CN108199033A - A kind of preparation method of lithium battery carbon/manganese dioxide composite material - Google Patents
A kind of preparation method of lithium battery carbon/manganese dioxide composite material Download PDFInfo
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- CN108199033A CN108199033A CN201810062661.5A CN201810062661A CN108199033A CN 108199033 A CN108199033 A CN 108199033A CN 201810062661 A CN201810062661 A CN 201810062661A CN 108199033 A CN108199033 A CN 108199033A
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- manganese dioxide
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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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of preparation methods of carbon/manganese dioxide composite material.The method of the present invention using graphite and potassium permanganate as raw material, the specific steps are:Raw graphite is subjected to intercalation expansion process, obtains class expansion of graphene graphite;Gained class expansion of graphene graphite is reacted under potassium permanganate earthquake or static conditions, after washing up to carbon/manganese dioxide composite material.The prices of raw materials of the present invention are cheap, and reaction condition is mild, without the strong external force input such as ultrasound, shearing, ball milling.The conjugated structure of carbon material keeps preferable in the composite material of gained, 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 ultracapacitor, 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 be further reacted for sulfide, nitride.
Description
Technical field
The invention belongs to field of material technology, are related to a kind of system with high specific area carbon/manganese dioxide composite material
Preparation Method specifically by intercalation-expanding method, obtains class expansion of graphene graphite;By the class expansion of graphene graphite of gained
The preparation method to get high specific area carbon/manganese dioxide composite material is reacted under earthquake or static conditions.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 technology
With environmental problem increasingly sharpen and Fossil fuel consumption is increasing, develop efficient energy stores and turn
It is most important to change device.Ultracapacitor 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 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 is led in itself
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 carry
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 grow acquisition in carbon material surface;The latter is existed by carbon material and 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.It 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
Formula, you can obtain composite material.Then, the carbon material surface defect that oxidized reduction method obtains 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.
Invention content
It is an object of the invention to overcome above-mentioned difficulties, a kind of preparation method of carbon/manganese dioxide composite material is provided.This
Carbon nanosheet conjugated structure keeps preferable in composite material prepared by inventive method, has the characteristics that few defect.Manganese dioxide is then
The vertical-growth on carbon nanosheet, and show tens nanometers of nanometer sheet pattern.Obtained composite material is without further
High temperature reduction is restored using reducing agent.Carbon/manganese dioxide composite material prepared by the present invention can apply to ultracapacitor, lithium
The fields such as ion battery, catalysis have the advantages such as operating process is simple, at low cost, controllability is good, are suitble to large-scale production and work
Industry application.
The present invention proposes a kind of preparation method of carbon/manganese dioxide composite material, is 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 to(1)In in obtained class expansion of graphene graphite, ultrasound, obtaining load has the class graphene swollen
The foam nickel material of swollen graphite, it is dry, obtain nickel foam-class expansion of graphene graphite material;
(3)By step(2)Obtained material is reacted under potassium permanganate earthquake or static conditions, potassium permanganate during this
Gradually reacted with carbon, formed manganese dioxide, and manganese dioxide can on carbon nanosheet vertical-growth;
(4)It will(3)In obtained intermediate product be filtered washing to get carbon/manganese dioxide composite material.
In the present invention, step(1)The raw graphite is Delanium or native graphite.
In the present invention, step(1)The intercalator by acid and oxidant form, concrete component be sulfuric acid, phosphoric acid, nitric acid,
Potassium permanganate, potassium ferrate, potassium bichromate one kind or combination thereof.The swelling agent for sulfuric acid, phosphoric acid, hydrogen peroxide,
One kind or combination thereof in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate.
In the present invention, step(3)Potassium permanganate dosage used is 0.1-10 times of class expansion of graphene graphite.
In the present invention, step(3)Reaction earthquake or static conditions under carry out, reaction temperature be 20-95 degrees Celsius.
In the present invention, step(4)The mode of washing be filtration washing, drying mode for vacuum drying, forced air drying,
Spray drying or freeze-drying.
In view of the deficienciess of the prior art, the present inventor passes through long-term practice and research, it is proposed that skill of the invention
Art scheme, this programme can realize the preparation of high quality carbon/manganese dioxide composite material.In the technology path of the present invention, without super
The strong external force effect such as sound, shearing, ball milling, condition carries out under normal pressure, and reaction temperature is relatively low.Mild reaction condition and it is low into
This characteristics of, causes the program that can realize efficient, the extensive preparation of carbon/manganese dioxide composite material.Obtained composite material
It can be widely used in the fields such as lithium ion battery, ultracapacitor, catalysis.
The present invention has the advantage that compared with prior art:
(1)It is raw material directly to buy business Delanium or native graphite, and raw material sources are extensive, of low cost.
(2)Operating condition of the present invention is mild, and without the high energy consumption process such as shearing, ball milling, high temperature, operation used is relatively low
At a temperature of carry out, low energy consumption and product morphology is controllable.
(3)Few the defects of carbon material in the obtained composite material of the present invention, electric conductivity is excellent, and manganese dioxide is in carbon nanosheet
On equably vertical-growth.
(4)The present invention by graphite complete oxidation without becoming graphene oxide, then prepare with manganese dioxide forerunner precursor reactant
Composite material, but directly reacted with class expansion of graphene graphite in potassium permanganate, without further reduction treatment after reaction.
While obtained composite material can more fully play carbon material and manganese dioxide advantage, it may have collaboration effect well
It should.
Specific embodiment
Illustrate technical scheme 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 also there are between other method and steps or these specifically mentioned steps also
It may be inserted into other method and steps.It should also be understood that these examples are merely to illustrate the present invention rather than limit the present invention's
Range.Unless otherwise indicated, the number of various method steps is only to differentiate the purpose of various method steps rather than to limit each method
Ordering or limit the present invention practical range, 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 under the conditions of ice-water bath in 30 milliliters of nitric acid, after mixing, are added into reaction solution
Enter 3 grams of crystalline flake graphites(150 microns of particle diameter, phosphorus content are higher than 95%), and stir 24 hours at ambient temperature.Then, will
Reaction solution is filtered with sand core funnel, and obtained solid is compound between graphite layers.Gained compound between graphite layers are added in into 135 millis
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, class graphite is obtained after washing
Alkene expanded graphite.
(2)Nickel foam after 10mm × 10mm × 2mm cleanings is dipped into containing 1g steps(1)Class expansion of graphene stone
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)By step(2)Obtained class expansion of graphene graphite-foam nickel material adds in 200 milliliter of 2% potassium permanganate water
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)It will(3)Middle products therefrom several times, is done with sand core funnel filtration washing under 60 degrees celsius in vacuum drying oven
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, 3 grams of crystalline flake graphites are added in into reaction solution(
150 microns of diameter of grain, phosphorus content are higher than 95%), and at ambient temperature stir 1 hour after, reaction solution is taken out with sand core funnel
Filter, obtained solid is compound between graphite layers.Gained compound between graphite layers are added in into 135 milliliters of hydrogen peroxide and 540 milliliters
In the mixed liquor of sulfuric acid, expansion 3 hours are stood after being stirred at room temperature 15 minutes, class expansion of graphene graphite is obtained after washing.
(2)Nickel foam after 10mm × 10mm × 2mm cleanings is dipped into containing 1g steps(1)Class expansion of graphene stone
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)By step(2)Obtained class expansion of graphene graphite-foam nickel material adds in 200 milliliter of 4% potassium permanganate water
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)It will(3)Middle products therefrom several times, is done with sand core funnel filtration washing under 60 degrees celsius in vacuum drying oven
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 are added in into reaction solution
(150 microns of particle diameter, phosphorus content are higher than 95%), and at ambient temperature stir 1 hour after, by reaction solution sand core funnel
It filters, obtained solid is compound between graphite layers.Gained compound between graphite layers are added in into 135 milliliters of hydrogen peroxide and 540 millis
In the mixed liquor for rising sulfuric acid, expansion 3 hours are stood after being stirred at room temperature 15 minutes, class expansion of graphene graphite is obtained after washing.
(2)Nickel foam after 10mm × 10mm × 2mm cleanings is dipped into containing 1g steps(1)Class expansion of graphene stone
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)By step(2)In obtained class expansion of graphene graphite-foam nickel material add in 200 milliliter of 2% potassium permanganate
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)It will(3)Middle products therefrom several times, is done with sand core funnel filtration washing under 60 degrees celsius in vacuum drying oven
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
Add in 3 grams of crystalline flake graphites(150 microns of particle diameter, phosphorus content are higher than 95%), and after stirring 1 hour at ambient temperature, it will be anti-
Liquid is answered to be filtered with sand core funnel, obtains compound between graphite layers.Gained compound between graphite layers are added in 30 grams of sodium peroxydisulfates to add in
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, class stone is obtained after washing
Black alkene expanded graphite.
(2)Nickel foam after 10mm × 10mm × 2mm cleanings is dipped into containing 1g steps(1)Class expansion of graphene stone
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)By step(2)In obtained class expansion of graphene graphite-foam nickel material add in 200 milliliter of 2% potassium permanganate
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)It will(3)Middle products therefrom several times, is lyophilized 24 hours in freeze dryer with sand core funnel filtration washing, obtains carbon/bis-
Manganese oxide composite material.
Embodiment 5
(1)90 milliliters of sulfuric acid are slowly added under the conditions of ice-water bath in 30 milliliters of nitric acid, after mixing, are added into reaction solution
Enter 3 grams of crystalline flake graphites(150 microns of particle diameter, phosphorus content are higher than 95%), and stir 24 hours at ambient temperature.Then, will
Reaction solution is filtered with sand core funnel, and obtained solid is compound between graphite layers.Gained compound between graphite layers are added in into 135 millis
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, class graphite is obtained after washing
Alkene expanded graphite.
(2)Nickel foam after 10mm × 10mm × 2mm cleanings is dipped into containing 1g steps(1)Class expansion of graphene stone
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)By step(2)In obtained class expansion of graphene graphite-foam nickel material add in 200 milliliter of 2% potassium permanganate
In aqueous solution, then reaction vessel is put into shaking table, concussion reaction 12 hours under 40 degrees celsius.
(4)It will(3)Middle products therefrom several times, is done with sand core funnel filtration washing under 60 degrees celsius in vacuum drying oven
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 dissolving, 3 grams of crystalline flake graphites are added in into reaction solution(150 microns of particle diameter, phosphorus content are higher than 95%), 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 add in 30 grams of sodium peroxydisulfates and add 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 cleanings is dipped into containing 1g steps(1)Class expansion of graphene stone
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)By step(2)In obtained class expansion of graphene graphite-foam nickel material add in 200 milliliter of 4.5% permanganic acid
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)It will(3)Middle products therefrom several times, is done with sand core funnel filtration washing under 60 degrees celsius in convection oven
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, 3 grams of crystalline flake graphites are added in into reaction solution(
150 microns of diameter of grain, phosphorus content are higher than 95%), and at ambient temperature stir 1 hour after, reaction solution is taken out with sand core funnel
Filter, obtained solid is compound between graphite layers.Gained compound between graphite layers are added in into 60 grams of potassium peroxydisulfates and add in 300 milliliters
In sulfuric acid mixture liquid, expansion 12 hours are stood after being stirred at room temperature 15 minutes, class expansion of graphene graphite is obtained after washing.
(2)Nickel foam after 10mm × 10mm × 2mm cleanings is dipped into containing 1g steps(1)Class expansion of graphene stone
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)By step(2)In obtained class expansion of graphene graphite-foam nickel material add in 200 milliliter of 5% potassium permanganate
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)It will(3)Middle products therefrom several times, is done with sand core funnel filtration washing under 60 degrees celsius in vacuum drying oven
Dry 6 hours, obtain carbon/manganese dioxide composite material.
Embodiment 8
(1)3 grams of potassium permanganate are slowly added under the conditions of ice-water bath in 90 milliliters of sulfuric acid, after being completely dissolved, into reaction solution
Add in 3 grams of crystalline flake graphites(150 microns of particle diameter, phosphorus content are higher than 95%), and after being stirred 1 hour under the conditions of 35 DEG C, it 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 in into 45 grams of mistakes
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 cleanings is dipped into containing 1g steps(1)Class expansion of graphene stone
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)By step(2)In obtained class expansion of graphene graphite-foam nickel material add in 200 milliliter of 6% potassium permanganate
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)It will(3)Middle products therefrom several times, is done with sand core funnel filtration washing under 80 degrees celsius in vacuum drying oven
Dry 4 hours, obtain carbon/manganese dioxide composite material.
Embodiment 9
(1)3 grams of potassium permanganate are slowly added under the conditions of ice-water bath in 90 milliliters of sulfuric acid, after being completely dissolved, into reaction solution
Add in 3 grams of crystalline flake graphites(150 microns of particle diameter, phosphorus content are higher than 95%), and after being stirred 1 hour under the conditions of 35 DEG C, it 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 in into 3 grams of over cures
Sour ammonium is added in 100 milliliters of sulfuric acid, is stirred at room temperature and is stood expansion 10 hours after twenty minutes, and class expansion of graphene stone is obtained after washing
Ink.
(2)Nickel foam after 10mm × 10mm × 2mm cleanings is dipped into containing 1g steps(1)Class expansion of graphene stone
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)By step(2)In obtained class expansion of graphene graphite-foam nickel material add in 200 milliliter of 1% potassium permanganate
It in aqueous solution, places reaction liquid into shaking table, is reacted 24 hours under 30 degrees celsius.
(4)It will(3)Middle products therefrom several times, after being freeze-dried 24 hours, obtains carbon/titanium dioxide with sand core funnel filtration washing
Manganese composite material.
Embodiment 10
(1)0.3 gram of potassium permanganate is slowly added under the conditions of ice-water bath in 30 milliliters of sulfuric acid, after being completely dissolved, to reaction solution
3 grams of crystalline flake graphites of middle addition(150 microns of particle diameter, phosphorus content are higher than 95%), and after being stirred 1 hour under the conditions of 35 DEG C, it will
Reaction solution is filtered with sand core funnel, and obtained solid is compound between graphite layers.Gained compound between graphite layers are added in into 300 millis
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 cleanings is dipped into containing 1g steps(1)Class expansion of graphene stone
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)By step(2)In obtained class expansion of graphene graphite-foam nickel material add in 200 milliliter of 6% potassium permanganate
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)It will(3)Middle products therefrom several times, is done with sand core funnel filtration washing under 60 degrees celsius in vacuum drying oven
Dry 6 hours, obtain carbon/manganese dioxide composite material.
Embodiment 11
(1)0.3 gram of potassium permanganate is slowly added under the conditions of ice-water bath in 30 milliliters of sulfuric acid, after being completely dissolved, to reaction solution
3 grams of crystalline flake graphites of middle addition(150 microns of particle diameter, phosphorus content are higher than 95%), and after being stirred 1 hour under the conditions of 35 DEG C, it will
Reaction solution is filtered with sand core funnel, and obtained solid is compound between graphite layers.Gained compound between graphite layers are added in 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 cleanings is dipped into containing 1g steps(1)Class expansion of graphene stone
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)The class expansion of graphene graphite obtained in step (2)-foam nickel material is added in into 200 milliliter of 10% potassium permanganate
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)It will(3)Middle products therefrom several times, after freeze-drying, it is compound to obtain carbon/manganese dioxide with sand core funnel filtration washing
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
Add in 3 grams of crystalline flake graphites(150 microns of particle diameter, phosphorus content are higher than 95%), and after stirring 1 hour at ambient temperature, it 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 in into 30 grams of mistakes
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 cleanings is dipped into containing 1g steps(1)Class expansion of graphene stone
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)By step(2)In obtained class expansion of graphene graphite-foam nickel material add in 200 milliliter of 10% potassium permanganate
In aqueous solution, by reaction solution in shaking table is placed in, reacted 6 hours under 40 degrees celsius.
(4)It will(3)Middle products therefrom several times, after freeze-drying, it is compound to obtain carbon/manganese dioxide with sand core funnel filtration washing
Material.
Embodiment 13
(1)6 grams of potassium ferrates are added in 90 milliliters of sulfuric acid, after being completely dissolved, 3 grams of crystalline flake graphites are added in into reaction solution(
150 microns of diameter of grain, phosphorus content are higher than 95%), and at ambient temperature stir 1 hour after, reaction solution is taken out with sand core funnel
Filter, obtained solid is compound between graphite layers.Obtained solid is compound between graphite layers.By gained compound between graphite layers
It adds in 60 grams of sodium peroxydisulfates to add in 300 milliliters of sulfuric acid mixture liquids, expansion 12 hours is stood after being stirred at room temperature 15 minutes, after washing
Obtain class expansion of graphene graphite.
(2)Nickel foam after 10mm × 10mm × 2mm cleanings is dipped into containing 1g steps(1)Class expansion of graphene stone
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)By step(2)In obtained class expansion of graphene graphite-foam nickel material add in 200 milliliter of 3% potassium permanganate
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)It will(3)With sand core funnel filtration washing several times, 90 degrees Celsius of dryings 2 are small in vacuum drying oven for middle products therefrom
When, obtain carbon/manganese dioxide composite material.
Embodiment 14
(1)3 grams of potassium permanganate are slowly added under the conditions of ice-water bath in 90 milliliters of sulfuric acid, after being completely dissolved, into reaction solution
Add in 3 grams of crystalline flake graphites(150 microns of particle diameter, phosphorus content are higher than 95%), and after being stirred 1 hour under the conditions of 35 DEG C, it 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 in 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, class graphene is obtained after washing
Expanded graphite.
(2)Nickel foam after 10mm × 10mm × 2mm cleanings is dipped into containing 1g steps(1)Class expansion of graphene stone
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)By step(2)In obtained class expansion of graphene graphite-foam nickel material add in 200 milliliter of 4% potassium permanganate
It in aqueous solution, places reaction liquid into shaking table, is reacted 3 hours under 50 degrees celsius.
(4)It will(3)Middle products therefrom several times, after freeze-drying, it is compound to obtain carbon/manganese dioxide with sand core funnel filtration washing
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)It will(1)In after obtained product washing and drying, obtain final product.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)It will(1)In after obtained product washing and drying, obtain final product.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 (6)
- A kind of 1. lithium battery preparation method of carbon/manganese dioxide composite material, it is characterised in that following specific steps:(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 to(1)In in obtained class expansion of graphene graphite, ultrasound, obtaining load has the class graphene swollen The foam nickel material of swollen graphite, it is dry, obtain nickel foam-class expansion of graphene graphite material;(3)By step(2)Obtained material is reacted under potassium permanganate earthquake or static conditions, potassium permanganate during this Gradually reacted with carbon, formed manganese dioxide, and manganese dioxide can on carbon nanosheet vertical-growth;(4)It will(3)In obtained intermediate product be filtered washing to get carbon/manganese dioxide composite material.
- 2. a kind of preparation method of lithium battery carbon/manganese dioxide composite material according to claim 1, it is characterised in that The graphite is natural or artificial graphite.
- 3. a kind of preparation method of lithium battery carbon/manganese dioxide composite material according to claim 1, it is characterised in that The intercalator is sulfuric acid, phosphoric acid, nitric acid, potassium permanganate, one kind of potassium ferrate or the combination between them;Described is swollen Swollen dose is sulfuric acid, phosphoric acid, hydrogen peroxide, ammonium persulfate, potassium peroxydisulfate, one kind in sodium peroxydisulfate or the combination between them.
- 4. a kind of preparation method of lithium battery carbon/manganese dioxide composite material according to claim 1, it is characterised in that Class expansion of graphene 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 preparation method of lithium battery carbon/manganese dioxide composite material according to claim 1, it is characterised in that The filter type is vacuum filtration or screen filtration.
- 6. a kind of preparation method of lithium battery carbon/manganese dioxide composite material according to claim 1, it is characterised in that In obtained composite material, the conjugated structure of carbon nanosheet lamella keeps preferable, and the graphene oxide compared to reduction has More low defect;Manganese dioxide nano-plates vertical-growth on carbon nanosheet, and be evenly distributed;Obtained composite material shows Porous structure, carbon nanosheet surface is there are apparent fold, since the conjugated structure of carbon nanosheet keeps preferable, without being gone back It manages original place.
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