CN110164702A - A kind of lithium battery carbon/manganese dioxide composite material and its application - Google Patents
A kind of lithium battery carbon/manganese dioxide composite material and its application Download PDFInfo
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- CN110164702A CN110164702A CN201810062843.2A CN201810062843A CN110164702A CN 110164702 A CN110164702 A CN 110164702A CN 201810062843 A CN201810062843 A CN 201810062843A CN 110164702 A CN110164702 A CN 110164702A
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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- 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
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to a kind of carbon/manganese dioxide composite material, and preparation method thereof, the composite material with high-specific surface area, there is graphene-structured.The method of the present invention is using graphite and potassium permanganate as raw material, specific steps are as follows: raw graphite is carried out intercalation-expansion process, obtains class expansion of graphene graphite；It will be reacted under gained class expansion of graphene graphite and potassium permanganate earthquake or static conditions, after washing up to carbon/manganese dioxide composite material.The conjugated structure of carbon material is kept preferably in the resulting composite material of the present invention, and manganese dioxide vertical-growth is on the surface of carbon nanosheet.Carbon/manganese dioxide composite material prepared by the present invention can be widely applied to the fields such as supercapacitor, lithium ion battery, fuel cell, energy conversion.In addition, obtained composite material still maintains the open structure of skeleton carbon, the manganese dioxide in composite material can further react for sulfide, nitride.
Description
Technical field
The invention belongs to field of material technology, are related to a kind of with high specific area carbon/manganese dioxide composite material system
Preparation Method obtains class expansion of graphene graphite specifically by intercalation-expanding method；By resulting class expansion of graphene graphite
Reaction is under earthquake or static conditions to get high specific area carbon/manganese dioxide composite material preparation method.Manganese dioxide exists
It vertical-growth and is uniformly distributed on carbon nanosheet.In addition, the conjugated structure of carbon nanosheet still remains intact after the reaction, thus nothing
It need to carry out reduction treatment.
Background technique
With environmental problem increasingly sharpen and Fossil fuel consumption is increasing, develop efficient energy stores and turn
It is most important to change device.Supercapacitor and lithium ion battery are ideal electrochemical energy storing devices.Prepare excellent electricity
Pole material is the key that improve electrochemical energy storing device performance.Manganese dioxide is due to its high theoretical specific capacitance, environmental-friendly, price
The advantages such as cheap, manganese dioxide have become one of the electrode material being widely studied.The nano material of manganese dioxide of different-shape
It is successfully prepared, including nano wire, nano flower, nano dot, nanotube, nanometer sheet etc..However, manganese dioxide itself is led
It is electrically bad, by it directly as electrode material in use, the deficiency of high rate performance and cyclical stability difference can be faced.In order to mention
The performance of high manganese dioxide base electrode material, by the carbon material of manganese dioxide and high conductivity it is compound be the most commonly used method.
The preparation method of carbon/manganese dioxide composite material mainly includes in situ synthesis and construction from part.The former passes through dioxy
Change manganese presoma and directly grows acquisition in carbon material surface；The latter is existed by carbon material with the nano material of manganese dioxide prepared
Assembling obtains in solution.Wherein, the grapheme material of high-specific surface area is the carbon matrix precursor being widely adopted.In general, will oxidation
Graphene or redox graphene mix in the solution with manganese dioxide presoma, pass through the side such as hydro-thermal, heating, microwave radiation
Composite material can be obtained in formula.Then, the carbon material surface defect obtained through oxidation-reduction method is more, gained composite material
High rate performance and cyclical stability are undesirable.Thus, develop the compound of high quality, high-specific surface area carbon material and manganese dioxide
Material is most important.
Summary of the invention
It is an object of the invention to overcome above-mentioned difficulties, a kind of carbon/manganese dioxide composite material and preparation method is provided,
And application of the material in supercapacitor.Carbon nanosheet conjugated structure is kept in the composite material of the method for the present invention preparation
Preferably, has the characteristics that few defect.The manganese dioxide then vertical-growth on carbon nanosheet, and show tens nanometers of nanometer sheet
Pattern.Obtained composite material is restored without further high temperature reduction or using reducing agent.Carbon/titanium dioxide prepared by the present invention
Manganese composite material can apply to the fields such as supercapacitor, lithium ion battery, catalysis, have operating process it is simple, it is at low cost, can
The advantages such as control property is good, are suitble to large-scale production and industrial applications.
