CN103426564A - Graphene electrode active material, preparing method thereof, application thereof, electrode material, electrode slice and electrochemical capacitor - Google Patents
Graphene electrode active material, preparing method thereof, application thereof, electrode material, electrode slice and electrochemical capacitor Download PDFInfo
- Publication number
- CN103426564A CN103426564A CN2012101514450A CN201210151445A CN103426564A CN 103426564 A CN103426564 A CN 103426564A CN 2012101514450 A CN2012101514450 A CN 2012101514450A CN 201210151445 A CN201210151445 A CN 201210151445A CN 103426564 A CN103426564 A CN 103426564A
- Authority
- CN
- China
- Prior art keywords
- active material
- electrode
- electrochemical capacitor
- graphene electrodes
- electrodes active
- 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 discloses a preparing method of a graphene electrode active material. The method comprises the following steps that (1) graphite oxide powder is dispersed in deionized water so that dispersion liquid can be obtained; (2) after the dispersion liquid obtained in the step (1) stands for 5 minutes to 240 minutes under the conditions that the hydrogen ion concentration is 0.01 mol/L-16 mol/L and the temperature is 0 DEG C-100 DEG C, solid-liquid separation is conducted and sediment is obtained; (3) the sediment obtained in the step (2) is dried and ground so that powder A can be obtained; (4) heat treatment is conducted on the powder A obtained in the step (3) for 1 second to 60 seconds at the temperature of 600 DEG C-1200 DEG C under the atmosphere of inert gases. The invention further discloses the graphene electrode active material prepared by the method, an electrode material, an electrode slice and an electrochemical capacitor. A large amount of carbonyl and a large amount of hydroxyl are contained in the surface of the graphene electrode active material, so that the electrochemical capacitor is high in specific electric capacity, capacity retention ratio and energy density.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene electrodes active material and the Graphene electrodes active material prepared by the method, and this Graphene electrodes active material application in preparing electrode material, electrode slice or electrochemical capacitor, the invention still further relates to the electrode material, electrode slice and the electrochemical capacitor that contain this electrode active material.
Background technology
Electrochemical capacitor (Electrochemical Capacitor, EC) also claim ultracapacitor (Supercapacitor), 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 ℃), good heavy current, storage power is large, there is the power density higher than battery, the higher energy density than traditional capacitor, not only can support the use and provide peak power for electric motor car etc. with battery, even can be separately provide power for electric tool or electric motor car, to reduce the negative effect that burning provides energy to bring ecology based on the petrochemical industry resource.And its quality is light, non-maintaining, hang down pollution, low price, performance brilliance, is described as novel green energy resource.Therefore, electrochemical capacitor 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 electrochemical capacitor performance, and people have more high-energy-density and the more electrode material of high power density in exploitation always.In prior art, for the electrode material of electrochemical capacitor, 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 the porous carbon materials such as activated carbon powder, activated carbon fiber, carbon aerogels can obtain higher ratio electric capacity, but conductive capability is low, and its lower specific power has limited its application as electrochemical capacitor, although its conductive capability of carbon nano-tube is superior, but 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 wide concerned two-dimensional material in recent years, and specific area is larger, the conductive capability excellence, and cost price is low, and manufacture craft is simple, is the splendid selection as electrochemical capacitor electrode material.
The method for preparing at present the Graphene electrodes active material is generally: by the graphite oxide powder directly under atmosphere of inert gases, heat treatment 3-30 minute at 600-1200 ℃ of temperature.Yet the surface of the Graphene electrodes active material obtained by current method has less carbonyl and hydroxyl, 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 for electrochemical capacitor, the specific capacitance of electrochemical capacitor, capability retention, energy density are high not enough, in order to prepare the more electrochemical capacitor of high-specific capacitance super, capability retention, energy density, need the more excellent Graphene electrodes active material of research and development.
Summary of the invention
Carbonyl and the hydroxyl on surface that the objective of the invention is to overcome the Graphene electrodes active material that current method obtains is less, the electrode material of preparation is for electrochemical capacitor thus, 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 obtained by the method, and this Graphene electrodes active material is preparing electrode material, application in electrode slice or electrochemical capacitor, and provide the electrode material that contains this electrode active material, electrode slice and electrochemical capacitor.
