CN107093525B - A kind of preparation method of the electrode material handled through graphene oxide water solution - Google Patents
A kind of preparation method of the electrode material handled through graphene oxide water solution Download PDFInfo
- Publication number
- CN107093525B CN107093525B CN201710216792.XA CN201710216792A CN107093525B CN 107093525 B CN107093525 B CN 107093525B CN 201710216792 A CN201710216792 A CN 201710216792A CN 107093525 B CN107093525 B CN 107093525B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- water solution
- electrode material
- obtains
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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)
- Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
Abstract
The invention discloses a kind of preparation methods of electrode material handled through graphene oxide water solution, the technique is by will obtain graphite oxide after graphite oxidation, it is handled again with graphene oxide water solution Hybrid Heating, then high-temperature process obtains activation products under nitrogen protection, it is modified again, then it is placed in reaction kettle and mixed solvent is added, polyvinylpyrrolidone and positive silicic acid propyl ester, intermediate is obtained through high-temperature process, then intermediate is subjected to the operation such as curing process, add other compositions, it is agitated, coating, drying, roll-in and etc. electrode slice is made.The electrode material handled through graphene oxide water solution being prepared, specific capacity is big, good cycling stability, stable electrochemical property, energy density are high, with good application prospect.Application of the electrode material handled as made from the preparation process through graphene oxide water solution in preparation supercapacitor is also disclosed simultaneously.
Description
Technical field
The present invention relates to this technical field of capacitor material, it is related specifically to a kind of handle through graphene oxide water solution
Electrode material preparation method.
Background technique
The demand of world today's energy relies primarily on chemical fuel, but chemical fuel is increasingly in short supply.There is an urgent need to height by people
Effect, cleaning, Ke Xunhuanliyong new energy.So novel renewable energy research is a hot spot.But renewable energy,
The utilization of such as wind energy, solar energy renewable energy is seriously affected by season, meteorology and regional condition, therefore develops novel storage
Energy device is one of the critical issue for efficiently using renewable energy.Scientists have successively developed different types of electrochemistry
Energy storage device, such as lithium ion battery, fuel cell, supercapacitor.
Supercapacitor is novel energy storage device, there is significant advantage: energy density is high, and the charge and discharge time is short, circulation
Service life is long.For a capacitor, core is electrode, and electrode material is the chemical property of determining electrode
Key.The principle for storing energy according to supercapacitor is different, and electrode material can probably be divided into three classes: carbon material is (as lived
Property charcoal, graphene etc.), metal hydroxides or oxide (such as ruthenium-oxide, nickel hydroxide, cobalt hydroxide, nickel oxide, titanium dioxide
Manganese etc.) and conducting polymer (such as polyacetylene, polythiophene).In recent years, use graphene as the super capacitor of electrode material
Device also appears in the newspapers repeatly, however since the Ultrahigh of carbon material is limited, the electricity of the supercapacitor based on graphene nano material
Capacitive energy is simultaneously unsatisfactory, usually only 100~200F/g.On the other hand, although though conducting polymer materials polyaniline has
There is specific capacitance value more higher than carbon material, but the conductivity of common polyaniline material is still lower, and cyclical stability is unsatisfactory,
This also just directly constrains its practical application.Therefore, in order to evade different materials the shortcomings that and finally obtain with high specific capacitance
And stable supercapacitor, need to develop a kind of new composite electrode with preferable synergistic effect.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of system of electrode material handled through graphene oxide water solution
Preparation Method, the technique are handled by will obtain graphite oxide after graphite oxidation, then with graphene oxide water solution Hybrid Heating,
Then high-temperature process obtains activation products under nitrogen protection, then is modified, and is then placed in reaction kettle and deionized water is added
With the mixed solvent, polyvinylpyrrolidone and positive silicic acid propyl ester of dehydrated alcohol, intermediate is obtained after high-temperature process, is connect
By intermediate curing process, ball-milling treatment, carbonization treatment, finally add tributyl 2-acetylcitrate, lead zinc niobate,
Barium stannate, conductive agent, binder, it is agitated, coating, drying, roll-in and etc. electrode slice is made.Be prepared through aoxidize stone
The electrode material of black aqueous solution processing, specific capacity is big, good cycling stability, stable electrochemical property, energy density are high, tool
There is preferable application prospect.The electrode material handled as made from the preparation process through graphene oxide water solution is also disclosed simultaneously
Expect the application in preparation supercapacitor.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of the electrode material handled through graphene oxide water solution, 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 for obtaining step (1) and the graphene oxide that 300 mL mass concentrations are 5 mg/mL are water-soluble
Then mixed liquor is placed in heating 30-40 min in 85 DEG C of baking oven, thick slurry is obtained, then in nitrogen protection by liquid mixing
Under at 1000-1200 DEG C high-temperature process 1.5h, obtain high-temperature activation product, high-temperature activation product carried out tentatively with dilute hydrochloric acid
It neutralizes, then high-temperature activation product is washed 3-5 times with deionized water, neutrality is fully achieved to pH, be 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), tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, 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, tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, 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 electrode materials handled through graphene oxide water solution obtained by above-mentioned preparation process to exist
Prepare the application in supercapacitor.
Compared with prior art, the present invention has the advantages that:
(1) of the invention to be obtained after the electrode material preparation process of graphene oxide water solution processing is by by graphite oxidation
It is handled to graphite oxide, then with graphene oxide water solution Hybrid Heating, 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 tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, conductive agent, binder, agitated,
Coating, drying, roll-in and etc. electrode slice is made.The electrode material handled through graphene oxide water solution being prepared,
Specific capacity is big, good cycling stability, stable electrochemical property, energy density are high, with good application prospect.
(2) the electrode material raw material of the invention handled through graphene oxide water solution is cheap, simple process, is suitable for big rule
Mould industrialization is used, practical.
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 15 g, temperature is risen to 70 DEG C rapidly after maintaining 10 min, with 200
The rate of rpm is stirred to react 80 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 for obtaining step (1) and the graphene oxide that 300 mL mass concentrations are 5 mg/mL are water-soluble
Liquid mixing, then mixed liquor is placed in 85 DEG C of baking oven and heats 30 min, obtain thick slurry, then under nitrogen protection in
High-temperature process 1.5h at 1000 DEG C, obtains high-temperature activation product, is tentatively neutralized with dilute hydrochloric acid to high-temperature activation product, then use
High-temperature activation product is washed 3 times and neutrality is fully achieved to pH by deionized water, is placed in 70 DEG C of vacuum ovens dry 8h, is obtained
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), tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, 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 the electrode material obtained handled through graphene oxide water solution 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 for obtaining step (1) and the graphene oxide that 300 mL mass concentrations are 5 mg/mL are water-soluble
Liquid mixing, then mixed liquor is placed in 85 DEG C of baking oven and heats 35 min, obtain thick slurry, then under nitrogen protection in
High-temperature process 1.5h at 1100 DEG C, obtains high-temperature activation product, is tentatively neutralized with dilute hydrochloric acid to high-temperature activation product, then use
High-temperature activation product is washed 4 times and neutrality is fully achieved to pH by deionized water, is placed in 70 DEG C of vacuum ovens dry 8h, is obtained
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, tributyl 2-acetylcitrate, lead zinc niobate, the barium stannate, 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 the electrode material obtained handled through graphene oxide water solution 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 20g, 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 for obtaining step (1) and the graphene oxide that 300 mL mass concentrations are 5 mg/mL are water-soluble
Liquid mixing, then mixed liquor is placed in 85 DEG C of baking oven and heats 40 min, obtain thick slurry, then under nitrogen protection in
High-temperature process 1.5h at 1200 DEG C, obtains high-temperature activation product, is tentatively neutralized with dilute hydrochloric acid to high-temperature activation product, then use
High-temperature activation product is washed 5 times and neutrality is fully achieved to pH by deionized water, is placed in 70 DEG C of vacuum ovens dry 8 h, is obtained
To 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), tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, 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 the electrode material obtained handled through graphene oxide water solution 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 15 g, temperature is risen to 70 DEG C rapidly after maintaining 10 min, with 200
The rate of rpm is stirred to react 80 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 for obtaining step (1) and the graphene oxide that 300 mL mass concentrations are 5 mg/mL are water-soluble
Liquid mixing, then mixed liquor is placed in 85 DEG C of baking oven and heats 30 min, obtain thick slurry, then under nitrogen protection in
High-temperature process 1.5h at 1000 DEG C, obtains high-temperature activation product, is tentatively neutralized with dilute hydrochloric acid to high-temperature activation product, then use
High-temperature activation product is washed 3 times and neutrality is fully achieved to pH by deionized water, is placed in 70 DEG C of vacuum ovens dry 8h, is obtained
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), tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, acetylene black,
Sodium carboxymethylcellulose according to 80:9:12:15:2:6 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 the electrode material obtained handled through graphene oxide water solution 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 for obtaining step (1) and the graphene oxide that 300 mL mass concentrations are 5 mg/mL are water-soluble
Liquid mixing, then mixed liquor is placed in 85 DEG C of baking oven and heats 35 min, obtain thick slurry, then under nitrogen protection in
High-temperature process 1.5h at 1100 DEG C, obtains high-temperature activation product, is tentatively neutralized with dilute hydrochloric acid to high-temperature activation product, then use
High-temperature activation product is washed 4 times and neutrality is fully achieved to pH by deionized water, is placed in 70 DEG C of vacuum ovens dry 8h, is obtained
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), tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, 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 the electrode material obtained handled through graphene oxide water solution are as shown in table 1.
Comparative example 3
(1) sulfuric acid of 50 g graphite and 120 mL mass concentrations 70% 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 30 g, temperature is risen to 90 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 for obtaining step (1) and the graphene oxide that 300 mL mass concentrations are 4 mg/mL are water-soluble
Liquid mixing, then mixed liquor is placed in 85 DEG C of baking oven and heats 40 min, obtain thick slurry, then under nitrogen protection in
High-temperature process 1.5h at 1500 DEG C, obtains high-temperature activation product, is tentatively neutralized with dilute hydrochloric acid to high-temperature activation product, then use
High-temperature activation product is washed 5 times and neutrality is fully achieved to pH by deionized water, is placed in 70 DEG C of vacuum ovens dry 8 h, is obtained
To 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 2, is stirred at 200 DEG C with the rate of 1200 rpm
Then 15 min are added 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters, then heat to 250 DEG C, are stirred to react 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
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), tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, 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 the electrode material obtained handled through graphene oxide water solution are as shown in table 1.
By made from embodiment 1-3 and comparative example 1-3 through graphene oxide water solution handle electrode material respectively into
This several row specific capacity, capacity retention rate, energy density, current density coefficient of stabilization performance tests.
Table 1
| Specific capacitance (F/g, 1A/g) | Capacity retention rate (%, 1000 cyclic voltammetries) | Energy density (Wh/kg) | Current density coefficient of stabilization (%, 12h, compared with original value) | |
| Embodiment 1 | 399 | 98.6 | 10.08 | 93.5 |
| Embodiment 2 | 397 | 99.1 | 10.03 | 94.4 |
| Embodiment 3 | 394 | 98.2 | 10.07 | 92.3 |
| Comparative example 1 | 257 | 79.3 | 7.03 | 72.9 |
| Comparative example 2 | 251 | 78.7 | 7.21 | 69.0 |
| Comparative example 3 | 287 | 82.7 | 7.51 | 75.7 |
Of the invention obtains after the electrode material preparation process of graphene oxide water solution processing is by by graphite oxidation
Graphite oxide, then handled with graphene oxide water solution Hybrid Heating, then high-temperature process is activated under nitrogen protection
Product, then be modified, it is then placed in reaction kettle and mixed solvent, the polyvinylpyrrolidine of deionized water and dehydrated alcohol is added
Ketone and positive silicic acid propyl ester obtain intermediate after high-temperature process, then by intermediate curing process, ball-milling treatment,
Carbonization treatment, finally add tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, conductive agent, binder it is agitated, coating,
Drying, roll-in and etc. electrode slice is made.The electrode material handled through graphene oxide water solution being prepared, specific capacity
Greatly, good cycling stability, stable electrochemical property, energy density are high, with good application prospect.It is of the invention through aoxidizing stone
The electrode material raw material of black aqueous solution processing 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 (4)
1. a kind of preparation method of the electrode material handled through graphene oxide water solution, 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) graphene oxide water solution that the graphite oxide obtained step (1) and 300 mL mass concentrations are 5 mg/mL is mixed
Close, then mixed liquor be placed in in 85 DEG C of baking oven heating 30-40 min, obtain thick slurry, then under nitrogen protection in
High-temperature process 1.5h at 1000-1200 DEG C, obtains high-temperature activation product, is carried out in preliminary with dilute hydrochloric acid to high-temperature activation product
With, then high-temperature activation product is washed 3-5 times with deionized water, neutrality is fully achieved to pH, it is placed in 70 DEG C of vacuum ovens and does
Dry 8h obtains modified graphite oxide；
(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, tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, the conductive agent, bonding obtained step (4)
Agent according to 68:11:8:7:4:3 ratio mix, be added appropriate amount of deionized water, be evenly stirred until it is thick, be coated in stainless steel
On the net, then by it 8-24 h is dried in 80-130 DEG C of vacuum oven, electrode slice is cut into after roll-in, obtains finished product.
2. the preparation method of the electrode material according to claim 1 handled through graphene oxide water solution, feature exist
In any one of conductive agent in acetylene black, carbon nanotubes carbon black, activated carbon in the step (5).
3. the preparation method of the electrode material according to claim 1 handled through graphene oxide water solution, feature exist
In any one of binder in sodium carboxymethylcellulose, hexafluoropropene, polyvinyl alcohol in the step (5).
