CN106887343A - A kind of all solid state fibrous flexible super capacitor and preparation method thereof - Google Patents
A kind of all solid state fibrous flexible super capacitor and preparation method thereof Download PDFInfo
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- CN106887343A CN106887343A CN201710089961.8A CN201710089961A CN106887343A CN 106887343 A CN106887343 A CN 106887343A CN 201710089961 A CN201710089961 A CN 201710089961A CN 106887343 A CN106887343 A CN 106887343A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- 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
- Y02E60/13—Energy storage using capacitors
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- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
Abstract
A kind of all solid state fibrous flexible super capacitor and preparation method thereof, belongs to field of material technology.The capacitor is made up of positive pole, negative pole, barrier film, solid-state electrolytic solution and collector, and preparation method is as follows：（1）Positive and negative pole material being prepared using the precipitation method, hydro-thermal method etc. and positive electrode being grown in fibrous substrate, negative material does film-like；（2）Solid-state electrolytic solution is prepared, temperature control is at 80 ~ 100 DEG C；（3）Both positive and negative polarity is immersed in 5 ~ 20 min in the solid-state electrolytic solution for having prepared respectively；（4）Two kinds of materials are separated with barrier film, solid being coated on the fiber of positive pole of negative electrode film is packaged into fibrous device, be put into 60 ~ 80 DEG C of h of drying 8 ~ 15 of baking oven.The method have the advantages that：Using solid-state electrolytic solution, in the absence of electrolyte leakage, explosion danger；With it is flexible high, have extended cycle life, cheap, economical environment-protective, recyclable, electrode material choose diversified advantage, and with energy density and power density higher, synthesis technique and simple for assembly process.
Description
Technical field
The invention belongs to field of material technology, it is related to a kind of all solid state fibrous flexible super capacitor and its preparation side
Method, more particularly to a kind of perfect adaptation of the fibre structure and negative material membrane structure for growing positive electrode, construct a kind of new
The design concept of type ultracapacitor.
Background technology
In recent years, with the new ideas such as Highgrade integration, light weight portability, wearable, implantable and flexibility, intelligence
The emergence of electronic product can be changed, in the urgent need to exploitation with its highly compatible with high energy storage density, flexibility, function collection
Into the micro-nano energy storage device changed, for it provides power source, their dynamical problem is solved.Some emerged in large numbers in the market are new
Concept, flexibility, intelligentized electronic product element and product, for example, Nokia companies in 2011 and Samsung public affairs in 2013
Take charge of conceptual, the bent flexibility mobile phone that releases one after another（flexible phone）Prototype and intelligent wrist-watch（smart
watch）；Google develops intelligent Google's glasses within 2013（Google glass）, can whenever and wherever possible enter row information
Collect, store and transmitting；2013 and LG company in 2015 produce flexibility, intelligentized mobile phone（flexible smart
phone）With intelligent health tracker（smart health tracker）；Intel Company in 2014 develops intelligentized
Earphone（smart headset）Deng the commercialization product for civilian use, and some have the micro-system of military use, such as miniature helicopter
Deng.However, in numerous energy storage devices, flexible ultracapacitor is due to high power, quick discharge and recharge and overlength
Cycle life the advantages of receive extensive concern.In various flexible super capacitors（Fibrous ultracapacitor,
The aeroge ultracapacitor of paper-like ultracapacitor and three-dimensional）, fibrous ultracapacitor is due to its small volume, wearable energy
The features such as power is strong and flexible high has turned into a kind of electrochmical power source having broad application prospects.With traditional non-flexible super electricity
Container is compared, and it can directly be taken as a portable power source to be embedded into the middle of yarn fabric or fabric.Although fibrous super electricity
Container have the advantages that it is a lot, it is known that fibrous ultracapacitor it is necessary to have a filamentary structure material as branch
Support body（Carbon nano-tube fibre, graphene fiber or NACF）.But these conventional fibers comparatively price is high
And synthesis technique is complicated.Therefore, it is imperative to design a kind of new cheap fibres shape ultracapacitor.
The content of the invention
The invention aims to overcome the deficiencies in the prior art, there is provided a kind of all solid state threadiness is flexible super
Level capacitor and preparation method thereof, its synthesis technique is simple, economical environment-protective, cheap, electrode material choose variation.
To achieve the above object, the technical scheme that the present invention takes is as follows：
A kind of all solid state fibrous flexible super capacitor, the capacitor include positive pole, barrier film, solid-state electrolytic solution, negative pole and
Collector is constituted, the just extremely flexible fiber construction, and the negative pole is flexible membrane, and the collector is fibrous substrate；
Collector structure in the shape of a spiral, the positive pole is enclosed in collector outside in the shape of a spiral, and the barrier film is cylindrical
Positive pole outside is enclosed in, the solid-state electrolytic solution is enclosed in outside barrier film, the negative pole is enclosed in solid-state electrolytic solution outside.
A kind of preparation method of described all solid state fibrous flexible super capacitor, methods described step is as follows：
Step one：Positive pole and negative pole are prepared using the precipitation method, hydro-thermal method, vacuum filtration method, chemical vapour deposition technique or ice bath method
Material, and positive electrode is grown in fibrous substrate, negative pole does film-like；
Step 2：Solid-state electrolytic solution is prepared, temperature control is at 80 ~ 100 DEG C；
Step 3：Positive pole and negative pole are immersed in respectively prepared in 5 ~ 20 min in gelatinous solid-state electrolytic solution；
Step 4：Finally two kinds of materials of positive pole and negative pole are separated with barrier film, negative electrode film is solid to be coated on the fiber of positive pole
Fibrous device is packaged into, the h of oven drying 8 ~ 15 is put into, oven temperature is set to 60 ~ 80 DEG C.
The present invention is relative to the beneficial effect of prior art：
（1）The present invention uses solid-state electrolytic solution, and electrolyte leakage, the danger of blast will not occur, and is expected to turn into future ideality
Energy storage material；
（2）Ultracapacitor of the invention has higher flexibility, can arbitrarily fold and bend, and with cheap, saving
Environmentally friendly, recyclable, electrode material chooses diversified advantage；
（3）The electrode material of ultracapacitor appropriate mix of the invention will be provided with energy density and power density higher, close
Into technique and simple for assembly process, it is expected to turn into the device of future ideality in energy storage.
（4）Capacitor of the invention has long cycle life and can be embedded into clothing as the energy of portable power source
Power.
Brief description of the drawings
Fig. 1 is a kind of structural representation of all solid state fibrous flexible super capacitor；
Fig. 2 is the polyster fibre that can arbitrarily bend of present invention selection as the substrate figure of growth positive electrode；
Fig. 3 is the flexible film figure that negative material is obtained by vacuum filtration；
Fig. 4 is the picture that all solid state fibrous flexible super capacitor prepared by the present invention shows differently curved degree；
As shown in figure 1, positive pole 1, barrier film 2, solid-state electrolytic solution 3, negative pole 4, collector 5.
Specific embodiment
Technical scheme is further described with reference to the accompanying drawings and examples, but is not limited thereto,
It is every technical solution of the present invention to be modified or equivalent, without deviating from the spirit and scope of technical solution of the present invention,
All should cover in protection scope of the present invention.
Specific embodiment one：As shown in figure 1, a kind of all solid state fibrous flexible super capacitor, the capacitor bag
Positive pole 1, barrier film 2, solid-state electrolytic solution 3, negative pole 4 and collector 5 are included, the positive pole 1 is flexible fiber construction, and the negative pole 4 is
Flexible membrane, the collector 5 is fibrous substrate；
The structure in the shape of a spiral of the collector 5, the positive pole 1 is enclosed in the outside of collector 5 in the shape of a spiral, and the barrier film 2 is in circle
Tubular is enclosed in the outside of positive pole 1, and the solid-state electrolytic solution 3 is enclosed in outside barrier film 2, and the negative pole 4 is enclosed in outside solid-state electrolytic solution 3
Face.
Specific embodiment two：A kind of system of all solid state fibrous flexible super capacitor described in specific embodiment one
Preparation Method, methods described step is as follows：
Step one：Positive pole 1 and negative pole are prepared using the precipitation method, hydro-thermal method, vacuum filtration method, chemical vapour deposition technique or ice bath method
4 materials, and the Material growth of positive pole 1, in fibrous substrate, negative pole 4 does film-like；
Step 2：Solid-state electrolytic solution 3 is prepared, temperature control is at 80 ~ 100 DEG C；
Step 3：Positive pole 1 and negative pole 4 are immersed in respectively prepared in gelatinous solid-state electrolytic solution 35 ~ 20
min；
Step 4：Finally 4 two kinds of material barrier films 2 of positive pole 1 and negative pole are separated, the solid fibre for being coated on positive pole 1 of negative electrode film
Fibrous device is packaged into dimension, the h of oven drying 8 ~ 15 is put into, oven temperature is set to 60 ~ 80 DEG C.
Specific embodiment three：The preparation side of all solid state fibrous flexible super capacitor described in specific embodiment two
In method, step one, the material of the positive pole 1 is one or two the mixture in cobalt acid nickel, nickel oxide, cobalt oxide, described negative
The material of pole 4 is Graphene, CNT or activated carbon.
Specific embodiment four：The preparation side of all solid state fibrous flexible super capacitor described in specific embodiment two
In method, step one, described fibrous substrate is one or more in polyster fibre, graphene fiber, carbon nano-tube fibre
Mixture.
Specific embodiment five：The preparation side of all solid state fibrous flexible super capacitor described in specific embodiment two
Method, in step 2, described solid-state electrolytic solution 3 is one or more in polyvinyl alcohol, lithium chloride, sodium sulphate, potassium hydroxide
Mixture.
Specific embodiment six：The preparation side of all solid state fibrous flexible super capacitor described in specific embodiment two
Method, in step 4, the barrier film 2 is cellulosic separator, polypropylene screen, diaphragm paper or polymer matrix.
Embodiment 1：
The present embodiment prepares all solid state fibrous flexible super capacitor in accordance with the following steps.
Step one：Prepare positive electrode：
（1）Choosing can be as one or two in the cobalt of supercapacitor positive electrode 1 acid nickel, nickel oxide or cobalt oxide by appropriate
Method synthesized, it is grown on polyster fibre substrate；
（2）So that hydro-thermal method prepares cobalt acid nickel nanostructured as an example, the cobalt acid nickel solution for preparing is poured into reactor, then one is washed
Synthetic fibre fiber（As shown in Figure 2）Reactor is put into, certain hour is reacted at a certain temperature, obtain the nanostructured of cobalt acid nickel；
（3）The cobalt being grown on the polyster fibre acid nickel nanostructured positive pole 1 that will have been made dries 12 in 60 DEG C of baking oven
h；
（4）The cobalt being grown on polyster fibre acid nickel nano material to obtaining carries out electro-chemical test and flexible test.
Step 2：Prepare negative material：
（1）By taking CNT as an example, the carbon nanotube powder that will have been prepared by ultrasonic disperse, finally by vacuum filtration
Method obtain single carbon nano-tube film, as shown in Figure 3；
（2）Carbon nano-tube film to preparing carries out electrochemistry and flexible test.
Step 3：Capacitor devices are prepared, as shown in Figure 4：
（1）The cobalt acid nickel and carbon nano-tube film that will be grown on polyster fibre are immersed in corresponding in gelatinous solid respectively
10min in state electrolyte 3；
（2）It is drawn off afterwards, carbon nano-tube film does negative pole 4, cobalt acid nickel does positive pole 1, and centre is separated with cellulosic separator, and carbon is received
Solid being coated on the polyster fibre of growth cobalt acid nickel of mitron film is packaged into all solid state fibrous flexible super capacitor；
（3）It is put into 80 DEG C of h of drying 10 of baking oven；
（4）Taken out after drying, electro-chemical test and flexible test are carried out to single capacitor devices.
Embodiment 2：
The present embodiment is as different from Example 1：Positive electrode is constant, the film that negative material is made of Graphene, will be positive and negative
Pole is immersed in the corresponding solid-state electrolytic solution 3 for preparing respectively, and centre is separated with cellulosic separator, is packaged into all solid state fibre
Dimension shape ultracapacitor, is put into 80 DEG C of h of drying 8 of baking oven, is taken out after drying.
Embodiment 3：
The present embodiment is as different from Example 1：Negative material is constant, and positive electrode uses nickel oxide, and positive and negative electrode is soaked respectively
Enter in the corresponding solid-state electrolytic solution 3 for preparing, centre is separated with diaphragm paper, is packaged into all solid state fibrous super capacitor
Device, is put into 60 DEG C of h of drying 15 of baking oven, is taken out after drying.
Embodiment 4：
The present embodiment is as different from Example 1：Positive electrode uses nickel oxide, the film that negative material is made of Graphene,
Positive and negative electrode is immersed in 15min in the corresponding solid-state electrolytic solution 3 for preparing respectively, centre is separated with cellulose membrane, is packaged into
All solid state fibrous ultracapacitor, is put into 80 DEG C of baking oven and dries 12h, is taken out after drying.
Embodiment 5：
The present embodiment is as different from Example 1：Negative material is constant, and positive electrode is answered using both nickel oxide and cobalt oxide
Condensation material, both positive and negative polarity is immersed in 15min in the corresponding solid-state electrolytic solution 3 for preparing respectively, is taken out afterwards, and centre is used
Cellulose membrane separates, and is packaged into all solid state fibrous ultracapacitor, is put into 80 DEG C of baking oven and dries 12h, is taken out after drying.
Embodiment 6：
The present embodiment is as different from Example 1：Positive electrode uses the composite of both nickel oxide and cobalt oxide, negative pole to adopt
The film being made of absorbent charcoal material, positive and negative electrode is immersed in 15min in the corresponding solid-state electrolytic solution 3 for preparing respectively, middle
Separated with cellulose membrane, be packaged into all solid state fibrous ultracapacitor, be put into 80 DEG C of baking oven and dry 12h, taken after drying
Go out.
Claims (6)
1. a kind of all solid state fibrous flexible super capacitor, it is characterised in that：The capacitor includes positive pole（1）, barrier film
（2）, solid-state electrolytic solution（3）, negative pole（4）And collector（5）Composition, the positive pole（1）It is flexible fiber construction, the negative pole
（4）It is flexible membrane, the collector（5）It is fibrous substrate；
The collector（5）Structure, the positive pole in the shape of a spiral（1）Collector is enclosed in the shape of a spiral（5）Outside, the barrier film
（2）It is cylindrical to be enclosed in positive pole（1）Outside, the solid-state electrolytic solution（3）It is enclosed in barrier film（2）Outward, the negative pole（4）Surround
In solid-state electrolytic solution（3）Outside.
2. the preparation method of all solid state fibrous flexible super capacitor described in a kind of claim 1, it is characterised in that：It is described
Method and step is as follows：
Step one：Positive pole is prepared using the precipitation method, hydro-thermal method, vacuum filtration method, chemical vapour deposition technique or ice bath method（1）With it is negative
Pole（4）Material, and positive pole（1）Material growth in fibrous substrate, negative pole（4）Do film-like；
Step 2：Prepare solid-state electrolytic solution（3）, temperature control is at 80 ~ 100 DEG C；
Step 3：By positive pole（1）And negative pole（4）Be immersed in respectively prepared in gelatinous solid-state electrolytic solution（3）In 5
~20 min；
Step 4：Finally by positive pole（1）And negative pole（4）Two kinds of material barrier films（2）Separate, negative electrode film it is solid be coated on positive pole
（1）Fiber on be packaged into fibrous device, be put into the h of oven drying 8 ~ 15, oven temperature is set to 60 ~ 80 DEG C.
3. the preparation method of all solid state fibrous flexible super capacitor according to claim 2, it is characterised in that：Step
In one, the positive pole（1）Material is one or two the mixture in cobalt acid nickel, nickel oxide, cobalt oxide, the negative pole（4）
Material is Graphene, CNT or activated carbon.
4. the preparation method of all solid state fibrous flexible super capacitor according to claim 2, it is characterised in that：Step
In one, described fibrous substrate is the mixture of one or more in polyster fibre, graphene fiber, carbon nano-tube fibre.
5. the preparation method of all solid state fibrous flexible super capacitor according to claim 2, it is characterised in that：Step
In two, described solid-state electrolytic solution（3）It is the mixing of one or more in polyvinyl alcohol, lithium chloride, sodium sulphate, potassium hydroxide
Thing.
6. the preparation method of all solid state fibrous flexible super capacitor according to claim 2, it is characterised in that：Step
In four, the barrier film（2）It is cellulosic separator, polypropylene screen, diaphragm paper or polymer matrix.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710089961.8A CN106887343A (en) | 2017-02-20 | 2017-02-20 | A kind of all solid state fibrous flexible super capacitor and preparation method thereof |
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| CN201710089961.8A CN106887343A (en) | 2017-02-20 | 2017-02-20 | A kind of all solid state fibrous flexible super capacitor and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110729134A (en) * | 2019-10-25 | 2020-01-24 | 陕西科技大学 | Nano NiCo2O4/rGO/ANF composite film and preparation method and application thereof |
| CN110957145A (en) * | 2019-12-17 | 2020-04-03 | 苏州盟维动力科技有限公司 | Flexible all-solid-state asymmetric fibrous energy storage device and manufacturing method thereof |
| CN110993359A (en) * | 2019-11-15 | 2020-04-10 | 广东轻工职业技术学院 | Flexible solid-state asymmetric supercapacitor device and preparation method and application thereof |
| WO2021093155A1 (en) * | 2019-11-15 | 2021-05-20 | 广东轻工职业技术学院 | Flexible device made by integration of microbial fuel cell and hybrid supercapacitor, preparation method therefor, and application thereof |
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| CN103247446A (en) * | 2013-04-26 | 2013-08-14 | 复旦大学 | Fibrous super capacitor with coaxial structure and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110729134A (en) * | 2019-10-25 | 2020-01-24 | 陕西科技大学 | Nano NiCo2O4/rGO/ANF composite film and preparation method and application thereof |
| CN110729134B (en) * | 2019-10-25 | 2021-07-23 | 陕西科技大学 | Nano NiCo2O4/rGO/ANF composite film and preparation method and application thereof |
| CN110993359A (en) * | 2019-11-15 | 2020-04-10 | 广东轻工职业技术学院 | Flexible solid-state asymmetric supercapacitor device and preparation method and application thereof |
| WO2021093155A1 (en) * | 2019-11-15 | 2021-05-20 | 广东轻工职业技术学院 | Flexible device made by integration of microbial fuel cell and hybrid supercapacitor, preparation method therefor, and application thereof |
| CN110993359B (en) * | 2019-11-15 | 2021-08-06 | 广东轻工职业技术学院 | Flexible solid-state asymmetric supercapacitor device and preparation method and application thereof |
| CN110957145A (en) * | 2019-12-17 | 2020-04-03 | 苏州盟维动力科技有限公司 | Flexible all-solid-state asymmetric fibrous energy storage device and manufacturing method thereof |
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