The invention proposes a kind of preparation methods of carbon/manganese dioxide composite material, the specific steps are as follows:
(1) by raw graphite carry out intercalation-expansion process, increase graphite layers away from while, introduce a small amount of oxygen-containing functional group,
Obtain class expansion of graphene graphite；
(2) nickel foam is taken to be added in class expansion of graphene graphite obtained in (1), ultrasound, obtaining load has class graphene swollen
The foam nickel material of swollen graphite, it is dry, obtain nickel foam-class expansion of graphene graphite material；
(3) it will be reacted under material and potassium permanganate earthquake or static conditions that step (2) obtains, potassium permanganate during this
Gradually reacted with carbon, formed manganese dioxide, and manganese dioxide can on carbon nanosheet vertical-growth；
(4) intermediate product obtained in (3) is filtered washing to get carbon/manganese dioxide composite material.
In the present invention, step (1) raw graphite is artificial graphite or natural graphite.
In the present invention, step (1) intercalator by acid and oxidant form, concrete component be sulfuric acid, phosphoric acid, nitric acid,
One kind or their combination of potassium permanganate, potassium ferrate, potassium bichromate.The swelling agent be sulfuric acid, phosphoric acid, hydrogen peroxide,
One of ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate or their combination.
In the present invention, potassium permanganate dosage used in step (3) is 0.1-10 times of class expansion of graphene graphite.
It in the present invention, is carried out under the reaction earthquake of step (3) or static conditions, reaction temperature is 20-95 degrees Celsius.
In the present invention, mode of washing described in step (4) be filtration washing, drying mode be vacuum drying, forced air drying,
Spray drying or freeze-drying.
Further, the application the invention further relates to carbon/manganese dioxide composite material in supercapacitor, and by this
The supercapacitor that material is prepared.
In view of the deficienciess of the prior art, the present inventor passes through long-term practice and research, skill of the invention is proposed
Art scheme, this programme can realize the preparation of high quality carbon/manganese dioxide composite material.In technology path of the invention, without super
The strong external force such as sound, shearing, ball milling, condition carries out under normal pressure, and reaction temperature is lower.Mild reaction condition and it is low at
This characteristics of, makes the program that can realize efficient, the large scale preparation of carbon/manganese dioxide composite material.Obtained composite material
It can be widely used in the fields such as lithium ion battery, supercapacitor, catalysis.
The present invention has the advantage that compared with prior art
(1) it directly buys business artificial graphite or natural graphite is raw material, raw material sources are extensive, low in cost.
(2) operation of the present invention mild condition, without high energy consumption process such as shearing, ball milling, high temperature, operation used is lower
At a temperature of carry out, low energy consumption and product morphology is controllable.
(3) defect of carbon material is few in the obtained composite material of the present invention, and electric conductivity is excellent, and manganese dioxide is in carbon nanosheet
On equably vertical-growth.
(4) present invention is without preparing graphite complete oxidation as graphene oxide, then with manganese dioxide forerunner's precursor reactant
Composite material, but directly reacted with potassium permanganate with class expansion of graphene graphite, further reduction treatment is not necessarily to after reaction.
While obtained composite material can more fully play carbon material and manganese dioxide advantage, it may have collaboration effect well
It answers.
Specific embodiment
Illustrate technical solution of the present invention below by way of specific example.It should be understood that the one or more that the present invention mentions
Step do not repel before and after the combination step there is also between other method and steps or these specifically mentioned steps also
Other method and steps can be inserted.It should also be understood that these examples are merely to illustrate the present invention rather than limitation is of the invention
Range.Unless otherwise indicated, the number of various method steps is only the purpose of identification various method steps, rather than to limit each method
Arrangement order or limit practical range of the invention, relativeness is altered or modified, in no substantial technological content alteration
Under conditions of, when being also considered as the enforceable scope of the present invention.
Embodiment 1
(1) 90 milliliters of sulfuric acid are slowly added in 30 milliliters of nitric acid under the conditions of ice-water bath, after mixing, are added into reaction solution
Entering 3 grams of crystalline flake graphites, (150 microns of particle diameter, 95%) phosphorus content is higher than, and stir 24 hours at room temperature.Then, will
Reaction solution is filtered with sand core funnel, and obtained solid is compound between graphite layers.135 millis are added in gained compound between graphite layers
In the mixed liquor for rising hydrogen peroxide and 540 milliliters of sulfuric acid, expansion 3 hours are stood after being stirred at room temperature 15 minutes, and class graphite is obtained after washing
Alkene expanded graphite.
(2) nickel foam after 10mm × 10mm × 2mm cleaning is dipped into the class expansion of graphene stone containing 1g step (1)
In the aqueous solution of ink, concentration of aqueous solution 1mg/mL, reaction temperature is 30 DEG C, frequency 40KHz in ultrasonic procedure, repeatedly ultrasonic quiet
Only, ultrasonic 30min, static 20min, it is repeatedly for three times, obtained to load the foam nickel material for having class expansion of graphene graphite.
(3) 200 milliliter of 2% potassium permanganate water is added in the class expansion of graphene graphite for obtaining step (2)-foam nickel material
In solution, reaction 12 hours are stood under 30 degrees celsius.In reaction process, solution is rocked once manually every 2 hours, is made
Solution is uniformly mixed.
(4) by products therefrom in (3) with sand core funnel filtration washing several times, under 60 degrees celsius in vacuum drying oven do
Dry 6 hours, obtain carbon/manganese dioxide composite material.
Embodiment 2
(1) 3 grams of potassium ferrates are added in 90 milliliters of sulfuric acid, after being completely dissolved, be added into reaction solution 3 grams of crystalline flake graphites (
95%) 150 microns of diameter of grain, phosphorus content are higher than, and at room temperature take out reaction solution with sand core funnel after stirring 1 hour
Filter, obtained solid is compound between graphite layers.135 milliliters of hydrogen peroxide and 540 milliliters are added in gained compound between graphite layers
In the mixed liquor of sulfuric acid, expansion 3 hours are stood after being stirred at room temperature 15 minutes, and class expansion of graphene graphite is obtained after washing.
(2) nickel foam after 10mm × 10mm × 2mm cleaning is dipped into the class expansion of graphene stone containing 1g step (1)
In the aqueous solution of ink, concentration of aqueous solution 1mg/mL, reaction temperature is 30 DEG C, frequency 40KHz in ultrasonic procedure, repeatedly ultrasonic quiet
Only, ultrasonic 30min, static 20min, it is repeatedly for three times, obtained to load the foam nickel material for having class expansion of graphene graphite.
(3) 200 milliliter of 4% potassium permanganate water is added in the class expansion of graphene graphite for obtaining step (2)-foam nickel material
In solution, reaction 12 hours are stood under 30 degrees celsius.In reaction process, solution is rocked once manually every 2 hours, is made
Solution is uniformly mixed.
(4) by products therefrom in (3) with sand core funnel filtration washing several times, under 60 degrees celsius in vacuum drying oven do
Dry 6 hours, obtain carbon/manganese dioxide composite material.
Embodiment 3
(1) 3 grams of potassium permanganate are slowly added in 90 milliliters of sulfuric acid, after being completely dissolved, 3 grams of crystalline flake graphites is added into reaction solution
(150 microns of particle diameter, 95%) phosphorus content is higher than, and at room temperature after stirring 1 hour, by reaction solution sand core funnel
It filters, obtained solid is compound between graphite layers.135 milliliters of hydrogen peroxide and 540 millis are added in gained compound between graphite layers
In the mixed liquor for rising sulfuric acid, expansion 3 hours are stood after being stirred at room temperature 15 minutes, and class expansion of graphene graphite is obtained after washing.
(2) nickel foam after 10mm × 10mm × 2mm cleaning is dipped into the class expansion of graphene stone containing 1g step (1)
In the aqueous solution of ink, concentration of aqueous solution 1mg/mL, reaction temperature is 30 DEG C, frequency 40KHz in ultrasonic procedure, repeatedly ultrasonic quiet
Only, ultrasonic 30min, static 20min, it is repeatedly for three times, obtained to load the foam nickel material for having class expansion of graphene graphite.
(3) 200 milliliter of 2% potassium permanganate is added in class expansion of graphene graphite obtained in step (2)-foam nickel material
In aqueous solution, reaction 12 hours are stood under 30 degrees celsius.In reaction process, solution is rocked once manually every 2 hours,
It is uniformly mixed solution.
(4) by products therefrom in (3) with sand core funnel filtration washing several times, under 60 degrees celsius in vacuum drying oven do
Dry 6 hours, obtain carbon/manganese dioxide composite material.
Embodiment 4
(1) 3 grams of potassium ferrates are added in the nitration mixture of 80 milliliters of sulfuric acid and 10 milliliters of phosphoric acid, after being completely dissolved, into reaction solution
3 grams of crystalline flake graphites are added, and (150 microns of particle diameter, 95%) phosphorus content is higher than, and at room temperature after stirring 1 hour, will be anti-
It answers liquid to be filtered with sand core funnel, obtains compound between graphite layers.30 grams of sodium peroxydisulfates are added in gained compound between graphite layers to be added
In in the nitration mixture of 270 milliliters of sulfuric acid and 30 milliliters of phosphoric acid, expansion 3 hours are stood after being stirred at room temperature 15 minutes, and class stone is obtained after washing
Black alkene expanded graphite.
(2) nickel foam after 10mm × 10mm × 2mm cleaning is dipped into the class expansion of graphene stone containing 1g step (1)
In the aqueous solution of ink, concentration of aqueous solution 1mg/mL, reaction temperature is 30 DEG C, frequency 40KHz in ultrasonic procedure, repeatedly ultrasonic quiet
Only, ultrasonic 30min, static 20min, it is repeatedly for three times, obtained to load the foam nickel material for having class expansion of graphene graphite.
(3) 200 milliliter of 2% potassium permanganate is added in class expansion of graphene graphite obtained in step (2)-foam nickel material
In aqueous solution, reaction 12 hours are stood under 30 degrees celsius.In reaction process, solution is rocked once manually every 2 hours,
It is uniformly mixed solution.
(4) by products therefrom in (3) with sand core funnel filtration washing several times, be lyophilized 24 hours in freeze dryer, obtain carbon/bis-
Manganese oxide composite material.
Embodiment 5
(1) 90 milliliters of sulfuric acid are slowly added in 30 milliliters of nitric acid under the conditions of ice-water bath, after mixing, are added into reaction solution
Entering 3 grams of crystalline flake graphites, (150 microns of particle diameter, 95%) phosphorus content is higher than, and stir 24 hours at room temperature.Then, will
Reaction solution is filtered with sand core funnel, and obtained solid is compound between graphite layers.135 millis are added in gained compound between graphite layers
In the mixed liquor for rising hydrogen peroxide and 540 milliliters of sulfuric acid, expansion 3 hours are stood after being stirred at room temperature 15 minutes, and class graphite is obtained after washing
Alkene expanded graphite.
(2) nickel foam after 10mm × 10mm × 2mm cleaning is dipped into the class expansion of graphene stone containing 1g step (1)
In the aqueous solution of ink, concentration of aqueous solution 1mg/mL, reaction temperature is 30 DEG C, frequency 40KHz in ultrasonic procedure, repeatedly ultrasonic quiet
Only, ultrasonic 30min, static 20min, it is repeatedly for three times, obtained to load the foam nickel material for having class expansion of graphene graphite.
(3) 200 milliliter of 2% potassium permanganate is added in class expansion of graphene graphite obtained in step (2)-foam nickel material
In aqueous solution, then reaction vessel is put into shaking table, concussion reaction 12 hours under 40 degrees celsius.
(4) by products therefrom in (3) with sand core funnel filtration washing several times, under 60 degrees celsius in vacuum drying oven do
Dry 6 hours, obtain carbon/manganese dioxide composite material.
Embodiment 6
(1) 3 grams of potassium permanganate are slowly added under the conditions of ice-water bath in the nitration mixture of 80 milliliters of sulfuric acid and 10 milliliters of phosphoric acid, completely
After dissolution, 3 grams of crystalline flake graphites are added into reaction solution, and (150 microns of particle diameter, 95%) phosphorus content is higher than, and in room temperature condition
After lower stirring 1 hour, reaction solution is filtered with sand core funnel, obtained solid is compound between graphite layers.By gained graphite linings
Between compound 30 grams of sodium peroxydisulfates be added be added in the nitration mixture of 270 milliliters of sulfuric acid and 30 milliliters of phosphoric acid, after being stirred at room temperature 15 minutes
Expansion 3 hours are stood, class expansion of graphene graphite is obtained after washing.
(2) nickel foam after 10mm × 10mm × 2mm cleaning is dipped into the class expansion of graphene stone containing 1g step (1)
In the aqueous solution of ink, concentration of aqueous solution 1mg/mL, reaction temperature is 30 DEG C, frequency 40KHz in ultrasonic procedure, repeatedly ultrasonic quiet
Only, ultrasonic 30min, static 20min, it is repeatedly for three times, obtained to load the foam nickel material for having class expansion of graphene graphite.
(3) 200 milliliter of 4.5% permanganic acid is added in class expansion of graphene graphite obtained in step (2)-foam nickel material
In aqueous solutions of potassium, reaction 4 hours are stood under 60 degrees celsius.In reaction process, solution is rocked one manually every 2 hours
It is secondary, it is uniformly mixed solution.
(4) by products therefrom in (3) with sand core funnel filtration washing several times, under 60 degrees celsius in convection oven do
Dry 12 hours, obtain carbon/manganese dioxide composite material.
Embodiment 7
(1) 3 grams of potassium ferrates are added in 90 milliliters of sulfuric acid, after being completely dissolved, be added into reaction solution 3 grams of crystalline flake graphites (
95%) 150 microns of diameter of grain, phosphorus content are higher than, and at room temperature take out reaction solution with sand core funnel after stirring 1 hour
Filter, obtained solid is compound between graphite layers.60 grams of potassium peroxydisulfates are added in gained compound between graphite layers and are added 300 milliliters
In sulfuric acid mixture liquid, expansion 12 hours are stood after being stirred at room temperature 15 minutes, and class expansion of graphene graphite is obtained after washing.
(2) nickel foam after 10mm × 10mm × 2mm cleaning is dipped into the class expansion of graphene stone containing 1g step (1)
In the aqueous solution of ink, concentration of aqueous solution 1mg/mL, reaction temperature is 30 DEG C, frequency 40KHz in ultrasonic procedure, repeatedly ultrasonic quiet
Only, ultrasonic 30min, static 20min, it is repeatedly for three times, obtained to load the foam nickel material for having class expansion of graphene graphite.
(3) 200 milliliter of 5% potassium permanganate is added in class expansion of graphene graphite obtained in step (2)-foam nickel material
In aqueous solution, reaction 18 hours are stood under 20 degrees celsius.In reaction process, solution is rocked once manually every 2 hours,
It is uniformly mixed solution.
(4) by products therefrom in (3) with sand core funnel filtration washing several times, under 60 degrees celsius in vacuum drying oven do
Dry 6 hours, obtain carbon/manganese dioxide composite material.
Embodiment 8
(1) 3 grams of potassium permanganate are slowly added in 90 milliliters of sulfuric acid under the conditions of ice-water bath, after being completely dissolved, into reaction solution
3 grams of crystalline flake graphites are added, and (150 microns of particle diameter, 95%) phosphorus content is higher than, and after stirring 1 hour under the conditions of 35 DEG C, will be anti-
Liquid is answered to be filtered with sand core funnel, obtained solid is compound between graphite layers.45 grams of mistakes are added in gained compound between graphite layers
Potassium sulfate is added in 350 milliliters of sulfuric acid, and expansion 312 hours are stood after being stirred at room temperature 15 minutes, and class expansion of graphene is obtained after washing
Graphite.
(2) nickel foam after 10mm × 10mm × 2mm cleaning is dipped into the class expansion of graphene stone containing 1g step (1)
In the aqueous solution of ink, concentration of aqueous solution 1mg/mL, reaction temperature is 30 DEG C, frequency 40KHz in ultrasonic procedure, repeatedly ultrasonic quiet
Only, ultrasonic 30min, static 20min, it is repeatedly for three times, obtained to load the foam nickel material for having class expansion of graphene graphite.
(3) 200 milliliter of 6% potassium permanganate is added in class expansion of graphene graphite obtained in step (2)-foam nickel material
In aqueous solution, reaction 3 hours are stood under 80 degrees celsius.In reaction process, solution is rocked one manually every 0.5 hour
It is secondary, it is uniformly mixed solution.
(4) by products therefrom in (3) with sand core funnel filtration washing several times, under 80 degrees celsius in vacuum drying oven do
Dry 4 hours, obtain carbon/manganese dioxide composite material.
Embodiment 9
(1) 3 grams of potassium permanganate are slowly added in 90 milliliters of sulfuric acid under the conditions of ice-water bath, after being completely dissolved, into reaction solution
3 grams of crystalline flake graphites are added, and (150 microns of particle diameter, 95%) phosphorus content is higher than, and after stirring 1 hour under the conditions of 35 DEG C, will be anti-
Liquid is answered to be filtered with sand core funnel, obtained solid is compound between graphite layers.3 grams of over cures are added in gained compound between graphite layers
Sour ammonium is added in 100 milliliters of sulfuric acid, is stirred at room temperature and stands expansion 10 hours after twenty minutes, and class expansion of graphene stone is obtained after washing
Ink.
(2) nickel foam after 10mm × 10mm × 2mm cleaning is dipped into the class expansion of graphene stone containing 1g step (1)
In the aqueous solution of ink, concentration of aqueous solution 1mg/mL, reaction temperature is 30 DEG C, frequency 40KHz in ultrasonic procedure, repeatedly ultrasonic quiet
Only, ultrasonic 30min, static 20min, it is repeatedly for three times, obtained to load the foam nickel material for having class expansion of graphene graphite.
(3) 200 milliliter of 1% potassium permanganate is added in class expansion of graphene graphite obtained in step (2)-foam nickel material
It in aqueous solution, places reaction liquid into shaking table, is reacted 24 hours under 30 degrees celsius.
(4) by products therefrom in (3) with sand core funnel filtration washing several times, freeze-drying 24 hours after, obtain carbon/titanium dioxide
Manganese composite material.
Embodiment 10
(1) 0.3 gram of potassium permanganate is slowly added in 30 milliliters of sulfuric acid under the conditions of ice-water bath, after being completely dissolved, to reaction solution
It is middle 3 grams of crystalline flake graphites to be added (150 microns of particle diameter, 95%) phosphorus content is higher than, and after stir 1 hour under the conditions of 35 DEG C, general
Reaction solution is filtered with sand core funnel, and obtained solid is compound between graphite layers.300 millis are added in gained compound between graphite layers
It rises in sulfuric acid and 60 milliliters of dioxygen water mixed liquids, expansion 4 hours is stood after being stirred at room temperature 15 minutes, it is swollen that class graphene is obtained after washing
Swollen graphite.
(2) nickel foam after 10mm × 10mm × 2mm cleaning is dipped into the class expansion of graphene stone containing 1g step (1)
In the aqueous solution of ink, concentration of aqueous solution 1mg/mL, reaction temperature is 30 DEG C, frequency 40KHz in ultrasonic procedure, repeatedly ultrasonic quiet
Only, ultrasonic 30min, static 20min, it is repeatedly for three times, obtained to load the foam nickel material for having class expansion of graphene graphite.
(3) 200 milliliter of 6% potassium permanganate is added in class expansion of graphene graphite obtained in step (2)-foam nickel material
In aqueous solution, reacted 2 hours under 95 degrees celsius.In reaction process, reaction solution is rocked once manually every 15 minutes, is made
It is uniformly mixed.
(4) by products therefrom in (3) with sand core funnel filtration washing several times, under 60 degrees celsius in vacuum drying oven do
Dry 6 hours, obtain carbon/manganese dioxide composite material.
Embodiment 11
(1) 0.3 gram of potassium permanganate is slowly added in 30 milliliters of sulfuric acid under the conditions of ice-water bath, after being completely dissolved, to reaction solution
It is middle 3 grams of crystalline flake graphites to be added (150 microns of particle diameter, 95%) phosphorus content is higher than, and after stir 1 hour under the conditions of 35 DEG C, general
Reaction solution is filtered with sand core funnel, and obtained solid is compound between graphite layers.Gained compound between graphite layers are added 30 grams
Ammonium persulfate is added in 300 milliliters of sulfuric acid in mixed liquor, and expansion 412 hours are stood after being stirred at room temperature 15 minutes, and class is obtained after washing
Expansion of graphene graphite.
(2) nickel foam after 10mm × 10mm × 2mm cleaning is dipped into the class expansion of graphene stone containing 1g step (1)
In the aqueous solution of ink, concentration of aqueous solution 1mg/mL, reaction temperature is 30 DEG C, frequency 40KHz in ultrasonic procedure, repeatedly ultrasonic quiet
Only, ultrasonic 30min, static 20min, it is repeatedly for three times, obtained to load the foam nickel material for having class expansion of graphene graphite.
(3) 200 milliliter of 10% potassium permanganate is added in class expansion of graphene graphite obtained in step (2)-foam nickel material
In aqueous solution, reacted 1 hour under 95 degrees celsius.In reaction process, reaction solution is rocked once manually every 10 minutes, is made
It is uniformly mixed.
(4) by products therefrom in (3) with sand core funnel filtration washing several times, after freeze-drying, it is compound to obtain carbon/manganese dioxide
Material.
Embodiment 12
(1) 3 grams of potassium ferrates are added in the nitration mixture of 80 milliliters of sulfuric acid and 10 milliliters of phosphoric acid, after being completely dissolved, into reaction solution
3 grams of crystalline flake graphites are added, and (150 microns of particle diameter, 95%) phosphorus content is higher than, and at room temperature after stirring 1 hour, will be anti-
Liquid is answered to be filtered with sand core funnel, obtained solid is compound between graphite layers.30 grams of mistakes are added in gained compound between graphite layers
Sodium sulphate is added in the mixed liquor of 270 milliliters of sulfuric acid and 30 milliliters of phosphoric acid, and expansion 12 hours are stood after being stirred at room temperature 15 minutes, are washed
Class expansion of graphene graphite is obtained after washing.
(2) nickel foam after 10mm × 10mm × 2mm cleaning is dipped into the class expansion of graphene stone containing 1g step (1)
In the aqueous solution of ink, concentration of aqueous solution 1mg/mL, reaction temperature is 30 DEG C, frequency 40KHz in ultrasonic procedure, repeatedly ultrasonic quiet
Only, ultrasonic 30min, static 20min, it is repeatedly for three times, obtained to load the foam nickel material for having class expansion of graphene graphite.
(3) 200 milliliter of 10% potassium permanganate is added in class expansion of graphene graphite obtained in step (2)-foam nickel material
In aqueous solution, by reaction solution in being placed in shaking table, reacted 6 hours under 40 degrees celsius.
(4) by products therefrom in (3) with sand core funnel filtration washing several times, after freeze-drying, it is compound to obtain carbon/manganese dioxide
Material.
Embodiment 13
(1) 6 grams of potassium ferrates are added in 90 milliliters of sulfuric acid, after being completely dissolved, be added into reaction solution 3 grams of crystalline flake graphites (
95%) 150 microns of diameter of grain, phosphorus content are higher than, and at room temperature take out reaction solution with sand core funnel after stirring 1 hour
Filter, obtained solid is compound between graphite layers.Obtained solid is compound between graphite layers.By gained compound between graphite layers
60 grams of sodium peroxydisulfates are added to be added in 300 milliliters of sulfuric acid mixture liquids, expansion 12 hours are stood after being stirred at room temperature 15 minutes, after washing
Obtain class expansion of graphene graphite.
(2) nickel foam after 10mm × 10mm × 2mm cleaning is dipped into the class expansion of graphene stone containing 1g step (1)
In the aqueous solution of ink, concentration of aqueous solution 1mg/mL, reaction temperature is 30 DEG C, frequency 40KHz in ultrasonic procedure, repeatedly ultrasonic quiet
Only, ultrasonic 30min, static 20min, it is repeatedly for three times, obtained to load the foam nickel material for having class expansion of graphene graphite.
(3) 200 milliliter of 3% potassium permanganate is added in class expansion of graphene graphite obtained in step (2)-foam nickel material
In aqueous solution, reacted 4 hours under 70 degrees celsius.In reaction process, reaction solution is rocked once manually every 10 minutes, is made
It is uniformly mixed.
(4) by products therefrom in (3) with sand core funnel filtration washing several times, 90 degrees Celsius of dryings 2 are small in vacuum drying oven
When, obtain carbon/manganese dioxide composite material.
Embodiment 14
(1) 3 grams of potassium permanganate are slowly added in 90 milliliters of sulfuric acid under the conditions of ice-water bath, after being completely dissolved, into reaction solution
3 grams of crystalline flake graphites are added, and (150 microns of particle diameter, 95%) phosphorus content is higher than, and after stirring 1 hour under the conditions of 35 DEG C, will be anti-
Liquid is answered to be filtered with sand core funnel, obtained solid is compound between graphite layers.Gained compound between graphite layers are added 40 milliliters
In hydrogen peroxide and 260 milliliters of sulfuric acid mixture liquids, expansion 412 hours are stood after being stirred at room temperature 15 minutes, and class graphene is obtained after washing
Expanded graphite.
(2) nickel foam after 10mm × 10mm × 2mm cleaning is dipped into the class expansion of graphene stone containing 1g step (1)
In the aqueous solution of ink, concentration of aqueous solution 1mg/mL, reaction temperature is 30 DEG C, frequency 40KHz in ultrasonic procedure, repeatedly ultrasonic quiet
Only, ultrasonic 30min, static 20min, it is repeatedly for three times, obtained to load the foam nickel material for having class expansion of graphene graphite.
(3) 200 milliliter of 4% potassium permanganate is added in class expansion of graphene graphite obtained in step (2)-foam nickel material
It in aqueous solution, places reaction liquid into shaking table, is reacted 3 hours under 50 degrees celsius.
(4) by products therefrom in (3) with sand core funnel filtration washing several times, after freeze-drying, it is compound to obtain carbon/manganese dioxide
Material.
Comparative example 1
(1) 1 gram of crystalline flake graphite is added in 200 milliliter of 3% potassium permanganate solution, reaction solution is placed in shaking table, 70 degrees Celsius of items
It is reacted 6 hours under part.
(2) by after product washing and drying obtained in (1), final product is obtained.Obtained composite material is only in graphite table
There is manganese dioxide generation in face, and product is piled up closely.
Comparative example 2
(1) 1 gram of crystalline flake graphite is added in 200 milliliter of 6% potassium permanganate solution, is reacted 8 hours under 70 degrees celsius.Instead
During answering, reaction solution is rocked once manually every 1 hour, is uniformly mixed it.
(2) by after product washing and drying obtained in (1), final product is obtained.Obtained composite material is only in graphite table
Face has a small amount of manganese dioxide to generate, and product is piled up closely.
Claims (8)
1. a kind of lithium battery carbon/manganese dioxide composite material, which is characterized in that it is prepared via a method which to obtain:
(1) by raw graphite carry out intercalation-expansion process, increase graphite layers away from while, introduce a small amount of oxygen-containing functional group,
Obtain class expansion of graphene graphite；
(2) nickel foam is taken to be added in class expansion of graphene graphite obtained in (1), ultrasound, obtaining load has class graphene swollen
The foam nickel material of swollen graphite, it is dry, obtain nickel foam-class expansion of graphene graphite material；
(3) it will be reacted under material and potassium permanganate earthquake or static conditions that step (2) obtains, potassium permanganate during this
Gradually reacted with carbon, formed manganese dioxide, and manganese dioxide can on carbon nanosheet vertical-growth；
(4) intermediate product obtained in (3) is filtered washing to get carbon/manganese dioxide composite material.
2. a kind of lithium battery carbon/manganese dioxide composite material according to claim 1, it is characterised in that the graphite
For natural or artificial graphite.
3. a kind of lithium battery carbon/manganese dioxide composite material according to claim 1, it is characterised in that the intercalation
Agent is sulfuric acid, phosphoric acid, nitric acid, potassium permanganate, one kind of potassium ferrate or the combination between them；The swelling agent is sulphur
One of acid, phosphoric acid, hydrogen peroxide, ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate or the combination between them.
4. a kind of lithium battery carbon/manganese dioxide composite material according to claim 1, it is characterised in that class graphene is swollen
Swollen graphite is reacted with potassium permanganate to carry out under earthquake or static conditions, and reaction temperature is 20-95 degrees Celsius.
5. a kind of lithium battery carbon/manganese dioxide composite material according to claim 1, it is characterised in that the filtering
Mode is vacuum filtration or the screen to filtrate.
6. a kind of lithium battery carbon/manganese dioxide composite material according to claim 1, it is characterised in that obtained multiple
In condensation material, the conjugated structure of carbon nanosheet lamella is kept preferably, has more low defect compared to the graphene oxide of reduction；Two
Manganese oxide nanometer sheet vertical-growth on carbon nanosheet, and be evenly distributed；Obtained composite material shows porous structure, carbon
There are apparent folds on nanometer sheet surface.Since the conjugated structure of carbon nanosheet is kept preferably, without carrying out reduction treatment.
7. a kind of lithium battery carbon/manganese dioxide composite material as described in claim 1 answering in preparation supercapacitor
With.
8. a kind of supercapacitor, it uses lithium battery as described in claim 1 carbon/manganese dioxide composite materials.
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