4. the electrode material handled through graphene oxide water solution that any one of -3 preparation methods obtain according to claim 1
Application in preparation supercapacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710216792.XA CN107093525B (en) | 2017-04-05 | 2017-04-05 | A kind of preparation method of the electrode material handled through graphene oxide water solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710216792.XA CN107093525B (en) | 2017-04-05 | 2017-04-05 | A kind of preparation method of the electrode material handled through graphene oxide water solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107093525A CN107093525A (en) | 2017-08-25 |
| CN107093525B true CN107093525B (en) | 2019-03-26 |
Family
ID=59646388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710216792.XA Active CN107093525B (en) | 2017-04-05 | 2017-04-05 | A kind of preparation method of the electrode material handled through graphene oxide water solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107093525B (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9017756B2 (en) * | 2010-01-07 | 2015-04-28 | Nanotek Instruments, Inc. | Continuous process for producing spacer-modified nano graphene electrodes for supercapacitors |
| CN102923698B (en) * | 2012-11-19 | 2014-11-12 | 中南大学 | Preparation method for three-dimensional porous graphene for supercapacitor |
| CN103198931B (en) * | 2013-03-22 | 2015-09-09 | 哈尔滨工业大学深圳研究生院 | A kind of preparation method of graphene nano fiber and supercapacitor applications thereof |
| CN103253658B (en) * | 2013-05-13 | 2016-06-29 | 常州第六元素材料科技股份有限公司 | A kind of high volumetric capacitance Graphene and preparation method thereof |
| CN103787317B (en) * | 2014-01-02 | 2016-01-06 | 上海应用技术学院 | A kind of preparation method of graphene oxide dispersion |
| CN105321726B (en) * | 2014-07-21 | 2019-02-05 | 中国科学院大连化学物理研究所 | High magnification active carbon/Activated Graphite alkene combination electrode material and preparation method thereof |
-
2017
- 2017-04-05 CN CN201710216792.XA patent/CN107093525B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107093525A (en) | 2017-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104269555B (en) | A kind of lithium ion power and energy-storage battery soft carbon negative material, preparation method and its usage | |
| CN104916452B (en) | A kind of ultracapacitor wood activated charcoal composite material and preparation method thereof | |
| CN107244664B (en) | Preparation method and application of graphene-like structure carbon electrode material | |
| CN105645410B (en) | 3D network pore structure Supercapacitor carbons and preparation method thereof | |
| CN105776182A (en) | Preparation method and application of hollow tubular biochar | |
| CN105384169B (en) | A kind of preparation method of electrode of super capacitor activated carbon | |
| CN106328890A (en) | Carbon-pillared MXene composite material and application thereof | |
| CN108899530B (en) | Silicon-carbon composite material and preparation method and application thereof | |
| CN106099108A (en) | A kind of preparation method of LITHIUM BATTERY graphite/absorbent charcoal composite material | |
| CN105174260B (en) | A kind of low alkali process for preparing activated of asphalt based active carbon and application | |
| CN103787311A (en) | Preparation methods of graphene-carbon nanotube composite thin film and electrochemical capacitor | |
| CN107555424A (en) | A kind of preparation method of porous class graphene active carbon material and products thereof and application | |
| CN104993174A (en) | Preparation method of material of negative electrode of lithium ion battery | |
| CN105321726B (en) | High magnification active carbon/Activated Graphite alkene combination electrode material and preparation method thereof | |
| CN109850892A (en) | A kind of activation industrialized process for preparing twice of super capacitor high conductivity cocoanut active charcoal | |
| CN111710529B (en) | Co/Mn-MOF/nitrogen-doped carbon-based composite material and preparation method and application thereof | |
| CN114122372A (en) | Low-expansion silicon-carbon negative electrode material for lithium ion battery and preparation method thereof | |
| CN103441280B (en) | The method of lithium ion battery negative material prepared by the sisal carbon fiber of hydro-thermal activation | |
| CN105481004A (en) | Stannic oxide nanotubes with high electrical properties and preparation method therefor | |
| CN107093526B (en) | With graphite oxide electrode material preparation method and applications as main component | |
| CN109273284A (en) | A kind of situ Nitrogen Doping porous carbon microsphere/Cu-base composites and the preparation method and application thereof | |
| CN108400022A (en) | A kind of preparation method of manganous silicate/carbon supercapacitor electrode material | |
| CN107093525B (en) | A kind of preparation method of the electrode material handled through graphene oxide water solution | |
| CN107017089B (en) | The preparation method and applications of supercapacitor nickel oxide combination electrode material | |
| CN103151532A (en) | Novel air electrode for metal-air battery |
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 |