CN112992553B - Ternary composite material, preparation method thereof, positive pole piece prepared from ternary composite material, and lithium ion capacitor - Google Patents

Ternary composite material, preparation method thereof, positive pole piece prepared from ternary composite material, and lithium ion capacitor Download PDF

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CN112992553B
CN112992553B CN202110173601.2A CN202110173601A CN112992553B CN 112992553 B CN112992553 B CN 112992553B CN 202110173601 A CN202110173601 A CN 202110173601A CN 112992553 B CN112992553 B CN 112992553B
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lithium
conductive polymer
composite material
carbon
ternary composite
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CN112992553A (en
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元金石
秦禄昌
张元赛
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Weihai Sanheyong New Energy Technology Co ltd
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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
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • 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
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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

Abstract

The invention provides a ternary composite material, a preparation method thereof, a positive pole piece prepared from the ternary composite material, and a lithium ion capacitor, and solves the technical problem that limited lithium ions in electrolyte are consumed due to the fact that an SEI (solid electrolyte interphase) film is formed on the surface of a negative pole in the first charge and discharge of the conventional lithium ion capacitor. The carbon material with electrochemical double-layer characteristics is used as a framework, a conductive polymer grows on the carbon framework through the polymerization reaction of a monomer, lithium salt is added before the polymerization reaction process of the conductive polymer monomer or after the reaction is completed, and finally the carbon material/conductive polymer/lithium salt ternary composite material is obtained. Uniformly mixing the ternary composite material, a conductive agent carbon black and a binder polytetrafluoroethylene in a mass ratio of 8:1:1 in an N-methylpyrrolidone solution, and coating the mixture on an aluminum foil to prepare the positive pole piece. And (3) assembling the positive pole piece and the negative pole piece into the lithium ion capacitor by taking lithium hexafluorophosphate as electrolyte and the glass fiber diaphragm as a diaphragm. Can be widely applied to the field of electrochemical energy storage material preparation.

Description

Ternary composite material, preparation method thereof, positive pole piece prepared from ternary composite material, and lithium ion capacitor
Technical Field
The application belongs to the field of electrochemical energy storage material preparation, and particularly relates to a ternary composite material, a preparation method thereof, and a positive pole piece and a lithium ion capacitor prepared from the ternary composite material.
Background
The construction of new energy systems and the rapid development of power electronic equipment put higher demands on energy storage devices. Among a plurality of energy storage devices, the super capacitor is widely applied to the fields of industry, traffic, new energy and the like as an energy storage device with high power density and long cycle life. Currently, commercial supercapacitors are mainly electric double layer supercapacitors (EDLC), but their lower energy density (< 10 wh/kg) limits their further applications.
Lithium Ion Batteries (LIBs) have found wide application as energy storage devices with high energy density in the fields of consumer electronics, new energy vehicles, and the like. Since lithium ion batteries rely on lithium ions (Li) + ) Reversible intercalation/deintercalation redox reaction occurs in the positive and negative electrode materials to store and release energy, so the rate charge and discharge performance is influenced by the dissociation of the electrolyteRate of daughter diffusion, Li + Migration rate at electrode/electrolyte phase interface and Li + The limitations of diffusion rate and the like in the electrode body phase are poor in power characteristics and cycle performance in practical applications.
Lithium Ion Capacitors (LIC) are becoming research and development hot spots as a new energy storage device with both high energy density and high power density. As a composite of a super capacitor and a lithium ion battery, a positive electrode active material of the lithium ion capacitor is generally a material having electrochemical double layer characteristics, such as activated carbon, graphene, carbon nanotubes, and the like. Accordingly, the negative active material is generally a material having lithium intercalation/deintercalation characteristics, such as graphite, hard carbon, soft carbon, and the like.
During the first charge and discharge of the negative electrodes of the lithium ion battery and the lithium ion capacitor, an SEI (solid electrolyte interphase) film is formed on the surface of the negative electrode material, so that limited lithium ions in the electrolyte are consumed. Meanwhile, due to the irreversible capacity of the carbon cathode, anions with the same quality in the system are irreversibly adsorbed on the surface of the anode, so that the concentration of ions in the electrolyte body is reduced, and the electrochemical performance of the lithium ion capacitor is seriously affected.
Disclosure of Invention
In order to realize the technical problem, the invention provides a ternary composite material, a preparation method thereof, a positive pole piece prepared from the ternary composite material, and a lithium ion capacitor.
The technical scheme adopted by the application is as follows: the ternary composite material is prepared by taking a carbon material with electrochemical double-layer characteristics as a carbon skeleton, growing a conductive polymer on the carbon skeleton through the polymerization reaction of a conductive polymer monomer under an acidic condition, and adding lithium salt before or after the polymerization reaction of the conductive polymer monomer.
The preparation method of the ternary composite material comprises the following steps:
(1) respectively dispersing and uniformly mixing a certain amount of carbon materials and conductive polymer monomers in deionized water, wherein the mass ratio of the carbon materials is 50-90 wt%, and the mass ratio of the conductive polymer monomers is 5-45 wt%;
(2) respectively adding a certain amount of dispersant and protonic acid into the mixture, and fully and uniformly mixing, wherein the concentration of hydrogen ions in the aqueous solution is controlled to be 0.5-5 mol/L, and the concentration of the dispersant in the aqueous solution is controlled to be 0.2-2 mol/L;
(3) adding a certain amount of oxidant into the mixed solution to perform electrochemical polymerization reaction, controlling the reaction temperature and continuously stirring for a period of time to complete the polymerization reaction; wherein the molar mass ratio of the oxidant to the conductive polymer monomer is 1: 1-10;
(4) filtering, cleaning and freeze-drying the obtained reaction product;
when lithium salt is added before the polymerization reaction of the conductive polymer monomer, 5-45 wt% of lithium salt is added in the step (1), protonic acid which does not react with the lithium salt is required to be added in the step (2), and then the carbon material/conductive polymer/lithium salt ternary composite material is obtained through the steps (3) and (4);
when lithium salt is added after the polymerization reaction of the conductive polymer monomer is completed, adding 5-45 wt% of lithium salt after the step (4) is completed, and fully mixing to obtain a carbon material/conductive polymer/lithium salt ternary composite material;
and adding lithium salt before the polymerization reaction of the conductive polymer monomer or after the polymerization reaction is completed, wherein the sum of the mass percentages of the carbon material, the conductive polymer monomer and the lithium salt is 100 wt%.
