film based on a cellulose network structure prepared by the method of any one of claims 1 to 7.
9. Use of a molecular brush polymer membrane based on a cellulose network structure according to claim 8 for the preparation of a lithium metal battery, characterized in that it comprises the following steps:
(a) uniformly mixing electrolyte, 2, 2-azobisisobutyronitrile and polyethylene glycol diacrylate in a glove box to prepare a precursor solution;
(b) cutting the molecular brush polymer film into the size of a diaphragm;
(c) using the precursor solution and the membrane-sized thin film in step (a) and step (b) for assembling a lithium metal battery;
(d) and (c) placing the battery in the step (c) in an oven at 50-80 ℃ for 3-6h to obtain the gelled lithium metal battery.
10. The use as claimed in claim 9, wherein the mass ratio of the electrolyte and the 2, 2-azobisisobutyronitrile in the step (a) is 100-300: 1, preferably 100: 1; the mass ratio of the polyethylene glycol diacrylate to the electrolyte is 1: 2 to 9, preferably 3 to 6.
CN202010893903.2A 2020-08-31 2020-08-31 Molecular brush polymer membrane based on cellulose network structure and preparation method and application thereof Active CN112072173B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010893903.2A CN112072173B (en) 2020-08-31 2020-08-31 Molecular brush polymer membrane based on cellulose network structure and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010893903.2A CN112072173B (en) 2020-08-31 2020-08-31 Molecular brush polymer membrane based on cellulose network structure and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112072173A true CN112072173A (en) 2020-12-11
CN112072173B CN112072173B (en) 2022-02-11

Family

ID=73664724

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010893903.2A Active CN112072173B (en) 2020-08-31 2020-08-31 Molecular brush polymer membrane based on cellulose network structure and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112072173B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113036208A (en) * 2021-02-26 2021-06-25 中山大学 Advanced porous polymer nanosheet and preparation method and application thereof
CN113036087A (en) * 2021-02-26 2021-06-25 中山大学 Ultrahigh-sulfur-content two-dimensional molecular brush and preparation method and application thereof
CN113036077A (en) * 2021-03-05 2021-06-25 中山大学 Artificial solid-phase electrolyte interface film modified lithium battery cathode and preparation method and application thereof
CN113178561A (en) * 2021-03-23 2021-07-27 中山大学 Negative electrode material modified by reactive two-dimensional molecular brush SEI film, and preparation method and application thereof
CN113502202A (en) * 2021-08-02 2021-10-15 惠风酒业发展(上海)有限公司 Health-care semi-sweet yellow wine and production process thereof
CN113644375A (en) * 2021-06-25 2021-11-12 中山大学 Two-dimensional polymer brush functional diaphragm and preparation method and application thereof
CN114181486A (en) * 2021-12-02 2022-03-15 昆明理工大学 Preparation method of cellulose microgel body reinforced propylene polyester