The present inventor is unexpected the discovery under study for action, the graphite oxide powder is dispersed in deionized water and obtains dispersion liquid, by dispersion liquid, in hydrogen ion concentration, be 0.01-16mol/L, under the condition that temperature is 0-100 ℃, place after 5-240 minute, be precipitated thing through Separation of Solid and Liquid, sediment is carried out to drying, the powder obtained after grinding, under atmosphere of inert gases, 600-1200 ℃ of lower heat treatment 1-60 second, the surface of the Graphene electrodes active material obtained has a large amount of carbonyls and hydroxyl, be prepared into electrode material by this Graphene electrodes active material, for electrochemical capacitor, can make electrochemical capacitor that higher specific capacitance is arranged, 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) the graphite oxide powder is dispersed in deionized water and obtains dispersion liquid;
(2) dispersion liquid step (1) obtained, after hydrogen ion concentration is to place 5-240 minute under 0.01-16mol/L, the temperature condition that is 0-100 ℃, carries out Separation of Solid and Liquid and is precipitated thing;
(3) sediment step (2) obtained carries out obtaining powders A after drying, grinding;
(4) powders A step (3) obtained, under atmosphere of inert gases, 600-1200 ℃ of lower heat treatment 1-60 second.
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 made 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 and it is characterized in that collector and load on the electrode material on described collector, and described electrode material is electrode material as above.
The 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.
The 6th aspect, the invention provides the application of Graphene electrodes active material as above in preparing 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 for electrochemical capacitor, can make electrochemical capacitor there is 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 will partly be described in detail in embodiment subsequently.
The accompanying drawing explanation
The cyclic voltammetry curve that Fig. 1 is the Graphene electrodes active material of preparation in embodiment 1.
The cyclic voltammetry curve that Fig. 2 is the Graphene electrodes active material of preparation in Comparative Examples 1.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation 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) the graphite oxide powder is dispersed in deionized water and obtains dispersion liquid;
(2) dispersion liquid step (1) obtained, after hydrogen ion concentration is to place 5-240 minute under 0.01-16mol/L, the temperature condition that is 0-100 ℃, carries out Separation of Solid and Liquid and is precipitated thing;
(3) sediment step (2) obtained carries out obtaining powders A after drying, grinding;
(4) powders A step (3) obtained, under atmosphere of inert gases, 600-1200 ℃ of lower heat treatment 1-60 second.
According to the inventive method, although adopt above-mentioned method can realize purpose of the present invention, even 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 for electrochemical capacitor, make electrochemical capacitor there is 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, more preferably 1.7-2.5, make electrode material for electrochemical capacitor by the Graphene electrodes active material of preparation, can make electrochemical capacitor have higher specific capacitance, capability retention and energy density.
In the present invention, the graphite oxide powder can adopt this area the whole bag of tricks commonly used preparation, preferably adopts document J.Am.Chem.Soc.1958, and the standby graphite oxide of Hummers legal system of record, then dry, grind in 80,1339., obtains the graphite oxide powder.For the carbon oxygen atom that makes the graphite oxide powder than being 1.5-3.0,1.7-2.5 more preferably, in the Hummers method, the weight ratio of graphite and potassium permanganate is preferably 1: 3-5, more preferably 1: 3-4.
In the present invention, in order to make the graphite oxide powder in dispersion liquid, can contact more fully with hydrogen ion, in step (1), the average grain diameter of graphite oxide powder is preferably the 5-600 micron, more preferably the 10-500 micron.
In step of the present invention (1), in dispersion liquid, the concentration of graphite oxide powder is preferably the 0.05-0.25 % by weight; 0.09-0.2 % by weight more preferably.
In the present invention, the method that the graphite oxide powder is dispersed in deionized water can adopt the whole bag of tricks known in the field.For example, after adding in deionized water by the graphite oxide powder, use ultrasonic method to be disperseed.Ultrasonic condition can adopt various condition known in the field, for example ultrasonic 10-100 minute under 20-80 ℃.
In step of the present invention (2), hydrogen ion concentration is preferably 0.1-16mol/L, and temperature is preferably 5-80 ℃, is preferably 10-120 minute standing time.
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 the whole bag of tricks known in the field to carry out drying, and the sediment for example step (2) obtained is at 30-120 ℃ of lower vacuumize 2-24 hour.Grinding can adopt the whole bag of tricks known in the field, such as hand-ground, pulverizer grinding, ball milling, vibration milling etc.For the degree of grinding, with the average grain diameter of the powders A that obtains after grinding, mean, the average grain diameter of powders A is preferably the 0.05-300 micron, more preferably the 5-150 micron.
In step of the present invention (4), heat treated temperature is preferably 700-1150 ℃, more preferably 900-1050 ℃; The heat treated time is preferably 5-60 second, 5-30 second more preferably, more preferably 10-30 second.Heat treatment is preferably carried out in tube furnace.For atmosphere of inert gases, be preferably one or more in nitrogen, argon gas, helium.
Second aspect, the present invention also provides a kind of Graphene electrodes active material, and this Graphene electrodes active material is made by method as above.
Preferably, in the 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, the total weight of electrode material of take is benchmark, and the content of binding agent is the 0.3-20 % by weight, and the content of Graphene electrodes active material is the 80-99.7 % by weight; More preferably in situation, the total weight of electrode material of take is benchmark, and the content of binding agent is the 1-15 % by weight, and the content of Graphene electrodes active material is the 85-99 % by weight.Binding agent can be the various binding agents that this area is commonly used, can be for example one or more in polytetrafluoroethylene, Kynoar, butyl rubber and polyacrylate.
Electrode material of the present invention can also comprise conductive agent, and conductive agent can be the various conductive agents that this area is commonly used, can be for example 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, the total weight of electrode material of take is benchmark, and the content of binding agent is the 1-15 % by weight, and the content of Graphene electrodes active material is 80-95 weight, and the content of conductive agent is the 0.1-10 % by weight.
Fourth aspect, the invention provides a kind of electrode slice, and this electrode slice comprises collector and load on the electrode material on this collector, and electrode material is electrode material as above.
Collector can be collector commonly used, for example sheet metal, wire netting, metal forming and foamed metal.
Electrode slice can adopt this area the whole bag of tricks commonly used preparation, for example with solvent, electrode material is prepared into to electrode slurries, then by prepared electrode slurries drying, is pressed on collector after being pressed into thin slice, obtains electrode slice.Dry temperature can be 80-150 ℃, and can be 2-10 hour drying time.
Preparation electrode slurries solvent used can be various solvent of the prior art, as be selected from one or more in 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.
The 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 be selected 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 is selected from one or more in ethylene carbonate, ethylene carbonate, propene carbonate and acetonitrile, and the electrolyte used salt is selected from one or more in 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.Concentration of electrolyte can be the 0.1-5 mol/L.
2, various ionic liquid at room temperature: be the following combination in any of two or more zwitterion arbitrarily.The cation majority is following a few class: quaternary ammonium cation, quaternary phosphonium cations, pyridylium, glyoxaline cation, sulfonium cation, anion is modal is BF
4 -, PF
6 -, also have in addition NO
3 -, SbF
6 -, CIO
4 -, CF
3SO
3 -, C
3F
7COO
-, C
4F
9SO
3 -, F
3COO
-Deng.
3, solid electrolyte (not needing with this understanding barrier film and shell): matrix is selected from one or more in polystyrene sulfonic acid, polyvinylpyrrolidone and polyvinyl alcohol, and 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 the 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.
The 6th aspect, the present invention also provides the application of Graphene electrodes active material as above in preparing 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, in technical conceive scope 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 characterictic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible compound modes.
In addition, between various execution mode of the present invention, also can carry out combination in any, 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: the XPS(X-X-ray photoelectron spectroscopy X).
The assay method of powder diameter: ESEM (SEM).
Adopt the surface topography of ESEM (HIT, Hitachi S-4800) observation Graphene electrodes active material.
Adopt specific area and porosity adsorption instrument (Micromeritics Instrument Corp. U.S.A, model ASAP 2020) to measure specific area, the average pore size of Graphene electrodes active material.
Adopt x-ray photoelectron spectroscopy (Shimadzu Instrument Ltd., Axis-Ultra) the surface functional group content of mensuration 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 specific capacitance, capability retention, energy density and the power density of electrochemical capacitor; Adopt CHI660d electrochemical workstation (Shanghai Chen Hua Instrument Ltd.) test to obtain the cyclic voltammetry curve of electrochemical capacitor.
The present embodiment is for illustrating the preparation method of Graphene electrodes active material provided by the invention and Graphene electrodes active material, electrode material, electrode slice and the electrochemical capacitor of preparation.
(1) take 10 gram natural flake graphites and (be purchased from A Faaisha company, below identical, average grain diameter 0.89mm), 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 35 ℃, keep stirring in this process always.The question response thing becomes pink, reactant is added in 1.5 liters of deionized waters, slowly add hydrogen peroxide that concentration is 3 % by weight to without till bubble formation, filtration obtains solid, first with the watery hydrochloric acid of 0.lmol/L, use again the deionized water rinsing solid until without chloride ion and sulfate ion, at 40 ℃ of lower vacuum dryings, to grind and make the graphite oxide powder, the average grain diameter that is ground to the graphite oxide powder is 120 microns.The carbon oxygen atom ratio of measuring the graphite oxide powder is 1.94.
(2) the above-mentioned graphite oxide powder of 1 gram is dispersed in 800 gram deionized waters, within ultrasonic 1 hour under 50 ℃, obtain dispersion liquid, by dispersion liquid after hydrogen ion concentration is to place 90 minutes under 1mol/L, the temperature condition that is 25 ℃, suction filtration is precipitated thing, by sediment 40 ℃ of lower vacuumizes after 24 hours, hand-ground obtains powders A, and the average grain diameter that is ground to powders A is 80 microns.Put into the tube furnace of 900 ℃ after powders A is inserted to quartzy half tube sealing under argon shield, heat treatment is taken out in 30 seconds afterwards, obtains the Graphene electrodes active material.
The surface topography of observing this Graphene electrodes active material is lamella microconfiguration.Measure specific area, average pore size, surperficial carbonyl and the hydroxy radical content of this Graphene electrodes active material, 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 to electrode material by weight the ratio of 80: 10: 10, under the state that drips distilled water, said mixture is stirred to pulpous state, under 100 ℃, oven dry is compressed on the nickel foam collector plate and obtains electrode slice after being pressed into thin slice after 8 hours.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 (be purchased from the brilliant intelligence of Shenzhen section and reach Science and Technology Ltd., be lower same) is shell, with the electrode slice obtained, forms electrochemical capacitor.
Be 0 ~ 4V at the operating voltage window, measure respectively specific capacitance, energy density and the power density of this electrochemical capacitor under the constant current density of 0.1A/g and 1A/g; Constant current density with 0.5A/g discharges and recharges after 5000 times, measures the capability retention of this electrochemical capacitor.The results are shown in Table 2.The cyclic voltammetry curve that Fig. 1 is this electrochemical capacitor.
Comparative Examples 1
This Comparative Examples is for the preparation method of Graphene electrodes active material that current employing is described and Graphene electrodes active material and the electrochemical capacitor of preparation.
(1) method according to step (1) in embodiment 1 prepares the graphite oxide powder, different, and the average grain diameter that is ground to the graphite oxide powder is 80 microns.The carbon oxygen atom ratio of measuring the graphite oxide powder is 1.94.
(2) put into the tube furnace of 900 ℃ after the above-mentioned graphite oxide powder of 1g is inserted to quartzy half tube sealing under argon shield, heat treatment is taken out in 200 seconds afterwards, obtains the Graphene electrodes active material.
The surface topography of observing this Graphene electrodes active material is lamella microconfiguration.Measure specific area, average pore size, surperficial carbonyl and the hydroxy radical content of this Graphene electrodes active material, the results are shown in Table 1.
(3) method according to step (3) in embodiment 1 forms electrochemical capacitor, and is 0 ~ 4V at the operating voltage window, measures respectively specific capacitance, energy density and the power density of this electrochemical capacitor under the constant current density of 0.1A/g and 1A/g; Constant current density with 0.5A/g discharges and recharges after 5000 times, measures the capability retention of this electrochemical capacitor.The results are shown in Table 2.The cyclic voltammetry curve that Fig. 2 is this electrochemical capacitor.
The present embodiment is for illustrating the preparation method of Graphene electrodes active material provided by the invention and Graphene electrodes active material, electrode material, electrode slice and the electrochemical capacitor of preparation.
(1) take 10 gram natural flake graphites (325 order), and 5 gram sodium nitrate, under ice bath, join in the 230m1 concentrated sulfuric acid (concentration 98 % by weight), add subsequently 35 gram potassium permanganate, remove ice bath, be warming up to 35 ℃, keep stirring in this process always.The question response thing becomes pink, reactant is added in 1.5 liters of deionized waters, slowly add hydrogen peroxide that concentration is 3 % by weight to without till bubble formation, filtration obtains solid, first with the watery hydrochloric acid of 0.lmol/L, use again the deionized water rinsing solid until without chloride ion and sulfate ion, at 40 ℃ of lower vacuum dryings, to grind and make the graphite oxide powder, the average grain diameter that is ground to the graphite oxide powder is 50 microns.The carbon oxygen atom ratio of measuring the graphite oxide powder is 2.15.
(2) the above-mentioned graphite oxide powder of 1 gram is dispersed in 1100 gram deionized waters, within ultrasonic 100 minutes under 20 ℃, obtain dispersion liquid, by dispersion liquid after hydrogen ion concentration is to place 120 minutes under 0.1mol/L, the temperature condition that is 5 ℃, suction filtration is precipitated thing, by sediment 80 ℃ of lower vacuumizes 10 hours, hand-ground obtains powders A, and the average grain diameter that is ground to powders A is 43 microns.Put into the tube furnace of 950 ℃ after powders A is inserted to quartzy half tube sealing under nitrogen protection, heat treatment is taken out in 25 seconds afterwards, obtains the Graphene electrodes active material.
The surface topography of observing this Graphene electrodes active material is lamella microconfiguration.Measure specific area, average pore size, surperficial carbonyl and the hydroxy radical content of this Graphene electrodes active material, 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 the ratio of 90: 5: 5 be mixed to get electrode material, under the state that drips distilled water, said mixture is stirred to pulpous state, under 80 ℃, oven dry is compressed on the nickel foam collector plate and obtains electrode slice after being pressed into thin slice after 10 hours.The carbonic allyl ester solution (1mol/L) of choosing lithium perchlorate is electrolyte, and polyethylene (number-average molecular weight is about 24000) microporous barrier is barrier film, and the CR2032 battery case is shell, with the electrode slice obtained, forms electrochemical capacitor.
Be 0 ~ 4V at the operating voltage window, measure respectively specific capacitance, energy density and the power density of this electrochemical capacitor under the constant current density of 0.1A/g and 1A/g; Constant current density with 0.5A/g discharges and recharges after 5000 times, measures the capability retention of this electrochemical capacitor.The results are shown in Table 2.Cyclic voltammetry curve (not shown in accompanying drawing) similar to Example 1.
The present embodiment is for illustrating the preparation method of Graphene electrodes active material provided by the invention and Graphene electrodes active material, electrode material, electrode slice and the electrochemical capacitor of preparation.
(1) take 10 gram natural flake graphites (average grain diameter 0.89mm), and 5 gram sodium nitrate, under ice bath, join in the 230m1 concentrated sulfuric acid (concentration 98 % by weight), add subsequently 40 gram potassium permanganate, remove ice bath, be warming up to 35 ℃, keep stirring in this process always.The question response thing becomes pink, reactant is added in 1.5 liters of deionized waters, slowly add hydrogen peroxide that concentration is 3 % by weight to without till bubble formation, filtration obtains solid, first with the watery hydrochloric acid of 0.lmol/L, use again the deionized water rinsing solid until without chloride ion and sulfate ion, after 40 ℃ of lower vacuum dryings, to grind and make the graphite oxide powder, the average grain diameter that is ground to the graphite oxide powder is 500 microns.The carbon oxygen atom ratio of measuring the graphite oxide powder is 2.33.
(2) the above-mentioned graphite oxide powder of 1 gram is dispersed in 500 gram deionized waters, within ultrasonic 1 hour under 50 ℃, obtain dispersion liquid, by dispersion liquid after hydrogen ion concentration is to place 20 minutes under 10mol/L, the temperature condition that is 70 ℃, suction filtration is precipitated thing, by sediment 100 ℃ of lower vacuumizes after 6 hours, hand-ground obtains powders A, and the average grain diameter that is ground to powders A is 150 microns.Put into the tube furnace of 1000 ℃ after powders A is inserted to quartzy half tube sealing under argon shield, heat treatment is taken out in 20 seconds afterwards, obtains the Graphene electrodes active material.
The surface topography of observing this Graphene electrodes active material is lamella microconfiguration.Measure specific area, average pore size, surperficial carbonyl and the hydroxy radical content of this Graphene electrodes active material, 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 the ratio of 90: 10 be mixed to get electrode material, under the state that drips distilled water, said mixture is stirred to pulpous state, under 120 ℃, oven dry is compressed on the nickel foam collector plate and obtains electrode slice after being pressed into thin slice after 5 hours.Choose and take lithium hexafluoro phosphate as solute, 1: 1 mixture of ethylene carbonate and ethylene carbonate volume ratio is solvent, the solution that concentration is 1mol/L is electrolyte, cellulose (number-average molecular weight is about 48000) microporous barrier is barrier film, the CR2032 battery case is shell, with the electrode slice obtained, forms electrochemical capacitor.
Be 0 ~ 4V at the operating voltage window, measure respectively specific capacitance, energy density and the power density of this electrochemical capacitor under the constant current density of 0.1A/g and 1A/g; Constant current density with 0.5A/g discharges and recharges after 5000 times, measures the capability retention of this electrochemical capacitor.The results are shown in Table 2.Cyclic voltammetry curve (not shown in accompanying drawing) similar to Example 1.
The present embodiment is for illustrating the preparation method of Graphene electrodes active material provided by the invention and Graphene electrodes active material, electrode material, electrode slice and the electrochemical capacitor of preparation.
(1) take 10 gram natural flake graphites (200 order), and 5 gram sodium nitrate, under ice bath, join in the 230m1 concentrated sulfuric acid (concentration 98 % by weight), add subsequently 30 gram potassium permanganate, remove ice bath, be warming up to 35 ℃, keep stirring in this process always.The question response thing becomes pink, reactant is added in 1.5 liters of deionized waters, slowly add hydrogen peroxide that concentration is 3 % by weight to without till bubble formation, filtration obtains solid, first with the watery hydrochloric acid of 0.lmol/L, use again the deionized water rinsing solid until without chloride ion and sulfate ion, after 40 ℃ of lower vacuum dryings, to grind and make the graphite oxide powder, the average grain diameter that is ground to the graphite oxide powder is 10 microns.The carbon oxygen atom ratio of measuring the graphite oxide powder is 1.77.
(2) the above-mentioned graphite oxide powder of 1 gram is dispersed in 600 gram deionized waters, within ultrasonic 10 minutes under 80 ℃, obtain dispersion liquid, by dispersion liquid after hydrogen ion concentration is to place 10 minutes under 1mol/L, the temperature condition that is 80 ℃, suction filtration is precipitated thing, by sediment 30 ℃ of lower vacuumizes after 24 hours, hand-ground obtains powders A, and the average grain diameter that is ground to powders A is 5 microns.Put into the tube furnace of 1050 ℃ after powders A is inserted to quartzy half tube sealing under nitrogen protection, heat treatment is taken out in 10 seconds afterwards, obtains the Graphene electrodes active material.
The surface topography of observing this Graphene electrodes active material is lamella microconfiguration.Measure specific area, average pore size, surperficial carbonyl and the hydroxy radical content of this Graphene electrodes active material, 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 the ratio of 95: 1: 4 be mixed to get electrode material, under the state that drips distilled water, said mixture is stirred to pulpous state, under 150 ℃, oven dry is compressed on the nickel foam collector plate and obtains electrode slice after being pressed into thin slice after 2 hours.Choosing solid electrolyte (containing 10% quality than the polystyrene sulfonic acid (number-average molecular weight is about 7000) of the perchlorate of tetramethyl-ammonium) is electrolyte, does not need barrier film and shell, with the electrode slice obtained, forms electrochemical capacitor.
Be 0 ~ 4.5V at the operating voltage window, measure respectively specific capacitance, energy density and the power density of this electrochemical capacitor under the constant current density of 0.1A/g and 1A/g; Constant current density with 0.5A/g discharges and recharges after 5000 times, measures the capability retention of this electrochemical capacitor.The results are shown in Table 2.Cyclic voltammetry curve (not shown in accompanying drawing) similar to Example 1.
Embodiment 5
The present embodiment is for illustrating the preparation method of Graphene electrodes active material provided by the invention and Graphene electrodes active material, electrode material, electrode slice and the electrochemical capacitor of preparation.
(1) take 10 gram natural flake graphites (32 order), and 5 gram sodium nitrate, under ice bath, join in the 230m1 concentrated sulfuric acid (concentration 98 % by weight), add subsequently 30 gram potassium permanganate, remove ice bath, be warming up to 35 ℃, keep stirring in this process always.The question response thing becomes pink, reactant is added in 1.5 liters of deionized waters, slowly add hydrogen peroxide that concentration is 3 % by weight to without till bubble formation, filtration obtains solid, first with the watery hydrochloric acid of 0.lmol/L, use again the deionized water rinsing solid until without chloride ion and sulfate ion, after 40 ℃ of lower vacuum dryings, to grind and make the graphite oxide powder, the average grain diameter that is ground to the graphite oxide powder is 320 microns.The carbon oxygen atom ratio of measuring the graphite oxide powder is 1.7.
(2) the above-mentioned graphite oxide powder of 1 gram is dispersed in 700 gram deionized waters, within ultrasonic 100 minutes under 20 ℃, obtain dispersion liquid, by dispersion liquid after hydrogen ion concentration is to place 120 minutes under 16mol/L, the temperature condition that is 5 ℃, suction filtration is precipitated thing, by sediment 120 ℃ of lower vacuumizes after 2 hours, hand-ground obtains powders A, and the average grain diameter that is ground to powders A is 100 microns.Put into the tube furnace of 1050 ℃ after powders A is inserted to quartzy half tube sealing under the helium protection, heat treatment is taken out in 10 seconds afterwards, obtains the Graphene electrodes active material.
The surface topography of observing this Graphene electrodes active material is lamella microconfiguration.Measure specific area, average pore size, surperficial carbonyl and the hydroxy radical content of this Graphene electrodes active material, the results are shown in Table 1.
(3) by above-mentioned Graphene electrodes active material and polyfluortetraethylene of binding element in mass ratio the ratio of 90: 10 be mixed to get electrode material, under the state that drips distilled water, said mixture is stirred to pulpous state, under 120 ℃, oven dry is compressed on the nickel foam collector plate and obtains electrode slice after being pressed into thin slice after 5 hours.The acetonitrile solution of choosing tetraethyl hexafluorophosphoric acid quaternary ammonium salt is electrolyte, and cellulose (number-average molecular weight is about 48000) microporous barrier is barrier film, and the CR2032 battery case is shell, with the electrode slice obtained, forms electrochemical capacitor.
Be 0-2.7V at the operating voltage window, measure respectively specific capacitance, energy density and the power density of this electrochemical capacitor under the constant current density of 0.1A/g and 1A/g; Constant current density with 0.5A/g discharges and recharges after 5000 times, measures the capability retention of this electrochemical capacitor.The results are shown in Table 2.Cyclic voltammetry curve (not shown in accompanying drawing) similar to Example 1.
Embodiment 6
Method according to embodiment 1 prepares Graphene electrodes active material, electrode material, electrode slice and electrochemical capacitor, different, and in step (1), the consumption of potassium permanganate is 50 grams, and the carbon oxygen atom ratio of measuring the graphite oxide powder is 2.93.
The surface topography of observing this Graphene electrodes active material is lamella microconfiguration.Measure specific area, average pore size, surperficial carbonyl and the hydroxy radical content of this Graphene electrodes active material, the results are shown in Table 1.
Be 0-4V at the operating voltage window, measure respectively specific capacitance, energy density and the power density of this electrochemical capacitor under the constant current density of 0.1A/g and 1A/g; Constant current density with 0.5A/g discharges and recharges after 5000 times, measures the capability retention of this electrochemical capacitor.The results are shown in Table 2.
Embodiment 7
Method according to embodiment 1 prepares Graphene electrodes active material, electrode material, electrode slice and electrochemical capacitor, different, and in step (2), hydrogen ion concentration is 0.05mol/L.
The surface topography of observing this Graphene electrodes active material is lamella microconfiguration.Measure specific area, average pore size, surperficial carbonyl and the hydroxy radical content of this Graphene electrodes active material, the results are shown in Table 1.
Be 0-4V at the operating voltage window, measure respectively specific capacitance, energy density and the power density of this electrochemical capacitor under the constant current density of 0.1A/g and 1A/g; Constant current density with 0.5A/g discharges and recharges after 5000 times, measures the capability retention of this electrochemical capacitor.The results are shown in Table 2.
Method according to embodiment 1 prepares Graphene electrodes active material, electrode material, electrode slice and electrochemical capacitor, different, and in step (2), the heat treated time is 60 seconds.
The surface topography of observing this Graphene electrodes active material is lamella microconfiguration.Measure specific area, average pore size, surperficial carbonyl and the hydroxy radical content of this Graphene electrodes active material, the results are shown in Table 1.
Be 0-4V at the operating voltage window, measure respectively specific capacitance, energy density and the power density of this electrochemical capacitor under the constant current density of 0.1A/g and 1A/g; Constant current density with 0.5A/g discharges and recharges after 5000 times, measures 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) | |
| |
398 | 2.6 | 7.57 | 15.16 |
| Comparative Examples 1 | 327 | 1.9 | 1.97 | 7.6 |
| |
412 | 2.8 | 8.66 | 19.23 |
| |
382 | 2.7 | 7.85 | 16.22 |
| |
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 |
| |
418 | 2.9 | 2.75 | 10.38 |
Table 2
In table 1, embodiment 1 is compared and can find out with Comparative Examples 1, the specific area of Graphene electrodes active material prepared by the inventive method is large, average pore size is also larger, and surperficial carbonyl and hydroxy radical content are far longer than Graphene electrodes active material prepared by art methods.In table 2, embodiment 1 is compared and can find out with Comparative Examples 1, 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.Contrast by Fig. 1 and Fig. 2 also can find out, the cyclic voltammetry curve of Fig. 1 much larger than Fig. 2, also illustrates that the energy density of electrochemical capacitor provided by the invention is higher and power characteristic is good close to the area of rectangle and encirclement.
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 for electrochemical capacitor, can make electrochemical capacitor there is higher specific capacitance, capability retention and energy density.The inventive method is simple, cost is low, can be widely used in industrial production.
Claims (13)
1. the preparation method of a Graphene electrodes active material, is characterized in that, said method comprising the steps of:
(1) the graphite oxide powder is dispersed in deionized water and obtains dispersion liquid;
(2) dispersion liquid step (1) obtained, after hydrogen ion concentration is to place 5-240 minute under 0.01-16mol/L, the temperature condition that is 0-100 ℃, carries out Separation of Solid and Liquid and is precipitated thing;
(3) sediment step (2) obtained carries out obtaining powders A after drying, grinding;
(4) powders A step (3) obtained, under atmosphere of inert gases, 600-1200 ℃ of lower heat treatment 1-60 second.
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 the 5-600 micron, is preferably the 10-500 micron.
4. according to the described method of any one in claim 1-3, wherein, in step (1), in dispersion liquid, the concentration of graphite oxide powder is the 0.05-0.25 % by weight, is preferably the 0.09-0.2 % by weight.
5. method according to claim 1, wherein, in step (2), hydrogen ion concentration is 0.1-16mol/L, and temperature is 5-80 ℃, and be 10-120 minute standing time.
6. method according to claim 1, wherein, in step (3), the average grain diameter of described powders A is the 0.05-300 micron, is preferably the 5-150 micron.
7. method according to claim 1, wherein, in step (4), described heat treated temperature is 700-1150 ℃, the time is 5-30 second.
8. a Graphene electrodes active material, is characterized in that, described Graphene electrodes active material described method of any one in claim 1-8 makes.
9. an electrode material, described electrode material contains binding agent and electrode active material, it is characterized in that, and described electrode active material is the described Graphene electrodes active material of claim 8 or 9.
10. electrode material according to claim 9, wherein, the total weight of described electrode material of take is benchmark, and the content of described binding agent is the 0.3-20 % by weight, and the content of described Graphene electrodes active material is the 80-99.7 % by weight.
11. an electrode slice, described electrode slice comprises and it is characterized in that collector and load on the electrode material on described collector, and described electrode material is the described electrode material of claim 9 or 10.
12. an electrochemical capacitor, described electrochemical capacitor comprises shell, barrier film, electrolyte and electrode slice, it is characterized in that, described electrode slice is the described electrode slice of claim 11.
13. the application of Graphene electrodes active material claimed in claim 8 in preparing electrode material, electrode slice or electrochemical capacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210151445.0A CN103426564B (en) | 2012-05-15 | 2012-05-15 | Graphene electrodes active material and its preparation method and application and electrode material, electrode slice and electrochemical capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210151445.0A CN103426564B (en) | 2012-05-15 | 2012-05-15 | Graphene electrodes active material and its preparation method and application and electrode material, electrode slice and electrochemical capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103426564A true CN103426564A (en) | 2013-12-04 |
| CN103426564B CN103426564B (en) | 2016-03-02 |
Family
ID=49651177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210151445.0A Expired - Fee Related CN103426564B (en) | 2012-05-15 | 2012-05-15 | Graphene electrodes active material and its preparation method and application and electrode material, electrode slice and electrochemical capacitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103426564B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104021946B (en) * | 2014-06-12 | 2017-02-01 | 吉林大学 | Super capacitor based on graphene material and manufacturing method of super capacitor |
Citations (4)
| 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 |
| 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 |
| CN102040217A (en) * | 2009-10-26 | 2011-05-04 | 国家纳米科学中心 | Method for preparing graphene |
-
2012
- 2012-05-15 CN CN201210151445.0A patent/CN103426564B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
|---|---|---|---|---|
| CN104021946B (en) * | 2014-06-12 | 2017-02-01 | 吉林大学 | Super capacitor based on graphene material and manufacturing method of super capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103426564B (en) | 2016-03-02 |
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 | |
| Zhang et al. | Honeycomb hard carbon derived from carbon quantum dots as anode material for K-ion batteries | |
| Wang et al. | ZIF-8@ MWCNT-derived carbon composite as electrode of high performance for supercapacitor | |
| Pokharel et al. | MOF-derived hierarchical carbon network as an extremely-high-performance supercapacitor electrode | |
| Liang et al. | A honeycomb-like porous carbon derived from pomelo peel for use in high-performance supercapacitors | |
| Xiao et al. | N, S-containing polycondensate-derived porous carbon materials for superior CO2 adsorption and supercapacitor | |
| Zou et al. | Cube-shaped porous carbon derived from MOF-5 as advanced material for sodium-ion batteries | |
| Sun et al. | Three-dimensional hierarchical porous carbon/graphene composites derived from graphene oxide-chitosan hydrogels for high performance supercapacitors | |
| Tang et al. | Sulfur-doped carbon spheres with hierarchical micro/mesopores as anode materials for sodium-ion batteries | |
| Chen et al. | Rich nitrogen-doped ordered mesoporous phenolic resin-based carbon for supercapacitors | |
| Qie et al. | Synthesis of functionalized 3D hierarchical porous carbon for high-performance supercapacitors | |
| JP4533876B2 (en) | Activated carbon and its production method and use | |
| Sun et al. | A graphene/carbon nanotube@ π-conjugated polymer nanocomposite for high-performance organic supercapacitor electrodes | |
| Guo et al. | Tailoring kirkendall effect of the KCu7S4 microwires towards CuO@ MnO2 core-shell nanostructures for supercapacitors | |
| CN105355884B (en) | Height ratio capacity lithium ion battery electrode material and preparation method thereof | |
| CN103787320B (en) | The Synthesis and applications of the carbon nanosheet material of one kind graphene sheet layer structure | |
| CN102867650A (en) | High-magnification supercapacitor composite electrode material and preparation method thereof | |
| Fan et al. | Easy fabrication and high electrochemical capacitive performance of hierarchical porous carbon by a method combining liquid-liquid phase separation and pyrolysis process | |
| CN103832996A (en) | Graphene/carbon nano-tube composite material, preparation method and application thereof | |
| CN106129374A (en) | A kind of transition metal oxide/binary carbon net anode composite material and aluminium ion battery | |
| CN103833011A (en) | Graphene/carbon black composite material, preparation method and application thereof | |
| Zhang et al. | Nitrogen-doped porous carbon nanoparticle derived from nitrogen containing conjugated microporous polymer as high performance lithium battery anode | |
| Zou et al. | Highly porous carbon spheres prepared by boron-templating and reactive H3PO4 activation as electrode of supercapacitors | |
| Xu et al. | High-density three-dimensional graphene cathode with a tailored pore structure for high volumetric capacity zinc-ion storage | |
| Kim et al. | Gas sorption and supercapacitive properties of hierarchical porous graphitic carbons prepared from the hard-templating of mesoporous ZnO/Zn (OH) 2 composite spheres |
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: 20160302 Termination date: 20210515 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |