CN106128788A - A kind of ultracapacitor and preparation method thereof - Google Patents
A kind of ultracapacitor and preparation method thereof Download PDFInfo
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- CN106128788A CN106128788A CN201610393476.5A CN201610393476A CN106128788A CN 106128788 A CN106128788 A CN 106128788A CN 201610393476 A CN201610393476 A CN 201610393476A CN 106128788 A CN106128788 A CN 106128788A
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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
- H01G11/30—Electrodes characterised by their material
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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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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
-
- 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
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
Abstract
The invention belongs to material science, disclose a kind of ultracapacitor and preparation method thereof, comprise the steps: that positively charged Cationic retention aid aqueous solution is joined in cellulose pulp by (1), stirring, obtain being enclosed with the fiber mixed pulp of retention agent；(2) again graphene oxide water solution is mixed with the fiber mixed pulp being enclosed with retention agent, be slowly stirred, obtain graphene oxide cellulose mixed pulp；(3) by obtained mixed pulp copy paper on manual handsheet machine, press dewatering obtains graphene oxide/cellulose extrusion coating paper after drying；(4) obtained extrusion coating paper is added reducing agent and be reduced into Graphene/cellulose extrusion coating paper；(5) being cut out above-mentioned extrusion coating paper, attached addition electrolyte and barrier film are packaged fixing on a current collector, are assembled into the ultracapacitor of symmetry.Preparation process of the present invention is simple, and the super capacitor quality prepared is slim and graceful, flexible.
Description
Technical field
The present invention relates to a kind of ultracapacitor based on Graphene/cellulose extrusion coating paper and preparation method thereof, belong to super
Level capacitor technology field.
Background technology
Ultracapacitor is a kind of a kind of Novel energy storage apparatus between physical capacitor and secondary cell.This dress
Put during its energy savings and release unique, be not only presented as burst rate charge and discharge process, the most also have
The advantage having high-energy and high-specific-power, i.e. discharge and recharge time the most tens of second, its power density, compared with accumulator, exceeds 10-
100 times；Energy density is then 100 times more than of physical capacitor.
Graphene is a kind of monolayer carbon molecule being carried out according to hexagon by carbon atom and arranging and be connected with each other.Through grinding
Study carefully discovery, using Graphene as the ultracapacitor of electrode material, there is the most excellent performance.Research shows that Young's modulus is about
For 1100Gpa, fracture strength is 125Gpa, and mechanical strength is 1060Gpa, thermal conductivity 5000W/m K, and has superior
Electron transport ability, since Graphene self-discovery, has caused the great interest of scientific circles, has been to study the most popular material in recent years
One of material.The specific surface area of single-layer graphene can reach 2630m2/ g, is highly desirable super capacitor energy-storage material.And
And, using the ultracapacitor that Graphene is made, the charging interval only needs several milliseconds.But, current graphene-based super capacitor exists
There is Graphene during preparation to be susceptible to reunite and the problem of stacking under van der Waals interaction, and be difficult to
Large-scale production under low cost.
Summary of the invention
It is an object of the invention to provide a kind of ultracapacitor based on Graphene/cellulose extrusion coating paper and preparation side thereof
Method.
According to one aspect of the present invention, it is provided that the preparation method of a kind of Graphene/cellulose extrusion coating paper electrode, bag
Include: Cationic retention aid is joined in cellulose pulp, after stirring is sufficiently mixed, then graphene oxide water solution is added
In above-mentioned paper pulp, after being uniformly mixed, on paper manual handsheet machine, copy paper shapes.Under squeezer, press dewatering is dried
After obtain graphene oxide/cellulose extrusion coating paper.Graphene/cellulose extrusion coating paper electrode is obtained again through reducing agent reduction.
The preparation method of a kind of ultracapacitor, comprises the steps:
(1) graphite oxide is added to the water, ultrasonic disperse, obtain graphene oxide water solution；By positively charged sun
Ion-type retention agent is added to the water, and stirs, and obtains retention agent aqueous solution；Cellulose paper is added to the water, discongests point
Dissipate, obtain cellulose pulp；
(2) retention agent aqueous solution is joined in cellulose pulp, stir (about 1～2min), obtain being enclosed with retention agent
Fiber mixed pulp；
(3) again graphene oxide water solution is mixed with the fiber mixed pulp being enclosed with retention agent, be slowly stirred (about 2
～4min), obtain graphene oxide cellulose mixed pulp；
(4) by obtained mixed pulp copy paper on manual handsheet machine, press dewatering obtain after drying graphene oxide/
Cellulose extrusion coating paper；
(5) obtained extrusion coating paper is added reducing agent and be reduced into Graphene/cellulose extrusion coating paper；
(6) being cut out above-mentioned extrusion coating paper, attached addition electrolyte and barrier film are packaged fixing on a current collector,
It is assembled into the ultracapacitor of symmetry.
The concentration of step (1) graphene oxide water solution is 0.001～0.005g/ml；The concentration of retention agent aqueous solution is
0.0005～0.001g/ml.
Step (1) described graphite oxide prepares through the Hummers method of Hummers or improvement.
Step (1) described retention agent is PAMC, diallyl dimethyl ammoniumchloride, polymine
With one or more in chitosan quaternary ammonium salt.
Step (1) described ultrasonic disperse ultrasonic cleaner or cell crushing instrument ultrasonic disperse, ultrasonic cleaner
Parameter Conditions be: 50～60 DEG C, 80～100W ultrasonic 2～4h；The Parameter Conditions of cell crushing instrument is 30～60 DEG C, 400～
600W ultrasonic 10～30min.The stirring condition of described Cationic retention aid is: rotating speed 50～150rpm, the time 10～12h.
The stirring condition of described cellulose cardboard is: 10000～20000 turns.
The stirring condition of step (1) described retention agent is: rotating speed 50～150rpm, the time 10～12h；Described cellulose paper
Condition of discongesting be: 10000～20000 turns.
The mass ratio of step (3) retention agent and graphite oxide is 0.4～4wt%, graphite oxide and the mass ratio of cellulose
It is 0.3～16wt%.
Step (5) described reducing condition is reductase 12-10h at 95 DEG C；Reducing agent is ascorbic acid, hydrazine hydrate and tea polyphenols
In one or more.
Collector described in step (6) is nickel foam, steel disc, titanium sheet or gold-plated polyethylene terephthalate (PET)
Thin film；Described electrolyte is potassium hydroxide, sodium hydroxide, and described barrier film is filter paper, polyvinyl alcohol gel.
Cellulose described in step (1) is cotton linter, needlebush paper pulp, leaf wood paper pulp or waste paper.
Invent relative and existing technology, have the advantage that
(1) present invention utilizes Cationic retention aid to keep graphene oxide, it is to avoid the loss of graphene oxide, and
And owing to Cationic retention aid is with positive charge, can make with fibrin fiber and the LBL self-assembly of graphene oxide
After the Graphene that obtains through reduction be uniformly dispersed in paper.
(2) cellulose and Graphene are combined by the present invention, and Graphene can adsorb on cellulose fibre, Ke Yiyou
Prevent the reunion between Graphene to effect.Prepared extrusion coating paper electrode is with Graphene and the character of cellulose, and performance is excellent
Different, such as the pliability folding property of paper, the mechanical performance that Graphene is high, good electric conductivity etc..The super capacitor quality of preparation
Merrily and lightheartedly, flexible.
(3) extrusion coating paper electrode material wide material sources prepared by the present invention, cheap, preparation process is simple, Er Qieke
Directly to carry out on traditional paper technology, it is very easy to realize extensive preparation.
Accompanying drawing explanation
Fig. 1 is the outside drawing of the Graphene/cellulose extrusion coating paper of embodiment 1 preparation.
Fig. 2 is the scanning electron microscope (SEM) photograph of the Graphene/cellulose extrusion coating paper of embodiment 1 preparation.Graphite as we can see from the figure
Alkene is attached to the surface of fiber, effectively prevents the reunion between Graphene.
Fig. 3 is that the square resistance of the Graphene/cellulose extrusion coating paper of embodiment 2 preparation is with different Graphene content increases
The curve chart reduced.
Fig. 4 is the picture of the extrusion coating paper connection circuit lightening LED lamp of embodiment 2 preparation.
Fig. 5 is that the super capacitor based on Graphene/cellulose extrusion coating paper of embodiment 3 preparation is under different scanning rates
Cyclic voltammetric (CV) curve.
Fig. 6 is that the super capacitor based on Graphene/cellulose extrusion coating paper of embodiment 3 preparation is under different electric current densities
Constant current charge-discharge curve.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is more specifically described in detail, but embodiments of the present invention do not limit
In this, for the technological parameter indicated the most especially, can refer to routine techniques and carry out.
Embodiment 1
(1) graphite oxide (the Hummers method of improvement prepares) of 0.192g is joined equipped with 80ml ultra-pure water
In beaker, stir 20min, then proceeds in cell crushing instrument by beaker, then surpasses with cell crushing instrument (30 DEG C, 400W)
Sound 10min.Obtain the graphene oxide aqueous dispersions that graphene oxide concentration is 0.0024g/ml.
(2) add after 2.208g old newsprint (after vacuum drying) being shredded in Pulp dredger, add 1000ml water and discongest
10000 turns.Obtain starching the dense paper pulp of about 0.22%.
(3) 0.01g PAMC is joined in the beaker equipped with 10ml ultra-pure water, 100rpm stirs
12h.Obtain the PAMC aqueous solution that concentration is about 0.001g/ml.
(4) take in the cellulose pulp that the PAMC aqueous solution in 3.84ml (3) joins (2), use glass
Glass rod is slowly stirred 2min.The graphene oxide aqueous dispersions being subsequently adding in (1), then Glass rod is slowly stirred 4min.Finally
Mixed pulp conversion paper manual handsheet machine copy paper shape, through squeezing with obtain grammes per square metre after drying and be about 120g/m2Oxidation stone
The extrusion coating paper of ink alkene content about 8%.
(5) extrusion coating paper shears is cut into 1cm × 1cm size, is immersed in water, add 1ml hydrazine hydrate solution, 95
Reductase 12 h at DEG C, the paper ultra-pure water obtained dries standby after washing away excessive hydrazine hydrate.
(6) the Graphene extrusion coating paper electrode obtained after reduction is attached in nickel foam, with filter paper as barrier film, instills 6M hydrogen
Two cube electrode materials, as electrolyte, are assembled into super capacitor by potassium oxide.
Embodiment 2
(1) graphite oxide (the Hummers method of improvement prepares) of 0.192g is joined equipped with 80ml ultra-pure water
In beaker, stir 20min, and then beaker proceeds to ultrasonic cleaner, 80W, 60 DEG C of ultrasonic 2h.Obtain graphene oxide
Concentration is the graphene oxide aqueous dispersions of 0.0024g/ml.
(2) 2.208g needlebush pulp material (after vacuum drying) is added in Pulp dredger, add 1000ml water and discongest
15000 turns.Obtain starching the dense needlebush paper pulp of about 0.22%.
(3) 0.01g chitosan quaternary ammonium salt is joined in the beaker equipped with 10ml ultra-pure water, 100rpm stirs 12h.
Obtain the chitosan quaternary ammonium saline solution that concentration is about 0.001g/ml.
(4) take in the cellulose pulp that the chitosan quaternary ammonium saline solution in 3.84ml (3) joins (2), use Glass rod
It is slowly stirred 2min.The graphene oxide aqueous dispersions being subsequently adding in (1), then Glass rod is slowly stirred 4min.Final is mixed
Combined paper slurry conversion paper manual handsheet machine copy paper shapes, through squeezing and obtaining extrusion coating paper after drying.
(5) extrusion coating paper shears is cut into 1cm × 2cm size, is immersed in water, add 0.008g ascorbic acid,
95 DEG C of reduction 10h under the conditions of lucifuge.
(6) the Graphene extrusion coating paper electrode obtained after reduction is attached in gold-plated polyethylene terephthalate thin film,
As electrolyte, two cube electrode materials are assembled into super capacitor as barrier film, instillation 6M potassium hydroxide with filter paper.
Embodiment 3
(1) graphite oxide (the Hummers method of improvement prepares) of 0.192g is joined equipped with 80ml ultra-pure water
In beaker, stir 20min, then proceeds in cell crushing instrument by beaker, then surpasses with cell crushing instrument (30 DEG C, 400W)
Sound 10min.Obtain the graphene oxide aqueous dispersions that graphene oxide concentration is 0.0024g/ml.
(2) 2.208g needlebush pulp material (after vacuum drying) is added in Pulp dredger, add 1000ml water and discongest
15000 turns.Obtain starching the dense needlebush paper pulp of about 0.22%.
(3) 0.01g PAMC is joined in the beaker equipped with 10ml ultra-pure water, 100rpm stirs
12h.Obtain the PAMC aqueous solution that concentration is about 0.001g/ml.
(4) take in the cellulose pulp that the PAMC aqueous solution in 3.84ml (3) joins (2), use glass
Glass rod is slowly stirred 2min.The graphene oxide aqueous dispersions being subsequently adding in (1), then Glass rod is slowly stirred 4min.Finally
Mixed pulp conversion paper manual handsheet machine copy paper shape, through squeezing with obtain grammes per square metre after drying and be about 120g/m2Oxidation stone
The extrusion coating paper of ink alkene content about 8%.
(5) extrusion coating paper shears is cut into 1cm × 1cm size, is immersed in water, add 0.004g ascorbic acid,
95 DEG C of reduction 10h under the conditions of lucifuge.
(6) the Graphene extrusion coating paper electrode obtained after reduction is attached in nickel foam, drips upper 1M potassium hydroxide/polyvinyl alcohol
Gel is as electrolyte and barrier film, after drying moisture, two pieces of identical electrodes material laminatings is assembled into super capacitor.
Embodiment 4
(1) graphite oxide (the Hummers method of improvement prepares) of 0.192g is joined equipped with 80ml ultra-pure water
In beaker, stir 20min, then proceeds in cell crushing instrument by beaker, then surpasses with cell crushing instrument (30 DEG C, 400W)
Sound 10min.Obtain the graphene oxide aqueous dispersions that graphene oxide concentration is 0.0024g/ml.
(2) 2.208g needlebush pulp material (after vacuum drying) is added in Pulp dredger, add 1000ml water and discongest
15000 turns.Obtain starching the dense needlebush paper pulp of about 0.22%.
(3) 0.01g PAMC is joined in the beaker equipped with 10ml ultra-pure water, 100rpm stirs
12h.Obtain the PAMC aqueous solution that concentration is about 0.001g/ml.
(4) take in the cellulose pulp that the PAMC aqueous solution in 3.84ml (3) joins (2), use glass
Glass rod is slowly stirred 2min.The graphene oxide aqueous dispersions being subsequently adding in (1), then Glass rod is slowly stirred 4min.Finally
Mixed pulp conversion paper manual handsheet machine copy paper shape, through squeezing with obtain grammes per square metre after drying and be about 120g/m2Oxidation stone
The extrusion coating paper of ink alkene content about 8%.
(5) extrusion coating paper shears is cut into 1cm × 1cm size, is immersed in water, add 0.004g ascorbic acid,
95 DEG C of reduction 10h under the conditions of lucifuge.
(6) it is attached to plate in the PET film of gold by the Graphene extrusion coating paper electrode obtained after reduction, drips upper 1M hydroxide
Potassium/polyvinyl alcohol gel is as electrolyte and barrier film, after drying moisture, two pieces of identical electrodes material laminatings is assembled into super electricity
Hold.
Embodiment 5
(1) graphite oxide (the Hummers method of improvement prepares) of 0.384g is joined equipped with 160ml ultra-pure water
In beaker, stir 0.5h, then proceeds in cell crushing instrument by beaker, then surpasses with cell crushing instrument (30 DEG C, 400W)
Sound 10min.Obtain the graphene oxide aqueous dispersions that graphene oxide concentration is 0.0024g/ml.
(2) 2.016g needlebush paper pulp (after vacuum drying) is added in Pulp dredger, add 1000ml water and discongest
20000 turns.Obtain starching the dense cellulose pulp of about 0.2%.
(3) 0.01g PAMC is joined in the beaker equipped with 10ml ultra-pure water, 100rpm stirs
12h.Obtain the PAMC aqueous solution that concentration is about 0.001g/ml.
(4) take in the cellulose pulp that the PAMC aqueous solution in 1.54ml (3) joins (2), use glass
Glass rod is slowly stirred 2min.The graphene oxide aqueous dispersions being subsequently adding in (1), then Glass rod is slowly stirred 4min.Finally
Mixed pulp conversion paper manual handsheet machine copy paper shape, through squeezing with obtain grammes per square metre after drying and be about 120g/m2Oxidation stone
The extrusion coating paper of ink alkene content about 16%.
(5) extrusion coating paper shears is cut into 1cm × 4cm size, is immersed in water, add 0.032g ascorbic acid,
Under the conditions of lucifuge after 95 DEG C of reduction 10h, dry standby.
(6) will after reduction Graphene extrusion coating paper electrode one end conductive silver glue of obtaining be stained with the aluminium foil of 1cm × 1cm as
Collector, upper 1M potassium hydroxide/polyvinyl alcohol gel is as electrolyte and barrier film, after drying moisture, by two pieces of identical electrodes
Material laminating is assembled into super capacitor.
The ratio electric capacity of the table 1 ultracapacitor prepared by embodiment 1-4 (CV curvilinear integral areal calculation institute under 5mV/s
)
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Electrolyte | KOH | KOH | KOH/PVA | KOH/PVA | KOH/PVA |
| Collector | Nickel foam | Gold-plated PET | Nickel foam | Gold-plated PET | Aluminium foil |
| Than electric capacity (F/g) | 134 | 159 | 98 | 112 | 86 |
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. the preparation method of a ultracapacitor, it is characterised in that comprise the steps:
(1) graphite oxide is added to the water, ultrasonic disperse, obtain graphene oxide water solution；By positively charged cation
Type retention agent is added to the water, and stirs, and obtains retention agent aqueous solution；Cellulose paper is added to the water, discongests dispersion,
To cellulose pulp；
(2) retention agent aqueous solution is joined in cellulose pulp, stirring, obtain being enclosed with the fiber mixed pulp of retention agent；
(3) again graphene oxide water solution is mixed with the fiber mixed pulp being enclosed with retention agent, be slowly stirred, aoxidized
Graphene fiber element mixed pulp；
(4) by obtained mixed pulp copy paper on manual handsheet machine, press dewatering obtains graphene oxide/fiber after drying
Element extrusion coating paper；
(5) obtained extrusion coating paper is added reducing agent and be reduced into Graphene/cellulose extrusion coating paper；
(6) being cut out above-mentioned extrusion coating paper, attached addition electrolyte and barrier film are packaged fixing on a current collector, assemble
Become symmetrical ultracapacitor.
Method the most according to claim 1, it is characterised in that the concentration of step (1) graphene oxide water solution is 0.001
～0.005g/ml；The concentration of retention agent aqueous solution is 0.0005～0.001g/ml.
Method the most according to claim 1, it is characterised in that step (1) described retention agent be PAMC,
One or more in diallyl dimethyl ammoniumchloride, polymine and chitosan quaternary ammonium salt.
Method the most according to claim 1, it is characterised in that step (1) described ultrasonic disperse ultrasonic cleaner or
Person's cell crushing instrument ultrasonic disperse, the Parameter Conditions of ultrasonic cleaner is: 50～60 DEG C, 80～100W ultrasonic 2～4h；Cell
The Parameter Conditions of broken instrument is 30～60 DEG C, 400～600W ultrasonic 10～30min.The stirring bar of described Cationic retention aid
Part is: rotating speed 50～150rpm, the time 10～12h.The stirring condition of described cellulose cardboard is: 10000～20000 turns.
Method the most according to claim 1, it is characterised in that the stirring condition of step (1) described retention agent is: rotating speed 50
～150rpm, time 10～12h；The condition of discongesting of described cellulose paper is: 10000～20000 turns.
Method the most according to claim 1, it is characterised in that the mass ratio of step (3) retention agent and graphite oxide is 0.4
～the mass ratio of 4wt%, graphite oxide and cellulose is 0.3～16wt%.
7. according to the method described in claim 1 or 2 or 3 or 4 or 5 or 6, it is characterised in that step (5) described reducing condition is
Reductase 12-10h at 95 DEG C；Reducing agent is one or more in ascorbic acid, hydrazine hydrate and tea polyphenols.
Method the most according to claim 7, it is characterised in that described in step (6), collector is nickel foam, steel disc, titanium
Sheet or gold-plated polyethylene terephthalate thin film；Described electrolyte is potassium hydroxide, sodium hydroxide, and described barrier film is filter
Paper, polyvinyl alcohol gel.
9. according to the method described in claim 1 or 2 or 3 or 4 or 5 or 6, it is characterised in that step (1) described graphite oxide warp
The Hummers method crossing Hummers or improvement prepares；Described cellulose is cotton linter, needlebush paper pulp, leaf wood paper pulp
Or waste paper.
10. a ultracapacitor, it is characterised in that it is by the method described in claim 1～9 any one claim
Prepare.
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| CN106469808A (en) * | 2016-04-01 | 2017-03-01 | 济南圣泉集团股份有限公司 | Composite for paper electrode and its paper electrode made, paper battery |
| CN106469809A (en) * | 2016-04-01 | 2017-03-01 | 济南圣泉集团股份有限公司 | Graphene conductive paper and paper battery and its application |
| CN106890605A (en) * | 2017-02-21 | 2017-06-27 | 中国林业科学研究院木材工业研究所 | A kind of three-dimensional grapheme composite aerogel and preparation method thereof |
| CN107161984A (en) * | 2017-06-28 | 2017-09-15 | 华南理工大学 | The method that a kind of ascorbic acid/Tea Polyphenols synergy prepares graphene |
| CN108922795A (en) * | 2018-07-15 | 2018-11-30 | 重庆文理学院 | A kind of preparation method of the excellent graphene-based composite conductive thin film of electric conductivity |
| CN108962629A (en) * | 2018-07-15 | 2018-12-07 | 重庆文理学院 | A kind of preparation method of flexible super capacitor |
| CN109098030A (en) * | 2018-08-24 | 2018-12-28 | 宿迁南航新材料与装备制造研究院有限公司 | A kind of preparation method of graphene modified glass-fiber paper |
| CN110184855A (en) * | 2019-05-15 | 2019-08-30 | 西安交通大学 | A kind of ventilative and composite and flexible conductive paper of washing and its preparation method and application |
| CN113643906A (en) * | 2021-08-18 | 2021-11-12 | 吉林大学重庆研究院 | High-flexibility graphene-based supercapacitor based on laser processing and preparation method thereof |
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