CN106025394B - Preparation method of color-changing power supply - Google Patents

Preparation method of color-changing power supply Download PDF

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Publication number
CN106025394B
CN106025394B CN201610343233.0A CN201610343233A CN106025394B CN 106025394 B CN106025394 B CN 106025394B CN 201610343233 A CN201610343233 A CN 201610343233A CN 106025394 B CN106025394 B CN 106025394B
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substrate
power supply
preparation
color
oxide
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CN106025394A (en
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张�诚
蔡志威
吕耀康
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/36Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38Construction or manufacture
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hybrid Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a preparation method of a color-changing power supply, which comprises the following steps: depositing a layer of conductive polymer on the substrate A by an electrochemical deposition method; the obtained substrate A deposited with the conductive polymer is dried in a ventilation mode, then an adhesive is applied along the periphery of the area on the surface of the substrate A deposited with the conductive polymer, then the gel electrolyte is coated on the inner side of the periphery applied with the adhesive, and then the substrate A is placed in an oven to stand and is taken out for standby; coating metal oxide slurry on the substrate B, bonding the substrate B and the prepared substrate A in a staggered manner after the coated metal oxide slurry is dried, and then compacting to obtain the color-changing power supply; the color-changing power supply prepared by the method can change along with the color in the charging and discharging process, the energy storage condition of the power supply can be known according to the color change, and the method can be used in the field of energy storage; the voltage of the two poles of the power supply can be changed, so that the power supply presents different colors and is used for the visual color development field.

