CN105679548B - A kind of electrode plates and preparation method thereof for graphene-based supercapacitor - Google Patents
A kind of electrode plates and preparation method thereof for graphene-based supercapacitor Download PDFInfo
- Publication number
- CN105679548B CN105679548B CN201610011998.4A CN201610011998A CN105679548B CN 105679548 B CN105679548 B CN 105679548B CN 201610011998 A CN201610011998 A CN 201610011998A CN 105679548 B CN105679548 B CN 105679548B
- Authority
- CN
- China
- Prior art keywords
- graphene
- electrode plates
- layer
- slurry
- graphite alkene
- 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.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- -1 Laminated Graphite alkene Chemical class 0.000 claims abstract description 32
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 22
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000011149 active material Substances 0.000 claims abstract description 17
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 16
- 239000004917 carbon fiber Substances 0.000 claims abstract description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000011268 mixed slurry Substances 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 238000005554 pickling Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 63
- 239000002002 slurry Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims 1
- 229910001950 potassium oxide Inorganic materials 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 239000003990 capacitor Substances 0.000 abstract description 3
- 239000007785 strong electrolyte Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 230000004087 circulation Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
-
- 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
-
- 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
-
- 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 electrode plates and preparation method thereof that the present invention provides a kind of for graphene-based supercapacitor, the electrode plates include current collector layers and active material layer, and the current collector layers are Laminated Graphite alkene layer, and the active material layer is porous graphene layer；The preparation method includes: 1) to prepare the mixed slurry containing the physics graphene removed and carbon nanotube or/and carbon fiber；2) mixed slurry containing graphene made from chemical oxidization method, pore creating material and carbon nanotube or/and carbon fiber is prepared；3) successively squeegeeing step 1) and step 2) obtained by mixed slurry heated in an inert atmosphere on matrix, then successively carry out pickling and washing, roll-in obtains electrode plates after drying.The active material layer and current collector layers of electrode plates of the invention are in close contact, and interface resistance and the internal resistance of cell is effectively reduced, and are had the absorption of very strong electrolyte and storage capacity, are improved the high-rate discharge ability and energy density of capacitor.
Description
Technical field
The present invention relates to a kind of electrode plates of supercapacitor, and in particular to one kind is used for graphene-based supercapacitor
Electrode plates and preparation method thereof.
Background technique
In recent years, as process of industrialization is constantly accelerated, increasingly serious, the people couple of world today's energy and environment problem
It is continuously increased in the demand of clean and effective and renewable energy, the Efficient Conversion of energy and storage are also of increasing concern.It is super
Capacitor has high power density as important energy storage device, can be quickly charged and discharged, million rank long circulation lifes
With the characteristics such as safe and reliable.However, current supercapacitor has the shortcomings that energy density is lower, the commercial super electricity of active carbon
The energy density of container only 5~7Wh/kg.In order to meet ever increasing need, develop light and there is high-energy density, function
The supercapacitor of rate density and good circulation stability is one of development trend of new energy field.
Currently, collector generallys use metal copper foil or aluminium foil in super-capacitor pole piece manufacture craft, manufacture craft is
Active material is coated in metal collector in a form of slurry, i.e., active material and collector realize two by binder
Connection between person.This connection type is often insufficient because of the adhesion strength of binder, and active material and collector is caused to fill
It is gradually disengaged in discharge process, is continuously increased the internal resistance of cell, cycle life shortens, and there is also safety to ask for battery
Topic.Additionally due to metal collector density is larger, ratio of the active material in entire electrode can be reduced, to limit battery
Energy density further increases.
Summary of the invention
The electrode plates and preparation method thereof that the purpose of the present invention is to provide a kind of for graphene-based supercapacitor,
Overcome the deficiencies in the prior art obtains graphene-based supercapacitor by Laminated Graphite alkene layer and the compound of porous graphene layer
Electrode plates, be in close contact active material layer and current collector layers, interface resistance and the internal resistance of cell be effectively reduced, has simultaneously
Very strong electrolyte absorption and storage capacity, improve the high-rate discharge ability of supercapacitor, super electricity are also effectively reduced
The weight of collector in container, improves the energy density of supercapacitor.
To achieve the goals above, the present invention takes following technical scheme:
A kind of electrode plates for graphene-based supercapacitor, the electrode plates include current collector layers and active matter
Matter layer, the current collector layers are Laminated Graphite alkene layer, and the active material layer is porous graphene layer.
First optimal technical scheme of the electrode plates, the Laminated Graphite alkene layer include carbon nanotube or/and carbon
Fiber；The porous graphene layer includes carbon nanotube or/and carbon fiber.
Second optimal technical scheme of the electrode plates, the graphene and carbon fiber or carbon of the Laminated Graphite alkene layer
The mass ratio of nanotube is 5~50:1；The graphene and carbon fiber of the porous graphene layer or the mass ratio of carbon nanotube are 5
~50:1.
The third optimal technical scheme of the electrode plates, the graphene of the Laminated Graphite alkene layer are that physics is removed
The carbon-to-oxygen ratio of 1~10 layer of the graphene film arrived, the graphene is greater than 20；The graphene of the porous graphene layer is chemistry
Graphene made from oxidizing process.
The graphene film of 4th optimal technical scheme of the electrode plates, the physics removing is single layer, in order to make
Good overlap joint is formed between Laminated Graphite alkene, lateral dimension is 1~100 μm, and preferred size is 10 μm.
5th optimal technical scheme of the electrode plates, the Laminated Graphite alkene layer with a thickness of 0.5~50 μm, institute
State porous graphene layer with a thickness of 10~100 μm.
6th optimal technical scheme of the electrode plates, the Laminated Graphite alkene layer with a thickness of 20 μm, it is described more
Hole graphene layer with a thickness of 20 μm.
A kind of preparation method of the electrode plates, the preparation method comprises the following steps:
1) it prepares Laminated Graphite alkene slurry: dispersing water for the graphene of physics removing and carbon nanotube or/and carbon fiber
In be made solid content be 1%~10% slurry；
2) porous graphene slurry is prepared: according to the mass ratio of 1:1~5 by graphene made from chemical oxidization method and pore-creating
Agent is dispersed in water, and carbon nanotube or/and carbon fiber formation solid content is added as 1%~10% slurry；
3) electrode plates are prepared: step 1) and 2) gained mixed slurry are painted on matrix in succession, in an inert atmosphere,
At a temperature of 400~1200 DEG C, successively pickling and washing after 0.5~12h is heated, roll-in obtains electrode plates after drying.
First optimal technical scheme of the preparation method, slurry solid content described in step 1) are 2%~5%.
Second optimal technical scheme of the preparation method, pore creating material described in step 2) are selected from potassium hydroxide, oxygen
Change one of potassium, potassium carbonate, sodium carbonate, sodium oxide molybdena, sodium hydroxide, metal nickel particle, iron granule and metal cobalt granule
Or several combination；The mass ratio of graphene made from the pore creating material and chemical oxidization method is 2:1.
Preferably 800~1100 DEG C of the step 3) heating temperature, most preferably 1000 DEG C；The heating time preferably 2~4h.
Heating rate when heating is 3~8 DEG C/min, preferably 4~6 DEG C/min, most preferably 5 DEG C/min.
Product after heating carries out pickling and filtering, to remove wherein remaining metallic catalyst or activator.The acid
The acid solution washed is one or both of hydrochloric acid, sulfuric acid and nitric acid, and the dip time of the pickling is 0.5~8h, preferably 1~
7h, more preferable 2~6h.
Product drying after pickling and washing is preferably dried, and the temperature of the drying is 100~150 DEG C, preferably 90~
140 DEG C, more preferable 100~120 DEG C, the time of the drying is 8~12h, preferably 10h.
The electrode plates are used to prepare the application of graphene-based supercapacitor.
Compared with the latest prior art, the invention has the following beneficial effects:
1) electrode plates of the invention, active material layer and current collector layers are in close contact, can be effectively reduced interface resistance and
The internal resistance of cell, while there is very strong electrolyte absorption and storage capacity, the high-rate discharge ability of supercapacitor is improved,
Also the weight of collector in supercapacitor is effectively reduced, improves the energy density of supercapacitor；
2) the preparation method is that with metal aluminum foil, copper foil, ceramics, glass etc. for matrix, Laminated Graphite alkene is prepared
Electrode plates are prepared using the method for layered coatings with porous graphene slurry；
3) the Laminated Graphite alkene of current collector layers of the present invention is the graphene of physics removing graphite preparation, and this graphene has
Perfect sp2 structure, in high-temperature process, this perfect lattice structure cannot be etched by pore creating material；Active material of the present invention
The porous graphene of layer is the graphene oxide prepared using the method for chemical oxidation graphite, and this graphene has a large amount of lack
It falls into, can be reacted under the high temperature conditions with pore creating material, generate a large amount of gas, form porous structure, while etching reaction in situ
A large amount of micropore and mesoporous can be formed.
Detailed description of the invention
Fig. 1: the photo of 1 Laminated Graphite alkene layer of the embodiment of the present invention；
Fig. 2: the photo of 1 porous graphene layer of the embodiment of the present invention；
Fig. 3: the scanning electron microscope (SEM) photograph of 1 Laminated Graphite alkene layer of the embodiment of the present invention；
Fig. 4: the scanning electron microscope (SEM) photograph of 1 porous graphene layer of the embodiment of the present invention；
Fig. 5: the scanning electron microscope (SEM) photograph of 1 electrode plates of the embodiment of the present invention；
Fig. 6: the specific capacitance figure of 1 electrode plates of the embodiment of the present invention 1 and comparative example；
Fig. 7: the specific resistance figure of 1 electrode plates of the embodiment of the present invention 1 and comparative example；
Fig. 8: the energy density figure of the embodiment of the present invention 1 and 1 electrode plates of comparative example in 2.7V；
Fig. 9: the cycle performance figure of 1 electrode plates of the embodiment of the present invention 1 and comparative example.
Specific embodiment
In order to illustrate more clearly of technical solution of the present invention and technical effect, below with reference to drawings and examples to this
Invention is described further.
Embodiment 1
A kind of preparation method of the electrode plates for graphene-based supercapacitor the following steps are included:
1) it prepares Laminated Graphite alkene slurry: dispersing the 2.5g graphene of physics removing preparation and 0.5g carbon nanotube in
Slurry is formed in 50ml water；
2) porous graphene slurry is prepared: by the 25g graphene of chemical oxidization method preparation, 5g carbon nanotube, 50g hydroxide
Potassium, which is scattered in 100ml water, forms slurry；
3) electrode plates are prepared: step 1) and 2) gained mixed slurry are painted on matrix in succession, in an inert atmosphere,
2h is heated at a temperature of 800 DEG C, gained sample is cleaned with the salt acid soak 2h of 1M, then washes with water, 100 DEG C of dry 10h,
The direct roll-in of sample after drying is obtained into electrode plates.
Fig. 1 show Laminated Graphite alkene layer (current collector layers), it can be seen that Laminated Graphite alkene layer surface is uniformly dispersed, and does not have
Big defect.Porous graphene layer (active material layer) shown in Fig. 2 shows also preferable, the Er Qieji of dispersibility of porous graphene
Tool intensity is high.Scanning electron microscope detection (SEM) is carried out to the current collector layers that the present embodiment obtains, as shown in figure 3, graphene sheet layer
Size is consistent, is uniformly dispersed；Fig. 4 show the SEM figure of porous graphene layer, it can be seen that porous graphene layer has apparent
Porous structure, this porous structure are conducive to the diffusion and transmission of electrolyte ion.Fig. 5 show the profile scanning of electrode plates
Figure, it can be seen that Laminated Graphite alkene layer and porous graphene layer closely connect, and are not detached from, while the thickness of Laminated Graphite alkene layer
About 20 microns, the thickness of porous graphene layer is also 20 microns.
Capacity measurement is carried out to electrode plates,
Cs=4Ccell
As shown in fig. 6, (this data is button cell to the specific capacitance 31.2F/g of supercapacitor in the case where 1mV/s sweeps speed
Specific capacitance, the specific capacitance of material are 124.8F/g), speed, which is swept, from 1mV/s sweeps speed, capacity retention ratio 55% to 200mV/s.Into one
Step tests its electrochemical impedance as shown in fig. 7, can include semicircle (capacitance resistance) and directly with the resistance of electrode plates from figure
Line (diffusion resistance) two parts.By comparison, it will be seen that the capacitance resistance and diffusion resistance of electrode plates are good due to graphene
The close contact of electric conductivity and porous graphene layer and Laminated Graphite alkene current collector layers, so that internal resistance is substantially reduced.By calculating,
The energy densities of electrode plates can be seen from the chart the electrode pole of the present embodiment as shown in figure 8, be 6.8Wh/kg in 2.7V
The energy density of piece is apparently higher than the energy density (5.2Wh/kg) of the electrode plates of comparative example 1, and main cause may be graphite
The quality of alkene is significantly lower than the quality of aluminium foil, so that Unit Weight, the ratio of active material is improved, so that energy is close
Degree is obviously improved.Further to its loop test as shown in figure 9, the capacity of electrode plates is kept after 10000 circulations
Rate is 91%, shows the excellent cycle performance of electrode plates.
Embodiment 2
A kind of preparation method of the electrode plates for graphene-based supercapacitor the following steps are included:
1) it prepares Laminated Graphite alkene slurry: dispersing 80ml for the 5g graphene of physics removing preparation and 0.5g carbon nanotube
Slurry is formed in water；
2) porous graphene slurry is prepared: by the 30g graphene of chemical oxidization method preparation, 5g carbon nanotube, 70g hydroxide
Sodium, which is scattered in 200ml water, forms slurry；
3) electrode plates are prepared: step 1) and 2) gained mixed slurry are painted on matrix in succession, in an inert atmosphere,
1h is heated at a temperature of 1000 DEG C, acquired sample is cleaned with the salt acid soak 2h of 1M, then washes with water, 100 DEG C of dryings
The direct roll-in of sample after drying is obtained electrode plates by 10h.
Embodiment 3
A kind of preparation method of the electrode plates for graphene-based supercapacitor the following steps are included:
1) it prepares Laminated Graphite alkene slurry: dispersing 90ml for the 5g graphene of physics removing preparation and 0.5g carbon nanotube
Slurry is formed in water；
2) porous graphene slurry is prepared: by the 100g graphene of chemical oxidization method preparation, 5g carbon nanotube, 400g cobalt
Grain, which is scattered in 900ml water, forms slurry；
3) electrode plates are prepared: step 1) and 2) gained mixed slurry are painted on matrix in succession, in an inert atmosphere,
8h is heated at a temperature of 500 DEG C, gained sample is cleaned with the salt acid soak 2h of 1M, then washes with water, 100 DEG C of dry 10h,
The direct roll-in of sample after drying is obtained into electrode plates.
Embodiment 4
A kind of preparation method of the electrode plates for graphene-based supercapacitor the following steps are included:
1) it prepares Laminated Graphite alkene slurry: dispersing 150ml for the 5g graphene of physics removing preparation and 0.3g carbon fiber
Slurry is formed in water；
2) porous graphene slurry is prepared: by the 50g graphene of chemical oxidization method preparation, 20g carbon nanotube, 150g nickel
Grain, which is scattered in 260ml water, forms slurry；
3) electrode plates are prepared: step 1) and 2) gained mixed slurry are painted on matrix in succession, in an inert atmosphere,
6h is heated at a temperature of 700 DEG C, obtained sample is cleaned with the salt acid soak 2h of 1M, then washes with water, 100 DEG C of dryings
The direct roll-in of sample after drying is obtained electrode plates by 10h.
Embodiment 5
A kind of preparation method of the electrode plates for graphene-based supercapacitor the following steps are included:
1) it prepares Laminated Graphite alkene slurry: dispersing 60ml water for the 5g graphene of physics removing preparation and 0.8g carbon fiber
Middle formation slurry；
2) porous graphene slurry is prepared: by the 200g graphene of chemical oxidization method preparation, 5g carbon nanotube, 250g carbonic acid
Sodium, which is scattered in 1200ml water, forms slurry；
3) electrode plates are prepared: step 1) and 2) gained mixed slurry are painted on matrix in succession, in an inert atmosphere,
5h is heated at a temperature of 1100 DEG C, obtained sample is cleaned with the salt acid soak 2h of 1M, then washes with water, 100 DEG C dry
Dry 10h, by the direct roll-in, that is, electrode plates of the sample after drying.
Comparative example 1
It disperses the 25g graphene of chemical oxidization method preparation, 5g carbon nanotube, 50g potassium hydroxide in 100ml water and is formed
Mixed slurry；By obtained mixed slurry brushing in foil substrate, in an inert atmosphere, at a temperature of 800 DEG C, 2h is heated,
Obtained sample is cleaned with the salt acid soak 2h of 1M, then is washed with water, 100 DEG C of dry 10h, by the sample after drying
Direct roll-in obtains electrode plates.
Using the performance of electro-chemical test electrode plates, as shown in fig. 6, in the case where 1mV/s sweeps speed, the ratio electricity of supercapacitor
Hold 27F/g, sweeps speed from 1mV/s and sweep speed, capacity retention ratio 51%, analysis shows the electrode plates of this comparative example to 200mV/s
Capacitive property be significantly lower than embodiment 1 electrode plates, electrode plates of the high rate performance also below embodiment 1.Further
Electrochemical impedance is tested as shown in fig. 7, the capacitance resistance of this comparative example electrode plates and diffusion resistance are all high as seen from the figure
In 1 electrode plates of embodiment, main cause may be active material contacted with the interface of aluminum foil current collector it is obvious not strictly according to the facts
Active material layer in 1 electrode slice of example is applied to contact with current collector layers.By calculating, the energy density of this comparative example electrode plates is such as
Shown in Fig. 8, in 2.7V, only 5.2Wh/kg, lower than the energy density (6.8Wh/kg) of 1 electrode plates of embodiment.It is right simultaneously
Test has also been made in cycle performance, as shown in figure 9, after 10000 circulations, capacity retention ratio 84%, lower than being the electricity of embodiment 1
Pole pole piece (91%).
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (5)
1. a kind of electrode plates for graphene-based supercapacitor, the electrode plates include current collector layers and active material
Layer, which is characterized in that the current collector layers are Laminated Graphite alkene layer, and the active material layer is porous graphene layer；
The Laminated Graphite alkene layer includes carbon nanotube or/and carbon fiber；The porous graphene layer include carbon nanotube or/and
Carbon fiber；
The graphene and carbon fiber of the Laminated Graphite alkene layer or the mass ratio of carbon nanotube are 5~50:1；The porous graphite
The graphene and carbon fiber of alkene layer or the mass ratio of carbon nanotube are 5~50:1；
The graphene of the Laminated Graphite alkene layer is 1~10 layer of the graphene film that physics is removed；The porous graphene
The graphene of layer is graphene made from chemical oxidization method；
The graphene film of the physics removing is single layer, and lateral dimension is 1~100 μm；
The preparation methods of the electrode plates the following steps are included:
1) it prepares Laminated Graphite alkene slurry: the graphene of physics removing and carbon nanotube or/and carbon fiber is dispersed in water system
Obtain the slurry that solid content is 1%~10%；
2) it prepares porous graphene slurry: dividing graphene made from chemical oxidization method and pore creating material according to the mass ratio of 1:1~5
Yu Shuizhong is dissipated, and carbon nanotube or/and carbon fiber formation solid content is added as 1%~10% slurry；
3) electrode plates are prepared: step 1) and 2) gained mixed slurry are painted on matrix in succession, in an inert atmosphere, in
At a temperature of 400~1200 DEG C, successively pickling and washing after 0.5~12h is heated, roll-in obtains electrode plates after drying.
2. electrode plates according to claim 1, which is characterized in that the Laminated Graphite alkene layer with a thickness of 0.5~50 μ
M, the porous graphene layer with a thickness of 10~100 μm.
3. electrode plates according to claim 1, which is characterized in that slurry solid content described in step 1) be 2%~
5%.
4. electrode plates according to claim 1, which is characterized in that pore creating material described in step 2) is selected from hydroxide
In potassium, potassium oxide, potassium carbonate, sodium carbonate, sodium oxide molybdena, sodium hydroxide, metal nickel particle, iron granule and metal cobalt granule
One or more of combinations；The mass ratio of graphene made from the pore creating material and chemical oxidization method is 2:1.
5. electrode plates according to claim 4, which is characterized in that the Laminated Graphite alkene layer with a thickness of 20 μm, institute
State porous graphene layer with a thickness of 20 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610011998.4A CN105679548B (en) | 2016-01-08 | 2016-01-08 | A kind of electrode plates and preparation method thereof for graphene-based supercapacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610011998.4A CN105679548B (en) | 2016-01-08 | 2016-01-08 | A kind of electrode plates and preparation method thereof for graphene-based supercapacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105679548A CN105679548A (en) | 2016-06-15 |
| CN105679548B true CN105679548B (en) | 2019-11-01 |
Family
ID=56299621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610011998.4A Active CN105679548B (en) | 2016-01-08 | 2016-01-08 | A kind of electrode plates and preparation method thereof for graphene-based supercapacitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105679548B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106158429A (en) * | 2016-08-24 | 2016-11-23 | 刘爽 | The method manufacturing graphene-based ultracapacitor |
| CN106475092B (en) * | 2016-11-23 | 2019-08-20 | 陕西瑞科新材料股份有限公司 | A kind of preparation method of alumina base platinum catalyst |
| CN107342173B (en) * | 2017-07-10 | 2019-02-19 | 中国科学院宁波材料技术与工程研究所 | A kind of flexible super capacitor electrode and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102354609A (en) * | 2011-08-23 | 2012-02-15 | 吉林大学 | Method for preparing graphene-nickel hydroxide composite electrode material for super capacitor |
| CN102403050A (en) * | 2010-09-08 | 2012-04-04 | 中国科学院金属研究所 | Composite material based on nanometer, preparation method of composite material and application in flexible energy storage device |
| CN103450477A (en) * | 2012-05-31 | 2013-12-18 | 海洋王照明科技股份有限公司 | Preparation method of graphene composite current collector |
