CN109817469A - Supercapacitor, energy packet, self-charging energy packet and preparation method thereof - Google Patents
Supercapacitor, energy packet, self-charging energy packet and preparation method thereof Download PDFInfo
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Abstract
Supercapacitor, energy packet, self-charging energy packet and preparation method thereof, wherein supercapacitor includes: interdigital electrode collector, which uses transparent conductive material；Active electrode is covered in above interdigital electrode collector, which uses electrochromic material；And solid electrolyte, it is distributed in active electrode upper surface.The active electrode of the supercapacitor of the disclosure uses electrochromic material, to in the charging process of supercapacitor, the color of active electrode can change with the change of supercapacitor storage state, so as to directly objectively reflect the electricity storage state of supercapacitor.
Description
Technical field
The invention belongs to New Green Energy source domain, relate more specifically to a kind of supercapacitor, energy packet, the self-charging energy
Packet and preparation method thereof.
Background technique
With increasingly severe, people's development green energy resource collection and the storing technology of energy crisis and problem of environmental pollution
Hope is increasingly strong.
Compared to traditional electromagnetic generator, nano generator is not influenced by weather and harsh environments, it is not
The mechanical energy of high-frequency motion can only be converted to electric energy, and can be used to collect the mechanical energy of low frequency movement, therefore
Nano generator is a kind of effective way that solution green energy resource is collected；In addition, supercapacitor is made due to the circulation of its overlength
With the service life, the advantages that the specific capacitance of superelevation and huge power density and it is widely studied, therefore supercapacitor is also one
Kind solves the effective way that green energy resource is collected.
Recently, the self-charging energy coating for being integrated with energy collection and storage function is invented to meet portable device
Use demand, such as Piezoelectric Driving the wearable self-charging energy packet of self-charging ultracapacitor cell, integral type or fill certainly
Electric energy fabric.But these self-charging energy packets lack the function of instruction storing state, and judge in actual use
Whether battery is full of or whether electricity has completely consumed and be very important.Therefore, inventing one kind can indicate that electricity stores
The self-charging energy packet of state is of great significance.
Summary of the invention
Based on problem above, the main purpose of the disclosure is to propose a kind of supercapacitor, energy packet, the self-charging energy
Packet and preparation method thereof, for solving at least one of above technical problem.
To achieve the goals above, as an aspect of this disclosure, the disclosure proposes a kind of supercapacitor, comprising:
Interdigital electrode collector, the interdigital electrode collector use transparent conductive material；Active electrode is covered in interdigital electrode collector
Top, the active electrode use electrochromic material；And solid electrolyte, it is distributed in active electrode upper surface.
In some embodiments of the present disclosure, above-mentioned electrochromic material includes transition metal oxide, conducting polymer
Or the nanocomposite of transition metal oxide metal material for coating；Preferably, transition metal oxide include nickel oxide and/
Or tungsten oxide；Preferably conducting polymer includes polyaniline and/or poly- 3,4-rthylene dioxythiophene；.
In some embodiments of the present disclosure, above-mentioned electrochromic material is the nanocomposite of nickel oxide coated with silver.
In some embodiments of the present disclosure, above-mentioned interdigital electrode collector be plane it is symmetrical/unsymmetric structure；And/or
Solid electrolyte includes polyvinyl alcohol/potassium hydroxide gel electrolyte and/or polyvinyl alcohol/sodium hydroxide gel electrolyte.
To achieve the goals above, as another aspect of the disclosure, the disclosure proposes a kind of energy packet, including multiple
The supercapacitor of series connection and/or parallel connection, the supercapacitor are supercapacitor set forth above, and surface encapsulation is coated with
Clad.
In some embodiments of the present disclosure, the material of above-mentioned clad includes dimethyl silicone polymer and/or asphalt mixtures modified by epoxy resin
Rouge.
To achieve the goals above, as the another aspect of the disclosure, the disclosure proposes a kind of self energizing energy packet, packet
It includes: nano generator, for being produced electricl energy under mechanical force；Energy packet set forth above, is affixed on friction nanometer power generator
Surface is used for storage energy；Rectifier is connect, for generate friction nanometer power generator with energy packet and nano generator
Energy packet is transmitted to after electric energy rectification.
In some embodiments of the present disclosure, above-mentioned friction nanometer power generator includes hybrid friction nanometer power generator；It should
Hybrid nano generator includes the hybrid nano generator being made of piezoelectric nano generator and friction nanometer power generator.
In some embodiments of the present disclosure, above-mentioned hybrid nano generator is generated electricity by the piezoelectric nano of common electrode layer
Machine and friction nanometer power generator composition comprising from bottom to top: first electrode layer, rise electric layer, the second electrode lay, piezoelectric layer,
Third electrode layer and substrate layer；Wherein, first electrode layer, electric layer and the second electrode lay constitute friction nanometer power generator；Second
Electrode layer, piezoelectric layer, third electrode layer and substrate layer constitute piezoelectric nano generator；The second electrode lay is made with electric layer is played on outer boundary
With lower change contact/discrete state, the dipole in piezoelectric layer changes ordered state under external influence.
