CN104867702B - A kind of preparation method of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite - Google Patents
A kind of preparation method of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite Download PDFInfo
- Publication number
- CN104867702B CN104867702B CN201510218295.4A CN201510218295A CN104867702B CN 104867702 B CN104867702 B CN 104867702B CN 201510218295 A CN201510218295 A CN 201510218295A CN 104867702 B CN104867702 B CN 104867702B
- Authority
- CN
- China
- Prior art keywords
- anthraquinone
- covalent modification
- polymer composite
- grapheme
- electroconductive polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
A kind of preparation method of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite：Including anthraquinone derivatives are dissolved in graphene oxide solution, after stirring and utilizing ultrasonic wave scattered, conducting polymer monomer is added in above-mentioned solution, after stirring and utilizing ultrasonic wave dispersion mixing uniform, stirring reaction prepares anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite under heating condition.The present invention is interacted its anchor in surface of graphene oxide using the hydrogen bond action between anthraquinone quasi-molecule and graphene oxide, π π, oxygen-containing functional group by the use of surface of graphene oxide is used as oxidant, monomer is oxidized to conducting polymer, simultaneous oxidation graphene is reduced to graphene in itself, the composite material exhibits of preparation go out higher electrical conductivity and stability, can be used as the potential electrode material of ultracapacitor.
Description
Technical field
The present invention relates to the preparation method of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite, belong to
Electrode of super capacitor Material Field.
Background technology
Anthraquinone and its derivative contain the quinonyl group of aromatic ring structure and good oxidation reduction characteristic, can directly be carried from plant
Take, with good electro-chemical activity, its good electronics and proton ability to accept make it in electrode material for super capacitor
Obtain widely studied.Anthraquinone covalently or non-covalently modifies the carbon materials of carbon fiber, activated carbon, CNT and graphene etc.
Material, compared with unmodified carbon material, its energy density can be significantly improved.With electric active molecule is directly added into electrolyte
Compared the specific capacitance that improves carbon material, anthraquinone-modified carbon electrode material can obtain more preferable stability and dispersive property.
Graphene is that, by a kind of tightly packed carbonaceous new material into bi-dimensional cellular shape crystal structure of single layer of carbon atom, have
The advantages of such as low production cost, high-specific surface area, good mechanical property and superior electric conductivity, these superior spies
Property cause graphene turn into substitute CNT electrode of super capacitor preferred material.Using graphene and conducting polymer
Graphene and conducting polymer are compounded to form graphene/ conductive polymer composite wood by the conductive synergy of thing conjugated structure
Material, to improve electric conductivity, while the enhancing of structure can be realized again.Graphene/ conductive polymer combination electrode material is as double
The representative of electric layer/pseudo-capacitance combination electrode material, can inherit the two advantage, material is nanoscale, higher than surface, there is prosperity
Pore structure and conductive network.Therefore conducting polymer/graphene combination electrode material turns into study hotspot in recent years.
The research of conducting polymer/graphene combination electrode material possessed good basis [Meng YN, Wang K,
Zhang YJ, Wei ZX. Hierarchical porous graphene/polyaniline composite film
with superior rate performance for flexible supercapacitors. Adv. Mater.,
2103, 25:6985-6990.Kumar NA, Choi HJ, Shin YR, Chang DW, Dai LM, Baek JB.
Polyanline-grafted reduced graphene oxide for efficient electrochemical
supercapacitors. ACS Nano, 2012,6:1715-1723. Zhao Y, Liu J, Hu Y, Cheng HH,
Hu CG, Jiang CC, et al. Highly compression-tolerant supercapacitor based on
polypyrrole-mediated graphene foam electrodes. Adv. Mater.,2013,25:591-595.],
But be due between graphene and conducting polymer pi-pi accumulation effect cause the effective ratio area of composite smaller, stone
The face face accumulation problem of black alkene piece in the composite is still the principal element for restricting its electrochemical capacitance characteristic.
The content of the invention
In order to solve problem above, the purpose of the present invention is to answer anthraquinone derivatives introducing graphene/ conductive polymer
Zoarium system, effectively solves the face face accumulation problem of graphene film in the composite.By this anthraquinone molecular non-covalent modification stone
Black alkene/conducting polymer composite material is as the positive pole and negative pole of ultracapacitor, and positive pole is available under fully oxidized state to lead
The oxidizing potential of electric polymer（Up to 0.8V）, negative pole under abundant reduction-state using anthraquinone derivative reduction potential（Can
Up to -0.9V）, in theory the operating voltage of the super capacitor system can widen to 1.7V, the energy density of combination electrode material
It can be effectively improved.There is not been reported both at home and abroad for such a method.
In order to realize above-mentioned goal of the invention, the technical solution adopted by the present invention is as follows：
A kind of preparation method of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite, step is as follows：
（1）Anthraquinone derivatives are dissolved in graphene oxide solution, stirs and forms solution, oxygen using ultrasonic wave is scattered
The concentration of graphite alkene is 0.01-0.5mg/mL.Described anthraquinone derivatives are：Anthraquinone-1-sulfonic acid sodium, anthraquinone-2-sulfonic acid
Sodium, acid blue 25, anthraquinone 2,6 disulfonic acid disodium, anthraquinone-2-carboxylic acid or anthraquinone -2,3- dicarboxylic acids;
（2）Conducting polymer monomer is added in above-mentioned dispersion liquid, stirs and forms reactant using ultrasonic wave is scattered
The mol ratio of system, conducting polymer monomer and anthraquinone molecular is 5:1-1:5；The concentration of conducting polymer monomer is 0.01M-
0.1M.Described conducting polymer monomer is pyrroles, aniline, 3,4-ethylene dioxythiophene;
（3）Above-mentioned reaction system is stirred reaction 6-48h at 30-120 DEG C, product is obtained;
（4）Obtained product is cleaned repeatedly with deionized water, and in drying 24h in 60 DEG C of vacuum drying chambers, obtains anthracene
Quinone molecule non-covalent modification grapheme/electroconductive polymer composite.
The positive effect of the present invention is as follows：
1st, functionalization graphene original position is introduced into conducting polymer by the present invention, with improve the ion of combination electrode material/
Electron transmission ability, potential window is widened, further improve energy density；By Anthraquinones electric active molecule non-covalent modification to stone
Black alkene surface, on the one hand can assign graphene good oxidation reducing activity and dispersiveness；On the other hand, Anthraquinones electric active molecule
There is p- π and π-pi-conjugated holding made effect, be conducive to graphene electrical conductivity between graphene, at home and abroad in document still
Have no report.
2nd, the present invention is by the use of the oxygen-containing functional group of surface of graphene oxide as oxidant, and monomer is oxidized to conducting polymer
Thing, simultaneous oxidation graphene is reduced graphene in itself, and the anthraquinone molecular non-covalent modification graphene/ conductive polymer of preparation is answered
Condensation material shows higher electrical conductivity and stability, is had a wide range of applications as electrode material for super capacitor.
3rd, the present invention uses one-step method in-situ polymerization, and equipment is simple, operation is easy, easily expands large-scale production.
Brief description of the drawings
Fig. 1 is anthraquinone-1-sulfonic acid sodium non-covalent modification graphene/Pt/Polypyrrole composite material prepared by the embodiment of the present invention 1
SEM photograph, using JSM-5610 type ESEMs（Japanese JEOL companies）Tested, sample gold,platinized before testing.By
SEM image is visible, and composite shows nano bar-shape polypyrrole (shown in such as Fig. 1 square frames) and graphene sheet layer（Such as circle
Shown in interior）The micro-structural of connection, nano bar-shape polypyrrole size is 50-100nm, and lamella size is 0.5-2 μm.
Fig. 2 are anthraquinone-1-sulfonic acid sodium non-covalent modification graphene/polypyrrole composite wood prepared by the embodiment of the present invention 1
The cyclic voltammetry curve of material（Electrolyte：1M H2SO4, sweep speed=10mV/s）.From Figure 2 it can be seen that anthraquinone -1- sulphurs prepared by embodiment 1
The CV curves of sour sodium non-covalent modification graphene/Pt/Polypyrrole composite material, it can be found that the redox peak shape of anthraquinone functional group
Shape shows preferable electrochemical capacitance characteristic close to rectangle.
Fig. 3 are that anthraquinone-1-sulfonic acid sodium non-covalent modification graphene/polypyrrole prepared by the embodiment of the present invention 1 is combined
The charging and discharging curve of material（Electrolyte：1M H2SO4, current density=1A/g）.As can be seen from Figure 3, the composite wood that prepared by embodiment 1
The specific capacitance of material can basis：Calculate,Wherein CmFor specific capacitance, I is discharge current, and △ t are discharge time,
M is the quality of active material, and △ V are the voltage drop in discharge process, calculates the ratio electricity for the composite for obtaining the preparation of embodiment 1
Rong Ze is up to 251F/g.
Embodiment
The above of the present invention is described in further detail below by way of specific embodiment.But this should not be understood
Following examples are only limitted to for present disclosure.
A kind of preparation method of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite of embodiment 1, step
It is as follows：
（1）By 1.5513g（5mmol）Anthraquinone-1-sulfonic acid sodium（Purchased from Shanghai Industrial Co., Ltd. in future）It is dissolved in 100mL
0.01mg/mL graphene oxide solutions（（Preparation method is referring to Hummers W S, Offeman R E. Preparation of
graphite oxide. J Am Chem Soc, 1958, 80: 1339））In, stir and form molten using ultrasonic wave is scattered
Liquid, it is standby;
（2）By 67 μ L（1mmol）Pyrrole monomer（Purchased from Aldrich）Add in above-mentioned dispersion liquid, stir and utilize ultrasound
Wavelength-division, which dissipates, forms reaction system, standby;
（3）Above-mentioned reaction system is stirred reaction 48h at 30 DEG C, product is obtained;
（4）Obtained product is cleaned repeatedly with deionized water, and in 60 DEG C in vacuum drying chamber dry 24h, obtains anthracene
Quinone molecule non-covalent modification grapheme/electroconductive polymer composite.
A kind of preparation method of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite of embodiment 2., its
The place different from embodiment 1 is that the concentration of graphene oxide is changed into 0.4mg/mL, 1.5513g（5mmol）Anthraquinone -1- sulphurs
Sour sodium is changed into 4.6539g（15mmol）Anthraquinone-2-sodium, 67 μ L（1mmol）Pyrrole monomer is changed into 450 μ L（5mmol）Aniline
Monomer, reaction 48h is stirred at 30 DEG C and is changed into 60 DEG C of reaction 36h.
A kind of preparation method of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite of embodiment 3., its
The place different from embodiment 1 is that the concentration of graphene oxide is changed into 0.2mg/mL, 1.5513g（5mmol）Anthraquinone-1-sulfonic acid
Sodium is changed into 1.6655g（4mmol）The μ L of acid blue 25,67（1mmol）Pyrrole monomer is changed into 220 μ L（2mmol）3,4- enedioxies
Thiophene, reaction 48h is stirred at 30 DEG C and is changed into 90 DEG C of reaction 24h.
A kind of preparation method of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite of embodiment 4., its
The place different from embodiment 1 is that the concentration of graphene oxide is changed into 0.1mg/mL, 1.5513g（5mmol）Anthraquinone-1-sulfonic acid
Sodium is changed into 1.4733g（4mmol）Anthraquinone -2,6- disulfonate, 67 μ L（1mmol）Pyrrole monomer is changed into 360 μ L（4mmol）Benzene
Amine monomers, reaction 48h is stirred at 30 DEG C and is changed into 100 DEG C of reaction 18h.
A kind of preparation method of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite of embodiment 5., its
The place different from embodiment 1 is that the concentration of graphene oxide is changed into 0.05mg/mL, 1.5513g（5mmol）Anthraquinone -1- sulphurs
Sour sodium is changed into 1.0088g（4mmol）Anthraquinone-2-carboxylic acid, 67 μ L（1mmol）Pyrrole monomer is changed into 880 μ L（8mmol）3,4- ethylenes
Dioxy thiophene, reaction 48h is stirred at 30 DEG C and is changed into 120 DEG C of reaction 48h.
A kind of preparation method of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite of embodiment 6., its
The place different from embodiment 1 is that the concentration of graphene oxide is changed into 0.5mg/mL, 1.5513g（5mmol）Anthraquinone-1-sulfonic acid
Sodium is changed into 0.5044g（2mmol）Anthraquinone-2-carboxylic acid, the volume of pyrrole monomer is changed into 670 μ L（10mmol）, stirred at 30 DEG C
Mix reaction 48h and be changed into 120 DEG C of reaction 6h.
Embodiment 1-6 prepares the performance parameter of composite as shown in table 1, and wherein reference examples are graphene/conducting polymers
Thing composite.
Table 1
Claims (6)
1. a kind of preparation method of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite, it is characterised in that step
It is rapid as follows：
(1) anthraquinone derivatives are dissolved in graphene oxide solution, stir and form solution using ultrasonic wave is scattered, it is standby；
(2) conducting polymer monomer is added in above-mentioned solution, stirs and form reaction system using ultrasonic wave is scattered, it is standby；
(3) above-mentioned reaction system is stirred reaction 6-48h at 30-120 DEG C, obtains product；
(4) obtained product is cleaned repeatedly with deionized water, and in being dried in vacuum drying chamber, obtains anthraquinone molecular non-covalent
Grapheme modified/conducting polymer composite material.
2. the preparation side of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite according to claim 1
Method, it is characterised in that anthraquinone derivatives described in step (1) are anthraquinone-1-sulfonic acid sodium, anthraquinone-2-sodium, acid blue 25,
One kind in anthraquinone -2,6- disulfonate, anthraquinone-2-carboxylic acid or anthraquinone -2,3- dicarboxylic acids.
3. the preparation side of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite according to claim 1
In method, it is characterised in that the conducting polymer monomer employed in step (2) is aniline, pyrroles or 3,4-ethylene dioxythiophene
It is a kind of.
4. the preparation side of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite according to claim 1
Method, it is characterised in that the concentration of graphene oxide solution is 0.01-0.5mg/mL in step (1).
5. the preparation side of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite according to claim 1
Method, it is characterised in that the mol ratio of conducting polymer monomer and anthraquinone molecular is 5 in step (2):1-1:5；Conducting polymer list
The concentration of body is 0.01M-0.1M.
6. the preparation side of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite according to claim 1
Method, it is characterised in that the drying temperature of step (4) is 60 DEG C, and drying time is 24h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510218295.4A CN104867702B (en) | 2015-04-30 | 2015-04-30 | A kind of preparation method of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510218295.4A CN104867702B (en) | 2015-04-30 | 2015-04-30 | A kind of preparation method of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104867702A CN104867702A (en) | 2015-08-26 |
| CN104867702B true CN104867702B (en) | 2017-08-11 |
Family
ID=53913475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510218295.4A Expired - Fee Related CN104867702B (en) | 2015-04-30 | 2015-04-30 | A kind of preparation method of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104867702B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106809815B (en) * | 2015-11-27 | 2019-10-08 | 中国科学院过程工程研究所 | A kind of carbon quantum dot, preparation method and the usage |
| CN107275601B (en) * | 2017-06-02 | 2020-01-07 | 电子科技大学 | Aromatic hyperconjugated dicarboxylate and application of graphene composite material thereof |
| CN109019596A (en) * | 2018-07-16 | 2018-12-18 | 西北师范大学 | The preparation and application of one organic molecular species non-covalent bond functionalization biomass carbon material |
| CN109603906B (en) * | 2019-01-15 | 2021-10-01 | 安徽大学 | Anthraquinone-2-sodium sulfonate/graphene oxide composite photocatalytic bactericide and preparation method and application thereof |
| CN109809398B (en) * | 2019-02-01 | 2022-05-24 | 锦州凯美能源有限公司 | Preparation method and application of graphene conductive agent dispersion liquid of high-capacity supercapacitor |
| CN110060879A (en) * | 2019-04-23 | 2019-07-26 | 太仓萃励新能源科技有限公司 | A kind of SnO2The synthetic method of-PEDOT-RGO ternary electrochemical capacitance material |
| CN110783113A (en) * | 2019-11-06 | 2020-02-11 | 西北师范大学 | Preparation and application of indanthrene functionalized graphene three-dimensional network structure composite material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102220027A (en) * | 2011-04-25 | 2011-10-19 | 北京航空航天大学 | Grapheme/electroconductive polymer composite and preparation method thereof |
| CN102496481A (en) * | 2011-12-23 | 2012-06-13 | 北京航空航天大学 | Graphene/polypyrrole nanotube composite material, super capacitor with graphene/polypyrrole nanotube composite material as electrode, and methods for preparing graphene/polypyrrole nanotube composite material and super capacitor |
| CN103801395A (en) * | 2014-02-26 | 2014-05-21 | 大连理工大学 | Graphene material modified by water-soluble anthraquinone compound and preparation method of graphene material |
| CN104332639A (en) * | 2014-11-05 | 2015-02-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of co-doped conductive polymer electrode material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110069201A (en) * | 2009-12-17 | 2011-06-23 | 거림테크 주식회사 | Dispertion method of carbon nano sheet |
-
2015
- 2015-04-30 CN CN201510218295.4A patent/CN104867702B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102220027A (en) * | 2011-04-25 | 2011-10-19 | 北京航空航天大学 | Grapheme/electroconductive polymer composite and preparation method thereof |
| CN102496481A (en) * | 2011-12-23 | 2012-06-13 | 北京航空航天大学 | Graphene/polypyrrole nanotube composite material, super capacitor with graphene/polypyrrole nanotube composite material as electrode, and methods for preparing graphene/polypyrrole nanotube composite material and super capacitor |
| CN103801395A (en) * | 2014-02-26 | 2014-05-21 | 大连理工大学 | Graphene material modified by water-soluble anthraquinone compound and preparation method of graphene material |
| CN104332639A (en) * | 2014-11-05 | 2015-02-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of co-doped conductive polymer electrode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104867702A (en) | 2015-08-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104867702B (en) | A kind of preparation method of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite | |
| Zhao et al. | Reduced graphene oxide and polypyrrole/reduced graphene oxide composite coated stretchable fabric electrodes for supercapacitor application | |
| Zhou et al. | Polyaniline/multi-walled carbon nanotube composites with core–shell structures as supercapacitor electrode materials | |
| Han et al. | Preparation and electrochemical performances of graphene/polypyrrole nanocomposite with anthraquinone-graphene oxide as active oxidant | |
| Li et al. | Covalently-grafted polyaniline on graphene oxide sheets for high performance electrochemical supercapacitors | |
| Dong et al. | Ultrasound-assisted preparation of electrospun carbon nanofiber/graphene composite electrode for supercapacitors | |
| Zhang et al. | Graphene/polyaniline nanofiber composites as supercapacitor electrodes | |
| Salinas-Torres et al. | Strategies to enhance the performance of electrochemical capacitors based on carbon materials | |
| CN101527202B (en) | Oxidized grapheme/polyaniline super capacitor composite electrode material and preparation method | |
| Tian et al. | Fabricating a high-energy-density supercapacitor with asymmetric aqueous redox additive electrolytes and free-standing activated-carbon-felt electrodes | |
| Lindfors et al. | Improved charging/discharging behavior of electropolymerized nanostructured composite films of polyaniline and electrochemically reduced graphene oxide | |
| Zhou et al. | Highly stable multi-wall carbon nanotubes@ poly (3, 4-ethylenedioxythiophene)/poly (styrene sulfonate) core–shell composites with three-dimensional porous nano-network for electrochemical capacitors | |
| Ega et al. | Quinone materials for supercapacitor: Current status, approaches, and future directions | |
| Tian et al. | Double layer capacitor based on active carbon and its improved capacitive properties using redox additive electrolyte of anthraquinonedisulphonate | |
| Liu et al. | Skeleton/skin structured (RGO/CNTs)@ PANI composite fiber electrodes with excellent mechanical and electrochemical performance for all-solid-state symmetric supercapacitors | |
| CN105118688B (en) | A kind of preparation method and applications of bacteria cellulose/activated carbon fiber/graphene film material | |
| Gao et al. | A three-dimensional graphene aerogel containing solvent-free polyaniline fluid for high performance supercapacitors | |
| Moyseowicz et al. | High-performance hybrid capacitor based on a porous polypyrrole/reduced graphene oxide composite and a redox-active electrolyte | |
| He et al. | Supercapacitors based on 3D network of activated carbon nanowhiskers wrapped-on graphitized electrospun nanofibers | |
| Sun et al. | Hybrid symmetric supercapacitor assembled by renewable corn silks based porous carbon and redox-active electrolytes | |
| Bilal et al. | Insight into capacitive performance of polyaniline/graphene oxide composites with ecofriendly binder | |
| CN107919233A (en) | A kind of high voltage flexible solid-state supercapacitor and preparation method thereof | |
| Han et al. | Preparation and electrochemical performances of PEDOT/sulfonic acid-functionalized graphene composite hydrogel | |
| Tan et al. | Polyaniline nanoparticles grown on the surface of carbon microspheres aggregations for electrochemical supercapacitors | |
| CN104201007B (en) | Carbon nanomaterial-based flexible super capacitor electrode material and preparation method for same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170811 Termination date: 20200430 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |