CN102436934A - Composite nanometer carbon paper and preparation method thereof - Google Patents
Composite nanometer carbon paper and preparation method thereof Download PDFInfo
- Publication number
- CN102436934A CN102436934A CN201110271170XA CN201110271170A CN102436934A CN 102436934 A CN102436934 A CN 102436934A CN 201110271170X A CN201110271170X A CN 201110271170XA CN 201110271170 A CN201110271170 A CN 201110271170A CN 102436934 A CN102436934 A CN 102436934A
- Authority
- CN
- China
- Prior art keywords
- paper
- cnt
- mno
- carbon
- preparation
- 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.)
- Granted
Links
Images
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
The invention discloses composite nanometer carbon paper and a preparation method thereof. The nanometer carbon paper uses carbon nanometer paper as a framework network, MnO2 metallic oxides are deposited on the surface, the outer layer is covered with grapheme, and the composite nanometer carbon paper belongs to a flexible composite film material. The preparation method of the composite nanometer carbon paper comprises the steps that carbon nanometer tubes are dispersed in a solvent, then, the suction filtering is carried out to obtain carbon nanometer tube paper, next, the carbon nanometer tube paper is used as a carrier for depositing the MnO2 metallic oxides on the surface, and finally, the grapheme is adhered on the product surface to obtain target products. The electrical conductivity, the heavy current charging and discharging capability, the specific capacitance and the cycle life of the composite nanometer carbon paper are respectively and obviously enhanced through being compared with those of the carbon nanometer tube-MnO2, the problems that in the existing super capacitor, the metallic oxides easily fall off from the surface of the carbon nanometer tubes, the electrical conductivity of the metallic oxides is poor, and the like are solved, the composite nanometer carbon paper also has the characteristics of light weight and flexibility of materials and high efficiency, simultaneously, the preparation process is simple, the operation is easy, the controllability is good, and in addition, the cost is low. The composite nanometer carbon paper and the preparation method have wide application prospects in fields of new energy sources, advanced chemical engineering, electronic devices, film preparation and the like.
Description
Technical field
The present invention be more particularly directed to a kind of by CNT, MnO
2Sandwich type composite Nano carbon paper that is compounded to form with Graphene and preparation method thereof belongs to the nano-carbon material preparing technical field.
Background technology
Ultracapacitor, especially light flexible capacitor are the focuses of present energy field research, and its electrode material is divided into material with carbon element, transition metal oxide material and conducting polymer materials.As electrode, material with carbon element has high power density and long cycle life; Metal oxide and conducting polymer have high specific capacitance, but power density is not high.In addition, come off because of change in volume causes active material easily in the work, make that the cycle life of material is not high.
For overcoming the deficiency of conventional art; Researchers are developed the scheme that materials such as the employing carbon nanotube dust and metal oxide form composite material, and it can produce the effect that the capacitive property that makes metal oxide significantly improves, but the composite material of preparation can not satisfy the requirement efficiently of material light flexible; Maximum operating currenbt is little; Power density is still very low, can not satisfy the requirement of the big current work of ultracapacitor high power, and the conductivity away from the metal oxide of CNT is still very poor in the composite material; In addition, metal oxide is ubiquitous also fails by good solution because of the active material phenomenon that the cycle life that causes reduces that comes off.
Summary of the invention
The object of the present invention is to provide a kind of by CNT, MnO
2Form with grapheme material, have composite Nano carbon paper of sandwich structure and preparation method thereof, to overcome deficiency of the prior art.
For realizing the foregoing invention purpose, the present invention has adopted following technical scheme:
A kind of composite Nano carbon paper is characterized in that, said nanometer carbon paper has composite sandwich, and it comprises:
The back bone network that forms by CNT paper with macroscopical nonwoven fabrics form;
Be deposited on the MnO of the carbon nano tube surface that constitutes CNT paper
2Metal oxide layer;
And, be covered in the graphene layer on the said back bone network;
The content of grapheme material is below 10wt% in the said nanometer carbon paper, MnO
2The content of metal oxide is below 50wt%.
Say that further said CNT paper has the porous network structure that is interweaved and formed by the disordered carbon nanotube, and in said porous network structure, also infiltrates grapheme material.
Said MnO
2Metal oxide layer is continuous rete or the discrete MnO that is modified at carbon nano tube surface that is wrapped in carbon nano tube surface
2Granuloplastic discontinuous rete.
Said graphene layer is by any one or two or more being combined to form in graphene oxide, reduction Graphene and the pure Graphene.
The preparation method of composite Nano carbon paper is characterized in that as stated, and this method is:
At first get CNT and process CNT suspended dispersed liquid, and filter formation CNT paper, thereafter, in CNT paper, deposit MnO
2Thereby, form MnO in carbon nano tube surface
2Metal oxide layer, last, on CNT paper, cover grapheme material, obtain target product.
Particularly, be to adopt the mode that CNT is scattered in the solvent to form CNT suspended dispersed liquid in this method;
Said solvent is selected from water, ethanol, isopropyl alcohol, N at least, more than any one in dinethylformamide, N-methyl pyrrolidone, ethyl acetate and the chloroform equal solvent;
Said process for dispersing is selected from more than any one of high speed shear, grinding, ball milling and ultra-sonic dispersion method at least.
Preferably; Also can contain dispersant in the said solvent; Said dispersant is selected from polymer such as polyvinyl alcohol, polyvinylpyrrolidone, cellulose, any one in lauryl sodium sulfate, neopelex, softex kw, Tween-80 and the TritonX-100 or two or more combinations at least.
Be to adopt no press filtration or the preparation of vacuum filtration method to form CNT paper in this method, and the thickness of said CNT paper is 1 μ m-1mm.
Thereby adopted in the following manner any one to be implemented in the CNT paper in this method at least and deposited MnO
2:
(1) MnO
2Mechanical mixture with CNT;
(2) constant current electro-deposition;
(3) cyclic voltammetric electro-deposition;
(4) constant voltage electro-deposition;
(5) electrophoretic deposition;
(6) chemical reaction deposit MnO
2, said chemical reaction comprises that hydro-thermal synthesizes MnO
2Reaction.
Thereby adopted in the following manner any one to be implemented in this method at least and deposited MnO
2CNT paper on cover grapheme material:
(1) CVD growth grapheme material on CNT paper;
(2) CNT paper is soaked in the Graphene dispersion liquid;
(3) at CNT paper surface-coated Graphene dispersion liquid.
The present invention is back bone network with the CNT, and passes through at its surface deposition MnO
2Metal oxide, outer parcel Graphene, thereby the flexible compound membrane material that acquisition has sandwich structure, it is adjustable that this thickness of composite material arrives thousands of microns at several microns, but self-supporting need not relied on other substrates.
More concretely, the one-dimentional structure that the present invention makes full use of CNT forms porous network, possesses characteristics such as high-specific surface area, high conduction, has given full play to MnO
2Faraday's electric capacity characteristic that metal oxide is good, and, improve package structure conductivity and electric capacity behavior activity through adopting Graphene, also obtain outstanding electrochemical capacitor behavior.
The invention solves that metal oxide comes off in carbon nano tube surface easily in the ultracapacitor work, problems such as metal conductive oxide property difference, and through regulating the content of Graphene in the composite material, also may command conductivity of composite material and electrolyte soak into MnO
2(Graphene is unfavorable for the raising of material conductivity to the balance of ability very little, the too high MnO that is unfavorable for of content
2And can stop the problem that specific area that the Graphene lamella can occur when thicker descends capacitive property performance).
Summarize it, compared with prior art, advantage of the present invention is at least:
(1) a kind of novel flexible composite film material is provided, its conductivity, large current density ability, specific capacitance, cycle life are than CNT-MnO
2Obvious enhancing is all arranged; Solved fully that metal oxide comes off in carbon nano tube surface easily in the existing ultracapacitor work; Metal conductive oxide property difference problem; Taken into account material light flexible characteristics of high efficiency simultaneously, the important application prospect has been arranged in fields such as new forms of energy (rechargeable battery, ultracapacitor), advanced chemical industry, electronic device, film preparations;
(2) technology of the aforementioned novel flexible composite film material of preparation is simple, easy operating, and controllability is good, and with low cost, is suitable for large-scale industrial production.
Description of drawings
Fig. 1 is preparation technology's flow chart of composite Nano carbon paper of the present invention;
Fig. 2 a is the stereoscan photograph of the CNT paper that obtains in the embodiment of the invention 1;
Fig. 2 b is the CNT-MnO that obtains in the embodiment of the invention 1
2The stereoscan photograph of paper;
Fig. 2 c is the target product Graphene/CNT-MnO that obtains in the embodiment of the invention 1
2The stereoscan photograph of/Graphene sandwich structure composite Nano carbon paper;
Fig. 3 a is than the change curve of electric capacity with charging and discharging currents density when the composite Nano carbon paper is as electrode of super capacitor in the embodiment of the invention 1;
Fig. 3 b is (three-electrode system test, the charging and discharging currents density: 1A/g) of cycle life curve when the composite Nano carbon paper is as electrode of super capacitor in the embodiment of the invention 1;
Fig. 4 is the CNT-MnO that obtains in the embodiment of the invention 2
2The electromicroscopic photograph of extrusion coating paper.
Embodiment
To many defectives of the prior art, this case inventor has proposed self-supporting Graphene/CNT of the present invention-MnO through long-term theory research and a large amount of practice
2/ Graphene sandwich structure composite Nano carbon paper, this self-supporting composite Nano carbon paper has following characteristic:
I, be made up of three-decker, skin is a Graphene, and internal layer is surface deposition MnO
2CNT, in fact because the carbon nanometer paper porous network structure that interweaves and forms by the disordered carbon nanotube, so also have among this porous network structure of part grapheme material infiltration;
II, thickness at several microns to thousands of microns and control thickness as required;
III, area are greater than 10 cm
2, and can control as required;
CNT, MnO in IV, the material
2, Graphene content controlled, comparatively preferably, Graphene accounts for nano-sized carbon paper weight percentage 0～10%, MnO
2Account for nano-sized carbon paper weight percentage 0～50%;
V, material have suitable flexibility;
But the VI self-supporting need not relied on other substrates;
VII, the common experimental provision of use and method can be accomplished.
Aforementioned CNT can adopt any one method in chemical vapour deposition technique, catalyse pyrolysis, arc discharge, template or the laser evaporation method etc. to process, and said CNT be in SWCN, multi-walled carbon nano-tubes or the carbon nano-fiber any one or multiple.In addition, said CNT can be through being modified with the CNT of groups such as carboxyl, amino, hydroxyl, fluorine or acid amides, also can not having modification.
Aforementioned Graphene can be prepared from any one method in chemical oxidization method, chemical vapour deposition (CVD), the firing method etc., and said Graphene be in graphene oxide, reduction Graphene, the pure Graphene any one or multiple.
Aforementioned MnO
2Oxide can be continuous rete or the discrete granuloplastic discontinuous layer structure of modifying that is wrapped in carbon nano tube surface.
Further, consult Fig. 1, this self-supporting Graphene/CNT-MnO
2/ Graphene sandwich structure composite Nano carbon paper prepares through following method:
A. prepare CNT paper: carbon nanotube dust is sneaked in the solvent; Through disperseing to process dispersion liquid relatively uniformly, wherein CNT needn't be realized single dispersion, and dispersion liquid is carried out suction filtration (certainly with pumping and filtering device; Can there be press filtration or vacuum filtration) yet; Remove residual impurity such as dispersant (certainly, also can not use dispersant) with the clear water washing afterwards, the CNT paper controllable thickness of acquisition is built in several microns to several millimeters;
B. deposit MnO
2: with CNT paper is carrier, surface deposition MnO
2, the method for deposition can be simple mechanical mixture, can be chemical reaction, also can be electro-deposition etc.;
C. surface attachment Graphene: will deposit MnO
2CNT paper surface attachment Graphene, the method for adhering to can be soak into, graphene coated solution, also can be to adopt method surface direct growth Graphene such as CVD.
The optional water of aforementioned solvents, ethanol, isopropyl alcohol, N; In dinethylformamide (DMF), N-methyl pyrrolidone (NMP), ethyl acetate, the chloroform equal solvent any one; And be not limited thereto; And high speed shear, grinding, ball milling, the method for dispersioning such as ultrasonic any one can selected and be not limited to the method for disperseing for use, and CNT wherein can be scattered in the solution with single form, also can become large stretch of reunion to be distributed in the solution.
If adopt dispersant; Then dispersant can be selected for use but be not limited to polymer such as polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), cellulose, any one of surfactants such as lauryl sodium sulfate (SDS), neopelex (SDBS), softex kw (CTAB), Tween-80, TritonX-100 or multiple.
Below in conjunction with accompanying drawing and some preferred embodiments technical scheme of the present invention is elaborated.
Embodiment 1Take by weighing the CNT of 500 mg behind the hydrochloric acid purifying, be scattered in the 1L deionized water, dispersant is a polyvinylpyrrolidone; With high-shear impeller stirred for several minute, in dispersion liquid, form pulpous state to CNT and distribute, cellulose filter paper is layered on the Buchner funnel bottom that diameter is 25 cm; Use the vacuum pump suction filtration, make CNT uniform deposition on filter paper, treat CNT paper to be separated with filter paper when half-dried; Obtain CNT paper, its thickness is approximately 65 um.Circular CNT paper is spent the direction lead-in conductor along four 90 at central angle; Process electrode; This electrode is immersed the mixed solution number minute of 0.8mol/L sulfuric acid and 0.6mol/L manganese sulfate monohydrate; Make electrolyte and CNT paper fully soak into, then carry out anode constant current electrochemical deposition, depositing current density is 5mA/cm
2, depositing temperature 0
oC, temperature is controlled with the condensation ice bag, and sedimentation time is 20min, is 40cm to electrode
2Graphite flake.Electrode is taken out, in deionized water, clean and took out in several minutes, immerse in the graphene aqueous solution of 0.05mg/ml.Soak into after 3.5 hours and take out, in baking oven, obtain target product after the drying, its performance is shown in Fig. 3 a and 2b.
CNT paper, the CNT-MnO of obtaining among table 1 embodiment 1
2, Graphene/CNT-MnO
2The variation of/Graphene sandwich structure composite Nano carbon paper (three's structure is shown in Fig. 2 a-2c) three's conductivity
| Sample | CNT paper | CNT-MnO 2 | Sandwich composite Nano carbon paper |
| Conductivity (S.m -1) | 4.2×10 3 | 2.0×10 3 | 3.6×10 3 |
Embodiment 2Take by weighing the CNT of 120mg behind the hydrochloric acid purifying, be scattered in the 1L deionized water, dispersant is for removing La Tong-100; With high-shear impeller stirred for several minute, in dispersion liquid, form pulpous state to CNT and distribute, cellulose filter paper is layered on the Buchner funnel bottom; Use the vacuum pump suction filtration, make CNT uniform deposition on filter paper, treat CNT paper to be separated with filter paper when half-dried; Obtaining diameter is the CNT paper of 6cm, and its thickness is approximately 60 um.With circular CNT paper lead-in conductor, process electrode, this electrode is immersed the mixed solution number minute of 1mol/L sodium acetate and 0.5mol/L manganese acetate; Make electrolyte and CNT paper fully soak into, then carry out the cyclic voltammetric electrochemical deposition, potential region is 0～1.2V; Sweep speed: 100mv/s; Sedimentation time is 10min, depositing temperature: room temperature is 8cm to electrode
2Graphite, reference electrode are saturated calomel.Electrode is taken out, in deionized water, clean and took out in several minutes, immerse in the graphene aqueous solution of 0.1mg/ml.Soak into after 1.5 hours and take out, in baking oven, obtain target product after the drying, its structure is as shown in Figure 4, and its electric property is close with embodiment 1.
Embodiment 3Take by weighing the CNT of 500 mg behind the hydrochloric acid purifying, be scattered in the 1L deionized water, dispersant is neopelex (SDBS); With high-shear impeller stirred for several minute, in dispersion liquid, form pulpous state to CNT and distribute, cellulose filter paper is layered on the Buchner funnel bottom that diameter is 25 cm; Use the vacuum pump suction filtration, make CNT uniform deposition on filter paper, treat CNT paper to be separated with filter paper when half-dried; Obtain CNT paper, its thickness is approximately 65 um.Circular CNT paper along four 90 at central angle degree direction lead-in conductor, is processed electrode, this electrode is immersed the mixed solution number minute of 0.8mol/L sulfuric acid and 0.6mol/L manganese sulfate monohydrate; Make electrolyte and CNT paper fully soak into; Then carry out anode constant voltage electrochemical deposition, sedimentation potential is 2.5V, and depositing temperature is a room temperature; Sedimentation time is 20min, is 40cm to electrode
2Graphite flake.Electrode is taken out, in deionized water, clean and took out in several minutes, immerse in the graphene aqueous solution of 0.05mg/ml, soak into after 5 hours and take out, in baking oven, obtain target product after the drying, its structure and electric property are close with embodiment 1,2.
Embodiment 4Take by weighing the CNT of 120 mg behind the hydrochloric acid purifying, be scattered in the 0.5L deionized water, dispersant is a polyvinylpyrrolidone; With ultrasonic dispersion 1 hour, in dispersion liquid, form pulpous state to CNT and distribute, cellulose filter paper is layered on the Buchner funnel bottom; Use the vacuum pump suction filtration, make CNT uniform deposition on filter paper, treat CNT paper to be separated with filter paper when half-dried; Obtaining diameter is 6cm CNT paper, and its thickness is approximately 65 um.With circular CNT paper lead-in conductor, process electrode, the mixed solution that this electrode is immersed 0.8mol/L sulfuric acid and 0.6mol/L manganese sulfate monohydrate carries out anode constant current electrochemical deposition, and depositing current density is 5mA/cm
2, sedimentation time 5min.Electrode is taken out, and the mixed solution of putting into 1mol/L sodium acetate and 0.5mol/L manganese acetate carries out the cyclic voltammetric electro-deposition, and potential region is 0～1.2V, and sweep speed: 100mv/s, sedimentation time are 3min, are 8cm to electrode
2Graphite flake, reference electrode are saturated calomel.Taking out electrode cleaned several minutes in deionized water.Immerse in the graphene aqueous solution of 0.05mg/ml.Soak into after 3.5 hours and take out, in baking oven, obtain target product after the drying, its structure and electric property are close with embodiment 1,2.
More than explanation, and the embodiment shown on drawing can not be resolved the design philosophy of the present invention surely of exceeding.In technical field of the present invention, holding identical knowledge the knowledgeable can be with technical thought of the present invention with various form improvement change, and such improvement and change are interpreted as belonging in protection scope of the present invention.
Claims (10)
1. a composite Nano carbon paper is characterized in that, said nanometer carbon paper has composite sandwich, and it comprises:
The back bone network that forms by CNT paper with macroscopical nonwoven fabrics form;
Be deposited on the MnO of the carbon nano tube surface that constitutes CNT paper
2Metal oxide layer;
And, be covered in the graphene layer on the said back bone network;
The content of grapheme material is below 10wt% in the said nanometer carbon paper, MnO
2The content of metal oxide is below 50wt%.
2. composite Nano carbon paper according to claim 1 is characterized in that, said CNT paper has the porous network structure that is interweaved and formed by the disordered carbon nanotube, and in said porous network structure, also infiltrates grapheme material.
3. composite Nano carbon paper according to claim 1 is characterized in that, said MnO
2Metal oxide layer is continuous rete or the discrete MnO that is modified at carbon nano tube surface that is wrapped in carbon nano tube surface
2Granuloplastic discontinuous rete.
4. composite Nano carbon paper according to claim 1 is characterized in that, said graphene layer is by any one or two or more being combined to form in graphene oxide, reduction Graphene and the pure Graphene.
5. the preparation method of composite Nano carbon paper according to claim 1 is characterized in that this method is:
At first get CNT and process CNT suspended dispersed liquid, and filter formation CNT paper, thereafter, in CNT paper, deposit MnO
2Thereby, form MnO in carbon nano tube surface
2Metal oxide layer, last, on CNT paper, cover grapheme material, obtain target product.
6. according to the preparation method of the said composite Nano carbon paper of claim 5, it is characterized in that, is to adopt the mode that CNT is scattered in the solvent to form CNT suspended dispersed liquid in this method;
Said solvent is selected from water, ethanol, isopropyl alcohol, N at least, more than any one in dinethylformamide, N-methyl pyrrolidone, ethyl acetate and the chloroform equal solvent.
7. according to the preparation method of the said composite Nano carbon paper of claim 6; It is characterized in that; Also contain dispersant in the said solvent; Said dispersant is selected from polymer such as polyvinyl alcohol, polyvinylpyrrolidone, cellulose, any one in lauryl sodium sulfate, neopelex, softex kw, Tween-80 and the TritonX-100 or two or more combinations at least.
8. according to the preparation method of the said composite Nano carbon paper of claim 5, it is characterized in that, be to adopt no press filtration or the preparation of vacuum filtration method to form CNT paper in this method, and the thickness of said CNT paper is 1 μ m-1mm.
9. according to the preparation method of the said composite Nano carbon paper of claim 5, it is characterized in that, deposit MnO thereby adopted in the following manner any one to be implemented in the CNT paper in this method at least
2:
(1) MnO
2Mechanical mixture with CNT;
(2) constant current electro-deposition;
(3) cyclic voltammetric electro-deposition;
(4) constant voltage electro-deposition;
(5) electrophoretic deposition;
(6) chemical reaction deposit MnO
2, said chemical reaction comprises that hydro-thermal synthesizes MnO
2Reaction.
10. according to the preparation method of the said composite Nano carbon paper of claim 5, it is characterized in that, deposit MnO thereby adopted in the following manner any one to be implemented in this method at least
2CNT paper on cover grapheme material:
(1) CVD growth grapheme material on CNT paper;
(2) CNT paper is soaked in the Graphene dispersion liquid;
(3) at CNT paper surface-coated Graphene dispersion liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110271170.XA CN102436934B (en) | 2011-09-15 | 2011-09-15 | Composite nanometer carbon paper and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110271170.XA CN102436934B (en) | 2011-09-15 | 2011-09-15 | Composite nanometer carbon paper and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102436934A true CN102436934A (en) | 2012-05-02 |
| CN102436934B CN102436934B (en) | 2014-06-11 |
Family
ID=45984941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110271170.XA Active CN102436934B (en) | 2011-09-15 | 2011-09-15 | Composite nanometer carbon paper and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102436934B (en) |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058172A (en) * | 2013-01-15 | 2013-04-24 | 清华大学 | Preparation method of carbon nanometer tube-graphene composite material |
| CN103346291A (en) * | 2013-07-10 | 2013-10-09 | 肖辉 | Carbon nano-paper-based in-situ loaded ferroferric oxide lithium-ion battery negative electrode and preparation method thereof |
| CN103343477A (en) * | 2013-07-10 | 2013-10-09 | 肖辉 | Method for largely loading Fe3O4 nanometer particles on carbon nanometer paper |
| CN103354296A (en) * | 2013-07-12 | 2013-10-16 | 肖辉 | Ultralight polymer lithium ion battery and manufacturing method thereof |
| CN103482620A (en) * | 2013-09-11 | 2014-01-01 | 黄镇东 | Graphene oxide or reduced graphene base mesh material and preparation method thereof |
| CN103626172A (en) * | 2013-11-29 | 2014-03-12 | 上海利物盛企业集团有限公司 | Method for preparing graphite paper with high thermal conductivity |
| CN104029461A (en) * | 2014-06-13 | 2014-09-10 | 江苏悦达新材料科技有限公司 | Graphene/carbon nano tube/graphite film composite material and preparation method thereof |
| CN105047427A (en) * | 2015-08-06 | 2015-11-11 | 清华大学 | Composite electrode material for supercapacitor, preparation method of composite electrode material and supercapacitor |
| CN105632790A (en) * | 2016-03-25 | 2016-06-01 | 上海工程技术大学 | MnO2 nano array supercapacitor electrode material and preparation method thereof |
| CN105871247A (en) * | 2016-04-27 | 2016-08-17 | 北京大学 | Friction generator and supercapacitor integration based self-charging energy unit and manufacturing method therefor |
| CN106252080A (en) * | 2016-07-29 | 2016-12-21 | 太原理工大学 | A kind of carbon nanomaterial is prepared as the DSSC method to electrode |
| CN106356196A (en) * | 2016-10-14 | 2017-01-25 | 安泰科技股份有限公司 | Manganese dioxide/carbon paper composite electrode material and preparation method thereof |
| CN107130462A (en) * | 2016-02-26 | 2017-09-05 | 昆明纳太科技有限公司 | Carbon nanometer paper and its preparation method and application |
| CN108493008A (en) * | 2018-03-15 | 2018-09-04 | 南通纺织丝绸产业技术研究院 | cotton fabric base flexible electrode material and preparation method thereof |
| CN110033948A (en) * | 2019-04-08 | 2019-07-19 | 宁波中车新能源科技有限公司 | A kind of low internal resistance, high power hybrid capacitors positive plate and preparation method thereof |
| CN110165229A (en) * | 2019-05-28 | 2019-08-23 | 东旭光电科技股份有限公司 | A kind of compound carbon fiber paper of graphene and its preparation method and application |
| CN110706937A (en) * | 2019-10-28 | 2020-01-17 | 常江 | Preparation method of graphene electrode material |
| CN110777331A (en) * | 2019-11-07 | 2020-02-11 | 苏州第一元素纳米技术有限公司 | Preparation method of metal-coated carbon nano tube |
| CN111403184A (en) * | 2020-04-21 | 2020-07-10 | 南昌航空大学 | Nano carbon doped MnO2Preparation method of heterojunction flexible electrode |
| CN111653780A (en) * | 2020-06-04 | 2020-09-11 | 山东大学 | Flexible graphene-based composite scaffold material and preparation method and application thereof |
| CN111816456A (en) * | 2020-06-30 | 2020-10-23 | 西安交通大学 | Electrode manufacturing method capable of enhancing conductivity of supercapacitor electrode and inhibiting falling of active substances |
| CN112981454A (en) * | 2021-02-03 | 2021-06-18 | 山东大学 | Manganese dioxide ultra-long nanowire catalyst with oxygen vacancy as well as preparation method and application thereof |
| CN115072707A (en) * | 2022-06-08 | 2022-09-20 | 哈尔滨工业大学 | Super-soft-tough multifunctional carbon aerogel and preparation method thereof |
| CN115159628A (en) * | 2022-06-16 | 2022-10-11 | 华南农业大学 | Modified electrochemical cathode for degrading perfluorinated compounds and preparation method thereof |
| US20230170158A1 (en) * | 2021-11-30 | 2023-06-01 | Nissan North America, Inc. | Integrated supercapacitor-battery structure |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1833352A (en) * | 2003-12-08 | 2006-09-13 | 独立行政法人科学技术振兴机构 | Actuator element and production method therefor |
-
2011
- 2011-09-15 CN CN201110271170.XA patent/CN102436934B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1833352A (en) * | 2003-12-08 | 2006-09-13 | 独立行政法人科学技术振兴机构 | Actuator element and production method therefor |
Non-Patent Citations (1)
| Title |
|---|
| 章仁毅等: "基于碳纳米管的超级电容器研究进展", 《应用化学》 * |
Cited By (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058172A (en) * | 2013-01-15 | 2013-04-24 | 清华大学 | Preparation method of carbon nanometer tube-graphene composite material |
| CN103346291A (en) * | 2013-07-10 | 2013-10-09 | 肖辉 | Carbon nano-paper-based in-situ loaded ferroferric oxide lithium-ion battery negative electrode and preparation method thereof |
| CN103343477A (en) * | 2013-07-10 | 2013-10-09 | 肖辉 | Method for largely loading Fe3O4 nanometer particles on carbon nanometer paper |
| CN103343477B (en) * | 2013-07-10 | 2015-10-21 | 昆明纳太能源科技有限公司 | One extensive load Fe on carbon nanometer paper 3o 4the method of nano particle |
| CN103346291B (en) * | 2013-07-10 | 2015-12-02 | 昆明纳太能源科技有限公司 | Lithium ion battery negative of a kind of carbon nanometer paper substrate original position load tri-iron tetroxide and preparation method thereof |
| CN103354296A (en) * | 2013-07-12 | 2013-10-16 | 肖辉 | Ultralight polymer lithium ion battery and manufacturing method thereof |
| CN103482620A (en) * | 2013-09-11 | 2014-01-01 | 黄镇东 | Graphene oxide or reduced graphene base mesh material and preparation method thereof |
| CN103482620B (en) * | 2013-09-11 | 2016-01-20 | 黄镇东 | Oxidation or reduced graphene base net grid material and preparation method thereof |
| CN103626172A (en) * | 2013-11-29 | 2014-03-12 | 上海利物盛企业集团有限公司 | Method for preparing graphite paper with high thermal conductivity |
| CN104029461A (en) * | 2014-06-13 | 2014-09-10 | 江苏悦达新材料科技有限公司 | Graphene/carbon nano tube/graphite film composite material and preparation method thereof |
| CN105047427B (en) * | 2015-08-06 | 2017-07-18 | 清华大学 | Ultracapacitor combination electrode material and preparation method thereof and ultracapacitor |
| CN105047427A (en) * | 2015-08-06 | 2015-11-11 | 清华大学 | Composite electrode material for supercapacitor, preparation method of composite electrode material and supercapacitor |
| CN107130462A (en) * | 2016-02-26 | 2017-09-05 | 昆明纳太科技有限公司 | Carbon nanometer paper and its preparation method and application |
| CN107130462B (en) * | 2016-02-26 | 2019-03-01 | 昆明纳太科技有限公司 | Carbon nanometer paper and its preparation method and application |
| CN105632790A (en) * | 2016-03-25 | 2016-06-01 | 上海工程技术大学 | MnO2 nano array supercapacitor electrode material and preparation method thereof |
| CN105632790B (en) * | 2016-03-25 | 2018-05-22 | 上海工程技术大学 | A kind of MnO2Nano-array electrode material for super capacitor and preparation method thereof |
| CN105871247A (en) * | 2016-04-27 | 2016-08-17 | 北京大学 | Friction generator and supercapacitor integration based self-charging energy unit and manufacturing method therefor |
| CN106252080A (en) * | 2016-07-29 | 2016-12-21 | 太原理工大学 | A kind of carbon nanomaterial is prepared as the DSSC method to electrode |
| CN106252080B (en) * | 2016-07-29 | 2019-03-12 | 太原理工大学 | A kind of carbon nanomaterial is prepared into dye-sensitized solar cells to the method for electrode |
| CN106356196A (en) * | 2016-10-14 | 2017-01-25 | 安泰科技股份有限公司 | Manganese dioxide/carbon paper composite electrode material and preparation method thereof |
| CN106356196B (en) * | 2016-10-14 | 2018-07-27 | 安泰科技股份有限公司 | A kind of manganese dioxide/carbon paper combination electrode material and preparation method thereof |
| CN108493008A (en) * | 2018-03-15 | 2018-09-04 | 南通纺织丝绸产业技术研究院 | cotton fabric base flexible electrode material and preparation method thereof |
| CN110033948A (en) * | 2019-04-08 | 2019-07-19 | 宁波中车新能源科技有限公司 | A kind of low internal resistance, high power hybrid capacitors positive plate and preparation method thereof |
| CN110165229A (en) * | 2019-05-28 | 2019-08-23 | 东旭光电科技股份有限公司 | A kind of compound carbon fiber paper of graphene and its preparation method and application |
| CN110706937A (en) * | 2019-10-28 | 2020-01-17 | 常江 | Preparation method of graphene electrode material |
| CN110777331A (en) * | 2019-11-07 | 2020-02-11 | 苏州第一元素纳米技术有限公司 | Preparation method of metal-coated carbon nano tube |
| CN111403184A (en) * | 2020-04-21 | 2020-07-10 | 南昌航空大学 | Nano carbon doped MnO2Preparation method of heterojunction flexible electrode |
| CN111653780A (en) * | 2020-06-04 | 2020-09-11 | 山东大学 | Flexible graphene-based composite scaffold material and preparation method and application thereof |
| CN111816456A (en) * | 2020-06-30 | 2020-10-23 | 西安交通大学 | Electrode manufacturing method capable of enhancing conductivity of supercapacitor electrode and inhibiting falling of active substances |
| CN111816456B (en) * | 2020-06-30 | 2021-08-13 | 西安交通大学 | Electrode manufacturing method capable of enhancing conductivity of supercapacitor electrode and inhibiting falling of active substances |
| CN112981454A (en) * | 2021-02-03 | 2021-06-18 | 山东大学 | Manganese dioxide ultra-long nanowire catalyst with oxygen vacancy as well as preparation method and application thereof |
| US20230170158A1 (en) * | 2021-11-30 | 2023-06-01 | Nissan North America, Inc. | Integrated supercapacitor-battery structure |
| US11817260B2 (en) * | 2021-11-30 | 2023-11-14 | Nissan North America, Inc. | Integrated supercapacitor-battery structure |
| CN115072707A (en) * | 2022-06-08 | 2022-09-20 | 哈尔滨工业大学 | Super-soft-tough multifunctional carbon aerogel and preparation method thereof |
| CN115159628A (en) * | 2022-06-16 | 2022-10-11 | 华南农业大学 | Modified electrochemical cathode for degrading perfluorinated compounds and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102436934B (en) | 2014-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102436934B (en) | Composite nanometer carbon paper and preparation method thereof | |
| Hu et al. | MXene-coated silk-derived carbon cloth toward flexible electrode for supercapacitor application | |
| Yang et al. | MXene/CNTs films prepared by electrophoretic deposition for supercapacitor electrodes | |
| CN108315834B (en) | Preparation method of array type magnetic reduced graphene oxide-carbon nanofiber | |
| CN104795252B (en) | Ultra-thin Ti3C2The preparation method of the electrode of super capacitor of nanometer sheet self assembly | |
| CN107946091B (en) | A kind of paper base flexible flat supercapacitor preparation method | |
| Yuan et al. | Synthesis of flexible and porous cobalt hydroxide/conductive cotton textile sheet and its application in electrochemical capacitors | |
| CN107934955B (en) | Method for activating commercial carbon fiber cloth | |
| CN108258334A (en) | A kind of composite and flexible electrode, preparation method and application | |
| CN100420626C (en) | Preparation method of pure nano-carbon tube film | |
| JP2012001865A (en) | Fibrous composite material and method for producing the same, and fiber member and functional device which include fibrous composite material | |
| CN102315462B (en) | Electrode used for vanadium redox flow battery and preparation method for electrode | |
| CN106784745A (en) | The sodium-ion battery method for manufacturing electric spinning of cobaltosic oxide carbon nano-fiber | |
| Zhang et al. | Preparation of inflorescence-like ACNF/PANI/NiO composite with three-dimension nanostructure for high performance supercapacitors | |
| CN103762356B (en) | Ni nano wire, NiO/Ni self-supported membrane and its preparation method and application | |
| CN107316752A (en) | A kind of preparation method of the grapheme modified paper capacitor electrode of manganese bioxide/carbon nano tube | |
| CN110335759A (en) | Load nickel hydroxide nano piece and the nanocrystalline carbon nano-fiber composite material and its preparation method and application of cobalt acid nickel | |
| Wu et al. | High flexibility and large energy density asymmetric fibered-supercapacitor based on unique NiCo2O4@ MnO2 core-shell nanobrush arrays electrode | |
| Mondal et al. | Manganese oxide based hybrid nanofibers for supercapacitors | |
| CN112103089B (en) | Nitrogen-doped graphene quantum dot/eupolyphaga powder-based porous carbon composite material electrode, application and preparation method thereof | |
| CN110165290B (en) | Solid sodium ion electrolyte, preparation method and application thereof | |
| Liu et al. | Excellent electrochemical stability of Co3O4 array with carbon hybridization derived from metal-organic framework | |
| CN105161319A (en) | Method for preparing amorphous carbon coated and oxygen vacancy modified titanium dioxide nanotube array supported nickel-cobalt oxide electrode material | |
| CN110172771B (en) | Novel wearable supercapacitor fabric and preparation method thereof | |
| CN107665996B (en) | Three-dimensional porous nickel hollow fiber electrode material, preparation method and battery based on electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |