CN107017096A - A kind of preparation method and applications of modified graphite electrode material - Google Patents
A kind of preparation method and applications of modified graphite electrode material Download PDFInfo
- Publication number
- CN107017096A CN107017096A CN201710212790.3A CN201710212790A CN107017096A CN 107017096 A CN107017096 A CN 107017096A CN 201710212790 A CN201710212790 A CN 201710212790A CN 107017096 A CN107017096 A CN 107017096A
- Authority
- CN
- China
- Prior art keywords
- electrode material
- modified graphite
- deionized water
- graphite electrode
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000007772 electrode material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000008367 deionised water Substances 0.000 claims abstract description 44
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 33
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 32
- 239000010439 graphite Substances 0.000 claims abstract description 32
- 238000000498 ball milling Methods 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 28
- 230000004913 activation Effects 0.000 claims abstract description 27
- 238000003763 carbonization Methods 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000012046 mixed solvent Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 11
- 239000006258 conductive agent Substances 0.000 claims abstract description 9
- 238000012545 processing Methods 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 24
- 238000001291 vacuum drying Methods 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000012065 filter cake Substances 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000002845 discoloration Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 230000004044 response Effects 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000007767 bonding agent Substances 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 239000003990 capacitor Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002085 enols Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
- H01G11/84—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 invention discloses the preparation method and applications of modified graphite electrode material, the technique after graphite oxidation by will obtain graphite oxide, again with the processing of ammoniacal liquor Hybrid Heating, then high-temperature process obtains activation products under nitrogen protection, it is modified again, then it is placed in reactor and adds the mixed solvent of deionized water and absolute ethyl alcohol, polyvinylpyrrolidone and positive silicic acid propyl ester, intermediate is obtained after high-temperature process, then by intermediate curing process, ball-milling treatment, carbonization treatment, finally add neopelex, magnetic iron powder, nickel hydroxide, conductive agent, binding agent, it is agitated, coating, drying, electrode slice is made in the steps such as roll-in.The modified graphite electrode material being prepared from, its specific surface area is big, and quality specific capacitance is high, and power density is big, with preferable application prospect.Also disclose simultaneously as application of the modified graphite electrode material in ultracapacitor is prepared made from the preparation technology.
Description
Technical field
The present invention relates to this technical field of capacitor material, the preparation method of modified graphite electrode material is related specifically to
And its application.
Background technology
Ultracapacitor is a kind of electrification between battery and traditional capacitor, based on electrode/electrolyte interface
The energy-storage travelling wave tube of process, the characteristics of it has big ordinary capacitor power density and high storage battery energy density concurrently, with excellent
Continuous fast charging and discharging performance, have extended cycle life, power density is high, temperature in use scope is wide, it is environmentally friendly the advantages of.It is super
Level capacitor all has wide practical use in many fields, such as mobile communication, information technology, Aero-Space, science and techniques of defence, the people
With field or adjustment electric load, storage electric power are individually used for, or with fuel cell, solar cell, wind-power electricity generation, internal combustion engine etc.
The device for producing electric energy is used in mixed way.
Ultracapacitor can be divided into double electric layers supercapacitor by energy storage mechnism and Faradic pseudo-capacitor (is called counterfeit electricity
Hold).But either double layer capacitor or Faradic pseudo-capacitor, the process of its energy storage occur mainly in the table of electrode
Face.Specific capacitance, electric conductivity, specific surface area and the structural stability of electrode material are super capacitor energy storage and conversion performance
Determinant.Therefore, in order to improve energy density and power density, either double electric layers supercapacitor, faraday are accurate electric
Container, or both hybrid super capacitors, its electrode material must possess that specific surface area is big, electrical conductivity is high and Stability Analysis of Structures
Etc. characteristic.
The carbon material of carbon material particularly Heteroatom doping has the characteristics such as high-specific surface area, high conductivity, high thermal conductivity,
There is specific capacitance height, high rate during charging-discharging, high power density and the spy such as have extended cycle life with its ultracapacitor prepared
Property, and aboundresources, various structures, moderate cost, are one of mostly important electrode materials in ultracapacitor.However, passing
The carbon material of system often has that specific surface area is small, and quality specific capacitance is low, the problems such as power density is small, and this is accomplished by by entering to it
The series of process operation such as modified of going reaches the purpose for improving it as electrode material performance.
The content of the invention
In order to solve the above technical problems, the present invention provides the preparation method of modified graphite electrode material, the technique is by inciting somebody to action
Graphite oxide is obtained after graphite oxidation, then is handled with ammoniacal liquor Hybrid Heating, then high-temperature process is lived under nitrogen protection
Change product, then be modified, be then placed in reactor and add mixed solvent, the polyvinyl pyrrole of deionized water and absolute ethyl alcohol
Alkanone and positive silicic acid propyl ester, obtain intermediate after high-temperature process, then by intermediate curing process, ball milling
Reason, carbonization treatment, finally add neopelex, magnetic iron powder, nickel hydroxide, conductive agent, binding agent, agitated,
Electrode slice is made in the steps such as coating, drying, roll-in.The modified graphite electrode material being prepared from, its specific surface area is big, mass ratio
Electric capacity is high, and power density is big, with preferable application prospect.Also disclose simultaneously as modified graphite electricity made from the preparation technology
Application of the pole material in ultracapacitor is prepared.
The purpose of the present invention can be achieved through the following technical solutions：
The preparation method of modified graphite electrode material, comprises the following steps：
（1）The sulfuric acid of 50 g graphite and 120 mL mass concentrations 85% is added in reaction vessel jointly, under 45 DEG C of water-bath
15-25 min are incubated, 15-20g potassium permanganate is added, temperature 70 DEG C are risen to rapidly after maintaining 10 min, with 200
Rpm speed stirring reaction 80-90 min, question response terminates to add the dioxygen that 300 mL mass fractions are 2.5% in backward container
Water, mixed liquor is stirred to discoloration, filter while hot with 150 rpm speed, by the gained filter cake hydrochloric acid solution of mass concentration 3%
Washing 2 times, then be washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C and dries 8h, graphite is obtained
Oxide；
（2）By step（1）Obtained graphite oxide is mixed with 250 mL concentration for 20% ammoniacal liquor, is then placed in mixed liquor
30-40 min are heated in 85 DEG C of baking oven, thick slurry is obtained, then under nitrogen protection at 1000-1200 DEG C at high temperature
1.5h is managed, high-temperature activation product is obtained, high-temperature activation product is tentatively neutralized with watery hydrochloric acid, then with deionized water by high temperature
Activation products are washed 3-5 times and neutrality are fully achieved to pH, are placed in 70 DEG C of vacuum drying chambers and are dried 8h, obtain modified graphite oxidation
Thing；
（3）By step（2）Obtained modified graphite oxide is as the deionized water that in reactor, adds 300 mL and anhydrous
The volume ratio of alcohol mixed solvent, deionized water and absolute ethyl alcohol is 1.5, and 15 are stirred at 200 DEG C with 1200 rpm speed
Min, then adds 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters, then heats to 250 DEG C, stirring reaction 2-3 h,
Obtained product is centrifuged according to 3000 rpm rotating speed, gained sediment is washed with deionized water, be placed in 90 DEG C
6 h are dried in vacuum drying chamber, intermediate is obtained；
（4）By step（3）Gained intermediate is put into the h of curing process 15 in 220 DEG C of drying box, is then used ball milling
Machine ball milling 2-3 h, powder obtained by ball milling is placed in atmosphere tube type stove, and carbonization treatment, treatment temperature are carried out under argon gas protection
For 950 DEG C, processing time is 5 h, obtains carbonization compound；
（5）By step（4）Obtained carbonization compound, neopelex, magnetic iron powder, nickel hydroxide, conductive agent, bonding
Agent according to（65-70）:（11-13）:（7-9）:（5-8）:（3-5）:（2-4）Ratio mixing, add appropriate amount of deionized water, stirring
It is uniform to be coated in thick on stainless (steel) wire, then it is dried into 8-24 h in 80-130 DEG C of vacuum drying chamber, through roll-in
After be cut into electrode slice, obtain finished product.
Preferably, the step（4）Diameter of particle after middle ball milling is less than 2 μm.
Preferably, the step（5）Middle carbonization compound, neopelex, magnetic iron powder, nickel hydroxide, conduction
Agent, binding agent are according to 68:11:8:7:4:3 ratio mixing.
Preferably, the step（5）In conductive agent it is any one in acetylene black, CNT carbon black, activated carbon
Kind.
Preferably, the step（5）In binding agent in sodium carboxymethylcellulose, hexafluoropropene, polyvinyl alcohol
Any one.
Present invention also offers the modified graphite electrode material obtained by above-mentioned preparation technology in ultracapacitor is prepared
Application.
Compared with prior art, its advantage is the present invention：
（1）The modified graphite electrode material preparation process of the present invention by will obtain graphite oxide after graphite oxidation, then with ammonia
The processing of water Hybrid Heating, then high-temperature process obtains activation products under nitrogen protection, then is modified, and is then placed in reactor
It is middle to add deionized water and mixed solvent, polyvinylpyrrolidone and the positive silicic acid propyl ester of absolute ethyl alcohol, after high-temperature process
To intermediate, then by intermediate curing process, ball-milling treatment, carbonization treatment, detergent alkylate is finally added
Electrode slice is made in sodium sulfonate, magnetic iron powder, nickel hydroxide, conductive agent, binding agent, the step such as agitated, coating, drying, roll-in.System
Standby modified graphite electrode material, its specific surface area is big, and quality specific capacitance is high, and power density is big, with preferable application
Prospect.
（2）Modified graphite electrode material feedstock of the invention is cheap, technique is simple, is used suitable for heavy industrialization, real
It is strong with property.
Embodiment
The technical scheme of invention is described in detail with reference to specific embodiment.