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003010267A1 (en) * 2001-07-20 2003-02-06 Unilever Plc Use of polymers in fabrics cleaning
CN103145918A (en) * 2013-01-18 2013-06-12 中国林业科学研究院林产化学工业研究所 Preparation method of cellulose-g-resin acid grafted copolymer
CN107919496A (en) * 2017-11-23 2018-04-17 齐鲁工业大学 Method for preparing quasi-single-ion solid polymer electrolyte with semi-interpenetrating network structure by using in-situ polymerization method
US20180131041A1 (en) * 2016-11-09 2018-05-10 Blue Solutions Canada Inc. Lithium salt grafted nanocrystalline cellulose for solid polymer electrolyte
CN109546205A (en) * 2018-06-13 2019-03-29 上海大学 Using the preparation method of the lithium ion battery of organo-mineral complexing gel polymer electrolyte
CN110350243A (en) * 2019-07-30 2019-10-18 华中科技大学 A kind of in-situ preparation method and its application of polymer dielectric
CN111082134A (en) * 2019-12-25 2020-04-28 中国科学院青岛生物能源与过程研究所 Polyoxymethylene all-solid-state polymer electrolyte prepared by in-situ ring-opening polymerization and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003010267A1 (en) * 2001-07-20 2003-02-06 Unilever Plc Use of polymers in fabrics cleaning
CN103145918A (en) * 2013-01-18 2013-06-12 中国林业科学研究院林产化学工业研究所 Preparation method of cellulose-g-resin acid grafted copolymer
US20180131041A1 (en) * 2016-11-09 2018-05-10 Blue Solutions Canada Inc. Lithium salt grafted nanocrystalline cellulose for solid polymer electrolyte
CN107919496A (en) * 2017-11-23 2018-04-17 齐鲁工业大学 Method for preparing quasi-single-ion solid polymer electrolyte with semi-interpenetrating network structure by using in-situ polymerization method
CN109546205A (en) * 2018-06-13 2019-03-29 上海大学 Using the preparation method of the lithium ion battery of organo-mineral complexing gel polymer electrolyte
CN110350243A (en) * 2019-07-30 2019-10-18 华中科技大学 A kind of in-situ preparation method and its application of polymer dielectric
CN111082134A (en) * 2019-12-25 2020-04-28 中国科学院青岛生物能源与过程研究所 Polyoxymethylene all-solid-state polymer electrolyte prepared by in-situ ring-opening polymerization and application thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113036208A (en) * 2021-02-26 2021-06-25 中山大学 Advanced porous polymer nanosheet and preparation method and application thereof
CN113036087A (en) * 2021-02-26 2021-06-25 中山大学 Ultrahigh-sulfur-content two-dimensional molecular brush and preparation method and application thereof
CN113036208B (en) * 2021-02-26 2022-05-10 中山大学 Advanced porous polymer nanosheet and preparation method and application thereof
CN113036077A (en) * 2021-03-05 2021-06-25 中山大学 Artificial solid-phase electrolyte interface film modified lithium battery cathode and preparation method and application thereof
CN113178561A (en) * 2021-03-23 2021-07-27 中山大学 Negative electrode material modified by reactive two-dimensional molecular brush SEI film, and preparation method and application thereof
CN113644375A (en) * 2021-06-25 2021-11-12 中山大学 Two-dimensional polymer brush functional diaphragm and preparation method and application thereof
CN113502202A (en) * 2021-08-02 2021-10-15 惠风酒业发展(上海)有限公司 Health-care semi-sweet yellow wine and production process thereof
CN114181486A (en) * 2021-12-02 2022-03-15 昆明理工大学 Preparation method of cellulose microgel body reinforced propylene polyester

Also Published As

Publication number Publication date
CN112072173B (en) 2022-02-11

Similar Documents

Publication Publication Date Title
CN112072173B (en) Molecular brush polymer membrane based on cellulose network structure and preparation method and application thereof
CN1174510C (en) Polymer-based hybroxide conducting membranes
CN106410270B (en) It is a kind of using carbon dioxide-base polycarbonate as lithium single-ion conductor solid polymer electrolyte of main chain and preparation method thereof
CN103413974B (en) Preparation method of lithium ion battery gel polymer electrolyte
CN100467504C (en) Preparing method and application of polymer gel electrolyte for lithium ion cell
CN105206872A (en) Grafting type comb polymer solid electrolyte material and preparation method thereof
CN107641170A (en) Polymer emulsion, preparation method and the aqueous binder of preparation, method and application
CN115458810A (en) Electrolyte and lithium ion battery
CN104151501A (en) Polymer containing polyethylene oxide as well as preparation method and application thereof
CN1362711A (en) Polymer gel electrolyte, lithium cell adopting said electrolytre and method for producing said electrolyte
JP3603383B2 (en) Polymer solid electrolyte
JP2003151632A (en) Gel electrolyte and nonaqueous electrolyte battery using the same
CN111934005A (en) Crosslinked nanocellulose-based gel polymer electrolyte for lithium ion battery and preparation method and application thereof
CN116231060A (en) Preparation method and application of single lithium ion conductive fluoropolymer solid electrolyte
CN109286040A (en) Four arm branched polymeric ionic liquid gel electrolyte membrances and preparation method thereof
CN114566700B (en) Flame-retardant polymer electrolyte membrane and preparation method and application thereof
JP2000306604A (en) Polymer gel electrolyte and lithium secondary battery using it
CN112072176B (en) Single-ion nano composite solid electrolyte and preparation method thereof
CN112993396B (en) Polymer solid electrolyte membrane, preparation method thereof and all-solid-state battery
JP3843505B2 (en) Polymer electrolyte and battery
CN107565166A (en) A kind of double fluoboric acid lithium salts of double trifluoro ethoxies and include its low temperature electrolytes for Li-ion batteries and lithium ion battery
CN113991174A (en) Organic-inorganic composite solid electrolyte membrane and preparation method and application thereof
CN111748061A (en) Solid polymer electrolyte, preparation method thereof and lithium ion battery
JP4155245B2 (en) battery
CN113540559B (en) ZIF-8@ PEGMEM-co-AMPS-Li single ion polymer solid electrolyte and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant