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 PDF

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Publication number
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
graphite
carbon
composite material
graphene
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倪佳辉
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Taishun Yongqing Electric Power Technology Co Ltd
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Taishun Yongqing Electric Power Technology Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy 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

A kind of preparation method of lithium battery carbon/manganese dioxide composite material
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)

  1. 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. 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. 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. 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. 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. 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.
CN201810062661.5A 2018-01-23 2018-01-23 A kind of preparation method of lithium battery carbon/manganese dioxide composite material Pending CN108199033A (en)

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