Description

A kind of preparation method of discoloration power supply
(1) technical field
The present invention relates to a kind of preparation methods of discoloration power supply.
(2) background technology
Energy storage device is now widely used for the every aspect of the lives such as smart mobile phone, laptop, electric vehicle, energy storage The electrode material of device is also the research hotspot of present society all circles.
With advances in technology with the development of society, people can also proposed requirement to the colourability of energy storage device.It can The energy storage device of discoloration can be widely applied to the numerous areas such as Electronic Paper, mobile phone screen, vehicle glass, Domestic glass, reach It can change colour and the purpose of energy storage, further promote the miniaturization of energy storage material.
(3) invention content
The object of the present invention is to provide a kind of preparation method of discoloration power supply, the discoloration power supply prepared by this method is filling Along with color change during electric discharge.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of preparation method of discoloration power supply, the preparation method include the following steps:
(1) by electrochemical deposition method, one layer of conducting polymer is deposited on substrate A;
In step (1), the electrochemical deposition method is specially:In three-electrode cell system, using substrate A as work Electrode, platinized platinum are auxiliary electrode, Ag/AgCl electrodes are that reference electrode, 0.001~1mol/L (preferably 0.01~0.5mol/L) are led The dichloromethane solution of electric polymer monomer is electrolyte, applies 0.5~2.5V's (preferably 0.6~1.4V) on the working electrode (s Constant voltage carries out 30~3600s of polymerisation (preferably 60~300s), and obtaining deposition has the substrate A of conducting polymer, in the base It also reserves some blank substrate region in addition to deposition has the region of conducting polymer and is used for and outer lead phase in the bottom surfaces A Even;
The conducting polymer monomer includes but not limited to:Aniline and its derivatives, pyrroles and its derivative, thiophene and its Derivative or metallo phthalocyanine, specifically for example:Aniline, triphenylamine, pyrroles, thiophene or ethylenedioxy thiophene etc..
(2) the substrate A aeration-dryings that deposition obtained by step (1) is had to conducting polymer, deposit then along the surfaces substrate A There is the region periphery of conducting polymer to apply adhesive, is then being applied on the inside of the periphery of adhesive (the i.e. surfaces substrate A deposition Have the part for not applying adhesive in the region of conducting polymer) coating gel electrolyte, substrate A is placed in 50~150 later 1~10 day is stood in the baking oven of DEG C (preferably 50~90 DEG C) (preferably 2~4 days), is taken out spare;
In step (2), double faced adhesive tape can be used in the adhesive, specifically for example:The 3M double faced adhesive tapes of 3M companies, product Model 3M103-96511;
The gel electrolyte mainly is mixed with to obtain by high molecular polymer with alkali metal salt;The macromolecule Polymer is polyethylene glycol oxide (PEO), polymethyl methacrylate (PMMA), polyacrylonitrile (PAN) or polyvinylidene fluoride (PVDF) etc.;The alkali metal salt is lithium perchlorate (LiClO4) etc.;
It is preferred that the gel electrolyte is polymethyl methacrylate-lithium perchlorate gel electrolyte, specifically, described Polymethyl methacrylate-lithium perchlorate gel electrolyte is prepared as follows to obtain:
Polymethyl methacrylate is added in propene carbonate, 12~48h of swelling in 50~100 DEG C of baking ovens is placed in, obtains To system A;Lithium perchlorate is dissolved in acetonitrile, system B is obtained;System B is added in system A, ultrasound (frequency is 20~ 50KHz) 1~10h of oscillation is to get the polymethyl methacrylate-lithium perchlorate gel electrolyte;Wherein, the poly- first The mass ratio of base methyl acrylate and propene carbonate is 1:1~10;The volumetric usage of the acetonitrile is with the quality of lithium perchlorate It is calculated as 2~20mL/g.
(3) the coated metal oxide slurry on substrate B, and coating when reserve a part of blank substrate region for and Outer lead is connected, and after good metal oxide paste drying to be coated, substrate B and the ready substrate A of step (1) are misplaced (dislocation bonding is meant that for bonding:Substrate A is with after substrate B bondings, and respectively reserved a part of blank substrate region is non- Overlapping region, for being connected with outer lead), compacting obtains the discoloration power supply;
In step (3), the metal oxide paste is formed by metal oxide solubilizer mixing preparation;The gold Belonging to oxide includes but not limited to:The metal oxides such as titanium dioxide, rhodium oxide, nickel oxide or manganese oxide;The solvent is logical Often it is selected from dichloromethane;The volumetric usage of the solvent is calculated as 50~100mL/g with the quality of metal oxide;
The method of the coating includes the modes such as the spraying, spin coating or drop coating of this field routine.
In the present invention, rigid conductive glass (the following letter with tin indium oxide may be used in the substrate A or substrate B Claim ITO), the flexible conductive film (hereinafter referred to as PET) with tin indium oxide can also be used.Hard can be made using ITO Ultracapacitor, ultracapacitor flexible can be made using PET.
Term " substrate A ", " substrate B " not special meaning is only intended to distinguish different operation step labeled as " A ", " B " The substrate used in rapid.
The beneficial effects of the present invention are:Discoloration power supply prepared by the method for the present invention can be during charge and discharge with face Color change learns the energy storage situation of power supply according to the variation of color, can be used for energy storage field;It can also be by changing two poles Voltage so that different colors is presented in power supply, for visualizing colour developing field.
(4) it illustrates
Fig. 1 is the preparation technology flow chart of discoloration power supply of the present invention;
Fig. 2 is photo of the discoloration power supply obtained of embodiment 2 under charge and discharge state;
Fig. 3 is the charging and discharging curve of the discoloration power supply obtained of embodiment 2.
(5) specific implementation mode
Below by specific embodiment, the invention will be further described, but protection scope of the present invention is not limited in This.
Embodiment 1 prepares gel electrolyte
3.5g polymethyl methacrylates are added in 5g propene carbonates, is placed in 80 DEG C of baking ovens and is swollen 18h, obtain body It is A;1g lithium perchlorates are dissolved in 4g acetonitriles, system B is obtained;System B is added in system A, the oscillation of 25KHz frequency ultrasounds 2h so that system B is uniformly blended into system A, obtains stable polymethyl methacrylate-lithium perchlorate gel electrolyte.
Embodiment 2 prepares discoloration power supply
Using electrochemical workstation (Shanghai Chen Hua CHI-660C), by the method for electrochemical deposition, with indium oxide One layer of uniform Polyglycolic acid fibre is deposited on rigid conductive glass (abbreviation ITO) the substrate A of tin, concrete operations are as follows:
In three-electrode cell system, using ITO substrate A as working electrode, platinized platinum (2cm × 2cm) be auxiliary electrode, Ag/AgCl electrodes are reference electrode, 0.1mol/L ethylenedioxy thiophenes (Aladdin company, CAS 126213-50-1, article No. E105649 dichloromethane solution) is electrolyte, polymerize 120s under the constant potential of 1.2V, and obtaining deposition has poly- enedioxy The ITO substrate A of thiophene;
There is the ITO substrate A of Polyglycolic acid fibre to be placed in ventilation drying deposition, later outside the surface of ITO substrate A The uniform one circle 3M double faced adhesive tapes (3M companies, model 3M103-96511) of adherency of circle, and enclosed in ITO substrate A surface adhesions one The inside of 3M double faced adhesive tapes coats polymethyl methacrylate-lithium perchlorate gel electrolyte prepared by one layer of uniform embodiment 1 Matter is placed in 80 DEG C of baking ovens and stands 4 days, takes out spare.
0.2g titanium dioxide is uniformly mixed with 10ml dichloromethane, then by spray gun spraying on ITO substrate B, room After temperature is dried, by ITO substrate B and ready ITO substrate A dislocation bondings, compacting obtains discoloration power supply.
The discoloration power supply prepared by this method can be during charge and discharge with the transformation of Yellow-Blue, such as Fig. 1 institutes Show, voltage is charged state when being charged to 1.4V from -0.6V, and corresponding color, which is yellow, becomes blue;Voltage is dropped from 1.4V It is discharge condition when to -0.6V, corresponding color, which is blue, becomes yellow.
Embodiment 3 prepares discoloration power supply
Using electrochemical workstation (Shanghai Chen Hua CHI-660C), by the method for electrochemical deposition, with indium oxide One layer of uniform polyaniline is deposited on rigid conductive glass (abbreviation ITO) the substrate A of tin, concrete operations are as follows:
In three-electrode cell system, using ITO substrate A as working electrode, platinized platinum (2cm × 2cm) be auxiliary electrode, Ag/AgCl electrodes are the dichloro of reference electrode, 0.1mol/L aniline (Aladdin company, CAS 62-53-3, article No. A112123) Dichloromethane is electrolyte, polymerize 120s under the constant potential of 1.2V, and obtaining deposition has the ITO substrate A of polyaniline;
There is the ITO substrate A of polyaniline to be placed in ventilation drying deposition, it is uniform along the surface outer ring of ITO substrate A later One circle 3M double faced adhesive tapes (3M companies, model 3M103-96511) of adherency, and enclose 3M double faced adhesive tapes in ITO substrate A surface adhesions one The inside of band coats polymethyl methacrylate-lithium perchlorate gel electrolyte prepared by one layer of uniform embodiment 1, is placed in 60 3 days are stood in DEG C baking oven, is taken out spare.
0.1g titanium dioxide is uniformly mixed with 10ml dichloromethane, then by spray gun spraying on ITO substrate B, room After temperature is dried, by ITO substrate B and ready ITO substrate A dislocation bondings, compacting obtains discoloration power supply.
Such discoloration power supply prepared by this method can be during charge and discharge with the transformation of green color-blue.

Claims (8)

1. a kind of preparation method of discoloration power supply, which is characterized in that the preparation method includes the following steps:
(1) by electrochemical deposition method, one layer of conducting polymer is deposited on substrate A;
The electrochemical deposition method is:It is auxiliary electricity by working electrode, platinized platinum of substrate A in three-electrode cell system Pole, Ag/AgCl electrodes be reference electrode, 0.001~1mol/L conducting polymer monomers dichloromethane solution be electrolyte, The constant voltage for applying 0.5~2.5V on working electrode carries out 30~3600s of polymerisation, and obtaining deposition has the base of conducting polymer Bottom A, on the surfaces substrate A, in addition to deposition has the region of conducting polymer, also reserve some blank substrate region be used for and Outer lead is connected;
The conducting polymer monomer is aniline, triphenylamine, pyrroles, thiophene or ethylenedioxy thiophene;
(2) the substrate A aeration-dryings that deposition obtained by step (1) is had to conducting polymer, lead then along the surfaces substrate A deposition The region periphery of electric polymer applies adhesive, gel electrolyte is then coated on the inside of the periphery for being applied with adhesive, later Substrate A is placed in 50~150 DEG C of baking oven and stands 1~10 day, is taken out spare;
The gel electrolyte mainly is mixed with to obtain by high molecular polymer with alkali metal salt;The high molecular polymerization Object is polyethylene glycol oxide, polymethyl methacrylate, polyacrylonitrile or polyvinylidene fluoride;The alkali metal salt is perchloric acid Lithium;
(3) the coated metal oxide slurry on substrate B, and reserve in coating a part of blank substrate region and be used for and external Conducting wire is connected, and after good metal oxide paste drying to be coated, substrate B and the ready substrate A of step (2) is misplaced viscous It closes, i.e. substrate A is with after substrate B bondings, and respectively reserved a part of blank substrate region is Non-overlapping Domain, for being led with outside Line is connected, and is compacted later, obtains the discoloration power supply;
The metal oxide is titanium dioxide, rhodium oxide, nickel oxide or manganese oxide.
2. the preparation method of discoloration power supply as described in claim 1, which is characterized in that the substrate A or substrate B is using attached There are the rigid conductive glass of tin indium oxide or the flexible conductive film with tin indium oxide.
3. the preparation method of discoloration power supply as described in claim 1, which is characterized in that in step (1), the electrolyte is The dichloromethane solution of 0.01~0.5mol/L conducting polymer monomers.
4. the preparation method of discoloration power supply as described in claim 1, which is characterized in that in step (1), the constant voltage is 0.6~1.4V, polymerization reaction time are 60~300s.
5. the preparation method of discoloration power supply as described in claim 1, which is characterized in that in step (2), the adhesive is adopted Use double faced adhesive tape.
6. the preparation method of discoloration power supply as described in claim 1, which is characterized in that in step (2), the gel electrolyte Matter is polymethyl methacrylate-lithium perchlorate gel electrolyte, also, the polymethyl methacrylate-lithium perchlorate is solidifying Glue electrolyte is prepared as follows to obtain:
Polymethyl methacrylate is added in propene carbonate, 12~48h of swelling in 50~100 DEG C of baking ovens is placed in, obtains body It is A;Lithium perchlorate is dissolved in acetonitrile, system B is obtained;System B is added in system A, 1~10h of sonic oscillation is to get institute The polymethyl methacrylate stated-lithium perchlorate gel electrolyte;Wherein, the polymethyl methacrylate and propene carbonate Mass ratio be 1: 1~10;The volumetric usage of the acetonitrile is calculated as 2~20mL/g with the quality of lithium perchlorate.
7. the preparation method of discoloration power supply as described in claim 1, which is characterized in that in step (3), metal oxidation Object slurry is formed by metal oxide solubilizer mixing preparation, and the solvent is dichloromethane, the volumetric usage of the solvent It is calculated as 50~100mL/g with the quality of metal oxide.
8. the preparation method of discoloration power supply as described in claim 1, which is characterized in that in step (3), the method for the coating For spraying, spin coating or drop coating.
CN201610343233.0A 2016-05-20 2016-05-20 Preparation method of color-changing power supply Active CN106025394B (en)

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CN110604561B (en) * 2019-06-19 2021-05-18 北京大学 Hydrogel-based electronic device and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5002700A (en) * 1988-08-30 1991-03-26 Osaka Gas Company Limited Permanently doped polyaniline and method thereof
CN101051697A (en) * 2007-04-10 2007-10-10 南京大学 Variable resistance conductive polymer/polyelectrolyte solid composite or mixed film and its preparing method
TW201025700A (en) * 2008-12-19 2010-07-01 Taiwan Textile Res Inst A method for forming an electrode with catalyst layer and application thereof
CN105372896A (en) * 2015-11-20 2016-03-02 浙江工业大学 Preparation of solid electrolyte electrochromic flexible device based on conductive polymer

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3164390B1 (en) * 2014-05-27 2019-09-18 Gentex Corporation Electrochromic devices and compounds therefor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5002700A (en) * 1988-08-30 1991-03-26 Osaka Gas Company Limited Permanently doped polyaniline and method thereof
CN101051697A (en) * 2007-04-10 2007-10-10 南京大学 Variable resistance conductive polymer/polyelectrolyte solid composite or mixed film and its preparing method
TW201025700A (en) * 2008-12-19 2010-07-01 Taiwan Textile Res Inst A method for forming an electrode with catalyst layer and application thereof
CN105372896A (en) * 2015-11-20 2016-03-02 浙江工业大学 Preparation of solid electrolyte electrochromic flexible device based on conductive polymer

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