| CN104425134A (en) * | 2014-11-11 | 2015-03-18 | 超威电源有限公司 | High-porosity and high-conductivity porous electrode, batch manufacturing process of porous electrode and super pseudo-capacitor using porous electrode |
| WO2015126464A2 (en) * | 2013-10-11 | 2015-08-27 | The Regents Of The University Of California | Stacked multilayers of alternating reduced graphene oxide and carbon nanotubes for ultrathin planar supercapacitors |
-
2016
- 2016-01-08 CN CN201610011998.4A patent/CN105679548B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102403050A (en) * | 2010-09-08 | 2012-04-04 | 中国科学院金属研究所 | Composite material based on nanometer, preparation method of composite material and application in flexible energy storage device |
| CN102354609A (en) * | 2011-08-23 | 2012-02-15 | 吉林大学 | Method for preparing graphene-nickel hydroxide composite electrode material for super capacitor |
| CN103450477A (en) * | 2012-05-31 | 2013-12-18 | 海洋王照明科技股份有限公司 | Preparation method of graphene composite current collector |
| WO2015126464A2 (en) * | 2013-10-11 | 2015-08-27 | The Regents Of The University Of California | Stacked multilayers of alternating reduced graphene oxide and carbon nanotubes for ultrathin planar supercapacitors |
| CN104425134A (en) * | 2014-11-11 | 2015-03-18 | 超威电源有限公司 | High-porosity and high-conductivity porous electrode, batch manufacturing process of porous electrode and super pseudo-capacitor using porous electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105679548A (en) | 2016-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108520985B (en) | Method for prolonging cycle life of zinc battery and application thereof | |
| CN108630920A (en) | A kind of nano-metal-oxide/MXene heterojunction structure composite material and preparation methods | |
| CN104916447B (en) | A kind of ultracapacitor high magnification porous carbon electrode material and preparation method | |
| CN106340633B (en) | A kind of high performance lithium ion battery composite nano materials and preparation method thereof | |
| Yang et al. | Cobalt–carbon derived from zeolitic imidazolate framework on Ni foam as high-performance supercapacitor electrode material | |
| CN106517133B (en) | Ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous structure and its preparation method and application | |
| CN104715936B (en) | A kind of classifying porous carbon electrode material and preparation method for ultracapacitor | |
| CN104495788A (en) | Preparation method of porous carbon | |
| CN105810456B (en) | A kind of activated graphene/needle-like nickel hydroxide nano composite and preparation method thereof | |
| CN106882841A (en) | A kind of titanium dioxide nano thread/two-dimensional layer carbonization titanium composite material and its low temperature preparation method | |
| CN105679548B (en) | A kind of electrode plates and preparation method thereof for graphene-based supercapacitor | |
| CN107244664A (en) | The preparation method and application of class graphene-structured carbon electrode material | |
| CN108545712A (en) | A method of synthesizing multi-stage porous carbon material with salt template carbonization ZIF-8 | |
| Wu et al. | Enhanced electrochemical performance of nickel hydroxide electrode with monolayer hollow spheres composed of nanoflakes | |
| CN108807961A (en) | A kind of zinc-base cell negative electrode material and preparation method thereof | |
| CN110364732A (en) | With the compound zinc load and preparation method and application of inorganic functional decorative layer in a kind of water system battery | |
| CN106024402A (en) | Supercapacitor carbon/titanium carbide core casing composite ball electrode material and preparation method thereof | |
| CN108046254A (en) | A kind of corncob derives active carbon electrode material and preparation method thereof | |
| CN104716311A (en) | Tin bisulfide nanosheet composite material, as well as preparation method and application thereof | |
| CN105609325B (en) | A kind of LaNiO with hollow structure3Sub-meter grade microballoon electrode material preparation method | |
| CN105776195B (en) | Preparation method and product of a kind of ultracapacitor rich in micro-nano hole superstructure porous graphene | |
| CN109360961B (en) | Hollow composite microsphere for lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN113314770B (en) | Alkaline secondary battery and preparation method thereof | |
| CN110491684A (en) | Needle-shaped colored cobalt nickel bimetal hydroxide composite material and its preparation method and application | |
| CN107221458A (en) | Nickel complex is carbon dope nickel oxide combination electrode material of precursor and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |