CN103426564B - Graphene electrodes active material and its preparation method and application and electrode material, electrode slice and electrochemical capacitor - Google Patents
Graphene electrodes active material and its preparation method and application and electrode material, electrode slice and electrochemical capacitor Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of Graphene electrodes active material, the method comprises the following steps: graphite oxide powder dispersion is obtained dispersion liquid by (1) in deionized water; (2) dispersion liquid step (1) obtained is 0.01-16mol/L in hydrogen ion concentration, after temperature places 5-240 minute under being the condition of 0-100 DEG C, carries out Separation of Solid and Liquid and be precipitated thing; (3) powders A is obtained after the sediment that step (2) obtains being carried out drying, grinding; (4) by the powders A that step (3) obtains, under atmosphere of inert gases, heat treatment 1-60 second at 600-1200 DEG C.The invention also discloses the Graphene electrodes active material prepared by said method, also disclose electrode material, electrode slice and electrochemical capacitor.Graphene electrodes active material surface of the present invention has a large amount of carbonyls and hydroxyl, and electrochemical capacitor has higher specific capacitance, capability retention and energy density.
Description
Technical field
The preparation method that the present invention relates to a kind of Graphene electrodes active material and the Graphene electrodes active material prepared by the method, and this Graphene electrodes active material is preparing the application in electrode material, electrode slice or electrochemical capacitor, the invention still further relates to the electrode material containing this electrode active material, electrode slice and electrochemical capacitor.
Background technology
Electrochemical capacitor (ElectrochemicalCapacitor, EC) ultracapacitor (Supercapacitor) is also claimed, as a kind of novel chemical power source, its long service life (105 circulations), specific power large (1500W/kg), energy quick charge (can be the several seconds), cryogenic property good (minimum operating temperature-50 DEG C), good heavy current, storage power is large, there is the power density higher than battery, the energy density higher than traditional capacitor, not only can support the use as electric motor car etc. provides peak power with battery, even can separately for electric tool or electric motor car provide power, to burn the negative effect providing energy to bring ecology based on fossil resources to reduce.And its quality is light, non-maintaining, low stain, low price, performance remarkable, is described as novel green energy resource.Therefore, electrochemical capacitor probably develops into a kind of efficient, practical energy accumulating device from now on, thus has very wide application prospect in fields such as traffic, the energy, communication, power electronics, military project national defence, industrial production.
The quality of electrode material is the deciding factor of electrochemical capacitor performance, and people are developing the electrode material with more high-energy-density and more high power density always.In prior art, for the electrode material of electrochemical capacitor, following three classes can be divided into: metal oxide containing precious metals, conducting polymer and carbon-based electrode material.Wherein, the resource-constrained, expensive of noble metal; Conducting polymer cyclical stability is poor, limits their application; Carbon electrode material mainly contains: activated carbon powder, activated carbon fiber, carbon aerogels, carbon nano-tube etc., but although the porous carbon materials such as activated carbon powder, activated carbon fiber, carbon aerogels can obtain higher ratio capacitance, but conductive capability is low, and its lower specific power limits its application as electrochemical capacitor, although its conductive capability of carbon nano-tube is superior, but its higher contact resistance, lower specific capacity, and high cost also limit its application.Grapheme material is as a kind of two-dimensional material extensively concerned in recent years, and specific area is comparatively large, and conductive capability is excellent, and cost price is low, and manufacture craft is simple, is the splendid selection as electrochemical capacitor electrode material.
The current method preparing Graphene electrodes active material is generally: by graphite oxide powder directly under atmosphere of inert gases, heat treatment 3-30 minute at 600-1200 DEG C of temperature.But the surface of the Graphene electrodes active material obtained by current method has less carbonyl and hydroxyl, and the content of carbonyl is generally 0.5-1.5 % by mole, and the content of hydroxyl is generally 3-10 % by mole.Electrode material prepared by this Graphene electrodes active material is used in electrochemical capacitor, the specific capacitance of electrochemical capacitor, capability retention, energy density are high not enough, in order to prepare the electrochemical capacitor of more high-specific capacitance super, capability retention, energy density, need the Graphene electrodes active material that research and development are more excellent.
Summary of the invention
The carbonyl and the hydroxyl that the object of the invention is the surface overcoming the Graphene electrodes active material that current method obtains are less, the electrode material prepared thus is in electrochemical capacitor, the specific capacitance of electrochemical capacitor, capability retention, the defect that energy density is lower, a kind of preparation method of new Graphene electrodes active material is provided, and the Graphene electrodes active material to be obtained by the method, and this Graphene electrodes active material is preparing electrode material, application in electrode slice or electrochemical capacitor, and the electrode material containing this electrode active material is provided, electrode slice and electrochemical capacitor.
The present inventor surprisingly finds under study for action, graphite oxide powder dispersion is obtained dispersion liquid in deionized water, be 0.01-16mol/L by dispersion liquid in hydrogen ion concentration, temperature is after placing 5-240 minute under the condition of 0-100 DEG C, thing is precipitated through Separation of Solid and Liquid, sediment is carried out drying, the powder obtained after grinding, under atmosphere of inert gases, heat treatment 1-60 second at 600-1200 DEG C, the surface of the Graphene electrodes active material obtained has a large amount of carbonyls and hydroxyl, electrode material is prepared into by this Graphene electrodes active material, for in electrochemical capacitor, electrochemical capacitor can be made to have higher specific capacitance, capability retention and energy density.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of preparation method of Graphene electrodes active material, it is characterized in that, said method comprising the steps of:
(1) graphite oxide powder dispersion is obtained dispersion liquid in deionized water;
(2) dispersion liquid step (1) obtained is 0.01-16mol/L in hydrogen ion concentration, after temperature places 5-240 minute under being the condition of 0-100 DEG C, carries out Separation of Solid and Liquid and be precipitated thing;
(3) powders A is obtained after the sediment that step (2) obtains being carried out drying, grinding;
(4) by the powders A that step (3) obtains, under atmosphere of inert gases, heat treatment 1-60 second at 600-1200 DEG C.
Preferably, the carbon oxygen atom of described graphite oxide powder is than being 1.5-3.0.
On the other hand, the invention provides a kind of Graphene electrodes active material, it is characterized in that, described Graphene electrodes active material is obtained by method as above.
The third aspect, the invention provides a kind of electrode material, and described electrode material contains binding agent and electrode active material, it is characterized in that, described electrode active material is Graphene electrodes active material as above.
Fourth aspect, the invention provides a kind of electrode slice, and described electrode slice comprises collector and the electrode material of load on described collector, it is characterized in that, described electrode material is electrode material as above.
5th aspect, the invention provides a kind of electrochemical capacitor, and described electrochemical capacitor comprises shell, barrier film, electrolyte and electrode slice, it is characterized in that, described electrode slice is electrode slice as above.
6th aspect, the invention provides Graphene electrodes active material as above and is preparing the application in electrode material, electrode slice or electrochemical capacitor.
The surface of Graphene electrodes active material prepared by the inventive method has a large amount of carbonyls and hydroxyl, the content of carbonyl is 2-10 % by mole, the content of hydroxyl is 8-30 % by mole, adopt Graphene electrodes active material of the present invention to make electrode material in electrochemical capacitor, electrochemical capacitor can be made to have higher specific capacitance, capability retention and energy density.The inventive method is simple, cost is low, can be widely used in industrial production.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Fig. 1 is the cyclic voltammetry curve of the Graphene electrodes active material of preparation in embodiment 1.
Fig. 2 is the cyclic voltammetry curve of the Graphene electrodes active material of preparation in comparative example 1.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind of preparation method of Graphene electrodes active material, the method comprises the following steps:
(1) graphite oxide powder dispersion is obtained dispersion liquid in deionized water;
(2) dispersion liquid step (1) obtained is 0.01-16mol/L in hydrogen ion concentration, after temperature places 5-240 minute under being the condition of 0-100 DEG C, carries out Separation of Solid and Liquid and be precipitated thing;
(3) powders A is obtained after the sediment that step (2) obtains being carried out drying, grinding;
(4) by the powders A that step (3) obtains, under atmosphere of inert gases, heat treatment 1-60 second at 600-1200 DEG C.
According to the inventive method, although adopt above-mentioned method can realize object of the present invention, even if the surface of the Graphene electrodes active material of preparation has a large amount of carbonyls and hydroxyl, the content of carbonyl is 2-10 % by mole, the content of hydroxyl is 8-30 % by mole, adopt this Graphene electrodes active material to make electrode material in electrochemical capacitor, make electrochemical capacitor have higher specific capacitance, capability retention and energy density.But under preferable case, the carbon oxygen atom of graphite oxide powder is than being 1.5-3.0, be more preferably 1.7-2.5, the Graphene electrodes active material of preparation made electrode material and is used in electrochemical capacitor, electrochemical capacitor can be made to have higher specific capacitance, capability retention and energy density.
In the present invention, the various method preparations that graphite oxide powder can adopt this area conventional, preferably adopt document J.Am.Chem.Soc.1958,80, the Hummers legal system recorded in 1339., for graphite oxide, is then dried, is ground, obtain graphite oxide powder.In order to make the carbon oxygen atom of graphite oxide powder than being 1.5-3.0, be more preferably 1.7-2.5, in Hummers method, the weight ratio of graphite and potassium permanganate is preferably 1: 3-5, is more preferably 1: 3-4.
In the present invention, in order to enable the graphite oxide powder in dispersion liquid contact more fully with hydrogen ion, in step (1), the average grain diameter of graphite oxide powder is preferably 5-600 micron, is more preferably 10-500 micron.
In step of the present invention (1), in dispersion liquid, the concentration of graphite oxide powder is preferably 0.05-0.25 % by weight; Be more preferably 0.09-0.2 % by weight.
In the present invention, graphite oxide powder dispersion method in deionized water can be adopted various method known in the field.Such as graphite oxide powder is added to after in deionized water, use ultrasonic method to disperse.Ultrasonic condition can adopt various condition known in the field, such as ultrasonic 10-100 minute at 20-80 DEG C.
In step of the present invention (2), hydrogen ion concentration is preferably 0.1-16mol/L, and temperature is preferably 5-80 DEG C, and standing time is preferably 10-120 minute.
In the present invention, hydrogen ion concentration can adopt acid to regulate, and described acid can be various acid known in the field.Under preferable case, described acid is one or more in hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, hydrobromic acid, hydroiodic acid and acetic acid, and more preferably in situation, described acid is hydrochloric acid or sulfuric acid.
In the present invention, in step (3), drying can adopt various method known in the field to carry out drying, the sediment vacuumize 2-24 hour at 30-120 DEG C such as step (2) obtained.Grinding can adopt various method known in the field, such as hand-ground, pulverizer grinding, ball milling, vibration milling etc.For the degree of grinding, represent with the average grain diameter of the powders A obtained after grinding, the average grain diameter of powders A is preferably 0.05-300 micron, is more preferably 5-150 micron.
In step of the present invention (4), heat treated temperature is preferably 700-1150 DEG C, is more preferably 900-1050 DEG C; The heat treated time is preferably 5-60 second, is more preferably 5-30 second, more preferably 10-30 second.Heat treatment is preferably carried out in tube furnace.For atmosphere of inert gases, be preferably nitrogen, argon gas, one or more in helium.
Second aspect, present invention also offers a kind of Graphene electrodes active material, and this Graphene electrodes active material is obtained by method as above.
Preferably, in Graphene electrodes active material, the content of carbonyl is 3-9 % by mole, and the content of hydroxyl is 12-25 % by mole.
The third aspect, the invention provides a kind of electrode material, and this electrode material contains binding agent and electrode active material, and electrode active material is Graphene electrodes active material as above.
In electrode material, the content of Graphene electrodes active material can be the customary amount of this area.Under preferable case, with the total weight of electrode material for benchmark, the content of binding agent is 0.3-20 % by weight, and the content of Graphene electrodes active material is 80-99.7 % by weight; More preferably in situation, with the total weight of electrode material for benchmark, the content of binding agent is 1-15 % by weight, and the content of Graphene electrodes active material is 85-99 % by weight.Binding agent can be the conventional various binding agents in this area, such as, can be one or more in polytetrafluoroethylene, Kynoar, butyl rubber and polyacrylate.
Electrode material of the present invention can also comprise conductive agent, the various conductive agents that conductive agent can be commonly used for this area, such as, can be one or more in acetylene black, carbon black, graphite powder and carbon fiber.The content of conductive agent can be customary amount, and under preferable case, with the total weight of electrode material for benchmark, the content of binding agent is 1-15 % by weight, and the content of Graphene electrodes active material is 80-95 weight, and the content of conductive agent is 0.1-10 % by weight.
Fourth aspect, the invention provides a kind of electrode slice, and this electrode slice comprises collector and the electrode material of load on this collector, and electrode material is electrode material as above.
Collector can for conventional collector, such as sheet metal, wire netting, metal forming and foamed metal.
The various method preparations that electrode slice can adopt this area conventional, such as, be prepared into electrode slurries with solvent by electrode material, then that obtained electrode slurries is dry, is pressed on collector, namely obtains electrode slice after being pressed into thin slice.Dry temperature can be 80-150 DEG C, and drying time can be 2-10 hour.
Preparation electrode slurries solvent used can be various solvent of the prior art, one or more as being selected from water, 1-METHYLPYRROLIDONE (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and alcohols.The weight ratio of electrode material and solvent is 1: 0.1-100.
5th aspect, the invention provides a kind of electrochemical capacitor, and this electrochemical capacitor comprises shell, barrier film, electrolyte and electrode slice, and electrode slice is electrode slice as above.
Shell can be metal or plastic material.
Barrier film can select polyethylene film, polypropylene screen, cellulose membrane or theirs is polymer-modified.
The optional following three kinds of systems of electrolyte:
1, organic system: electrolyte solvent be selected from ethylene carbonate, ethylene carbonate, propene carbonate and acetonitrile one or more, electrolyte used salt be selected from tetraethyl tetrafluoroborate, tetraethyl tetrafluoro boric acid quaternary alkylphosphonium salt, four n-pro-pyl tetrafluoro boric acid quaternary alkylphosphonium salts, tetraethyl hexafluorophosphoric acid quaternary ammonium salt, lithium hexafluoro phosphate, lithium perchlorate and LiBF4 one or more.Concentration of electrolyte can be 0.1-5 mol/L.
2, various ionic liquid at room temperature: be the combination in any of following two or more zwitterion arbitrarily.Cation majority is following a few class: quaternary ammonium cation, quaternary phosphonium cations, pyridylium, glyoxaline cation, sulfonium cation, and anion is modal is BF
4 -, PF
6 -, also have NO in addition
3 -, SbF
6 -, CIO
4 -, CF
3sO
3 -, C
3f
7cOO
-, C
4f
9sO
3 -, F
3cOO
-deng.
3, solid electrolyte (not needing barrier film and shell with this understanding): matrix be selected from polyvinylbenzenesulfonic acid, polyvinylpyrrolidone and polyvinyl alcohol one or more, used salt is selected from tetraethyl tetrafluoroborate, tetraethyl tetrafluoro boric acid quaternary alkylphosphonium salt, four n-pro-pyl tetrafluoro boric acid quaternary alkylphosphonium salts, tetraethyl hexafluorophosphoric acid quaternary alkylphosphonium salt, lithium hexafluoro phosphate, LiBF4 and containing one or more in the perchlorate of the tetramethyl-ammonium of 10% mass ratio.Solid electrolyte concentration can be 0.1-2 mol/L.
In the present invention, the method that shell, barrier film, electrolyte and electrode slice form electrochemical capacitor is conventionally known to one of skill in the art, does not repeat them here.
6th aspect, present invention also offers Graphene electrodes active material as above and is preparing the application in electrode material, electrode slice or electrochemical capacitor.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned execution mode, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible compound mode.
In addition, also can carry out combination in any between various different execution mode of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Embodiment
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.
In the following Examples and Comparative Examples:
The assay method of the carbon oxygen atom ratio of graphite oxide powder: XPS(X-X-ray photoelectron spectroscopy X).
The assay method of powder diameter: ESEM (SEM).
ESEM (HIT, HitachiS-4800) is adopted to observe the surface topography of Graphene electrodes active material.
Specific area and porosity adsorption instrument (Micromeritics Instrument Corp. U.S.A, model ASAP2020) is adopted to measure specific area, the average pore size of Graphene electrodes active material.
X-ray photoelectron spectroscopy (Shimadzu Instrument Ltd., Axis-Ultra) is adopted to measure the surface functional group content of Graphene electrodes active material.
Adopt CT2001A, LAND battery test system (Wuhan Jin Nuo Electronics Co., Ltd.), under the condition of constant current charge-discharge, measure the specific capacitance of electrochemical capacitor, capability retention, energy density and power density; CHI660d electrochemical workstation (Shanghai Chen Hua Instrument Ltd.) test is adopted to obtain the cyclic voltammetry curve of electrochemical capacitor.
Embodiment 1
The present embodiment is for illustration of the Graphene electrodes active material of the preparation method of Graphene electrodes active material provided by the invention and preparation, electrode material, electrode slice and electrochemical capacitor.
(1) take 10 grams of natural flake graphites and (be purchased from AlfaAesar company, identical below, average grain diameter 0.89mm), and 5 grams of sodium nitrate, under ice bath, join in the 230ml concentrated sulfuric acid (concentration 98 % by weight), add 30 grams of potassium permanganate subsequently, remove ice bath, be warming up to 35 DEG C, keep in the process stirring always.Question response thing becomes pink, reactant is added in 1.5 liters of deionized waters, slowly adding concentration is that the hydrogen peroxide of 3 % by weight is to bubble-free generates, filtration obtains solid, first use deionized water rinsing solid again until without chloride ion and sulfate ion with the watery hydrochloric acid of 0.lmol/L, vacuum drying at 40 DEG C, the obtained graphite oxide powder of grinding, the average grain diameter being ground to graphite oxide powder is 120 microns.The carbon oxygen atom ratio measuring graphite oxide powder is 1.94.
(2) by 1 gram of above-mentioned graphite oxide powder dispersion in 800 grams of deionized waters, within ultrasonic 1 hour at 50 DEG C, obtain dispersion liquid, by dispersion liquid hydrogen ion concentration be 1mol/L, temperature places after 90 minutes under being the condition of 25 DEG C, suction filtration is precipitated thing, by sediment vacuumize after 24 hours at 40 DEG C, hand-ground obtains powders A, and the average grain diameter being ground to powders A is 80 microns.Put into the tube furnace of 900 DEG C after powders A is inserted quartzy half tube sealing under argon shield, heat treatment was taken out after 30 seconds, obtained Graphene electrodes active material.
The surface topography of this Graphene electrodes active material is observed to be lamella microconfiguration.Measure the specific area of this Graphene electrodes active material, average pore size, surperficial carbonyl and hydroxy radical content, the results are shown in Table 1.
(3) above-mentioned Graphene electrodes active material and conductive agent acetylene black, polyfluortetraethylene of binding element (number-average molecular weight is about 2000000) are mixed to get electrode material by weight the ratio of 80: 10: 10, under the state dripping distilled water, said mixture is stirred to pulpous state, at 100 DEG C, oven dry is compressed in nickel foam collector plate after being pressed into thin slice after 8 hours and obtains electrode slice.Choosing 1-butyl-3-methyl imidazolium tetrafluoroborate is electrolyte, polypropylene (number-average molecular weight is about 59000) microporous barrier is barrier film, CR2032 battery case (being purchased from Ke Jingzhida Science and Technology Ltd. of Shenzhen, lower same) is shell, forms electrochemical capacitor with the electrode slice obtained.
Be 0 ~ 4V at operating voltage window, under the constant current density of 0.1A/g and 1A/g, measure the specific capacitance of this electrochemical capacitor, energy density and power density respectively; After the constant current density discharge and recharge 5000 times of 0.5A/g, measure the capability retention of this electrochemical capacitor.The results are shown in Table 2.Fig. 1 is the cyclic voltammetry curve of this electrochemical capacitor.
Comparative example 1
This comparative example is for illustration of the preparation method of Graphene electrodes active material adopted at present and the Graphene electrodes active material of preparation and electrochemical capacitor.
(1) graphite oxide powder is prepared according to the method for step (1) in embodiment 1, unlike, the average grain diameter being ground to graphite oxide powder is 80 microns.The carbon oxygen atom ratio measuring graphite oxide powder is 1.94.
(2) put into the tube furnace of 900 DEG C after above-mentioned for 1g graphite oxide powder being inserted quartzy half tube sealing under argon shield, heat treatment was taken out after 200 seconds, obtained Graphene electrodes active material.
The surface topography of this Graphene electrodes active material is observed to be lamella microconfiguration.Measure the specific area of this Graphene electrodes active material, average pore size, surperficial carbonyl and hydroxy radical content, the results are shown in Table 1.
(3) form electrochemical capacitor according to the method for step (3) in embodiment 1, and be 0 ~ 4V at operating voltage window, under the constant current density of 0.1A/g and 1A/g, measure the specific capacitance of this electrochemical capacitor, energy density and power density respectively; After the constant current density discharge and recharge 5000 times of 0.5A/g, measure the capability retention of this electrochemical capacitor.The results are shown in Table 2.Fig. 2 is the cyclic voltammetry curve of this electrochemical capacitor.
Embodiment 2
The present embodiment is for illustration of the Graphene electrodes active material of the preparation method of Graphene electrodes active material provided by the invention and preparation, electrode material, electrode slice and electrochemical capacitor.
(1) 10 grams of natural flake graphites (325 order) are taken, and 5 grams of sodium nitrate, under ice bath, join in the 230m1 concentrated sulfuric acid (concentration 98 % by weight), add 35 grams of potassium permanganate subsequently, remove ice bath, be warming up to 35 DEG C, keep in the process stirring always.Question response thing becomes pink, reactant is added in 1.5 liters of deionized waters, slowly adding concentration is that the hydrogen peroxide of 3 % by weight is to bubble-free generates, filtration obtains solid, first use deionized water rinsing solid again until without chloride ion and sulfate ion with the watery hydrochloric acid of 0.lmol/L, vacuum drying at 40 DEG C, the obtained graphite oxide powder of grinding, the average grain diameter being ground to graphite oxide powder is 50 microns.The carbon oxygen atom ratio measuring graphite oxide powder is 2.15.
(2) by 1 gram of above-mentioned graphite oxide powder dispersion in 1100 grams of deionized waters, within ultrasonic 100 minutes at 20 DEG C, obtain dispersion liquid, by dispersion liquid hydrogen ion concentration be 0.1mol/L, temperature places after 120 minutes under being the condition of 5 DEG C, suction filtration is precipitated thing, by sediment vacuumize 10 hours at 80 DEG C, hand-ground obtains powders A, and the average grain diameter being ground to powders A is 43 microns.Put into the tube furnace of 950 DEG C after powders A being inserted under nitrogen protection quartzy half tube sealing, heat treatment was taken out after 25 seconds, obtained Graphene electrodes active material.
The surface topography of this Graphene electrodes active material is observed to be lamella microconfiguration.Measure the specific area of this Graphene electrodes active material, average pore size, surperficial carbonyl and hydroxy radical content, the results are shown in Table 1.
(3) by above-mentioned Graphene electrodes active material and conductive agent carbon black, binding agent Kynoar (number-average molecular weight is about 71000) in mass ratio 90: 5: 5 ratio be mixed to get electrode material, under the state dripping distilled water, said mixture is stirred to pulpous state, at 80 DEG C, oven dry is compressed in nickel foam collector plate after being pressed into thin slice after 10 hours and obtains electrode slice.The carbonic allyl ester solution (1mol/L) choosing lithium perchlorate is electrolyte, and polyethylene (number-average molecular weight is about 24000) microporous barrier is barrier film, and CR2032 battery case is shell, forms electrochemical capacitor with the electrode slice obtained.
Be 0 ~ 4V at operating voltage window, under the constant current density of 0.1A/g and 1A/g, measure the specific capacitance of this electrochemical capacitor, energy density and power density respectively; After the constant current density discharge and recharge 5000 times of 0.5A/g, measure the capability retention of this electrochemical capacitor.The results are shown in Table 2.Cyclic voltammetry curve (attached not shown) similar to Example 1.
Embodiment 3
The present embodiment is for illustration of the Graphene electrodes active material of the preparation method of Graphene electrodes active material provided by the invention and preparation, electrode material, electrode slice and electrochemical capacitor.
(1) 10 grams of natural flake graphites (average grain diameter 0.89mm) are taken, and 5 grams of sodium nitrate, under ice bath, join in the 230m1 concentrated sulfuric acid (concentration 98 % by weight), add 40 grams of potassium permanganate subsequently, remove ice bath, be warming up to 35 DEG C, keep in the process stirring always.Question response thing becomes pink, reactant is added in 1.5 liters of deionized waters, slowly adding concentration is that the hydrogen peroxide of 3 % by weight is to bubble-free generates, filtration obtains solid, first use deionized water rinsing solid again until without chloride ion and sulfate ion with the watery hydrochloric acid of 0.lmol/L, at 40 DEG C after vacuum drying, the obtained graphite oxide powder of grinding, the average grain diameter being ground to graphite oxide powder is 500 microns.The carbon oxygen atom ratio measuring graphite oxide powder is 2.33.
(2) by 1 gram of above-mentioned graphite oxide powder dispersion in 500 grams of deionized waters, within ultrasonic 1 hour at 50 DEG C, obtain dispersion liquid, by dispersion liquid hydrogen ion concentration be 10mol/L, temperature places after 20 minutes under being the condition of 70 DEG C, suction filtration is precipitated thing, by sediment vacuumize after 6 hours at 100 DEG C, hand-ground obtains powders A, and the average grain diameter being ground to powders A is 150 microns.Put into the tube furnace of 1000 DEG C after powders A is inserted quartzy half tube sealing under argon shield, heat treatment was taken out after 20 seconds, obtained Graphene electrodes active material.
The surface topography of this Graphene electrodes active material is observed to be lamella microconfiguration.Measure the specific area of this Graphene electrodes active material, average pore size, surperficial carbonyl and hydroxy radical content, the results are shown in Table 1.
(3) by above-mentioned Graphene electrodes active material and polyfluortetraethylene of binding element (number-average molecular weight is about 2000000) in mass ratio 90: 10 ratio be mixed to get electrode material, under the state dripping distilled water, said mixture is stirred to pulpous state, at 120 DEG C, oven dry is compressed in nickel foam collector plate after being pressed into thin slice after 5 hours and obtains electrode slice.Choose with lithium hexafluoro phosphate is solute, ethylene carbonate and ethylene carbonate volume ratio 1: 1 mixture are solvent, concentration is the solution of 1mol/L is electrolyte, cellulose (number-average molecular weight is about 48000) microporous barrier is barrier film, CR2032 battery case is shell, forms electrochemical capacitor with the electrode slice obtained.
Be 0 ~ 4V at operating voltage window, under the constant current density of 0.1A/g and 1A/g, measure the specific capacitance of this electrochemical capacitor, energy density and power density respectively; After the constant current density discharge and recharge 5000 times of 0.5A/g, measure the capability retention of this electrochemical capacitor.The results are shown in Table 2.Cyclic voltammetry curve (attached not shown) similar to Example 1.
Embodiment 4
The present embodiment is for illustration of the Graphene electrodes active material of the preparation method of Graphene electrodes active material provided by the invention and preparation, electrode material, electrode slice and electrochemical capacitor.
(1) 10 grams of natural flake graphites (200 order) are taken, and 5 grams of sodium nitrate, under ice bath, join in the 230m1 concentrated sulfuric acid (concentration 98 % by weight), add 30 grams of potassium permanganate subsequently, remove ice bath, be warming up to 35 DEG C, keep in the process stirring always.Question response thing becomes pink, reactant is added in 1.5 liters of deionized waters, slowly adding concentration is that the hydrogen peroxide of 3 % by weight is to bubble-free generates, filtration obtains solid, first use deionized water rinsing solid again until without chloride ion and sulfate ion with the watery hydrochloric acid of 0.lmol/L, at 40 DEG C after vacuum drying, the obtained graphite oxide powder of grinding, the average grain diameter being ground to graphite oxide powder is 10 microns.The carbon oxygen atom ratio measuring graphite oxide powder is 1.77.
(2) by 1 gram of above-mentioned graphite oxide powder dispersion in 600 grams of deionized waters, within ultrasonic 10 minutes at 80 DEG C, obtain dispersion liquid, by dispersion liquid hydrogen ion concentration be 1mol/L, temperature places after 10 minutes under being the condition of 80 DEG C, suction filtration is precipitated thing, by sediment vacuumize after 24 hours at 30 DEG C, hand-ground obtains powders A, and the average grain diameter being ground to powders A is 5 microns.Put into the tube furnace of 1050 DEG C after powders A being inserted under nitrogen protection quartzy half tube sealing, heat treatment was taken out after 10 seconds, obtained Graphene electrodes active material.
The surface topography of this Graphene electrodes active material is observed to be lamella microconfiguration.Measure the specific area of this Graphene electrodes active material, average pore size, surperficial carbonyl and hydroxy radical content, the results are shown in Table 1.
(3) by above-mentioned Graphene electrodes active material and conductive agent graphite powder, binding agent butyl rubber (number-average molecular weight is about 16000) in mass ratio 95: 1: 4 ratio be mixed to get electrode material, under the state dripping distilled water, said mixture is stirred to pulpous state, at 150 DEG C, oven dry is compressed in nickel foam collector plate after being pressed into thin slice after 2 hours and obtains electrode slice.Choosing solid electrolyte (containing the polyvinylbenzenesulfonic acid (number-average molecular weight be about 7000) of 10% quality than the perchlorate of tetramethyl-ammonium) is electrolyte, does not need barrier film and shell, forms electrochemical capacitor with the electrode slice obtained.
Be 0 ~ 4.5V at operating voltage window, under the constant current density of 0.1A/g and 1A/g, measure the specific capacitance of this electrochemical capacitor, energy density and power density respectively; After the constant current density discharge and recharge 5000 times of 0.5A/g, measure the capability retention of this electrochemical capacitor.The results are shown in Table 2.Cyclic voltammetry curve (attached not shown) similar to Example 1.
Embodiment 5
The present embodiment is for illustration of the Graphene electrodes active material of the preparation method of Graphene electrodes active material provided by the invention and preparation, electrode material, electrode slice and electrochemical capacitor.
(1) 10 grams of natural flake graphites (32 order) are taken, and 5 grams of sodium nitrate, under ice bath, join in the 230m1 concentrated sulfuric acid (concentration 98 % by weight), add 30 grams of potassium permanganate subsequently, remove ice bath, be warming up to 35 DEG C, keep in the process stirring always.Question response thing becomes pink, reactant is added in 1.5 liters of deionized waters, slowly adding concentration is that the hydrogen peroxide of 3 % by weight is to bubble-free generates, filtration obtains solid, first use deionized water rinsing solid again until without chloride ion and sulfate ion with the watery hydrochloric acid of 0.lmol/L, at 40 DEG C after vacuum drying, the obtained graphite oxide powder of grinding, the average grain diameter being ground to graphite oxide powder is 320 microns.The carbon oxygen atom ratio measuring graphite oxide powder is 1.7.
(2) by 1 gram of above-mentioned graphite oxide powder dispersion in 700 grams of deionized waters, within ultrasonic 100 minutes at 20 DEG C, obtain dispersion liquid, by dispersion liquid hydrogen ion concentration be 16mol/L, temperature places after 120 minutes under being the condition of 5 DEG C, suction filtration is precipitated thing, by sediment vacuumize after 2 hours at 120 DEG C, hand-ground obtains powders A, and the average grain diameter being ground to powders A is 100 microns.Put into the tube furnace of 1050 DEG C after powders A is inserted quartzy half tube sealing under helium protection, heat treatment was taken out after 10 seconds, obtained Graphene electrodes active material.
The surface topography of this Graphene electrodes active material is observed to be lamella microconfiguration.Measure the specific area of this Graphene electrodes active material, average pore size, surperficial carbonyl and hydroxy radical content, the results are shown in Table 1.
(3) by above-mentioned Graphene electrodes active material and polyfluortetraethylene of binding element in mass ratio 90: 10 ratio be mixed to get electrode material, under the state dripping distilled water, said mixture is stirred to pulpous state, at 120 DEG C, oven dry is compressed in nickel foam collector plate after being pressed into thin slice after 5 hours and obtains electrode slice.The acetonitrile solution choosing tetraethyl hexafluorophosphoric acid quaternary ammonium salt is electrolyte, and cellulose (number-average molecular weight is about 48000) microporous barrier is barrier film, and CR2032 battery case is shell, forms electrochemical capacitor with the electrode slice obtained.
Be 0-2.7V at operating voltage window, under the constant current density of 0.1A/g and 1A/g, measure the specific capacitance of this electrochemical capacitor, energy density and power density respectively; After the constant current density discharge and recharge 5000 times of 0.5A/g, measure the capability retention of this electrochemical capacitor.The results are shown in Table 2.Cyclic voltammetry curve (attached not shown) similar to Example 1.
Embodiment 6
Graphene electrodes active material, electrode material, electrode slice and electrochemical capacitor is prepared according to the method for embodiment 1, unlike, in step (1), the consumption of potassium permanganate is 50 grams, and the carbon oxygen atom ratio measuring graphite oxide powder is 2.93.
The surface topography of this Graphene electrodes active material is observed to be lamella microconfiguration.Measure the specific area of this Graphene electrodes active material, average pore size, surperficial carbonyl and hydroxy radical content, the results are shown in Table 1.
Be 0-4V at operating voltage window, under the constant current density of 0.1A/g and 1A/g, measure the specific capacitance of this electrochemical capacitor, energy density and power density respectively; After the constant current density discharge and recharge 5000 times of 0.5A/g, measure the capability retention of this electrochemical capacitor.The results are shown in Table 2.
Embodiment 7
Graphene electrodes active material, electrode material, electrode slice and electrochemical capacitor is prepared according to the method for embodiment 1, unlike, in step (2), hydrogen ion concentration is 0.05mol/L.
The surface topography of this Graphene electrodes active material is observed to be lamella microconfiguration.Measure the specific area of this Graphene electrodes active material, average pore size, surperficial carbonyl and hydroxy radical content, the results are shown in Table 1.
Be 0-4V at operating voltage window, under the constant current density of 0.1A/g and 1A/g, measure the specific capacitance of this electrochemical capacitor, energy density and power density respectively; After the constant current density discharge and recharge 5000 times of 0.5A/g, measure the capability retention of this electrochemical capacitor.The results are shown in Table 2.
Embodiment 8
Graphene electrodes active material, electrode material, electrode slice and electrochemical capacitor is prepared according to the method for embodiment 1, unlike, in step (2), the heat treated time is 60 seconds.
The surface topography of this Graphene electrodes active material is observed to be lamella microconfiguration.Measure the specific area of this Graphene electrodes active material, average pore size, surperficial carbonyl and hydroxy radical content, the results are shown in Table 1.
Be 0-4V at operating voltage window, under the constant current density of 0.1A/g and 1A/g, measure the specific capacitance of this electrochemical capacitor, energy density and power density respectively; After the constant current density discharge and recharge 5000 times of 0.5A/g, measure the capability retention of this electrochemical capacitor.The results are shown in Table 2.
Table 1
| Specific area (m 2/g） | Average pore size (nanometer) | Carbonyl content (% by mole) | Hydroxy radical content (% by mole) | |
| Embodiment 1 | 398 | 2.6 | 7.57 | 15.16 |
| Comparative example 1 | 327 | 1.9 | 1.97 | 7.6 |
| Embodiment 2 | 412 | 2.8 | 8.66 | 19.23 |
| Embodiment 3 | 382 | 2.7 | 7.85 | 16.22 |
| Embodiment 4 | 418 | 2.4 | 5.13 | 12.98 |
| Embodiment 5 | 376 | 2.6 | 3.22 | 12.51 |
| Embodiment 6 | 457 | 3.1 | 9.9 | 23.26 |
| Embodiment 7 | 305 | 2.1 | 7.21 | 14.98 |
| Embodiment 8 | 418 | 2.9 | 2.75 | 10.38 |
Table 2
In table 1, embodiment 1 and comparative example 1 are compared and can find out, the specific area of Graphene electrodes active material prepared by the inventive method is comparatively large, average pore size is also comparatively large, and surperficial carbonyl and hydroxy radical content are far longer than Graphene electrodes active material prepared by art methods.In table 2, embodiment 1 and comparative example 1 are compared and can be found out, the specific capacitance of electrochemical capacitor provided by the invention, energy density and capability retention are all higher than the electrochemical capacitor of prior art.Also can be found out by the contrast of Fig. 1 and Fig. 2, the cyclic voltammetry curve of Fig. 1 close to rectangle and surround area much larger than Fig. 2, also illustrate that the energy density of electrochemical capacitor provided by the invention is higher and power characteristic is good.
Embodiment 1 and embodiment 6 are compared and can be found out, the weight ratio of graphite and potassium permanganate is more conducive to the raising of the specific capacitance of electrochemical capacitor, energy density and capability retention in the scope of 1: 3-4; Embodiment 1 and embodiment 7 are compared and can find out, is place under the condition of 0.1-16mol/L in hydrogen ion concentration by the dispersion liquid of graphite oxide powder, is more conducive to the raising of the specific capacitance of electrochemical capacitor, energy density and capability retention; Embodiment 1 and embodiment 8 are compared and can be found out, heat treatment time is 5-30 second, is more conducive to the carbonyl of Graphene electrodes active material surface that obtains and the maintenance of hydroxyl, is more conducive to the specific capacitance of electrochemical capacitor and the raising of energy density.
The surface of Graphene electrodes active material prepared by the inventive method has a large amount of carbonyls and hydroxyl, the content of carbonyl is 2-10 % by mole, the content of hydroxyl is 8-30 % by mole, adopt Graphene electrodes active material of the present invention to make electrode material in electrochemical capacitor, electrochemical capacitor can be made to have higher specific capacitance, capability retention and energy density.The inventive method is simple, cost is low, can be widely used in industrial production.
Claims (16)
1. a preparation method for Graphene electrodes active material, is characterized in that, said method comprising the steps of:
(1) graphite oxide powder dispersion is obtained dispersion liquid in deionized water;
(2) dispersion liquid step (1) obtained is 0.01-16mol/L in hydrogen ion concentration, after temperature places 5-240 minute under being the condition of 0-100 DEG C, carries out Separation of Solid and Liquid and be precipitated thing;
(3) powders A is obtained after the sediment that step (2) obtains being carried out drying, grinding;
(4) by the powders A that step (3) obtains, under atmosphere of inert gases, heat treatment 1-60 second at 600-1200 DEG C.
2. method according to claim 1, wherein, in step (1), the carbon oxygen atom of described graphite oxide powder is than being 1.5-3.0.
3. method according to claim 2, wherein, in step (1), the average grain diameter of graphite oxide powder is 5-600 micron.
4. method according to claim 3, wherein, in step (1), the average grain diameter of graphite oxide powder is 10-500 micron.
5., according to the method in claim 1-4 described in any one, wherein, in step (1), in dispersion liquid, the concentration of graphite oxide powder is 0.05-0.25 % by weight.
6. method according to claim 5, wherein, in step (1), in dispersion liquid, the concentration of graphite oxide powder is 0.09-0.2 % by weight.
7. method according to claim 1, wherein, in step (2), hydrogen ion concentration is 0.1-16mol/L, and temperature is 5-80 DEG C, and standing time is 10-120 minute.
8. method according to claim 1, wherein, in step (3), the average grain diameter of described powders A is 0.05-300 micron.
9. method according to claim 8, wherein, in step (3), the average grain diameter of described powders A is 5-150 micron.
10. method according to claim 1, wherein, in step (4), described heat treated temperature is 700-1150 DEG C, and the time is 5-30 second.
11. 1 kinds of Graphene electrodes active materials, is characterized in that, described Graphene electrodes active material is obtained by the method in claim 1-10 described in any one.
12. 1 kinds of electrode materials, described electrode material contains binding agent and electrode active material, it is characterized in that, described electrode active material is Graphene electrodes active material according to claim 11.
13. electrode materials according to claim 12, wherein, with the total weight of described electrode material for benchmark, the content of described binding agent is 0.3-20 % by weight, and the content of described Graphene electrodes active material is 80-99.7 % by weight.
14. 1 kinds of electrode slices, described electrode slice comprises collector and the electrode material of load on described collector, it is characterized in that, described electrode material is the electrode material described in claim 12 or 13.
15. 1 kinds of electrochemical capacitors, described electrochemical capacitor comprises shell, barrier film, electrolyte and electrode slice, it is characterized in that, described electrode slice is electrode slice according to claim 14.
16. Graphene electrodes active materials according to claim 11 are preparing the application in electrode material, electrode slice or electrochemical capacitor.
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| CN101768012A (en) * | 2008-12-30 | 2010-07-07 | 国家纳米科学中心 | Method for preparing single-layer graphene film on SiO2 substrate directly |
| CN101997120A (en) * | 2010-10-09 | 2011-03-30 | 深圳市贝特瑞纳米科技有限公司 | Lithium ion battery conductive additive and preparation method thereof |
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| CN101527202A (en) * | 2009-04-24 | 2009-09-09 | 南京理工大学 | Oxidized grapheme/polyaniline super capacitor composite electrode material and preparation method and application thereof |
| CN102040217A (en) * | 2009-10-26 | 2011-05-04 | 国家纳米科学中心 | Method for preparing graphene |
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