CN111681884A - Full-carbon-based mixed alkali metal ion capacitor and manufacturing method thereof - Google Patents
Full-carbon-based mixed alkali metal ion capacitor and manufacturing method thereof Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 94
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- 229910001413 alkali metal ion Inorganic materials 0.000 title claims abstract description 68
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 7
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
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Abstract
An all-carbon-based mixed alkali metal ion capacitor comprises a positive plate, a negative plate, electrolyte and a diaphragm between the positive plate and the negative plate. The positive plate comprises a positive current collector and a positive active material layer combined on the surface of the positive current collector, wherein the positive active material layer comprises a positive active material, and the positive active material is a carbon material. The negative plate comprises a negative current collector and a negative active material layer combined on the surface of the negative current collector, wherein the negative active material layer comprises a negative active material, and the negative active material comprises one or more of but not limited to natural graphite, artificial graphite, modified natural graphite and mesocarbon microbeads. The cation in the electrolyte is lithium ion, sodium ion or potassium ion. The all-carbon-based mixed alkali metal ion capacitor has the advantages of high energy density, high power density, long cycle life and good stability. In addition, the invention also provides a manufacturing method of the all-carbon-based mixed alkali metal ion capacitor.
Description
Technical Field
The invention relates to an electrochemical energy storage device, in particular to an all-carbon-based mixed alkali metal ion capacitor and a manufacturing method thereof.
Background
With the rapid development of informatization and intellectualization in modern society, energy crisis and environmental pollution are becoming more serious, and products using electrochemical energy storage devices, such as electronic products and electric vehicles, are increasing, so that the development and utilization of high-performance electrochemical energy storage devices are urgently needed to relieve the energy crisis and alleviate the environmental pollution. In addition, the large-scale intelligent grid connection and the block energy storage of renewable energy sources such as pure electric and hybrid electric vehicles, wind energy and solar energy and the like are rapidly developed, and higher requirements are provided for the energy density, the power density, the service life and the cost of an electrochemical energy storage device.
Electrochemical energy storage devices mainly comprise batteries and supercapacitors. Batteries have high energy density but require hours of charging time and corresponding low output power. Both electric double layer supercapacitors and hybrid capacitors belong to supercapacitors. The electric double layer super capacitor has high power density characteristics, can realize rapid charge and discharge within one minute, but has low energy density. The hybrid capacitor is used as a novel electrochemical energy storage device, and combines the advantages of high energy density of a battery and high power density of a super capacitor by introducing a Faraday reaction electrode, so that the hybrid capacitor can simultaneously realize high power density and high energy density, and is a next-generation high-performance electrochemical energy storage device.
The lithium ion capacitor is one of mixed ion capacitors, and the positive electrode of the lithium ion capacitor adopts activated carbon based on physical adsorption and desorption of double electric layer capacitance, and the negative electrode of the lithium ion capacitor adopts graphite or lithium titanate and other negative electrode materials based on lithium ion embedding and desorption reaction. Compared with the traditional double electric layer super capacitor, the energy density of the lithium ion capacitor is greatly improved, and the lithium ion capacitor has the characteristics of high power density and long cycle life. However, the existing lithium ion capacitor has many problems: the graphite negative electrode needs to be subjected to pre-lithiation treatment, including the steps of coating the electrode with a lithium metal sheet and superfine lithium powder or introducing a third electrode and performing electrochemical pre-activation and the like, and the processes are complex in technology and high in cost; the lithium ion intercalation reaction kinetics of the graphite cathode is slow, the multiplying power performance is poor, an excessive graphite cathode is actually needed, and the material utilization rate is low; under the high-power working condition, lithium dendrites are easy to grow on the surface of graphite, and potential safety hazards exist.
At present, commercial mixed ion capacitors are mainly lithium ion capacitors, but the lithium resource is very limited. According to the reaction mechanism of the mixed ion capacitor, if abundant sodium and potassium resources in the earth crust are utilized to develop the mixed ion capacitor based on sodium ions and potassium ions, the mixed sodium ion capacitor and the mixed potassium ion capacitor which are low in cost, high in energy density, high in power density and long in cycle life are obtained, and the method has a wide sustainable development prospect.
Disclosure of Invention
In view of the above, it is desirable to provide an all-carbon-based mixed alkali metal ion capacitor with low cost, high energy density, high power density and long cycle life, so as to solve the above problems.
In addition, a method for manufacturing the all-carbon-based mixed alkali metal ion capacitor is also needed.
An all-carbon-based mixed alkali metal ion capacitor comprises a positive plate, a negative plate, electrolyte and a diaphragm between the positive plate and the negative plate. The positive plate comprises a positive current collector and a positive active material layer, wherein the positive active material layer is obtained by mixing a positive active material, a conductive additive and a positive binder in proportion into positive slurry and coating the positive slurry on the positive current collector; the negative plate comprises a negative current collector and a negative active material layer, wherein the negative active material layer is obtained by mixing a negative active material, a conductive additive and a negative binder in proportion into a negative slurry and coating the negative slurry on the negative current collector. The positive electrode active material is a carbon material; the negative active material comprises one or more of but not limited to natural graphite, artificial graphite, modified natural graphite and mesocarbon microbeads; the positive ions in the electrolyte are lithium ions, sodium ions or potassium ions, and the negative ions in the electrolyte include but are not limited to one or more of hexafluorophosphate, perchloric acid, tetrafluoroborate and bistrifluoromethanesulfonylimide.
Preferably, the cathode active material includes, but is not limited to, one or more of porous activated carbon, nanocarbon, graphene, and mesoporous carbon.
Preferably, the mass percentage of the graphite in the negative electrode active material layer is greater than or equal to 85%.
Preferably, in the all-carbon-based mixed alkali metal ion capacitor, the mass ratio of the positive electrode active material to the negative electrode active material is in a range of (3:1) to (10: 1).
Preferably, the negative electrode binder includes, but is not limited to, one or more of carboxylic styrene-butadiene latex, sodium carboxymethyl cellulose, sodium alginate, polyvinylidene fluoride and polyacrylic acid.
A manufacturing method of an all-carbon-based mixed alkali metal ion capacitor comprises the following steps:
step S1: providing a positive electrode active material, a conductive additive, a positive electrode binder and a positive electrode current collector, wherein the positive electrode active material is a carbon material, mixing the positive electrode active material, the conductive additive and the positive electrode binder in proportion to obtain positive electrode slurry, coating the positive electrode slurry on the surface of the positive electrode current collector to obtain a positive electrode plate, and welding a lug on the positive electrode plate;
step S2: providing a negative electrode active material, a conductive additive, a negative electrode binder and a negative electrode current collector, wherein the negative electrode active material comprises but is not limited to one or more of natural graphite, artificial graphite, modified natural graphite and mesocarbon microbeads, mixing the negative electrode active material, the conductive additive and the negative electrode binder in proportion to obtain negative electrode slurry, coating the negative electrode slurry on the surface of the negative electrode current collector to obtain a negative electrode sheet, and welding a lug on the negative electrode sheet;
step S3: providing a diaphragm, and sequentially stacking the positive plate, the diaphragm and the negative plate in sequence to manufacture a battery cell;
step S4: providing a shell and an electrolyte, wherein cations in the electrolyte are lithium ions, sodium ions or potassium ions, and anions in the electrolyte comprise but are not limited to one or more of hexafluorophosphate radicals, perchloric acid, tetrafluoroborate radicals and bis (trifluoromethanesulfonyl) imide radicals, filling the battery cell into the shell, injecting the electrolyte into the shell, and then packaging the shell to obtain the all-carbon-based mixed alkali metal ion capacitor.
The positive electrode active material and the negative electrode active material of the all-carbon-based mixed alkali metal ion capacitor are both carbon materials, so that the lithium ions, the sodium ions, the potassium ions and solvent molecules can be jointly embedded into the negative electrode containing graphite, and excellent high-rate performance can be realized. The mass percentage of graphite in the negative active material layer of the all-carbon-based mixed alkali metal ion capacitor is greater than or equal to 85%, so that the occurrence of side reactions can be effectively reduced. The cathode binder of the all-carbon-based mixed alkali metal ion capacitor does not use polytetrafluoroethylene, so that the cathode active material can show high first coulombic efficiency. In addition, the positive ions of the electrolyte of the all-carbon-based mixed alkali metal ion capacitor can adopt sodium ions or potassium ions which are rich in resources and low in price, and the manufacturing cost can be effectively saved. In addition, the all-carbon-based mixed alkali metal ion capacitor has the advantages of high working voltage, high energy density, high power density, long cycle life and good stability, and has good application prospect in the field of new energy.
Drawings
FIG. 1 is a constant current charge/discharge curve diagram of an all-carbon-based mixed alkali metal ion capacitor according to example 1 of the present invention.
Fig. 2 is a constant current charge and discharge curve diagram of the all-carbon-based mixed alkali metal ion capacitor of example 2 of the present invention.
Fig. 3 is a cyclic voltammogram of an all-carbon based mixed alkali metal ion capacitor of example 2 of the present invention.
Fig. 4 is a constant current charge and discharge curve diagram of the sodium intercalation reaction of the negative electrode sheet of the all-carbon-based mixed alkali metal ion capacitor according to example 2 of the present invention.
Fig. 5 is a coulombic efficiency graph for 5 cycles before the sodium intercalation reaction of the negative electrode sheet of the all-carbon-based mixed alkali metal ion capacitor according to example 2 of the present invention.
Description of the main elements
Is free of
The following detailed description will further illustrate the invention in conjunction with the above-described figures.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the following detailed description of the present invention is provided with reference to the accompanying drawings.
The preferred embodiment of the present invention provides an all-carbon-based mixed alkali metal ion capacitor (not shown), which comprises a housing, and a positive plate, a negative plate, an electrolyte and a diaphragm which are positioned in the housing. The positive plate, the diaphragm and the negative plate are sequentially stacked, in other words, the diaphragm is arranged between the positive plate and the negative plate. The electrolyte is filled among the positive plate, the diaphragm and the negative plate.
The positive plate comprises a positive current collector and a positive active material layer combined on the surface of the positive current collector. The negative plate comprises a negative current collector and a negative active material layer combined on the surface of the negative current collector.
The positive current collector and the negative current collector are metal foils. The metal foil may be aluminum foil, copper foil, stainless steel foil or the like conventionally used for positive and negative current collectors. Preferably, the metal foil is a non-porous metal foil, in other words, the aluminum foil is a non-porous aluminum foil, the copper foil is a non-porous copper foil, and the stainless steel foil is a non-porous stainless steel foil, so that the manufacturing cost of the all-carbon-based mixed alkali metal ion capacitor can be effectively saved.
The positive active material layer is obtained by mixing a positive active material, a conductive additive and a positive binder according to a mass ratio of (80% -90%) (5% -10%) to form a positive slurry and coating the positive slurry on a positive current collector. The negative electrode active material layer is obtained by mixing a negative electrode active material, a conductive additive and a negative electrode binder according to a mass ratio of (90-95) to (2-5) to (3-5) to form a negative electrode slurry and coating the negative electrode slurry on a negative electrode current collector.
The positive electrode active material is a carbon material having a high specific surface area. The carbon material with high specific surface area includes, but is not limited to, one or more of porous activated carbon, nano carbon, graphene, and mesoporous carbon.
The negative active material includes, but is not limited to, one or more of natural graphite, artificial graphite, modified natural graphite, and mesocarbon microbeads. In at least one embodiment, the mass percentage of the graphite in the negative active material layer is greater than or equal to 85%, so that the use of conductive carbon with side reactions can be reduced, and the occurrence of the side reactions can be effectively reduced.
In the all-carbon-based mixed alkali metal ion capacitor, the mass ratio of the positive electrode active material to the negative electrode active material is (3:1) - (10:1), so that charges stored in the positive electrode active material and the negative electrode active material can be fully utilized, and the positive electrode active material and the negative electrode active material have high utilization rate. The utilization rate of graphite in the cathode sheet of the all-carbon-based mixed alkali metal ion capacitor is 100%, excessive graphite does not need to be additionally used, and resources and cost can be saved.
The conductive additive includes, but is not limited to, one or more of acetylene black, Super P (carbon black), ketjen black, carbon fiber, carbon nanotube, and graphene.
The positive binder includes, but is not limited to, one or more of polyvinylidene fluoride, polytetrafluoroethylene, carboxylic styrene-butadiene latex, sodium carboxymethylcellulose, sodium alginate and polyacrylic acid.
The negative electrode binder comprises one or more of carboxylic styrene-butadiene latex, sodium carboxymethylcellulose, sodium alginate, polyvinylidene fluoride and polyacrylic acid. The negative electrode binder does not include Polytetrafluoroethylene (PTFE), and as such, the negative electrode active material may be made to exhibit a first coulombic efficiency of greater than 90%.
The cation in the electrolyte may be lithium ion, sodium ion, or potassium ion. The anion in the electrolyte includes but is not limited to one or more of hexafluorophosphate, perchloric acid, tetrafluoroborate and bistrifluoromethanesulfonimide. The solvent of the electrolyte includes, but is not limited to, one or more of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether. The cations in the electrolyte can be intercalated into a negative active material layer containing graphite together with solvent molecules, thereby achieving excellent high rate performance and having very high first coulombic efficiency.
The concentration range of the electrolyte is preferably 0.5mol/L to 3 mol/L.
The diaphragm is a diaphragm which is conventionally applied to a capacitor, such as a polyethylene diaphragm, a polypropylene diaphragm, a polyethylene/polypropylene composite diaphragm, a biomass cellulose diaphragm, a glass fiber diaphragm and the like.
The housing is a housing conventionally applied to capacitors.
The preparation method of the full-carbon-based mixed alkali metal ion capacitor provided by the embodiment of the invention comprises the following steps of:
step S1: providing the positive electrode active material, the conductive additive, the positive electrode binder, the positive electrode current collector and a slurry solvent, mixing the positive electrode active material, the conductive additive and the positive electrode binder in proportion and dissolving the mixture in the slurry solvent to obtain positive electrode slurry, coating the positive electrode slurry on the surface of the positive electrode current collector to obtain a positive electrode plate, and welding a lug on the positive electrode plate;
step S2: providing the negative electrode active material, the conductive additive, the negative electrode binder, the negative electrode current collector and a slurry solvent, mixing the negative electrode active material, the conductive additive and the negative electrode binder in proportion and dissolving the mixture in the slurry solvent to obtain negative electrode slurry, coating the negative electrode slurry on the surface of the negative electrode current collector to obtain a negative electrode sheet, and welding a tab on the negative electrode sheet;
step S3: providing the diaphragm, and sequentially stacking the positive plate, the diaphragm and the negative plate in sequence to manufacture a battery cell;
step S4: and providing a shell and the electrolyte, loading the battery cell into the shell, injecting the electrolyte into the shell, and then packaging the shell to obtain the all-carbon-based mixed alkali metal ion capacitor.
The slurry solvent is an organic solvent or an inorganic solvent which is conventionally applied to capacitor preparation. In at least one embodiment, the organic solvent is methyl pyrrolidone or isopropyl alcohol and the inorganic solvent is water. In the preparation process of the all-carbon-based mixed alkali metal ion capacitor, the organic solvent is finally recycled and does not exist in the all-carbon-based mixed alkali metal ion capacitor.
The preparation process of the full-carbon-based mixed alkali metal ion capacitor is simple, the prepared positive plate and the prepared negative plate are directly assembled in a matching mode, no additional active metal electrode (such as lithium foil, sodium foil or potassium foil) is needed to be added, any electrochemical pretreatment is not needed to be carried out on the positive plate or the negative plate in the preparation process, and the manufacturing cost can be effectively saved.
The present invention will be specifically described below with reference to specific examples.
Example 1
Dissolving graphene, a conductive additive carbon nano tube and a positive adhesive polyvinylidene fluoride in methyl pyrrolidone according to a mass ratio of 90:5:5, mixing and stirring uniformly to obtain positive slurry, coating the positive slurry on the surface of an aluminum foil current collector to obtain a positive plate, cutting the size of the positive plate to 4cm multiplied by 4cm, and welding a lug.
Dissolving ground natural graphite, conductive additive acetylene black, carbon fiber and negative binder sodium alginate in water according to a mass ratio of 90:3:2:5, uniformly mixing and stirring to obtain negative electrode slurry, uniformly coating the negative electrode slurry on the surface of a copper foil current collector to obtain a negative electrode sheet, cutting the size of the negative electrode sheet to 4cm multiplied by 4cm, and welding a lug.
And sequentially stacking the positive plate, the polyethylene diaphragm and the negative plate in sequence to form a battery core, and loading the chip into a shell.
Dissolving lithium tetrafluoroborate in diethylene glycol dimethyl ether to prepare electrolyte with the concentration of 1 mol/L. And injecting the electrolyte into the shell with the chip, and then packaging the shell to obtain the all-carbon-based mixed alkali metal ion capacitor.
The mass ratio of the positive electrode active material to the negative electrode active material in the all-carbon-based mixed alkali metal ion capacitor of the embodiment is 5:1, that is, the mass ratio of the graphene to the natural graphite is 5: 1.
Example 2
Dissolving activated carbon, conductive additive Keqin black, carbon fiber and positive adhesive polyvinylidene fluoride in methyl pyrrolidone according to the mass ratio of 90:3:2:5, mixing and stirring uniformly to obtain positive slurry, uniformly coating the positive slurry on the surface of an aluminum foil current collector to obtain a positive plate, cutting the size of the positive plate into 4cm multiplied by 4cm, and welding a lug.
Dissolving mesocarbon microbeads, conductive additive acetylene black, carbon fibers and negative binder sodium alginate in water according to a mass ratio of 90:3:2:5, uniformly mixing and stirring to obtain negative electrode slurry, uniformly coating the negative electrode slurry on the surface of an aluminum foil current collector to obtain a negative electrode sheet, cutting the size of the negative electrode sheet to 4cm multiplied by 4cm, and welding a lug.
And sequentially stacking the positive plate, the polypropylene diaphragm and the negative plate to form a battery cell, and loading the battery cell into a shell.
And dissolving sodium hexafluorophosphate in diethylene glycol dimethyl ether to prepare the electrolyte with the concentration of 1 mol/L. And injecting the electrolyte into the shell with the chip, and then packaging the shell to obtain the all-carbon-based mixed alkali metal ion capacitor.
The mass ratio of the positive electrode active material to the negative electrode active material in the all-carbon-based mixed alkali metal ion capacitor of the embodiment is 3:1, that is, the mass ratio of the activated carbon to the mesocarbon microbeads is 3: 1.
Example 3
Dissolving activated carbon, conductive additive acetylene black and carbon fibers, and positive adhesive carboxymethylcellulose sodium and carboxylic styrene butadiene latex in water according to the mass ratio of 90:3:2:3:2, uniformly mixing and stirring to obtain positive slurry, uniformly coating the positive slurry on the surface of an aluminum foil current collector to obtain a positive plate, cutting the size of the positive plate to 4cm multiplied by 4cm, and welding a lug.
Dissolving the ground artificial graphite, the conductive additive acetylene black and the negative adhesive sodium alginate in water according to the mass ratio of 95:2:3, uniformly mixing and stirring to obtain negative electrode slurry, uniformly coating the negative electrode slurry on the surface of an aluminum foil current collector to obtain a negative electrode sheet, cutting the size of the negative electrode sheet to 4cm multiplied by 4cm, and welding a lug.
And sequentially stacking the positive plate, the glass fiber diaphragm and the negative plate in sequence to manufacture a battery core, and loading the chip into a shell.
Sodium perchlorate is dissolved in tetraethylene glycol dimethyl ether to prepare electrolyte with the concentration of 3 mol/L. And injecting the electrolyte into the shell with the chip, and then packaging the shell to obtain the all-carbon-based mixed alkali metal ion capacitor.
The mass ratio of the positive electrode active material to the negative electrode active material in the all-carbon-based mixed alkali metal ion capacitor of this example was 5:1, that is, the mass ratio of the activated carbon to the artificial graphite was 5: 1.
Example 4
Dissolving mesoporous carbon, a conductive additive Super P, carbon fiber and a positive adhesive polyvinylidene fluoride in methyl pyrrolidone according to a mass ratio of 80:5:5:10, mixing and stirring uniformly to obtain positive slurry, coating the positive slurry on the surface of an aluminum foil current collector to obtain a positive plate, cutting the size of the positive plate to 4cm multiplied by 4cm, and welding a lug.
Dissolving the ground modified natural graphite, the conductive additive acetylene black and the carbon fibers, and the negative adhesive carboxymethylcellulose sodium and the carboxylic styrene-butadiene latex in water according to the mass ratio of 85:3:2:5:5, uniformly mixing and stirring to obtain negative electrode slurry, uniformly coating the negative electrode slurry on the surface of an aluminum foil current collector to obtain a negative electrode plate, cutting the size of the negative electrode plate to 4cm multiplied by 4cm, and welding a tab.
And sequentially stacking the positive plate, the biomass cellulose diaphragm and the negative plate to form a battery core, and loading the chip into a shell.
Potassium hexafluorophosphate was dissolved in diethylene glycol dimethyl ether to prepare an electrolyte having a concentration of 0.5 mol/L. And injecting the electrolyte into the shell with the chip, and then packaging the shell to obtain the all-carbon-based mixed alkali metal ion capacitor.
The mass ratio of the positive electrode active material to the negative electrode active material in the all-carbon-based mixed alkali metal ion capacitor of the embodiment is 10:1, that is, the mass ratio of the mesoporous carbon to the modified natural graphite is 10: 1.
Example 5
Dissolving nano carbon, a conductive additive carbon nano tube, graphene and a positive adhesive polytetrafluoroethylene in isopropanol according to a mass ratio of 85:3:2:10, uniformly mixing and stirring to obtain positive slurry, uniformly coating the positive slurry on the surface of an aluminum foil current collector to obtain a positive plate, cutting the size of the positive plate into 4cm multiplied by 4cm, and welding a lug.
Dissolving mesocarbon microbeads, conductive additive acetylene black, carbon fibers and negative binder polyacrylic acid in water according to the mass ratio of 90:3:2:5, uniformly mixing and stirring to obtain negative electrode slurry, uniformly coating the negative electrode slurry on the surface of an aluminum foil current collector to obtain a negative electrode sheet, cutting the size of the negative electrode sheet to 4cm multiplied by 4cm, and welding a lug.
And sequentially stacking the positive plate, the polyethylene/polypropylene composite diaphragm and the negative plate to form a battery cell, and packaging the battery cell into a shell.
Dissolving sodium bistrifluoromethanesulfonylimide in ethylene glycol dimethyl ether to prepare electrolyte with the concentration of 1 mol/L. And injecting the electrolyte into the shell with the chip, and then packaging the shell to obtain the all-carbon-based mixed alkali metal ion capacitor.
The mass ratio of the positive electrode active material to the negative electrode active material in the all-carbon-based mixed alkali metal ion capacitor of the embodiment is 6:1, that is, the mass ratio of the nanocarbon to the mesocarbon microbeads is 6: 1.
Example 6
Dissolving activated carbon, conductive additive acetylene black, carbon fiber and positive adhesive sodium alginate in water according to a mass ratio of 90:3:2:5, uniformly mixing and stirring to obtain positive slurry, uniformly coating the positive slurry on the surface of an aluminum foil current collector to obtain a positive plate, cutting the size of the positive plate to 4cm multiplied by 4cm, and welding a lug.
Dissolving ground natural graphite, mesocarbon microbeads, conductive additive acetylene black, carbon fibers and negative adhesive sodium alginate in water according to the mass ratio of 45:45:3:2:5, uniformly mixing and stirring to obtain negative electrode slurry, uniformly coating the negative electrode slurry on the surface of an aluminum foil current collector to obtain a negative electrode plate, cutting the size of the negative electrode plate to 4cm multiplied by 4cm, and welding a lug.
And sequentially stacking the positive plate, the polypropylene diaphragm and the negative plate to form a battery cell, and loading the battery cell into a shell.
And dissolving sodium hexafluorophosphate in diethylene glycol dimethyl ether to prepare the electrolyte with the concentration of 1 mol/L. And injecting the electrolyte into the shell with the chip, and then packaging the shell to obtain the all-carbon-based mixed alkali metal ion capacitor.
The mass ratio of the positive electrode active material to the negative electrode active material in the all-carbon-based mixed alkali metal ion capacitor of the embodiment is 4:1, that is, the mass ratio of the activated carbon to the natural graphite and the mesocarbon microbeads is 4: 1.
Comparative example 1
Dissolving active carbon serving as a positive electrode active material, acetylene black serving as a conductive additive, carbon fiber and polyvinylidene fluoride serving as a positive electrode binder in methyl pyrrolidone according to a mass ratio of 90:3:2:5, uniformly mixing and stirring to obtain positive electrode slurry, uniformly coating the positive electrode slurry on the surface of an aluminum foil current collector to obtain a positive electrode plate, cutting the size of the positive electrode plate to 4cm multiplied by 4cm, and welding a lug.
Dissolving a negative electrode active material, namely activated carbon, a conductive additive, acetylene black, carbon fiber and a negative electrode binder, namely polyvinylidene fluoride, in methyl pyrrolidone according to a mass ratio of 90:3:2:5, mixing and stirring uniformly to obtain negative electrode slurry, uniformly coating the negative electrode slurry on the surface of an aluminum foil current collector to obtain a negative electrode sheet, cutting the size of the negative electrode sheet to 4cm multiplied by 4cm, and welding a lug.
And sequentially stacking the positive plate, the polypropylene composite diaphragm and the negative plate to form a battery core, and packaging the battery core into a shell.
Tetraethylammonium tetrafluoroborate is dissolved in acetonitrile to prepare electrolyte with the concentration of 1 mol/L. And injecting the electrolyte into the shell with the chip, and packaging the shell to obtain the double-electric-layer super capacitor.
The mass ratio of the positive electrode active material to the negative electrode active material in the electric double layer supercapacitor of this comparative example was 1: 1.
Comparative example 2
Dissolving active carbon serving as a positive electrode active material, acetylene black serving as a conductive additive, carbon fiber and polyvinylidene fluoride serving as a positive electrode binder in methyl pyrrolidone according to a mass ratio of 90:3:2:5, uniformly mixing and stirring to obtain positive electrode slurry, uniformly coating the positive electrode slurry on the surface of an aluminum foil current collector to obtain a positive electrode plate, cutting the size of the positive electrode plate to 4cm multiplied by 4cm, and welding a lug.
Dissolving a negative electrode active material lithium titanate, a conductive additive acetylene black, carbon fiber and a negative electrode binder sodium alginate in water according to a mass ratio of 85:8:2:5, mixing and stirring uniformly to obtain negative electrode slurry, coating the negative electrode slurry on the surface of a copper foil current collector uniformly to obtain a negative electrode sheet, cutting the size of the negative electrode sheet to 4cm multiplied by 4cm, and welding a lug.
And sequentially stacking the positive plate, the polypropylene composite diaphragm and the negative plate to form a battery core, and packaging the battery core into a shell.
Lithium hexafluorophosphate was dissolved in ethylene carbonate and dimethyl carbonate at a volume ratio of 1:1 to prepare an electrolyte solution having a concentration of 1 mol/L. The electrolyte is injected into the above-mentioned case with the chip, and then the case is encapsulated to obtain a conventional hybrid lithium ion capacitor.
The mass ratio of the positive electrode active material to the negative electrode active material in the conventional hybrid lithium ion capacitor of this comparative example is 6:1, that is, the mass ratio of the activated carbon to the lithium titanate is 6: 1.
The all-carbon-based mixed alkali metal ion capacitors prepared in examples 1 to 6, the electric double layer supercapacitor prepared in comparative example 1 and the conventional mixed lithium ion capacitor prepared in comparative example 2 were subjected to a constant current charge and discharge test, a maximum energy density test, an energy density test at high power density and a cycle performance test, and the test results are shown in table one. Wherein the maximum specific capacity and the maximum energy density are calculated based on the sum of the masses of the positive electrode active material and the negative electrode active material; the energy density at high power density means an energy density at an average power density of 8 kW/kg; the cycle stability is 30mA/cm at a current density2Capacity retention after 20000 cycles under the conditions of (1).
Referring to fig. 1-2, the constant current charging and discharging curve of the all-carbon based mixed alkali metal ion capacitor of example 1 is shown in fig. 1, and the constant current charging and discharging curve of the all-carbon based mixed alkali metal ion capacitor of example 2 is shown in fig. 2.
Table one:
as can be seen from the table I, the working voltage of the all-carbon-based mixed alkali metal ion capacitor can reach 4.4V, and the all-carbon-based mixed alkali metal ion capacitor has high energy density, high power density, long cycle life and good stability.
Referring to fig. 3, the cyclic voltammogram of the all-carbon-based mixed alkali metal ion capacitor of example 2 is shown in fig. 3.
As can be seen from fig. 2 and 3, the all-carbon-based mixed alkali metal ion capacitor obtained in example 2 has a plurality of redox peaks resulting from the co-intercalation reaction of cations and solvent molecules in the negative electrode sheet.
Referring to fig. 4 to 5, the negative electrode sheet prepared in example 2 is assembled into a half-cell using a sodium metal sheet as a counter electrode and a reference electrode to perform a graphite negative electrode co-intercalation test, so as to obtain a constant current charge-discharge curve of the negative electrode sheet sodium intercalation reaction, which is shown in fig. 4, and a coulombic efficiency curve of the negative electrode sheet in the first 5 cycles of the negative electrode sheet sodium intercalation reaction, which is shown in fig. 5.
As can be seen from fig. 5, the negative electrode sheet of example 2 has very high first coulombic efficiency, which is as high as 90.1%, and the subsequent cycle coulombic efficiency can reach more than 99.6%.
The positive electrode active material and the negative electrode active material of the all-carbon-based mixed alkali metal ion capacitor are both carbon materials, so that the lithium ions, the sodium ions, the potassium ions and solvent molecules can be jointly embedded into the negative electrode containing graphite, and excellent high-rate performance can be realized. The mass percentage of the graphite in the cathode active material layer of the all-carbon-based mixed alkali metal ion capacitor is greater than or equal to 85%, the occurrence of side reactions can be effectively reduced, the utilization rate of the graphite is as high as 100%, and excessive graphite does not need to be additionally utilized. The cathode binder of the all-carbon-based mixed alkali metal ion capacitor does not use polytetrafluoroethylene, so that the cathode active material shows the first coulombic efficiency of more than 90%. In addition, the all-carbon-based mixed alkali metal ion capacitor is simple in preparation process, the prepared positive plate and the prepared negative plate are directly assembled in a matching mode, no additional active metal electrode needs to be added, any electrochemical pretreatment on the positive plate or the negative plate is not needed in the preparation process, and the manufacturing cost can be effectively saved. The full-carbon-based mixed alkali metal ion capacitor has the advantages of working voltage as high as 4.4V, high energy density, high power density, long cycle life and good stability, and has good application prospect in the field of new energy.
It should be noted that, although the present invention has been described with reference to specific embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. An all-carbon-based mixed alkali metal ion capacitor comprises a positive plate, a negative plate, electrolyte and a diaphragm between the positive plate and the negative plate, wherein the positive plate comprises a positive current collector and a positive active material layer, and the positive active material layer is obtained by mixing a positive active material, a conductive additive and a positive binder in proportion into positive slurry and coating the positive slurry on the positive current collector; this negative pole piece includes negative pole mass flow body and negative pole active material layer, and this negative pole active material layer is through mixing negative pole active material, conductive additive and negative pole binder proportionally into negative pole thick liquids and coating in the negative pole mass flow body and obtain its characterized in that: the positive electrode active material is a carbon material; the negative active material includes, but is not limited to, one or more of natural graphite, artificial graphite, modified natural graphite, and mesocarbon microbeads.
2. The all-carbon based mixed alkali metal ion capacitor of claim 1, wherein: the positive active material includes, but is not limited to, one or more of porous activated carbon, nanocarbon, graphene, and mesoporous carbon.
3. The all-carbon based mixed alkali metal ion capacitor of claim 1, wherein: the mass percentage of the graphite in the negative active material layer is more than or equal to 85 percent.
4. The all-carbon based mixed alkali metal ion capacitor of claim 1, wherein: in the all-carbon-based mixed alkali metal ion capacitor, the mass ratio of the positive electrode active material to the negative electrode active material is in a range of (3:1) to (10: 1).
5. The all-carbon based mixed alkali metal ion capacitor of claim 1, wherein: the negative electrode binder comprises one or more of carboxylic styrene-butadiene latex, sodium carboxymethylcellulose, sodium alginate, polyvinylidene fluoride and polyacrylic acid.
6. A manufacturing method of an all-carbon-based mixed alkali metal ion capacitor comprises the following steps:
step S1: providing a positive electrode active material, a conductive additive, a positive electrode binder and a positive electrode current collector, wherein the positive electrode active material is a carbon material, mixing the positive electrode active material, the conductive additive and the positive electrode binder in proportion to obtain positive electrode slurry, coating the positive electrode slurry on the surface of the positive electrode current collector to obtain a positive electrode plate, and welding a lug on the positive electrode plate;
step S2: providing a negative electrode active material, a conductive additive, a negative electrode binder and a negative electrode current collector, wherein the negative electrode active material comprises but is not limited to one or more of natural graphite, artificial graphite, modified natural graphite and mesocarbon microbeads, mixing the negative electrode active material, the conductive additive and the negative electrode binder in proportion to obtain negative electrode slurry, coating the negative electrode slurry on the surface of the negative electrode current collector to obtain a negative electrode sheet, and welding a lug on the negative electrode sheet;
step S3: providing a diaphragm, and sequentially stacking the positive plate, the diaphragm and the negative plate in sequence to manufacture a battery cell;
step S4: providing a shell and an electrolyte, wherein cations in the electrolyte are lithium ions, sodium ions or potassium ions, and anions in the electrolyte comprise but are not limited to one or more of hexafluorophosphate radicals, perchloric acid, tetrafluoroborate radicals and bis (trifluoromethanesulfonyl) imide radicals, filling the battery cell into the shell, injecting the electrolyte into the shell, and then packaging the shell to obtain the all-carbon-based mixed alkali metal ion capacitor.
7. The method of manufacturing an all-carbon-based mixed alkali metal ion capacitor according to claim 6, wherein: the positive active material includes, but is not limited to, one or more of porous activated carbon, nanocarbon, graphene, and mesoporous carbon.
8. The method of manufacturing an all-carbon-based mixed alkali metal ion capacitor according to claim 6, wherein: the mass percentage of the graphite in the negative active material layer is more than or equal to 85 percent.
9. The method of manufacturing an all-carbon-based mixed alkali metal ion capacitor according to claim 6, wherein: in the all-carbon-based mixed alkali metal ion capacitor, the mass ratio of the positive electrode active material to the negative electrode active material is in a range of (3:1) to (10: 1).
10. The method of manufacturing an all-carbon-based mixed alkali metal ion capacitor according to claim 6, wherein: the negative electrode binder comprises one or more of carboxylic styrene-butadiene latex, sodium carboxymethylcellulose, sodium alginate, polyvinylidene fluoride and polyacrylic acid.
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