Embodiment 1
（1）The sulfuric acid of 50 g graphite and 120 mL mass concentrations 85% is added in reaction vessel jointly, under 45 DEG C of water-bath
15 min are incubated, 15g potassium permanganate is added, temperature 70 DEG C are risen to rapidly after maintaining 10 min, with 200 rpm speed
The min of rate stirring reaction 80, question response terminates to add the hydrogen peroxide that 300 mL mass fractions are 2.5% in backward container, with 150
Rpm speed stirs mixed liquor to discoloration, filters while hot, and gained filter cake is washed 2 times with the hydrochloric acid solution of mass concentration 3%, then
It is washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C and dries 8h, graphite oxide is obtained；
（2）By step（1）Obtained graphite oxide is mixed with 250 mL concentration for 20% ammoniacal liquor, is then placed in mixed liquor
30 min are heated in 85 DEG C of baking oven, thick slurry is obtained, then obtained under nitrogen protection in high-temperature process 1.5h at 1000 DEG C
To high-temperature activation product, high-temperature activation product is tentatively neutralized with watery hydrochloric acid, then with deionized water by high-temperature activation product
Wash 3 times and neutrality is fully achieved to pH, be placed in 70 DEG C of vacuum drying chambers and dry 8h, obtain modified graphite oxide；
（3）By step（2）Obtained modified graphite oxide is as the deionized water that in reactor, adds 300 mL and anhydrous
The volume ratio of alcohol mixed solvent, deionized water and absolute ethyl alcohol is 1.5, and 15 are stirred at 200 DEG C with 1200 rpm speed
Min, then adds 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters, then heats to 250 DEG C, the h of stirring reaction 2 will
Obtained product is centrifuged according to 3000 rpm rotating speed, and gained sediment is washed with deionized water, is placed in 90 DEG C very
6 h are dried in empty drying box, intermediate is obtained；
（4）By step（3）Gained intermediate is put into the h of curing process 15 in 220 DEG C of drying box, is then used ball milling
The h of machine ball milling 2, gained diameter of particle is less than 2 μm, and powder obtained by ball milling is placed in atmosphere tube type stove, enters under argon gas protection
Row carbonization treatment, treatment temperature is 950 DEG C, and processing time is 5 h, obtains carbonization compound；
（5）By step（4）Obtained carbonization compound, neopelex, magnetic iron powder, nickel hydroxide, acetylene black, carboxylic first
Base sodium cellulosate is according to 68:11:8:7:4:3 ratio mixing, adds appropriate amount of deionized water, is evenly stirred until thick, coating
8 h are dried in 80 DEG C of vacuum drying chamber on stainless (steel) wire, then by it, electrode slice is cut into after roll-in, finished product is obtained.
The performance test results of obtained modified graphite electrode material are as shown in table 1.
Embodiment 2
（1）The sulfuric acid of 50 g graphite and 120 mL mass concentrations 85% is added in reaction vessel jointly, under 45 DEG C of water-bath
20 min are incubated, 17 g potassium permanganate is added, temperature 70 DEG C are risen to rapidly after maintaining 10 min, with 200 rpm's
The min of speed stirring reaction 85, question response terminates to add the hydrogen peroxide that 300 mL mass fractions are 2.5% in backward container, with 150
Rpm speed stirs mixed liquor to discoloration, filters while hot, and gained filter cake is washed 2 times with the hydrochloric acid solution of mass concentration 3%, then
It is washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C and dries 8h, graphite oxide is obtained；
（2）By step（1）Obtained graphite oxide is mixed with 250 mL concentration for 20% ammoniacal liquor, is then placed in mixed liquor
35 min are heated in 85 DEG C of baking oven, thick slurry is obtained, then obtained under nitrogen protection in high-temperature process 1.5h at 1100 DEG C
To high-temperature activation product, high-temperature activation product is tentatively neutralized with watery hydrochloric acid, then with deionized water by high-temperature activation product
Wash 4 times and neutrality is fully achieved to pH, be placed in 70 DEG C of vacuum drying chambers and dry 8h, obtain modified graphite oxide；
（3）By step（2）Obtained modified graphite oxide is as the deionized water that in reactor, adds 300 mL and anhydrous
The volume ratio of alcohol mixed solvent, deionized water and absolute ethyl alcohol is 1.5, and 15 are stirred at 200 DEG C with 1200 rpm speed
Min, then adds 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters, then heats to 250 DEG C, the h of stirring reaction 2.5,
Obtained product is centrifuged according to 3000 rpm rotating speed, gained sediment is washed with deionized water, be placed in 90 DEG C
6 h are dried in vacuum drying chamber, intermediate is obtained；
（4）By step（3）Gained intermediate is put into the h of curing process 15 in 220 DEG C of drying box, is then used ball milling
The h of machine ball milling 2.5, gained diameter of particle is less than 2 μm, and powder obtained by ball milling is placed in atmosphere tube type stove, under argon gas protection
Carbonization treatment is carried out, treatment temperature is 950 DEG C, and processing time is 5 h, obtains carbonization compound；
（5）By step（4）Obtained carbonization compound, neopelex, magnetic iron powder, nickel hydroxide, CNT carbon
Black, hexafluoropropene is according to 68:11:8:7:4:3 ratio mixing, adds appropriate amount of deionized water, is evenly stirred until thick, coating
16 h are dried in 105 DEG C of vacuum drying chamber on stainless (steel) wire, then by it, electrode slice is cut into after roll-in, finished product is obtained.
The performance test results of obtained modified graphite electrode material are as shown in table 1.
Embodiment 3
（1）The sulfuric acid of 50 g graphite and 120 mL mass concentrations 85% is added in reaction vessel jointly, under 45 DEG C of water-bath
25 min are incubated, 20 g potassium permanganate is added, temperature 70 DEG C are risen to rapidly after maintaining 10 min, with 200 rpm's
The min of speed stirring reaction 90, question response terminates to add the hydrogen peroxide that 300 mL mass fractions are 2.5% in backward container, with 150
Rpm speed stirs mixed liquor to discoloration, filters while hot, and gained filter cake is washed 2 times with the hydrochloric acid solution of mass concentration 3%, then
It is washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C and dries 8h, graphite oxide is obtained；
（2）By step（1）Obtained graphite oxide is mixed with 250 mL concentration for 20% ammoniacal liquor, is then placed in mixed liquor
40 min are heated in 85 DEG C of baking oven, thick slurry is obtained, then obtained under nitrogen protection in high-temperature process 1.5h at 1200 DEG C
To high-temperature activation product, high-temperature activation product is tentatively neutralized with watery hydrochloric acid, then with deionized water by high-temperature activation product
Wash 5 times and neutrality is fully achieved to pH, be placed in 70 DEG C of vacuum drying chambers and dry 8h, obtain modified graphite oxide；
（3）By step（2）Obtained modified graphite oxide is as the deionized water that in reactor, adds 300 mL and anhydrous
The volume ratio of alcohol mixed solvent, deionized water and absolute ethyl alcohol is 1.5, and 15 are stirred at 200 DEG C with 1200 rpm speed
Min, then adds 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters, then heats to 250 DEG C, the h of stirring reaction 3 will
Obtained product is centrifuged according to 3000 rpm rotating speed, and gained sediment is washed with deionized water, is placed in 90 DEG C very
6 h are dried in empty drying box, intermediate is obtained；
（4）By step（3）Gained intermediate is put into the h of curing process 15 in 220 DEG C of drying box, is then used ball milling
The h of machine ball milling 3, gained diameter of particle is less than 2 μm, and powder obtained by ball milling is placed in atmosphere tube type stove, enters under argon gas protection
Row carbonization treatment, treatment temperature is 950 DEG C, and processing time is 5 h, obtains carbonization compound；
（5）By step（4）Obtained carbonization compound, neopelex, magnetic iron powder, nickel hydroxide, activated carbon, poly- second
Enol is according to 68:11:8:7:4:3 ratio mixing, adds appropriate amount of deionized water, is evenly stirred until thick, be coated in stainless
On steel mesh, then it is dried into 24 h in 130 DEG C of vacuum drying chamber, electrode slice is cut into after roll-in, finished product is obtained.
The performance test results of obtained modified graphite electrode material are as shown in table 1.
Comparative example 1
（1）The sulfuric acid of 50 g graphite and 120 mL mass concentrations 85% is added in reaction vessel jointly, under 45 DEG C of water-bath
15 min are incubated, 15g potassium permanganate is added, temperature 70 DEG C are risen to rapidly after maintaining 10 min, with 200 rpm speed
The min of rate stirring reaction 80, question response terminates to add the hydrogen peroxide that 300 mL mass fractions are 2.5% in backward container, with 150
Rpm speed stirs mixed liquor to discoloration, filters while hot, and gained filter cake is washed 2 times with the hydrochloric acid solution of mass concentration 3%, then
It is washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C and dries 8h, graphite oxide is obtained；
（2）By step（1）Obtained graphite oxide is mixed with 250 mL concentration for 20% ammoniacal liquor, is then placed in mixed liquor
30 min are heated in 85 DEG C of baking oven, thick slurry is obtained, then obtained under nitrogen protection in high-temperature process 1.5h at 1000 DEG C
To high-temperature activation product, high-temperature activation product is tentatively neutralized with watery hydrochloric acid, then with deionized water by high-temperature activation product
Wash 3 times and neutrality is fully achieved to pH, be placed in 70 DEG C of vacuum drying chambers and dry 8h, obtain modified graphite oxide；
（3）By step（2）Obtained modified graphite oxide is as the deionized water that in reactor, adds 300 mL and anhydrous
The volume ratio of alcohol mixed solvent, deionized water and absolute ethyl alcohol is 1.5, and 15 are stirred at 200 DEG C with 1200 rpm speed
Min, then adds 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters, then heats to 250 DEG C, the h of stirring reaction 2 will
Obtained product is centrifuged according to 3000 rpm rotating speed, and gained sediment is washed with deionized water, is placed in 90 DEG C very
6 h are dried in empty drying box, intermediate is obtained；
（4）By step（3）Gained intermediate is put into the h of curing process 15 in 220 DEG C of drying box, is then used ball milling
The h of machine ball milling 2, gained diameter of particle is less than 2 μm, and powder obtained by ball milling is placed in atmosphere tube type stove, enters under argon gas protection
Row carbonization treatment, treatment temperature is 950 DEG C, and processing time is 5 h, obtains carbonization compound；
（5）By step（4）Obtained carbonization compound, neopelex, magnetic iron powder, nickel hydroxide, acetylene black, carboxylic first
Base sodium cellulosate is according to 75:10:5:12:9:5 ratio mixing, adds appropriate amount of deionized water, is evenly stirred until thick, coating
8 h are dried in 80 DEG C of vacuum drying chamber on stainless (steel) wire, then by it, electrode slice is cut into after roll-in, finished product is obtained.
The performance test results of obtained modified graphite electrode material are as shown in table 1.
Comparative example 2
（1）The sulfuric acid of 50 g graphite and 120 mL mass concentrations 85% is added in reaction vessel jointly, under 45 DEG C of water-bath
20 min are incubated, 17 g potassium permanganate is added, temperature 70 DEG C are risen to rapidly after maintaining 10 min, with 200 rpm's
The min of speed stirring reaction 85, question response terminates to add the hydrogen peroxide that 300 mL mass fractions are 2.5% in backward container, with 150
Rpm speed stirs mixed liquor to discoloration, filters while hot, and gained filter cake is washed 2 times with the hydrochloric acid solution of mass concentration 3%, then
It is washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C and dries 8h, graphite oxide is obtained；
（2）By step（1）Obtained graphite oxide is mixed with 250 mL concentration for 20% ammoniacal liquor, is then placed in mixed liquor
35 min are heated in 85 DEG C of baking oven, thick slurry is obtained, then obtained under nitrogen protection in high-temperature process 1.5h at 1100 DEG C
To high-temperature activation product, high-temperature activation product is tentatively neutralized with watery hydrochloric acid, then with deionized water by high-temperature activation product
Wash 4 times and neutrality is fully achieved to pH, be placed in 70 DEG C of vacuum drying chambers and dry 8h, obtain modified graphite oxide；
（3）By step（2）Obtained modified graphite oxide is as the deionized water that in reactor, adds 300 mL and anhydrous
The volume ratio of alcohol mixed solvent, deionized water and absolute ethyl alcohol is 1.5, and 15 are stirred at 200 DEG C with 1200 rpm speed
Min, then adds 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters, then heats to 250 DEG C, the h of stirring reaction 2.5,
Obtained product is centrifuged according to 3000 rpm rotating speed, gained sediment is washed with deionized water, be placed in 90 DEG C
6 h are dried in vacuum drying chamber, intermediate is obtained；
（4）By step（3）Gained intermediate is put into the h of curing process 15 in 220 DEG C of drying box, is then used ball milling
The h of machine ball milling 2.5, gained diameter of particle is less than 2 μm；
（5）By step（4）Obtained powder, neopelex, magnetic iron powder, nickel hydroxide, CNT carbon black, hexafluoro
Propylene is according to 68:11:8:7:4:3 ratio mixing, adds appropriate amount of deionized water, is evenly stirred until thick, be coated in stainless
On steel mesh, then it is dried into 16 h in 105 DEG C of vacuum drying chamber, electrode slice is cut into after roll-in, finished product is obtained.
The performance test results of obtained modified graphite electrode material are as shown in table 1.
Comparative example 3
（1）The sulfuric acid of 50 g graphite and 120 mL mass concentrations 75% is added in reaction vessel jointly, under 70 DEG C of water-bath
25 min are incubated, 30g potassium permanganate is added, temperature 70 DEG C are risen to rapidly after maintaining 10 min, with 200 rpm speed
The min of rate stirring reaction 90, question response terminates to add the hydrogen peroxide that 300 mL mass fractions are 2.5% in backward container, with 150
Rpm speed stirs mixed liquor to discoloration, filters while hot, and gained filter cake is washed 2 times with the hydrochloric acid solution of mass concentration 3%, then
It is washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C and dries 8h, graphite oxide is obtained；
（2）By step（1）Obtained graphite oxide is mixed with 250 mL concentration for 20% ammoniacal liquor, is then placed in mixed liquor
40 min are heated in 60 DEG C of baking oven, thick slurry is obtained, then obtained under nitrogen protection in high-temperature process 1.5h at 1000 DEG C
To high-temperature activation product, high-temperature activation product is tentatively neutralized with watery hydrochloric acid, then with deionized water by high-temperature activation product
Wash 5 times and neutrality is fully achieved to pH, be placed in 70 DEG C of vacuum drying chambers and dry 8h, obtain modified graphite oxide；
（3）By step（2）Obtained modified graphite oxide is as the deionized water that in reactor, adds 300 mL and anhydrous
The volume ratio of alcohol mixed solvent, deionized water and absolute ethyl alcohol is 1.5, and 15 are stirred at 200 DEG C with 1200 rpm speed
Min, then adds 15 g polyvinylpyrrolidones and 10 g positive silicic acid propyl esters, then heats to 250 DEG C, the h of stirring reaction 3 will
Obtained product is centrifuged according to 3000 rpm rotating speed, and gained sediment is washed with deionized water, is placed in 90 DEG C very
6 h are dried in empty drying box, intermediate is obtained；
（4）By step（3）Gained intermediate is put into the h of curing process 15 in 220 DEG C of drying box, is then used ball milling
The h of machine ball milling 3, gained diameter of particle is less than 2 μm, and powder obtained by ball milling is placed in atmosphere tube type stove, enters under argon gas protection
Row carbonization treatment, treatment temperature is 950 DEG C, and processing time is 5 h, obtains carbonization compound；
（5）By step（4）Obtained carbonization compound, neopelex, magnetic iron powder, nickel hydroxide, activated carbon, poly- second
Enol is according to 68:11:8:7:4:3 ratio mixing, adds appropriate amount of deionized water, is evenly stirred until thick, be coated in stainless
On steel mesh, then it is dried into 24 h in 130 DEG C of vacuum drying chamber, electrode slice is cut into after roll-in, finished product is obtained.
The performance test results of obtained modified graphite electrode material are as shown in table 1.
By embodiment 1-3 and comparative example 1-3 obtained modified graphite electrode material respectively with 1 mol/L aqueous sodium sulfates
Liquid is electrolyte, and polypropylene film is that barrier film is assembled into after capacitor, in 1.5V voltages, 15 mA/cm2Carried out under current condition
This two performance tests of quality specific capacitance, power density, while determining its specific surface area.
Table 1
| Quality specific capacitance（F/g） | Power density（W/kg） | Specific surface area（m2/g） | |
| Embodiment 1 | 325.2 | 165.9 | 2320 |
| Embodiment 2 | 308.7 | 158.8 | 2260 |
| Embodiment 3 | 301.5 | 153.4 | 2170 |
| Comparative example 1 | 218.6 | 126.3 | 1830 |
| Comparative example 2 | 190.4 | 110.1 | 1650 |
| Comparative example 3 | 212.3 | 124.8 | 1740 |
The modified graphite electrode material preparation process of the present invention is mixed by will obtain graphite oxide after graphite oxidation, then with ammoniacal liquor
Close and heat, then high-temperature process obtains activation products under nitrogen protection, then is modified, be then placed in reactor and add
Enter deionized water and mixed solvent, polyvinylpyrrolidone and the positive silicic acid propyl ester of absolute ethyl alcohol, in being obtained after high-temperature process
Between compound, then by intermediate curing process, ball-milling treatment, carbonization treatment, finally add DBSA
Electrode slice is made in the steps such as sodium, magnetic iron powder, nickel hydroxide, conductive agent, binding agent are agitated, coating, drying, roll-in.Prepare and
Into modified graphite electrode material, its specific surface area is big, and quality specific capacitance is high, and power density is big, with preferable application prospect.
Modified graphite electrode material feedstock of the invention is cheap, technique is simple, is used suitable for heavy industrialization, practical.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair
Equivalent structure or equivalent flow conversion that bright description is made, or directly or indirectly it is used in other related technology necks
Domain, is included within the scope of the present invention.
Claims (6)
1. a kind of preparation method of modified graphite electrode material, it is characterised in that comprise the following steps：
（1）The sulfuric acid of 50 g graphite and 120 mL mass concentrations 85% is added in reaction vessel jointly, under 45 DEG C of water-bath
15-25 min are incubated, 15-20g potassium permanganate is added, temperature 70 DEG C are risen to rapidly after maintaining 10 min, with 200
Rpm speed stirring reaction 80-90 min, question response terminates to add the dioxygen that 300 mL mass fractions are 2.5% in backward container
Water, mixed liquor is stirred to discoloration, filter while hot with 150 rpm speed, by the gained filter cake hydrochloric acid solution of mass concentration 3%
Washing 2 times, then be washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C and dries 8h, graphite is obtained
Oxide；
（2）By step（1）Obtained graphite oxide is mixed with 250 mL concentration for 20% ammoniacal liquor, is then placed in mixed liquor
30-40 min are heated in 85 DEG C of baking oven, thick slurry is obtained, then under nitrogen protection at 1000-1200 DEG C at high temperature
1.5h is managed, high-temperature activation product is obtained, high-temperature activation product is tentatively neutralized with watery hydrochloric acid, then with deionized water by high temperature
Activation products are washed 3-5 times and neutrality are fully achieved to pH, are placed in 70 DEG C of vacuum drying chambers and are dried 8h, obtain modified graphite oxidation
Thing；
（3）By step（2）Obtained modified graphite oxide is as the deionized water that in reactor, adds 300 mL and anhydrous
The volume ratio of alcohol mixed solvent, deionized water and absolute ethyl alcohol is 1.5, and 15 are stirred at 200 DEG C with 1200 rpm speed
Min, then adds 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters, then heats to 250 DEG C, stirring reaction 2-3 h,
Obtained product is centrifuged according to 3000 rpm rotating speed, gained sediment is washed with deionized water, be placed in 90 DEG C
6 h are dried in vacuum drying chamber, intermediate is obtained；
（4）By step（3）Gained intermediate is put into the h of curing process 15 in 220 DEG C of drying box, is then used ball milling
Machine ball milling 2-3 h, powder obtained by ball milling is placed in atmosphere tube type stove, and carbonization treatment, treatment temperature are carried out under argon gas protection
For 950 DEG C, processing time is 5 h, obtains carbonization compound；
（5）By step（4）Obtained carbonization compound, neopelex, magnetic iron powder, nickel hydroxide, conductive agent, bonding
Agent according to（65-70）:（11-13）:（7-9）:（5-8）:（3-5）:（2-4）Ratio mixing, add appropriate amount of deionized water, stirring
It is uniform to be coated in thick on stainless (steel) wire, then it is dried into 8-24 h in 80-130 DEG C of vacuum drying chamber, through roll-in
After be cut into electrode slice, obtain finished product.
2. the preparation method of modified graphite electrode material according to claim 1, it is characterised in that the step（4）In
Diameter of particle after ball milling is less than 2 μm.
3. the preparation method of modified graphite electrode material according to claim 1, it is characterised in that the step（5）In
Compound, neopelex, magnetic iron powder, nickel hydroxide, conductive agent, binding agent be carbonized according to 68:11:8:7:4:3
Ratio is mixed.
4. the preparation method of modified graphite electrode material according to claim 1, it is characterised in that the step（5）In
Any one in acetylene black, CNT carbon black, activated carbon of conductive agent.
5. the preparation method of modified graphite electrode material according to claim 1, it is characterised in that the step（5）In
Any one in sodium carboxymethylcellulose, hexafluoropropene, polyvinyl alcohol of binding agent.
6. ultracapacitor is being prepared according to the modified graphite electrode material that any one of the claim 1-5 preparation technologies are obtained
In application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710212790.3A CN107017096B (en) | 2017-04-01 | 2017-04-01 | A kind of preparation method and applications of modified graphite electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710212790.3A CN107017096B (en) | 2017-04-01 | 2017-04-01 | A kind of preparation method and applications of modified graphite electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107017096A true CN107017096A (en) | 2017-08-04 |
| CN107017096B CN107017096B (en) | 2019-07-19 |
Family
ID=59445355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710212790.3A Active CN107017096B (en) | 2017-04-01 | 2017-04-01 | A kind of preparation method and applications of modified graphite electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107017096B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112599741A (en) * | 2020-12-15 | 2021-04-02 | 广东凯金新能源科技股份有限公司 | Preparation method of modified graphite electrode material |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717081A (en) * | 2009-11-20 | 2010-06-02 | 哈尔滨工程大学 | Carbon/carbon composite material based on nano graphite sheet and preparation method thereof |
| CN101923962A (en) * | 2010-03-23 | 2010-12-22 | 集盛星泰(北京)科技有限公司 | Active carbon electrode and super capacitor containing same |
| US20110165321A1 (en) * | 2010-01-07 | 2011-07-07 | Aruna Zhamu | Continuous process for producing spacer-modified nano Graphene electrodes for supercapacitors |
| WO2012030415A1 (en) * | 2010-09-03 | 2012-03-08 | Board Of Regents, The University Of Texas System | Ultracapacitor with a novel carbon |
| CN102923698A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Preparation method for three-dimensional porous graphene for supercapacitor |
| CN103123967A (en) * | 2011-11-18 | 2013-05-29 | 宁波杉杉新材料科技有限公司 | SiO/C composite cathode material of lithium ion battery and preparation method of SiO/C composite cathode material |
| CN103280560A (en) * | 2013-05-20 | 2013-09-04 | 北京科技大学 | Preparation method of mesoporous SiOx/C composite negative material of lithium-ion battery |
| CN103787317A (en) * | 2014-01-02 | 2014-05-14 | 上海应用技术学院 | Preparation method of graphene oxide dispersion liquid |
| CN104064371A (en) * | 2014-06-20 | 2014-09-24 | 四川能宝电源制造有限公司 | Preparation method of Ni/C positive pole slurry and piece for super-capacitor battery |
| CN104810526A (en) * | 2015-04-02 | 2015-07-29 | 北京师范大学 | Preparation method and application of graphene based porous carbon supported metallic catalyst |
| CN104828810A (en) * | 2015-05-07 | 2015-08-12 | 中国人民解放军国防科学技术大学 | Preparation method of graphene aerogel with ultrahigh specific surface area |
| CN105551830A (en) * | 2015-12-22 | 2016-05-04 | 宁波南车新能源科技有限公司 | Preparation method of active graphene/active carbon composite electrode plate |
-
2017
- 2017-04-01 CN CN201710212790.3A patent/CN107017096B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717081A (en) * | 2009-11-20 | 2010-06-02 | 哈尔滨工程大学 | Carbon/carbon composite material based on nano graphite sheet and preparation method thereof |
| US20110165321A1 (en) * | 2010-01-07 | 2011-07-07 | Aruna Zhamu | Continuous process for producing spacer-modified nano Graphene electrodes for supercapacitors |
| CN101923962A (en) * | 2010-03-23 | 2010-12-22 | 集盛星泰(北京)科技有限公司 | Active carbon electrode and super capacitor containing same |
| WO2012030415A1 (en) * | 2010-09-03 | 2012-03-08 | Board Of Regents, The University Of Texas System | Ultracapacitor with a novel carbon |
| CN103123967A (en) * | 2011-11-18 | 2013-05-29 | 宁波杉杉新材料科技有限公司 | SiO/C composite cathode material of lithium ion battery and preparation method of SiO/C composite cathode material |
| CN102923698A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Preparation method for three-dimensional porous graphene for supercapacitor |
| CN103280560A (en) * | 2013-05-20 | 2013-09-04 | 北京科技大学 | Preparation method of mesoporous SiOx/C composite negative material of lithium-ion battery |
| CN103787317A (en) * | 2014-01-02 | 2014-05-14 | 上海应用技术学院 | Preparation method of graphene oxide dispersion liquid |
| CN104064371A (en) * | 2014-06-20 | 2014-09-24 | 四川能宝电源制造有限公司 | Preparation method of Ni/C positive pole slurry and piece for super-capacitor battery |
| CN104810526A (en) * | 2015-04-02 | 2015-07-29 | 北京师范大学 | Preparation method and application of graphene based porous carbon supported metallic catalyst |
| CN104828810A (en) * | 2015-05-07 | 2015-08-12 | 中国人民解放军国防科学技术大学 | Preparation method of graphene aerogel with ultrahigh specific surface area |
| CN105551830A (en) * | 2015-12-22 | 2016-05-04 | 宁波南车新能源科技有限公司 | Preparation method of active graphene/active carbon composite electrode plate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112599741A (en) * | 2020-12-15 | 2021-04-02 | 广东凯金新能源科技股份有限公司 | Preparation method of modified graphite electrode material |
| CN112599741B (en) * | 2020-12-15 | 2021-09-24 | 广东凯金新能源科技股份有限公司 | Preparation method of modified graphite electrode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107017096B (en) | 2019-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105253871B (en) | Ultracapacitor nitrogenous carbon material and preparation method thereof, electrode material for super capacitor | |
| CN103641174B (en) | Nano-sheet MnO 2-graphene composite material, its preparation method and ultracapacitor | |
| CN106024408B (en) | A kind of ruthenium-oxide-vulcanization carbon/carbon-copper composite material, using and a kind of electrode slice of ultracapacitor | |
| CN102522218A (en) | Nano nickel oxide/graphene composite electrode material as well as preparation method and application thereof | |
| CN105645410B (en) | 3D network pore structure Supercapacitor carbons and preparation method thereof | |
| CN107640757A (en) | A kind of preparation method of compound carbosphere and compound carbosphere and its lithium-ion capacitor being prepared | |
| CN107134372A (en) | Ultracapacitor based on transient metal sulfide/nitrogen-doped graphene Yu di-iron trioxide/graphene | |
| CN108557892A (en) | A kind of oxide preparation method and application for the manganese that object is mutually controllable | |
| CN105810456A (en) | Activated graphene/needle-shaped nickel hydroxide nanocomposite material and preparation method thereof | |
| CN108538612A (en) | A kind of preparation method of the N doping carbon/manganese dioxide composite electrode material of porous intercommunication network | |
| CN106067385A (en) | Preparation method as the manganese dioxide/conductive polymer nanometer network structure electrode material of ultracapacitor | |
| CN105788881B (en) | A kind of preparation method of nitrogen doped corrugated carbon nanotube | |
| CN106847532A (en) | A kind of preparation method of the high performance material for ultracapacitor | |
| CN111768976B (en) | Polypyrrole/silver/graphene oxide composite material and preparation method and application thereof | |
| CN104733189B (en) | Lithium ion-type supercapacitor ternary composite negative electrode material and preparation method thereof | |
| CN107017089B (en) | The preparation method and applications of supercapacitor nickel oxide combination electrode material | |
| CN112038113A (en) | Preparation method of polypyrrole nanotube and graphene material in super capacitor | |
| CN107017096A (en) | A kind of preparation method and applications of modified graphite electrode material | |
| CN110010360B (en) | Near-spherical nickel molybdate/subphthalocyanine composite material and preparation method and application thereof | |
| CN108010732A (en) | A kind of preparation of new nanocomposite applied to ultracapacitor | |
| CN101546652B (en) | Method for improving electric capacity of anode of electrochemical capacitor of organic system | |
| CN107093526A (en) | Electrode material preparation method and applications by main component of graphite oxide | |
| CN104835651B (en) | A kind of high durable activated carbon and the preparation method using its ultracapacitor | |
| CN111710532B (en) | Antimony trioxide-carbon nanotube composite material and preparation and application thereof | |
| CN105118680A (en) | Titanium-contained supercapacitor electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | 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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231212 Address after: 030600 500 meters northeast of Yitang Village, Yitang Town, Jiexiu City, Jinzhong City, Shanxi Province Patentee after: Jiexiu Jinsheng New Materials Co.,Ltd. Address before: 558 FenHu Avenue, Lili Town, Wujiang District, Suzhou City, Jiangsu Province Patentee before: SUZHOU HAILINGDA EIECTRONIC TECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right |