In some embodiments of the present disclosure, the material of main part of above-mentioned first electrode layer and/or the second electrode lay includes gold
Belong to material, multi-layer graphene, carbon nanotube and/or two-dimentional transparent conductive material；And/or the material of main part of substrate layer includes poly- pair
Phthalic acid ethylene glycol, polyethylene naphthalate, polyurethanes and/or polyimides；And/or the main body of piezoelectric layer
Material is piezoelectric material, which includes piezopolymer, zinc oxide nanowire and/or lead zirconate titanate；Wherein, piezoelectricity is poly-
Closing object includes organic ferroelectric material and/or Kynoar and its copolymer；And/or playing the material of main part of electric layer includes polytetrafluoro
Ethylene, polyimides and/or fluorinated ethylene propylene copolymer.
To achieve the goals above, the disclosure also proposes a kind of preparation method of supercapacitor, comprising: etching is transparent to be led
Electric material forms interdigitated electrode structure, obtains interdigital electrode collector；Electroluminescent change is prepared in interdigital electrode collection liquid surface
The active electrode of color material；Solid electrolyte is added dropwise in active electrode area, completes the preparation of supercapacitor.
In some embodiments of the present disclosure, electrochromic material is prepared in above-mentioned interdigital electrode collection liquid surface
Active electrode includes: the mixed solution that interdigital electrode collection liquid surface coating silver nanowires is placed on Nickelous nitrate hexahydrate and urea
In, it is put into reaction kettle growth in situ, obtains coating the nickel hydroxide of the silver nanowires in interdigital electrode collection liquid surface；By table
The interdigital electrode collector of nickel hydroxide of the face with cladding silver nanowires, which is placed in Muffle furnace, to be calcined, in interdigital electrode collector
The active electrode of the composite nanostructure of nickel oxide cladding silver nanowires is prepared in surface.
To achieve the goals above, the disclosure also proposes a kind of preparation method of self energizing energy packet, comprising: series-parallel more
The supercapacitor that the preparation method of a supercapacitor set forth above is prepared, obtains energy packet；Energy packet is affixed on
The surface of previously prepared obtained nano generator；Rectifier be connected to energy packet positive and negative electrode and nano generator it is positive and negative
Electrode completes the preparation of self energizing energy packet.
In some embodiments of the present disclosure, the preparation of above-mentioned nano generator includes: to be formed in the of substrate surface
Three electrode layer surface spin coating piezopolymer solution, and piezoelectric layer is obtained in upper surface of substrate after high-voltage corona polarization；Exist respectively
The second electrode lay and first electrode layer are deposited on piezoelectric layer and PTFE film；By the second electrode lay/piezoelectric layer/third electrode layer/base
Bottom structure and first electrode layer/PTFE film structure back-off after, the both ends of two structures are fixed as one, and by substrate/
Third electrode layer/piezoelectric layer/the second electrode lay structure intermediate region bending completes nano generator to separate with PTFE film
Preparation.
Supercapacitor that the disclosure proposes, energy packet, self-charging energy packet and preparation method thereof, have below beneficial to effect
Fruit:
1, the active electrode of supercapacitor uses electrochromic material, thus in the charging process of supercapacitor,
The color of active electrode can change with the change of supercapacitor storage state, so as to directly objectively reaction excess of export
The electricity storage state of grade capacitor；
2, the collector of supercapacitor uses plane interdigitated electrode structure, so as to shorten between positive electrode and negative electrode away from
From so as to shorten the diffusion length of ion when energy storage, therefore the capacitor of supercapacitor being capable of increasing, so that supercapacitor
Output energy is big, power density is high；
3, active electrode uses the nanocomposite of nickel oxide coated with silver, therefore can be improved supercapacitor activity electricity
The electric conductivity of pole, increases the specific surface area of active electrode material, to increase the specific capacity of supercapacitor；
4, the energy packet that forms multiple supercapacitors in series and parallel is, it can be achieved that when controllable voltage window and charge and discharge
Between, to meet the actual use demand of miniaturized electronics；And on the energy packet surface series-parallel by multiple supercapacitors
Clad is formed, fixed connection can not only be played the role of, and can play prevents solid electrolyte moisture from evaporating
Effect；
5, using the self-charging energy packet of supercapacitor, intelligence is realized for the first time, is filled certainly using supercapacitor
Color change (light transmittance variation) in electric process indicates the energy storage state of energy packet, collection self-charging and indicates charged state
Function is in one, not only energy saving, but also can more be widely used in wearable and mobile electronic device, gives the energy
The use of packet brings great convenience；
6, the generator of self-charging energy packet uses hybrid-type nano generator, can collect small mechanical energy and turn
It is changed to electric energy, and its function is protected from weather influences, power generation process is pollution-free, so as to effectively reduce environmental pollution, one
Determine alleviating energy crisis in degree, is able to solve small-sized electronic product and the external perishability of power supply and not convenient of providing is provided
Property, reduce energy consumption；
7, the preparation cost of self-charging energy packet is cheap, and preparation process is simple, it can be achieved that large-scale industrial production.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the supercapacitor that one embodiment of the disclosure proposes.
Fig. 2 is the structural schematic diagram of interdigital electrode in the supercapacitor of one embodiment of disclosure proposition.
Fig. 3 (a) is the composed structure schematic diagram of hybrid friction nanometer power generator in one embodiment of the disclosure.
Fig. 3 (b) is the final structure schematic diagram of the hybrid friction nanometer power generator in one embodiment of the disclosure.
Fig. 4 is the structural schematic diagram for the self-charging energy packet that one embodiment of the disclosure proposes.
Fig. 5 (a) is the output voltage schematic diagram of hybrid friction nanometer power generator in one embodiment of the disclosure.
Fig. 5 (b) is the output current diagram of hybrid friction nanometer power generator in one embodiment of the disclosure.
Fig. 5 (c) is to be illustrated in one embodiment of the disclosure by the energy packet charging process that 9 supercapacitors assemble
Figure.
Fig. 5 (d) is the change curve of single supercapacitor light transmittance in charge and discharge process in one embodiment of the disclosure
Schematic diagram.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in further detail.
Based on reversible electrochemical reaction, electrochromic material can reversibly change its optical property and can be widely applied
In fields such as large area display, intelligent glass and military camouflage materials.Electrochromic material mainly includes WO3Equal transition metal
The conducting polymers such as oxide and PANI (polyaniline), since its apparent color change has been widely studied, if utilizing
Active electrode material of the electrochromic material as supercapacitor, being expected to, which can be realized, indicates storing state according to color change
Function, for solve the problems, such as lack instruction charge storage state effective way is provided.
Based on the above analysis, the disclosure proposes a kind of supercapacitor, comprising: interdigital electrode collector, the interdigital electrode
Collector uses transparent conductive material；Active electrode is covered in above interdigital electrode collector, which uses electroluminescent change
Color material；And solid electrolyte, it is distributed in active electrode upper surface.Therefore, in the charging process of supercapacitor, activity
The color of electrode can change with the change of supercapacitor storage state, so as to directly objectively reflect super electricity
The electricity storage state of container.It should be noted that solid electrolyte herein refers to gelatinous electrolyte.
In some embodiments of the present disclosure, above-mentioned electrochromic material includes transition metal oxide, conducting polymer
Or the nanocomposite of transition metal oxide metal material for coating；Transition metal oxide therein may be, for example, nickel oxide
And/or tungsten oxide；Conducting polymer therein may be, for example, polyaniline and/or poly- 3,4-rthylene dioxythiophene.
In some embodiments of the present disclosure, above-mentioned electrochromic material is the nanocomposite of nickel oxide coated with silver,
Due to the nanocomposite for coated with silver, that is, includes silver nanowires, therefore the electric conductivity of electrode of super capacitor can be improved, increase
Add the specific surface area of active electrode material, to increase the specific capacity of supercapacitor.
In some embodiments of the present disclosure, above-mentioned interdigital electrode collector be plane it is symmetrical/unsymmetric structure, to shorten
The distance between positive electrode and negative electrode increase the capacitor of supercapacitor so as to shorten the diffusion length of ion when energy storage, so that super
Grade capacitor goes out that energy is big, power density is high.
In some embodiments of the present disclosure, above-mentioned solid electrolyte includes polyvinyl alcohol/potassium hydroxide gel electrolyte
And/or polyvinyl alcohol/sodium hydroxide gel electrolyte.
Based on above-mentioned supercapacitor, the disclosure also proposes a kind of preparation method of supercapacitor, comprising: etching is saturating
Bright conductive material forms interdigitated electrode structure, obtains interdigital electrode collector；Electricity is prepared in interdigital electrode collection liquid surface
Cause the active electrode of off-color material；Solid electrolyte is added dropwise in active electrode area, completes the preparation of supercapacitor.
In some embodiments of the invention, wherein electrochromic material is prepared in interdigital electrode collection liquid surface
Active electrode may be, for example: interdigital electrode collection liquid surface coating silver nanowires is placed on the mixing of Nickelous nitrate hexahydrate and urea
In solution, it is put into reaction kettle growth in situ, obtains the nickel hydroxide of cladding silver nanowires in interdigital electrode collection liquid surface；By table
The interdigital electrode collector of nickel hydroxide of the face with cladding silver nanowires, which is placed in Muffle furnace, to be calcined, in interdigital electrode collector
The active electrode of the composite nanostructure of nickel oxide cladding silver nanowires is prepared in surface.
Specifically, the specific structure of supercapacitor 100 is as shown in Figure 1, include shape in some embodiments of the present disclosure
At the activity in the interdigital electrode collector 102 in transparent glass substrate 101, being covered in 102 top of interdigital electrode collector
Electrode 103 (active electrode 103 and interdigital electrode collector 102 partly overlap in the figure), and be added dropwise and be coated on active electrode
The solid electrolyte 104 of 103 tops (only shows the solid electrolyte 104 of partial region, actually it is also located at activity in figure
Other regions of 102 upper surface of electrode).Wherein, interdigital electrode collector 102 includes anode 102-1 and cathode 102-2, the work
Property electrode 103 use electrochromic material, such as the nanocomposite of nickel oxide coated with silver can be used, solid electrolyte 104
It is transparent configuration for gel-like electrolyte.In supercapacitor charging, the positive and negative anodes of interdigital electrode collector connect respectively
Electricity starts to charge, in charging process, due to the electrochemical reaction of the solid electrolyte above active electrode and its, so that
The NiO of the active electrode of positive top is converted to NiO (OH), i.e. Ni ion is by Ni2+It is changed into Ni3+, therefore, as described in Figure 1,
The color of the anode top active material shown is different from color (cathode is actually transparent) above cathode, and participates in anti-
The ion answered is more, and positive color change is more obvious in interdigital electrode, shows that the charge of supercapacitor storage is more.
