CN114334473A - Conductive enhancing liquid for paper substrate of super capacitor, paper substrate and preparation method - Google Patents
Conductive enhancing liquid for paper substrate of super capacitor, paper substrate and preparation method Download PDFInfo
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Abstract
The application relates to the field of paper-based supercapacitors, and particularly discloses a conductive reinforcing liquid for a paper substrate of a supercapacitor, the paper substrate and a preparation method of the paper substrate. The conductive reinforcing liquid comprises the following components in percentage by weight: 81-90% of conductive polymer, 2-5% of cosolvent, 1-3% of wetting agent, 5-9% of flow aid and 2-4% of conductive promoter, wherein the cosolvent is mono-alcohol and/or polyhydric alcohol, the wetting agent is polyethylene glycol, the flow aid is sugar alcohol, and the conductive promoter is sulfate and/or carbonate; the surface of the paper substrate is coated with the conductive enhancing liquid. The conductive enhanced liquid has excellent conductivity, and can form a conductive film on a paper substrate, so that the conductivity of the paper substrate is greatly improved, and the preparation process of the paper substrate is simple and the production cost is low.
Description
Technical Field
The application relates to the field of paper-based supercapacitors, in particular to a conductive reinforcing liquid for a paper substrate of a supercapacitor, the paper substrate and a preparation method.
Background
The super capacitor is an energy storage device between a battery and a conventional capacitor and used for storing electric energy, and is a novel component for storing energy through an interface double layer formed between an electrode and an electrolyte.
The electrode of the super capacitor is mostly made of a metal substrate, and is made by covering or attaching an active electrode material on the metal substrate. However, the flexibility of the metal substrate electrode is poor, and when a wound supercapacitor is manufactured, the active electrode material is easy to fall off from the metal substrate, so that the conductivity of the electrode is poor. Based on this, paper is adopted as the electrode substrate of the supercapacitor in the related art, and compared with a metal substrate electrode, the paper substrate electrode has the advantages of good flexibility, difficulty in falling off of an active electrode material during winding, and low production cost.
However, compared with a metal substrate, the conductivity of a paper substrate is poor, and along with the development of a super capacitor, the performance requirement of the super capacitor is higher and higher, and the requirement of the super capacitor on the conductivity of an electrode cannot be met only by covering or attaching an active electrode material on the paper substrate, so that how to improve the conductivity of the paper substrate is a problem which needs to be solved urgently.
Disclosure of Invention
In order to improve the conductivity of the paper-based supercapacitor paper substrate, the application provides a conductivity enhancing liquid for the supercapacitor paper substrate, the paper substrate and a preparation method.
In a first aspect, the application provides a conductive reinforcing liquid for a paper substrate of a supercapacitor, which adopts the following technical scheme:
the conductive reinforcing liquid for the paper substrate of the super capacitor is characterized by comprising the following components in percentage by weight:
conductive polymer: 81% -90%;
cosolvent: 2% -5%;
wetting agent: 1% -3%;
flow aid: 5% -9%;
conductivity accelerator: 2% -4%;
the cosolvent is mono-alcohol and/or polyol, the wetting agent is polyethylene glycol, the flow aid is sugar alcohol, and the conduction promoter is sulfate and/or carbonate.
By adopting the technical scheme, the main component of the conductive reinforcing liquid is a conductive polymer with excellent conductive performance, methyl, sulfydryl and carbonyl in the molecules of the conductive accelerant can exchange with acid H atoms of hydroxyl, sulfydryl, amino or imino of other compound molecules under an alkaline condition, the polarization degree of the conductive polymer is improved, so that the conductive performance of the molecules of the conductive polymer is improved, the molecules of the cosolvent, the wetting agent and the flow assistant all contain hydroxyl groups, and the molecules in the same system can form hydrogen bonds to generate affinity, so that the generated synergistic effect enables the conductive reinforcing liquid system to be stable, a conductive film is formed after the conductive reinforcing liquid is coated on the surface of a paper substrate, and the conductive performance of the paper substrate is greatly improved; in addition, the cosolvent is also beneficial to promoting the components to be better dissolved and mixed, and the mixing uniformity of the system is improved; the flow assistant can also improve the fluidity of the system, so that the conductive enhancement liquid can more easily form a conductive film on the paper substrate and coat the paper substrate, thereby more comprehensively improving the conductive performance of the paper substrate; the wetting agent is also used for enhancing the strength of a conductive film formed by the conductive enhancing liquid on the paper substrate, so that the paper substrate is not easy to break when being wound, and excellent conductive performance is kept, and cohesion (such as hydrogen bonds) can be generated between the polyethylene glycol substances and the conductive polymer, and adhesion force can be generated between the polyethylene glycol substances and hydrophilic groups on the paper substrate, so that the conductive polymer is easier to adhere to the paper substrate and is not easy to fall off, and the paper substrate is kept stable in conductive performance.
Preferably, the conductive polymer is one or a combination of several of polythiophene, polysulfonic acid, polypyrrole, polyphenylene sulfide, polyacetylene, polyaniline and poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) aqueous dispersion liquid.
Preferably, the conductive polymer is an aqueous dispersion of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS).
By adopting the technical scheme, the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT/PSS) aqueous dispersion liquid is a polythiophene/polysulfonic acid aqueous dispersion liquid and has good conductivity, and the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT/PSS) aqueous dispersion liquid is a highly dispersed aqueous dispersion system, so that the dispersion uniformity degree of the system is improved.
Preferably, the cosolvent is one or a combination of ethanol, ethylene glycol, isopropanol and glycerol.
By adopting the technical scheme, the monohydric alcohol and the polyhydric alcohol are alcohols with small molecular weights, hydrogen bonds can be generated between the conductive polymer and water molecules, a net-shaped linked structure is formed, and the mixing uniformity and stability of the system are improved.
Preferably, the wetting agent is one or a combination of more of polyethylene glycol-200, polyethylene glycol-400, polyethylene glycol-600 and polyethylene glycol-800.
Through tests, polyethylene glycol with the molecular weight less than 1000 is easier to generate cohesion with conductive polymer macromolecules and improve the adhesive force with the surface of a paper substrate, and when the molecular weight of the polyethylene glycol exceeds 1000, the polyethylene glycol is not easy to generate cohesion with the conductive polymer macromolecules due to the volume effect and is not easy to attach to the surface of the paper substrate.
Preferably, the flow aid is sorbitol and/or mannitol.
By adopting the technical scheme, sorbitol and mannitol molecules both contain a plurality of hydroxyl groups, have extremely strong hydrophilicity, can perform cross-linking reaction with a conductive polymer, a cosolvent and a wetting agent in a water-based system, and can greatly improve the fluidity of the conductive reinforcing liquid.
Preferably, the conduction promoter is one or a combination of dimethyl sulfate, ethylene sulfite and ethylene carbonate.
Preferably, the viscosity of the conductive reinforcing liquid is 10-30 mPas.
Tests prove that when the viscosity of the conductive reinforcing liquid exceeds 30 mPas, the subsequent spraying treatment of the paper substrate by the conductive reinforcing liquid can result in large spraying granularity, the coating formed on the paper substrate is too thick, and even a nozzle can be blocked, when the viscosity of the conductive reinforcing liquid is less than 10 mPas, the coating formed on the paper substrate is too thin, the conductivity is affected, and the coating is easy to crack during the subsequent rolling of the paper substrate, so that the requirement can be met only by spraying for many times, and the production efficiency is affected.
In a second aspect, the present application provides a paper substrate for a supercapacitor, which adopts the following technical solution:
the surface of the paper substrate is coated with the conductive enhancing liquid in the technical scheme.
By adopting the technical scheme, the paper substrate coated with the conductive reinforcing liquid has excellent conductivity, and can well meet the requirement of a super capacitor on the conductivity of the electrode.
Preferably, the paper substrate is a long fiber non-woven paper material, the thickness of the paper substrate is 50-80 μm, and the pore size is 2-9 μm.
By adopting the technical scheme, the long fiber non-woven paper material has low cost, uniform gaps among fibers and high thermal stability, and the mechanical tensile strength is high, the toughness is good, the paper base plate can be well rolled, and through tests, when the thickness of the paper base plate is less than 50 mu m, the crease resistance and the tensile strength of the paper base plate are too low, the mechanical property of the paper base electrode is influenced, when the thickness of the paper substrate exceeds 80 micrometers, the active electrode material coated on the surface of the paper substrate is easy to fall off when the paper substrate is wound, the aperture of the paper substrate is controlled to be 2-9 micrometers, the paper substrate can be well combined with the conductive reinforcing liquid, when the aperture is less than 2 micrometers, the difficulty of the conductive reinforcing liquid entering the aperture of the paper substrate is too large, the combination is poor, the aperture is larger than 9 micrometers, the conductive reinforcing liquid can directly permeate, the combination is poor, and the conductive reinforcing liquid is difficult to form a continuous and complete membrane on the paper substrate.
In a third aspect, the present application provides a method for manufacturing a paper substrate, which adopts the following technical scheme:
a preparation method of a paper substrate comprises the following steps:
spraying: spraying conductive enhancing liquid on two sides of the paper substrate simultaneously, wherein in the spraying process, a rolling shaft is adopted for discharging and receiving the paper substrate;
drying: and drying the sprayed part of the paper substrate by an infrared light emitting tube at the drying temperature of 110-155 ℃, and winding the dried paper substrate into a coil.
By adopting the technical scheme, the process is simple, the rapid spraying of the paper substrate is realized, the spraying quality is good, the film forming is uniform, the infrared light emitting tube is adopted for heating and drying, the advantages of high efficiency and economy are achieved, the surface and the thin layer of an object can be rapidly heated, the drying speed is high, and the rapid film forming of the conductive reinforcing liquid coating is facilitated.
Preferably, the discharge speed of the paper substrate during spraying is 0.5-1.5 m/min.
By adopting the technical scheme, when the discharging speed is lower than 0.5m/min, the drying time of the coating is too long, the phenomenon of dry cracking is easy to occur, the production efficiency is reduced, the energy consumption is increased, when the discharging speed is higher than 1.5m/min, the coating is not dried thoroughly, and the film forming effect is poor.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the main components of the conductive reinforcing liquid are conductive polymers with excellent conductive performance, methyl, sulfydryl and carbonyl in molecules of a conductive promoter can be exchanged with acid H atoms of hydroxyl, sulfydryl, amino or imino of other compound molecules under an alkaline condition, the polarization degree of the conductive polymers is improved, so that the conductive performance of the conductive polymer molecules is improved, the molecules of a cosolvent, a wetting agent and a flow aid all contain hydroxyl groups, hydrogen bonds can be formed among the molecules in the same system to generate affinity, so that the generated synergistic effect enables the conductive reinforcing liquid system to be stable, a conductive film is formed after the conductive reinforcing liquid system is coated on the surface of a paper substrate, and the conductive performance of the paper substrate is greatly improved.
2. The paper substrate prepared by the method is excellent in conductivity, the requirement of the supercapacitor on the conductivity of the electrode can be well met, and the development of the paper-based supercapacitor is promoted.
3. The preparation technology of the paper substrate is simple, the quick spraying of the paper substrate is realized, the spraying quality is good, the film forming is uniform, the infrared light emitting tube is adopted for heating and drying, the advantages of high efficiency and economy are achieved, the drying speed is high, and the quick film forming of the conductive reinforcing liquid coating is facilitated.
Drawings
FIG. 1 is a comparison of a paper substrate of the present application before and after treatment with a conductive enhancing fluid.
Detailed Description
Because the metal substrate electrode of the conventional supercapacitor is poor in flexibility, when a winding type supercapacitor is manufactured, an attached active electrode material is easy to fall off from the metal substrate, therefore, paper is used as the electrode substrate of the supercapacitor in research, compared with the metal substrate electrode, the paper substrate electrode is good in flexibility, the active electrode material is not easy to fall off during winding, the production cost is low, but the requirement of the supercapacitor on the electrode conductivity is limited by the weak conductivity of the paper substrate.
Through a large number of researches, the applicant finds that the conductivity of the conductive polymer poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) aqueous dispersion can be improved by 1-3 times by compounding and mixing the conductive polymer poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) aqueous dispersion with polyethylene glycol, ethylene glycol, sorbitol and ethylene carbonate, and then the compounded conductive reinforcing liquid is sprayed to a paper substrate material for pretreatment by using a spraying process, so that conductive polymer molecules are filled in pores and surfaces of the paper substrate, and the conductivity of the paper substrate is improved. 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 a long fiber non-woven paper material from Hitachi high and new technology Limited companyThe model is ASS040-010-200-060R, the thickness is 60 μm, and the density is 0.67g/cm3The aperture is 8.1 mu m, the temperature resistance can reach 260 ℃, and the method can be well suitable for the temperature of a drying process and the temperature of the subsequent operation of the super capacitor.
Aqueous dispersions of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT/PSS) were obtained from Guang Donghua hong technology Inc., model AL-16.
Examples
Example 1
According to the weight percentage, 81 percent of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) aqueous dispersion liquid is taken as a conductive polymer, 5 percent of ethanol is taken as a cosolvent, 3 percent of polyethylene glycol-400 is taken as a wetting agent, 7 percent of mannitol is taken as a flow assistant, and 4 percent of dimethyl sulfate 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 performing ultrasonic vibration on the mixed solution at the frequency of 40KHz for 1.5 hours to obtain a conductive reinforcing solution, and detecting that the viscosity of the conductive reinforcing solution is 14.5 mPas.
The method comprises the steps of adding the conductive reinforcing liquid into a liquid storage tank of a vertical spraying machine, realizing discharging and receiving of the paper substrate to be processed by adopting a rolling shaft in a rolling mode, spraying the conductive reinforcing liquid onto two sides of the paper substrate simultaneously by the vertical spraying machine, and controlling the discharging speed to be 0.5 m/min. And heating the sprayed part of the paper substrate by an infrared light emitting tube to dry, controlling the drying temperature to be 110 ℃, and winding the dried paper substrate into a coil.
Example 2
The difference from the embodiment 1 is that the weight percentage ratio of the conductive reinforcing liquid is as follows: 82% of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) aqueous dispersion liquid is used as a conductive polymer, 3% of ethylene glycol is used as a cosolvent, 3% of polyethylene glycol-600 is used as a wetting agent, 8% of sorbitol is used as a flow aid, 4% of ethylene carbonate is used as a conductive promoter, and the viscosity of a conductive reinforcing liquid is 22.5 mPas. The discharging speed is 0.7m/min during spraying, and the drying temperature is 115 ℃.
Example 3
The difference from the embodiment 1 is that the weight percentage ratio of the conductive reinforcing liquid is as follows: 83% of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) aqueous dispersion liquid is taken as a conductive polymer, 2.5% of isopropanol is taken as a cosolvent, 2.5% of polyethylene glycol-600 is taken as a wetting agent, 9% of sorbitol is taken as a flow aid, 3% of ethylene sulfite is taken as a conductive promoter, and the viscosity of a conductive reinforcing liquid is 22.2 mPas. The discharging speed is 0.9m/min during spraying, and the drying temperature is 120 ℃.
Example 4
The difference from the embodiment 1 is that the weight percentage ratio of the conductive reinforcing liquid is as follows: 84% of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) aqueous dispersion liquid is used as a conductive polymer, 2% of ethylene glycol is used as a cosolvent, 2% of polyethylene glycol-600 is used as a wetting agent, 9% of sorbitol is used as a flow aid, 3% of ethylene carbonate is used as a conductive promoter, and the viscosity of a conductive reinforcing liquid is 22 mPas. The discharge speed is 1m/min during spraying, and the drying temperature is 125 ℃.
Example 5
The difference from the embodiment 1 is that the weight percentage ratio of the conductive reinforcing liquid is as follows: 85% of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) aqueous dispersion liquid is used as a conductive polymer, 3% of glycerol is used as a cosolvent, 2% of polyethylene glycol-600 is used as a wetting agent, 7% of mannitol is used as a flow aid, 3% of ethylene carbonate is used as a conductive promoter, and the viscosity of a conductive reinforcing liquid is 18.4 mPas. The discharge speed is 1.1m/min during spraying, and the drying temperature is 130 ℃.
Example 6
The difference from the embodiment 1 is that the weight percentage ratio of the conductive reinforcing liquid is as follows: 86% of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) aqueous dispersion liquid is used as a conductive polymer, 2.5% of glycerol is used as a cosolvent, 2.5% of polyethylene glycol-200 is used as a wetting agent, 6% of mannitol is used as a flow assistant, 3% of ethylene carbonate is used as a conductive promoter, and the viscosity of a conductive reinforcing liquid is 10.8 mPas. The discharging speed is 1.2m/min during spraying, and the drying temperature is 135 ℃.
Example 7
The difference from the embodiment 1 is that the weight percentage ratio of the conductive reinforcing liquid is as follows: 87% of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) aqueous dispersion liquid is used as a conductive polymer, 3% of ethanol is used as a cosolvent, 2% of polyethylene glycol-800 is used as a wetting agent, 5% of mannitol is used as a flow assistant, 3% of ethylene sulfate is used as a conductive promoter, and the viscosity of a conductive reinforcing liquid is 28.2 mPas. The discharge speed is 1.3m/min during spraying, and the drying temperature is 140 ℃.
Example 8
The difference from the embodiment 1 is that the weight percentage ratio of the conductive reinforcing liquid is as follows: 88% of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) aqueous dispersion liquid is used as a conductive polymer, 2% of isopropanol is used as a cosolvent, 2% of polyethylene glycol-600 is used as a wetting agent, 6% of sorbitol is used as a flow aid, 2% of ethylene sulfite is used as a conductive promoter, and the viscosity of a conductive reinforcing liquid is 14.7 mPas. The discharging speed is 1.4m/min during spraying, and the drying temperature is 145 ℃.
Example 9
The difference from the embodiment 1 is that the weight percentage ratio of the conductive reinforcing liquid is as follows: 89% of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) aqueous dispersion liquid is used as a conductive polymer, 3% of isopropanol is used as a cosolvent, 1% of polyethylene glycol-400 is used as a wetting agent, 5% of sorbitol is used as a flow aid, 2% of ethylene sulfite is used as a conductive promoter, and the viscosity of a conductive reinforcing liquid is 12.5 mPas. The discharging speed is 1.4m/min during spraying, and the drying temperature is 150 ℃.
Example 10
The difference from the embodiment 1 is that the weight percentage ratio of the conductive reinforcing liquid is as follows: 90% of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) aqueous dispersion liquid is used as a conductive polymer, 2% of isopropanol is used as a cosolvent, 1% of polyethylene glycol-400 is used as a wetting agent, 5% of sorbitol is used as a flow aid, 2% of ethylene sulfite is used as a conductive promoter, and the viscosity of a conductive reinforcing liquid is 12.6 mPas. The discharge speed during spraying is 1.5m/min, and the drying temperature is 155 ℃.
Comparative example
Comparative example 1
The difference from the embodiment 1 is that the weight percentage ratio of the conductive reinforcing liquid is as follows: 78% of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) aqueous dispersion liquid is used as a conductive polymer, 5% of ethanol is used as a cosolvent, 3% of polyethylene glycol-400 is used as a wetting agent, 9% of mannitol is used as a flow aid, and 4% of dimethyl sulfate is used as a conductive promoter.
Comparative example 2
The difference from the embodiment 1 is that the weight percentage ratio of the conductive reinforcing liquid is as follows: 93% of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) aqueous dispersion liquid is used as a conductive polymer, 1% of ethanol is used as a cosolvent, 1% of polyethylene glycol-400 is used as a wetting agent, 4% of mannitol is used as a flow aid, and 1% of dimethyl sulfate is used as a conductive promoter.
Comparative example 3
The difference from example 1 is that the conductivity enhancing solution only uses aqueous dispersion of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS).
Comparative example 4
The difference from the embodiment 8 is that the weight percentage ratio of the conductive reinforcing liquid is as follows: 88% of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) aqueous dispersion liquid is used as a conductive polymer, 2% of polyethylene glycol-400 is used as a wetting agent, 7% of mannitol is used as a flow additive, and 3% of dimethyl sulfate is used as a conductive promoter.
Comparative example 5
The difference from the embodiment 8 is that the weight percentage ratio of the conductive reinforcing liquid is as follows: 88% of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) aqueous dispersion liquid is used as a conductive polymer, 2% of ethanol is used as a cosolvent, 7% of mannitol is used as a flow aid, and 3% of dimethyl sulfate is used as a conductive promoter.
Comparative example 6
The difference from the embodiment 8 is that the weight percentage ratio of the conductive reinforcing liquid is as follows: 88% of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) aqueous dispersion liquid is used as a conductive polymer, 5% of ethanol is used as a cosolvent, 3% of polyethylene glycol-400 is used as a wetting agent, and 4% of dimethyl sulfate is used as a conductive promoter.
Comparative example 7
The difference from the embodiment 8 is that the weight percentage ratio of the conductive reinforcing liquid is as follows: 88% of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) aqueous dispersion liquid is used as a conductive polymer, 3% of ethanol is used as a cosolvent, 2% of polyethylene glycol-400 is used as a wetting agent, and 7% of mannitol is used as a flow aid.
Table 1: component proportions of examples 1 to 10 and comparative examples 1 to 7
Performance test
Testing the impedance value of the paper substrate:
10 paper substrates of 5cm x 5cm were cut out from the paper substrates prepared in examples 1 to 10 and comparative examples 1 to 7, the paper substrates treated with the conductive reinforcing agent were clamped by two clamps on a bridge tester with an automatic balance impedance function, a frequency of 100KHz and a room temperature of 20 ℃, a distance between the two clamps was maintained at 2 to 3mm, a value was directly read from a display window of the bridge tester, i.e., an impedance value of the paper substrates, and a maximum value of each set of impedance value data was obtained, as shown in table 2.
The conductivity enhancement factor in table 2 is characterized relative to comparative example 3 for a paper substrate pretreated with only an aqueous dispersion of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS). The conduction boost ratio is equal to the impedance value/30.
Table 2: impedance values of paper substrates in examples 1 to 10 and comparative examples 1 to 7
By combining the data of examples 1-10, comparative example 3 and table 2, it can be seen that the resistance value of the paper substrate coated with the conductive reinforcing liquid of the formulation of the present application is significantly reduced and the guiding performance is significantly improved compared to the paper substrate coated with only the aqueous dispersion of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS), wherein the conductive reinforcing liquid prepared by the formulation of example 4 has better conductive performance, the resistance value is only 10.0 Ω, and the conductivity improvement rate can reach 3 times.
Combining the data of example 1, comparative examples 1-2 and table 2, it can be seen that when the weight percentage of the conductive polymer is less than 81% or exceeds 90%, the effect of the conductive enhancing liquid on improving the conductivity of the paper substrate is significantly reduced, and is only 1 times more.
It can be seen from the data in example 8, comparative examples 4 to 6, and table 2 that, when no cosolvent or no wetting agent or no flow aid is added, the effect of the conductivity enhancement solution on the paper substrate is not significant, and it can be seen that, the cosolvent, the wetting agent, and the flow aid cooperate with each other to improve the conductivity of the conductivity enhancement solution, and all of the analysis molecule cosolvent, the wetting agent, and the flow aid contain hydroxyl groups, and hydrogen bonds can be formed among additive molecules in the same system to generate affinity, so that the synergistic effect is helpful for improving the stability of the system, and further the conductivity of the conductive film formed on the substrate is better.
It can be seen by combining the data of example 8, comparative example 7 and table 2 that the conductivity enhancing solution has an effect of enhancing the conductivity of the paper substrate without adding the conductivity enhancing agent, but the enhancing range is limited, and it can be seen that the conductivity enhancing agent plays an important role in enhancing the conductivity of the conductivity enhancing solution.
To sum up, this application electrically conductive reinforcing liquid is excellent to the promotion effect of paper base plate electric conductivity, and the surface of the paper base plate of having coated this application electrically conductive reinforcing liquid can form the complete conductive film of one deck, makes the electric conductive property of paper base plate obtain fine promotion. Referring to fig. 1, fig. 1 is a comparison of the conductive enhancing solution prepared in example 4 before and after coating a paper substrate, and it is apparent that a film is formed on the surface of the paper substrate, and the film continuously and completely covers the surface of the paper substrate, indicating that the film formed on the paper substrate by the conductive enhancing solution is stable.
The above-mentioned embodiments are merely illustrative and not restrictive of the present application, and those skilled in the art can modify the above-mentioned embodiments as required and without any inventive contribution thereto after reading this specification, but rather should be protected by the following patent laws within the scope of the present application.
Claims (9)
1. The conductive reinforcing liquid for the paper substrate of the super capacitor is characterized by comprising the following components in percentage by weight:
conductive polymer: 81% -90%;
cosolvent: 2% -5%;
wetting agent: 1% -3%;
flow aid: 5% -9%;
conductivity accelerator: 2% -4%;
the cosolvent is mono-alcohol and/or polyol, the wetting agent is polyethylene glycol, the flow aid is sugar alcohol, and the conduction promoter is sulfate and/or carbonate.
2. The electrical conduction enhancing fluid for the paper substrate of the supercapacitor as claimed in claim 1, wherein: the conductive polymer is one or a combination of several of polythiophene, polysulfonic acid, polypyrrole, polyphenylene sulfide, polyacetylene, polyaniline and poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT/PSS) aqueous dispersion liquid.
3. The electrical conduction enhancing fluid for the paper substrate of the supercapacitor as claimed in claim 1, wherein: the cosolvent is one or a combination of ethanol, glycol, isopropanol and glycerol.
4. The electrical conduction enhancing fluid for the paper substrate of the supercapacitor as claimed in claim 1, wherein: the wetting agent is one or a combination of more of polyethylene glycol-200, polyethylene glycol-400, polyethylene glycol-600 and polyethylene glycol-800.
5. The electrical conduction enhancing fluid for the paper substrate of the supercapacitor as claimed in claim 1, wherein: the flow aid is sorbitol and/or mannitol.
6. The electrical conduction enhancing fluid for the paper substrate of the supercapacitor as claimed in claim 1, wherein: the conductive promoter is one or a combination of more of dimethyl sulfate, ethylene sulfite and ethylene carbonate.
7. The electrical conduction enhancing fluid for the paper substrate of the supercapacitor as claimed in claim 1, wherein: the viscosity of the conductive reinforcing liquid is 10-30 mPa.
8. A paper substrate, characterized in that the surface of the paper substrate is coated with the conductive reinforcing liquid for the paper substrate of the super capacitor in any one of claims 1-7.
9. The method of making a paper substrate as recited in claim 8, comprising the steps of:
spraying: spraying conductive enhancing liquid on two sides of the paper substrate simultaneously, wherein in the spraying process, a rolling shaft is adopted for discharging and receiving the paper substrate;
drying: and drying the sprayed part of the paper substrate by an infrared light emitting tube at the drying temperature of 110-155 ℃, and winding the dried paper substrate into a coil.
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| US20160268015A1 (en) * | 2015-03-11 | 2016-09-15 | Shin-Etsu Chemical Co., Ltd. | Conductive material and substrate |
| JP2017052850A (en) * | 2015-09-08 | 2017-03-16 | 信越ポリマー株式会社 | Conductive polymer solution and conductive coated film |
| JP2017179324A (en) * | 2016-03-25 | 2017-10-05 | 東ソー株式会社 | Conductive polymer aqueous solution, conductive polymer film and coated article thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016060850A (en) * | 2014-09-19 | 2016-04-25 | 三菱樹脂株式会社 | Coated film |
| US20160189822A1 (en) * | 2014-12-27 | 2016-06-30 | National University Of Kaohsiung | Conductive Film and Method for Preparing the Same |
| US20160268015A1 (en) * | 2015-03-11 | 2016-09-15 | Shin-Etsu Chemical Co., Ltd. | Conductive material and substrate |
| JP2017052850A (en) * | 2015-09-08 | 2017-03-16 | 信越ポリマー株式会社 | Conductive polymer solution and conductive coated film |
| JP2017179324A (en) * | 2016-03-25 | 2017-10-05 | 東ソー株式会社 | Conductive polymer aqueous solution, conductive polymer film and coated article thereof |
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