The polymerization mechanism of the polymer monomers in different media is different, and the molecular structure and the physical properties of the finally generated polymer are greatly different. When the polymerization reaction is carried out in an aqueous solution, the polymer produced in an acidic aqueous solution has a high molecular weight and good electrical conductivity. The product obtained from the neutral aqueous solution has more side reactions such as head-to-head or tail-to-tail coupling, and the like, and the conductivity of the obtained product is low and is different from that of the product obtained under the acidic condition by orders of magnitude. The polymer synthesized in the alkaline aqueous solution has low molecular weight, poor regularity of molecular structure and almost no conductivity. Therefore, the protonic acid is added in the preparation process of the invention mainly to provide an acidic environment for polymerization reaction and promote the generation of the polymer with a regular structure. The hydrogen ions in the protonic acid are doped to the main chain of the conductive polymer in the forming process of the conductive polymer, and the corresponding acid radical ions are used as anions to form a balance ion pair with the cations doped to the main chain of the conductive polymer, so that the whole polyaniline is ensured to keep electric neutrality.
Preferably, the carbon material in the step (1) is any one of activated carbon, graphene, carbon nanotubes and carbon aerogel, and all of the carbon materials have electrochemical double-layer characteristics and capacitance characteristics, and serve as a main active material in the positive electrode composite material to provide capacity.
Preferably, the conductive polymer monomer in step (1) is any one of aniline, pyrrole and thiophene, aniline, pyrrole and thiophene are respectively monomers of conductive polymers polyaniline, polypyrrole and polythiophene, and are in a liquid state at room temperature, and the three can respectively form corresponding conductive polymers through polymerization reaction.
Preferably, when the lithium salt is added before the polymerization of the conductive polymer monomer, the lithium salt in the step (1) is lithium sulfate or lithium phosphate, the protonic acid in the step (2) is hydrochloric acid or phosphoric acid, and when the lithium salt is lithium sulfate, the protonic acid is hydrochloric acid which does not react with lithium sulfate; when the lithium salt is lithium phosphate, the protonic acid is phosphoric acid that does not react with lithium phosphate. Lithium sulfate and lithium phosphate are used as two different lithium salts, and can release lithium ions through a reaction with hydrogen ions, and the lithium salts are used as lithium sources to provide irreversible lithium ions for the negative electrode. Hydrochloric acid or phosphoric acid is protonic acid, and can provide an acidic environment for the polymerization reaction of polymer monomers, so that the generated polymer has a regular structure and high conductivity.
Preferably, when the lithium salt is added after the polymerization reaction of the conductive polymer monomer is completed, the protonic acid in step (2) is any one of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, carbonic acid and oxalic acid, which can provide an acidic environment for the polymerization reaction of the conductive polymer monomer, so that the generated polymer has a regular structure and high conductivity. The lithium salt in the step (4) is any one of lithium sulfate, lithium phosphate, lithium carbonate, lithium borate, lithium oxalate and lithium silicate, and can release lithium ions after reacting with hydrogen ions, and the lithium salt can be used as a lithium source to provide irreversible lithium ions for the negative electrode. Since the lithium salt is added after the polymerization reaction of the conductive polymer monomer is completed, the types of the added protonic acid and the lithium salt are not limited by the incapability of reaction between the protonic acid and the lithium salt.
Preferably, the dispersant in step (2) is sodium dodecylbenzene sulfonate or cetyl trimethyl ammonium bromide, which not only can perform a dispersing function to fully contact the components in the solution, but also can provide nucleation sites for the growth of the polymer in the benzene polymerization process.
Preferably, the oxidant in step (3) is any one of ammonium persulfate, potassium dichromate, hydrogen peroxide, potassium iodate, potassium permanganate, acyl peroxide, hydroperoxide, dialkyl peroxide, ester peroxide, ketone peroxide and dicarbonate peroxide, and the oxidant has oxidizability and can enable the conductive polymer monomer to generate a polymerization reaction to generate a corresponding conductive polymer.
Preferably, the reaction temperature in the step (3) is controlled to be 0-25 ℃; the mixing time of the steps (1) to (3) is 1-24 h respectively. Wherein the mixing and dispersing means comprises: dispersing by using an ultrasonic cleaning machine; dispersing by using an ultrasonic crusher; dispersing by using a mechanical stirring mode; the specific dispersion method is any of the above dispersion methods.
Preferably, the lithium salt is added to fully mix after the polymerization reaction of the conductive polymer monomer is completed, and the mixing mode includes any one of high-speed ball milling and mechanical stirring.
A positive pole piece is prepared by uniformly mixing the carbon material/conductive polymer/lithium salt ternary composite material obtained by any one of the methods, conductive agent carbon black and binder polytetrafluoroethylene in a proper amount of N-methyl pyrrolidone solution according to the mass ratio of 8:1:1 to prepare a paste, and uniformly coating the paste on an aluminum foil. Wherein, the N-methyl pyrrolidone solution is used as a solvent for dissolving the adhesive polytetrafluoroethylene, and the ternary composite material, the conductive agent carbon black and the adhesive polytetrafluoroethylene are uniformly mixed to prepare a paste.
A lithium ion capacitor is provided with a negative pole piece, such as the positive pole piece; uniformly mixing artificial graphite, conductive agent carbon black and binder polytetrafluoroethylene in a proper amount of N-methyl pyrrolidone solution according to the mass ratio of 8:1:1 to prepare paste, and uniformly coating the paste on copper foil to prepare a negative pole piece; lithium hexafluorophosphate is used as electrolyte, a glass fiber diaphragm is used as a diaphragm, and the dried positive pole piece and the dried negative pole piece are assembled into the lithium ion capacitor. Wherein, the N-methyl pyrrolidone solution is used as a solvent for dissolving the adhesive polytetrafluoroethylene, and the artificial graphite, the conductive agent carbon black and the adhesive polytetrafluoroethylene are uniformly mixed to prepare a paste.
The invention has the beneficial effects that: the invention provides a ternary composite material and a preparation method thereof, and a positive pole piece and a lithium ion capacitor prepared from the ternary composite material. Namely, a carbon material having electrochemical double layer characteristics is used as a carbon skeleton, and the carbon material grows on the carbon skeleton through the polymerization reaction of a conductive polymer monomer under an acidic condition, so that the generated conductive polymer has P-type doping characteristics. Lithium salt is added before the polymerization reaction of the conductive polymer monomer or after the reaction is finished, and finally the carbon material/conductive polymer/lithium salt ternary composite material is prepared. When the ternary composite material prepared by the method is used as the anode of the lithium ion capacitor, the purpose of pre-embedding lithium into the cathode can be achieved by utilizing a cascade reaction, lithium salts in the ternary composite material can release lithium ions after the reaction of the lithium salts and hydrogen ions, and the lithium salts can be used as a lithium source to provide irreversible lithium ions for the cathode, so that the working voltage of the capacitor is improved, the energy density of the capacitor is improved, the consumption of the lithium ions in electrolyte is compensated, and the service life of the capacitor is prolonged. The preparation method of the lithium ion capacitor anode composite material with the pre-lithium intercalation function has the advantages of simple process, low cost, easy industrial production and the like.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise.
FIG. 1 is a scanning electron micrograph of an activated carbon/polyaniline/lithium sulfate ternary composite material of example 2;
FIG. 2 is a scanning electron micrograph of the activated carbon/polyaniline/lithium sulfate ternary composite material of comparative example 1;
FIG. 3 is a scanning electron micrograph of the activated carbon/polyaniline/lithium phosphate ternary composite material of example 6;
FIG. 4 is a scanning electron micrograph of the activated carbon/polyaniline/lithium phosphate ternary composite material of comparative example 2;
FIG. 5 is a schematic diagram of the action of polyaniline/lithium sulfate in the active carbon/polyaniline/lithium sulfate ternary composite positive electrode material of example 2;
FIG. 6 is a comparison of the cycle performance of activated carbon/polyaniline/lithium sulfate// artificial graphite lithium ion capacitor and activated carbon// artificial graphite lithium ion capacitor
FIG. 7 is a schematic view of a production flow for preparing a ternary composite material of carbon material/conductive polymer/lithium salt when lithium salt is added before the polymerization of the conductive polymer monomer;
fig. 8 is a schematic view of a production flow for preparing a carbon material/conductive polymer/lithium salt ternary composite material when lithium salt is added after polymerization of conductive polymer monomers is completed.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application clearer, the present application is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application. The method used in the invention is a conventional method if not specially specified; the raw materials and the apparatus used are, unless otherwise specified, conventional commercially available products.
Example 1
The invention provides a preparation method of a carbon material/conductive polymer/lithium salt ternary composite material, which comprises the following steps:
(1) respectively dispersing and uniformly mixing a certain amount of active carbon, aniline monomer and lithium sulfate in deionized water for 1 h; wherein the mass percentage of the activated carbon is 90 wt%, the mass percentage of the aniline monomer is 5 wt%, and the mass percentage of the lithium sulfate is 5 wt%;
(2) respectively adding a certain amount of cetyl trimethyl ammonium bromide and hydrochloric acid into the mixture, fully and uniformly mixing, controlling the concentration of the cetyl trimethyl ammonium bromide in the aqueous solution to be 0.2mol/L, controlling the concentration of hydrogen ions in the aqueous solution to be 0.5mol/L, and dispersing for 1 h;
(3) adding a certain amount of ammonium persulfate into the mixed solution to perform electrochemical polymerization reaction, controlling the reaction temperature at 25 ℃, and continuously stirring for 1h to complete the polymerization reaction; wherein the molar mass ratio of the added ammonium persulfate to the aniline monomer is 1: 1;
(4) and filtering, cleaning and freeze-drying the obtained reaction product to obtain the active carbon/polyaniline/lithium sulfate ternary composite material.
Example 2
The invention provides a preparation method of a carbon material/conductive polymer/lithium salt ternary composite material, which comprises the following steps:
(1) respectively dispersing and mixing a certain amount of active carbon, aniline monomer and lithium sulfate in deionized water for 6 hours; wherein the mass percentage of the activated carbon is 70 wt%, the mass percentage of the aniline monomer is 20 wt%, and the mass percentage of the lithium sulfate is 10 wt%;
(2) respectively adding a certain amount of cetyl trimethyl ammonium bromide and hydrochloric acid into the mixture, fully and uniformly mixing, controlling the concentration of the cetyl trimethyl ammonium bromide in the aqueous solution to be 0.5mol/L, controlling the concentration of hydrogen ions in the aqueous solution to be 1mol/L, and dispersing for 6 h;
(3) adding a certain amount of ammonium persulfate into the mixed solution to perform electrochemical polymerization reaction, controlling the reaction temperature at 10 ℃, and continuously stirring for 6 hours to complete the polymerization reaction; wherein the molar mass ratio of the added ammonium persulfate to the aniline monomer is 1: 4;
(4) and filtering, cleaning and freeze-drying the obtained reaction product to obtain the active carbon/polyaniline/lithium sulfate ternary composite material.
