CN114005682B - Multilayer electrode for double electric layer capacitor and preparation method thereof - Google Patents

Multilayer electrode for double electric layer capacitor and preparation method thereof Download PDF

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CN114005682B
CN114005682B CN202111642699.8A CN202111642699A CN114005682B CN 114005682 B CN114005682 B CN 114005682B CN 202111642699 A CN202111642699 A CN 202111642699A CN 114005682 B CN114005682 B CN 114005682B
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electrode
electrode layer
conductive agent
porous carbon
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CN114005682A (en
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袁峻
晏鹤凤
吴希强
李晶
张力
荆葛
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Ningbo CRRC New Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention belongs to the technical field of capacitors, and particularly relates to a multilayer electrode for a double electric layer capacitor and a preparation method thereof. The invention correspondingly adjusts the aperture of the porous carbon by the inner electrode layer and the outer electrode layer according to the different contents of the conductive agent, wherein the content of the conductive agent in the inner electrode layer is higher than that of the conductive agent in the outer electrode layer; the aperture of the porous carbon in the inner electrode layer is smaller than that of the porous carbon in the outer electrode layer, so that the density and the capacity of the electrode are greatly improved; and the requirements of different areas on ion transmission and electron transmission channels on the channel performance are utilized through the reasonable design of the electrode structure, the redundant design of the electrode is reduced, and the physical performance of the electrode is improved.

Description

Multilayer electrode for double electric layer capacitor and preparation method thereof
Technical Field
The invention belongs to the technical field of capacitors, and particularly relates to a multilayer electrode for a double electric layer capacitor and a preparation method thereof.
Background
An electric double layer capacitor (also called a super capacitor) is one of the most popular high-power energy storage devices in the current market, is an energy storage device based on an electric double layer energy storage principle, and has the advantages of high power density, short charging and discharging time, long cycle life, wide working temperature range and the like, and meanwhile, has the disadvantages of relatively low energy density and the like.
At present, the conventional EDLC electrodes are all single-layer electrodes, the adding proportion of the conductive agent is different from 5 to 10 percent, and the electrode density is about 0.55g/cc to 0.61 g/cc. Taking the 60138 structure as an example, the monomer capacity is about 3300F, the DC (5 s) internal resistance is above 0.24 mOmega, the direct current life is 2.7V2000h-65 ℃ or 2.85V1500h, and the cycle life is about 90% capacity retention rate after 5 ten thousand times. The ion adsorption of the EDLC is mainly a carbon material pore-size structure on the outer layer of an electrode, and the EDLC is not enough in both electron transport capacity and ion adsorption capacity from the electrode structure of the current commercial EDLC.
Disclosure of Invention
In view of the disadvantages in the prior art, the present invention provides a multilayer electrode for an electric double layer capacitor that has a balance among specific energy, specific power, and service life.
In order to achieve the purpose, the invention adopts the following technical scheme: the multilayer electrode for the double electric layer capacitor is characterized by comprising a current collector layer, an inner electrode layer and an outer electrode layer from inside to outside in sequence, wherein the inner electrode layer and the outer electrode layer respectively comprise a conductive agent, a binder, a dispersing agent and porous carbon;
the content of the conductive agent in the inner electrode layer is higher than that in the outer electrode layer;
the pore diameter of the porous carbon in the inner electrode layer is smaller than that of the porous carbon in the outer electrode layer.
In the above multilayer electrode for an electric double layer capacitor, the inner electrode layer comprises the following raw materials in percentage by mass: 8-10% of conductive agent, 2-3% of binder, 1-2% of dispersant and 85-89% of porous carbon.
In the above multilayer electrode for an electric double layer capacitor, the outer electrode layer comprises the following raw materials in percentage by mass: 1-3% of conductive agent, 1-3% of binder, 1-2% of dispersant and 93-97% of porous carbon.
Preferably, the conductive agent is one or more of conductive carbon black, ketjen carbon, graphene and carbon nanotubes.
Preferably, the binder is one or more of CMC, SBR, acrylate and PVDF.
Preferably, the current collector is one of a carbon-coated aluminum foil, a corrosion aluminum foil, a perforated aluminum foil, a copper foil and a perforated copper foil.
More preferably, the current collector is a carbon-coated aluminum foil or a corrosion aluminum foil.
In the above-mentioned multilayer electrode for an electric double layer capacitor, the pore size distribution of the porous carbon in the inner electrode layer is 0.5 to 1.5 nm.
Preferably, the porous carbon in the inner electrode layer is petroleum coke alkali activated carbon.
In the above-mentioned multilayer electrode for an electric double layer capacitor, the pore size distribution of the porous carbon in the outer electrode layer is 2 to 3 nm.
Preferably, the porous carbon in the outer electrode layer is steam activated wood charcoal.
According to the cake, the design of the cake structure realizes that the ohmic internal resistance of the inner layer is mainly ensured to be low by taking the electron transmission performance as the main characteristic, the polarization internal resistance of the outer layer is ensured to be low by taking the ion adsorption performance as the main characteristic, and meanwhile, the high-capacity carbon is selected for the inner layer, and the high compaction performance of the low-conductivity agent is selected for the outer layer, so that the capacity of the whole electrode is greatly improved.
In the above multilayer electrode for an electric double layer capacitor, the density of the inner electrode layer is 0.52 to 0.62 g/cc.
In the above multilayer electrode for an electric double layer capacitor, the density of the outer electrode layer is 0.58 to 0.68 g/cc.
In the above-described multilayer electrode for an electric double layer capacitor, the area density ratio of the inner electrode layer and the outer electrode layer is 1: (0.1-0.8).
The present invention also provides a method for preparing a multilayer electrode for an electric double layer capacitor, the method comprising the steps of:
s1, preparing inner layer electrode slurry and outer layer electrode slurry: the inner layer electrode slurry comprises the following raw materials in percentage by mass: 8-10% of conductive agent, 2-3% of binder, 1-3% of dispersant and 85-89% of porous carbon; the outer-layer electrode slurry comprises the following raw materials in percentage by mass: 1-3% of conductive agent, 1-3% of binder, 1-2% of dispersant and 93-97% of porous carbon;
s2, coating the inner electrode slurry and the outer electrode slurry on the surface of the current collector at the same time, and drying to obtain a semi-finished electrode product which sequentially comprises a current collector layer, an inner electrode layer and an outer electrode layer from inside to outside;
and S3, rolling the electrode semi-finished product to obtain a multi-layer electrode.
In the above-described method for manufacturing a multilayer electrode for an electric double layer capacitor, the inner layer electrode paste and the outer layer electrode paste have a viscosity of 1000-.
In the above method for manufacturing a multilayer electrode for an electric double layer capacitor, the temperature in the drying process of step S2 is 55 to 130 ℃, the rate of temperature rise is 25 to 50 ℃/min, and the time is 1 to 3 min.
Preferably, the first drying temperature needs to be < 80 ℃. When the invention is used for drying, the first-cut drying temperature and the heating rate need to be controlled to ensure the cohesiveness of the slurry, and the short drying time can cause the pole piece to be wet, and the long drying time can cause the phenomenon of belt breakage.
In the above-mentioned method for producing a multilayer electrode for an electric double layer capacitor, the temperature in the rolling treatment of step S3 is 100-160 ℃, the compression ratio is 5-9%, and the rolling density is 0.57-0.66 g/cc. The invention needs to strictly control the compression ratio, if the compression ratio is too large, the pole piece is wrinkled and broken, if the compression ratio is too small, the adhesive effect is poor, the temperature suitability is ensured during compression, if the temperature is too high, the adhesive loses effectiveness, and if the temperature is too low, the rolling density of the inner layer and the outer layer cannot be ensured.
Compared with the prior art, the invention has the following beneficial effects: according to the invention, the pore size of the porous carbon is correspondingly adjusted by the inner electrode layer and the outer electrode layer according to different contents of the conductive agent, so that the density and the capacity of the electrode are greatly improved; and the requirements of different areas on ion transmission and electron transmission channels on the channel performance are utilized through the reasonable design of the electrode structure, the redundant design of the electrode is reduced, and the physical performance of the electrode is improved.
Drawings
FIG. 1 is a schematic cross-sectional view of an electrode according to example 1: 1. an electrode inner layer; 2. an outer electrode layer; 3 a conductive agent; 4. outer layer active carbon; 5. the inner layer is active carbon.
Detailed Description
The technical solutions of the present invention are further described below by way of specific examples, but the present invention is not limited to these examples.
Example 1:
s1, respectively preparing inner-layer electrode slurry and outer-layer electrode slurry according to the following raw materials in percentage by mass;
the inner layer electrode slurry comprises the following raw materials in percentage by mass: 9% of conductive agent, 2.5% of binder, 1.5% of dispersant and 87% of petroleum coke alkali activated carbon (the average pore size distribution is more than 90% of the proportion of 1 nm); the inner layer slurry viscosity was 1500 cps.
The outer-layer electrode slurry comprises the following raw materials in percentage by mass: 2 percent of conductive agent, 1.6 percent of binder, 1.2 percent of dispersant and 95.2 percent of coconut shell water vapor activated carbon (the average pore diameter is distributed at 2.5nm and the proportion is more than 95 percent); the viscosity of the outer layer slurry is 1500 cps;
the conductive agent is prepared from the following components in a mass ratio of 1: 1, SBR as a binder and CMC as a dispersant.
S2, passing the inner layer slurry and the outer layer slurry through an extrusion coating machine, simultaneously coating the two layers of slurries on the surface of a current collector to form a multilayer electrode which sequentially comprises a current collector layer, an inner layer electrode layer and an outer layer electrode layer from bottom to top, and drying, wherein the temperature of a drying oven is set to 55/70/85/100/110/100 sequentially, the coating speed is 22m/min, and the total length of the drying oven is 36 m;
the density of the inner electrode layer was 0.61 g/cc; the density of the outer electrode layer was 0.65 g/cc; the surface density ratio of the inner electrode layer to the outer electrode layer is 1: 0.8.
s3, rolling the semi-finished product to obtain a plurality of layers of electrodes; the rolling treatment temperature was 120 ℃, the compression ratio was 9%, and the rolling density was 0.64 g/cc.
The schematic cross-sectional view of the multilayer electrode is shown in FIG. 1: an electrode inner layer; 2. an outer electrode layer; 3 a conductive agent; 4. outer layer active carbon; 5. the inner layer is active carbon.
The positive and negative electrodes are respectively prepared by the method, wherein the positive and negative current collectors are all corrosion aluminum foils, and then the positive and negative electrodes are wound, placed into a shell, assembled, dried and injected to obtain 60138 type monomers and the capacity, internal resistance and service life of the 60138 type monomers are tested.
Example 2:
s1, respectively preparing inner-layer electrode slurry and outer-layer electrode slurry according to the following raw materials in percentage by mass;
the inner layer electrode slurry comprises the following raw materials in percentage by mass: 10% of conductive agent, 3% of binder, 2% of dispersant, 85% of carbon aerogel (the average pore diameter distribution is more than 90% at the ratio of 0.5 nm); the inner layer slurry viscosity was 2000 cps.
The outer-layer electrode slurry comprises the following raw materials in percentage by mass: 3% of conductive agent, 1.8% of binder, 1.2% of dispersant and 94% of coconut shell steam activated carbon (the average pore size distribution is more than 95% of 2.0nm proportion); the outer layer slurry viscosity was 2000 cps.
The conductive agent is conductive carbon black, the binder is SBR, and the dispersant is CMC.
S2, passing the inner layer slurry and the outer layer slurry through an extrusion coating machine, simultaneously coating the two layers of slurries on the surface of a current collector to form a multilayer electrode which is a current collector layer, an inner layer electrode layer and an outer layer electrode layer from bottom to top, and performing drying treatment, wherein the temperature of a drying treatment oven is set to be 55/70/85/100/110/100 in sequence, the coating speed is 18m/min, and the total length of the oven is 36 m;
the density of the inner electrode layer was 0.59 g/cc; the outer electrode layer had a density of 0.64 g/cc; the surface density ratio of the inner electrode layer to the outer electrode layer is 1: 0.8.
s3, rolling the semi-finished product to obtain a plurality of layers of electrodes; the rolling treatment temperature was 120 ℃, the compression ratio was 9%, and the rolling density was 0.62 g/cc.
The positive and negative electrodes are respectively prepared by the method, wherein the positive and negative current collectors are carbon-coated aluminum foils, and then the positive and negative electrodes are wound, placed into a shell, assembled, dried and injected to obtain 60138 type monomers and the capacity, internal resistance and service life of the 60138 type monomers are tested.
Example 3:
s1, respectively preparing inner-layer electrode slurry and outer-layer electrode slurry according to the following raw materials in percentage by mass;
the inner layer electrode slurry comprises the following raw materials in percentage by mass: 8 percent of conductive agent, 2.2 percent of binder, 1.3 percent of dispersant and 88.5 percent of petroleum coke alkali activated carbon (the proportion of the average pore diameter distribution is 1.5nm is more than 90 percent); the inner layer slurry viscosity was 1000 cps.
The outer-layer electrode slurry comprises the following raw materials in percentage by mass: 1% of conductive agent, 1.4% of binder, 1% of dispersant, 96.6% of coconut shell water vapor activated carbon (the average pore size distribution is 3.0nm, and the proportion exceeds 95%); the outer layer slurry viscosity was 1000 cps.
The conductive agent is prepared from the following components in a mass ratio of 1: 1, SBR as a binder and CMC as a dispersant.
S2, passing the inner layer slurry and the outer layer slurry through an extrusion coating machine, simultaneously coating the two layers of slurries on the surface of a current collector to form a multilayer electrode which is a current collector layer, an inner layer electrode layer and an outer layer electrode layer from bottom to top, and performing drying treatment, wherein the temperature of a drying treatment oven is set to be 55/70/85/100/110/100 in sequence, the coating speed is 25m/min, and the total length of the oven is 36 m;
the density of the inner electrode layer was 0.61 g/cc; the density of the outer electrode layer was 0.66 g/cc; the surface density ratio of the inner electrode layer to the outer electrode layer is 1: 0.6.
s3, rolling the semi-finished product to obtain a plurality of layers of electrodes; the rolling treatment temperature was 130 ℃, the compression ratio was 9%, and the rolling density was 0.66 g/cc.
The positive and negative electrodes are respectively prepared by the method, wherein the positive and negative current collectors are all corrosion aluminum foils, and then the positive and negative electrodes are wound, placed into a shell, assembled, dried and injected to obtain 60138 type monomers and the capacity, internal resistance and service life of the 60138 type monomers are tested.
Example 4:
the difference from the embodiment 1 is only that the inner layer electrode slurry comprises the following raw materials in percentage by mass: 13 percent of conductive agent, 4 percent of binder, 2.5 percent of dispersant and 80.5 percent of petroleum coke alkali activated carbon (the proportion of 1nm of average pore size distribution is more than 90 percent); the inner layer slurry viscosity was 1500 cps. The outer-layer electrode slurry comprises the following raw materials in percentage by mass: 5% of conductive agent, 3% of binder, 2% of dispersant, and 90% of coconut shell steam activated carbon (the average pore size distribution is more than 95% of 2.5nm proportion); the outer layer slurry viscosity was 1500 cps.
Example 5:
the difference from the example 1 is only that the inner layer electrode slurry comprises the following raw materials in percentage by mass: 7 percent of conductive agent, 2.2 percent of binder, 1.3 percent of dispersant and 89.5 percent of petroleum coke alkali activated carbon (the proportion of 1nm of average pore size distribution is more than 90 percent); the inner layer slurry viscosity was 1500 cps. The outer-layer electrode slurry comprises the following raw materials in percentage by mass: 0.5 percent of conductive agent, 1.5 percent of binder, 1 percent of dispersant and 97 percent of coconut shell water vapor activated carbon (the proportion of the average pore diameter distribution is 2-3nm is more than 95 percent); the outer layer slurry viscosity was 1500 cps.
Comparative example 1:
the difference from the example 1 is only that the inner layer electrode slurry comprises the following raw materials in percentage by mass: 2 percent of conductive agent, 1.6 percent of binder, 1.2 percent of dispersant and 95.2 percent of petroleum coke alkali activated carbon (the proportion of the average pore diameter distribution of 1nm is more than 90 percent); the inner layer slurry viscosity was 1500 cps. The outer-layer electrode slurry comprises the following raw materials in percentage by mass: 9% of conductive agent, 2.5% of binder, 1.5% of dispersant and 87% of coconut shell water vapor activated carbon (the average pore size distribution is more than 95% of 2.5nm proportion); the outer layer slurry viscosity was 1500 cps.
Comparative example 2:
the difference from the example 1 is only that the inner layer electrode slurry comprises the following raw materials in percentage by mass: 9% of conductive agent, 2.5% of binder, 1.5% of dispersant and 87% of petroleum coke alkali activated carbon (the proportion of 1nm of average pore size distribution exceeds 90%); the inner layer slurry viscosity was 1500 cps. The outer-layer electrode slurry comprises the following raw materials in percentage by mass: 2 percent of conductive agent, 2.2 percent of binder, 1.3 percent of dispersant and 94.5 percent of petroleum coke alkali activated carbon (the proportion of the average pore diameter distribution of 1nm is more than 90 percent); the outer layer slurry viscosity was 1500 cps.
Comparative example 3:
the difference from the example 1 is only that the inner layer electrode slurry comprises the following raw materials in percentage by mass: 9 percent of conductive agent, 2.2 percent of binder, 1.4 percent of dispersant, 87.4 percent of coconut shell water vapor activated carbon (the average pore diameter distribution is 2.5nm and the proportion is more than 95 percent), and the viscosity of the slurry is 1500 cps. The outer-layer electrode slurry comprises the following raw materials in percentage by mass: 2 percent of conductive agent, 1.6 percent of binder, 1.2 percent of dispersant, 95.2 percent of coconut shell water vapor activated carbon (the average pore size distribution is more than 95 percent in the proportion of 2.5 nm), and the viscosity of the slurry is 1500 cps.
Comparative example 4:
the difference from the example 1 is only that the inner layer electrode slurry comprises the following raw materials in percentage by mass: 9% of conductive agent, 2.5% of binder, 1.5% of dispersant and 87% of petroleum coke alkali activated carbon (the average pore size distribution is more than 90% of the proportion of 1 nm); the viscosity of the inner layer slurry is 1500 cps; the outer-layer electrode slurry comprises the following raw materials in percentage by mass: 9 percent of conductive agent, 1.6 percent of binder, 1.2 percent of dispersant and 95.2 percent of coconut shell water vapor activated carbon (the average pore diameter is distributed at 2.5nm and the proportion is more than 95 percent); the outer layer slurry viscosity was 1500 cps.
Comparative example 5:
the difference from the example 1 is only that the inner layer electrode slurry comprises the following raw materials in percentage by mass: 2 percent of conductive agent, 2.5 percent of binder, 1.5 percent of dispersant and 87 percent of petroleum coke alkali activated carbon (the average pore diameter distribution is more than 90 percent of the proportion of 1 nm); the viscosity of the inner layer slurry is 1500 cps; the outer-layer electrode slurry comprises the following raw materials in percentage by mass: 2 percent of conductive agent, 1.6 percent of binder, 1.2 percent of dispersant and 95.2 percent of coconut shell water vapor activated carbon (the average pore diameter is distributed at 2.5nm and the proportion is more than 95 percent); the outer layer slurry viscosity was 1500 cps.
Table 1: results of measuring the performance of electric double layer capacitors fabricated by the multi-layer electrodes of examples 1 to 5 and comparative examples 1 to 5
Examples capacity/F Internal resistance/m omega Retention ratio of DC capacity Retention ratio of circulating capacity
Example 1 4700 0.16 85.6% 92.5%
Example 2 4600 0.15 86.6% 94.1%
Example 3 5000 0.18 84.3% 90.8%
Example 4 4100 0.14 86.7% 94.6%
Example 5 4800 0.21 84.3% 86.8%
Comparative example 1 4300 0.25 84.9% 84.6%
Comparative example 2 4800 0.23 84.6% 87.8%
Comparative example 3 4200 0.16 86.1% 92.9%
Comparative example 4 4300 0.15 85.80% 92.60%
Comparative example 5 4700 0.28 84.20% 83.20%
Wherein the method for testing the capacity retention rate of the direct current service life is the capacity retention rate of 1000h of floating charge at the temperature of 2.85V/65 ℃;
the method for testing the capacity retention ratio of the cycle life is the capacity retention ratio of 5 ten thousand cycles from rated voltage to half voltage of 100A.
FIG. 1 is a schematic cross-sectional view of an electrode according to example 1: 1. an electrode inner layer; 2. an outer electrode layer; 3 a conductive agent; 4. outer layer active carbon; 5. the inner layer is active carbon. As can be seen from the figure, the invention improves the density and the capacity of the electrode by correspondingly adjusting the pore size of the porous carbon according to the content of the conductive agent in the inner electrode layer and the outer electrode layer.
In conclusion, the invention reasonably utilizes the requirements of different areas on ion transmission and electron transmission channels on the channel performance through the design of the cake structure, reduces the redundant design of the electrode and improves the physical performance of the electrode.
The technical scope of the invention claimed by the embodiments herein is not exhaustive and new solutions formed by equivalent replacement of single or multiple technical features in the embodiments are also within the scope of the invention, and all parameters involved in the solutions of the invention do not have mutually exclusive combinations if not specifically stated.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims (6)

1. A multilayer electrode for a double electric layer capacitor is characterized by comprising a current collector layer, an inner electrode layer and an outer electrode layer from inside to outside in sequence, wherein the inner electrode layer and the outer electrode layer respectively comprise a conductive agent, a binder, a dispersing agent and porous carbon,
the content of the conductive agent in the inner electrode layer is higher than that in the outer electrode layer;
the aperture of the porous carbon in the inner electrode layer is smaller than that of the porous carbon in the outer electrode layer; the inner electrode layer comprises the following raw materials in percentage by mass: 8-10% of a conductive agent, 2-3% of a binder, 1-3% of a dispersing agent and 85-89% of porous carbon; the outer electrode layer comprises the following raw materials in percentage by mass: 1-3% of conductive agent, 1-3% of binder, 1-2% of dispersant and 93-97% of porous carbon; the pore size distribution of porous carbon in the inner electrode layer is 0.5-1.5 nm; the pore size distribution of the porous carbon in the outer electrode layer is 2-3 nm.
2. The multilayer electrode for an electric double layer capacitor according to claim 1, wherein the areal density ratio of the inner electrode layer to the outer electrode layer is 1: (0.1-0.8).
3. A method for producing a multilayer electrode for an electric double layer capacitor according to claim 1, comprising the steps of:
s1, preparing inner layer electrode slurry and outer layer electrode slurry:
the inner layer electrode slurry comprises the following raw materials in percentage by mass: 8-10% of conductive agent, 2-3% of binder, 1-3% of dispersant and 85-89% of porous carbon;
the outer-layer electrode slurry comprises the following raw materials in percentage by mass: 1-3% of conductive agent, 1-3% of binder, 1-2% of dispersant and 93-97% of porous carbon;
s2, coating the inner electrode slurry and the outer electrode slurry on the surface of the current collector, and drying to obtain a semi-finished electrode product which sequentially comprises a current collector layer, an inner electrode layer and an outer electrode layer from inside to outside;
and S3, rolling the electrode semi-finished product to obtain a multi-layer electrode.
4. The method of claim 3, wherein the inner layer electrode slurry and the outer layer electrode slurry have a viscosity of 1000-3000 cps.
5. The method of claim 3, wherein the drying treatment at step S2 is performed at a temperature of 55-130 ℃, a temperature rise rate of 25-50 ℃/min, and a time of 1-3 min.
6. The method of claim 3, wherein the temperature in the rolling treatment of step S3 is 100-160 ℃, the compression ratio is 5-9%, and the rolling density is 0.57-0.66 g/cc.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102324493A (en) * 2011-08-26 2012-01-18 东莞新能源科技有限公司 Thick electrode with good electrochemical performance and its preparation method
CN109546080A (en) * 2018-11-29 2019-03-29 中国科学院过程工程研究所 A kind of anode pole piece, and its preparation method and application

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007214174A (en) * 2006-02-07 2007-08-23 Teijin Ltd Laminated electrode and electric double-layer capacitor using the same
JP4797851B2 (en) * 2006-07-19 2011-10-19 三菱電機株式会社 COATING TYPE ELECTRODE SHEET, METHOD FOR PRODUCING COATING TYPE ELECTRODE SHEET, AND ELECTRIC DOUBLE LAYER CAPACITOR OR LITHIUM ION BATTERY USING COATING TYPE ELECTRODE SHEET
KR101783445B1 (en) * 2015-03-17 2017-09-29 주식회사 엘지화학 Multilayer-Structured Electrode and Lithium Secondary Battery Comprising The Same
CN107633953B (en) * 2017-09-08 2019-10-15 西安科技大学 A kind of multi-layered electrode and its supercapacitor of preparation
CN112242258B (en) * 2020-10-20 2022-05-27 上海海事大学 Electric double-layer super capacitor with asymmetric porous electrode structure under variable pore

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102324493A (en) * 2011-08-26 2012-01-18 东莞新能源科技有限公司 Thick electrode with good electrochemical performance and its preparation method
CN109546080A (en) * 2018-11-29 2019-03-29 中国科学院过程工程研究所 A kind of anode pole piece, and its preparation method and application

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