CN109065212A - The preparation method of the conducting solution of conductive electrode and the preparation method of conductive electrode - Google Patents

The preparation method of the conducting solution of conductive electrode and the preparation method of conductive electrode Download PDF

Info

Publication number
CN109065212A
CN109065212A CN201810898077.3A CN201810898077A CN109065212A CN 109065212 A CN109065212 A CN 109065212A CN 201810898077 A CN201810898077 A CN 201810898077A CN 109065212 A CN109065212 A CN 109065212A
Authority
CN
China
Prior art keywords
solution
polymer
conductive electrode
preparation
conducting
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201810898077.3A
Other languages
Chinese (zh)
Other versions
CN109065212B (en
Inventor
吴飞
夏亮
佘勇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201810898077.3A priority Critical patent/CN109065212B/en
Publication of CN109065212A publication Critical patent/CN109065212A/en
Application granted granted Critical
Publication of CN109065212B publication Critical patent/CN109065212B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/30—Drying; Impregnating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/002—Auxiliary arrangements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • 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
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Thermal Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

A kind of preparation method of the conducting solution of conductive electrode and the preparation method of conductive electrode, this method is polymerize using esters of acrylic acid with styrene sulfonate, it is formed after polymer, appropriate amount of deionized water is added, form the first solution, then it is chemically reacted into the first solution by conducting polymer monomer EDOT is fully dispersed, form the second solution --- PEDOT- polymer solution, thereafter suitable siliceous aqueous solution is added in the second solution, form third solution, then the third solution is uniformly coated on through on the processed flexible parent metal of UV by way of coating, finally solidified.When solidification, since flexible parent metal surface has natural affinity to the polymer in PEDOT- polymer, so PEDOT- polymer is gradually deposited in substrate surface in solidification process, silicon-containing material arrives upper layer by exclusion, so that it is conductive layer that the effect after solidifying, which is lower layer, surface layer is the network of silica of hydrolysis, so as to have insulating protection effect.