The supercapacitor of the present embodiment specific the preparation method is as follows:
The preparation of interdigital electrode collector: in ITO (tin indium oxide) glass for the 1cm × 1cm for being fixed on transparent glass 101
On with the revolving speed spin coating AZ5214 photoresist of 4000r/s, develop after uv-exposure, etched with the HCl solution of 1mol/L such as Fig. 2
Shown in interdigitated electrode structure, complete the preparation of the interdigital electrode collector；
The preparation of solid electrolyte: the polyvinyl alcohol of the KOH of 3.58g and 6g being added in the deionized water of 60ml, heating
To after 95 DEG C, stirring to solution is clarified, and completes the preparation of solid electrolyte；
The preparation of active electrode: silver nanowires is sprayed on interdigital electrode collector with air compressor machine, then by 0.4375g's
The urea of Nickelous nitrate hexahydrate and 1.4583g are added in 70ml deionized water and stir, the silver nanowires that is coated with that will be prepared
Interdigital electrode collector and the solution being stirred are added in the polytetrafluoroethyllining lining of 100ml, and will be using transparent glass as substrate
Interdigital electrode collector place vertically, under the conditions of 120 DEG C heat 12h after, interdigital electrode collector is taken from reaction kettle
Out, after 70 DEG C of dry 20min, the structure that interdigital electrode collection liquid surface has been attached with nickel hydroxide is obtained；Then by the knot
It sets up in Muffle furnace, calcines 2h under 350 DEG C of air conditions, so that oxidation nickel coated be made in interdigital electrode collection liquid surface
The composite nanostructure active electrode of silver nanowires；
Finally, the solid electrolyte of 0.3g is added dropwise in active electrode region, it is small to be placed in a vacuum drying oven under normal temperature condition 8
When, obtain supercapacitor as shown in Figure 1.
It should be noted that indium oxide tin glass etches the pattern of interdigital electrode herein, can be covered by using different
Diaphragm design makes different patterns by lithography, to obtain the device of different pattern, the present embodiment is not limited specific pattern
System, all patterns that can satisfy supercapacitor operating condition.
Multiple supercapacitors can be formed into energy packet in series and parallel, when can be realized controllable voltage window and charge and discharge
Between, to meet the actual use demand of miniaturized electronics.
Meanwhile the evaporation in order to prevent solid electrolyte moisture, it can encapsulate and be coated on above-mentioned energy packet surface
Coating may be, for example, dimethyl siloxane clad and/or epoxy resin clad, can play fixed connection simultaneously
Effect.
The disclosure is investigated the component part using nano generator as collecting mechanical energy, and above-mentioned energy packet is as storage
The component part of the energy is deposited, the intelligent self-charging energy packet based on nano generator and electrochromic material is developed.
Based on the studies above, the disclosure proposes a kind of self energizing energy packet, comprising: nano generator, in mechanical force
It is produced electricl energy under effect；The above-mentioned energy packet formed in series and parallel by multiple supercapacitors, is affixed on friction nanometer power generator surface,
For storage energy；Rectifier is connect with energy packet and nano generator, and the electric energy for generating friction nanometer power generator is whole
Energy packet is transmitted to after stream.
Then, the self-charging energy packet for using supercapacitor, realizes intelligence for the first time, certainly using supercapacitor
Color change (light transmittance variation) in charging process indicates the energy storage state of energy packet, collection self-charging and instruction charged state
Function in one, not only energy saving, but also can more be widely used in wearable and mobile electronic device gives energy
The use of source packet brings great convenience.
In disclosed some embodiments, friction nanometer power generator includes hybrid friction nanometer power generator；Such as it can be with
The hybrid nano generator being made of piezoelectric nano generator and friction nanometer power generator, so that the generator can
It collects small mechanical energy and is converted to electric energy, and its function is protected from weather influences, power generation process is pollution-free, so as to effective
Reduce environmental pollution, alleviating energy crisis to a certain extent solves small-sized electronic product using external and provides the non-of power supply
Persistence and inconvenience reduce energy consumption.
In some embodiments of the present disclosure, as Fig. 3 (a) show the structure of hybrid nano generator in the present embodiment
Sectional view, the hybrid nano generator 30 are made of the piezoelectric nano generator and friction nanometer power generator of common electrode layer,
It includes from bottom to top: first electrode layer 301 plays electric layer 302, the second electrode lay 303, piezoelectric layer 304, third electrode layer
305 and substrate layer 306；First electrode layer 301 plays electric layer 302 and the composition friction nanometer power generator of the second electrode lay 303；Second
Electrode layer 303, piezoelectric layer 304, third electrode layer 305 and substrate layer 306 constitute piezoelectric nano generator；The second electrode lay 303
Change contact/discrete state under external influence with electric layer 302 is played, meanwhile, the dipole in piezoelectric layer can be in the external influence
Lower change ordered state；When being connect with rectifier, connected by first electrode layer 301 and third electrode layer 305, and rectifier with
The connection of energy packet is then the anode and cathode for being connected to interdigital electrode in the supercapacitor of energy packet two sides.
Wherein, the material of main part of first electrode layer 301 and/or the second electrode lay 303 includes metal material, Multi-layer graphite
Alkene, carbon nanotube and/or two-dimentional transparent conductive material；The material of main part of substrate layer 306 includes polyethylene terephthalate, gathers
The polymer materials such as (ethylene naphthalate), polyurethanes and/or polyimides；The material of main part of piezoelectric layer 304 is
Piezoelectric material, piezoelectric material include the materials such as piezopolymer, zinc oxide nanowire and/or lead zirconate titanate；Piezopolymer packet
Include organic ferroelectric material and/or Kynoar and its copolymer；The material of main part for playing electric layer includes polytetrafluoroethylene (PTFE), polyamides Asia
The polymer materials such as amine and/or fluorinated ethylene propylene copolymer.
In some embodiments of the invention, above-mentioned hybrid nano generator uses PTFE film to play electric layer, preparation
Method are as follows: in the third electrode layer surface spin coating piezopolymer solution for being formed in substrate surface, and after high-voltage corona polarization
Upper surface of substrate obtains piezoelectric layer；The second electrode lay and first electrode layer is deposited on piezoelectric layer and PTFE film respectively；By second
After electrode layer/piezoelectric layer/third electrode layer/substrate structure and the back-off of first electrode layer/PTFE film structure, by two structures
Both ends be fixed as one, and substrate/third electrode layer/piezoelectric layer/the second electrode lay structure intermediate region is bent, with
PTFE film separation, completes the preparation of the hybrid nano generator, finally obtains the structure as shown in Fig. 3 (b).
For example, hybrid nano generator used in self-charging energy packet is in some embodiments of the present disclosure with 7: 3
Organic ferroelectric material P (VDF-TrFE) is piezo-electric crystal as piezoelectric layer, is with the strong PTFE of electronegativity (polytetrafluoroethylene (PTFE))
Electric layer, to improve open-circuit voltage and short circuit current；And due to the electrochemistry and electrochromic property of NiO brilliance, using temperature
NiO nanowire is synthesized with effective, cheap hydro-thermal method, super electricity is prepared using the active electrode material as supercapacitor
Container, therefore the self energizing energy packet of the present embodiment indicates its storage using color change of supercapacitor during self-charging
It can state.Mixing nano generator is integrated with electrochromism supercapacitor；And by collector plane electrode
Patterned process is carried out, the practicability of discoloration instruction storing state function can be improved.
Based on above-mentioned self energizing energy packet, the disclosure also proposes a kind of preparation method of self energizing energy packet, comprising: string
The supercapacitor that the preparation method of supercapacitor is prepared in multiple above-described embodiments in parallel, obtains energy packet；It will
Wrap the surface for being affixed on previously prepared obtained nano generator in source；Rectifier is connected to the positive and negative electrode and nanometer generating of energy packet
The positive and negative electrode of machine completes the preparation of self energizing energy packet.
Specifically, as shown in figure 4, in some embodiments of the present disclosure, propose it is a kind of it is flexible, efficiently, intelligence from
Charge energy packet 1, it is assembled based on mixing nano generator and all solid state electrochromism ultracapacitor arrays, has
With good grounds color change indicates the function of its self-charging storage state.Mix nano generator 30 by piezoelectric type nano generator and
Frictional nano generator shares a silver electrode and is composed, and can produce the electric current of the up to voltage of 200V and 20 μ A.Electricity
Mutagens color ultracapacitor arrays 10 are in a row by 3 electrochromism supercapacitor parallel connections first, then in parallel by 3 rows
Supercapacitor series connection, 9 units form an arrays, using as energy packet；Rectifier 20, with energy packet and nano generator
200 connections are transmitted to energy packet after the electric energy rectification for generating friction nanometer power generator.Electrochromism supercapacitor by
NiO coats the nanocomposite of Ag as active electrode, the ITO electrode of the symmetrical interdigitated electrode structure of plane as collector,
PVA (polyvinyl alcohol)/KOH gel is composed as solid electrolyte.Prepared electrochromism supercapacitor specific capacity
Up to 3.46mF/cm2, specific capacity remains original 80.7% after 10000 circulations.By the lasting beating of manpower, this
The kind self-charging energy packet self-charging can reach 3V in 900s.It is worth noting that, plane supercapacitor interdigital electrode
Anode color during self-charging changes, this is because Ni2+/Ni3+The reversible transition of ion pair.The electricity of storage is got over
More, positive electrode color is deeper, may determine that the storing state of supercapacitor according to the variation of electrode color.It is this simple, honest and clean
Valence, effective preparation method have pushed the development of intelligent electronic device.
The preparation method of the self energizing energy packet of the present embodiment specifically includes the following steps:
1, prepare material: organic ferroelectric material P (VDF-TrFE), Nickelous nitrate hexahydrate, urea, ito glass, poly dimethyl
Siloxanes PDMS (Sylgrad 184, Dow corning), PTFE film, PET-ITO (polyethylene terephthalate-oxidation
Indium tin) substrate, silver nanowires, conductive metal (such as Au, Ag etc.), acetone, isopropanol, deionized water, AZ5214 photoresist, positive photoresist
Developer solution, DMF (dimethylformamide) solution and Kapton Tape (Kapton adhesive tape) etc.；
2, the preparation of interdigital electrode collector: in ITO (tin indium oxide) glass for the 1cm × 1cm being formed on transparent glass
With the rate spin coating AZ5214 photoresist of 4000r/s on glass, developed after uv-exposure with developer for positive photoresist, with the HCl of 1mol/L
Interdigitated electrode structure is etched, the preparation of interdigital electrode collector is completed；
3,60ml deionized water the preparation of PVA/KOH gel electrolyte: is added in the polyvinyl alcohol of the KOH of 3.58g and 6g
In, it is heated to 95 DEG C of stirrings to solution and clarifies；
4, the preparation of active electrode: silver nanowires is sprayed on interdigital electrode collector with air compressor machine, then by 0.4375g
Nickelous nitrate hexahydrate and 1.4583g urea be added 70ml deionized water in stir, be coated with silver nanowires for what is prepared
Interdigital electrode collector and the solution that is stirred be added in the polytetrafluoroethyllining lining of 100ml, and will be lining with transparent glass
The interdigital electrode collector at bottom is placed vertically, after heating 12h under the conditions of 120 DEG C, by interdigital electrode collector from reaction kettle
It takes out, after 70 DEG C of dry 20min, obtains the structure that interdigital electrode collection liquid surface has been attached with nickel hydroxide；Then should
Structure is placed in Muffle furnace, calcines 2h under 350 DEG C of air conditions, so that nickel oxide packet be made in interdigital electrode collection liquid surface
Cover the composite nanostructure active electrode of silver nanowires；
5, the preparation of energy packet: the PVA/KOH gel electrolyte of 0.3g is added dropwise in active electrode region, is placed in vacuum drying
Lower 8 hours of normal temperature condition in case；Then, by 3 electrochromism supercapacitors it is in parallel it is in a row after, by parallel super of 3 rows
Grade capacitor series connection, 9 units are formed an energy packet, are finally mixed PDMS prepolymer with 10: 1 weight ratios with curing agent
Even, vacuum degassing bubble is cast in the energy and wraps to encapsulate, the energy packet after being encapsulated after 60 DEG C of drying 1h curing moldings；
6, the preparation of hybrid nano generator: by 7: 3 piezopolymer P (VDF-TrFE) and DMF solvent with 1: 4
Weight ratio mixing stirs evenly rear spare；Then it is dissolved in advance on the PET-ITO substrate of 5cm × 5cm with the rate spin coating of 2000r/s
Good piezopolymer solution is polarized with the voltage corona of 5000V, obtains piezoelectric polymer film on PET-ITO substrate；So
Afterwards, heat steams and crosses the silver electrode of 100nm on polymer film and PTFE, then by the PET-ITO/P (VDF-TrFE) at top/silver and
The PTFE/ silver of bottom is fixed with kapton adhesive tape, obtains the structure as shown in Fig. 3 (a)；Wherein, it needs to keep top wider than bottom
5mm, when fixed, two-part both ends are fixed together, and the bending of the intermediate region at top is arched, are formed such as Fig. 3 (b) institute
The structure shown, to complete the preparation of hybrid nano generator, wherein PET-ITO substrate, piezoelectric membrane and and piezoelectric membrane
The silver electrode of surface vapor deposition constitutes piezoelectric nano generator, and the silver electrode of piezoelectric membrane surface vapor deposition, the surface PTFE and PTFT are steamed
The silver electrode of plating constitutes friction nanometer power generator, and piezoelectric nano generator and friction nanometer power generator share piezoelectric membrane surface and steam
The silver electrode of plating；
7, the preparation of self energizing energy packet: the PDMS that enclosed inside there are ultracapacitor arrays is attached to hybrid nanometer and is sent out
Above the PET of motor, group becomes self-charging energy packet as shown in Figure 4；
The working principle of self energizing energy packet obtained above specifically: in the initial state, piezoelectric membrane P (VDF-
TrFE dipole) forms a line, and free electron is located at piezoelectric membrane and ITO electrode interface, and positive charge is located at piezoelectric membrane
With silver electrode interface；After applying certain external influence, charge is in ITO electrode (or silver electrode) and P (VDF-TrFE) film
Interface aggregation, form electric double layer to generating potential difference；Simultaneously as friction nanometer power generator and piezoelectric nano generator
A silver electrode is shared, and since the electronegativity of metallic silver is less than the electronegativity of PTFE, PTFE obtains the ability of electronics more
By force, the free electron in silver electrode can be made to be transferred in PTFE when two kinds of materials are close to each other, so that potential difference is generated, it should
Potential difference drives the free electron in external circuit mobile, the electric current in forming circuit, to charge to energy packet；Energy packet is filling
Color change in electric process is due to Ni2+And Ni3+Reversible sex reversal, participate in the ion pair Ni of reaction2+/Ni3+It is more, surpass
The color change of grade capacitor interdigital electrode is more obvious, and shows that the charge of energy packet storage is more.
Wherein, it is stimulated by the strain of external influence, hybrid nano generator can effectively turn low frequency mechanical energy
Electric energy is turned to, after rectifier rectification, collects the signal of unidirectional open-circuit voltage and short circuit current, what is generated opens
Respectively as shown in Fig. 5 (a) and Fig. 5 (b), rectifier and ultracapacitor arrays connect the curve synoptic diagram of road voltage and short circuit current
After connecing, as shown in Fig. 5 (c), the voltage of energy packet can be made to be charged to 3v；During the energy packet self-charging, single super capacitor
The light transmittance of device occurs to change as shown in Fig. 5 (d), and since light transmittance changes, the color presented changes, therefore
Can determine that the charged state of supercapacitor according to the variation of this color, for intelligent, miniaturized electronic device development and
Using bringing bigger convenience and may.
Wherein, the interdigital electrode of supercapacitor can further pattern processing, so as to show during its self-charging
Different patterns designs different patternings by different mask plates, can to current collector of super capacitor electrode into
Row patterning processing, makes self-charging energy packet show different colors under external influence, and can according to the variation of this color
Determine the charged state of supercapacitor.When it is in full of state of charge, showing different patterns may be used as showing
Device；Simultaneously because electric energy is provided by hybrid generator, and there is no need to external power supply, pattern needed for display that can be reversible.
It should also be noted that, the direction term mentioned in embodiment, for example, "upper", "lower", "front", "rear", " left side ",
" right side " etc. is only the direction with reference to attached drawing, not is used to limit the protection scope of the disclosure.Through attached drawing, identical element by
Same or similar appended drawing reference indicates.When may cause understanding of this disclosure and cause to obscure, conventional structure will be omitted
Or construction.
And the shape and size of each component do not reflect actual size and ratio in figure, and only illustrate the embodiment of the present disclosure
Content.In addition, in the claims, any reference symbol between parentheses should not be configured to the limit to claim
System.
It unless there are known entitled phase otherwise anticipates, the numerical parameter in this specification and appended claims is approximation, energy
Enough bases pass through the resulting required characteristic changing of content of this disclosure.Specifically, all be used in specification and claim
The middle content for indicating composition, the number of reaction condition etc., it is thus understood that repaired by the term of " about " in all situations
Decorations.Under normal circumstances, the meaning expressed refers to include by specific quantity ± 10% variation in some embodiments, some
± 5% variation in embodiment, ± 1% variation in some embodiments, in some embodiments ± 0.5% variation.
Furthermore word "comprising" does not exclude the presence of element or step not listed in the claims.It is located in front of the element
Word "a" or "an" does not exclude the presence of multiple such elements.
The word of ordinal number such as " first ", " second ", " third " etc. used in specification and claim, with modification
Corresponding element, itself is not meant to that the element has any ordinal number, does not also represent the suitable of a certain element and another element
Sequence in sequence or manufacturing method, the use of those ordinal numbers are only used to enable an element and another tool with certain name
Clear differentiation can be made by having the element of identical name.
In addition, unless specifically described or the step of must sequentially occur, there is no restriction in the above institute for the sequence of above-mentioned steps
Column, and can change or rearrange according to required design.And above-described embodiment can be based on the considerations of design and reliability, that
This mix and match is used using or with other embodiments mix and match, i.e., the technical characteristic in different embodiments can be freely combined
Form more embodiments.
Similarly, it should be understood that in order to simplify the disclosure and help to understand one or more of each open aspect,
Above in the description of the exemplary embodiment of the disclosure, each feature of the disclosure is grouped together into single implementation sometimes
In example, figure or descriptions thereof.However, the disclosed method should not be interpreted as reflecting the following intention: i.e. required to protect
The disclosure of shield requires features more more than feature expressly recited in each claim.More precisely, as following
Claims reflect as, open aspect is all features less than single embodiment disclosed above.Therefore,
Thus the claims for following specific embodiment are expressly incorporated in the specific embodiment, wherein each claim itself
All as the separate embodiments of the disclosure.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in protection of the invention
Within the scope of.
Claims (14)
1. a kind of supercapacitor, comprising:
Interdigital electrode collector, the interdigital electrode collector use transparent conductive material；
Active electrode is covered in above the interdigital electrode collector, which uses electrochromic material；And
Solid electrolyte is distributed in the active electrode upper surface.
2. supercapacitor according to claim 1, in which:
The electrochromic material includes transition metal oxide, conducting polymer or transition metal oxide metal material for coating
Nanocomposite；
Preferably, the transition metal oxide includes nickel oxide and/or tungsten oxide；
Preferably, the conducting polymer includes polyaniline and/or poly- 3,4-rthylene dioxythiophene.
3. supercapacitor according to any one of claim 1 to 2, in which:
The electrochromic material is the nanocomposite of nickel oxide coated with silver.
4. supercapacitor according to any one of claim 1 to 3, in which:
The interdigital electrode collector be plane it is symmetrical/unsymmetric structure；And/or
The solid electrolyte includes polyvinyl alcohol/potassium hydroxide gel electrolyte and/or polyvinyl alcohol/sodium hydroxide gel electricity
Xie Zhi.
5. a kind of energy packet, the supercapacitor including multiple series connection and/or parallel connection, the supercapacitor is claim 1
To supercapacitor described in any one of 4, surface encapsulation is coated with coating layer.
6. energy packet according to claim 5, wherein the material of the clad include dimethyl silicone polymer and/or
Epoxy resin.
7. a kind of self energizing energy packet, comprising:
Nano generator, for being produced electricl energy under mechanical force；
Energy packet as described in any one of claim 5 to 6 is affixed on the friction nanometer power generator surface, for storing energy
Amount；
Rectifier is connect with the energy packet and nano generator, and the electric energy for generating the friction nanometer power generator is whole
The energy packet is transmitted to after stream.
8. self energizing energy packet according to claim 7, in which:
The friction nanometer power generator includes hybrid friction nanometer power generator；
The hybrid nano generator includes the hybrid nanometer being made of piezoelectric nano generator and friction nanometer power generator
Generator.
9. self energizing energy packet according to claim 8, in which:
The hybrid nano generator is made of the piezoelectric nano generator and friction nanometer power generator of common electrode layer, packet
Include from bottom to top: first electrode layer plays electric layer, the second electrode lay, piezoelectric layer, third electrode layer and substrate layer；
The first electrode layer plays electric layer and the second electrode lay composition friction nanometer power generator；
The second electrode lay, piezoelectric layer, third electrode layer and substrate layer constitute piezoelectric nano generator；
The second electrode lay and the electric layer that serves change contact/discrete state, the idol in the piezoelectric layer under outer boundary
Extremely son changes ordered state under external influence.
10. self energizing energy packet according to claim 9, in which:
The material of main part of the first electrode layer and/or the second electrode lay includes metal material, multi-layer graphene, carbon nanotube
And/or two-dimentional transparent conductive material；And/or
The material of main part of the substrate layer includes polyethylene terephthalate, polyethylene naphthalate, polyurethane
Ester and/or polyimides；And/or
The material of main part of the piezoelectric layer be piezoelectric material, the piezoelectric material include piezopolymer, zinc oxide nanowire and/
Or lead zirconate titanate；The piezopolymer includes organic ferroelectric material and/or Kynoar and its copolymer；And/or
The material of main part of described electric layer includes polytetrafluoroethylene (PTFE), polyimides and/or fluorinated ethylene propylene copolymer.
11. a kind of preparation method of supercapacitor, comprising:
It etches transparent conductive material and forms interdigitated electrode structure, obtain interdigital electrode collector；
The active electrode of electrochromic material is prepared in the interdigital electrode collection liquid surface；
Solid electrolyte is added dropwise in the active electrode area, completes the preparation of the supercapacitor.
12. the preparation method of supercapacitor according to claim 11, wherein in the interdigital electrode collection liquid surface
The active electrode that electrochromic material is prepared includes:
Interdigital electrode collection liquid surface coating silver nanowires is placed in the mixed solution of Nickelous nitrate hexahydrate and urea, is put into anti-
Kettle growth in situ is answered, obtains coating the nickel hydroxide of the silver nanowires in the interdigital electrode collection liquid surface；
There is the interdigital electrode collector for the nickel hydroxide for coating the silver nanowires to be placed in Muffle furnace surface to calcine, in institute
State the active electrode that the composite nanostructure of silver nanowires described in oxidation nickel coated is prepared in interdigital electrode collection liquid surface.
13. a kind of preparation method of self energizing energy packet, comprising:
The preparation method of series-parallel multiple supercapacitors as described in any one of claim 11 to 12 is prepared super
Grade capacitor, obtains energy packet；
Energy packet is affixed on to the surface of previously prepared obtained nano generator；
Rectifier is connected to the positive and negative electrode of the energy packet and the positive and negative electrode of nano generator, completes the self energizing energy
The preparation of packet.
14. the preparation method of self energizing energy packet according to claim 13, wherein the preparation packet of the nano generator
It includes:
In the third electrode layer surface spin coating piezopolymer solution for being formed in substrate surface, and in substrate after high-voltage corona polarization
Upper surface obtains piezoelectric layer；
The second electrode lay and first electrode layer is deposited on piezoelectric layer and PTFE film respectively；
After the second electrode lay/piezoelectric layer/third electrode layer/substrate structure and the back-off of first electrode layer/PTFE film structure,
The both ends of two structures are fixed as one, and by substrate/third electrode layer/piezoelectric layer/the second electrode lay structure middle area
Domain bending, to separate with the PTFE film, completes the preparation of the nano generator.
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