CN110707325A - Preparation method and application of conductive adhesive based on reinforced polysulfide ion adsorption - Google Patents

Preparation method and application of conductive adhesive based on reinforced polysulfide ion adsorption Download PDF

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CN110707325A
CN110707325A CN201910971122.8A CN201910971122A CN110707325A CN 110707325 A CN110707325 A CN 110707325A CN 201910971122 A CN201910971122 A CN 201910971122A CN 110707325 A CN110707325 A CN 110707325A
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aniline
cyclodextrin
sulfur
deionized water
inclusion compound
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李洲鹏
夏银萍
刘宾虹
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

Abstract

The invention relates to a lithium-sulfur battery technology, and aims to provide a preparation method of a conductive adhesive based on reinforced polysulfide ion adsorption. The method comprises the following steps: adding beta-cyclodextrin dissolved in deionized water into an aniline solution, and performing ultrasonic dispersion and vacuum drying to obtain an aniline cyclodextrin inclusion compound; preparing a solution from the aniline cyclodextrin inclusion compound and deionized water; dropwise adding hydrogen peroxide into the mixture, and performing ultrasonic dispersion to polymerize aniline in adjacent aniline cyclodextrin inclusion compounds; and (4) drying in vacuum to obtain the conductive adhesive. Compared with the traditional binder, the product of the invention has excellent conductivity, can greatly reduce the electrode impedance, and the used binder is environment-friendly and green. The obtained modified porous carbon has the characteristics of large specific surface area and large pore volume, can carry more sulfur, has extremely strong capability of adsorbing polysulfide, is favorable for inhibiting the shuttling of polysulfide ions by the iron oxide dispersed and distributed on the inner wall of the carbon, is suitable for preparing high-performance sulfur electrode materials, and prolongs the service life of a sulfur battery.

Description

Preparation method and application of conductive adhesive based on reinforced polysulfide ion adsorption
Technical Field
The invention relates to a lithium-sulfur battery technology, in particular to a conductive adhesive for strengthening polysulfide ion adsorption, a modified macroporous carbon material for strengthening polysulfide ion adsorption, and a long-life lithium-sulfur battery based on the conductive adhesive and the macroporous carbon material.
Background
The binder used in the lithium ion battery not only requires that the binder has basic functions and performances; such as: the uniformity and the safety of the active substances during pulping are ensured; the adhesive has an adhesive effect among the active material particles; bonding an active material to a current collector; maintaining the adhesion between the active material and the current collector; the method is beneficial to forming an SEI film on the surface of the carbon material (graphite), and the like, and also requires special physical and chemical properties such as: the heat stability can be kept under the condition of heating to 130-180 ℃ in the drying and dewatering processes; can be wetted by organic electrolyte; the processing performance is good; is not easy to burn; the electrolyte in the electrolyte is stable; has relatively high electron ion conductivity; low dosage and low cost.
The binder is divided into water-based and oil-based binders, and the corresponding solvents are water-based deionized water and oil-based N-methylpyrrolidone (NMP) solvents. The oil-based binder is usually polyvinylidene fluoride (PVDF), is a polymer material with high dielectric constant, has good chemical stability and temperature characteristic, excellent mechanical property and processability, has a positive effect on improving the binding property, and is widely applied to lithium ion batteries as a positive and negative electrode binder. Aqueous binders such as sodium carboxymethylcellulose (CMC), Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), polyvinyl alcohol (PVA), acrylonitrile multipolymer (LA132), Polybutylacrylate (PBA), Polyacrylonitrile (PA), and the like, are environmentally friendly and have become mainstream binders. Although the water-based binder improves ion conductivity to some extent, it is an insulating material and hardly has any electron conductivity.
The lithium-sulfur battery has high energy density, but generates a large amount of polysulfide ions in the working process, because the molecules of the polysulfide ions are relatively small, and most of the polysulfide ions move in the electrolyte along with the action of concentration gradient and electric field force. When the long-chain polysulfide ions move to the negative electrode, the long-chain polysulfide ions react with lithium simple substances to generate short-chain polysulfide ions, the short-chain polysulfide ions move to the positive electrode under the action of concentration gradient force and electric field force and react with sulfur simple substances to generate the long-chain polysulfide ions again, the polysulfide ions move in the electrolyte ceaselessly, a large amount of energy is consumed in the reaction, and the actual efficiency of the battery reaction is reduced. In the charging process, the directions of electric field forces borne by polysulfide ions are opposite, and the polysulfide ions point to the anode from the cathode, but the concentration of the polysulfide ions near the anode is high, and the concentration gradient force still points to the cathode from the anode, so that an obvious shuttle effect is presented. The "shuttle effect" not only results in a decrease in the charging efficiency of the battery, but also makes it difficult to fully utilize the active material. The reinforced adsorption of polysulfide ions has great significance for inhibiting shuttle effect and prolonging the service life of the lithium-sulfur battery.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a preparation method and application of a conductive adhesive based on reinforced polysulfide ion adsorption.
In order to solve the technical problem, the solution of the invention is as follows:
the preparation method of the conductive adhesive based on the reinforced polysulfide ion adsorption comprises the following steps:
(1) dissolving 2-5 g of aniline in 98-95 mL of deionized water at room temperature, and dispersing for 5 minutes by ultrasonic vibration to obtain an aniline solution with the concentration of 2-5 wt%; dissolving 2-10 g of beta-cyclodextrin in 40mL of deionized water, adding the beta-cyclodextrin into an aniline solution, and ultrasonically vibrating and dispersing for 30 minutes to enable aniline molecules to enter a cyclodextrin cavity; vacuum drying to obtain aniline cyclodextrin inclusion compound;
(2) preparing a solution with the mass concentration of 2-5 wt% by taking the aniline cyclodextrin inclusion compound and deionized water; 5-20 mL of hydrogen peroxide with the mass concentration of 3 wt% is dropwise added into 100mL of aniline cyclodextrin inclusion compound solution, and after ultrasonic vibration dispersion is carried out for 30 minutes, aniline in adjacent aniline cyclodextrin inclusion compounds is polymerized to form linear polyaniline penetrating through cyclodextrin cavities; and (4) drying in vacuum to obtain the conductive adhesive.
In the present invention, the frequency of the ultrasonic vibration is 40 kHz.
The present invention further provides a method for preparing a sulfur electrode using a conductive binder, comprising the steps of:
taking a sulfur electrode material, acetylene black and a conductive adhesive according to the mass ratio of 7:2:1, grinding and uniformly mixing; adding deionized water as dispersant to prepare paste, coating the paste on an aluminum film, and drying the aluminum film in the shade; at 100 ℃ and 100Kg cm-2Pressing and forming under pressure to obtain a sulfur electrode; wherein the content of the first and second substances,
the sulfur electrode material is prepared by the following method: taking the modified porous carbon and sulfur according to the mass ratio of 1:9, uniformly mixing, heating to 155 ℃, and preserving heat for 2 hours to complete sulfur loading; cooling to obtain a sulfur electrode material;
the modified porous carbon material is prepared by the following method:
(A) dissolving 20g of beta-cyclodextrin in 200mL of deionized water at 90 ℃; continuously adding 1g of ferrocene powder, stirring and mixing for 24 hours to enable ferrocene molecules to enter a cyclodextrin cavity; cooling to room temperature, and drying in vacuum to obtain a ferrocene cyclodextrin inclusion compound;
(B) adding 10g of agar into 1L of boiling water, stirring, and adding 50g of sodium chloride; adding 5g of ferrocene cyclodextrin inclusion compound after agar is completely dissolved, stirring and dissolving for 1h to obtain yellow solution; after cooling to 35 ℃, a yellow gel was formed; moving to a freeze dryer, and drying for 12h to obtain a precursor;
(C) heating the precursor to 900 ℃ at the speed of 10 ℃/min under the protection of nitrogen atmosphere, and carbonizing at constant temperature for 5 hours; and after cooling, washing with deionized water, and drying in vacuum to obtain the modified porous carbon material.
The invention also provides a lithium-sulfur battery, which comprises a diaphragm, a positive electrode, a negative electrode and electrolyte, wherein the positive electrode is the sulfur electrode, the diaphragm adopts a microporous polypropylene film, and the negative electrode is a lithium metal sheet; the positive electrode and the negative electrode are respectively arranged on two sides of the diaphragm in opposite directions to form a sandwich structure, and the electrolyte is arranged in the sandwich structure; the electrolyte is LiClO4As solute, dioxolane (C)3H6O2) And ethylene glycol methyl ether (C)4H10O2) The mixture of (1) is a solvent, the volume ratio of dioxolane to ethylene glycol monomethyl ether is 1: 1, and one liter of electrolyte contains 1 mole (106.4g) of LiClO4。
The invention relates to a polyaniline cyclodextrin inclusion compound forming and conducting principle:
cyclodextrin is a general term for a series of cyclic oligosaccharides produced by amylose under the action of cyclodextrin glucosyltransferase produced by Bacillus, and generally contains 6 to 12D-glucopyranose units. Among them, the more studied and of great practical significance are molecules containing 6, 7, 8, 9 glucose units, called α -, β -, γ -and δ -cyclodextrins, respectively. The cyclodextrin molecule has a slightly conical hollow cylindrical three-dimensional annular structure, in the hollow structure of the cyclodextrin molecule, the upper end (larger opening end) of the outer side is composed of secondary hydroxyl groups of C2 and C3, the lower end (smaller opening end) is composed of primary hydroxyl groups of C6, the cyclodextrin molecule has hydrophilicity and bonding capability, and a hydrophobic region is formed in the cavity due to the shielding effect of C-H bonds. Various organic compounds can be embedded into the hydrophobic cavity to form an inclusion compound, and the physical and chemical properties of the enveloped substance are changed; the cyclodextrin molecule can be crosslinked with a plurality of functional groups or the cyclodextrin is crosslinked on a polymer to carry out chemical modification or carry out polymerization by taking the cyclodextrin as a monomer. The larger the number of molecules of the cyclodextrin molecule containing glucose units, the larger the void volume of the cavity of the hydrophobic region, and the larger hydrophobic molecules can be contained. The size of the cavity of the beta-cyclodextrin is equivalent to the size of aniline molecules, so that a stable aniline cyclodextrin inclusion compound is formed.
Aniline is also known as anilin, anilin oil, aminobenzene, and has a molecular formula: c6H7And N is added. A colorless oily liquid. Melting point-6.3 deg.C, boiling point 184 deg.C, relative density, heating to 370 deg.C for decomposition, and slightly dissolving in water. The polyaniline is obtained by free radical polymerization by taking aniline as a monomer, has special electrical and optical properties, and can have conductivity after being doped. The electrical activity of polyaniline comes from the P-electron conjugated structure in the molecular chain: as the P electron system in the molecular chain expands, the P bonding state and the P-reverse bonding state form a valence band and a conduction band respectively, and the non-localized P electron conjugated structure can form a P type and an N type conduction state after doping. Different from the doping mechanism of other conducting polymers which generate cation vacancy under the action of an oxidant, the electron number is not changed in the doping process of polyaniline, but H is generated by the decomposition of doped protonic acid+And for anions (e.g. Cl)-Sulfuric acid, sulfuric acidRadical, phosphate radical, etc.) into the main chain, and combines with N atoms in amine and imine groups to form a polar ion and a dipole ion delocalized into a P bond of the whole molecular chain, so that the polyaniline has higher conductivity. The unique doping mechanism makes the doping and de-doping of polyaniline completely reversible, the doping degree is influenced by factors such as pH value, potential and the like, and the polyaniline also has electrochemical activity.
And adding cyclodextrin into the aniline solution, wherein aniline molecules enter the cyclodextrin cavity to form a cyclodextrin inclusion compound of aniline due to the hydrophobicity of the cyclodextrin cavity, and the aniline molecules are wrapped by the cyclodextrin molecules. Hydrogen peroxide as a pyrrole initiator is hydrophilic and is difficult to enter the obtained aniline cyclodextrin cavity, so that aniline in the cyclodextrin cavity cannot be promoted to undergo free radical polymerization, amino is hydrophilic and is exposed at the mouth of the cyclodextrin cavity and promoted by hydrogen peroxide free radicals to form amino free radicals at the mouth of the cyclodextrin cavity, and aniline at two adjacent cyclodextrin cavity mouths is polymerized to form linear polyaniline penetrating through the cyclodextrin cavity. LiClO containing polyaniline long-chain molecules in cyclodextrin cavity4And after the lithium polysulfide is doped, a transmission channel of electrons is formed.
And the hydroxyl outside the cyclodextrin molecule forms a plurality of groups to improve strong hydrophilicity and bonding capability, so that the basic function of the cyclodextrin molecule as a bonding agent is met, the plurality of hydroxyl adsorbs polysulfide ions, shuttle of the polysulfide ions is effectively inhibited, and the service life of the lithium-sulfur battery is prolonged.
Compared with the prior art, the invention has the beneficial effects that:
compared with the conventional aqueous insulating binder which can only improve ion conduction, the polyaniline cyclodextrin inclusion compound obtained by the invention has hydrophilic and adhesive force on the outer hydroxyl group, can improve ion conduction, can adsorb polysulfide ions and inhibit the shuttling of polysulfide ions, and the polyaniline long-chain polymer existing in the inner cavity realizes the transfer of electrons in the cavity of the cyclodextrin molecule.
Different from the conventional porous carbon, the modified porous carbon obtained by the invention has the characteristics of large specific surface area and large pore volume, and can carry more sulfur. The iron oxide on the inner wall of the carbon has strong coordination with sulfur, so that the capacity of adsorbing polysulfide is particularly strong, and the iron oxide dispersed and distributed on the inner wall of the carbon is favorable for inhibiting the shuttle of polysulfide ions, is suitable for preparing a high-performance sulfur electrode material, and prolongs the service life of a sulfur battery.
Drawings
Fig. 1 is a graph of the cycling performance of a lithium sulfur battery prepared using the conductive binder and modified porous carbon of the present invention.
Wherein, the curve 1 is the charging and discharging coulombic efficiency of the lithium-sulfur battery, and the curve 2 is the capacity decline curve of the lithium-sulfur battery; the working temperature is 25 ℃, the current density is 0.2C, and the sulfur loading is 10mg/cm2。
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
Example 1: preparation of aniline solution
Dissolving 2g of aniline in 98mL of deionized water, and dispersing for 5 minutes by ultrasonic vibration (ultrasonic frequency of 40kHz) to obtain an aniline solution with the concentration of 2 wt%.
Example 2: preparation of cyclodextrin inclusion compound of aniline
3.5g of aniline was dissolved in 96.5mL of deionized water, and dispersed for 5 minutes by ultrasonic vibration (ultrasonic frequency 40kHz) to obtain an aniline solution with a concentration of 3.5 wt%.
Dissolving 2g of beta-cyclodextrin in 40mL of deionized water, adding an aniline solution, dispersing for 30 minutes by ultrasonic vibration (ultrasonic frequency is 40kHz), allowing aniline molecules to enter a cyclodextrin cavity to form an aniline cyclodextrin inclusion compound, and drying in vacuum to obtain the aniline cyclodextrin inclusion compound.
Example 3: cyclodextrin inclusion compound polymerization of aniline
Dissolving 5g of aniline in 95mL of deionized water respectively at room temperature, dispersing for 5 minutes by ultrasonic vibration (ultrasonic frequency 40kHz) to obtain an aniline solution with the concentration of 5 wt%, dissolving 5g of beta-cyclodextrin in 40mL of deionized water, adding the aniline solution, dispersing for 30 minutes by ultrasonic vibration (ultrasonic frequency 40kHz), allowing aniline molecules to enter a cyclodextrin cavity to form a cyclodextrin inclusion compound of aniline, and drying in vacuum to obtain the aniline cyclodextrin inclusion compound;
preparing aniline cyclodextrin inclusion compound solution with the concentration of 2 wt% by taking the aniline cyclodextrin inclusion compound and deionized water. 5mL of hydrogen peroxide (3 wt%) is slowly dropped into 100mL of the aniline cyclodextrin inclusion compound solution, and aniline in adjacent aniline cyclodextrin inclusion compounds is polymerized after ultrasonic vibration (ultrasonic frequency 40kHz) is dispersed for 30 minutes.
Example 4: preparation of conductive adhesive
Dissolving 5g of aniline in 95mL of deionized water respectively at room temperature, dispersing for 5 minutes by ultrasonic vibration (ultrasonic frequency 40kHz) to obtain an aniline solution with the concentration of 5 wt%, dissolving 10g of beta-cyclodextrin in 40mL of deionized water, adding the aniline solution, dispersing for 30 minutes by ultrasonic vibration (ultrasonic frequency 40kHz), allowing aniline molecules to enter a cyclodextrin cavity to form a cyclodextrin inclusion compound of aniline, and drying in vacuum to obtain the aniline cyclodextrin inclusion compound;
preparing aniline cyclodextrin inclusion compound solution with the concentration of 3.5 wt% by taking the aniline cyclodextrin inclusion compound and deionized water. And (3) slowly adding 10mL of hydrogen peroxide (3 wt%) into 100mL of the aniline cyclodextrin inclusion compound solution, dispersing for 30 minutes by ultrasonic vibration (ultrasonic frequency is 40kHz), polymerizing aniline in adjacent aniline cyclodextrin inclusion compounds to form linear polyaniline penetrating through a cyclodextrin cavity, and drying in vacuum to obtain the conductive adhesive.
Example 5: preparation of modified porous carbon material
And (2) dissolving 20g of beta-cyclodextrin in 200mL of deionized water at 90 ℃, adding 1g of ferrocene powder, stirring and mixing for 24h, allowing ferrocene molecules to enter a cyclodextrin cavity to form a ferrocene cyclodextrin inclusion compound, cooling to room temperature, and drying in vacuum to obtain the ferrocene cyclodextrin inclusion compound.
Adding 10g of agar into 1L of boiling water, stirring, adding 50g of sodium chloride, adding 5g of the ferrocene cyclodextrin inclusion compound obtained in the previous step when the agar is completely dissolved, stirring and dissolving for 1h to obtain a yellow solution, and cooling to 35 ℃ to obtain yellow gel. And moving to a freeze dryer, and drying for 12h to obtain a precursor. Heating the precursor to 900 ℃ at the speed of 10 ℃/min under the protection of nitrogen atmosphere, and carbonizing at constant temperature for 5 hours; and washing with deionized water, and then drying in vacuum to obtain the modified porous carbon material.
Example 6: preparation of sulfur electrode material
And (3) taking the modified porous carbon material obtained in the embodiment 5, uniformly mixing the modified porous carbon material and sulfur according to the mass ratio of 1:9, heating to 155 ℃, preserving the heat for 2h, completing sulfur carrying, and cooling to obtain the sulfur electrode material.
Example 7: sulfur electrode preparation
The aniline cyclodextrin inclusion compound obtained in example 2 and deionized water were taken to prepare an aniline cyclodextrin inclusion compound solution with a concentration of 5 wt%. And (3) slowly adding 20mL of hydrogen peroxide (3 wt%) into 100mL of aniline cyclodextrin inclusion compound solution, dispersing for 30 minutes by ultrasonic vibration (ultrasonic frequency is 40kHz), polymerizing aniline in adjacent aniline cyclodextrin inclusion compounds to form linear polyaniline penetrating through cyclodextrin cavities, and drying in vacuum to obtain the conductive adhesive.
Taking the sulfur electrode material obtained in the example 6, acetylene black and the binder according to the mass ratio of 7:2:1, grinding and mixing uniformly, adding deionized water serving as a dispersing agent, preparing into paste, coating the paste on an aluminum film, drying the aluminum film in the shade, and then coating the paste at 100Kg cm at 100 DEG C-2Is pressed and molded under the pressure of the sulfur electrode, and the sulfur electrode is obtained.
Example 8: lithium sulfur battery preparation
The lithium-sulfur battery consists of a diaphragm, a sulfur electrode, a negative electrode and electrolyte, wherein the electrode material of the sulfur electrode obtained in example 7 and commercially available lithium metal sheets are respectively oppositely arranged on two sides of the diaphragm to form a sandwich structure, and the electrolyte is arranged in the sandwich structure;
the electrolyte is characterized in that: with LiClO4As solute, dioxolane (C)3H6O2) And ethylene glycol methyl ether (C)4H10O2) The mixture of (a) is a solvent, and the volume ratio of dioxolane to ethylene glycol monomethyl ether is 1: 1, one liter of the electrolyte contained 1 mole (106.4g) of LiClO4。
The separator was a microporous polypropylene separator (Celguard 2400) manufactured by Celgard. Placing a sulfur electrode in a battery positive electrode shell under argon atmosphere, covering a diaphragm on the sulfur electrode, and dripping into the electrolyteAnd wetting the solution, enabling the diaphragm to be tightly attached to the anode, placing the lithium cathode on the diaphragm wetted by the electrolyte, placing the gasket and the elastic sheet on the lithium cathode, covering a battery cathode shell, and packaging to obtain the lithium-sulfur battery. FIG. 1 shows sulfur loading 10mg/cm2And 0.2C discharge rate. The charge-discharge efficiency is close to 100%, and the performance of the battery is stable after 50 cycles.
Finally, the foregoing disclosure is directed to only certain embodiments of the invention. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.

Claims (4)

1. A preparation method of a conductive adhesive based on reinforced polysulfide ion adsorption is characterized by comprising the following steps:
(1) dissolving 2-5 g of aniline in 98-95 mL of deionized water at room temperature, and dispersing for 5 minutes by ultrasonic vibration to obtain an aniline solution with the concentration of 2-5 wt%; dissolving 2-10 g of beta-cyclodextrin in 40mL of deionized water, adding the beta-cyclodextrin into an aniline solution, and ultrasonically vibrating and dispersing for 30 minutes to enable aniline molecules to enter a cyclodextrin cavity; vacuum drying to obtain aniline cyclodextrin inclusion compound;
(2) preparing a solution with the mass concentration of 2-5 wt% by taking the aniline cyclodextrin inclusion compound and deionized water; 5-20 mL of hydrogen peroxide with the mass concentration of 3 wt% is dropwise added into 100mL of aniline cyclodextrin inclusion compound solution, and after ultrasonic vibration dispersion is carried out for 30 minutes, aniline in adjacent aniline cyclodextrin inclusion compounds is polymerized to form linear polyaniline penetrating through cyclodextrin cavities; and (4) drying in vacuum to obtain the conductive adhesive.
2. The method of claim 1, wherein the ultrasonic vibration has a frequency of 40 kHz.
3. A method for preparing a sulfur electrode using the conductive binder obtained by the method of claim 1, comprising the steps of:
taking sulfur electrode material, acetylene black and conductive adhesive according to the mass ratio of 7:2:1Grinding and mixing the binder uniformly; adding deionized water as dispersant to prepare paste, coating the paste on an aluminum film, and drying the aluminum film in the shade; at 100 ℃ and 100Kg cm-2Pressing and forming under pressure to obtain a sulfur electrode; wherein the content of the first and second substances,
the sulfur electrode material is prepared by the following method: taking the modified porous carbon and sulfur according to the mass ratio of 1:9, uniformly mixing, heating to 155 ℃, and preserving heat for 2 hours to complete sulfur loading; cooling to obtain a sulfur electrode material;
the modified porous carbon material is prepared by the following method:
(A) dissolving 20g of beta-cyclodextrin in 200mL of deionized water at 90 ℃; continuously adding 1g of ferrocene powder, stirring and mixing for 24 hours to enable ferrocene molecules to enter a cyclodextrin cavity; cooling to room temperature, and drying in vacuum to obtain a ferrocene cyclodextrin inclusion compound;
(B) adding 10g of agar into 1L of boiling water, stirring, and adding 50g of sodium chloride; adding 5g of ferrocene cyclodextrin inclusion compound after agar is completely dissolved, stirring and dissolving for 1h to obtain yellow solution; after cooling to 35 ℃, a yellow gel was formed; moving to a freeze dryer, and drying for 12h to obtain a precursor;
(C) heating the precursor to 900 ℃ at the speed of 10 ℃/min under the protection of nitrogen atmosphere, and carbonizing at constant temperature for 5 hours; and after cooling, washing with deionized water, and drying in vacuum to obtain the modified porous carbon material.
4. A lithium-sulfur battery, comprising a diaphragm, a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode is the sulfur electrode prepared by the method of claim 3, the diaphragm adopts a microporous polypropylene film, and the negative electrode is a lithium metal sheet; the positive electrode and the negative electrode are respectively arranged on two sides of the diaphragm in opposite directions to form a sandwich structure, and the electrolyte is arranged in the sandwich structure;
the electrolyte is LiClO4As solute, mixture of dioxolane and ethylene glycol monomethyl ether is used as solvent, the volume ratio of dioxolane and ethylene glycol methyl ether is 1: 1, and one liter of electrolyte contains 1 mol of LiClO4。
CN201910971122.8A 2019-10-14 2019-10-14 Preparation method and application of conductive adhesive based on reinforced polysulfide ion adsorption Pending CN110707325A (en)

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