CN114284075A - Electrode slurry for paper-based supercapacitor, paper-based electrode, preparation method and application - Google Patents
Electrode slurry for paper-based supercapacitor, paper-based electrode, preparation method and application Download PDFInfo
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Abstract
The application relates to the field of paper-based super capacitors, and particularly discloses electrode slurry for the paper-based super capacitors, a paper-based electrode, a preparation method and application. The electrode slurry consists of a solvent and a solute dissolved in the solvent, and the weight of the solvent is 1.5-2 times of that of the solute; the solute comprises the following components in percentage by weight: 85% -95% of active electrode material, 0.5% -4.5% of binder, 0.1% -5% of propping agent and 0.1% -8% of conductive agent; the paper-based electrode comprises a paper substrate, the surface of the paper substrate is coated with the electrode slurry, the paper substrate is made of long fiber non-woven paper materials, and the thickness of the paper substrate is 50-80 microns. The adhesive force between the electrode slurry and the paper substrate is good, the bonding strength is high, the falling is not prone to occurring, the paper-based electrode is suitable for large-scale production of winding-type super capacitors, the conductivity of the prepared paper-based electrode is excellent, the surface of the paper-based electrode is provided with a plurality of microporous structures, and the super capacitors are enabled to have higher capacity values.
Description
Technical Field
The application relates to the field of paper-based super capacitors, in particular to electrode slurry for the paper-based super capacitors, a paper-based electrode, a preparation method and application.
Background
The super capacitor is a chemical energy storage device, is between ordinary capacitor and battery, and is different from the battery, and super capacitor energy density is big, and the storage electric energy is many, because super capacitor's capacity is very big, often can directly regard as the battery to use. The super capacitor is characterized in that the charging and discharging speed is only a few seconds even at the temperature of minus a few degrees, and the charging and discharging times can reach millions of times.
At present, the electrode base material of the super capacitor is mainly a metal-based electrode made of a metal substrate, and the electrode is covered or attached with an active electrode material to make the super capacitor electrode. However, the flexibility of the metal-based electrode is poor, and the bending and curling of the metal-based electrode easily cause the falling off of the active electrode material when the winding type super capacitor is manufactured. In order to improve the flexibility of the supercapacitor electrode, a paper substrate is used as an electrode base material of the supercapacitor, the paper-based electrode has better flexibility compared with a metal-based electrode, the extrusion force of the surface of the paper-based electrode on an active electrode material is smaller during winding, and the production cost of the paper-based electrode is lower compared with that of the metal-based electrode.
Although the extrusion force of the paper-based electrode on the active electrode material in a winding mode is small, the paper-based electrode has the defect that the problem is difficult to solve, the adhesive force between the paper substrate and the active electrode material is poor, and the active electrode material is easy to fall off in the coating stage, so that most of the existing paper-based super capacitors are stopped in the laboratory research stage and are difficult to produce in a large scale.
Disclosure of Invention
In order to solve the problem that the adhesion force of an active electrode material and a paper substrate is poor and large-scale production is difficult, the application provides an electrode slurry for a paper-based supercapacitor, a paper-based electrode, a preparation method and application.
In a first aspect, the application provides an electrode paste for a paper-based electrode of a supercapacitor, which adopts the following technical scheme: the electrode slurry for the paper-based electrode of the supercapacitor is composed of a solvent and a solute dissolved in the solvent, wherein the weight of the solvent is 1.5-2 times that of the solute;
the solute comprises the following components in percentage by weight:
active electrode material: 85% -95%;
adhesive: 0.5 to 4.5 percent;
proppant: 0.1 to 5 percent;
conductive agent: 0.1 to 8 percent.
By adopting the technical scheme, the adhesive can improve the adhesiveness and stability of each component in the electrode slurry, and is beneficial to improving the bonding strength of the active electrode material on the surface of the paper electrode substrate; the propping agent is wrapped by the active electrode material, so that the porosity of the electrode structure is increased, the surface void degree in the active electrode is increased, the specific surface area of the active electrode is increased, and the purpose of increasing the capacity of the paper-based electrode is realized; the conductive agent can improve the conductive capability of the electrode slurry, so that the prepared paper-based electrode has better conductive performance.
Meanwhile, the adhesion and the stability of various materials in the electrode slurry are improved by matching the binder and the propping agent, a conductive contact with strong adhesion can be formed even at high temperature, the contact resistance of the electrode plate of the super capacitor can be effectively reduced, a lower Equivalent Series Resistance (ESR) value is shown, and the performance of the super capacitor for resisting large ripple current is favorably improved.
Through tests, when the weight of the solvent is controlled to be 1.5-2 times of that of the solute, the adhesion between the electrode slurry and the paper substrate is better, when the weight of the solvent is less than 1.5 times of that of the solute, the electrode slurry is too viscous, the electrode slurry is difficult to be uniformly coated on the paper substrate, the uniformity of the active electrode material on the paper substrate is influenced, the difference of conductivity of different areas of the paper-based electrode is caused, and when the weight of the solvent is more than 2 times of that of the solute, the electrode slurry is too thin and is difficult to be adhered on the paper substrate.
The electrode paste and the paper substrate have good adhesive force and high bonding strength, are not easy to fall off, are very suitable for manufacturing the winding type super capacitor, realize the large-scale production of the winding type paper base super capacitor and promote the development of the winding type paper base super capacitor.
Preferably, the active electrode material is one or a combination of several of porous activated carbon, graphite and graphene.
Preferably, the active electrode material is prepared by compounding 65-85 wt% of porous active carbon, 5-30 wt% of graphite and 0.5-11 wt% of graphene.
Through tests, the compound active electrode material of the porous active carbon, the graphite and the graphene is adopted, the porous active carbon material has the advantages of large specific surface area, rich pore channel structure and low cost, the graphite has the characteristics of large specific surface area, good conductivity and stable structure, the graphene has the maximum surface area in unit volume, high chemical stability and excellent conductivity, the compound synergistic effect of the three components is favorable for improving the activity and energy density of the paper-based electrode, and the prepared active electrode of the super capacitor has excellent electrochemical performance, high specific capacitance and stable cycle performance.
In addition, when the porous activated carbon, the graphite and the graphene are compounded, the porous activated carbon layer can uniformly coat the proppant particles, so that the active electrode material contains abundant porous structures, the possibility of extrusion and re-bonding between the graphite or graphene layers is reduced, the system dispersibility is improved, and the conductivity of the active electrode material is more uniform.
Preferably, the binder is one or a combination of more of polyvinyl alcohol, polypropylene alcohol, polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid, polyacrylonitrile and CMC cellulose.
Preferably, the proppant is one or a combination of more of alumina powder, silicon nanoparticles, zeolite powder and molecular sieve powder, and the particle size D90 of the proppant is less than 10 μm.
By adopting the technical scheme, in the system, the particulate proppant can be uniformly coated in the active electrode material, so that the active electrode material contains rich porous structures, and the possibility of extrusion and re-bonding of the active electrode material is reduced.
Preferably, the conductive agent is metal powder and/or metal microparticles.
Preferably, the conductive agent is one or a combination of several of silver nanowires, micron silver powder, nickel powder and micron gold powder.
Preferably, the solvent is one or a combination of more of sulfolane, N-methyl pyrrolidone, gamma butyrolactone, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethylene carbonate and propylene carbonate.
Tests prove that the selected solvent has a better dispersing effect on active electrode material particles and conductive agent particles, so that the prepared electrode slurry has good fluidity, the subsequent coating of a paper substrate is facilitated, the solvent is easier to volatilize in the subsequent drying process, in addition, electrons in molecules of the solvents can be polarized in an electric field, the function of enhancing the conductive performance of the conductive agent is achieved, and the conductive performance of the prepared paper-based electrode cannot be influenced even if a small amount of residues exist in the drying process.
In a second aspect, the present application provides a paper-based electrode, which adopts the following technical scheme:
the paper-based electrode comprises a paper substrate, wherein the surface of the paper substrate is coated with the electrode slurry for the paper-based supercapacitor in the technical scheme.
Through adopting above-mentioned technical scheme, the paper base electrode's that the paper base plate made after having coated this application electrode thick liquids surface has more microporous structure, and specific surface is big, has improved ultracapacitor system's capacity value greatly.
Preferably, the thickness of the paper-based substrate is 50-80 μm, and the thickness of the paper-based electrode is 165-185 μm.
Through tests, when the thickness of a paper substrate is less than 50 microns, the crease resistance and tensile strength of the paper substrate are too low, the mechanical performance of the paper-based electrode is affected, when the thickness of the paper-based electrode exceeds 185 microns, an active electrode material of the paper-based electrode is easy to fall off during subsequent winding, and under the condition that the thickness of the paper-based electrode is kept to be certain, when the thickness of the paper-based electrode is greater than 80 microns, the coating thickness of electrode slurry is small, so that the capacitance of the paper-based electrode is reduced, therefore, when the thickness of the paper-based electrode is controlled to be 50-80 microns and the thickness of the paper-based electrode is controlled to be 165-185 microns, the performance of the paper-based electrode is better, and the active electrode material is not easy to fall off during winding.
Preferably, the paper substrate is a long fiber non-woven paper material.
By adopting the technical scheme, the long fiber non-woven paper material is low in cost, uniform in gaps among fibers, high in thermal stability, high in mechanical tensile strength and good in toughness, and can be well rolled.
In a third aspect, the application provides a preparation method of a paper-based electrode, which adopts the following technical scheme:
a preparation method of a paper-based electrode comprises the following steps:
continuously performing ultrasonic dispersion on the electrode slurry, uniformly coating the electrode slurry on one surface of the paper substrate, baking the paper substrate for 8-12 hours at 50-165 ℃ through a vacuum oven, turning over the dried paper substrate through a roller type rotating shaft, coating and drying the surface of the paper substrate, which is not coated with the electrode slurry, in the same way, and obtaining the paper-based electrode.
By adopting the technical scheme, the method is simple in process, low in production difficulty, high in efficiency, good in spraying quality and even in film forming, provides technical support for manufacturing the winding type paper-based supercapacitor with high stability, and promotes large-scale production of the winding type paper-based supercapacitor.
Preferably, the thickness of the electrode paste applied to one surface of the paper substrate is controlled to be 50 to 60 μm during coating.
In a fourth aspect, the application provides an application of the paper-based electrode in the above technical scheme in a winding type paper-based supercapacitor, and the following technical scheme is adopted:
the winding type paper-based supercapacitor comprises a positive paper-based electrode pole piece and a negative paper-based electrode pole piece, wherein the positive paper-based electrode pole piece and the negative paper-based electrode pole piece both adopt the paper-based electrodes in the technical scheme.
Through adopting above-mentioned technical scheme, the coiling formula paper base ultracapacitor system electric conductive property that this application made is excellent and stable, even also can form the strong conductive contact of adhesive force under high temperature between the inner structure, the contact resistance and Equivalent Series Resistance (ESR) value of electrode sheet are low, and the performance of resistant big ripple electric current is excellent.
In summary, the present application includes at least one of the following beneficial technical effects:
1. according to the method, the active electrode material with good conductivity is used as a main raw material, and the adhesion and stability of each component in the electrode slurry are improved through the binder, so that the bonding strength of the active electrode material on the surface of the paper substrate is higher, the active electrode material is not easy to fall off, the method is very suitable for manufacturing the winding type super capacitor, and the large-scale production of the winding type paper-based super capacitor is realized; in addition, the porosity of the electrode structure and the surface porosity inside the active electrode are increased through the propping agent, the specific surface area of the active electrode is increased, and the purpose of increasing the capacity of the paper-based active electrode is realized; the binder is matched with the added propping agent, so that the electrode structure can form a conductive contact with strong adhesive force even at high temperature, and the conductivity is stable.
2. The paper-based electrode has the advantages that the surface of the paper-based electrode has more microporous structures, the surface area is large, and the capacitance value of the supercapacitor is greatly improved.
3. The preparation method of the paper-based electrode is simple in process, low in production difficulty, high in efficiency, good in spraying quality and uniform in film forming, provides technical support for manufacturing the high-stability winding paper-based supercapacitor, and promotes large-scale production of the winding paper-based supercapacitor.
4. The coiling formula paper base ultracapacitor system that this application made electric conductive property is excellent and stable, even also can form the conductive contact that strong adhesive force is strong under high temperature between the inner structure, the contact resistance and Equivalent Series Resistance (ESR) value of electrode sheet are low, and resistant big ripple current's performance is excellent.
Drawings
FIG. 1 is a schematic diagram of a wound paper based capacitor of the present application;
FIG. 2 is a schematic structural view of a wound paper-based capacitor element of the present application;
FIG. 3 is a schematic view of a positive conductive metal tab, a positive paper-based electrode and a positive guide pin riveted structure in the element of the winding paper-based capacitor of the present application;
FIG. 4 is a schematic structural view of another view angle of riveting of the positive conductive metal connecting sheet, the positive paper-based electrode and the positive guide pin in the element of the winding type paper-based capacitor of the present application;
description of reference numerals: 1. a housing; 2. a prime; 21. a positive conductive metal connecting sheet; 22. a positive paper-based electrode plate; 23. electrolyzing paper; 24. a negative paper-based electrode plate; 25. a negative conductive metal connecting sheet; 3. a positive guide pin; 4. and (4) a negative electrode guide pin.
Detailed Description
A super capacitor has been widely used in various fields as a large capacity energy storage device, and is mainly classified into a laminated type and a wound type from a structural point of view. At present, an electrode base material of a super capacitor is mainly made of a metal substrate covered or attached with an active electrode material, but the flexibility of a metal-based electrode is poor, and when a winding type super capacitor is manufactured, the active electrode material is easy to fall off due to bending and curling of the metal-based electrode. In research, paper materials with better flexibility are tried to be used as electrodes of the supercapacitor, but the problem that the paper-based supercapacitor is difficult to produce in a large scale due to the fact that the adhesion force of the active electrode materials and the paper-based electrodes is poor and the active electrode materials and the paper-based electrodes are easy to fall off in a coating stage is difficult to solve.
Based on the above, the applicant has conducted a great deal of research on how to improve the adhesive force between the paper-based electrode and the active electrode material, and found that the electrode slurry prepared by compounding the porous active carbon, the graphite and the graphene as the active electrode material and mixing the polyvinyl alcohol, the zeolite powder and the silver nanowires is excellent in bonding effect with the paper-based electrode, so that the problem of the adhesive force between the active electrode material and the paper-based electrode is solved, and the large-scale production of the paper-based supercapacitor is realized. The present application has been made based on the above findings.
In order to facilitate understanding of the technical solutions of the present application, the following detailed descriptions of the present application are provided with reference to tables and examples, but the present application is not limited to the scope of protection defined by the present application.
In the embodiment of the application, the paper substrate is made of a long fiber non-woven paper material from Hitachi high and New technology Limited, the type is ASS 040-010-.
Pretreatment of a paper substrate:
before coating the paper substrates in the following examples and comparative examples, the paper substrates are pretreated by the conductive liquid, and the method comprises the following specific steps:
according to the weight percentage, 84 percent of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) aqueous dispersion liquid is taken as a conductive agent, 2 percent of ethylene glycol is taken as a cosolvent, 2 percent of polyethylene glycol-600 is taken as a wetting agent, 9 percent of sorbitol is taken as a flow aid, and 3 percent of ethylene carbonate is taken as a conductive promoter. Adding the components into a stirring container, adjusting the stirring frequency to be 50Hz and the rotating speed to be 650rpm, stirring for 15 minutes, then adjusting the stirring frequency to be 40Hz and the rotating speed to be 3500rpm, continuing stirring for 15 minutes to obtain a mixed solution, then ultrasonically vibrating the mixed solution for 1.5 hours at the frequency of 40KHz to obtain a conductive solution, and detecting the viscosity of the conductive solution to be 22 mPas. Wherein the aqueous dispersion of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT/PSS) is available from Guang Donghua Honghong scientific and technological Limited and has the model of AL-16.
The conductive liquid is added into a liquid storage tank of a vertical spraying machine, the roller pressing type rolling shaft is adopted to realize the discharging and receiving of the paper substrate to be treated, the vertical spraying machine is used for spraying the conductive enhancement liquid to the two sides of the paper substrate at the same time, the discharging speed is controlled to be 1m/min, the total thickness of the coating is controlled to be 5 mu m, and the total thickness of the paper substrate after being sprayed with the conductive enhancement liquid is 65 mu m. The sprayed part of the paper substrate is dried by heating through an infrared light emitting tube, the drying temperature is controlled to be 125 ℃, the dried paper substrate is rolled into a coil to prepare the electrode substrate, the electrode substrate has excellent conductivity, and the requirement of the supercapacitor on the conductivity of the electrode can be well met.
Through experimental verification, in the pretreatment process of the paper substrate, the promotion of the conductivity of the paper substrate can be realized by controlling the component proportion of the conductive liquid in the following range: conductive agent: 81% -90% of cosolvent: 2% -5%, wetting agent: 1% -3%, flow assistant: 5% -9%, conductive accelerator: 2 to 4 percent. Wherein, the cosolvent can also be one or a combination of more of ethanol, isopropanol and glycerol, the wetting agent can also be one or a combination of more of polyethylene glycol-200, polyethylene glycol-400 and polyethylene glycol-800, the flow assistant can also be mannitol, and the conduction promoter can also be one or a combination of more of dimethyl sulfate, ethylene sulfate and ethylene sulfite.
Example 1
According to the weight percentage, 85% of porous activated carbon, 4.5% of CMC cellulose, 2.5% of alumina powder and 8% of nickel powder are added into a mixing tank of a vacuum mixer, the materials are rolled and rotated for 60 minutes to obtain a mixture, sulfolane with the weight 1 time of that of the mixture is added into the mixing tank, the slurry is led into a dispersion machine after 2 hours of mixing, then the sulfolane with the weight 0.5 time of that of the mixture is used for cleaning the mixing tank, a cleaning solution is led into the dispersion machine, and the slurry in the dispersion machine is dispersed and mixed for 4 hours to obtain electrode slurry.
The electrode slurry is led into a slurry tank of a coating machine, the slurry tank adopts 304 stainless steel materials to prevent electrode slurry from being polluted by other chemical impurities, the electrode slurry in the slurry tank is continuously subjected to ultrasonic dispersion to prevent the electrode slurry from being deposited or separated, then the electrode slurry is uniformly coated on one surface of a paper substrate through reciprocating motion of a pressure nozzle, the coating thickness is controlled to be 50 micrometers, then the surface of the paper substrate is dried through baking for 12 hours at 50 ℃ in a vacuum oven, then the dried paper substrate is turned over through a roller type rotating shaft, the surface of the paper substrate, which is not coated with the electrode slurry, is coated and dried in the same mode to obtain a paper-based electrode, and finally the dried paper-based electrode is wound into a coil.
Example 2
The difference from the example 1 is that 87.5% of porous activated carbon, 2.5% of polyacrylic acid, 5% of silicon nanoparticles and 5% of micron silver powder are added into a mixing tank of a vacuum mixer according to the weight percentage, the materials are mixed for 60 minutes in a rolling and rotating mode to obtain a mixture, N-methyl pyrrolidone 1.1 times the weight of the mixture is added into the mixing tank, the slurry is introduced into a dispersing machine after being mixed for 2 hours, then the mixing tank is cleaned by N-methyl pyrrolidone 0.5 times the weight of the mixture, a cleaning solution is introduced into the dispersing machine, and the slurry in the dispersing machine is dispersed and mixed for 4 hours to obtain electrode slurry.
Example 3
The difference from example 1 is that 90% porous activated carbon, 2.5% polyvinyl alcohol, 2.5% zeolite powder and 5% silver nanowires are added to a mixing tank of a vacuum mixer by weight percentage, a mixture is obtained by rolling, rotating and mixing for 60 minutes, gamma butyrolactone 1.3 times the weight of the mixture is added to the mixing tank, the slurry is introduced into a dispersion machine after mixing for 2 hours, then the mixing tank is cleaned by gamma butyrolactone 0.5 times the weight of the mixture, a cleaning solution is introduced into the dispersion machine, and the slurry in the dispersion machine is dispersed and mixed for 4 hours to obtain electrode slurry.
Example 4
The difference from the embodiment 1 is that 92.5% of porous activated carbon, 4% of polypropylene alcohol, 0.1% of molecular sieve powder and 3.4% of micron gold powder are added into a mixing tank of a vacuum mixer according to weight percentage, the materials are mixed for 60 minutes in a rolling and rotating mode to obtain a mixture, dimethyl carbonate with the weight 1.5 times that of the mixture is added into the mixing tank, the slurry is introduced into a dispersion machine after being mixed for 2 hours, then the mixing tank is cleaned by the dimethyl carbonate with the weight 0.5 times that of the mixture, a cleaning solution is introduced into the dispersion machine, and the slurry in the dispersion machine is dispersed and mixed for 4 hours to obtain electrode slurry.
Example 5
The difference from example 1 is that 95% porous activated carbon, 0.5% polyvinyl alcohol, 4.4% zeolite powder and 0.1% silver nanowires are added to a mixing tank of a vacuum mixer by weight percentage, a mixture is obtained by rolling, rotating and mixing for 60 minutes, ethylene carbonate 1 time the weight of the mixture is added to the mixing tank, the slurry is introduced into a dispersion machine after mixing for 2 hours, then the mixing tank is cleaned by ethylene carbonate 0.5 time the weight of the mixture, a cleaning solution is introduced into the dispersion machine, and the slurry in the dispersion machine is dispersed and mixed for 4 hours to obtain electrode slurry.
Example 6
The difference from example 1 is that the active electrode material is graphite.
Example 7
The difference from example 1 is that the active electrode material is graphene.
Comparative example 1
The difference from the example 1 is that the solute comprises the following components in percentage by weight: 84% of porous activated carbon, 4.5% of CMC cellulose, 3.5% of alumina powder and 8% of nickel powder.
Comparative example 2
The difference from the example 1 is that the solute comprises the following components in percentage by weight: 96% of porous activated carbon, 3.8% of CMC cellulose, 0.1% of alumina powder and 0.1% of nickel powder.
Comparative example 3
The difference from the embodiment 4 is that the solute comprises the following components in percentage by weight: 92.5 percent of porous active carbon, 4 percent of polypropylene glycol and 3.5 percent of micron gold powder.
Comparative example 4
The difference from the embodiment 4 is that the solute comprises the following components in percentage by weight: 92.5 percent of porous active carbon, 4 percent of polypropylene alcohol and 3.5 percent of molecular sieve powder.
Comparative example 5
The difference from example 1 is that the mixing bowl was cleaned with 0.4 times the weight of the mix of sulfolane and the total weight of solvent was 1.4 times the total weight of solute.
Comparative example 6
The difference from example 1 is that the mixing bowl was cleaned with 1.1 times the weight of the mix of sulfolane and the total weight of solvent was 2.1 times the total weight of solute.
Table 1: the ratio of each component of solute of electrode slurry and the amount of solvent used in examples 1-7 and comparative examples 1-6
The electrode pastes prepared in examples 1 to 7 and comparative examples 1 to 4 were well adhered to the paper substrate, had good adhesion and could form a continuous and complete coating, while when the electrode paste prepared in comparative example 5 was used to coat the paper substrate, the electrode paste was too viscous to be uniformly coated on the paper substrate, and the surface of the coating was uneven, and when the electrode paste prepared in comparative example 6 was used to coat the paper substrate, the electrode paste was too thin to be adhered to the surface of the paper substrate, and a continuous and complete coating could not be formed.
The paper-based electrodes prepared in examples 1 to 7 and comparative examples 1 to 4 were subjected to performance testing, and the test items were as follows: discharge capacity, leakage current and equivalent series internal resistance (ESR); detection standard: IEC 62391-1; since the electrode pastes prepared in comparative examples 5 and 6 did not meet the product requirements due to adhesion to the paper substrates upon coating, performance tests were not performed.
The test method comprises the following steps:
the paper-based electrode and other electric core materials prepared in the examples 1-7 and the comparative examples 1-4 are respectively adopted, cutting, nailing and rolling are carried out according to the design size of the winding type super capacitor, drying is carried out, the electric core is impregnated with electrolyte and assembled under the vacuum environment, aging, detection and other manufacturing procedures are completed, finally, winding type paper-based super capacitor samples with the specification of 2.7V/1F are prepared, ten paper-based super capacitor samples are respectively taken from the super capacitors prepared by the paper-based electrodes in the examples 1-7 and the comparative examples 1-4, the following tests are carried out, the test results are averaged, and specific data are shown in a table 2.
And (3) testing discharge capacity: by adopting a constant-current discharge method, the capacitance deviation is within the range of +/-30% of the rated capacitance, namely the discharge capacity is between 0.7 and 1.3F, and the larger the value of the discharge capacity in the range is, the better the electrical property of the super capacitor is; the method comprises the steps of connecting a super capacitor into a direct current circuit with a constant current/constant voltage source, charging the super capacitor for 30min at a constant voltage after the constant current/constant voltage source reaches a rated voltage UR, connecting the super capacitor into a circuit with a constant current discharging device to discharge at a constant current I, measuring the voltage at two ends of the super capacitor, starting timing from U1 equal to 0.8UR to t1, stopping timing from U2 equal to 0.4UR to t2, and calculating a discharge capacity value according to a formula C equal to I (t2-t 1)/U1-U2.
And (3) leakage current testing: by adopting a direct current test, the leakage current is less than or equal to 0.01mA (24 hours), and the smaller the leakage current is, the better the electrical property of the super capacitor is; discharging the super capacitor for 1h, then charging until 95% charging voltage is reached, continuously charging for 24 hours, connecting a direct current gear of the digital multimeter and the super capacitor in series, and then connecting the direct current gear and the super capacitor into a circuit with a linear direct current voltage stabilizing and stabilizing power supply, wherein the output voltage of the voltage stabilizing and stabilizing power supply is lower than the rated voltage of the super capacitor, and after 10 time constants, the reading displayed by the digital multimeter is the leakage current of the capacitor.
ESR test: and (3) testing by adopting alternating current, wherein the equivalent series resistance ESR of the super capacitor is less than or equal to 200m omega, and measuring by adopting an internal resistance tester, wherein the frequency is set to be 1kHz, and the smaller the ESR value is, the better the electrical property of the super capacitor is.
Table 2: performance test data of supercapacitors produced using the electrode pastes of examples 1-7 and comparative examples 1-4
The data of examples 1-5 and table 2 show that the discharge capacity, the leakage current value, and the ESR value of the supercapacitor made from the electrode paste of the formulation of the present application can all reach the qualified standards, and the electrical properties are excellent, wherein the supercapacitor made from the electrode paste formulation of example 3 has better performance, the discharge capacity can reach 0.965F, the leakage current value is 0.006mA, and the ESR value is 87m Ω.
As can be seen from comparison of example 1 and comparative examples 1-2 with the data in table 2, the leakage current and ESR of the resulting supercapacitor did not meet the acceptable standards when no proppant or no conductive agent was added to the electrode slurry.
As can be seen from comparative example 1, comparative examples 3 to 4, and the data in Table 2, when the amount of the active electrode material added is less than 85% or more than 95% of the solute weight of the electrode slurry, the discharge capacity, the leakage current value and the ESR value of the prepared supercapacitor can not meet the acceptable standards.
As can be seen from the data in examples 1, 6, 7 and table 2, the discharge capacity, the leakage current value and the ESR value of the supercapacitor made by using graphite and graphene as the active electrode material of the electrode slurry respectively can also reach the acceptable standards, and the discharge capacity, the leakage current value and the ESR value of the supercapacitor made by using graphite or graphene as the active electrode material of the electrode slurry are better, and the active electrode material of the electrode slurry is better. However, the price of graphite and graphene is more expensive than that of porous activated carbon, and the performance of the supercapacitor made by using graphite or graphene as an active electrode material of electrode slurry is improved more than that of porous activated carbon, so that the porous activated carbon is more suitable as the active electrode material of electrode slurry in combination with the actual production cost.
Example 8
The difference from example 3 is that the active electrode material is composed of 60% of porous activated carbon, 30% of graphite and 10% of graphene.
Example 9
The difference from example 3 is that the active electrode material is composed of 65% porous activated carbon, 24% graphite and 11% graphene.
Example 10
The difference from example 3 is that the active electrode material is composed of 69.5% porous activated carbon, 30% graphite and 0.5% graphene.
Example 11
The difference from example 3 is that the active electrode material is composed of 80% porous activated carbon, 15% graphite and 5% graphene.
Example 12
The difference from example 3 is that the active electrode material is composed of 85% of porous activated carbon, 5% of graphite and 10% of graphene.
Example 13
The difference from example 3 is that the active electrode material is composed of 90% porous activated carbon, 5% graphite and 5% graphene.
Table 3: composition ratios of active electrode materials in examples 8 to 13
The paper-based electrodes prepared in examples 8 to 13 were subjected to the performance tests, and the test items, test standards and test methods were as above, and the specific data are shown in table 4.
Table 4: performance test data for supercapacitors made using the electrode pastes of examples 3, 8-13
It can be seen by combining the data of examples 3, 8-13 and table 4 that, compared with the electrode slurry using only porous activated carbon as the active electrode material, the supercapacitor made by using the electrode slurry using porous activated carbon, graphite and graphene compounded as the active electrode material has better electrical properties, wherein the discharge capacity, the leakage current value and the ESR value of the supercapacitor are better improved by using the compounded active electrode material prepared in the proportion in example 11, the discharge capacity can reach 1.286F, the leakage current value is as low as 0.004mA, and the ESR value is only 84m Ω.
Example 14
The difference from example 11 is that the paper-based substrate was coated with an electrode paste having a thickness of 55 μm on each side and a paper-based electrode having a thickness of 175 μm was produced.
In example 11, the thickness of the pretreated paper substrate was 65 μm, the thickness of the electrode paste coated on each side was 50 μm, and the thickness of the paper-based electrode prepared by coating the electrode paste was 165 μm.
Example 15
The difference from example 11 is that the paper-based substrate was coated with an electrode paste having a thickness of 60 μm on each side and a paper-based electrode having a thickness of 185 μm was produced.
Comparative example 5
The difference from example 11 is that the paper-based substrate was coated with an electrode paste having a thickness of 65 μm on each side and a paper-based electrode having a thickness of 195 μm was produced.
Comparative example 6
The difference from example 11 is that the thickness of the electrode paste coated on each side of the paper substrate was 45 μm and the thickness of the paper-based electrode prepared was 155 μm.
In the test process, the paper-based electrode prepared in the comparative example 5 is found to have cracking and falling phenomena when being wound.
The paper-based electrodes prepared in examples 14 and 15 and comparative example 6 were subjected to performance testing, the testing items, testing standards and testing methods were the same as above, and the specific data are shown in table 5; the paper-based electrode prepared in comparative example 5 was not subjected to performance testing because the coating cracked and dropped off during winding.
Table 5: performance test data for supercapacitors produced using the paper-based electrodes of examples 11, 14, 15 and comparative example 6
When the paper substrate with the thickness of 60 μm is used, the super capacitor with the discharge capacity of 1.292F, the leakage current value of 0.003mA and the ESR value of 82m omega is obtained when the paper-based electrode is 175 μm.
To sum up, the electrode paste and the paper substrate of this application embodiment's bonding effect is excellent, and adhesive force is good, and active electrode material is difficult for droing to the paper base electrode that adopts this application electrode paste to make has fine promotion to ultracapacitor system's discharge capacity, leakage current value, ESR value, especially adopts the ratio of electrode paste and the coating thickness of paper base electrode in embodiment 14, and is more excellent to ultracapacitor system's electric property's promotion.
The embodiment of the application also provides a winding type paper-based supercapacitor, referring to fig. 1 and 2, the winding type paper-based supercapacitor comprises a shell 1 and a prime mover 2 installed in the shell 1, the prime mover 2 is soaked with electrolyte, and the prime mover 2 is connected with a positive guide pin 3 and a negative guide pin 4.
Referring to fig. 2, the element 2 is formed by sequentially laminating and winding a positive electrode conductive metal connecting sheet 21, a positive electrode paper-based electrode pole piece 22, electrolytic paper 23, a negative electrode paper-based electrode pole piece 24, a negative electrode conductive metal connecting sheet 25 and the electrolytic paper 23, wherein the positive electrode paper-based electrode pole piece 22 and the negative electrode paper-based electrode pole piece 24 are paper-based electrodes prepared in the above embodiment.
In this embodiment, the positive conductive metal connecting piece 21 and the negative conductive metal connecting piece 25 are both made of copper foil, and in other embodiments, the positive conductive metal connecting piece 21 and the negative conductive metal connecting piece 25 may also be made of metal foil with good conductive performance, such as aluminum foil.
Referring to fig. 3 and 4, the positive electrode guide pin 3 is riveted to the positive electrode paper-based electrode piece 22 and the positive electrode conductive metal connecting piece 21, and the positive electrode conductive metal connecting piece 21 is located between the positive electrode guide pin 3 and the positive electrode paper-based electrode piece 22.
The negative electrode guide pin 4 is riveted on the negative electrode paper-based electrode pole piece 24 and the negative electrode conductive metal connecting piece 25, and the negative electrode conductive metal connecting piece 25 is positioned between the negative electrode guide pin 4 and the negative electrode paper-based electrode pole piece 24. The positive conductive metal connecting sheet 21 can improve the connection firmness of the positive paper-based electrode plate 22 and the positive guide pin 3, and the negative conductive metal connecting sheet.
Claims (10)
1. The electrode slurry for the paper-based supercapacitor is characterized by comprising a solvent and a solute dissolved in the solvent, wherein the weight of the solvent is 1.5-2 times that of the solute;
the solute comprises the following components in percentage by weight:
active electrode material: 85% -95%;
adhesive: 0.5% -4.5%;
proppant: 0.1% -5%;
conductive agent: 0.1% -8%.
2. The electrode slurry for the paper-based supercapacitor according to claim 1, wherein the active electrode material is one or a combination of porous activated carbon, graphite and graphene.
3. The paper-based electrode paste for the supercapacitor as claimed in claim 2, wherein the active electrode material is prepared by compounding 65-85% of porous activated carbon, 5-30% of graphite and 0.5-11% of graphene in percentage by weight.
4. The electrode paste for the paper-based supercapacitor according to claim 1, wherein the binder is one or a combination of polyvinyl alcohol, polypropylene alcohol, polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid, polyacrylonitrile and CMC cellulose.
5. The electrode slurry for the paper-based supercapacitor according to claim 1, wherein the propping agent is one or a combination of several of alumina powder, silicon nanoparticles, zeolite powder and molecular sieve powder, and the granularity D90 of the propping agent is less than 10 μm.
6. The electrode slurry for the paper-based supercapacitor according to claim 1, wherein the solvent is one or a combination of sulfolane, N-methyl pyrrolidone, gamma butyrolactone, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethylene carbonate and propylene carbonate.
7. A paper-based electrode characterized by: comprising a paper substrate, the surface of which is coated with the electrode paste for paper-based supercapacitors according to any one of claims 1-6.
8. The paper-based electrode according to claim 7, wherein the paper-based substrate has a thickness of 50 to 80 μm and the paper-based electrode has a thickness of 165 to 185 μm.
9. The method of making the paper-based electrode of claim 7, comprising the steps of:
continuously performing ultrasonic dispersion on the electrode slurry, uniformly coating the electrode slurry on one surface of the paper substrate, baking the paper substrate for 8-12 hours at 50-165 ℃ through a vacuum oven, turning over the dried paper substrate through a roller type rotating shaft, coating and drying the surface of the paper substrate, which is not coated with the electrode slurry, in the same way, and obtaining the paper-based electrode.
10. A winding type paper-based supercapacitor is characterized by comprising a positive paper-based electrode pole piece (22) and a negative paper-based electrode pole piece (24), wherein the positive paper-based electrode pole piece (22) and the negative paper-based electrode pole piece (24) both adopt the paper-based electrode in claim 7 or claim 8.
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