Example 3
The invention provides a preparation method of a carbon material/conductive polymer/lithium salt ternary composite material, which comprises the following steps:
(1) respectively dispersing and uniformly mixing a certain amount of activated carbon, aniline monomer and lithium sulfate in deionized water for 12 hours; wherein the mass percentage of the activated carbon is 50 wt%, the mass percentage of the aniline monomer is 5 wt%, and the mass percentage of the lithium sulfate is 45 wt%;
(2) respectively adding a certain amount of cetyl trimethyl ammonium bromide and hydrochloric acid into the mixture, fully and uniformly mixing, controlling the concentration of the cetyl trimethyl ammonium bromide in the aqueous solution to be 1mol/L, controlling the concentration of hydrogen ions in the aqueous solution to be 2mol/L, and dispersing for 12 h;
(3) adding a certain amount of ammonium persulfate into the mixed solution to perform electrochemical polymerization reaction, controlling the reaction temperature at 5 ℃, and continuously stirring for 12 hours to complete the polymerization reaction; wherein the molar mass ratio of the added ammonium persulfate to the aniline monomer is 1: 7;
(4) and filtering, cleaning and freeze-drying the obtained reaction product to obtain the active carbon/polyaniline/lithium sulfate ternary composite material.
Example 4
The invention provides a preparation method of a carbon material/conductive polymer/lithium salt ternary composite material, which comprises the following steps:
(1) respectively dispersing and uniformly mixing a certain amount of activated carbon, aniline monomer and lithium sulfate in deionized water for 24 hours; wherein the mass percentage of the activated carbon is 50 wt%, the mass percentage of the aniline monomer is 45 wt%, and the mass percentage of the lithium sulfate is 5 wt%;
(2) respectively adding a certain amount of cetyl trimethyl ammonium bromide and hydrochloric acid into the mixture, fully and uniformly mixing, controlling the concentration of the cetyl trimethyl ammonium bromide in the aqueous solution to be 2mol/L, controlling the concentration of hydrogen ions in the aqueous solution to be 5mol/L, and dispersing for 24 hours;
(3) adding a certain amount of ammonium persulfate into the mixed solution to perform electrochemical polymerization reaction, controlling the reaction temperature at 0 ℃, and continuously stirring for 24 hours to complete the polymerization reaction; wherein the molar mass ratio of the added ammonium persulfate to the aniline monomer is 1: 10;
(4) and filtering, cleaning and freeze-drying the obtained reaction product to obtain the active carbon/polyaniline/lithium sulfate ternary composite material.
Example 5
The invention provides a preparation method of a carbon material/conductive polymer/lithium salt ternary composite material, which comprises the following steps:
(1) respectively dispersing and uniformly mixing a certain amount of activated carbon and aniline monomers in deionized water for 1 h; wherein the mass percentage of the activated carbon is 90 wt%, and the mass percentage of the aniline monomer is 5 wt%;
(2) respectively adding a certain amount of cetyl trimethyl ammonium bromide and hydrochloric acid into the mixture, fully and uniformly mixing, controlling the concentration of the cetyl trimethyl ammonium bromide in the aqueous solution to be 0.2mol/L, controlling the concentration of hydrogen ions in the aqueous solution to be 0.5mol/L, and dispersing for 1 h;
(3) adding a certain amount of ammonium persulfate into the mixed solution to perform electrochemical polymerization reaction, controlling the reaction temperature at 25 ℃, and continuously stirring for 1h to complete the polymerization reaction; wherein the molar mass ratio of ammonium persulfate to aniline monomer is 1: 1;
(4) and filtering, cleaning and freeze-drying the obtained reaction product to obtain the active carbon/polyaniline binary composite material.
(5) Adding lithium phosphate into the activated carbon/polyaniline binary composite material, and fully mixing for 1h, wherein the mass ratio of the lithium phosphate is 5 wt%, and finally obtaining the activated carbon/polyaniline/lithium phosphate ternary composite material.
Remarking: the sum of the mass of the activated carbon, the aniline monomer and the lithium phosphate used in the embodiment is 100 wt%.
Example 6
The invention provides a preparation method of a carbon material/conductive polymer/lithium salt ternary composite material, which comprises the following steps:
(1) respectively dispersing and uniformly mixing a certain amount of activated carbon and aniline monomers in deionized water for 6 hours; wherein the mass percentage of the activated carbon is 70 wt%, and the mass percentage of the aniline monomer is 20 wt%;
(2) respectively adding a certain amount of cetyl trimethyl ammonium bromide and hydrochloric acid into the mixture, fully and uniformly mixing, controlling the concentration of the cetyl trimethyl ammonium bromide in the aqueous solution to be 0.5mol/L, controlling the concentration of hydrogen ions in the aqueous solution to be 1mol/L, and dispersing for 6 h;
(3) adding a certain amount of ammonium persulfate into the mixed solution to perform electrochemical polymerization reaction, controlling the reaction temperature at 10 ℃, and continuously stirring for 6 hours to complete the polymerization reaction; wherein the molar mass ratio of ammonium persulfate to aniline monomer is 1: 10;
(4) and filtering, cleaning and freeze-drying the obtained reaction product to obtain the active carbon/polyaniline binary composite material.
(5) Adding lithium phosphate into the activated carbon/polyaniline binary composite material, and fully mixing for 6 hours, wherein the mass ratio of the lithium phosphate is 10 wt%, and finally obtaining the activated carbon/polyaniline/lithium phosphate ternary composite material.
Remarking: the sum of the mass of the activated carbon, the aniline monomer and the lithium phosphate used in the embodiment is 100 wt%.
Example 7
The invention provides a preparation method of a carbon material/conductive polymer/lithium salt ternary composite material, which comprises the following steps:
(1) respectively dispersing and uniformly mixing a certain amount of activated carbon and aniline monomers in deionized water for 12 hours; wherein the mass percentage of the activated carbon is 50 wt%, and the mass percentage of the aniline monomer is 5 wt%;
(2) respectively adding a certain amount of cetyl trimethyl ammonium bromide and hydrochloric acid into the mixture, fully and uniformly mixing, controlling the concentration of the cetyl trimethyl ammonium bromide in the aqueous solution to be 2mol/L, controlling the concentration of hydrogen ions in the aqueous solution to be 1mol/L, and dispersing for 12 h;
(3) adding a certain amount of ammonium persulfate into the mixed solution to perform electrochemical polymerization reaction, controlling the reaction temperature at 5 ℃, and continuously stirring for 12 hours to complete the polymerization reaction; wherein the molar mass ratio of ammonium persulfate to aniline monomer is 1: 7;
(4) and filtering, cleaning and freeze-drying the obtained reaction product to obtain the active carbon/polyaniline binary composite material.
(5) Adding lithium phosphate into the activated carbon/polyaniline binary composite material, and fully mixing for 12 hours, wherein the mass ratio of the lithium phosphate is 45 wt%, and finally obtaining the activated carbon/polyaniline/lithium phosphate ternary composite material.
Remarking: the sum of the mass of the activated carbon, the aniline monomer and the lithium phosphate used in the embodiment is 100 wt%.
Example 8
The invention provides a preparation method of a carbon material/conductive polymer/lithium salt ternary composite material, which comprises the following steps:
(1) respectively dispersing and mixing a certain amount of activated carbon and aniline monomers in deionized water uniformly, wherein the dispersion time is 24 hours; wherein the mass percentage of the activated carbon is 50 wt%, and the mass percentage of the aniline monomer is 45 wt%;
(2) respectively adding a certain amount of cetyl trimethyl ammonium bromide and hydrochloric acid into the mixture, fully and uniformly mixing, controlling the concentration of the cetyl trimethyl ammonium bromide in the aqueous solution to be 2mol/L, controlling the concentration of hydrogen ions in the aqueous solution to be 5mol/L, and dispersing for 24 h;
(3) adding a certain amount of ammonium persulfate into the mixed solution to perform electrochemical polymerization reaction, controlling the reaction temperature at 0 ℃, and continuously stirring for 24 hours to complete the polymerization reaction; wherein the molar mass ratio of ammonium persulfate to aniline monomer is 1: 10;
(4) and filtering, cleaning and freeze-drying the obtained reaction product to obtain the active carbon/polyaniline binary composite material.
(5) Adding lithium phosphate into the activated carbon/polyaniline binary composite material, and fully mixing for 24 hours, wherein the mass ratio of the lithium phosphate is 5 wt%, and finally obtaining the activated carbon/polyaniline/lithium phosphate ternary composite material.
Remarking: the sum of the mass ratios of the activated carbon, the aniline monomer and the lithium phosphate used in the present example is 100 wt%.
Comparative example 1
Comparative example 1 is a comparative example to example 2 except that the surfactant cetyltrimethylammonium bromide was not added in step (2) of comparative example 1, and the rest is the same.
Comparative example 1 provides a method for preparing a carbon material/conductive polymer/lithium salt ternary composite material, which comprises the following steps:
(1) respectively dispersing and uniformly mixing a certain amount of active carbon, aniline monomer and lithium sulfate in deionized water for 6 hours; wherein the mass percentage of the activated carbon is 70 wt%, the mass percentage of the aniline monomer is 20 wt%, and the mass percentage of the lithium sulfate is 10 wt%;
(2) adding a certain amount of hydrochloric acid into the mixture, fully and uniformly mixing, controlling the concentration of hydrogen ions in the aqueous solution to be 1mol/L, and dispersing for 6 hours;
(3) adding a certain amount of ammonium persulfate into the mixed solution to perform electrochemical polymerization reaction, controlling the reaction temperature at 10 ℃, and continuously stirring for 6 hours to complete the polymerization reaction; wherein the molar mass ratio of the added ammonium persulfate to the aniline monomer is 1: 4;
(4) and filtering, cleaning and freeze-drying the obtained reaction product to obtain the active carbon/polyaniline/lithium sulfate ternary composite material.
Comparative example 2
Comparative example 2 is a comparative example to example 6 except that step (4) of comparative example 2 does not employ freeze-drying but employs a general drying treatment, and the rest is the same.
Comparative example 2 provides a method for preparing a carbon material/conductive polymer/lithium salt ternary composite material, which comprises the following steps:
(1) respectively dispersing and uniformly mixing a certain amount of activated carbon and aniline monomers in deionized water for 6 hours; wherein the mass percentage of the activated carbon is 70 wt%, and the mass percentage of the aniline monomer is 20 wt%;
(2) respectively adding a certain amount of cetyl trimethyl ammonium bromide and hydrochloric acid into the mixture, fully and uniformly mixing, controlling the concentration of the cetyl trimethyl ammonium bromide in the aqueous solution to be 0.5mol/L, controlling the concentration of hydrogen ions in the aqueous solution to be 1mol/L, and dispersing for 6 h;
(3) adding a certain amount of ammonium persulfate into the mixed solution to perform electrochemical polymerization reaction, controlling the reaction temperature at 10 ℃, and continuously stirring for 6 hours to complete the polymerization reaction; wherein the molar mass ratio of ammonium persulfate to aniline monomer is 1: 10;
(4) and filtering, cleaning and normally drying the obtained reaction product to obtain the active carbon/polyaniline composite material.
(5) Adding lithium phosphate into the activated carbon/polyaniline composite material, and fully mixing for 6 hours, wherein the mass ratio of the lithium phosphate is 10 wt%, and finally obtaining the activated carbon/polyaniline/lithium phosphate ternary composite material.
Remarking: the mass of the activated carbon, the aniline monomer and the lithium phosphate used in the comparative example accounts for 100 wt%.
And (3) performance testing:
(1) specific surface area test
Specific surface area tests of the carbon material/conductive polymer/lithium salt ternary composite material and the pure activated carbon prepared in the examples 1 to 8 and the comparative examples 1 to 2 were respectively carried out by using a nitrogen specific surface area tester ASAP 2460 under the condition of a temperature of 77K, the calculation method of the specific surface area is a Brunauer-Emmett-Teller (BET) method, the analysis of the pore size distribution adopts a dense-functional-Depth (DFT) model, and the results are shown in the following table 1:
TABLE 1 results of specific surface area test of examples 1 to 8, comparative examples 1 to 2, pure activated carbon
Figure BDA0002939631020000111
Specific surface area test data of the carbon material/conductive polymer/lithium salt ternary composite material and pure activated carbon prepared in the examples 1 to 8 and the comparative examples 1 to 2 in the table 1 are analyzed, and the following results are obtained:
the specific surface area of the carbon material/conductive polymer/lithium salt ternary composite material prepared in the embodiments 1-8 and the comparative examples 1-2 is lower than that of pure activated carbon because the specific surface area of polyaniline and lithium salt in the composite material is lower, so that the specific surface area of the composite material after the polyaniline and the lithium salt are added is lower than that of the pure activated carbon.
The specific surface area of the carbon material/conductive polymer/lithium salt ternary composite material prepared in the embodiment 2 is higher than that of the ternary composite material prepared in the comparative example 1, because the surfactant is adopted in the embodiment 2, the surfactant can enable activated carbon to be dispersed more uniformly, and the activated carbon, polyaniline and lithium salt are directly and uniformly compounded together to obtain a higher specific surface area. The specific surface area of the carbon material/conductive polymer/lithium salt ternary composite material prepared in example 6 is higher than that of comparative example 2, because the freeze drying method is adopted in example 6, and compared with ordinary drying, the freeze drying method has the advantage that more pore structures are formed in the composite material in the process of removing moisture, so that the specific surface area of the composite material is increased.
③ the lithium salt is added before the polymerization reaction of the conductive polymer monomer in the embodiments 1 to 4, and the lithium salt is added after the polymerization reaction of the conductive polymer monomer in the embodiments 5 to 8, so as to finally prepare the carbon material/conductive polymer/lithium salt ternary composite material. The specific surface area of the ternary composite material of carbon material/conductive polymer/lithium salt prepared in examples 1 and 2 is higher than that of the ternary composite material prepared in examples 3 and 4 because the specific surface area of the ternary composite material prepared in examples 1 and 2 is higher as the ratio of the activated carbon is higher. Similarly, the carbon material/conductive polymer/lithium salt ternary composite materials prepared in examples 5 and 6 have a higher specific surface area than those prepared in examples 7 and 8, for the same reason as above, which will not be described again.
Fourthly, compared with the addition of the lithium salt before the polymerization reaction of the conductive polymer monomer, the addition of the lithium salt after the polymerization reaction can obviously improve the specific surface area of the ternary composite material, for example, the specific surface area of the ternary composite material prepared by adding the lithium salt before the polymerization reaction in example 6 is 1792m 2 A specific surface area of 1623m, which is higher than that of the ternary composite prepared by adding lithium salt before polymerization in example 2 2 (ii) in terms of/g. Because the requirement for dispersion is higher with the addition of the lithium salt first, agglomeration is more likely to occur. Meanwhile, the lithium salt is low in proportion in the composite material, so that different types of the lithium salt have little influence on the specific surface area of the composite material.
(3) Scanning test of electron microscope
The carbon material/conductive polymer/lithium salt ternary composite materials obtained in example 2, example 6, comparative example 1 and comparative example 2 were subjected to electron microscope scanning. As shown in fig. 1 and 3, it is obvious that in the ternary composite materials prepared by the methods of examples 2 and 6, polyaniline and lithium salt are uniformly attached to the surface of the activated carbon, no obvious agglomeration phenomenon is formed, and the good composite structure can more easily and fully exert the synergistic effect of the polyaniline and the lithium salt. As shown in fig. 2 and 4, in the ternary composite materials prepared by the methods of comparative examples 1 and 2, it can be found that the surface of the activated carbon has both an exposed smooth surface and a portion to which lithium salt and polyaniline are attached, and the three are not well compounded together.
Comparative example 1 is a comparative example to example 2 except that step (2) of comparative example 1 is free of the addition of the surfactant cetyl trimethylammonium bromide; comparative example 2 is a comparative example to example 6 except that step (4) of comparative example 2 does not employ freeze-drying but employs a general drying treatment. Therefore, the step (2) of the method is added with the surfactant, and the step (4) of the method adopts freeze drying treatment, so that the polyaniline and the lithium salt are favorably and uniformly attached to the surface of the activated carbon.
(4) Electrochemical performance of lithium ion capacitor
Preparing a negative pole piece: the method comprises the steps of uniformly mixing artificial graphite, conductive agent carbon black and binder polytetrafluoroethylene in a proper amount of N-methyl pyrrolidone solution according to the mass ratio of 8:1:1 to prepare paste, and uniformly coating the paste on copper foil to prepare the negative pole piece.
② preparing the lithium ion capacitor with the anode being the active carbon/polyaniline/lithium phosphate ternary composite material
The active carbon/polyaniline/lithium sulfate ternary composite material prepared in the example 2, a conductive agent, carbon black and a binder, namely polytetrafluoroethylene, are uniformly mixed in a proper amount of N-methyl pyrrolidone solution according to the mass ratio of 8:1:1 to prepare a paste, and the paste is uniformly coated on an aluminum foil to prepare a positive electrode plate. And (2) taking lithium hexafluorophosphate as electrolyte and a glass fiber diaphragm as a diaphragm, and assembling the dried positive pole piece and the negative pole piece prepared in the step (1) into the lithium ion capacitor.
Preparation of lithium ion capacitor with active carbon as anode
Uniformly mixing activated carbon, conductive agent carbon black and binder polytetrafluoroethylene in a proper amount of N-methyl pyrrolidone solution according to the mass ratio of 8:1:1 to prepare paste, and uniformly coating the paste on aluminum foil to prepare the positive electrode plate. And (2) taking lithium hexafluorophosphate as electrolyte and a glass fiber diaphragm as a diaphragm, and assembling the dried positive pole piece and the negative pole piece prepared in the step (1) into the lithium ion capacitor.
And respectively testing the electrochemical performances of the two lithium ion batteries respectively taking the activated carbon/polyaniline/lithium sulfate ternary composite material and the activated carbon as the positive electrodes.
As shown in fig. 5, in the lithium ion capacitor with the positive and negative electrodes made of activated carbon/polyaniline/lithium sulfate// artificial graphite, during the first charging process, the polyaniline in the positive electrode material undergoes an irreversible de-doping reaction to release H + Proton, then H + Reaction of protons with lithium sulfate releases Li + ，Li + Then transferring the electrolyte to the negative electrode to supplement the electrolyte, wherein the SEI film is formed by the artificial graphite of the negative electrodeResulting Li + And (4) loss. After the first ring of irreversible de-doping reaction, the polyaniline still can perform reversible doping/de-doping reaction in the anode material, and can be used as an active substance to provide stable capacity output so as to avoid becoming dead weight. Therefore, compared with the traditional activated carbon material, the ternary composite material of activated carbon/polyaniline/lithium sulfate can obviously improve the cycle stability and energy density of the lithium ion capacitor.
As shown in fig. 6, by comparing the cycle performance of the lithium ion capacitor with positive and negative electrodes made of activated carbon/polyaniline/lithium sulfate// artificial graphite respectively and the lithium ion capacitor with positive and negative electrodes made of activated carbon/polyaniline/lithium sulfate// artificial graphite respectively, after 2000 cycles, the capacity retention rate of the activated carbon/polyaniline/lithium sulfate// artificial graphite lithium ion capacitor is still as high as 85%, while the capacity retention rate of the activated carbon/artificial graphite is only 65%. Therefore, the active carbon/polyaniline/lithium sulfate ternary composite material is used as a positive electrode material, and the cycle life of the lithium ion capacitor can be remarkably prolonged.
Description of the drawings: in the above "activated carbon/polyaniline/lithium sulfate// artificial graphite", the left side of the symbol "//" of the "activated carbon/polyaniline/lithium sulfate" represents a positive electrode material, and the right side of the "/" of the "artificial graphite" represents a negative electrode material. Similarly, in activated carbon// artificial graphite, the left side of the symbol "//" of "activated carbon" represents a positive electrode material, and the right side of "//" of "artificial graphite" represents a negative electrode material.
The invention provides a ternary composite material and a preparation method thereof, and a positive pole piece and a lithium ion capacitor prepared from the ternary composite material. Namely, a carbon material having electrochemical double layer characteristics is used as a carbon skeleton, and the carbon material grows on the carbon skeleton through the polymerization reaction of a conductive polymer monomer under an acidic condition, so that the generated conductive polymer has P-type doping characteristics. In a conductive polymerLithium salt is added before the process of the polymerization reaction of the monomers or after the reaction is completed, wherein the lithium salt is added before the process of the polymerization reaction of the conductive polymer monomers in the embodiments 1 to 4, and the preparation process is shown in fig. 7; examples 5 to 8 lithium salt was added after the polymerization of the conductive polymer monomer was completed, and the preparation process is shown in fig. 8, and finally the carbon material/conductive polymer/lithium salt ternary composite material was prepared. When the ternary composite material is used as a lithium ion capacitor anode material and assembled into a corresponding lithium ion capacitor, the active substance of the main body is a carbon material with the characteristic of an electric double layer, and the synthesized conductive polymer with the characteristic of P type doping provides H through oxidation reaction + Then trapping H by inorganic lithium salt + And release Li by an irreversible delithiation process + And further completing the pre-lithium intercalation of the negative electrode.
The invention provides an active carbon/polyaniline/lithium sulfate ternary composite material as a positive electrode material, which has the following advantages:
the synthesized conductive polymer with the P-type doping characteristic can be contacted with inorganic lithium salt more fully, the transmission path from generation of H + to acquisition is reduced, and Li is improved + The production efficiency of (a);
secondly, a carbon material with double electric layer characteristics is used as a framework, so that the synthesized conductive polymer with the P-type doping characteristics is more stable in structure and is not easy to fall off from an electrode material;
the density difference of the positive active material of the conventional super capacitor, the inorganic lithium salt and the conductive polymer with the P-type doping characteristic is large, and the dispersion is difficult to be uniform;
the raw materials have wide sources, the preparation is easy, the reaction condition is mild, the composite material has no special requirement on the environment, and the large-scale production is facilitated.
It should be noted that:
(1) the carbon materials in examples 1 to 8 may be any of graphene, carbon nanotubes, and carbon aerogel, in addition to activated carbon, and all of them have electrochemical double layer characteristics and capacitance characteristics, and function as a main active material in the positive electrode composite material to provide capacity.
(2) The conductive polymer monomer in embodiments 1 to 8 may be any of pyrrole and thiophene in addition to aniline. The aniline, the pyrrole and the thiophene are respectively monomers of conductive polymers polyaniline, polypyrrole and polythiophene, are liquid at normal temperature, and can form corresponding conductive polymers through polymerization reaction.
(3) The lithium salt in examples 1 to 4 may be lithium phosphate in addition to lithium sulfate, and when the lithium salt is lithium sulfate, the protonic acid is hydrochloric acid that does not react with lithium sulfate; when the lithium salt is lithium phosphate, the protonic acid is phosphoric acid that does not react with the lithium phosphate. Lithium sulfate and lithium phosphate are used as two different lithium salts, and can release lithium ions through a reaction with hydrogen ions, and the lithium salts are used as a lithium source to provide irreversible lithium ions for the negative electrode. Hydrochloric acid or phosphoric acid is protonic acid, and can provide an acid environment for the polymer monomer to perform a reaction polymerization reaction, so that the generated polymer has a regular structure and high conductivity.
(4) The protonic acid in examples 5 to 8 may be any of sulfuric acid, nitric acid, phosphoric acid, carbonic acid, and oxalic acid, in addition to hydrochloric acid, and provides an acidic environment for the polymerization reaction of the conductive polymer monomer, so that the resulting polymer has a regular structure and high conductivity. The lithium salt may be any one of lithium sulfate, lithium carbonate, lithium borate, lithium oxalate, and lithium silicate, in addition to lithium phosphate, and may release lithium ions after a reaction with hydrogen ions, thereby serving as a lithium source to supply irreversible lithium ions to the negative electrode. Since the lithium salt is added after the polymerization reaction of the conductive polymer monomer is completed, the types of the added protonic acid and the lithium salt are not limited by the incapability of reaction between the protonic acid and the lithium salt.
(5) The dispersant of examples 1-8, which may be sodium dodecylbenzene sulfonate in addition to cetyltrimethylammonium bromide, not only serves to disperse the components of the solution into intimate contact, but also provides nucleation sites for polymer growth during the benzene polymerization process.
(6) The oxidizing agent in examples 1 to 8 may be any of potassium dichromate, hydrogen peroxide, potassium iodate, potassium permanganate, acyl peroxides, hydroperoxides, dialkyl peroxides, ester peroxides, ketone peroxides, and dicarbonate peroxides, in addition to ammonium persulfate, and all of these oxidizing agents are capable of oxidizing and polymerizing polymer monomers to produce corresponding conductive polymers.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (3)

1. A ternary composite material characterized by: taking a carbon material with electrochemical double-layer characteristics as a carbon skeleton, growing a conductive polymer on the carbon skeleton through the polymerization reaction of a conductive polymer monomer under an acidic condition, and adding a lithium salt before the polymerization reaction of the conductive polymer monomer to obtain a carbon material/conductive polymer/lithium salt ternary composite material;
the preparation method of the ternary composite material comprises the following steps:
(1) respectively dispersing and uniformly mixing a certain amount of carbon materials and conductive polymer monomers in deionized water to obtain a mixture; wherein the mass ratio of the carbon material is 50-90 wt%, and the mass ratio of the conductive polymer monomer is 5-45 wt%;
(2) respectively adding a certain amount of dispersant and protonic acid into the mixture, and fully and uniformly mixing to obtain a mixed solution; controlling the concentration of hydrogen ions in the aqueous solution to be 0.5-5 mol/L, and controlling the concentration of the dispersing agent in the aqueous solution to be 0.2-2 mol/L;
(3) adding a certain amount of oxidant into the mixed solution to perform electrochemical polymerization reaction, controlling the reaction temperature and continuously stirring for a period of time to complete the polymerization reaction; wherein the molar mass ratio of the oxidant to the conductive polymer monomer is 1: 1-10;
(4) filtering, cleaning and freeze-drying the obtained reaction product;
adding lithium salt before the polymerization reaction of the conductive polymer monomer, adding 5-45 wt% of lithium salt in the step (1), wherein protonic acid which does not react with the lithium salt is required to be added in the step (2), and then performing the steps (3) and (4) to obtain the carbon material/conductive polymer/lithium salt ternary composite material;
adding lithium salt before the conductive polymer monomer is subjected to polymerization reaction, wherein the sum of the mass ratios of the carbon material, the conductive polymer monomer and the lithium salt is 100 wt%;
the carbon material in the step (1) is any one of activated carbon, graphene, carbon nano tubes and carbon aerogel; the conductive polymer monomer is any one of aniline, pyrrole and thiophene;
adding a lithium salt before the polymerization reaction of the conductive polymer monomer, wherein the lithium salt in the step (1) is lithium sulfate or lithium phosphate, the protonic acid in the step (2) is hydrochloric acid or phosphoric acid, and when the lithium salt is lithium sulfate, the protonic acid is hydrochloric acid; when the lithium salt is lithium phosphate, the protonic acid is phosphoric acid;
the dispersant in the step (2) is sodium dodecyl benzene sulfonate or hexadecyl trimethyl ammonium bromide;
the oxidant in the step (3) is any one of ammonium persulfate, potassium dichromate, potassium iodate, potassium permanganate, acyl peroxides, hydroperoxide, dialkyl peroxides, ester peroxides, ketone peroxides and dicarbonate peroxides;
the reaction temperature in the step (3) is controlled to be 0-25 ℃; the mixing time of the steps (1) to (3) is 1-24 h respectively.
2. A positive pole piece is characterized in that: the ternary composite material as claimed in claim 1, a conductive agent carbon black and a binder polytetrafluoroethylene are uniformly mixed in a proper amount of N-methyl pyrrolidone solution according to the mass ratio of 8:1:1 to prepare a paste, and the paste is uniformly coated on an aluminum foil to prepare the positive electrode plate.
3. A lithium ion capacitor, characterized by: provided with a negative electrode plate, a positive electrode plate according to claim 2; uniformly mixing artificial graphite, conductive agent carbon black and binder polytetrafluoroethylene in a proper amount of N-methyl pyrrolidone solution according to the mass ratio of 8:1:1 to prepare paste, and uniformly coating the paste on copper foil to prepare the negative pole piece; and (3) assembling the dried positive pole piece and the dried negative pole piece into the lithium ion capacitor by taking lithium hexafluorophosphate as electrolyte and a glass fiber diaphragm as a diaphragm.
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