Description

The preparation method of the conducting solution of conductive electrode and the preparation method of conductive electrode
[technical field]
The present invention relates to compliant conductive electrode, in particular to a kind of the preparation method and conduction of the conducting solution of conductive electrode The preparation method of electrode.
[background technique]
For in the flexible display apparatus such as flexible LCD, flexible electronic paper, inside be typically provided with conductive electrode.It is this to lead Electrode is usually to be coated on conducting solution on flexible parent metal and formed.In the prior art, it is led for this flexible and transparent The conducting solution of electrode is usually polythiophene solution, and polythiophene conductive layer is formed when being coated on flexible parent metal.It is existing poly- Thiophene fails as conductive electrode, due to can be after moisture content in air or volatile solvent contact；Secondly, traditional PEDOT/PSS is due to so whole have highly acid, causing electronics, display etc. to limit and answering using PSS as balanced ionic With, while self-conductance rate is relatively low；On the other hand, when this conducting solution is coated, to the adhesiveness of flexible parent metal It is relatively low.In addition, existing conductive electrode, when it is applied to liquid crystal handwriting pad, flexibility LCD, flexible electronic paper, 3~8 is micro- The other box of meter level is thick, will cause partial short-circuit in actual production manufacture, is easy to cause entire component failure.
[summary of the invention]
Present invention seek to address that the above problem, and a kind of preparation method of the conducting solution of novel conductive electrode is provided. In addition, the present invention also provides a kind of preparation methods of conductive electrode.
To achieve the above object, the present invention provides a kind of preparation method of the conducting solution of conductive electrode, feature exists In comprising following steps:
S1, the styrene sulfonate that weight fraction ratio is 5~7:3~5 is polymerize with esters of acrylic acid, forms polymerization Object；
S2, appropriate amount of deionized water is added in the polymer that step S1 is formed, forming amount concentration is 0.1~0.3mol/L's First solution；
S3, conducting polymer monomer is dispersed in the first solution, forms the second solution；The conducting polymer monomer with The molfraction ratio of the polymer is 1~3:100~120；
S4, siliceous aqueous solution is added into the second solution, forms third solution；The siliceous aqueous solution with it is described The weight fraction ratio of second solution is 1~3:7~9；
Further, step S1 includes:
S11, esters of acrylic acid, styrene sulfonate, solvent and initiator are placed in reaction vessel, at 80~100 DEG C At a temperature of react 10~14h；The parts by weight of the esters of acrylic acid and styrene sulfonate are 14~16 parts, the solvent Parts by weight are 83~85 parts；The parts by weight of the initiator are 1~2 part；
S12,4~6h of vacuum distillation, use thereafter 22~26h of deionized water dialysis；
S13, vacuum distillation remove moisture content, carry out 22~26h of vacuum drying at a temperature of 70~90 DEG C thereafter, are done Dry polymer.
Further, the solvent includes one of N.N- dimethyl acetamide, N.N- dimethylformamide or a variety of； The initiator includes one of BPO, LPO or a variety of.
Further, step S3 includes:
S31, the conducting polymer monomer of the ratio is added into the first solution, 0.5~1.5h of ultrasonic disperse, is formed Dispersion liquid；
S32, ammonium persulfate solution is added into the dispersion liquid, reacts 22~26h at room temperature；The ammonium persulfate is molten The molfraction ratio of liquid and the conducting polymer monomer is 1~2:1~2；
S33, using deionized water 70~74h of dialysis, remove unreacted substance, obtain second solution.
Further, the siliceous aqueous solution includes water solubility SiO2One of solution, silica solution, silicate solutions Or it is a variety of.
Further, the conducting polymer monomer is EDOT.
Further, the esters of acrylic acid includes one of amyl acrylate, butyl acrylate or a variety of；The benzene Vinyl sulfonate include styrene sulfonic acid receive, one of styrene sulfonic acid calcium or a variety of.
In addition, the present invention also provides a kind of preparation methods of conductive electrode, which is characterized in that itself the following steps are included:
A, flexible parent metal is subjected to UV processing: is 3~11mW/cm in light intensity2UV lamp under irradiate 1~11min；
B, 22~26h is stirred at room temperature in third solution described in claim 1~7, thereafter using coating machine by the Three solution are uniformly coated on through on the processed flexible parent metal of UV；
C, 9~11min of precuring at a temperature of 80~100 DEG C；
D, solidify 4~6min at a temperature of 140~160 DEG C；
E, solidify 9~11min at a temperature of 55~65 DEG C.
Further, the UV lamp is the UV-A lamp that wavelength is 365nm；The coating machine is dimple coating machine；
Further, the flexible parent metal is one of PET film, PC film or a variety of.
Favorable attributes of the invention are, efficiently solve the above problem.The conducting solution of conductive electrode of the invention The conducting solution prepared of preparation method, can effectively be adhered to flexible parent metal by coating methods such as dimple, slit, blade coatings On, dry finish of conducting solution will form conductive layer, and one layer of insulation based on element silicon is formed on the surface of conductive layer Protective layer avoids conductive layer from directly contacting with conductive layer and cause short circuit so as to play the role of insulation protection, and can prevent Conductive electrode meets the problem of water failure in air.
[specific embodiment]
The following example is that of the invention is explained further and being supplemented, and is not limited in any way to the present invention.
Broad outlines of the invention are, are polymerize using esters of acrylic acid with styrene sulfonate, are formed after polymer, Be added appropriate amount of deionized water, formed the first solution, then by conducting polymer monomer EDOT it is fully dispersed into the first solution into Row chemical reaction, forms the second solution --- PEDOT- polymer solution, is added in the second solution thereafter suitable siliceous Aqueous solution forms third solution, is then uniformly coated on the third solution by way of coating processed soft through UV On property substrate, finally solidified.When solidification, since flexible parent metal PET resin surface is to poly- in PEDOT- polymer It closes object and has natural affinity, so PEDOT- polymer is gradually deposited in resin surface in solidification process, siliceous object Matter arrives upper layer by exclusion, so that it is conductive layer that the effect after solidifying, which is lower layer, surface layer is the silicon network of hydrolysis, surface layer On the one hand silicon network has protective effect, the conductive layer that still further aspect can avoid ultrathin flexible device directly connects with conductive layer Touching.To introduce the contents of the present invention in more detail, it is illustrated below with different embodiments:
Embodiment 1
The preparation method of the conducting solution of the conductive electrode of the present embodiment, its step are as follows:
S1, styrene sulfonate is polymerize with esters of acrylic acid, forms polymer:
Sodium styrene sulfonate and amyl acrylate that weight fraction ratio is 6:4 are placed in three-neck flask, are added thereafter molten Agent and initiator make resin monomer react 12h at a temperature of 90 DEG C and are polymerize.Wherein, the sodium styrene sulfonate and propylene Sour pentyl ester is resin monomer, and the solvent selects N.N- dimethyl acetamide, and the initiator selects BPO.The resin monomer, The additive amount of solvent, initiator are as follows: resin monomer accounts for the 15% of total weight, and solvent accounts for the 84% of total weight, and initiator accounts for gross weight The 1% of amount.After polymerization reaction, it is evaporated under reduced pressure 5h with the method for vacuum distillation, to evaporate the solvent of the overwhelming majority；Thereafter Dialysis is carried out with deionized water, dialysis is for 24 hours, higher to obtain purity to remove unreacted resin monomer and other impurities Polymer；Thereafter the moisture content in polymer is removed with the method for vacuum distillation again.Finally, by surplus materials at a temperature of 80 DEG C It is dried in vacuo for 24 hours, to obtain dry polymer.
S2, dried polymer is dissolved in deionized water, the amount of being formulated as concentration is the first solution of 0.1mol/L；
S3, conducting polymer monomer is dispersed in the first solution, forms the second solution:
By conducting polymer monomer --- EDOT is added into the first solution, ultrasonic disperse 1h, forms EODT- polymer point Dispersion liquid；During being somebody's turn to do, the additive amount of conducting polymer monomer is added according to the amount of polymer, and in the present embodiment, conduction is poly- The molfraction of monomer adduct and polymer ratio is 2:100；For example, conducting polymer monomer adds when polymer is 0.1mol Dosage is 2mmol.After ultrasonic disperse forms EODT- polymer dispersion liquid, ammonium persulfate solution is added to the EODT- and is polymerize In object dispersion liquid, reacts at room temperature for 24 hours, form PEDOT- polymer solution；The ammonium persulfate solution is for providing acyclic acidic Border, in the present embodiment, the molfraction ratio with the conducting polymer monomer is 1:1, for example, conducting polymer monomer adds When dosage is 2mmol, the additive amount of ammonium persulfate solution is 2mmol.After end of reaction, dialysis 72h is carried out, removes unreacted Substance, with obtain purification the second solution --- PEDOT- polymer solution.
S4, siliceous aqueous solution is added into the second solution, forms third solution；It is described siliceous in the present embodiment Aqueous solution selects water solubility SiO2Solution, the weight fraction ratio with second solution are 1:8.
The third solution as made from above method is the conducting solution that can be used for flexible and transparent conductive electrode, is led to It crosses following methods to be coated, flexible and transparent conductive electrode can be made:
A, flexible parent metal is subjected to UV processing: is 10mW/cm in light intensity2, wavelength be 365nm UV-A lamp under irradiate 10min；In the present embodiment, the flexible parent metal is PET film.The grease type that the step can be eliminated on flexible parent metal surface is dirty Dirt keeps the surface of flexible parent metal lower, is coated with to be conducive to surface.
B, third solution is subjected to mechanical stirring for 24 hours at room temperature, be then placed in dimple coating machine, use the painting thereafter Third solution is uniformly coated on through on the processed flexible parent metal of UV by cloth machine；
C, after coating, precuring 10min at a temperature of 90 DEG C；
D, solidify 5min at a temperature of 150 DEG C of high temperature thereafter；
E, finally solidify 10min at a temperature of 60 DEG C.
When solidification, due to flexible parent metal PET resin surface have to the polymer in PEDOT- polymer it is natural affine Power, so PEDOT- polymer gradually deposits on the surface of flexible parent metal, and SiO in solidification process2Substance is squeezed Upper layer, the i.e. side opposite with flexible parent metal.So that it is conductive that the effect after solidifying, which is close to the side of flexible parent metal, Layer, the side far from flexible parent metal are the SiO of hydrolysis2Network.The SiO2Network has insulation protection, not only can avoid Conductive layer directly contacts with conductive layer and causes short circuit, and can prevent conductive electrode from meeting the problem of water fails in air.
Embodiment 2
The preparation method of the conducting solution of the conductive electrode of the present embodiment, its step are as follows:
S1, styrene sulfonate is polymerize with esters of acrylic acid, forms polymer:
Sodium styrene sulfonate and butyl acrylate that weight fraction ratio is 5:3 are placed in three-neck flask, are added thereafter molten Agent and initiator make resin monomer react 14h at a temperature of 80 DEG C and are polymerize.Wherein, the sodium styrene sulfonate and propylene Acid butyl ester is resin monomer, and the solvent selects N.N- dimethylformamide, and the initiator selects LPO.The resin monomer, The additive amount of solvent, initiator are as follows: resin monomer accounts for the 14% of total weight, and solvent accounts for the 85% of total weight, and initiator accounts for gross weight The 1% of amount.After polymerization reaction, it is evaporated under reduced pressure 4h with the method for vacuum distillation, to evaporate the solvent of the overwhelming majority；Thereafter Dialysis is carried out with deionized water, dialysis 22h is higher to obtain purity to remove unreacted resin monomer and other impurities Polymer；Thereafter the moisture content in polymer is removed with the method for vacuum distillation again.Finally, by surplus materials at a temperature of 70 DEG C It is dried in vacuo 26h, to obtain dry polymer.
S2, dried polymer is dissolved in deionized water, the amount of being formulated as concentration is the first solution of 0.2mol/L；
S3, conducting polymer monomer is dispersed in the first solution, forms the second solution:
By conducting polymer monomer --- EDOT is added into the first solution, ultrasonic disperse 0.5h, forms EODT- polymer Dispersion liquid；During being somebody's turn to do, the additive amount of conducting polymer monomer is added according to the amount of polymer, conductive in the present embodiment The molfraction of polymer monomer and polymer ratio is 1:100；For example, when polymer is 0.1mol, conducting polymer monomer Additive amount is 1mmol.After ultrasonic disperse forms EODT- polymer dispersion liquid, ammonium persulfate solution is added to the EODT- and is gathered It closes in object dispersion liquid, reacts 22h at room temperature, form PEDOT- polymer solution；The ammonium persulfate solution is for providing acidity Environment, in the present embodiment, the molfraction ratio with the conducting polymer monomer is 1:2, for example, conducting polymer monomer When additive amount is 1mmol, the additive amount of ammonium persulfate solution is 0.5mmol.After end of reaction, dialysis 70h is carried out, removal is not The substance of reaction, to obtain the second solution --- the PEDOT- polymer solution of purification.
S4, siliceous aqueous solution is added into the second solution, forms third solution；It is described siliceous in the present embodiment Aqueous solution selects silica solution, and the weight fraction ratio with second solution is 1:7.
The third solution as made from above method is the conducting solution that can be used for flexible and transparent conductive electrode, is led to It crosses following methods to be coated, flexible and transparent conductive electrode can be made:
A, flexible parent metal is subjected to UV processing: is 8mW/cm in light intensity2, wavelength be 365nm UV-A lamp under irradiate 6min； In the present embodiment, the flexible parent metal is PET film.The grease type that the step can be eliminated on flexible parent metal surface is dirty, makes soft Property substrate surface can be lower, thus be conducive to surface be coated with.
B, third solution is subjected to mechanical stirring 22h at room temperature, is then placed in dimple coating machine, uses the painting thereafter Third solution is uniformly coated on through on the processed flexible parent metal of UV by cloth machine；
C, after coating, precuring 11min at a temperature of 80 DEG C；
D, solidify 6min at a temperature of 140 DEG C of high temperature thereafter；
E, finally solidify 11min at a temperature of 55 DEG C.
When solidification, due to flexible parent metal PET resin surface have to the polymer in PEDOT- polymer it is natural affine Power, so PEDOT- polymer gradually deposits on the surface of flexible parent metal, and SiO in solidification process2Substance is squeezed Upper layer, the i.e. side opposite with flexible parent metal.So that it is conductive that the effect after solidifying, which is close to the side of flexible parent metal, Layer, the side far from flexible parent metal are the SiO of hydrolysis2Network.The SiO2Network has insulation protection, not only can avoid Conductive layer directly contacts with conductive layer and causes short circuit, and can prevent conductive electrode from meeting the problem of water fails in air.
Embodiment 3
The preparation method of the conducting solution of the conductive electrode of the present embodiment, its step are as follows:
S1, styrene sulfonate is polymerize with esters of acrylic acid, forms polymer:
Styrene sulfonic acid calcium and butyl acrylate that weight fraction ratio is 7:5 are placed in three-neck flask, are added thereafter molten Agent and initiator make resin monomer react 10h at a temperature of 100 DEG C and are polymerize.Wherein, the styrene sulfonic acid calcium and propylene Acid butyl ester is resin monomer, and the solvent selects N.N- dimethyl acetamide, and the initiator selects LPO.The resin monomer, The additive amount of solvent, initiator are as follows: resin monomer accounts for the 15% of total weight, and solvent accounts for the 83% of total weight, and initiator accounts for gross weight The 2% of amount.After polymerization reaction, it is evaporated under reduced pressure 6h with the method for vacuum distillation, to evaporate the solvent of the overwhelming majority；Thereafter Dialysis is carried out with deionized water, dialysis 26h is higher to obtain purity to remove unreacted resin monomer and other impurities Polymer；Thereafter the moisture content in polymer is removed with the method for vacuum distillation again.Finally, by surplus materials at a temperature of 90 DEG C It is dried in vacuo 22h, to obtain dry polymer.
S2, dried polymer is dissolved in deionized water, the amount of being formulated as concentration is the first solution of 0.3mol/L；
S3, conducting polymer monomer is dispersed in the first solution, forms the second solution:
By conducting polymer monomer --- EDOT is added into the first solution, ultrasonic disperse 1.5h, forms EODT- polymer Dispersion liquid；During being somebody's turn to do, the additive amount of conducting polymer monomer is added according to the amount of polymer, conductive in the present embodiment The molfraction of polymer monomer and polymer ratio is 3:120；After ultrasonic disperse forms EODT- polymer dispersion liquid, by over cure Acid ammonium solution is added into the EODT- polymer dispersion liquid, reacts 26h at room temperature, forms PEDOT- polymer solution；It is described Ammonium persulfate solution is for providing acidic environment, and in the present embodiment, the molfraction ratio with the conducting polymer monomer is 2:1, for example, the additive amount of ammonium persulfate solution is 2mmol when the additive amount of conducting polymer monomer is 1mmol.End of reaction Later, dialysis 74h is carried out, unreacted substance is removed, to obtain the second solution --- the PEDOT- polymer solution of purification.
S4, siliceous aqueous solution is added into the second solution, forms third solution；It is described siliceous in the present embodiment Aqueous solution selects sodium silicate solution, and the weight fraction ratio with second solution is 3:9.
The third solution as made from above method is the conducting solution that can be used for flexible and transparent conductive electrode, is led to It crosses following methods to be coated, flexible and transparent conductive electrode can be made:
A, flexible parent metal is subjected to UV processing: is 3mW/cm in light intensity2, wavelength be 365nm UV-A lamp under irradiate 11min；In the present embodiment, the flexible parent metal is PET film.The grease type that the step can be eliminated on flexible parent metal surface is dirty Dirt keeps the surface of flexible parent metal lower, is coated with to be conducive to surface.
B, third solution is subjected to mechanical stirring 26h at room temperature, is then placed in dimple coating machine, uses the painting thereafter Third solution is uniformly coated on through on the processed flexible parent metal of UV by cloth machine；
C, after coating, precuring 9min at a temperature of 100 DEG C；
D, solidify 4min at a temperature of 160 DEG C of high temperature thereafter；
E, finally solidify 9min at a temperature of 65 DEG C.
When solidification, due to flexible parent metal PET resin surface have to the polymer in PEDOT- polymer it is natural affine Power, so PEDOT- polymer gradually deposits on the surface of flexible parent metal, and SiO in solidification process2Substance is squeezed Upper layer, the i.e. side opposite with flexible parent metal.So that it is conductive that the effect after solidifying, which is close to the side of flexible parent metal, Layer, the side far from flexible parent metal are the SiO of hydrolysis2Network.The SiO2Network has insulation protection, not only can avoid Conductive layer directly contacts with conductive layer and causes short circuit, and can prevent conductive electrode from meeting the problem of water fails in air.
Embodiment 4
The preparation method of the conducting solution of the conductive electrode of the present embodiment, its step are as follows:
S1, sodium styrene sulfonate is polymerize with esters of acrylic acid, forms polymer:
Styrene sulfonic acid calcium and amyl acrylate that weight fraction ratio is 6:5 are placed in three-neck flask, are added thereafter molten Agent and initiator make resin monomer react 13h at a temperature of 90 DEG C and are polymerize.Wherein, the styrene sulfonic acid calcium and propylene Sour pentyl ester is resin monomer, and the solvent selects N.N- dimethylformamide, and the initiator selects BPO.The resin monomer, The additive amount of solvent, initiator are as follows: resin monomer accounts for the 16% of total weight, and solvent accounts for the 83% of total weight, and initiator accounts for gross weight The 1% of amount.After polymerization reaction, it is evaporated under reduced pressure 5h with the method for vacuum distillation, to evaporate the solvent of the overwhelming majority；Thereafter Dialysis is carried out with deionized water, dialysis 25h is higher to obtain purity to remove unreacted resin monomer and other impurities Polymer；Thereafter the moisture content in polymer is removed with the method for vacuum distillation again.Finally, by surplus materials at a temperature of 85 DEG C It is dried in vacuo 23h, to obtain dry polymer.
S2, dried polymer is dissolved in deionized water, the amount of being formulated as concentration is the first solution of 0.15mol/L；
S3, conducting polymer monomer is dispersed in the first solution, forms the second solution:
By conducting polymer monomer --- EDOT is added into the first solution, ultrasonic disperse 1h, forms EODT- polymer point Dispersion liquid；During being somebody's turn to do, the additive amount of conducting polymer monomer is added according to the amount of polymer, and in the present embodiment, conduction is poly- The molfraction of monomer adduct and polymer ratio is 2:110；After ultrasonic disperse forms EODT- polymer dispersion liquid, by persulfuric acid Ammonium salt solution is added into the EODT- polymer dispersion liquid, reacts 25h at room temperature, forms PEDOT- polymer solution；The mistake Ammonium sulfate is for providing acidic environment, and in the present embodiment, the molfraction ratio with the conducting polymer monomer is 1: 1, for example, the additive amount of ammonium persulfate solution is 1mmol when the additive amount of conducting polymer monomer is 1mmol.End of reaction it Afterwards, dialysis 73h is carried out, unreacted substance is removed, to obtain the second solution --- the PEDOT- polymer solution of purification.
S4, siliceous aqueous solution is added into the second solution, forms third solution；It is described siliceous in the present embodiment Aqueous solution selects water solubility SiO2Solution, the weight fraction ratio with second solution are 1:9.
The third solution as made from above method is the conducting solution that can be used for flexible and transparent conductive electrode, is led to It crosses following methods to be coated, flexible and transparent conductive electrode can be made:
A, flexible parent metal is subjected to UV processing: is 11mW/cm in light intensity2, wavelength be 365nm UV-A lamp under irradiate 1min；In the present embodiment, the flexible parent metal is PC film.The grease type that the step can be eliminated on flexible parent metal surface is dirty, Keep the surface of flexible parent metal lower, is coated with to be conducive to surface.
B, third solution is subjected to mechanical stirring 15h at room temperature, is then placed in dimple coating machine, uses the painting thereafter Third solution is uniformly coated on through on the processed flexible parent metal of UV by cloth machine；
C, after coating, precuring 10min at a temperature of 95 DEG C；
D, solidify 5min at a temperature of 150 DEG C of high temperature thereafter；
E, finally solidify 10min at a temperature of 60 DEG C.
When solidification, due to flexible parent metal PC film surface have to the polymer in PEDOT- polymer it is natural affine Power, so PEDOT- polymer gradually deposits on the surface of flexible parent metal, and SiO in solidification process2Substance is squeezed Upper layer, the i.e. side opposite with flexible parent metal.So that it is conductive that the effect after solidifying, which is close to the side of flexible parent metal, Layer, the side far from flexible parent metal are the SiO of hydrolysis2Network.The SiO2Network has insulation protection, not only can avoid Conductive layer directly contacts with conductive layer and causes short circuit, and can prevent conductive electrode from meeting the problem of water fails in air.
Although being disclosed by above embodiments to the present invention, the scope of the invention is not limited to this, Under conditions of present inventive concept, above each component can with technical field personnel understand similar or equivalent element come Replacement.

Claims (10)

1. a kind of preparation method of the conducting solution of conductive electrode, which is characterized in that itself the following steps are included:
S1, the styrene sulfonate that weight fraction ratio is 5~7:3~5 is polymerize with esters of acrylic acid, forms polymer；
S2, appropriate amount of deionized water is added in the polymer that step S1 is formed, forming amount concentration is the first of 0.1~0.3mol/L Solution；
S3, conducting polymer monomer is dispersed in the first solution, forms the second solution；The conducting polymer monomer with it is described The molfraction ratio of polymer is 1~3:100~120；
S4, siliceous aqueous solution is added into the second solution, forms third solution；The siliceous aqueous solution and described second The weight fraction ratio of solution is 1~3:7~9.
2. the preparation method of the conducting solution of conductive electrode as described in claim 1, which is characterized in that step S1 includes:
S11, esters of acrylic acid, styrene sulfonate, solvent and initiator are placed in reaction vessel, in 80~100 DEG C of temperature 10~14h of lower reaction；The parts by weight of the esters of acrylic acid and styrene sulfonate are 14~16 parts, the weight of the solvent Number is 83~85 parts；The parts by weight of the initiator are 1~2 part；
S12,4~6h of vacuum distillation, use thereafter 22~26h of deionized water dialysis；
S13, vacuum distillation remove moisture content, carry out 22~26h of vacuum drying at a temperature of 70~90 DEG C thereafter, obtain dry Polymer.
3. the preparation method of the conducting solution of conductive electrode as claimed in claim 2, which is characterized in that the solvent includes One of N.N- dimethyl acetamide, N.N- dimethylformamide are a variety of；The initiator includes one of BPO, LPO Or it is a variety of.
4. the preparation method of the conducting solution of conductive electrode as described in claim 1, which is characterized in that step S3 includes:
S31, the conducting polymer monomer of the ratio is added into the first solution, 0.5~1.5h of ultrasonic disperse, forms dispersion Liquid；
S32, ammonium persulfate solution is added into the dispersion liquid, reacts 22~26h at room temperature；The ammonium persulfate solution with The molfraction ratio of the conducting polymer monomer is 1~2:1~2；
S33, using deionized water 70~74h of dialysis, remove unreacted substance, obtain second solution.
5. the preparation method of the conducting solution of conductive electrode as described in claim 1, which is characterized in that described siliceous water-soluble Liquid includes water solubility SiO2One of solution, silica solution, silicate solutions are a variety of.
6. the preparation method of the conducting solution of conductive electrode as described in claim 1, which is characterized in that the conducting polymer Monomer is EDOT.
7. the preparation method of the conducting solution of conductive electrode as described in claim 1, which is characterized in that the esters of acrylic acid Including one of amyl acrylate, butyl acrylate or a variety of；The styrene sulfonate include styrene sulfonic acid receive, benzene second One of alkene sulfoacid calcium is a variety of.
8. a kind of preparation method of conductive electrode, which is characterized in that itself the following steps are included:
A, flexible parent metal is subjected to UV processing: is 3~11mW/cm in light intensity2UV lamp under irradiate 1~11min；
B, 22~26h is stirred at room temperature in third solution described in claim 1~7, it is using coating machine that third is molten thereafter Liquid is uniformly coated on through on the processed flexible parent metal of UV；
C, 9~11min of precuring at a temperature of 80~100 DEG C；
D, solidify 4~6min at a temperature of 140~160 DEG C；
E, solidify 9~11min at a temperature of 55~65 DEG C.
9. the preparation method of conductive electrode as claimed in claim 8, which is characterized in that the UV lamp is that wavelength is 365nm's UV-A lamp；The coating machine is dimple coating machine.
10. the preparation method of conductive electrode as claimed in claim 8, which is characterized in that the flexible parent metal be PET film, One of PC film is a variety of.
CN201810898077.3A 2018-08-08 2018-08-08 Preparation method of conductive solution of conductive electrode and preparation method of conductive electrode Active CN109065212B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810898077.3A CN109065212B (en) 2018-08-08 2018-08-08 Preparation method of conductive solution of conductive electrode and preparation method of conductive electrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810898077.3A CN109065212B (en) 2018-08-08 2018-08-08 Preparation method of conductive solution of conductive electrode and preparation method of conductive electrode

Publications (2)

Publication Number Publication Date
CN109065212A true CN109065212A (en) 2018-12-21
CN109065212B CN109065212B (en) 2023-09-05

Family

ID=64678833

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810898077.3A Active CN109065212B (en) 2018-08-08 2018-08-08 Preparation method of conductive solution of conductive electrode and preparation method of conductive electrode

Country Status (1)

Country Link
CN (1) CN109065212B (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060062958A1 (en) * 2004-09-22 2006-03-23 Kazuyoshi Yoshida Conductive composition and production method thereof, antistatic coating material, antistatic coating, antistatic film, optical filter, and optical information recording medium, and capacitors and production method thereof
CN101845136A (en) * 2010-06-02 2010-09-29 北京化工大学 Water-soluble poly(3,4-ethylenedioxythiophene) and preparation method for conductive coating thereof
US20100252782A1 (en) * 2007-10-05 2010-10-07 Shin-Etsu Polymer Co., Ltd. Conductive polymer solution, conductive coating film, and input device
JP2011191735A (en) * 2010-02-17 2011-09-29 Nof Corp Anti-reflective film
US20110291058A1 (en) * 2010-05-28 2011-12-01 Kunishi Yousuke Transparent conductive film and conductive substrate using the same
JP2015023284A (en) * 2013-07-18 2015-02-02 ダエハ マンテック シーオー エルティディ Conductive coating solution composition with electromagnetic interference shielding function, production method of the same, and conductive coating film with electromagnetic interference shielding function produced using the composition
CN105679394A (en) * 2016-01-27 2016-06-15 广州中国科学院先进技术研究所 UV conductive paste and method for printing silver nanowire flexible transparent conductive film from same
CN106893084A (en) * 2017-03-03 2017-06-27 南昌大学 A kind of dispersant makees the method that template in-situ polymerization prepares conducting polymer
JP2017125094A (en) * 2016-01-12 2017-07-20 信越ポリマー株式会社 Conductive polymer dispersion liquid and method for producing the same, and method for producing conductive film

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060062958A1 (en) * 2004-09-22 2006-03-23 Kazuyoshi Yoshida Conductive composition and production method thereof, antistatic coating material, antistatic coating, antistatic film, optical filter, and optical information recording medium, and capacitors and production method thereof
US20100252782A1 (en) * 2007-10-05 2010-10-07 Shin-Etsu Polymer Co., Ltd. Conductive polymer solution, conductive coating film, and input device
JP2011191735A (en) * 2010-02-17 2011-09-29 Nof Corp Anti-reflective film
US20110291058A1 (en) * 2010-05-28 2011-12-01 Kunishi Yousuke Transparent conductive film and conductive substrate using the same
CN101845136A (en) * 2010-06-02 2010-09-29 北京化工大学 Water-soluble poly(3,4-ethylenedioxythiophene) and preparation method for conductive coating thereof
JP2015023284A (en) * 2013-07-18 2015-02-02 ダエハ マンテック シーオー エルティディ Conductive coating solution composition with electromagnetic interference shielding function, production method of the same, and conductive coating film with electromagnetic interference shielding function produced using the composition
JP2017125094A (en) * 2016-01-12 2017-07-20 信越ポリマー株式会社 Conductive polymer dispersion liquid and method for producing the same, and method for producing conductive film
CN105679394A (en) * 2016-01-27 2016-06-15 广州中国科学院先进技术研究所 UV conductive paste and method for printing silver nanowire flexible transparent conductive film from same
CN106893084A (en) * 2017-03-03 2017-06-27 南昌大学 A kind of dispersant makees the method that template in-situ polymerization prepares conducting polymer

Also Published As

Publication number Publication date
CN109065212B (en) 2023-09-05

Similar Documents

Publication Publication Date Title
CN104183303B (en) A kind of stable PEDOT/PSS conducting layer electrode and preparation method thereof
CN104212243B (en) A kind of preparation method of PEDOT/PSS electrically conductive ink and coating
CN102559047A (en) Organosilicon coating and preparation method thereof
CN102898932B (en) Composite ultraviolet-curing coating containing vinyl-terminated fluorinated alkyl ester polymer, its preparation and application
KR20180097140A (en) Electro-conductive polymer composite and substrate
JP2011068909A (en) Printed conductor
CN105542685A (en) Frame sealing adhesive, liquid crystal panel, liquid crystal display device and preparation method thereof
CN105085937A (en) Preparation method for fullerene/PEDOT: PSS mixed solution and preparation method for substrate of fullerene/PEDOT: PSS composite transparent conductive film
CN109897509A (en) A kind of UV photocureable coating for aluminum-based copper-clad plate
CN106784603A (en) A kind of preparation method of current collector coatings
CN109065212A (en) The preparation method of the conducting solution of conductive electrode and the preparation method of conductive electrode
CN106893101B (en) Photosensitive-ink, preparation method and its application of tung oil base photo-sensistive polyimide
CN102443179B (en) Preparation method of poly(3,4-ethylene dithio-thiofuran) aqueous dispersion
KR20170024549A (en) Conductive polymer composite and substrate
JP2003286336A (en) Method for producing transparent electrically conductive layer, thus produced layer and its use
CN110041791B (en) Light-transmitting peelable glue and preparation method thereof
CN115058004B (en) Easily-soluble reactive permanent antistatic agent and preparation method thereof
CN112409889A (en) UV nano anticorrosive paint, circuit board obtained from UV nano anticorrosive paint, and preparation method and application of circuit board
CN113755035B (en) Epoxy silane modified nano alumina and polymer cement-based waterproof coating
CN105038799B (en) A kind of etching liquid performed etching to ito film
CN109439241A (en) A kind of environment-friendly type blister packaging sealant and its preparation method and application
CN110628321B (en) Photocuring conductive coating and preparation method thereof
CN108624106B (en) Peelable glue with etching function and etching method
CN113130138A (en) Nano-silver conductive film and preparation method thereof
JP2011228222A (en) Conductive coating composition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant