CN102891014A - Grapheme electrode active material, preparation method of grapheme electrode active material, electrode material, electrode slice, and application of grapheme electrode active material - Google Patents
Grapheme electrode active material, preparation method of grapheme electrode active material, electrode material, electrode slice, and application of grapheme electrode active material Download PDFInfo
- Publication number
- CN102891014A CN102891014A CN2011102024613A CN201110202461A CN102891014A CN 102891014 A CN102891014 A CN 102891014A CN 2011102024613 A CN2011102024613 A CN 2011102024613A CN 201110202461 A CN201110202461 A CN 201110202461A CN 102891014 A CN102891014 A CN 102891014A
- Authority
- CN
- China
- Prior art keywords
- active material
- graphite oxide
- oxide powder
- electrode
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides a grapheme electrode active material, a preparation method of the grapheme electrode active material, and an electrode material and an electrode slice of a supercapacitor, and an application of the grapheme electrode active material, wherein the method for preparing the grapheme electrode active material comprises the steps of dispersing graphite oxide powder into deionized water to obtain a dispersion liquid, performing solid-liquid separation after the dispersion liquid contacts acid to obtain a solid precipitate, and drying and grinding the solid precipitate to obtain acid precipitated graphite oxide powder; and carrying out heat treatment on the acid precipitated graphite oxide powder for 1-60 seconds at a temperature of 600-1200 DEG C. in the presence of inert gas. According to the invention, the grapheme electrode active material has the advantages of simple preparation method, easiness in operation, low equivalent series resistance, high specific capacitance, good cycling performance and the like.
Description
Technical field
The present invention relates to Graphene electrodes active material and method for making thereof and electrode material and electrode slice and application.
Background technology
In the world, the energy more and more is subject to people's great attention as one of pillar industry of human modern civilization.Yet the various environmental problems that accompany with production of energy, storage and transmission have also become the focus that the whole world is paid close attention to the most.For these problems, the eighties in last century, western developed country begins one's study, and exploitation is cleaned, efficient novel power supply.Super capacitor energy storage system is with the energy and environmental protection unified " green technology ", and it is positive key tactics to the environment of preserving our planet, air conservation and greenhouse effect, thereby also is subject to the generally attention of various countries.
Ultracapacitor (supercapacitors) also claims electrochemical capacitor (electro-chemicalcapacitors, ECs) as a kind of novel chemical power source, its long service life (10
5Inferior circulation), specific power large (1500W/kg), can quick charge (can be the several seconds), cryogenic property (minimum operating temperature-50 ℃), good heavy current, storage power be large, have than battery and have higher power density, has higher energy density than traditional capacitor, not only can support the use as electric motor car etc. with battery peak power is provided, even can be separately for electric tool or electric motor car provide power, to reduce the negative effect that burning provides energy that ecology is brought based on the petrochemical industry resource.And its quality is light, non-maintaining, low pollution, low price, performance are remarkable, is described as novel green energy resource.Therefore, ultracapacitor probably develops into a kind of efficient, practical energy accumulating device from now on, thereby in fields such as traffic, the energy, communication, power electronics, military project national defence, industrial production very wide application prospect is arranged.
The quality of electrode material is the deciding factor of ultracapacitor performance, and people have more high-energy-density and the more electrode material of high power density in exploitation always.In the prior art, be used for the electrode material of ultracapacitor, can be divided into following three classes: metal oxide containing precious metals, conducting polymer and carbon-based electrode material.Wherein, the resource-constrained of noble metal, expensive, the conducting polymer cyclical stability is poor, has limited their application.Carbon electrode material mainly contains: activated carbon powder, activated carbon fiber, carbon aerogels, carbon nano-tube etc.Although but porous carbon materials can obtain higher ratio electric capacity, conductive capability is low, and its lower specific power has limited its application as ultracapacitor.Although its conductive capability of carbon nano-tube is superior, the contact resistance that it is higher, lower specific capacity, and high cost has also limited its application.Grapheme material is as a kind of in recent years wide concerned two-dimensional material, larger specific area and excellent conductive capability, and cost price is low, and manufacture craft is simple, is the splendid selection as electrode material for super capacitor.
Yet in the prior art of preparation Graphene, the specific energy density of the grapheme material that obtains is high not enough, in order to prepare the more ultracapacitor of high-energy-density density, also need prepare the more Graphene electrodes material of height ratio capacity.
Summary of the invention
The purpose of this invention is to provide that a kind of to have an equivalent series resistance low, specific capacitance is high, good cycle, Graphene electrodes active material that cost is low and preparation method thereof, and comprise electrode material for super capacitor and the electrode slice of this Graphene electrodes active material.
The present inventor finds through research, the graphite oxide powder is dispersed in obtains dispersion liquid in the deionized water, dispersion liquid and sour contact precipitation are obtained solid sediment by Separation of Solid and Liquid, solid sediment is carried out obtaining the graphite oxide powder that acid precipitates after drying, the grinding; Under atmosphere of inert gases, be 600-1200 ℃ lower heat treatment 1-60 second after in temperature with the graphite oxide powder of this precipitation, can access that a kind of to have an equivalent series resistance low, specific capacitance is high, the Graphene electrodes active material of good cycle.
That is, the invention provides a kind of preparation method of Graphene electrodes active material, it is characterized in that, the method may further comprise the steps:
1) the graphite oxide powder is dispersed in obtains dispersion liquid in the deionized water, obtain solid sediment with carrying out Separation of Solid and Liquid behind dispersion liquid and the sour contact precipitation, solid sediment is carried out drying, obtains the graphite oxide powder of acid precipitation after grinding;
2) with step 1) in the graphite oxide powder of the acid precipitation that obtains, under atmosphere of inert gases, be 600-1200 ℃ of lower heat treatment 1-60 second in temperature.
The present invention also provides a kind of Graphene electrodes active material, and wherein, this Graphene electrodes active material is by the Graphene electrodes active material of above-mentioned method preparation.
The present invention further provides a kind of electrode material for super capacitor, this electrode material for super capacitor contains binding agent, and wherein, this electrode material for super capacitor also contains above-mentioned Graphene electrodes active material.
The present invention further provides a kind of super capacitor electrode slice, this electrode slice comprises collector and the electrode material that loads on this collector, and wherein, described electrode material is above-mentioned electrode material for super capacitor.
The present invention further provides the above-mentioned application of Graphene electrodes active material in ultracapacitor.
The method according to this invention obtains the Graphene electrodes active material, and to have an equivalent series resistance low, and specific capacitance is high, good cycle, the advantage that cost is low.
Description of drawings
Fig. 1 is the electron-microscope scanning picture of the Graphene electrodes active material of preparation among the embodiment 1;
Fig. 2 be among the embodiment 1 preparation Graphene electrodes active material, hydrochloric acid precipitation graphite oxide powder, Comparative Examples 1 in the infared spectrum of preparation Graphene electrodes active material and raw material graphite;
Fig. 3 is the cyclic voltammetry curve of the Graphene electrodes active material of preparation among the embodiment 1;
Fig. 4 is the cyclical stability comparison diagram of the electrode active material for preparing among the Graphene electrodes active material of preparation among the embodiment 1 and the Comparative Examples 1-3, and wherein, charging and discharging currents density is 1A/g;
Fig. 5 is the electron-microscope scanning picture of the Graphene electrodes active material of preparation in the Comparative Examples 1.
Embodiment
The invention provides a kind of preparation method of Graphene electrodes active material, it is characterized in that, the method may further comprise the steps:
1) the graphite oxide powder is dispersed in obtains dispersion liquid in the deionized water, obtain solid sediment with carrying out Separation of Solid and Liquid behind dispersion liquid and the sour contact precipitation, solid sediment is carried out drying, obtains the graphite oxide powder of acid precipitation after grinding;
2) with step 1) in the graphite oxide powder of the acid precipitation that obtains, under atmosphere of inert gases, be 600-1200 ℃ of lower heat treatment 1-60 second in temperature.
According to the preparation method of Graphene electrodes active material of the present invention, in the preferred situation, step 1) in the dispersion liquid concentration of graphite oxide powder be the 0.05-0.25 % by weight; More preferably step 1) in the dispersion liquid concentration of graphite oxide powder be the 0.09-0.2 % by weight.
According to the preparation method of Graphene electrodes active material of the present invention, the method that the graphite oxide powder is dispersed in the deionized water can adopt the whole bag of tricks known in the field.After for example adding to the graphite oxide powder in the deionized water, use ultrasonic method to disperse.Its ultrasonic condition can adopt various condition known in the field, for example descends ultrasonic 10-100 minute at 20-80 ℃.
Preparation method according to Graphene electrodes active material of the present invention, when making dispersion liquid and sour contact precipitation, acid can contact preferred steps 1 more fully with graphite oxide powder in the dispersion liquid) average grain diameter of graphite oxide powder is the 5-600 micron in the middle dispersion liquid; More preferably average grain diameter is the 10-500 micron.
According to the preparation method of Graphene electrodes active material of the present invention, the consumption of described acid can be selected according to the amount of graphite oxide powder in the dispersion liquid.In the preferred situation, with respect to every gram step 1) described graphite oxide powder, step 2) described in the consumption of acid be the 0.05-0.8 mole; More preferably with respect to every gram step 1) described graphite oxide powder, step 2) described in acid consumption be the 0.07-0.7 mole.
According to the preparation method of Graphene electrodes active material of the present invention, described acid can be various acid known in the field.In the preferred situation, described acid is one or more in hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, hydrobromic acid, hydroiodic acid and the acetic acid.The concentration of described hydrochloric acid, hydrobromic acid, hydroiodic acid can be the 1-40 % by weight, preferred 10-37 % by weight; The concentration of described sulfuric acid, phosphoric acid can be the 5-98 % by weight, is preferably the 10-50 % by weight; Described concentration of nitric acid is the 5-67 % by weight, is preferably the 10-50 % by weight; Described acetate concentration is the 10-100 % by weight, is preferably the 50-100 % by weight.
According to the preparation method of Graphene electrodes active material of the present invention, described temperature with dispersion liquid and sour contact precipitation can in very large range change.In the preferred situation, described temperature with dispersion liquid and sour contact precipitation is 0-100 ℃; More preferably described temperature with dispersion liquid and sour contact precipitation is 5-80 ℃.
According to the preparation method of Graphene electrodes active material of the present invention, under the preferable case, the described time with dispersion liquid and sour contact precipitation is 5-240 minute; More preferably the described time with dispersion liquid and sour contact precipitation is 10-120 minute.
According to the preparation method of Graphene electrodes active material of the present invention, the method comprises step 1) described in solid sediment carry out drying, obtain the graphite oxide powder of acid precipitation after grinding.Described drying can adopt the whole bag of tricks known in the field, for example with described solid sediment at 30-120 ℃ of lower vacuumize 2-24 hour.Described grinding can be adopted the whole bag of tricks known in the field, such as hand-ground, pulverizer grinding, ball milling, vibration milling etc.
According to the preparation method of Graphene electrodes active material of the present invention, be the 1-300 micron by the average grain diameter that obtains the sour graphite oxide powder that precipitates after the above-mentioned grinding preferably, the average grain diameter of the graphite oxide powder of more preferably acid precipitation is the 5-150 micron.
Preparation method according to Graphene electrodes active material of the present invention, the method comprises step 1) in the graphite oxide powder of the acid precipitation that obtains, under atmosphere of inert gases, be 600-1200 ℃ of lower heat treatment 1-60 after second in temperature, obtain Graphene electrodes active material of the present invention.
In the preferred situation, described heat treated temperature is 700-1150 ℃; More preferably described heat treated temperature is 900-1050 ℃.
In the preferred situation, the described heat treated time is 5-60 second; 5-30 second more preferably; 10-30 second more preferably.Preferred above-mentioned heat treatment is carried out in tube furnace.
Above-mentioned inert gas is that ability is known.One or more of the inert gases such as preferred nitrogen of the present invention, argon gas, helium.
According to the preparation method of Graphene electrodes active material of the present invention, described graphite oxide can be various graphite oxides known in the field.The present invention preferably adopts document J.Am.Chem.Soc.1958, and the Hummers method of record is prepared graphite oxide in 80,1339..
The present invention also provides a kind of Graphene electrodes active material, and wherein, this Graphene electrodes active material is by the Graphene electrodes active material of above-mentioned method preparation.
According to Graphene electrodes active material of the present invention, this Graphene electrodes active material is lamellar structure.The surface of this Graphene electrodes active material has the oxygen-containing functional groups such as more carbonyl, hydroxyl.Fast reversible redox reaction can occur in these oxygen-containing functional groups in electrode material surface in charge and discharge process, certain fake capacitance is provided, thereby improves the ratio electric capacity of whole electrode material.
The present invention further provides a kind of electrode material for super capacitor, this electrode material for super capacitor contains binding agent, and wherein, this electrode material for super capacitor also contains above-mentioned Graphene electrodes active material.
The content of described Graphene electrodes active material can be the customary amount of this area, a kind of preferred embodiment in, take the total weight of described Graphene electrodes active material and binding agent as benchmark, the content of described binding agent can be the 0.3-20 % by weight, is preferably the 1-15 % by weight; The content of described Graphene electrodes active material can be the 80-99.7 % by weight, is preferably the 85-99 % by weight.Described binding agent can be conventional binding agent known in the field, for example can be in polytetrafluoroethylene, Kynoar, butyl rubber and the polyacrylate one or more.
Negative material of the present invention can also comprise conductive agent, and described conductive agent can be the conductive agent of routine.One or more in acetylene black, carbon black, graphite powder and the carbon fiber for example.The content of described conductive agent can be customary amount, is preferably total weight take Graphene electrodes active material, conductive agent and binding agent as benchmark, and the content of described binding agent is the 1-15 % by weight; The content of described Graphene electrodes active material is the 80-95 % by weight; The content of described conductive agent is the 0-10 % by weight.
The present invention further provides a kind of super capacitor electrode slice, this electrode slice comprises collector and the electrode material that loads on this collector, and wherein, described electrode material is above-mentioned electrode material for super capacitor.
Described collector can be for collector commonly used in the ultracapacitor, such as sheet metal, wire netting, metal forming and foamed metal.
The preparation method of super capacitor electrode slice can carry out in accordance with the following methods, with solvent Graphene electrodes active material, binding agent and conductive agent is prepared into electrode slurries, and the addition of solvent is known in those skilled in the art.Then prepared electrode slurries is dry, be pressed on the collector after being pressed into thin slice, obtain super capacitor electrode slice.The temperature of described drying can be 80-150 ℃, and can be 2-10 hour drying time.
The used solvent of described electrode slurries can be various solvent of the prior art, as being selected from one or more in water, 1-METHYLPYRROLIDONE (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols.
The present invention also provides the above-mentioned application of Graphene electrodes active material in ultracapacitor.
By the following examples the present invention is further detailed, but the present invention is not limited in following embodiment.
Adopt the surface topography of ESEM (HIT, Hitachi S-4800) test Graphene electrode active material in following examples.
The specific area of resulting Graphene electrodes active material, average pore size adopt specific area and porosity adsorption instrument (Micromeritics Instrument Corp. U.S.A in following examples, model ASAP 2020) to measure, assay method is that BET analyzes pore-size distribution and lacunarity analysis method.
Adopt CT2001A in following examples, LAND battery test system (Wuhan Jin Nuo Electronics Co., Ltd.), use specific capacitance and the capability retention of the method mensuration ultracapacitor of constant current charge-discharge, adopt CHI660d electrochemical workstation (Shanghai occasion China Instr Ltd.), use the AC impedence method method to measure the equivalent series resistance of ultracapacitor.
1) takes by weighing 10 gram natural flake graphites and (be purchased from A Faaisha company, below identical,-10 orders), and 5 the gram sodium nitrate, under ice bath, join in the 230ml concentrated sulfuric acid (concentration 98 % by weight), add subsequently 30 gram potassium permanganate, remove ice bath, be warming up to 32-38 ℃, in this process, keep stirring always.The question response thing becomes pink, reactant is added in 1.5 liters of deionized waters, the hydrogen peroxide that slow adding concentration is 3 % by weight is extremely without till the bubble formation, filtration obtains solid, use again the deionized water rinsing solid until without chloride ion and sulfate ion with the watery hydrochloric acid of 0.1mol/L first, at 40 ℃ of lower vacuum dryings, grind and make the graphite oxide powder.The average grain diameter of described graphite oxide powder is 120 microns.
2) then the above-mentioned graphite oxide powder of 1 gram is dispersed in the 500 gram deionized waters, 20 ℃ lower ultrasonic (150W water-baths) 1 hour, then at 25 ℃ of lower dense HCl (concentration is 37 % by weight) that add 50mL, after 10 minutes suction filtration be precipitated thing, with sediment in 40 ℃ of lower vacuum dryings, grinding, obtain the graphite oxide powder of hydrochloric acid precipitation.The average grain diameter of the graphite oxide powder of this hydrochloric acid precipitation is 80 microns.
3) with the graphite oxide powder of above-mentioned hydrochloric acid precipitation, put into after inserting quartzy half tube sealing under the Ar protection and be preheated to 900 ℃ tube furnace, heat treatment was taken out in 30 seconds afterwards, obtained the Graphene electrodes active material.Measure the surface topography of this Graphene electrodes active material by scanning electron microscopy, as shown in Figure 1, this Graphene electrodes active material is lamella microconfiguration as can be known.The specific area of this Graphene electrodes active material is 390m
2/ g, average pore size is 2.5nm.By infrared spectrum (referring to Fig. 2) as can be known, the surface of this Graphene electrodes active material has carbonyl and hydroxyl.
4) with above-mentioned Graphene electrodes active material and conductive agent acetylene black, polyfluortetraethylene of binding element in mass ratio 80: 10: 10 ratio mix, said mixture is stirred to pulpous state dripping under the state of distilled water, is pressed into after the oven dry to be compressed on the nickel foam collector plate behind the thin slice and obtains super capacitor electrode slice.Its ultracapacitor correlated performance of test in three-electrode system, the KOH aqueous solution that this system is chosen 6mol/L is electrolyte, and platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode.
Under the constant current density of 0.1A/g, specific capacitance is 503F/g, and under the constant current density of 1A/g, specific capacitance reaches 353F/g, discharges and recharges after 5000 times with the constant current density of 1A/g, and capability retention is 87%.Its equivalent series resistance is 0.21 ohm.Fig. 3 is the cyclic voltammetry curve of the graphene powder of preparation among the embodiment 1.
Comparative Examples 1
1) step 1 among the employing embodiment 1) identical method obtains the graphite oxide powder, and it is 80 microns that the graphite oxide powder is ground to form average grain diameter.
2) get the above-mentioned graphite oxide powder of 1g, put into after inserting quartzy half tube sealing under the Ar protection and be preheated to 900 ℃ tube furnace, heat treatment was taken out in 30 seconds afterwards, obtained the Graphene electrodes active material.The surface topography of measuring this Graphene electrodes active material by scanning electron microscopy is lamella microconfiguration (referring to Fig. 5).The specific area of this Graphene electrodes active material is 317m
2/ g, average pore size is 1.9nm.By infrared spectrum (referring to Fig. 2) as can be known, the surface of this Graphene electrodes active material has less carbonyl and hydroxyl.
3) with above-mentioned Graphene electrodes active material and conductive agent acetylene black, polyfluortetraethylene of binding element in mass ratio 80: 10: 10 ratio mix, said mixture is stirred to pulpous state dripping under the state of distilled water, is compressed on the nickel foam collector plate after being pressed into thin slice after the oven dry.Its ultracapacitor correlated performance of test in three-electrode system, the KOH aqueous solution that this system is chosen 6mol/L is electrolyte, and platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode.
Under the constant current density of 0.1A/g, specific capacitance is 203F/g, and under the constant current density of 1A/g, specific capacitance reaches 147F/g, discharges and recharges after 5000 times with the constant current density of 1A/g, and capability retention is 80%.Its equivalent series resistance is 0.33 ohm.
Comparative Examples 2
Graphene powder is replaced with mesoporous carbon (specific area 459m available from Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences
2/ g, average pore size is 3.3nm) carry out the test of ultracapacitor correlated performance according to the method among the embodiment 1.
Under the constant current density of 0.1A/g, specific capacitance is 98F/g, and under the constant current density of 1A/g, specific capacitance is 96F/g, discharges and recharges after 5000 times with the constant current density of 1A/g, and capability retention is 82%.Its equivalent series resistance is 0.62 ohm.
Comparative Examples 3
Graphene powder is replaced with active carbon (specific area 1300m available from Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences
2/ g, average pore size is 0.8nm) carry out the test of ultracapacitor correlated performance according to the method among the embodiment 1,
Under the constant current density of 0.1A/g, specific capacitance is 274F/g, and under the constant current density of 1A/g, specific capacitance is 160F/g, discharges and recharges after 5000 times with the constant current density of 1A/g, and capability retention is 62%.Its equivalent series resistance is 0.46 ohm.
Embodiment 2
1) take by weighing 10 gram natural flake graphites (325 order), and 5 gram sodium nitrate, under ice bath, join in the 230ml concentrated sulfuric acid (concentration 98 % by weight), add subsequently 30 gram potassium permanganate, remove ice bath, be warming up to 32-38 ℃, in this process, keep stirring always.The question response thing becomes pink, reactant is added in 1.5 liters of deionized waters, the hydrogen peroxide that slow adding concentration is 3 % by weight is extremely without till the bubble formation, filtration obtains solid, use again the deionized water rinsing solid until without chloride ion and sulfate ion with the watery hydrochloric acid of 0.1mol/L first, at 40 ℃ of lower vacuum dryings, grind and make the graphite oxide powder.The average grain diameter of described graphite oxide powder is 50 microns.
2) then above-mentioned 1 gram graphite oxide is dispersed in the 1000 gram deionized waters, 20 ℃ lower ultrasonic (150W water-baths) 1 hour, then at 10 ℃ of lower sulfuric acid (concentration is 20 % by weight) that add 50mL, after 30 minutes through suction filtration be precipitated thing, with sediment behind 40 ℃ of lower vacuum dryings, grinding obtains the graphite oxide powder of sulfuric acid precipitation, and the average grain diameter of the graphite oxide powder of this sulfuric acid precipitation is 43 microns.
3) get the graphite oxide powder of above-mentioned sulfuric acid precipitation, at N
2Protection is lower inserts to put into behind quartzy half tube sealing and is preheated to 700 ℃ tube furnace, and heat treatment was taken out in 10 seconds afterwards, obtained the Graphene electrodes active material.The surface topography of measuring this Graphene electrodes active material by scanning electron microscopy is lamella microconfiguration.The specific area of this Graphene electrodes active material is 412m
2/ g, average pore size is 2.8nm.By infrared spectrum as can be known, the surface of this Graphene electrodes active material has carbonyl and hydroxyl.
4) with above-mentioned Graphene electrodes active material and conductive agent acetylene black, polyfluortetraethylene of binding element in mass ratio 80: 10: 10 ratio mix, said mixture is stirred to pulpous state dripping under the state of distilled water, is pressed into after the oven dry to be compressed on the nickel foam collector plate behind the thin slice and obtains super capacitor electrode slice.Its ultracapacitor correlated performance of test in three-electrode system, the KOH aqueous solution that this system is chosen 6mol/L is electrolyte, and platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode.
Under the constant current density of 0.1A/g, specific capacitance is 483F/g, and under the constant current density of 1A/g, specific capacitance reaches 275F/g, discharges and recharges after 5000 times with the constant current density of 1A/g, and capability retention is 85%.Its equivalent series resistance is 0.29 ohm.
Embodiment 3
1) take by weighing 10 gram natural flake graphites (10 order), and 5 gram sodium nitrate, under ice bath, join in the 230ml concentrated sulfuric acid (concentration 98 % by weight), add subsequently 30 gram potassium permanganate, remove ice bath, be warming up to 32-38 ℃, in this process, keep stirring always.The question response thing becomes pink, and reactant is added in 1.5 liters of deionized waters, slowly adds concentration and be the hydrogen peroxide of 3 % by weight to without till the bubble formation, filters and obtains solid.Use again the deionized water rinsing solid with the watery hydrochloric acid of 0.1mol/L first until without chloride ion and sulfate ion, behind 40 ℃ of lower vacuum dryings, grind and make the graphite oxide powder.The average grain diameter of described graphite oxide powder is 500 microns.
2) then above-mentioned 1 gram graphite oxide is dispersed in the 1000 gram deionized waters, 50 ℃ lower ultrasonic (150W water-baths) 2 hours, then at 70 ℃ of lower dense HCl (concentration is 37 % by weight) that add 50mL, suction filtration is precipitated thing after 60 minutes, sediment behind 40 ℃ of lower vacuum dryings, is ground the graphite oxide powder that obtains the hydrochloric acid precipitation.The average grain diameter of the graphite oxide powder of this hydrochloric acid precipitation is 150 microns.
3) get the graphite oxide powder that above-mentioned hydrochloric acid precipitates, put into after inserting quartzy half tube sealing under the Ar protection and be preheated to 1000 ℃ tube furnace, heat treatment was taken out in 20 seconds afterwards, obtained the Graphene electrodes active material.The surface topography of measuring this Graphene electrodes active material by scanning electron microscopy is lamella microconfiguration.The specific area of this Graphene electrodes active material is 382m
2/ g, average pore size is 2.7nm.By infrared spectrum as can be known, the surface of this Graphene electrodes active material has carbonyl and hydroxyl.
4) with above-mentioned Graphene electrodes active material and polyfluortetraethylene of binding element in mass ratio 90: 10 ratio mix, under the state that drips distilled water, said mixture is stirred to pulpous state, be compressed on the nickel foam collector plate after being pressed into thin slice after the oven dry.Its ultracapacitor correlated performance of test in three-electrode system, the KOH aqueous solution that this system is chosen 6mol/L is electrolyte, and platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode.
Under the constant current density of 0.1A/g, specific capacitance is 528F/g, and under the constant current density of 1A/g, specific capacitance reaches 373F/g, discharges and recharges after 5000 times with the constant current density of 1A/g, and capability retention is 86%.Its equivalent series resistance is 0.24 ohm.
Embodiment 4
1) take by weighing 10 gram natural flake graphites (200 order), and 5 gram sodium nitrate, under ice bath, join in the 230ml concentrated sulfuric acid (concentration 98 % by weight), add subsequently 30 gram potassium permanganate, remove ice bath, be warming up to 32-38 ℃, in this process, keep stirring always.The question response thing becomes pink, reactant is added in 1.5 liters of deionized waters, the hydrogen peroxide that slow adding concentration is 3 % by weight is extremely without till the bubble formation, filtration obtains solid, use again the deionized water rinsing solid until without chloride ion and sulfate ion with the watery hydrochloric acid of 0.1mol/L first, behind 40 ℃ of lower vacuum dryings, grind and make the graphite oxide powder.The average grain diameter of described graphite oxide powder is 10 microns.
2) then above-mentioned 1 gram graphite oxide is dispersed in the 500 gram deionized waters, 80 ℃ lower ultrasonic (150W water-baths) 1 hour, then at 80 ℃ of lower sulfuric acid (concentration is 20 % by weight) that add 50mL, after 30 minutes suction filtration be precipitated thing, with sediment behind 40 ℃ of lower vacuum dryings, grind the graphite oxide powder obtain sulfuric acid precipitation.The average grain diameter of the graphite oxide powder of this sulfuric acid precipitation is 5 microns.
3) get the graphite oxide powder that above-mentioned hydrochloric acid precipitates, at N
2Protection is lower inserts to put into behind quartzy half tube sealing and is preheated to 1100 ℃ tube furnace, and heat treatment was taken out in 20 seconds afterwards, obtained the Graphene electrodes active material.The surface topography of measuring this Graphene electrodes active material by scanning electron microscopy is lamella microconfiguration.The specific area of this Graphene electrodes active material is 418m
2/ g, average pore size is 2.4nm.By infrared spectrum as can be known, the surface of this Graphene electrodes active material has carbonyl and hydroxyl.
4) with above-mentioned Graphene electrodes active material and conductive agent acetylene black, polyfluortetraethylene of binding element in mass ratio 80: 10: 10 ratio mix, said mixture is stirred to pulpous state dripping under the state of distilled water, is compressed on the nickel foam collector plate after being pressed into thin slice after the oven dry.Its ultracapacitor correlated performance of test in three-electrode system, the KOH aqueous solution that this system is chosen 6mol/L is electrolyte, and platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode.
Under the constant current density of 0.1A/g, specific capacitance is 463F/g, and under the constant current density of 1A/g, specific capacitance reaches 262F/g, discharges and recharges after 5000 times with the constant current density of 1A/g, and capability retention is 85%.Its equivalent series resistance is 0.27 ohm.
Embodiment 5
1) take by weighing 10 gram natural flake graphites (32 order), and 5 gram sodium nitrate, under ice bath, join in the 230ml concentrated sulfuric acid (concentration 98 % by weight), add subsequently 30 gram potassium permanganate, remove ice bath, be warming up to 32-38 ℃, in this process, keep stirring always.The question response thing becomes pink, reactant is added in 1.5 liters of deionized waters, the hydrogen peroxide that slow adding concentration is 3 % by weight is extremely without till the bubble formation, filtration obtains solid, use again the deionized water rinsing solid until without chloride ion and sulfate ion with the watery hydrochloric acid of 0.1mol/L first, behind 40 ℃ of lower vacuum dryings, to grind and make the graphite oxide powder, the average grain diameter of described graphite oxide powder is 130 microns.
2) then above-mentioned 1 gram graphite oxide is dispersed in the 1000 gram deionized waters, 20 ℃ lower ultrasonic (150W water-baths) 2 hours, then at 5 ℃ of lower dense HCl (concentration is 37 % by weight) that add 50mL, suction filtration is precipitated thing after 120 minutes, sediment behind 40 ℃ of lower vacuum dryings, is ground the graphite oxide powder that obtains the hydrochloric acid precipitation.The average grain diameter of the graphite oxide powder of this hydrochloric acid precipitation is 100 microns.
3) get the graphite oxide powder that above-mentioned hydrochloric acid precipitates, put into after inserting quartzy half tube sealing under the Ar protection and be preheated to 1150 ℃ tube furnace, heat treatment was taken out in 10 seconds afterwards, obtained the Graphene electrodes active material.The surface topography of measuring this Graphene electrodes active material by scanning electron microscopy is lamella microconfiguration.The specific area of this Graphene electrodes active material is 376m
2/ g, average pore size is 2.6nm.By infrared spectrum as can be known, the surface of this Graphene electrodes active material has carbonyl and hydroxyl.
4) with above-mentioned Graphene electrodes active material and polyfluortetraethylene of binding element in mass ratio 90: 10 ratio mix, under the state that drips distilled water, said mixture is stirred to pulpous state, be compressed on the nickel foam collector plate after being pressed into thin slice after the oven dry.Its ultracapacitor correlated performance of test in three-electrode system, the KOH aqueous solution that this system is chosen 6mol/L is electrolyte, and platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode.
Under the constant current density of 0.1A/g, specific capacitance is 513F/g, and under the constant current density of 1A/g, specific capacitance reaches 361F/g, discharges and recharges after 5000 times with the constant current density of 1A/g, and capability retention is 83%.Its equivalent series resistance is 0.26 ohm.
Embodiment 6
1) take by weighing 10 gram natural flake graphites (200 order), and 5 gram sodium nitrate, under ice bath, join in the 230ml concentrated sulfuric acid (concentration 98 % by weight), add subsequently 30 gram potassium permanganate, remove ice bath, be warming up to 32-38 ℃, in this process, keep stirring always.The question response thing becomes pink, reactant is added in 1.5 liters of deionized waters, the hydrogen peroxide that slow adding concentration is 3 % by weight is extremely without till the bubble formation, filtration obtains solid, use again the deionized water rinsing solid until without chloride ion and sulfate ion with the watery hydrochloric acid of 0.1mol/L first, behind 40 ℃ of lower vacuum dryings, grind and make the graphite oxide powder.The average grain diameter of described graphite oxide powder is 80 microns.
2) then above-mentioned 1 gram graphite oxide is dispersed in the 500 gram deionized waters, 20 ℃ lower ultrasonic (150W water-baths) 1 hour, then at 35 ℃ of lower concentrated sulfuric acids (concentration is 20 % by weight) that add 50mL, after 60 minutes suction filtration be precipitated thing, with sediment behind 40 ℃ of lower vacuum dryings, grinding obtains the graphite oxide powder of sulfuric acid precipitation, and the average grain diameter of the graphite oxide powder of this sulfuric acid precipitation is 60 microns.
3) get the graphite oxide powder of above-mentioned sulfuric acid precipitation, put into after inserting quartzy half tube sealing under the He protection and be preheated to 800 ℃ tube furnace, heat treatment was taken out in 30 seconds afterwards, obtained the Graphene electrodes active material.The surface topography of measuring this Graphene electrodes active material by scanning electron microscopy is lamella microconfiguration.The specific area of this Graphene electrodes active material is 452m
2/ g, average pore size is 2.9nm.By infrared spectrum as can be known, the surface of this Graphene electrodes active material has carbonyl and hydroxyl.
4) with above-mentioned Graphene electrodes active material and conductive agent acetylene black, polyfluortetraethylene of binding element in mass ratio 80: 10: 10 ratio mix, said mixture is stirred to pulpous state dripping under the state of distilled water, is compressed on the nickel foam collector plate after being pressed into thin slice after the oven dry.Its ultracapacitor correlated performance of test in three-electrode system, the KOH aqueous solution that this system is chosen 6mol/L is electrolyte, and platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode.
Under the constant current density of 0.1A/g, specific capacitance is 463F/g, and under the constant current density of 1A/g, specific capacitance reaches 255F/g, discharges and recharges after 5000 times with the constant current density of 1A/g, and capability retention is 89%.Its equivalent series resistance is 0.29 ohm.
Embodiment 7
1) take by weighing 10 gram natural flake graphites (32 order), and 5 gram sodium nitrate, under ice bath, join in the 230ml concentrated sulfuric acid (concentration 98 % by weight), add subsequently 30 gram potassium permanganate, remove ice bath, be warming up to 32-38 ℃, in this process, keep stirring always.The question response thing becomes pink, reactant is added in 1.5 liters of deionized waters, the hydrogen peroxide that slow adding concentration is 3 % by weight is extremely without till the bubble formation, filtration obtains solid, use again the deionized water rinsing solid until without chloride ion and sulfate ion with the watery hydrochloric acid of 0.1mol/L first, behind 40 ℃ of lower vacuum dryings, grind and make the graphite oxide powder.The average grain diameter of described graphite oxide powder is 90 microns.
2) then above-mentioned 1 gram graphite oxide is dispersed in the 800 gram deionized waters, 20 ℃ lower ultrasonic (150W water-baths) 1 hour, then at 35 ℃ of lower SPAs (concentration is 30 % by weight) that add 50mL, after 70 minutes suction filtration be precipitated thing, with sediment behind 40 ℃ of lower vacuum dryings, grinding obtains the graphite oxide powder of sulfuric acid precipitation, and the average grain diameter of the graphite oxide powder of this sulfuric acid precipitation is 50 microns.
3) get the graphite oxide powder of above-mentioned sulfuric acid precipitation, at nitrogen and argon gas (1: 1 volume ratio) protection is lower puts into after inserting quartzy half tube sealing and be preheated to 800 ℃ tube furnace, heat treatment afterwards taking-up in 30 seconds obtains the Graphene electrodes active material.The surface topography of measuring this Graphene electrodes active material by scanning electron microscopy is lamella microconfiguration.The specific area of this Graphene electrodes active material is 417m
2/ g, average pore size is 2.2nm.By infrared spectrum as can be known, the surface of this Graphene electrodes active material has carbonyl and hydroxyl.
4) with above-mentioned Graphene electrodes active material and conductive agent acetylene black, polyfluortetraethylene of binding element in mass ratio 80: 10: 10 ratio mix, said mixture is stirred to pulpous state dripping under the state of distilled water, is compressed on the nickel foam collector plate after being pressed into thin slice after the oven dry.Its ultracapacitor correlated performance of test in three-electrode system, the KOH aqueous solution that this system is chosen 6mol/L is electrolyte, and platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode.
Under the constant current density of 0.1A/g, specific capacitance is 423F/g, and under the constant current density of 1A/g, specific capacitance reaches 235F/g, discharges and recharges after 5000 times with the constant current density of 1A/g, and capability retention is 85%.Its equivalent series resistance is 0.22 ohm.
Embodiment 8
1) take by weighing 10 gram natural flake graphites (2000 order), and 5 gram sodium nitrate, under ice bath, join in the 230ml concentrated sulfuric acid (concentration 98 % by weight), add subsequently 30 gram potassium permanganate, remove ice bath, be warming up to 32-38 ℃, in this process, keep stirring always.The question response thing becomes pink, reactant is added in 1.5 liters of deionized waters, the hydrogen peroxide that slow adding concentration is 3 % by weight is extremely without till the bubble formation, filtration obtains solid, use again the deionized water rinsing solid until without chloride ion and sulfate ion with the watery hydrochloric acid of 0.1mol/L first, behind 40 ℃ of lower vacuum dryings, grind and make the graphite oxide powder.The average grain diameter of described graphite oxide powder is 20 microns.
2) then above-mentioned 1 gram graphite oxide is dispersed in the 500 gram deionized waters, 20 ℃ lower ultrasonic (150W water-baths) 1 hour, then at 35 ℃ of lower hydrobromic acids (concentration is 10 % by weight) that add 60mL, after 120 minutes suction filtration be precipitated thing, with sediment behind 40 ℃ of lower vacuum dryings, grinding obtains the graphite oxide powder of sulfuric acid precipitation, and the average grain diameter of the graphite oxide powder of this sulfuric acid precipitation is 12 microns.
3) get the graphite oxide powder of above-mentioned sulfuric acid precipitation, at He and nitrogen (1: 1 volume ratio) protection is lower puts into after inserting quartzy half tube sealing and be preheated to 800 ℃ tube furnace, heat treatment afterwards taking-up in 60 seconds obtains the Graphene electrodes active material.The surface topography of measuring this Graphene electrodes active material by scanning electron microscopy is lamella microconfiguration.The specific area of this Graphene electrodes active material is 462m
2/ g, average pore size is 2.6nm.By infrared spectrum as can be known, the surface of this Graphene electrodes active material has carbonyl and hydroxyl.
4) with above-mentioned Graphene electrodes active material and conductive agent acetylene black, polyfluortetraethylene of binding element in mass ratio 80: 10: 10 ratio mix, said mixture is stirred to pulpous state dripping under the state of distilled water, is compressed on the nickel foam collector plate after being pressed into thin slice after the oven dry.Its ultracapacitor correlated performance of test in three-electrode system, the KOH aqueous solution that this system is chosen 6mol/L is electrolyte, and platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode.
Under the constant current density of 0.1A/g, specific capacitance is 385F/g, and under the constant current density of 1A/g, specific capacitance reaches 172F/g, discharges and recharges after 5000 times with the constant current density of 1A/g, and capability retention is 84%.Its equivalent series resistance is 0.32 ohm.
Embodiment 9
1) take by weighing 10 gram natural flake graphites (100 order), and 5 gram sodium nitrate, under ice bath, join in the 230ml concentrated sulfuric acid (concentration 98 % by weight), add subsequently 30 gram potassium permanganate, remove ice bath, be warming up to 32-38 ℃, in this process, keep stirring always.The question response thing becomes pink, reactant is added in 1.5 liters of deionized waters, the hydrogen peroxide that slow adding concentration is 3 % by weight is extremely without till the bubble formation, filtration obtains solid, use again the deionized water rinsing solid until without chloride ion and sulfate ion with the watery hydrochloric acid of 0.1mol/L first, behind 40 ℃ of lower vacuum dryings, grind and make the graphite oxide powder.The average grain diameter of described graphite oxide powder is 120 microns.
2) then above-mentioned 1 gram graphite oxide is dispersed in the 500 gram deionized waters, 20 ℃ lower ultrasonic (150W water-baths) 1 hour, then at 35 ℃ of lower acetic acid (concentration is 80 % by weight) that add 50mL, after 120 minutes suction filtration be precipitated thing, with sediment behind 40 ℃ of lower vacuum dryings, grinding obtains the graphite oxide powder of sulfuric acid precipitation, and the average grain diameter of the graphite oxide powder of this sulfuric acid precipitation is 90 microns.
3) get the graphite oxide powder of above-mentioned sulfuric acid precipitation, insert to put into behind quartzy half tube sealing under argon shield and be preheated to 800 ℃ tube furnace, heat treatment was taken out in 5 seconds afterwards, obtained the Graphene electrodes active material.The surface topography of measuring this Graphene electrodes active material by scanning electron microscopy is lamella microconfiguration.The specific area of this Graphene electrodes active material is 402m
2/ g, average pore size is 2.1nm.By infrared spectrum as can be known, the surface of this Graphene electrodes active material has carbonyl and hydroxyl.
4) with above-mentioned Graphene electrodes active material and conductive agent acetylene black, polyfluortetraethylene of binding element in mass ratio 80: 10: 10 ratio mix, said mixture is stirred to pulpous state dripping under the state of distilled water, is compressed on the nickel foam collector plate after being pressed into thin slice after the oven dry.Its ultracapacitor correlated performance of test in three-electrode system, the KOH aqueous solution that this system is chosen 6mol/L is electrolyte, and platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode.
Under the constant current density of 0.1A/g, specific capacitance is 337F/g, and under the constant current density of 1A/g, specific capacitance reaches 165F/g, discharges and recharges after 5000 times with the constant current density of 1A/g, and capability retention is 88%.Its equivalent series resistance is 0.32 ohm.
Can find out by embodiment 1-9, Comparative Examples 1-3 and Fig. 4, the electrode of super capacitor by Graphene electrodes active material of the present invention is under the current density of 0.1A/g, and specific capacitance reaches 337-528F/g; Specific capacitance reaches 165-373F/g under the current density of 1A/g; Current density with 1A/g discharges and recharges after 5000, and capability retention remains on more than 83%, be apparently higher than the electrode of super capacitor of the electrode active material among the Comparative Examples 1-3.And, the equivalent series resistance of the electrode of super capacitor by Graphene electrodes active material of the present invention also be significantly less than documents 1-3 the electrode of super capacitor of electrode active material.In addition, as seen in Figure 2, the surface of the Graphene electrodes active material that obtains according to the present invention has the oxy radicals such as more carbonyl and hydroxyl.Curve shape is similar to rectangle as seen in Figure 3, and along with the raising of sweep speed, curve shape keeps rectangle substantially, illustrates that to use the ultracapacitor power characteristic of Graphene active material of the present invention good.
Claims (14)
1. the preparation method of a Graphene electrodes active material is characterized in that, the method may further comprise the steps:
1) the graphite oxide powder be dispersed in obtain dispersion liquid in the deionized water, with dispersion liquid with carry out Separation of Solid and Liquid after acid contact and obtain solid sediment, solid sediment is carried out drying, obtains the graphite oxide powder that acid precipitates after grinding;
2) with step 1) in the graphite oxide powder of the acid precipitation that obtains, under atmosphere of inert gases, be 600-1200 ℃ of lower heat treatment 1-60 second in temperature.
2. method according to claim 1, wherein, step 1) in the dispersion liquid concentration of graphite oxide powder be the 0.05-0.25 % by weight.
3. method according to claim 1, wherein, step 1) in the dispersion liquid concentration of graphite oxide powder be the 0.09-0.2 % by weight.
4. method according to claim 1, wherein, step 1) in the dispersion liquid average grain diameter of graphite oxide powder be the 5-600 micron.
5. method according to claim 1 is wherein, with respect to every gram step 1) described graphite oxide powder, step 2) described in the consumption of acid be the 0.05-0.8 mole.
6. method according to claim 5 is wherein, with respect to every gram step 1) described graphite oxide powder, step 2) described in the consumption of acid be the 0.07-0.7 mole.
7. acid method according to claim 1, wherein, step 2) is one or more in hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, hydrobromic acid, hydroiodic acid and the acetic acid.
8. according to claim 1 or 6 described methods, wherein, described temperature with dispersion liquid and sour contact precipitation is 0-100 ℃, and the time of contact precipitation is 5-240 minute minute.
9. method according to claim 1, wherein, step 2) described heat treated temperature is 700-1150 ℃, and the heat treated time is 5-30 second.
10. the average grain diameter that obtains the graphite oxide powder of acid precipitation method according to claim 1, wherein, step 1) is the 0.05-300 micron.
11. a Graphene electrodes active material is characterized in that, this Graphene electrodes active material is by the Graphene electrodes active material of the described method preparation of any one among the claim 1-10.
12. an electrode material for super capacitor, this electrode material for super capacitor contains binding agent, it is characterized in that, this electrode material for super capacitor also contains the described Graphene electrodes active material of claim 11.
13. a super capacitor electrode slice, this electrode slice comprise collector and the electrode material that loads on this collector, it is characterized in that, described electrode material is the described electrode material for super capacitor of claim 12.
14. the application of the described Graphene electrodes active material of claim 11 in ultracapacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110202461.3A CN102891014B (en) | 2011-07-19 | 2011-07-19 | Graphene electrodes active substance and method for making thereof and electrode material and electrode slice and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110202461.3A CN102891014B (en) | 2011-07-19 | 2011-07-19 | Graphene electrodes active substance and method for making thereof and electrode material and electrode slice and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102891014A true CN102891014A (en) | 2013-01-23 |
| CN102891014B CN102891014B (en) | 2016-06-01 |
Family
ID=47534492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110202461.3A Expired - Fee Related CN102891014B (en) | 2011-07-19 | 2011-07-19 | Graphene electrodes active substance and method for making thereof and electrode material and electrode slice and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102891014B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105270077A (en) * | 2015-11-26 | 2016-01-27 | 张正西 | Ink painting drawing plate made of graphene and manufacturing method of ink painting drawing plate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101693534A (en) * | 2009-10-09 | 2010-04-14 | 天津大学 | Preparation method of single-layer graphene |
| CN101728535A (en) * | 2009-10-30 | 2010-06-09 | 北京化工大学 | Lithium ion battery conducting material and preparation method and application thereof |
| CN101935035A (en) * | 2010-09-02 | 2011-01-05 | 中国科学院宁波材料技术与工程研究所 | Ultra-low temperature thermal expansion preparation method of high specific area graphene |
| 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 |
-
2011
- 2011-07-19 CN CN201110202461.3A patent/CN102891014B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101693534A (en) * | 2009-10-09 | 2010-04-14 | 天津大学 | Preparation method of single-layer graphene |
| CN101728535A (en) * | 2009-10-30 | 2010-06-09 | 北京化工大学 | Lithium ion battery conducting material and preparation method and application thereof |
| CN101935035A (en) * | 2010-09-02 | 2011-01-05 | 中国科学院宁波材料技术与工程研究所 | Ultra-low temperature thermal expansion preparation method of high specific area graphene |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105270077A (en) * | 2015-11-26 | 2016-01-27 | 张正西 | Ink painting drawing plate made of graphene and manufacturing method of ink painting drawing plate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102891014B (en) | 2016-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Babu et al. | Asymmetric supercapacitor based on carbon nanofibers as the anode and two-dimensional copper cobalt oxide nanosheets as the cathode | |
| Liu et al. | Nanosheet-assembled porous MnCo2O4. 5 microflowers as electrode material for hybrid supercapacitors and lithium-ion batteries | |
| Shrivastav et al. | ZIF-67 derived Co3S4 hollow microspheres and WS2 nanorods as a hybrid electrode material for flexible 2V solid-state supercapacitor | |
| Fang et al. | Anchoring sea urchin-like cobalt-nickel carbonate hydroxide on 3D carbon sponge for electrochemical energy storage | |
| Wen et al. | An asymmetric supercapacitor with ultrahigh energy density based on nickle cobalt sulfide nanocluster anchoring multi-wall carbon nanotubes hybrid | |
| Isacfranklin et al. | Heterostructured SmCoO3/rGO composite for high-energy hybrid supercapacitors | |
| Jin et al. | Hybrid supercapacitor based on MnO2 and columned FeOOH using Li2SO4 electrolyte solution | |
| Xu et al. | Novel mesoporous MnO2 for high-rate electrochemical capacitive energy storage | |
| Wei et al. | Flexible asymmetric supercapacitors made of 3D porous hierarchical CuCo2O4@ CQDs and Fe2O3@ CQDs with enhanced performance | |
| Ding et al. | Using biochar and coal as the electrode material for supercapacitor applications | |
| Zhan et al. | Facile synthesis of biomass-derived porous carbons incorporated with CuO nanoparticles as promising electrode materials for high-performance supercapacitor applications | |
| Chaitra et al. | Nanocomposite of hexagonal β-Ni (OH) 2/multiwalled carbon nanotubes as high performance electrode for hybrid supercapacitors | |
| Tan et al. | Growth of Al and Co co-doped NiO nanosheets on carbon cloth as the air electrode for Zn-air batteries with high cycling stability | |
| CN103854881A (en) | Preparation method for graphene/carbon nano-tube combined electrode | |
| Xing et al. | Synthesis of mesoporous α-Ni (OH) 2 for high-performance supercapacitors | |
| Wei et al. | Inherently porous Co3O4@ NiO core–shell hierarchical material for excellent electrochemical performance of supercapacitors | |
| Zhang et al. | Sol-gel synthesis and electrochemical performance of NiCo2O4 nanoparticles for supercapacitor applications | |
| Anjana et al. | Direct growth of Mn (OH) 2/Co (OH) 2 nanocomposite on carbon cloth for flexible supercapacitor electrodes | |
| Yang et al. | Nano SnO2 loaded on N-doped carbon nanorods derived from metal-complex covalent organic frameworks for anode in lithium ion batteries | |
| JP2007186411A (en) | Activated carbon, process of making the same and use of the same | |
| Zhang et al. | High-specific-energy aqueous supercapacitor with extended operating potential using trichloroacetic acid electrolyte | |
| Huang et al. | Preparation of metal-organic framework-derived nitrogen-doped porous carbon and study of its supercapacitive performance in potassium citrate electrolyte | |
| Zhan et al. | Manganese/copper bimetal-decorated biomass porous carbons as advanced electrode materials for high-performance supercapacitors | |
| Olatoye et al. | Synthesis of γ-MnS/nanoporous carbon/reduced graphene oxide composites for high-performance supercapacitor | |
| Li et al. | A manganese oxide/biomass porous carbon composite for high-performance supercapacitor electrodes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160601 Termination date: 20200719 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |