CN117153576B - Preparation method of solid lithium ion capacitor based on double-doped activated carbon - Google Patents
Preparation method of solid lithium ion capacitor based on double-doped activated carbon Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 95
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 95
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007787 solid Substances 0.000 title claims abstract description 14
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- 229910052799 carbon Inorganic materials 0.000 claims abstract description 38
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims abstract description 20
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- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011245 gel electrolyte Substances 0.000 claims abstract description 9
- 238000006138 lithiation reaction Methods 0.000 claims abstract description 5
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 52
- 238000001035 drying Methods 0.000 claims description 41
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 40
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- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
-
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- 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
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
A preparation method of a solid lithium ion capacitor based on double-doped active carbon relates to a preparation method of a solid lithium ion capacitor. The invention aims to solve the problems of low capacity and power density and unsafe electrolyte of the lithium ion capacitor caused by unmatched anode-cathode reaction dynamics of the existing lithium ion capacitor. The method comprises the following steps: 1. preparing nitrogen-sulfur doped porous carbon; 2. preparing a gel electrolyte; 3. preparing positive and negative electrode plates; 4. pre-lithiation; 5. and assembling the battery to obtain the button gel lithium ion capacitor and the soft package gel lithium ion capacitor. The nitrogen-sulfur doped porous carbon prepared by taking the corn straw as the raw material is used as the electrode material of the negative electrode of the lithium ion capacitor, so that the problem of slow dynamics of the negative electrode material is solved, and the corn straw raw material with high yield and low cost is adopted, so that the large-scale production of LIC is facilitated. The invention can obtain a solid lithium ion capacitor based on double-doped active carbon.
Description
Technical Field
The invention relates to a preparation method of a solid lithium ion capacitor.
Background
Lithium Ion Capacitors (LIC) have high energy density, combined with high power density and long cycle life, and are considered as important technologies to meet the storage requirements of portable electronics, hybrid electric vehicles, and large-scale power grids. The global LIC development work began in the beginning of the 21 st century and Japanese JM Energy company in 2007 became the first manufacturer in the world to produce and sell LIC. At the end of 2008, various companies such as japanese chemical industry electronics, japanese ACT (advanced capacitor technology), japanese electric company NEC, japanese JM Energy, japanese FDK, japanese solar induction, and the like are developing LIC products.
Electrode materials applied to LIC include capacitive materials and battery-type materials. The capacitive electrode is typically carbon-based including commercial Activated Carbon (AC), biomass carbon, graphene, carbon nanotubes, template carbon, and the like. The battery type electrode material mainly includes alloy, conversion and embedded type materials. The capacitance type material has good conductivity, and the dynamics of embedding and extraction is lower than that of the battery type electrode material.
The commercialized LIC adopts organic liquid electrolyte, which is easy to leak to cause safety accidents such as combustion and explosion. The solid electrolyte comprises gel electrolyte and all-solid electrolyte, and can effectively improve the safety performance of the device by replacing liquid organic electrolyte. The gel electrolyte has high conductivity of liquid electrolyte and high safety of all-solid electrolyte, so that the gel electrolyte has important practical application value in LIC. Compared with button cells, the soft-package battery has high energy density, good safety and excellent heat dissipation performance, and has the advantages of quick charge, battery system integration, low-temperature performance and the like, thereby being a preferential choice of new energy passenger cars.
The challenge with lithium ion capacitors is mainly that the kinetic mismatch between slow diffusion of lithium ions at the battery electrode terminal and fast adsorption/desorption at the capacitive electrode terminal results in energy density and power density that are difficult to achieve in an ideal state. For example: the capacity of the lithium ion capacitor assembled by the traditional graphite and the active carbon is not high, and is difficult to reach 40mAh/g, and the rate of lithium ions which are intercalated into and deintercalated from the graphite cathode is relatively slow, so that the multiplying power performance is poor, and the voltage platform of the graphite is very low, the voltage interval which is generally selected is relatively narrow and is generally 2-4V, and the highest energy density is 97.9Wh/kg, and the power density is about 109.8W/kg. At present, a plurality of relevant scholars at home and abroad conduct extensive researches on the problem, including schemes of controlling the size of electrode materials, optimizing conductivity, doping hetero atoms and the like. Current research on lithium ion capacitors has focused mainly on the study of negative electrode materials, with metal oxides being the dominant. For example: niobium pentoxide, manganese dioxide, and the like. Metal oxides have high capacity but poor electrical conductivity, and composite materials of metal oxides have been the subject of research in recent years. However, this strategy makes the preparation process more complex and cost prohibitive.
Disclosure of Invention
The invention aims to solve the problems of low capacity and power density and unsafe electrolyte of the existing lithium ion capacitor caused by unmatched anode and cathode reaction dynamics of the lithium ion capacitor, and provides a preparation method of a solid lithium ion capacitor based on double-doped active carbon.
The invention adopts corn straw as a carbon source to prepare nitrogen-sulfur co-doped porous carbon to relieve the problem of low capacity and power density of a lithium ion capacitor caused by slow intercalation and deintercalation kinetics of a graphite anode material of the lithium ion capacitor, and simultaneously adopts a PVDF-HFP/PAN solid electrolyte film which has good elasticity, is easy to form a film and is nonflammable to replace a traditional commercial diaphragm to improve the safety performance of the lithium ion capacitor, and in particular, the preparation method of the solid lithium ion capacitor based on double-doped active carbon is completed according to the following steps:
1. preparing nitrogen-sulfur doped porous carbon:
(1) immersing corn stalks in a dilute sulfuric acid solution, then preserving the corn stalks in an oven at 170-180 ℃ for a period of time, cleaning a reactant product to be neutral, and drying to obtain dark brown powder; adding a sulfur source, a nitrogen source and potassium hydroxide into water, adding dark brown powder, and uniformly stirring to obtain a mixed solution;
(2) transferring the mixed solution into a vacuum oven for drying until a solid mixture is formed; placing the solid mixture into a porcelain boat, transferring the porcelain boat into a tube furnace, heating to a sintering temperature under the protection of nitrogen atmosphere, and calcining at the sintering temperature to obtain nitrogen-sulfur doped porous carbon;
2. preparing a gel electrolyte:
(1) firstly, drying PVDF-HFP and PAN, then adding a certain amount of PVDF-HFP and PAN into DMF, heating in a water bath, and stirring for a period of time to obtain membrane preparation liquid;
(2) sequentially carrying out ultrasonic treatment and vacuumizing on the film-forming liquid to remove internal bubbles, thereby obtaining the film-forming liquid with the bubbles removed;
(3) uniformly coating the bubble-removed film-forming liquid on a flat and smooth glass plate to form a wet film, then placing the glass plate into deionized water for phase inversion, taking out the glass plate from the deionized water after the phase inversion is finished, wiping off surface moisture by using filter paper, airing at normal temperature, and finally placing the glass plate into an oven for drying to obtain the PVDF-HFP/PAN gel film;
3. preparing positive and negative electrode plates:
(1) preparing a negative electrode plate:
mixing nitrogen-sulfur doped porous carbon, conductive carbon black and polyvinylidene fluoride, grinding at room temperature, then dropwise adding N-methyl-2-pyrrolidone, and stirring to obtain slurry; coating the slurry on a copper foil, drying, and rolling by using a rolling machine to obtain a negative electrode plate;
(2) preparing a positive electrode plate:
mixing commercial activated carbon, conductive carbon black and polyvinylidene fluoride, grinding at room temperature, then dropwise adding N-methyl-2-pyrrolidone, and stirring to obtain slurry; coating the slurry on a copper foil, drying, and rolling by using a rolling machine to obtain an anode electrode plate;
4. pre-lithiation: firstly, laminating a negative electrode plate, a diaphragm and a lithium belt, shorting the negative electrode plate and the lithium belt, and then placing the short circuit into electrolyte for a period of time to obtain a pre-lithiated negative electrode plate;
5. and (3) battery assembly:
and forming the buckle type gel lithium ion capacitor and the soft package gel lithium ion capacitor by the positive electrode plate, the pre-lithiated negative electrode plate and the PVDF-HFP/PAN gel film.
The principle of the invention is as follows:
the nitrogen-sulfur doped porous carbon prepared by taking the corn straw as the raw material is used as the electrode material of the negative electrode of the lithium ion capacitor, so that the problem of slow dynamics of the negative electrode material is solved, and the corn straw raw material with high yield and low cost is adopted, so that the large-scale production of LIC is facilitated; the PVDF-HFP/PAN gel electrolyte designed by the invention can replace the traditional commercial diaphragm, can improve the safety performance of a lithium ion capacitor device, and provides technical support for realizing a safe solid lithium ion capacitor with excellent power density and service life under a certain energy density.
The invention has the advantages that:
1. firstly, corn straw is used as a raw material to prepare nitrogen-sulfur doped porous carbon as a negative electrode material of a lithium ion capacitor, so that the problem of unmatched positive and negative electrode dynamics can be well solved, a capacitor electrode stores and releases charges by utilizing physical adsorption and desorption, the generation process is faster, a battery electrode stores or releases charges by utilizing reversible electrochemical reaction, the generation process is slower, and the problem of unmatched positive and negative electrode dynamics of LIC is caused, so that the power density of the lithium ion capacitor is influenced; the key to solving the entire problem requires two aspects to be grasped. First: the conductivity of the battery type electrode is improved or a material with higher conductivity is adopted, and the electrode material with high conductivity can be used for improving the condition that a large amount of electrons are extracted from a current collector in a short time; by comprehensively considering the two points, the nitrogen-sulfur doped porous carbon can be well satisfied by nanocrystallization, so that the problem of matching of the anode-cathode kinetic ratio of LIC is solved;
2. secondly, the electrolyte of the traditional lithium ion capacitor adopts the organic electrolyte of a lithium battery, and the organic electrolyte is toxic and inflammable, and if leakage, internal circuits of the battery and the like occur, serious safety accidents can be caused when naked flame is encountered; therefore, the traditional lithium ion capacitor also has the safety problem, and the PVDF-HFP/PAN solid electrolyte film is adopted to replace the traditional commercial diaphragm, so that the electrolyte can be locked in the diaphragm, and the problem of electrolyte leakage can be well solved; and meanwhile, the PVDF-HFP/PAN solid electrolyte film has the characteristics of good elasticity, easiness in film formation, nonflammability and the like, and can well solve the safety problem of the lithium ion capacitor.
Drawings
FIG. 1 is a microscopic morphology of the PVDF-HFP/PAN gel film prepared in step two of example 1, wherein a is an SEM image of the front side of the PVDF-HFP/PAN gel film and b is a cross-sectional scanning electron microscope image of the PVDF-HFP/PAN gel film;
FIG. 2 is a microscopic morphology chart of CNSN prepared in the first step of example 1 and CNN prepared in the comparative example 2 under different magnifications, wherein a and b are CNNs, c and d are CNSNs;
FIG. 3 is an XRD spectrum of CNN and CNSN;
fig. 4 is an XPS spectrum of CNSN, wherein a is a nitrogen element spectrum, and b is a sulfur element spectrum;
fig. 5 is charge and discharge curves of the snap gel lithium ion capacitor SNLIC prepared in example 1 and the snap gel lithium ion capacitor ACLIC prepared in comparative example 1 at different current densities;
FIG. 6 is a graph showing the cycle performance at 1000mA/g of the snap gel lithium ion capacitor SNLIC prepared in example 1 and the snap gel lithium ion capacitor ACLIC prepared in comparative example 1;
fig. 7 is a graph showing energy density comparisons of the snap gel lithium ion capacitor SNLIC prepared in example 1 and the snap gel lithium ion capacitor ACLIC prepared in comparative example 1 at different power densities;
fig. 8 is a graph showing the rate performance of the snap gel lithium ion capacitor SNLIC prepared in example 1 and the snap gel lithium ion capacitor ACLIC prepared in comparative example 1 at different current densities;
fig. 9 is a graph showing the long cycle performance at 1000mA/g of the snap gel lithium ion capacitor SNLIC prepared in example 1 and the snap gel lithium ion capacitor ACLIC prepared in comparative example 1;
fig. 10 is a graph showing CV curves of the snap gel lithium ion capacitor SNLIC prepared in example 1 and the snap gel lithium ion capacitor ACLIC prepared in comparative example 1 at different sweep rates;
FIG. 11 is a graph showing the cycle performance of the soft pack gel lithium ion capacitor SNLIC prepared in example 2 and the buckle gel lithium ion capacitor ACLIC prepared in comparative example 1 at 1000 mA/g;
fig. 12 is a graph showing the long cycle performance at 1000mA/g of the soft pack gel lithium ion capacitor SNLIC prepared in example 2 and the buckle gel lithium ion capacitor ACLIC prepared in comparative example 1.
Detailed Description
The first embodiment is as follows: the preparation method of the solid lithium ion capacitor based on the double-doped active carbon is completed according to the following steps:
1. preparing nitrogen-sulfur doped porous carbon:
(1) immersing corn stalks in a dilute sulfuric acid solution, then preserving the corn stalks in an oven at 170-180 ℃ for a period of time, cleaning a reactant product to be neutral, and drying to obtain dark brown powder; adding a sulfur source, a nitrogen source and potassium hydroxide into water, adding dark brown powder, and uniformly stirring to obtain a mixed solution;
(2) transferring the mixed solution into a vacuum oven for drying until a solid mixture is formed; placing the solid mixture into a porcelain boat, transferring the porcelain boat into a tube furnace, heating to a sintering temperature under the protection of nitrogen atmosphere, and calcining at the sintering temperature to obtain nitrogen-sulfur doped porous carbon;
2. preparing a gel electrolyte:
(1) firstly, drying PVDF-HFP and PAN, then adding a certain amount of PVDF-HFP and PAN into DMF, heating in a water bath, and stirring for a period of time to obtain membrane preparation liquid;
(2) sequentially carrying out ultrasonic treatment and vacuumizing on the film-forming liquid to remove internal bubbles, thereby obtaining the film-forming liquid with the bubbles removed;
(3) uniformly coating the bubble-removed film-forming liquid on a flat and smooth glass plate to form a wet film, then placing the glass plate into deionized water for phase inversion, taking out the glass plate from the deionized water after the phase inversion is finished, wiping off surface moisture by using filter paper, airing at normal temperature, and finally placing the glass plate into an oven for drying to obtain the PVDF-HFP/PAN gel film;
3. preparing positive and negative electrode plates:
(1) preparing a negative electrode plate:
mixing nitrogen-sulfur doped porous carbon, conductive carbon black and polyvinylidene fluoride, grinding at room temperature, then dropwise adding N-methyl-2-pyrrolidone, and stirring to obtain slurry; coating the slurry on a copper foil, drying, and rolling by using a rolling machine to obtain a negative electrode plate;
(2) preparing a positive electrode plate:
mixing commercial activated carbon, conductive carbon black and polyvinylidene fluoride, grinding at room temperature, then dropwise adding N-methyl-2-pyrrolidone, and stirring to obtain slurry; coating the slurry on a copper foil, drying, and rolling by using a rolling machine to obtain an anode electrode plate;
4. pre-lithiation: firstly, laminating a negative electrode plate, a diaphragm and a lithium belt, shorting the negative electrode plate and the lithium belt, and then placing the short circuit into electrolyte for a period of time to obtain a pre-lithiated negative electrode plate;
5. and (3) battery assembly:
and forming the buckle type gel lithium ion capacitor and the soft package gel lithium ion capacitor by the positive electrode plate, the pre-lithiated negative electrode plate and the PVDF-HFP/PAN gel film.
The second embodiment is as follows: the present embodiment differs from the specific embodiment in that: the mass fraction of the dilute sulfuric acid solution in the step one (1) is 5%; the preservation time in the step one (1) is 16-18 h. The other steps are the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: the sulfur source in the step one (1) is thiourea; the nitrogen source in the step one (1) is thiourea; the mass ratio of the corn stalk to the sulfur source to the nitrogen source to the potassium hydroxide in the step one (1) is 1 (1-1.5) (2-2.5); the volume ratio of the sulfur source substance to water in the step one (1) is (0.5-0.6) (1-1.1). The other steps are the same as those of the first or second embodiment.
The specific embodiment IV is as follows: one difference between this embodiment and the first to third embodiments is that: the temperature of the vacuum oven in the step one (2) is 100-105 ℃; the temperature rising speed in the step one (2) is 5 ℃ for min -1 ～10℃min -1 The method comprises the steps of carrying out a first treatment on the surface of the The sintering temperature in the step one (2) is 800-1000 ℃; the calcination time in the step one (2) is 3-5 h. The other steps are the same as those of the first to third embodiments.
Fifth embodiment: one to four differences between the present embodiment and the specific embodiment are: the drying in the step two (1) is carried out in an oven at 70-80 ℃ for 12-24 h; the mass ratio of PVDF-HFP to PAN in the second step (1) is 9:1; the volume ratio of PVDF-HFP to DMF in the second step (1) is (0.7 g-1 g) (4 mL-5 mL); the temperature of the water bath heating in the second step (1) is 45-50 ℃; and (3) stirring in the second step (1) for 4-6 hours. Other steps are the same as those of the first to fourth embodiments.
Specific embodiment six: the present embodiment differs from the first to fifth embodiments in that: the phase inversion time in the second step (3) is 22-24 hours; the temperature of drying in the baking oven in the second step (3) is 45-50 ℃, and the drying time is 22-24 hours; the PVDF-HFP/PAN gel film in step two (3) has a thickness of 100-120 microns. Other steps are the same as those of the first to fifth embodiments.
Seventh embodiment: one difference between the present embodiment and the first to sixth embodiments is that: the total mass ratio of the volume of the N-methyl-2-pyrrolidone to the nitrogen-sulfur doped porous carbon, the conductive carbon black and the polyvinylidene fluoride in the step III (1) is (4-5 mL) (0.9-1 g); step three (1), mixing nitrogen-sulfur doped porous carbon, conductive carbon black and polyvinylidene fluoride according to the mass ratio of 8:1:1, grinding for 0.5-1 h at room temperature, then dropwise adding N-methyl-2-pyrrolidone, and stirring for 5.5-6 h on a magnetic stirrer at the stirring speed of 450r/min to obtain slurry; coating the slurry on copper foil, drying at 65-70 ℃ for 6-8 hours, and rolling by a rolling machine to obtain a negative electrode plate; the thickness of the film on the negative electrode plate is 30-35 mu m. Other steps are the same as those of embodiments one to six.
Eighth embodiment: one difference between the present embodiment and the first to seventh embodiments is that: the volume of the N-methyl-2-pyrrolidone in the step III (2) and the total mass ratio of the commercial activated carbon, the conductive carbon black and the polyvinylidene fluoride are (4-5 mL) to (0.9-1 g); mixing commercial activated carbon, conductive carbon black and polyvinylidene fluoride according to the mass ratio of 8:1:1, grinding for 0.5-1 h at room temperature, then dropwise adding N-methyl-2-pyrrolidone, and stirring for 6-8 h on a magnetic stirrer at the stirring speed of 450r/min to obtain slurry; coating the slurry on copper foil, drying at 70-80 ℃ for 6-8 hours, and rolling by a rolling machine to obtain an anode electrode plate; the thickness of the upper film of the positive electrode plate is 28-32 mu m. The other steps are the same as those of embodiments one to seven.
Detailed description nine: one of the differences between this embodiment and the first to eighth embodiments is: the time for placing the electrolyte in the fourth step is 45-48 hours; the electrolyte in the fourth step is LiPF 6 Dissolving in a mixed solvent; the mixed solvent is prepared by mixing EC, DEC and EMC according to a volume ratio of 1:1:1; liPF in the electrolyte 6 The concentration of (2) is 1mol/L; the diaphragm in the fourth step is a PP isolating film or a PE isolating film, and the thickness is 20 mu m; the assembling method of the buckle gel lithium ion capacitor in the fifth step comprises the following steps: (1) immersing the PVDF-HFP/PAN gel film into the electrolyte for 2-3 h to obtain the PVDF-HFP/PAN gel film immersed in the electrolyte; the electrolyte is LiPF 6 Dissolving in a mixed solvent; the mixed solvent is prepared by mixing EC, DEC and EMC according to a volume ratio of 1:1:1; liPF in the electrolyte 6 The concentration of (2) is 1mol/L; (2) and assembling the battery in a glove box filled with argon, sequentially placing the positive electrode plate, the PVDF-HFP/PAN gel film soaked in the electrolyte, the pre-lithiated negative electrode plate, the gasket and the spring piece between the positive electrode shell and the negative electrode shell, and compacting the negative electrode plate and the positive electrode plate by using a die to obtain the buckling gel lithium ion capacitor. Other steps are the same as those of embodiments one to eight.
Detailed description ten: the present embodiment differs from the first to ninth embodiments in that: the method for assembling the soft package gel lithium ion capacitor in the fifth step comprises the following steps: (1) punching the positive electrode plate and the pre-lithiated negative electrode plate, and then laminating the positive electrode plate and the pre-lithiated negative electrode plate according to the sequence of the negative electrode plate, namely PVDF-HFP/PAN gel film; (2) welding the positive electrode plate and the aluminum electrode lug, welding the negative electrode plate and the nickel electrode lug, and then attaching high-temperature insulating glue to fix the welding standard to prevent short circuit to obtain the battery cell; (3) packaging the battery cell in an aluminum plastic bag, and filling argon gasDropwise adding excessive electrolyte into a glove box to fully soak the PVDF-HFP/PAN gel film with the electrolyte, extruding the excessive electrolyte from an aluminum-plastic bag after 2-3 hours, and finally extracting vacuum and sealing to obtain the soft-package gel lithium ion capacitor; the electrolyte in the step (3) is LiPF 6 Dissolving in a mixed solvent; the mixed solvent is prepared by mixing EC, DEC and EMC according to a volume ratio of 1:1:1; liPF in the electrolyte 6 The concentration of (C) was 1mol/L. The other steps are the same as those of embodiments one to nine.
The following examples are used to verify the benefits of the present invention:
example 1: the preparation method of the button gel lithium ion capacitor (SNLIC) is completed according to the following steps:
1. preparing nitrogen-sulfur doped porous carbon:
(1) immersing corn stalks in a dilute sulfuric acid solution, then preserving the corn stalks in an oven at 180 ℃ for 18 hours, washing reactant products to be neutral by using deionized water, and drying to obtain dark brown powder; adding a sulfur source, a nitrogen source and potassium hydroxide into water, adding dark brown powder, and uniformly stirring to obtain a mixed solution;
the mass fraction of the dilute sulfuric acid solution in the step one (1) is 5%;
the sulfur source in the step one (1) is thiourea;
the nitrogen source in the step one (1) is thiourea;
the mass ratio of the corn stalks to the sulfur source to the nitrogen source to the potassium hydroxide in the step one (1) is 1:1.2:1.2:2.5;
the volume ratio of the sulfur source substance to water in the step (1) is 0.6:1;
(2) transferring the mixed solution into a vacuum oven for drying until a solid mixture is formed; placing the solid mixture into a porcelain boat, transferring the porcelain boat into a tube furnace, heating to a sintering temperature under the protection of nitrogen atmosphere, and calcining at the sintering temperature to obtain nitrogen-sulfur doped porous Carbon (CNSN);
the temperature of the vacuum oven in the step one (2) is 105 ℃;
the step one (2)The temperature rise rate of (2) is 5 ℃ min -1 ；
The sintering temperature in the step one (2) is 800 ℃;
the calcination time in the step one (2) is 3 hours;
2. preparing a gel electrolyte:
(1) firstly, drying PVDF-HFP and PAN, then adding a certain amount of PVDF-HFP and PAN into DMF, heating in a water bath, and stirring for a period of time to obtain membrane preparation liquid;
the drying in the step two (1) is carried out in an oven at 70 ℃ for 24 hours;
the mass ratio of PVDF-HFP to PAN in the second step (1) is 9:1;
the volume ratio of PVDF-HFP to DMF in the second step (1) is 0.9g:4.7mL;
the temperature of the water bath heating in the step two (1) is 50 ℃;
the stirring time in the second step (1) is 6 hours;
(2) sequentially carrying out ultrasonic treatment and vacuumizing on the film-forming liquid to remove internal bubbles, thereby obtaining the film-forming liquid with the bubbles removed;
(3) uniformly coating the bubble-removed film-forming liquid on a flat and smooth glass plate to form a wet film, then placing the glass plate into deionized water for phase inversion, taking out the glass plate from the deionized water after the phase inversion is finished, wiping off surface moisture by using filter paper, airing at normal temperature, and finally placing the glass plate into an oven for drying to obtain the PVDF-HFP/PAN gel film;
the phase inversion time in the second step (3) is 24 hours;
the temperature of the drying in the drying oven in the second step (3) is 50 ℃, and the drying time is 24 hours;
the PVDF-HFP/PAN gel film in step two (3) has a thickness of 120 microns;
3. preparing positive and negative electrode plates:
(1) preparing a negative electrode plate:
mixing nitrogen-sulfur doped porous carbon, conductive carbon black and polyvinylidene fluoride according to the mass ratio of 8:1:1, grinding for 1h at room temperature, then dropwise adding N-methyl-2-pyrrolidone, and stirring for 6h on a magnetic stirrer at the stirring speed of 450r/min to obtain slurry; coating the slurry on a copper foil, drying at 70 ℃ for 8 hours, and rolling by using a rolling machine to obtain a negative electrode plate; the thickness of the upper film of the negative electrode plate is 32 mu m;
the total mass ratio of the volume of the N-methyl-2-pyrrolidone to the nitrogen-sulfur doped porous carbon, the conductive carbon black and the polyvinylidene fluoride in the step (1) is 4.6m to 1g;
(2) preparing a positive electrode plate:
mixing commercial activated carbon, conductive carbon black and polyvinylidene fluoride according to the mass ratio of 8:1:1, grinding for 1h at room temperature, then dropwise adding N-methyl-2-pyrrolidone, and stirring for 6h on a magnetic stirrer at the stirring speed of 450r/min to obtain slurry; coating the slurry on a copper foil, drying at 70 ℃ for 8 hours, and rolling by using a rolling machine to obtain a positive electrode plate; the thickness of the upper film of the positive electrode plate is 29 mu m;
the volume of the N-methyl-2-pyrrolidone in the step three (2) to the total mass ratio of the commercial activated carbon, the conductive carbon black and the polyvinylidene fluoride is 4.7 mL/1 g;
4. pre-lithiation: firstly, laminating a negative electrode plate, a diaphragm and a lithium belt, shorting the negative electrode plate and the lithium belt, and then placing the short circuit into electrolyte for a period of time to obtain a pre-lithiated negative electrode plate;
the time for placing the electrolyte in the fourth step is 48 hours;
the electrolyte in the fourth step is LiPF 6 Dissolving in a mixed solvent; the mixed solvent is prepared by mixing EC, DEC and EMC according to a volume ratio of 1:1:1; liPF in the electrolyte 6 The concentration of (2) is 1mol/L;
the diaphragm in the fourth step is a PP isolating diaphragm with the thickness of 20 mu m;
5. and (3) battery assembly:
forming a button gel lithium ion capacitor by the positive electrode plate, the pre-lithiated negative electrode plate and the PVDF-HFP/PAN gel film;
the assembling method of the buckle gel lithium ion capacitor in the fifth step comprises the following steps:
(1) immersing the PVDF-HFP/PAN gel film into the electrolyte for 2 hours to obtain the PVDF-HFP/PAN gel film immersed in the electrolyte; the electrolyte is LiPF 6 Dissolving in a mixed solvent; the mixed solvent is prepared by mixing EC, DEC and EMC according to a volume ratio of 1:1:1; liPF in the electrolyte 6 The concentration of (2) is 1mol/L;
(2) and assembling the battery in a glove box filled with argon, sequentially placing the positive electrode plate, the PVDF-HFP/PAN gel film soaked in the electrolyte, the pre-lithiated negative electrode plate, the gasket and the spring piece between the positive electrode shell and the negative electrode shell, and then compacting the negative electrode plate and the positive electrode plate by using a die to obtain the button gel lithium ion capacitor (SNLIC).
Comparative example 1: the preparation method of the buckle gel lithium ion capacitor ACLIC is different from that of example 1 in that: step three (1), preparing a negative electrode plate: mixing commercial activated carbon, conductive carbon black and polyvinylidene fluoride according to the mass ratio of 8:1:1, grinding for 1h at room temperature, then dropwise adding N-methyl-2-pyrrolidone, and stirring for 6h on a magnetic stirrer at the stirring speed of 450r/min to obtain slurry; coating the slurry on a copper foil, drying at 70 ℃ for 8 hours, and rolling by using a rolling machine to obtain a negative electrode plate; the thickness of the upper film of the negative electrode plate is 32 mu m; the volume of N-methyl-2-pyrrolidone described in step three (1) was 4.6m to 1g of the total mass ratio of commercial activated carbon, conductive carbon black, and polyvinylidene fluoride. Other steps and parameters were the same as in example 1.
Example 2: the preparation method of the soft-package gel lithium ion capacitor SNLIC is different from that of example 1 in that: forming a soft package gel lithium ion capacitor SNLIC by the positive electrode plate, the pre-lithiated negative electrode plate and the PVDF-HFP/PAN gel film;
the method for assembling the soft package gel lithium ion capacitor in the fifth step comprises the following steps:
(1) punching the positive electrode plate and the pre-lithiated negative electrode plate, and then laminating the positive electrode plate and the pre-lithiated negative electrode plate according to the sequence of the negative electrode plate, namely PVDF-HFP/PAN gel film;
(2) welding the positive electrode plate and the aluminum electrode lug, welding the negative electrode plate and the nickel electrode lug, and then attaching high-temperature insulating glue to fix the welding standard to prevent short circuit to obtain the battery cell;
(3) placing the battery cell into an aluminum-plastic bag for packaging, then dripping excessive electrolyte into a glove box filled with argon so that the electrolyte is fully soaked in the PVDF-HFP/PAN gel film, extruding the excessive electrolyte from the aluminum-plastic bag after 2 hours, and finally extracting vacuum and sealing to obtain the soft package gel lithium ion capacitor;
the electrolyte in the step (3) is LiPF 6 Dissolving in a mixed solvent; the mixed solvent is prepared by mixing EC, DEC and EMC according to a volume ratio of 1:1:1; liPF in the electrolyte 6 The concentration of (C) was 1mol/L. Other steps and parameters were the same as in example 1.
Comparative example 2: the preparation method of the N-doped activated Carbon (CNN) is completed by the following steps:
1. preparing nitrogen-sulfur doped porous carbon:
(1) immersing corn stalks in a dilute sulfuric acid solution, then preserving the corn stalks in an oven at 180 ℃ for 18 hours, washing reactant products to be neutral by using deionized water, and drying to obtain dark brown powder; adding a nitrogen source and potassium hydroxide into water, adding dark brown powder, and uniformly stirring to obtain a mixed solution;
the mass fraction of the dilute sulfuric acid solution in the step one (1) is 5%;
the nitrogen source in the step one (1) is urea;
the mass ratio of the corn stalks to the nitrogen source to the potassium hydroxide in the step one (1) is 1:1.2:2.5;
the volume ratio of the amount of the nitrogen source substance to water in the step one (1) is 0.6:1;
(2) transferring the mixed solution into a vacuum oven for drying until a solid mixture is formed; placing the solid mixture into a porcelain boat, transferring the porcelain boat into a tube furnace, heating to a sintering temperature under the protection of nitrogen atmosphere, and calcining at the sintering temperature to obtain nitrogen-sulfur doped porous Carbon (CNN);
the temperature of the vacuum oven in the step one (2) is 105 ℃;
the temperature rising speed in the step one (2) is 5 ℃ for min -1 ；
The sintering temperature in the step one (2) is 800 ℃;
the calcination time in step one (2) was 3h.
FIG. 1 is a microscopic morphology of the PVDF-HFP/PAN gel film prepared in step two of example 1, wherein a is an SEM image of the front side of the PVDF-HFP/PAN gel film and b is a cross-sectional scanning electron microscope image of the PVDF-HFP/PAN gel film;
as can be seen from fig. 1: forming a plurality of pores with the size of 0.1-1 mu m on the surface of the PVDF-HFP/PAN gel film after phase conversion; it can also be seen from the sectional electron microscopy that a number of pores are also distributed within the membrane to form interconnecting channels, which facilitate penetration of the electrolyte to increase the electrolyte's wicking.
FIG. 2 is a microscopic morphology chart of CNSN prepared in the first step of example 1 and CNN prepared in the comparative example 2 under different magnifications, wherein a and b are CNNs, c and d are CNSNs;
as can be seen from figure 2, the CNSN morphology takes on a bulk shape, with a size of about 10 μm.
FIG. 3 is an XRD spectrum of CNN and CNSN;
as can be seen from fig. 3: due to the large number of pore structures, the XRD patterns of the two materials do not show obvious characteristic peaks, but rather show broad peaks between 20 DEG to 30 DEG and 40 DEG to 50 deg.
Fig. 4 is an XPS spectrum of CNSN, wherein a is a nitrogen element spectrum, and b is a sulfur element spectrum;
the N1s orbitals shown in FIG. 4a can be fit to N Ⅰ 398.5eV and N Ⅱ ～400.2eV，N Ⅲ A peak of about 402.2eV, which is related to the interaction between the carbon element and the nitrogen element, and represents the nitrogen element in the porous material. Similar to fig. 4a, fig. 4b demonstrates the presence of elemental sulfur within the porous material.
Fig. 5 is charge and discharge curves of the snap gel lithium ion capacitor SNLIC prepared in example 1 and the snap gel lithium ion capacitor ACLIC prepared in comparative example 1 at different current densities;
in FIG. 5, the current densities are respectively 0.1A/g, 0.3A/g, 0.5A/g, 1A/g, 2A/g, 5A/g and 8A/g, and the current density is respectively charged and discharged, and the current density is cycled ten times; as can be seen from FIG. 5, SNLIC provides a specific capacity of approximately 46mAh/g at 0.1A/g and 20mAh/g even at 8A/g, which is superior to ACLIC at different current densities.
FIG. 6 is a graph showing the cycle performance at 1000mA/g of the snap gel lithium ion capacitor SNLIC prepared in example 1 and the snap gel lithium ion capacitor ACLIC prepared in comparative example 1;
as can be seen from fig. 6: the cycling performance of both lithium ion capacitors at 1A/g, it can be seen that the capacity retention of SNLIC after 2000 cycles is 89% better than that of ACLIC.
Fig. 7 is a graph showing energy density comparisons of the snap gel lithium ion capacitor SNLIC prepared in example 1 and the snap gel lithium ion capacitor ACLIC prepared in comparative example 1 at different power densities;
as can be seen from fig. 7: at different power densities, SNLIC has a higher energy density than ACLIC.
Fig. 8 is a graph showing the rate performance of the snap gel lithium ion capacitor SNLIC prepared in example 1 and the snap gel lithium ion capacitor ACLIC prepared in comparative example 1 at different current densities;
from fig. 8, it can be seen that the charge and discharge curves represented at different current densities are diagonal lines, which proves that the energy storage mechanism is not changed at different current densities.
Fig. 9 is a graph showing the long cycle performance at 1000mA/g of the snap gel lithium ion capacitor SNLIC prepared in example 1 and the snap gel lithium ion capacitor ACLIC prepared in comparative example 1;
FIG. 9 shows a performance plot of 10000 cycles at 1A/g, and it can be seen that SNLIC still has a specific capacity of 31mAh/g after 10000 cycles, and the capacity retention rate is 81.1%.
Fig. 10 is a graph showing CV curves of the snap gel lithium ion capacitor SNLIC prepared in example 1 and the snap gel lithium ion capacitor ACLIC prepared in comparative example 1 at different sweep rates;
FIG. 10 is a graph of CV tests from 2mV/s to 50mV/s, showing rectangular shapes at different sweep rates, demonstrating that the overall device exhibits capacitive behavior consistent with the results of FIG. 5.
FIG. 11 is a graph showing the cycle performance of the soft pack gel lithium ion capacitor SNLIC prepared in example 2 and the buckle gel lithium ion capacitor ACLIC prepared in comparative example 1 at 1000 mA/g;
as can be seen from fig. 11: the soft gel lithium ion capacitor SNLIC prepared in example 2 can still keep 92% after 8500 circles, and shows good performance, but the corresponding ac cycle performance is drastically reduced.
FIG. 12 is a graph showing the long cycle performance at 1000mA/g of the soft pack gel lithium ion capacitor SNLIC prepared in example 2 and the buckle gel lithium ion capacitor ACLIC prepared in comparative example 1;
as can be seen from fig. 12: the soft gel lithium ion capacitor SNLIC prepared in example 2 still maintains 91.4% of its capacity after 4000 cycles.
Claims (3)
1. The preparation method of the solid lithium ion capacitor based on the double-doped active carbon is characterized by comprising the following steps of:
1. preparing nitrogen-sulfur doped porous carbon:
(1) immersing corn stalks in a dilute sulfuric acid solution, then storing the corn stalks in an oven at 170-180 ℃ for a period of time, cleaning a reactant product to be neutral, and drying to obtain dark brown powder; adding a sulfur source, a nitrogen source and potassium hydroxide into water, adding dark brown powder, and uniformly stirring to obtain a mixed solution;
the mass fraction of the dilute sulfuric acid solution in the step one (1) is 5%; the preservation time in the first step (1) is 16-18 h;
the sulfur source in the step one (1) is thiourea; the nitrogen source in the step one (1) is thiourea; the mass ratio of the corn stalk to the sulfur source to the nitrogen source to the potassium hydroxide in the step (1) is 1 (1-1.5) (2-2.5); the volume ratio of the sulfur source substances to water in the step (1) is (0.5-0.6) (1-1.1);
(2) transferring the mixed solution into a vacuum oven for drying until a solid mixture is formed; placing the solid mixture into a porcelain boat, transferring the porcelain boat into a tube furnace, heating to a sintering temperature under the protection of nitrogen atmosphere, and calcining at the sintering temperature to obtain nitrogen-sulfur doped porous carbon;
the temperature of the vacuum oven in the step one (2) is 100-105 ℃; the temperature rising speed in the step one (2) is 5 ℃ for min -1 ~10℃min -1 The method comprises the steps of carrying out a first treatment on the surface of the The sintering temperature in the step one (2) is 800-1000 ℃; the calcination time in the step one (2) is 3-5 h;
2. preparing a gel electrolyte:
(1) firstly, drying PVDF-HFP and PAN, then adding a certain amount of PVDF-HFP and PAN into DMF, heating in a water bath, and stirring for a period of time to obtain membrane preparation liquid;
the drying in the second step (1) is carried out in an oven at 70-80 ℃ for 12-24 hours; the mass ratio of PVDF-HFP to PAN in the second step (1) is 9:1; the volume ratio of PVDF-HFP to DMF in the second step (1) is (0.7 g-1 g) (4 mL-5 mL); the temperature of the water bath heating in the second step (1) is 45-50 ℃; the stirring time in the second step (1) is 4-6 hours;
(2) sequentially carrying out ultrasonic treatment and vacuumizing on the film-forming liquid to remove internal bubbles, thereby obtaining the film-forming liquid with the bubbles removed;
(3) uniformly coating the bubble-removed film-forming liquid on a flat and smooth glass plate to form a wet film, then placing the glass plate into deionized water for phase inversion, taking out the glass plate from the deionized water after the phase inversion is finished, wiping off surface moisture by using filter paper, airing at normal temperature, and finally placing the glass plate into an oven for drying to obtain the PVDF-HFP/PAN gel film;
the phase inversion time in the second step (3) is 22-24 hours; the temperature of drying in the baking oven in the second step (3) is 45-50 ℃, and the drying time is 22-24 hours; the thickness of the PVDF-HFP/PAN gel film in the second step (3) is 100-120 micrometers;
3. preparing positive and negative electrode plates:
(1) preparing a negative electrode plate:
mixing nitrogen-sulfur doped porous carbon, conductive carbon black and polyvinylidene fluoride, grinding at room temperature, then dropwise adding N-methyl-2-pyrrolidone, and stirring to obtain slurry; coating the slurry on a copper foil, drying, and rolling by using a rolling machine to obtain a negative electrode plate;
the total mass ratio of the volume of the N-methyl-2-pyrrolidone to the nitrogen-sulfur doped porous carbon, the conductive carbon black and the polyvinylidene fluoride in the step III (1) is (4 mL-5 mL) (0.9 g-1 g); step three (1), mixing nitrogen-sulfur doped porous carbon, conductive carbon black and polyvinylidene fluoride according to the mass ratio of 8:1:1, grinding for 0.5-1 h at room temperature, then dropwise adding N-methyl-2-pyrrolidone, and stirring for 5.5-6 h on a magnetic stirrer at the stirring speed of 450r/min to obtain slurry; coating the slurry on a copper foil, drying at 65-70 ℃ for 6-8 hours, and rolling by a rolling machine to obtain a negative electrode plate; the thickness of the film on the negative electrode plate is 30-35 mu m;
(2) preparing a positive electrode plate:
mixing commercial activated carbon, conductive carbon black and polyvinylidene fluoride, grinding at room temperature, then dropwise adding N-methyl-2-pyrrolidone, and stirring to obtain slurry; coating the slurry on a copper foil, drying, and rolling by using a rolling machine to obtain an anode electrode plate;
the volume of the N-methyl-2-pyrrolidone in the step III (2) and the total mass ratio of the commercial activated carbon, the conductive carbon black and the polyvinylidene fluoride are (4 mL-5 mL) (0.9 g-1 g); mixing commercial activated carbon, conductive carbon black and polyvinylidene fluoride according to the mass ratio of 8:1:1, grinding for 0.5-1 h at room temperature, then dropwise adding N-methyl-2-pyrrolidone, and stirring for 6-8 h on a magnetic stirrer at the stirring speed of 450r/min to obtain slurry; coating the slurry on a copper foil, drying at 70-80 ℃ for 6-8 hours, and rolling by using a rolling machine to obtain a positive electrode plate; the thickness of the upper film of the positive electrode plate is 28-32 mu m;
4. pre-lithiation: firstly, laminating a negative electrode plate, a diaphragm and a lithium belt, shorting the negative electrode plate and the lithium belt, and then placing the short circuit into electrolyte for a period of time to obtain a pre-lithiated negative electrode plate;
5. and (3) battery assembly:
and forming the buckle type gel lithium ion capacitor and the soft package gel lithium ion capacitor by the positive electrode plate, the pre-lithiated negative electrode plate and the PVDF-HFP/PAN gel film.
2. The preparation method of the solid lithium ion capacitor based on the double-doped active carbon, which is characterized in that the time of putting the solid lithium ion capacitor into electrolyte in the fourth step is 45-48 h; the electrolyte in the fourth step is LiPF 6 Dissolving in a mixed solvent; the mixed solvent is prepared by mixing EC, DEC and EMC according to a volume ratio of 1:1:1; liPF in the electrolyte 6 The concentration of (2) is 1mol/L; the diaphragm in the fourth step is a PP isolating film or a PE isolating film, and the thickness is 20 mu m; the assembling method of the buckle gel lithium ion capacitor in the fifth step comprises the following steps: (1) immersing the PVDF-HFP/PAN gel film into the electrolyte for 2-3 hours to obtain the PVDF-HFP/PAN gel film immersed in the electrolyte; the electrolyte is LiPF 6 Dissolving in a mixed solvent; the mixed solvent is prepared by mixing EC, DEC and EMC according to a volume ratio of 1:1:1; liPF in the electrolyte 6 The concentration of (2) is 1mol/L; (2) and assembling the battery in a glove box filled with argon, sequentially placing the positive electrode plate, the PVDF-HFP/PAN gel film soaked in the electrolyte, the pre-lithiated negative electrode plate, the gasket and the spring piece between the positive electrode shell and the negative electrode shell, and compacting the negative electrode plate and the positive electrode plate by using a die to obtain the buckling gel lithium ion capacitor.
3. The method for preparing a solid lithium ion capacitor based on double-doped activated carbon according to claim 1, wherein the method for assembling the soft-package gel lithium ion capacitor in the fifth step is as follows: (1) punching the positive electrode plate and the pre-lithiated negative electrode plate, and then laminating the positive electrode plate and the pre-lithiated negative electrode plate according to the sequence of the negative electrode plate, namely PVDF-HFP/PAN gel film; (2) welding the positive electrode plate and the aluminum electrode lug, welding the negative electrode plate and the nickel electrode lug, and then attaching high-temperature insulating glue to fix the welding standard to prevent short circuit to obtain the battery cell; (3) a step ofPlacing the battery cell into an aluminum-plastic bag for packaging, then dripping excessive electrolyte into a glove box filled with argon so that the electrolyte is fully soaked into a PVDF-HFP/PAN gel film, extruding the excessive electrolyte from the aluminum-plastic bag after 2-3 hours, and finally extracting vacuum and sealing to obtain the soft package gel lithium ion capacitor; the electrolyte in the step (3) is LiPF 6 Dissolving in a mixed solvent; the mixed solvent is prepared by mixing EC, DEC and EMC according to a volume ratio of 1:1:1; liPF in the electrolyte 6 The concentration of (C) was 1mol/L.
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