CN110707324A - Preparation of conductive adhesive and application of conductive adhesive in battery electrode - Google Patents
Preparation of conductive adhesive and application of conductive adhesive in battery electrode Download PDFInfo
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- CN110707324A CN110707324A CN201910970514.2A CN201910970514A CN110707324A CN 110707324 A CN110707324 A CN 110707324A CN 201910970514 A CN201910970514 A CN 201910970514A CN 110707324 A CN110707324 A CN 110707324A
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- pyrrole
- dimethyl sulfoxide
- cyclodextrin
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
- C08B37/0015—Inclusion compounds, i.e. host-guest compounds, e.g. polyrotaxanes
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- 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
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8668—Binders
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02E60/13—Energy storage using capacitors
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- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a synthesis technology of a binder, and aims to provide preparation of a conductive binder and application of the conductive binder in a battery electrode. The preparation method comprises the following steps: dissolving pyrrole in dimethyl sulfoxide, and dispersing to obtain a pyrrole solution; dissolving beta-cyclodextrin in dimethyl sulfoxide, and adding into pyrrole solution; dispersing to make pyrrole molecule enter into cyclodextrin cavity; after vacuum drying, obtaining a pyrrole cyclodextrin inclusion compound; adding the pyrrole cyclodextrin inclusion compound into dimethyl sulfoxide; adding the dimethyl sulfoxide mixed solution of the hydrogen peroxide into the dimethyl sulfoxide solution of the pyrrole cyclodextrin inclusion compound; and (3) ultrasonically vibrating for dispersion, and heating to evaporate dimethyl sulfoxide to obtain the polypyrrole cyclodextrin inclusion compound conductive adhesive. Compared with the traditional binder, the water-soluble binder with conductivity, which is obtained by the invention, can greatly reduce the electrode impedance; the prepared binder is environment-friendly and green, and can effectively improve the performances of fuel cells, lithium ion batteries and super capacitors.
Description
Technical Field
The invention relates to a synthesis technology of a binder, in particular to a conductive binder for improving the conductivity of the binder and a preparation method thereof, which are used for preparing various battery electrodes.
Background
The battery electrode requires the electrode material to have better mass transfer capacity and higher specific surface area to improve the performance of the battery, so the particle size of the electrode material is often micron-sized or nanometer-sized. Micro-scale or nano-scale electrode material particles require a binder to bind them together to form an electrode. Since the binder is generally an insulator, although the mass ratio of the binder in the electrode is not large, the influence on the performance of the electrode is significant, and the function of the binder is irreplaceable regardless of a secondary battery such as a fuel cell or a lithium ion battery, a supercapacitor, and the like.
Taking the electrode binder of a lithium ion battery as an example, the binder is required to have 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 water removing processes; can be wetted by organic electrolyte; the processing performance is good; is not easy to burn; for LiClO in electrolyte4，LiPF6And the like are 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.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a preparation method of a conductive adhesive and application of the conductive adhesive in a battery electrode.
In order to solve the technical problem, the solution of the invention is as follows:
provided is a method for preparing a conductive adhesive, comprising the steps of:
(1) dissolving 0.15-0.9 g of pyrrole in 50mL of dimethyl sulfoxide (DMSO) at room temperature, and performing ultrasonic vibration dispersion for 5 minutes to obtain a pyrrole solution; dissolving 2-10 g of beta-cyclodextrin in 40mL of DMSO, and adding the dissolved beta-cyclodextrin into a pyrrole solution; ultrasonic vibration is carried out for 30 minutes to ensure that pyrrole molecules enter a cyclodextrin cavity; after vacuum drying, obtaining a pyrrole cyclodextrin inclusion compound;
(2) taking 2-5 g of pyrrole cyclodextrin inclusion compound, and adding into 30mL of DMSO; adding 0.2-2 mL of 10 wt% hydrogen peroxide solution with mass concentration into 70mL of DMSO, and then dropwise adding the DMSO mixed solution of the hydrogen peroxide solution into the DMSO solution of the pyrrole cyclodextrin inclusion compound; after ultrasonic vibration dispersion for 30 minutes, pyrrole in the adjacent pyrrole cyclodextrin inclusion compound is polymerized to form linear polypyrrole penetrating through a cyclodextrin cavity; heating to evaporate DMSO, and obtaining the polypyrrole cyclodextrin inclusion compound conductive adhesive.
In the present invention, the frequency of the ultrasonic vibration is 40 kHz.
The invention further provides a method for preparing an electrode by using the conductive adhesive prepared by the method, which comprises the following steps: taking an electrode material, acetylene black and a conductive binder according to a mass ratio of 70-90: 5-20: 5-10, grinding and uniformly mixing, adding deionized water serving as a dispersing agent, and preparing into paste; after drying in the shade, the coating is applied to a collector at 100 ℃ and 100Kg cm-2And (4) pressing and forming under pressure to obtain the electrode.
In the present invention, the electrode is any one of: in the negative electrode of the lithium ion battery, the collector electrode is a copper film; in the positive electrode of the lithium ion battery, a collector is an aluminum film; an anode in the fuel cell, wherein a current collector is hydrophilic carbon paper; the cathode in the fuel cell, its current collector is hydrophobic carbon paper; the collector of the positive electrode or the negative electrode of the super capacitor is a stainless steel film.
In the present invention, the electrode material is any one of: negative electrode material in lithium ion batteries (commercial lithium intercalation material): graphite, nano-silicon, lithium titanate or carbon-coated tin; cathode material in lithium ion battery: lithium cobaltate, lithium iron phosphate, lithium manganate and a ternary cathode material; anode catalyst or cathode catalyst of fuel cell: carbon-supported noble metal or catalyst, porous carbon-supported noble metal or non-noble metal catalyst; anode and cathode materials of the super capacitor: carbon nanotubes, graphene, microporous carbon, or carbon material supporting transition metal oxides.
The invention further provides a proton exchange membrane fuel cell, which takes pure hydrogen as fuel, air or pure oxygen as oxidant, a proton exchange membrane as electrolyte and platinum carbon as cathode and anode catalysts; the cathode and the anode of the fuel cell use the polypyrrole cyclodextrin inclusion compound prepared by the method in claim 1 as a binder.
The invention further provides a lithium ion battery, wherein the anode material and the cathode material 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; graphite is used as a negative electrode material, lithium-containing transition metal oxide is used as a positive electrode material, and microporous polypropylene is used as a diaphragm; the cathode and the anode of the lithium ion battery use the polypyrrole cyclodextrin inclusion compound prepared by the method in claim 1 as a binder.
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 further provides a super capacitor, wherein the anode material and the cathode material of the super capacitor 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; porous carbon is a positive electrode material, a negative electrode material and microporous polypropylene is a diaphragm; the polypyrrole cyclodextrin inclusion compound prepared by the method of claim 1 is used as a binder for the positive electrode and the negative electrode of the super capacitor.
The electrolyte is Li [ CF ]3SO2)2N](LiTFSI) as 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 one mole (263g) of LiTFSI.
Description of the inventive principles:
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 cavity size of the beta-cyclodextrin is equivalent to the size of pyrrole rings, which is beneficial to forming a stable pyrrole cyclodextrin inclusion compound.
The pure pyrrole monomer is colorless oily liquid at normal temperature and is an N five-membered heterocyclic molecule. Polypyrrole is a common conductive polymer, is a heterocyclic conjugated conductive polymer, is usually an amorphous black solid, is a conductive polymer which has good air stability and is easy to electrochemically polymerize into a film, is insoluble and infusible, and has properties such as conductivity, mechanical strength and the like closely related to polymerization conditions such as anions, solvents, pH values, temperatures and the like of an electrolyte. Pyrrole is used as a monomer and is prepared by oxidative polymerization, and the oxidant is ferric trichloride, ammonium persulfate and the like. The conductive polypyrrole has a conjugated chain oxidation structure and a corresponding anion doping structure, the conductivity of the conductive polypyrrole can reach 102-103S/cm, the tensile strength of the conductive polypyrrole can reach 50-100 MPa, and the conductive polypyrrole has good electrochemical oxidation-reduction reversibility. The conduction mechanism is as follows: the polypyrrole structure has a conjugated structure formed by alternately arranging carbon-carbon single bonds and carbon-carbon double bonds, wherein the double bonds are formed by sigma electrons and pi electrons, the sigma electrons are fixed and cannot move freely, and covalent bonds are formed between carbon atoms. The 2 pi electrons in the conjugated double bonds are not fixed to a carbon atom and they can be translocated from one carbon atom to another, i.e. have a tendency to extend throughout the molecular chain. I.e. the overlapping of the pi electron clouds within the molecule creates an energy band common to the whole molecule, the pi electrons being similar to the free electrons in a metal conductor. When an electric field is present, electrons constituting pi bonds can move along the molecular chain. In the polymer, the pyrrole structural units are linked to each other mainly in the alpha position. The pyrrole hydrogen on the polypyrrole can be replaced by alkali metal ions, and becomes a good conductor of the alkali metal ions. Although polypyrrole is a linear polymer, the α -site interconnection is rotatable, and it is difficult to form a regular linear polymer crystal, and polypyrrole is generally present in an amorphous form and is difficult to deform.
Cyclodextrin is added into the pyrrole solution of dimethyl sulfoxide, pyrrole molecules enter a cyclodextrin cavity to form a cyclodextrin inclusion compound of pyrrole due to the hydrophobicity of the cyclodextrin cavity, and the pyrrole molecules are wrapped by the cyclodextrin molecules. Hydrogen peroxide as a pyrrole initiator is hydrophilic and is difficult to enter an obtained pyrrole cyclodextrin cavity, so that the pyrrole in the cyclodextrin cavity cannot be promoted to perform free radical polymerization, the pyrrole at the opening of the cyclodextrin cavity can only be promoted to perform free radical polymerization, and the pyrroles at the openings of two adjacent cyclodextrin cavities are polymerized to form linear polypyrrole penetrating through the cyclodextrin cavity. The 2 pi electrons in the conjugated double bonds of the long-chain molecules of polypyrrole in the cyclodextrin cavity are not fixed to a carbon atom, and they can be translocated from one carbon atom to another, i.e. have a tendency to extend throughout the molecular chain. That is, the overlapping of pi electron clouds in the molecules generates a common energy band of the whole molecules, pi electrons are similar to free electrons in a metal conductor, and electrons forming pi bonds can move along a molecular chain, so that the transfer of the electrons in the cavity of the cyclodextrin molecule is realized.
And the hydroxyl outside the cyclodextrin molecule is formed to improve strong hydrophilicity and bonding capability, which is enough to meet the basic function of serving as a bonding agent.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the conventional aqueous insulating binder, the polypyrrole cyclodextrin inclusion compound obtained by the invention can only improve ion conduction, the hydroxyl on the outer side of the polypyrrole cyclodextrin inclusion compound has hydrophilicity and cohesive force, and can also improve the ion conduction, and the polypyrrole long-chain polymer existing in the cavity on the inner side of the polypyrrole cyclodextrin inclusion compound realizes the transfer of electrons in the cavity of a cyclodextrin molecule;
2. the prepared binder is environment-friendly and green, and can effectively improve the performances of fuel cells, lithium ion batteries and super capacitors.
Drawings
Fig. 1 is a discharge curve of the lithium ion battery prepared in example 7.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
Example 1: preparation of dimethyl sulfoxide solution of pyrrole
At room temperature, 50mL of dimethyl sulfoxide (DMSO) is taken to dissolve 0.15g of pyrrole, and the solution is dispersed for 5 minutes by ultrasonic vibration (ultrasonic frequency 40kHz) to obtain the dimethyl sulfoxide solution of the pyrrole.
Example 2: preparation of cyclodextrin inclusion compound of pyrrole
At room temperature, 50mL of dimethyl sulfoxide (DMSO) was dissolved in 0.4g of pyrrole, and dispersed for 5 minutes by ultrasonic vibration (ultrasonic frequency 40kHz) to obtain a dimethyl sulfoxide solution of pyrrole.
Dissolving 2g of beta-cyclodextrin in 40mL of DMSO, adding a pyrrole solution, dispersing for 30 minutes by ultrasonic vibration (ultrasonic frequency is 40kHz), allowing pyrrole molecules to enter a cyclodextrin cavity to form a cyclodextrin inclusion compound of pyrrole, and drying in vacuum to obtain the pyrrole cyclodextrin inclusion compound.
Example 3: cyclodextrin inclusion compound polymerization of pyrrole
At room temperature, 50mL of dimethyl sulfoxide (DMSO) is taken to dissolve 0.9g of pyrrole, ultrasonic vibration (ultrasonic frequency 40kHz) is carried out to disperse for 5 minutes to obtain a pyrrole solution, 40mL of DMSO is taken to dissolve 6g of beta-cyclodextrin, then the pyrrole solution is added, ultrasonic vibration (ultrasonic frequency 40kHz) is carried out to disperse for 30 minutes, pyrrole molecules enter a cyclodextrin cavity to form a cyclodextrin inclusion compound of the pyrrole, and vacuum drying is carried out to obtain the pyrrole cyclodextrin inclusion compound.
70mL of DMSO is added with 0.2mL of hydrogen peroxide (10 wt%), slowly dropped into 30mL of DMSO solution containing 2g of the pyrrole cyclodextrin inclusion compound, and after ultrasonic vibration (ultrasonic frequency 40kHz) is dispersed for 30 minutes, pyrrole in the adjacent pyrrole cyclodextrin inclusion compound is polymerized.
Example 4: preparation of conductive adhesive
At room temperature, 50mL of dimethyl sulfoxide (DMSO) is taken to dissolve 0.9g of pyrrole, ultrasonic vibration (ultrasonic frequency 40kHz) is carried out to disperse for 5 minutes to obtain a pyrrole solution, 40mL of DMSO is taken to dissolve 10g of beta-cyclodextrin, then the pyrrole solution is added, ultrasonic vibration (ultrasonic frequency 40kHz) is carried out to disperse for 30 minutes, pyrrole molecules enter a cyclodextrin cavity to form a cyclodextrin inclusion compound of the pyrrole, and vacuum drying is carried out to obtain the pyrrole cyclodextrin inclusion compound.
70mL of DMSO was added with 1mL of hydrogen peroxide (10 wt%) to obtain a hydrogen peroxide DMSO solution. Dissolving 3.5g of the pyrrole cyclodextrin inclusion compound in 30mL of DMSO (dimethyl sulfoxide), slowly dropwise adding a hydrogen peroxide DMSO solution, dispersing for 30 minutes by ultrasonic vibration (ultrasonic frequency of 40kHz), polymerizing pyrrole in the adjacent pyrrole cyclodextrin inclusion compound to form linear polypyrrole penetrating through a cyclodextrin cavity, and heating to evaporate the DMSO solvent to obtain the conductive adhesive.
Example 5: preparation of negative electrode of lithium ion battery
Taking 70mL of DMSO, adding 2mL of hydrogen peroxide (10 wt%) to obtain a hydrogen peroxide DMSO solution, dissolving 5g of the pyrrole cyclodextrin inclusion compound obtained in example 2 in 30mL of DMSO, slowly dropwise adding the hydrogen peroxide DMSO solution, dispersing for 30 minutes by ultrasonic vibration (ultrasonic frequency 40kHz), polymerizing pyrrole in adjacent pyrrole cyclodextrin inclusion compounds to form linear polypyrrole penetrating through a cyclodextrin cavity, and heating to evaporate the solvent DMSO to obtain the conductive adhesive.
Grinding and mixing graphite material, acetylene black and the binder, adding deionized water as dispersant, making into paste, coating on copper film, drying in the shade at 100 deg.C under 100Kg cm-2The graphite cathode is obtained by pressing and molding under the pressure of the pressure, wherein the mass ratio of the graphite to the acetylene black to the binder is 70: 20: 10.
The graphite material is changed into nano silicon, lithium titanate, carbon-coated tin and the like, and the silicon cathode, the lithium titanate cathode, the tin cathode and the like are respectively obtained by adopting the same process.
Example 6: preparation of positive electrode of lithium ion battery
After a lithium cobaltate material from vendor, acetylene black and the conductive binder obtained in example 4 were ground and mixed uniformly, deionized water was added as a dispersant to prepare a paste, the paste was applied to an aluminum film and dried in the shade at 100 ℃ under 100Kg cm-2And (3) pressing and forming under the pressure of the pressure to obtain the lithium cobaltate anode, wherein the mass ratio of the lithium cobaltate to the acetylene black to the binder is 80: 12.5: 7.5.
And replacing the lithium cobaltate material with lithium iron phosphate, lithium manganate, a ternary material and the like, and respectively obtaining a lithium iron phosphate anode, a lithium manganate anode, a ternary material anode and the like by adopting the same process.
Example 7: lithium ion battery preparation
Taking the graphite negative electrode obtained in example 5 and the lithium cobaltate positive electrode obtained in example 6, the electrode material side is opposite to the microporous polypropylene diaphragm of vendor to form a sandwich structure, and electrolyte is filled in the sandwich structure; the electrolyte is LiClO4As solute, dioxolane (C)3H6O2) And ethylene glycol methyl ether (C)4H10O2) The mixture of (A) isAnd the volume ratio of dioxolane to ethylene glycol monomethyl ether is 1: 1, one liter of the electrolyte contained 1 mole (106.4g) of LiClO4And obtaining the rechargeable lithium battery.
Example 8: fuel cell electrode preparation
0.1 g of carbon-supported Pt catalyst powder from vendors (28.6 wt% Pt, less than 400 meshes) is put into a mortar, ground with acetylene black and the conductive binder obtained in example 4, and added with a proper amount of deionized water to be ground and mixed, wherein the mass ratio of the catalyst to the acetylene black to the binder is 90: 5. The semi-fluid obtained after mixing is slowly coated on hydrophilic carbon paper and dried in the shade at 100 deg.C and 100kg cm under pressure-2And (4) performing lower pressing forming to obtain the anode.
Similarly, the semifluid was slowly applied to a hydrophobic carbon paper and dried in the shade at 100 deg.C under a pressure of 100kg cm-2And pressing and forming to obtain the cathode.
Example 9: fuel cell preparation
The anode and cathode obtained in example 8 were assembled in a sandwich structure with the catalyst layer sides of the anode and cathode facing the separator, which was a proton exchange membrane. The anode, the membrane, the cathode, a stainless steel splint with a fuel inlet and a fuel outlet and an air inlet and an air outlet and a sealing ring are assembled into the fuel cell.
Example 10: electrode preparation of super capacitor
Dissolving thiourea in deionized water with the mass 4 times that of the solution to obtain a thiourea solution, and dissolving glucose monohydrate in deionized water with the same mass according to the molar ratio of the glucose to the thiourea used for preparing the thiourea solution being 3:1 to obtain a glucose solution; placed in a water bath at 85 ℃, 10 wt% hydrochloric acid is added dropwise to keep the pH value at 1, and the mixture is fully stirred. After 45 minutes of polymerization, the polymerization was terminated by adding a sodium chloride solution in which the number of moles of sodium chloride was 10 times that of glucose used and the sodium chloride was dissolved in deionized water in an amount of 4 times the mass thereof. And cooling to obtain a mixed solution of the platinum glucose thiourea prepolymer and sodium chloride. Dripping the mixture into a Dewar flask filled with liquid nitrogen for flash freezing by a peristaltic pump to obtain spherical particles, and transferring the spherical particles to a freezing vacuum drier for drying for 24 hours to obtain a precursor. Placing the precursor in a tube is a furnaceIn N2Under the protection of atmosphere, the temperature is firstly 10 ℃ for min-1Heating to 160 ℃ at the same rate, preserving heat for 2h to fully polymerize the prepolymer, and then heating to 900 ℃ at the same rate, preserving heat for 2h to complete the carbonization process. And grinding and crushing after furnace cooling, washing with deionized water, filtering, and drying in vacuum to obtain the porous carbon material.
And (2) putting the porous carbon material into a mortar, grinding the porous carbon material, acetylene black and the conductive binder obtained in the embodiment 4, adding a proper amount of deionized water, grinding and mixing, wherein the mass ratio of the porous carbon material to the acetylene black to the binder is 85: 10: 5. The semi-fluid obtained after mixing is coated on a stainless steel film of market and dried in the shade at the temperature of 100 ℃ and the pressure of 100kg cm-2And performing lower pressing forming to obtain the porous carbon electrode.
Example 11: preparation of super capacitor
Taking two porous carbon electrodes obtained in the embodiment 10, wherein the electrode materials face each other and form a sandwich structure with a vendor microporous polypropylene diaphragm, and electrolyte is filled in the sandwich structure; the electrolyte is Li [ CF ]3SO2)2N](LiTFSI) as 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: one liter of electrolyte contains one mole (263g) of LiTFSI. So as to obtain the organic electrolyte super capacitor.
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 (10)
1. The preparation method of the conductive adhesive is characterized by comprising the following steps of:
(1) dissolving 0.15-0.9 g of pyrrole in 50mL of dimethyl sulfoxide at room temperature, and performing ultrasonic vibration dispersion for 5 minutes to obtain a pyrrole solution; dissolving 2-10 g of beta-cyclodextrin in 40mL of dimethyl sulfoxide, and adding the solution into a pyrrole solution; ultrasonic vibration is carried out for 30 minutes to ensure that pyrrole molecules enter a cyclodextrin cavity; after vacuum drying, obtaining a pyrrole cyclodextrin inclusion compound;
(2) adding 2-5 g of pyrrole cyclodextrin inclusion compound into 30mL of dimethyl sulfoxide; adding 0.2-2 mL of hydrogen peroxide with the mass concentration of 10 wt% into 70mL of dimethyl sulfoxide, and then dropwise adding the dimethyl sulfoxide mixed solution of the hydrogen peroxide into the dimethyl sulfoxide solution of the pyrrole cyclodextrin inclusion compound; after ultrasonic vibration dispersion for 30 minutes, pyrrole in the adjacent pyrrole cyclodextrin inclusion compound is polymerized to form linear polypyrrole penetrating through a cyclodextrin cavity; heating to evaporate dimethyl sulfoxide to obtain the polypyrrole cyclodextrin inclusion compound conductive adhesive.
2. The method of claim 1, wherein the ultrasonic vibration has a frequency of 40 kHz.
3. A method for preparing an electrode using the conductive adhesive prepared by the method of claim 1, comprising the steps of: taking an electrode material, acetylene black and a conductive binder according to a mass ratio of 70-90: 5-20: 5-10, grinding and uniformly mixing, adding deionized water serving as a dispersing agent, and preparing into paste; after drying in the shade, the coating is applied to a collector at 100 ℃ and 100Kg cm-2And (4) pressing and forming under pressure to obtain the electrode.
4. The method of claim 3, wherein the electrode is any one of: in the negative electrode of the lithium ion battery, the collector electrode is a copper film; in the positive electrode of the lithium ion battery, a collector is an aluminum film; an anode in the fuel cell, wherein a current collector is hydrophilic carbon paper; the cathode in the fuel cell, its current collector is hydrophobic carbon paper; the collector of the positive electrode or the negative electrode of the super capacitor is a stainless steel film.
5. The method of claim 3, wherein the electrode material is any one of: negative electrode materials in lithium ion batteries: graphite, nano-silicon, lithium titanate or carbon-coated tin; cathode material in lithium ion battery: lithium cobaltate, lithium iron phosphate, lithium manganate and a ternary cathode material; anode catalyst or cathode catalyst of fuel cell: carbon-supported noble metal or catalyst, porous carbon-supported noble metal or non-noble metal catalyst; anode and cathode materials of the super capacitor: carbon nanotubes, graphene, microporous carbon, or carbon material supporting transition metal oxides.
6. A proton exchange membrane fuel cell, regard pure hydrogen as the fuel, air or pure oxygen as the oxidizing agent, the proton exchange membrane is the electrolyte, platinum carbon is negative pole and anode catalyst; characterized in that the polypyrrole cyclodextrin inclusion compound prepared by the method of claim 1 is used as a binder for the cathode and the anode of the fuel cell.
7. A lithium ion battery is characterized in that a positive electrode material and a negative electrode material are respectively arranged on two sides of a diaphragm in opposite directions to form a sandwich structure, and electrolyte is arranged in the sandwich structure; graphite is used as a negative electrode material, lithium-containing transition metal oxide is used as a positive electrode material, and microporous polypropylene is used as a diaphragm; characterized in that the polypyrrole cyclodextrin inclusion compound prepared by the method of claim 1 is used as a binder for the cathode and the anode of the lithium ion battery.
8. The lithium ion battery of claim 7, wherein 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。
9. A super capacitor is characterized in that positive and negative electrode materials are respectively arranged on two sides of a diaphragm in opposite directions to form a sandwich structure, and electrolyte is arranged in the sandwich structure; porous carbon is a positive electrode material, a negative electrode material and microporous polypropylene is a diaphragm; the method is characterized in that the polypyrrole cyclodextrin inclusion compound prepared by the method in claim 1 is used as a binder for the positive electrode and the negative electrode of the super capacitor.
10. The supercapacitor of claim 9, wherein the electricity isThe electrolyte is Li [ CF ]3SO2)2N]The solute is a mixture of dioxolane and ethylene glycol monomethyl ether, the volume ratio of dioxolane to ethylene glycol methyl ether is 1: 1, and one liter of electrolyte contains one mole of LiTFSI.
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