CN107017089B - The preparation method and applications of supercapacitor nickel oxide combination electrode material - Google Patents
The preparation method and applications of supercapacitor nickel oxide combination electrode material Download PDFInfo
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Abstract
The invention discloses a kind of supercapacitor preparation method and applications of nickel oxide combination 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 nickel oxide, the ingredients such as 3- TSL 8330, it is agitated, coating, drying, roll-in and etc. electrode slice is made.The supercapacitor being prepared nickel oxide combination electrode material, dielectric constant is high, excellent electrical properties, with good application prospect.Application of the supercapacitor nickel oxide combination 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, and it is compound to be related specifically to a kind of supercapacitor nickel oxide
The preparation method and applications of electrode material.
Background technique
Supercapacitor is called electrochemical capacitor, has that charge-discharge velocity is fast, have extended cycle life, power density is high, ring
The advantages that protecting, is non-maintaining, receives the extensive concern of people.Supercapacitor as power compensation and energy storage device,
Storage electricity number show as the size of capacitor.According to the storage of electric energy and transformation mechanism, supercapacitor is divided into electric double layer
Capacitor and faraday's capacitor, wherein double layer capacitor is a kind of new electronic component using electric double layer come storage energy,
Electronics or ion cause the face-off of charge in aligning for Cathode/Solution Interface, to produce electric double layer capacitance.Compared to
Electric double layer capacitance, faraday's capacitor are that electroactive material carries out on the two-dimentional or quasi- two-dimensional space in electrode surface or body phase
Chemisorption/the desorption or oxidation/reduction reaction of high reversible occur for underpotential deposition, generate related with electrode charge current potential
Capacitor, the process of storage charge not only includes storage on electric double layer, while further including ion in electrolyte in electrode
Redox reaction occurs in active material and stores charge in electrode.So faraday's capacitance is significantly greater than double
Electric layer capacitor, faraday's capacitor also referred to as bears capacitor.
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.But another
Aspect, only be used only carbon material make supercapacitor electrode material performance be not also very well, such as efficiency for charge-discharge it is low, than electricity
It is serious and easy to reunite etc. to hold not bery high, self-discharge phenomenon.Meanwhile the energy density and power density for the carbon material reported at present
It would generally occur to decay rapidly under the conditions of high magnification, be difficult to meet electric car etc. to supercapacitor high-energy/high power
The urgent need of density.Metal oxide has 10-100 times higher than carbon material of pseudo capacitance.If by carbon material with
Metal oxide combines, while the advantages of two class material of performance, the overall performance of capacitor can be improved.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of preparation of supercapacitor nickel oxide combination electrode material
Method, which is handled by will obtain graphite oxide after graphite oxidation, then with ammonium hydroxide Hybrid Heating, then in nitrogen protection
Lower high-temperature process obtains activation products, then is modified, and is then placed in reaction kettle and the mixed of deionized water and dehydrated alcohol is added
Bonding solvent, polyvinylpyrrolidone and positive silicic acid propyl ester obtain intermediate after high-temperature process, then by intermediate
Curing process, ball-milling treatment, carbonization treatment finally add nickel oxide, 3- TSL 8330, mica powder, lead
Electric agent, binder, it is agitated, coating, drying, roll-in and etc. electrode slice is made.The supercapacitor oxidation being prepared
Nickel combination electrode material, dielectric constant is high, excellent electrical properties, with good application prospect.It also discloses simultaneously by the system
Application of the supercapacitor made from standby technique with nickel oxide combination electrode material in preparation supercapacitor.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of supercapacitor nickel oxide combination 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) by carbonization compound that step (4) obtains, nickel oxide, 3- TSL 8330, mica powder, lead
Electric agent, binder are according to (65-70): (11-13): (7-9): (5-8): (3-5): (2-4) ratio mixing, be added in right amount go from
Sub- water, is evenly stirred until thick, is coated on stainless (steel) wire, then it is dried 8-24 in 80-130 DEG C of vacuum oven
H 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, carbonization compound in the step (5), nickel oxide, 3- TSL 8330, mica powder,
Conductive 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 supercapacitor nickel oxide combination electrode materials obtained by above-mentioned preparation process to make
Application in standby supercapacitor.
Compared with prior art, the present invention has the advantages that:
(1) supercapacitor of the invention is with nickel oxide combination electrode material preparation process by will obtain after graphite oxidation
Graphite oxide, then handled with ammonium hydroxide Hybrid Heating, then high-temperature process obtains activation products under nitrogen protection, then is changed
Property, it is then placed in reaction kettle and mixed solvent, polyvinylpyrrolidone and the positive silicic acid third of deionized water and dehydrated alcohol is added
Ester obtains intermediate after high-temperature process, then by intermediate curing process, ball-milling treatment, carbonization treatment, finally
Add nickel oxide, 3- TSL 8330, mica powder, conductive agent, binder, agitated, coating, drying, roller
Pressure and etc. electrode slice is made.The supercapacitor being prepared nickel oxide combination electrode material, dielectric constant is high, electrically
Can be excellent, with good application prospect.
(2) supercapacitor of the invention with nickel oxide combination electrode material raw material cheap, simple process, be suitable for extensive
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 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 1.5 at 1000 DEG C under nitrogen protection
H obtains high-temperature activation product, is tentatively neutralized with dilute hydrochloric acid to high-temperature activation product, then with deionized water by high-temperature activation
Product washs 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) carbonization compound, nickel oxide, 3- TSL 8330, the mica powder, second obtained step (4)
Acetylene black, sodium carboxymethylcellulose are mixed according to the ratio of 68:11:8:7:4:3, and appropriate amount of deionized water is added, is evenly stirred until viscous
Thick shape is coated on stainless (steel) wire, then it is dried 8 h in 80 DEG C of vacuum oven, electrode slice is cut into after roll-in, is obtained
To finished product.
Supercapacitor obtained is as shown in table 1 with the performance test results of nickel oxide combination electrode material.
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 18 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) by carbonization compound that step (4) obtains, nickel oxide, 3- TSL 8330, mica powder, receive
Rice carbon pipe carbon black, hexafluoropropene are mixed according to the ratio of 68:11:8:7:4:3, and appropriate amount of deionized water is added, is evenly stirred until viscous
Thick shape is coated on stainless (steel) wire, then it is dried 16 h in 105 DEG C of vacuum oven, electrode slice is cut into after roll-in,
Obtain finished product.
Supercapacitor obtained is as shown in table 1 with the performance test results of nickel oxide combination electrode material.
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 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) carbonization compound, nickel oxide, 3- TSL 8330, the mica powder, work obtained step (4)
Property carbon, polyvinyl alcohol according to 68:11:8:7:4:3 ratio mix, be added appropriate amount of deionized water, be evenly stirred until it is thick, apply
It overlays 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, is obtained into
Product.
Supercapacitor obtained is as shown in table 1 with the performance test results of nickel oxide combination electrode material.
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 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 1.5 at 1000 DEG C under nitrogen protection
H obtains high-temperature activation product, is tentatively neutralized with dilute hydrochloric acid to high-temperature activation product, then with deionized water by high-temperature activation
Product washs 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) carbonization compound, nickel oxide, 3- TSL 8330, the mica powder, second obtained step (4)
Acetylene black, sodium carboxymethylcellulose are mixed according to the ratio of 60:17:10:4:9:5, and appropriate amount of deionized water is added, is evenly stirred until viscous
Thick shape is coated on stainless (steel) wire, then it is dried 8 h in 80 DEG C of vacuum oven, electrode slice is cut into after roll-in, is obtained
To finished product.
Supercapacitor obtained is as shown in table 1 with the performance test results of nickel oxide combination electrode material.
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 18 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, nickel oxide, 3- TSL 8330, the mica powder, carbon nanotubes obtained step (4)
Carbon black, hexafluoropropene are mixed according to the ratio of 68:11:8:7:4:3, and appropriate amount of deionized water is added, and are evenly stirred until thick, painting
It overlays 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, is obtained into
Product.
Supercapacitor obtained is as shown in table 1 with the performance test results of nickel oxide combination electrode material.
Comparative example 3
(1) sulfuric acid of 50 g graphite and 120 mL mass concentrations 80% is added in reaction vessel jointly, in 45 DEG C of water
Bath is lower to keep the temperature 25 min, adds the potassium bichromate 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% hydrogen peroxide, with 150
The rate of rpm stirs mixed liquor to discoloration, filters while hot, and gained filter cake is washed 2 times with 3% hydrochloric acid solution of mass concentration, then
It is 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%, then by mixed liquor
It is placed in 85 DEG C of baking oven and heats 60 min, obtain thick slurry, then the high-temperature process at 1500 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, 5 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) carbonization compound, nickel oxide, 3- TSL 8330, the mica powder, work obtained step (4)
Property carbon, polyvinyl alcohol according to 68:11:8:7:4:3 ratio mix, be added appropriate amount of deionized water, be evenly stirred until it is thick, apply
It overlays 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, is obtained into
Product.
Supercapacitor obtained is as shown in table 1 with the performance test results of nickel oxide combination electrode material.
The supercapacitor obtained of embodiment 1-3 and comparative example 1-3 is carried out respectively with nickel oxide combination electrode material
Specific capacity, 0.1C first charge discharge efficiency carry out this several performance tests for the first time by relative dielectric constant, 0.1C.
Table 1
| Relative dielectric constant (εr) | 0.1C specific capacity (mAh/g) for the first time | 0.1C first charge discharge efficiency (%) | |
| Embodiment 1 | 16283 | 135 | 96.6 |
| Embodiment 2 | 15957 | 129 | 95.8 |
| Embodiment 3 | 16031 | 133 | 96.3 |
| Comparative example 1 | 8659 | 67 | 91.4 |
| Comparative example 2 | 7553 | 59 | 90.9 |
| Comparative example 3 | 8048 | 62 | 91.2 |
Supercapacitor of the invention is with nickel oxide combination electrode material preparation process by will obtain stone after graphite oxidation
Black oxide, then handled with ammonium hydroxide Hybrid Heating, then high-temperature process obtains activation products under nitrogen protection, then is changed
Property, it is then placed in reaction kettle and mixed solvent, polyvinylpyrrolidone and the positive silicic acid third of deionized water and dehydrated alcohol is added
Ester obtains intermediate after high-temperature process, then by intermediate curing process, ball-milling treatment, carbonization treatment, finally
Add agitated nickel oxide, 3- TSL 8330, mica powder, conductive agent, binder, coating, drying, roll-in
And etc. electrode slice is made.The supercapacitor being prepared nickel oxide combination electrode material, dielectric constant is high, electrical property
It is excellent, with good application prospect.Supercapacitor of the invention is cheap with nickel oxide combination electrode material raw material, technique is simple
It is single, it is suitable for heavy industrialization and uses, it is 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 (2)
1. a kind of supercapacitor preparation method of nickel oxide combination 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) the carbonization compound that obtains step (4), nickel oxide, 3- TSL 8330, mica powder, conductive agent,
Binder is mixed according to the ratio of 68:11:8:7:4:3, and wherein conductive agent is in acetylene black, carbon nanotubes carbon black, activated carbon
Any one, any one of binder in sodium carboxymethylcellulose, hexafluoropropene, polyvinyl alcohol is then added suitable
Deionized water is measured, is evenly stirred until thick, is coated on stainless (steel) wire, then it is dried in 80-130 DEG C of vacuum oven
Dry 8-24 h, electrode slice is cut into after roll-in, obtains finished product.
2. the supercapacitor that preparation process obtains according to claim 1 with nickel oxide combination electrode material prepare it is super
Application in capacitor.
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| 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 |
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| CN102923698A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Preparation method for three-dimensional porous graphene for supercapacitor |
| 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 |
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