CN107017096B - 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
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- CN107017096B CN107017096B CN201710212790.3A CN201710212790A CN107017096B CN 107017096 B CN107017096 B CN 107017096B CN 201710212790 A CN201710212790 A CN 201710212790A CN 107017096 B CN107017096 B CN 107017096B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000007772 electrode material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 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 34
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 32
- 239000010439 graphite Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000003763 carbonization Methods 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000498 ball milling Methods 0.000 claims abstract description 22
- 230000004913 activation Effects 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 20
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 19
- 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 239000006258 conductive agent Substances 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 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
- 238000012545 processing Methods 0.000 claims description 10
- 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
- 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
- 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
- 238000005406 washing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 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 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000001768 carboxy methyl cellulose 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
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 239000003990 capacitor Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 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
- 238000007599 discharging Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 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 1
- 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 compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 239000002105 nanoparticle Substances 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010396 two-hybrid screening Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Manufacturing & Machinery (AREA)
- Fuel Cell (AREA)
Abstract
The invention discloses the preparation method and applications of modified graphite electrode material, the technique is by will obtain graphite oxide after graphite oxidation, it is handled again with ammonium hydroxide Hybrid Heating, then high-temperature process obtains activation products under nitrogen protection, it is modified again, then it is placed in reaction kettle and the mixed solvent of deionized water and dehydrated alcohol is added, 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, binder, it is agitated, coating, drying, roll-in and etc. electrode slice is made.The modified graphite electrode material being prepared, large specific surface area, quality specific capacitance is high, and power density is big, with good application prospect.Application of the modified graphite electrode material as made from the preparation process in preparation supercapacitor is also disclosed simultaneously.
Description
Technical field
The present invention relates to this technical fields of capacitor material, are related specifically to the preparation method of modified graphite electrode material
And its application.
Background technique
Supercapacitor is a kind of electrification between battery and traditional capacitor, based on electrode/electrolyte interface
The energy-storage travelling wave tube of process, it has the feature that ordinary capacitor power density is big and storage battery energy density is high concurrently, has excellent
Continuous fast charging and discharging performance, have extended cycle life, the advantages that power density is high, use temperature range is wide, environmentally friendly.It is super
Grade capacitor all has wide practical use in many fields, such as mobile communication, information technology, aerospace, science and techniques of defence, the people
With field or it is individually used for adjustment electric load, storage electric power, or with fuel cell, solar battery, wind-power electricity generation, internal combustion engine etc.
The device produced electricl energy is used in mixed way.
Supercapacitor can be divided into double electric layers supercapacitor by energy storage mechnism and Faradic pseudo-capacitor (is called counterfeit electricity
Hold).But the process of either double layer capacitor or Faradic pseudo-capacitor, energy storage occurs 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 is quasi- electric
Container or the two hybrid super capacitor, electrode material must have large specific surface area, conductivity height and stable structure
Etc. characteristics.
The carbon material of carbon material especially 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 with the supercapacitor of its preparation and have extended cycle life etc. special
Property, and resourceful, various structures, moderate cost, it is one of electrode material mostly important in supercapacitor.However, passing
Often there is the problems such as specific surface area is small, and quality specific capacitance is low, and power density is small in the carbon material of system, this just need by its into
The series of process operation such as modified of going achievees the purpose that improve it as electrode material performance.
Summary of the invention
In order to solve the above technical problems, the present invention provide modified graphite electrode material preparation method, the technique pass through by
Graphite oxide is obtained after graphite oxidation, then is handled with ammonium hydroxide Hybrid Heating, and then high-temperature process is lived under nitrogen protection
Change product, then be modified, is then placed in reaction kettle and mixed solvent, the polyvinyl pyrrole of deionized water and dehydrated alcohol is added
Alkanone and positive silicic acid propyl ester obtain intermediate after high-temperature process, then will be at intermediate curing process, ball milling
Reason, carbonization treatment, finally add neopelex, magnetic iron powder, nickel hydroxide, conductive agent, binder, agitated,
Coating, drying, roll-in and etc. electrode slice is made.The modified graphite electrode material being prepared, large specific surface area, mass ratio
Capacitor is high, and power density is big, with good application prospect.The electricity of the modified graphite as made from the preparation process is also disclosed simultaneously
Application of the pole material in preparation supercapacitor.
The purpose of the present invention can be achieved through the following technical solutions:
The preparation method of modified graphite electrode material, comprising the following steps:
(1) sulfuric acid of 50 g graphite and 120 mL mass concentrations 85% is added in reaction vessel jointly, in 45 DEG C of water
Bath is lower to keep the temperature 15-25 min, adds the potassium permanganate of 15-20g, temperature is risen to 70 DEG C rapidly after maintaining 10 min, with
The rate of 200 rpm is stirred to react 80-90 min, is 2.5% to add 300 mL mass fractions into container after reaction
Mixed liquor is stirred to discoloration with the rate of 150 rpm, is filtered while hot by hydrogen peroxide, by gained filter cake 3% hydrochloric acid of mass concentration
Solution washs 2 times, then is washed with deionized 2 times, and the filter cake after cleaning is placed in drying box at 75 DEG C dry 8h, is obtained
Graphite oxide；
(2) graphite oxide that step (1) obtains is mixed with the ammonium hydroxide that 250 mL concentration are 20%, then by mixed liquor
It is placed in heating 30-40 min in 85 DEG C of baking oven, obtains thick slurry, it is then high at 1000-1200 DEG C under nitrogen protection
Temperature processing 1.5h, obtains high-temperature activation product, is tentatively neutralized with dilute hydrochloric acid to high-temperature activation product, then will with deionized water
High-temperature activation product washs 3-5 times and neutrality is fully achieved to pH, is placed in 70 DEG C of vacuum ovens dry 8h, obtains modified graphite
Oxide；
(3) by modified graphite oxide that step (2) obtains as the deionized water in reaction kettle, adding 300 mL and
The volume ratio of dehydrated alcohol mixed solvent, deionized water and dehydrated alcohol is 1.5, is stirred at 200 DEG C with the rate of 1200 rpm
15 min are mixed, 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters are then added, then heats to 250 DEG C, is stirred to react 2-
Obtained product is centrifuged by 3 h according to the revolving speed of 3000 rpm, and gained sediment is washed with deionized water, is placed in
Dry 6 h, obtain intermediate in 90 DEG C of vacuum ovens；
(4) intermediate obtained by step (3) is put into 15 h of curing process in 220 DEG C of drying box, is then used
Powder obtained by ball milling is placed in atmosphere tube type furnace, carries out carbonization treatment under protection of argon gas by ball mill ball milling 2-3 h, handles
Temperature is 950 DEG C, and the processing time is 5 h, obtains carbonization compound；
(5) the carbonization compound that obtains step (4), neopelex, magnetic iron powder, nickel hydroxide, conductive agent,
Binder is according to (65-70): (11-13): (7-9): (5-8): (3-5): appropriate amount of deionized water is added in the ratio mixing of (2-4),
It is evenly stirred until thick, is coated on stainless (steel) wire, then it dry into 8-24 h in 80-130 DEG C of vacuum oven, warp
It is cut into electrode slice after roll-in, obtains finished product.
Preferably, the diameter of particle in the step (4) after ball milling is less than 2 μm.
Preferably, be carbonized compound, neopelex, magnetic iron powder, nickel hydroxide, conduction in the step (5)
Agent, binder are mixed according to the ratio of 68:11:8:7:4:3.
Preferably, the conductive agent in the step (5) is any one in acetylene black, carbon nanotubes carbon black, activated carbon
Kind.
Preferably, the binder in the step (5) is in sodium carboxymethylcellulose, hexafluoropropene, polyvinyl alcohol
Any one.
The present invention also provides the modified graphite electrode materials obtained by above-mentioned preparation process in preparation supercapacitor
Application.
Compared with prior art, the present invention has the advantages that:
(1) modified graphite electrode material preparation process of the invention is by will obtain graphite oxide after graphite oxidation, then
With the processing of ammonium hydroxide Hybrid Heating, then high-temperature process obtains activation products under nitrogen protection, then is modified, and is then placed in anti-
Mixed solvent, polyvinylpyrrolidone and the positive silicic acid propyl ester that deionized water and dehydrated alcohol are added in kettle are answered, through high-temperature process
After obtain intermediate, then by intermediate curing process, ball-milling treatment, carbonization treatment, finally add dodecane
Base benzene sulfonic acid sodium salt, magnetic iron powder, nickel hydroxide, conductive agent, binder, it is agitated, coating, drying, roll-in and etc. electrode is made
Piece.The modified graphite electrode material being prepared, large specific surface area, quality specific capacitance is high, and power density is big, has preferable
Application prospect.
(2) modified graphite electrode material feedstock of the invention is cheap, simple process, is suitable for heavy industrialization and uses, real
It is strong with property.
Specific embodiment
The technical solution of invention is described in detail combined with specific embodiments below.
Embodiment 1
(1) sulfuric acid of 50 g graphite and 120 mL mass concentrations 85% is added in reaction vessel jointly, in 45 DEG C of water
Bath is lower to keep the temperature 15 min, adds the potassium permanganate of 15g, temperature is risen to 70 DEG C rapidly after maintaining 10 min, with 200 rpm
Rate be stirred to react 80 min, to added after reaction into container 300 mL mass fractions be 2.5% hydrogen peroxide, with
The rate of 150 rpm stirs mixed liquor to discoloration, filters while hot, and gained filter cake is washed 2 with 3% hydrochloric acid solution of mass concentration
It is secondary, then be washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C dry 8h, obtains graphite oxidation
Object；
(2) graphite oxide that step (1) obtains is mixed with the ammonium hydroxide that 250 mL concentration are 20%, then by mixed liquor
It is placed in 85 DEG C of baking oven and heats 30 min, obtain thick slurry, then the high-temperature process at 1000 DEG C under nitrogen protection
1.5h obtains high-temperature activation product, is tentatively neutralized with dilute hydrochloric acid to high-temperature activation product, then with deionized water that high temperature is living
Change product washing 3 times and neutrality is fully achieved to pH, is placed in 70 DEG C of vacuum ovens dry 8h, obtains modified graphite oxide；
(3) by modified graphite oxide that step (2) obtains as the deionized water in reaction kettle, adding 300 mL and
The volume ratio of dehydrated alcohol mixed solvent, deionized water and dehydrated alcohol is 1.5, is stirred at 200 DEG C with the rate of 1200 rpm
15 min are mixed, 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters are then added, then heats to 250 DEG C, is stirred to react 2
Obtained product is centrifuged by h according to the revolving speed of 3000 rpm, and gained sediment is washed with deionized water, is placed in 90
Dry 6 h, obtain intermediate in DEG C vacuum oven；
(4) intermediate obtained by step (3) is put into 15 h of curing process in 220 DEG C of drying box, is then used
Powder obtained by ball milling is placed in atmosphere tube type furnace by 2 h of ball mill ball milling, gained diameter of particle less than 2 μm, is protected in argon gas
Lower carry out carbonization treatment, treatment temperature are 950 DEG C, and the processing time is 5 h, obtains carbonization compound；
(5) the carbonization compound that obtains step (4), neopelex, magnetic iron powder, nickel hydroxide, acetylene black,
Sodium carboxymethylcellulose according to 68:11:8:7:4:3 ratio mix, be added appropriate amount of deionized water, be evenly stirred until it is thick,
8 h are dried in 80 DEG C of vacuum oven coated on stainless (steel) wire, then by it, and electrode slice is cut into after roll-in, is obtained into
Product.
The performance test results of modified graphite electrode material obtained are as shown in table 1.
Embodiment 2
(1) sulfuric acid of 50 g graphite and 120 mL mass concentrations 85% is added in reaction vessel jointly, in 45 DEG C of water
Bath is lower to keep the temperature 20 min, adds the potassium permanganate of 17 g, temperature is risen to 70 DEG C rapidly after maintaining 10 min, with 200
The rate of rpm is stirred to react 85 min, the hydrogen peroxide for being 2.5% to add 300 mL mass fractions into container after reaction,
Mixed liquor is stirred to discoloration with the rate of 150 rpm, is filtered while hot, gained filter cake is washed with 3% hydrochloric acid solution of mass concentration
2 times, then be washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C dry 8h, obtains graphite oxidation
Object；
(2) graphite oxide that step (1) obtains is mixed with the ammonium hydroxide that 250 mL concentration are 20%, then by mixed liquor
It is placed in 85 DEG C of baking oven and heats 35 min, obtain thick slurry, then the high-temperature process at 1100 DEG C under nitrogen protection
1.5h obtains high-temperature activation product, is tentatively neutralized with dilute hydrochloric acid to high-temperature activation product, then with deionized water that high temperature is living
Change product washing 4 times and neutrality is fully achieved to pH, is placed in 70 DEG C of vacuum ovens dry 8h, obtains modified graphite oxide；
(3) by modified graphite oxide that step (2) obtains as the deionized water in reaction kettle, adding 300 mL and
The volume ratio of dehydrated alcohol mixed solvent, deionized water and dehydrated alcohol is 1.5, is stirred at 200 DEG C with the rate of 1200 rpm
15 min are mixed, 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters are then added, then heats to 250 DEG C, is stirred to react
Obtained product is centrifuged by 2.5 h according to the revolving speed of 3000 rpm, and gained sediment is washed with deionized water, is set
Dry 6 h, obtain intermediate in 90 DEG C of vacuum ovens；
(4) intermediate obtained by step (3) is put into 15 h of curing process in 220 DEG C of drying box, is then used
Powder obtained by ball milling is placed in atmosphere tube type furnace by 2.5 h of ball mill ball milling, gained diameter of particle less than 2 μm, is protected in argon gas
Shield is lower to carry out carbonization treatment, and treatment temperature is 950 DEG C, and the processing time is 5 h, obtains carbonization compound；
(5) carbonization compound, neopelex, magnetic iron powder, the nickel hydroxide, nano-sized carbon obtained step (4)
Pipe carbon black, hexafluoropropene according to 68:11:8:7:4:3 ratio mix, be added appropriate amount of deionized water, be evenly stirred until it is thick,
16 h are dried in 105 DEG C of vacuum oven coated on stainless (steel) wire, then by it, and electrode slice is cut into after roll-in, is obtained
Finished product.
The performance test results of modified graphite electrode material obtained are as shown in table 1.
Embodiment 3
(1) sulfuric acid of 50 g graphite and 120 mL mass concentrations 85% is added in reaction vessel jointly, in 45 DEG C of water
Bath is lower to keep the temperature 25 min, adds the potassium permanganate of 20 g, temperature is risen to 70 DEG C rapidly after maintaining 10 min, with 200
The rate of rpm is stirred to react 90 min, the hydrogen peroxide for being 2.5% to add 300 mL mass fractions into container after reaction,
Mixed liquor is stirred to discoloration with the rate of 150 rpm, is filtered while hot, gained filter cake is washed with 3% hydrochloric acid solution of mass concentration
2 times, then be washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C dry 8h, obtains graphite oxidation
Object；
(2) graphite oxide that step (1) obtains is mixed with the ammonium hydroxide that 250 mL concentration are 20%, then by mixed liquor
It is placed in 85 DEG C of baking oven and heats 40 min, obtain thick slurry, then the high-temperature process at 1200 DEG C under nitrogen protection
1.5h obtains high-temperature activation product, is tentatively neutralized with dilute hydrochloric acid to high-temperature activation product, then with deionized water that high temperature is living
Change product washing 5 times and neutrality is fully achieved to pH, is placed in 70 DEG C of vacuum ovens dry 8h, obtains modified graphite oxide；
(3) by modified graphite oxide that step (2) obtains as the deionized water in reaction kettle, adding 300 mL and
The volume ratio of dehydrated alcohol mixed solvent, deionized water and dehydrated alcohol is 1.5, is stirred at 200 DEG C with the rate of 1200 rpm
15 min are mixed, 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters are then added, then heats to 250 DEG C, is stirred to react 3
Obtained product is centrifuged by h according to the revolving speed of 3000 rpm, and gained sediment is washed with deionized water, is placed in 90
Dry 6 h, obtain intermediate in DEG C vacuum oven；
(4) intermediate obtained by step (3) is put into 15 h of curing process in 220 DEG C of drying box, is then used
Powder obtained by ball milling is placed in atmosphere tube type furnace by 3 h of ball mill ball milling, gained diameter of particle less than 2 μm, is protected in argon gas
Lower carry out carbonization treatment, treatment temperature are 950 DEG C, and the processing time is 5 h, obtains carbonization compound；
(5) the carbonization compound that obtains step (4), neopelex, magnetic iron powder, nickel hydroxide, activated carbon,
Polyvinyl alcohol is mixed according to the ratio of 68:11:8:7:4:3, and appropriate amount of deionized water is added, is evenly stirred until thick, is coated in
On stainless (steel) wire, then it is dried into 24 h in 130 DEG C of vacuum oven, electrode slice is cut into after roll-in, obtains finished product.
The performance test results of modified graphite electrode material obtained are as shown in table 1.
Comparative example 1
(1) sulfuric acid of 50 g graphite and 120 mL mass concentrations 85% is added in reaction vessel jointly, in 45 DEG C of water
Bath is lower to keep the temperature 15 min, adds the potassium permanganate of 15g, temperature is risen to 70 DEG C rapidly after maintaining 10 min, with 200 rpm
Rate be stirred to react 80 min, to added after reaction into container 300 mL mass fractions be 2.5% hydrogen peroxide, with
The rate of 150 rpm stirs mixed liquor to discoloration, filters while hot, and gained filter cake is washed 2 with 3% hydrochloric acid solution of mass concentration
It is secondary, then be washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C dry 8h, obtains graphite oxidation
Object；
(2) graphite oxide that step (1) obtains is mixed with the ammonium hydroxide that 250 mL concentration are 20%, then by mixed liquor
It is placed in 85 DEG C of baking oven and heats 30 min, obtain thick slurry, then the high-temperature process at 1000 DEG C under nitrogen protection
1.5h obtains high-temperature activation product, is tentatively neutralized with dilute hydrochloric acid to high-temperature activation product, then with deionized water that high temperature is living
Change product washing 3 times and neutrality is fully achieved to pH, is placed in 70 DEG C of vacuum ovens dry 8h, obtains modified graphite oxide；
(3) by modified graphite oxide that step (2) obtains as the deionized water in reaction kettle, adding 300 mL and
The volume ratio of dehydrated alcohol mixed solvent, deionized water and dehydrated alcohol is 1.5, is stirred at 200 DEG C with the rate of 1200 rpm
15 min are mixed, 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters are then added, then heats to 250 DEG C, is stirred to react 2
Obtained product is centrifuged by h according to the revolving speed of 3000 rpm, and gained sediment is washed with deionized water, is placed in 90
Dry 6 h, obtain intermediate in DEG C vacuum oven；
(4) intermediate obtained by step (3) is put into 15 h of curing process in 220 DEG C of drying box, is then used
Powder obtained by ball milling is placed in atmosphere tube type furnace by 2 h of ball mill ball milling, gained diameter of particle less than 2 μm, is protected in argon gas
Lower carry out carbonization treatment, treatment temperature are 950 DEG C, and the processing time is 5 h, obtains carbonization compound；
(5) the carbonization compound that obtains step (4), neopelex, magnetic iron powder, nickel hydroxide, acetylene black,
Sodium carboxymethylcellulose according to 75:10:5:12:9:5 ratio mix, be added appropriate amount of deionized water, be evenly stirred until it is thick,
8 h are dried in 80 DEG C of vacuum oven coated on stainless (steel) wire, then by it, and electrode slice is cut into after roll-in, is obtained into
Product.
The performance test results of modified graphite electrode material obtained are as shown in table 1.
Comparative example 2
(1) sulfuric acid of 50 g graphite and 120 mL mass concentrations 85% is added in reaction vessel jointly, in 45 DEG C of water
Bath is lower to keep the temperature 20 min, adds the potassium permanganate of 17 g, temperature is risen to 70 DEG C rapidly after maintaining 10 min, with 200
The rate of rpm is stirred to react 85 min, the hydrogen peroxide for being 2.5% to add 300 mL mass fractions into container after reaction,
Mixed liquor is stirred to discoloration with the rate of 150 rpm, is filtered while hot, gained filter cake is washed with 3% hydrochloric acid solution of mass concentration
2 times, then be washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C dry 8h, obtains graphite oxidation
Object；
(2) graphite oxide that step (1) obtains is mixed with the ammonium hydroxide that 250 mL concentration are 20%, then by mixed liquor
It is placed in 85 DEG C of baking oven and heats 35 min, obtain thick slurry, then the high-temperature process at 1100 DEG C under nitrogen protection
1.5h obtains high-temperature activation product, is tentatively neutralized with dilute hydrochloric acid to high-temperature activation product, then with deionized water that high temperature is living
Change product washing 4 times and neutrality is fully achieved to pH, is placed in 70 DEG C of vacuum ovens dry 8h, obtains modified graphite oxide；
(3) by modified graphite oxide that step (2) obtains as the deionized water in reaction kettle, adding 300 mL and
The volume ratio of dehydrated alcohol mixed solvent, deionized water and dehydrated alcohol is 1.5, is stirred at 200 DEG C with the rate of 1200 rpm
15 min are mixed, 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters are then added, then heats to 250 DEG C, is stirred to react
Obtained product is centrifuged by 2.5 h according to the revolving speed of 3000 rpm, and gained sediment is washed with deionized water, is set
Dry 6 h, obtain intermediate in 90 DEG C of vacuum ovens；
(4) intermediate obtained by step (3) is put into 15 h of curing process in 220 DEG C of drying box, is then used
2.5 h of ball mill ball milling, gained diameter of particle is less than 2 μm；
(5) powder that obtains step (4), neopelex, magnetic iron powder, nickel hydroxide, carbon nanotubes carbon black,
Hexafluoropropene is mixed according to the ratio of 68:11:8:7:4:3, and appropriate amount of deionized water is added, is evenly stirred until thick, is coated in
On stainless (steel) wire, then it is dried into 16 h in 105 DEG C of vacuum oven, electrode slice is cut into after roll-in, obtains finished product.
The performance test results of modified graphite electrode material obtained are as shown in table 1.
Comparative example 3
(1) sulfuric acid of 50 g graphite and 120 mL mass concentrations 75% is added in reaction vessel jointly, in 70 DEG C of water
Bath is lower to keep the temperature 25 min, adds the potassium permanganate of 30g, temperature is risen to 70 DEG C rapidly after maintaining 10 min, with 200 rpm
Rate be stirred to react 90 min, to added after reaction into container 300 mL mass fractions be 2.5% hydrogen peroxide, with
The rate of 150 rpm stirs mixed liquor to discoloration, filters while hot, and gained filter cake is washed 2 with 3% hydrochloric acid solution of mass concentration
It is secondary, then be washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C dry 8h, obtains graphite oxidation
Object；
(2) graphite oxide that step (1) obtains is mixed with the ammonium hydroxide that 250 mL concentration are 20%, then by mixed liquor
It is placed in 60 DEG C of baking oven and heats 40 min, obtain thick slurry, then the high-temperature process at 1000 DEG C under nitrogen protection
1.5h obtains high-temperature activation product, is tentatively neutralized with dilute hydrochloric acid to high-temperature activation product, then with deionized water that high temperature is living
Change product washing 5 times and neutrality is fully achieved to pH, is placed in 70 DEG C of vacuum ovens dry 8h, obtains modified graphite oxide；
(3) by modified graphite oxide that step (2) obtains as the deionized water in reaction kettle, adding 300 mL and
The volume ratio of dehydrated alcohol mixed solvent, deionized water and dehydrated alcohol is 1.5, is stirred at 200 DEG C with the rate of 1200 rpm
15 min are mixed, 15 g polyvinylpyrrolidones and 10 g positive silicic acid propyl esters are then added, then heats to 250 DEG C, is stirred to react 3
Obtained product is centrifuged by h according to the revolving speed of 3000 rpm, and gained sediment is washed with deionized water, is placed in 90
Dry 6 h, obtain intermediate in DEG C vacuum oven；
(4) intermediate obtained by step (3) is put into 15 h of curing process in 220 DEG C of drying box, is then used
Powder obtained by ball milling is placed in atmosphere tube type furnace by 3 h of ball mill ball milling, gained diameter of particle less than 2 μm, is protected in argon gas
Lower carry out carbonization treatment, treatment temperature are 950 DEG C, and the processing time is 5 h, obtains carbonization compound；
(5) the carbonization compound that obtains step (4), neopelex, magnetic iron powder, nickel hydroxide, activated carbon,
Polyvinyl alcohol is mixed according to the ratio of 68:11:8:7:4:3, and appropriate amount of deionized water is added, is evenly stirred until thick, is coated in
On stainless (steel) wire, then it is dried into 24 h in 130 DEG C of vacuum oven, electrode slice is cut into after roll-in, obtains finished product.
The performance test results of modified graphite electrode material obtained are as shown in table 1.
By the modified graphite electrode material obtained of embodiment 1-3 and comparative example 1-3 respectively with 1 mol/L aqueous sodium sulfate
Liquid is electrolyte, and polypropylene film is after diaphragm is assembled into capacitor, in 1.5V voltage, 15 mA/cm2It is carried out under current condition
This two performance tests of quality specific capacitance, power density, while measuring 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 |
Modified graphite electrode material preparation process of the 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 reaction kettle
Middle mixed solvent, polyvinylpyrrolidone and the positive silicic acid propyl ester that deionized water and dehydrated alcohol is added, after high-temperature process
To intermediate, then by intermediate curing process, ball-milling treatment, carbonization treatment, detergent alkylate is finally added
Sodium sulfonate, magnetic iron powder, nickel hydroxide, conductive agent, binder be agitated, coating, drying, roll-in and etc. electrode slice is made.System
Modified graphite electrode material made of standby, large specific surface area, quality specific capacitance is high, and power density is big, has preferable application
Prospect.Modified graphite electrode material feedstock of the invention is cheap, simple process, is suitable for heavy industrialization and uses, practical.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (3)
1. a kind of preparation method of modified graphite electrode material, which comprises the following steps:
(1) 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 is kept the temperature, the potassium permanganate of 15-20g is added, temperature is risen to 70 DEG C rapidly after maintaining 10 min, with 200
The rate of rpm is stirred to react 80-90 min, the dioxygen for being 2.5% to add 300 mL mass fractions into container after reaction
Mixed liquor is stirred to discoloration with the rate of 150 rpm, is filtered while hot by water, by gained filter cake 3% hydrochloric acid solution of mass concentration
Washing 2 times, then be washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C dry 8h, obtains graphite
Oxide；
(2) graphite oxide that step (1) obtains is mixed with the ammonium hydroxide that 250 mL concentration are 20%, is then placed in mixed liquor
30-40 min is 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 dilute hydrochloric acid, then with deionized water by high temperature
Activation products wash 3-5 times and neutrality are fully achieved to pH, are placed in 70 DEG C of vacuum ovens dry 8h, obtain modified graphite oxidation
Object；
(3) by modified graphite oxide that step (2) obtains as the deionized water that in reaction kettle, adds 300 mL and anhydrous
The volume ratio of alcohol mixed solvent, deionized water and dehydrated alcohol is 1.5, stirs 15 at 200 DEG C with the rate of 1200 rpm
Then min is added 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters, then heats to 250 DEG C, is stirred to react 2-3 h,
Obtained product is centrifuged according to the revolving speed of 3000 rpm, gained sediment is washed with deionized water, is placed in 90 DEG C
Dry 6 h, obtain intermediate in vacuum oven；
(4) intermediate obtained by step (3) is put into 15 h of curing process in 220 DEG C of drying box, is then used ball milling
Powder obtained by ball milling is placed in atmosphere tube type furnace by machine ball milling 2-3 h, the diameter of particle after ball milling less than 2 μm, is protected in argon gas
Shield is lower to carry out carbonization treatment, and treatment temperature is 950 DEG C, and the processing time is 5 h, obtains carbonization compound；
(5) carbonization compound, neopelex, magnetic iron powder, nickel hydroxide, the conductive agent, bonding obtained step (4)
Agent is according to (65-70): (11-13): (7-9): (5-8): (3-5): appropriate amount of deionized water, stirring is added in the ratio mixing of (2-4)
It is uniformly extremely thick, it is coated on stainless (steel) wire, then it is dried into 8-24 h in 80-130 DEG C of vacuum oven, through roll-in
After be cut into electrode slice, obtain finished product, any one of conductive agent in acetylene black, carbon nanotubes carbon black, activated carbon, binder
Any one in sodium carboxymethylcellulose, hexafluoropropene, polyvinyl alcohol.
2. the preparation method of modified graphite electrode material according to claim 1, which is characterized in that in the step (5)
Compound, neopelex, magnetic iron powder, nickel hydroxide, conductive agent, binder be carbonized according to 68:11:8:7:4:3's
Ratio mixing.
3. the modified graphite electrode material that any one of -2 preparation processes obtain according to claim 1 is in preparation supercapacitor
In application.
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