CN104037416B - The preparation method of the coated nickel sulfide structure electrode of three-dimensional drape Graphene selfreparing - Google Patents

The preparation method of the coated nickel sulfide structure electrode of three-dimensional drape Graphene selfreparing Download PDF

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CN104037416B
CN104037416B CN201410286560.8A CN201410286560A CN104037416B CN 104037416 B CN104037416 B CN 104037416B CN 201410286560 A CN201410286560 A CN 201410286560A CN 104037416 B CN104037416 B CN 104037416B
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CN104037416A (en
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麦立强
刘学
赵云龙
黄磊
石长玮
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Wuhan University of Technology WUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to the preparation method of the coated nickel sulfide structure electrode of three-dimensional drape Graphene selfreparing, comprise the following steps: 1) prepare NaOH solution, add S wherein, Na 2s9H 2o, stirring in water bath; 2) graphene dispersing solution is added, magnetic agitation; 3) add watery hydrochloric acid, regulate pH value of solution, magnetic agitation; 4) suction filtration obtains graphene coated sulfur granules, dries in air; 5) use Commercial foam nickel, soak, reserved stand-by; 6) be placed in inner liner of reaction kettle, add deionized water, packaged rear hydro-thermal reaction, is cooled to room temperature; 7) use alcohol and water respectively to rinse one time, then soak in hydrazine hydrate aqueous solution, finally dry in atmosphere.The invention has the beneficial effects as follows: prepare the coated nickel sulfide structure electrode of three-dimensional drape Graphene selfreparing based on contraction strain drive mechanism, can realize big current fast charging and discharging, can to reach 1000 capacity substantially unattenuated for cycle-index in addition.

Description

The preparation method of the coated nickel sulfide structure electrode of three-dimensional drape Graphene selfreparing
Technical field
The invention belongs to nano material and technical field of electrochemistry, be specifically related to the preparation method of the coated nickel sulfide structure electrode of three-dimensional drape Graphene selfreparing, this material can be used as lithium ion battery negative material.
Background technology
Along with the increase of energy demand, energy storage device serves more and more important effect in raising energy utilization efficiency.Recently, as the important composition form of energy storage device, lithium ion battery, due to its higher energy density, is widely used in hybrid vehicle and portable equipment.Research has the lithium ion battery electrode material of more long circulation life, higher reversible capacity, more low production cost, is one of the forward position and focus of research at present.Transition metal oxide, sulfide, fluoride are subject to extensive concern and the research of scientists due to the theoretical specific capacity (part can reach 1000mAh/g) of its superelevation, nickel sulfide material is a kind of up-and-coming lithium ion battery electrode material as one typical transient metal sulfide material, but it is low that its development is limited by its conductivity, and in charge and discharge cycles process, electrode structure changes the shortcomings such as excessive.
In recent years, in order to shorten the diffusion length of lithium ion in electrode material inside, improve lithium ion battery power density, use three-dimensional co-continuous electrode to become a kind of trend, use the graphene carbon meterial additive of conductivity superhigh specific surface area super large also can greatly improve lithium ion battery chemical property.
In addition, three-dimensional drape Graphene selfreparing coated nickel sulfide structure electrode does not need any additive, directly as electrode, can greatly reduce battery preparation flow, meet the requirement of Green Chemistry, be conducive to marketing.
Summary of the invention
The object of the present invention is to provide the preparation method of the coated nickel sulfide structure electrode of a kind of three-dimensional drape Graphene selfreparing, its preparation process is simple, energy consumption is lower, and the three-dimensional drape Graphene selfreparing coated nickel sulfide structure electrode of gained has good chemical property.
To achieve these goals, technical scheme of the present invention is: the preparation method of the coated nickel sulfide structure electrode of three-dimensional drape Graphene selfreparing, comprises the following steps:
1) preparing mass fraction is the NaOH solution 50mL of 10%, adds 0.25gS wherein, 0.65gNa 2s9H 2o, stirring in water bath is until form orange-yellow clear solution, and bath temperature is between 60-80 degree Celsius;
2) to step 1) in add the graphene dispersing solution of 15mL in gained solution, magnetic agitation stirs 1 hour;
3) to step 2) in add 72mL in gained solution mass fraction be the watery hydrochloric acid of 5%, regulate pH value of solution to 2, adularescent Precipitation, magnetic agitation 1 hour;
4) by step 3) gained suspension suction filtration obtains graphene coated sulfur granules, dries 24 hours in 70 degrees Celsius of air;
5) use Commercial foam nickel a slice, diameter is 18mm, soaks 15 minutes in the watery hydrochloric acid of 2mol/L, then soaks 10 minutes in alcohol, then soaks 10 minutes in deionized water, reserved stand-by;
6) by step 4) the 40mg graphene coated sulfur granules that obtains, step 5) a slice nickel foam of obtaining, be placed in the polytetrafluoroethylene inner liner of reaction kettle of 100mL, add 40mL deionized water, 180 degrees Celsius of lower hydro-thermal reactions 4 hours after packaged, be cooled to room temperature after completion of the reaction;
7) by step 6) the coated nickel sulfide structure electrode of the three-dimensional drape Graphene selfreparing that obtains uses alcohol and water respectively to rinse one time, then mass fraction be in 0.048% hydrazine hydrate aqueous solution soak 3 hours, finally in 70 degrees Celsius of lower air dry more than 24 hours.
By such scheme, step 2) described in graphene dispersing solution preparation according to the following steps:
A) in 250ml conical flask, 1g graphite powder and the 23ml concentrated sulfuric acid is added, at room temperature mix and blend 24 hours;
B) conical flask is put into thermostat water bath, reaction temperature 40 degrees Celsius, in step a) gained dispersion liquid, add 100mgNaNO 3, stir 5 minutes, slowly add 1500mgKMnO subsequently 4, and keep solution temperature below 45 degrees Celsius, stir 30 minutes;
C) to step b) in gained dispersion liquid, add 3ml deionized water, stir after 5 minutes, then add 3ml deionized water, stir 5 minutes subsequently, then add 40ml deionized water, stir 15 minutes;
D) conical flask is shifted out water-bath, add 140ml deionized water and 10ml mass fraction is 30%H 2o 2to stop oxidation reaction;
E) by steps d) gained suspension service quality mark is 5%HCl solution washing twice, spends deionized water subsequently to neutral, is dispersed in 100ml deionized water, ultrasonic 60 minutes;
F) by step e) gained suspension 8000 revs/min is centrifugal, and the time is 5 minutes, repeatedly gets supernatant liquor, until isolate uniform graphene dispersing solution, concentration is 4.7mg/ml.
The coated nickel sulfide structure electrode of three-dimensional drape Graphene selfreparing prepared by the present invention can be used as lithium ion battery negative; fold Graphene can not only improve electrode material conductivity greatly; add the contact area of electrode material and electrolyte; improve the diffusion rate of lithium ion; adaptive deformation relaxation character serves good protected effect to the great variety of structure in buffer electrode material charge and discharge process simultaneously, and all the other steps of the preparation method of lithium ion battery are identical with common preparation method.
The invention has the beneficial effects as follows: by water-bath-hydro-thermal two-step method, the coated nickel sulfide structure electrode of three-dimensional drape Graphene selfreparing is prepared based on contraction strain drive mechanism, big current fast charging and discharging can be realized (under 20A/g current density, only need can complete charging in about 1 minute), can to reach 1000 capacity substantially unattenuated for cycle-index in addition.
Accompanying drawing explanation
Fig. 1 be the embodiment of the present invention 1 the coated nickel sulfide structure electrode of three-dimensional drape Graphene selfreparing on fold graphene coated nickel sulphide particles XRD scheme (Ni 3s 2represent curing three nickel);
Fig. 2 is the SEM figure on the three-dimensional drape Graphene selfreparing coated nickel sulfide structure electrode surface of the embodiment of the present invention 1;
Fig. 3 be the embodiment of the present invention 1 the coated nickel sulfide structure electrode of three-dimensional drape Graphene selfreparing on fold graphene coated nickel sulphide particles TEM figure;
Fig. 4 be the embodiment of the present invention 1 the coated nickel sulfide structure electrode of three-dimensional drape Graphene selfreparing on fold graphene coated nickel sulphide particles marginal fold Graphene TEM figure;
Fig. 5 be the embodiment of the present invention 1 the coated nickel sulfide structure electrode of three-dimensional drape Graphene selfreparing on fold graphene coated nickel sulphide particles marginal fold Graphene bend lattice TEM and scheme;
Fig. 6 is the three-dimensional drape Graphene selfreparing coated nickel sulfide structure electrode synthesis mechanism figure of the embodiment of the present invention 1;
Fig. 7 is the coated nickel sulfide structure electrode of three-dimensional drape Graphene selfreparing of the embodiment of the present invention 1, cycle performance of battery figure under three-dimensional nickel sulfide electrode different multiplying.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1: as shown in Figure 6
One, the preparation of graphene dispersing solution:
A) in 250ml conical flask, 1g graphite powder and the 23ml concentrated sulfuric acid is added, at room temperature mix and blend 24 hours;
B) conical flask is put into thermostat water bath, reaction temperature 40 degrees Celsius, in step a) gained dispersion liquid, add 100mgNaNO 3, stir 5 minutes, slowly add 1500mgKMnO subsequently 4, and keep solution temperature below 45 degrees Celsius, stir 30 minutes;
C) to step b) in gained dispersion liquid, add 3ml deionized water, stir after 5 minutes, then add 3ml deionized water, stir 5 minutes subsequently, then add 40ml deionized water, stir 15 minutes;
D) conical flask is shifted out water-bath, add 140ml deionized water and 10ml mass fraction is 30%H 2o 2to stop oxidation reaction;
E) by steps d) gained suspension service quality mark is 5%HCl solution washing twice, spends deionized water subsequently to neutral, is dispersed in 100ml deionized water, ultrasonic 60 minutes;
F) by step e) gained suspension 8000 revs/min is centrifugal, and the time is 5 minutes, repeatedly gets supernatant liquor, until isolate uniform graphene dispersing solution, concentration is 4.7mg/ml.
Two. the coated nickel sulfide structure electrode preparation of three-dimensional drape Graphene selfreparing
1) preparing mass fraction is the NaOH solution 50mL of 10%, adds 0.25gS wherein, 0.65gNa 2s9H 2o, stirring in water bath is until form orange-yellow clear solution, and bath temperature is 60 degrees Celsius;
2) to step 1) in add the graphene dispersing solution (concentration is 4.7mg/mL) of 15mL in gained solution, magnetic agitation stirs 1 hour;
3) to step 2) in the gained solution mass fraction that adds 72mL be the watery hydrochloric acid of 5%, regulate pH value of solution to 2, adularescent Precipitation, magnetic agitation 1 hour;
4) by step 3) gained suspension suction filtration obtains graphene coated sulfur granules, dries 24 hours in 70 degrees Celsius of air;
5) Commercial foam nickel is used (in alcohol, acetone, to distinguish ultrasonic cleaning 30 minutes in advance, come again) a slice, disk diameter is 18mm, first soak 15 minutes in the watery hydrochloric acid of 2mol/L, then soak 10 minutes in alcohol, soak 10 minutes in deionized water again, reserved stand-by;
6) by step 4) the 40mg graphene coated sulfur granules that obtains, step 5) a slice nickel foam of obtaining, be placed in the polytetrafluoroethylene inner liner of reaction kettle of 100mL, add 40mL deionized water, at 180 degrees Celsius of lower hydro-thermal reaction 4h after packaged, be cooled to room temperature after completion of the reaction;
7) by step 6) the coated nickel sulfide structure electrode of the three-dimensional drape Graphene selfreparing that obtains uses alcohol and water respectively to rinse one time, then mass fraction be in 0.048% hydrazine hydrate aqueous solution soak 3 hours, finally in 70 degrees Celsius of lower air dry more than 24 hours.
For the coated nickel sulfide structure electrode of three-dimensional drape Graphene of the present invention selfreparing, its structure and composition is determined by x-ray diffractometer.As Fig. 1, the coated nickel sulphide particles principal phase of three-dimensional drape Graphene selfreparing is curing three nickel, and dephasign is nickel sulfide, and curing three nickel peak contrasts very consistent with JCPDF card No.00-044-1418.
As shown in Figure 2, field emission scanning electron microscope figure shows three-dimensional drape Graphene selfreparing coated nickel sulfide structure electrode surface three dimension fold Graphene and is tightly wrapped in nickel sulfide surface.As shown in Figure 3, transmission electron microscope picture display Graphene is wrapped in nickel sulfide surface.As shown in Figure 4, high-resolution-ration transmission electric-lens picture display fold Graphene is distributed in nickel sulfide edge.As shown in Figure 5, the lattice that high-resolution-ration transmission electric-lens picture display fold Graphene is bending.
With the coated nickel sulfide structure electrode of three-dimensional drape Graphene selfreparing of the present embodiment gained for positive pole, 1 is dissolved in the LiTFSI of 1M, as electrolyte in 3-dioxolanes (DOL) and dimethyl second diether (DME), with lithium sheet for negative pole, Celgard2325 is barrier film, and CR2025 type stainless steel is that battery case is assembled into fastening lithium ionic cell.
As shown in Figure 7, for the coated nickel sulfide structure electrode of three-dimensional drape Graphene selfreparing of the present embodiment gained, at 8Ag -1under constant current charge-discharge, through 600 circles with cocycle, battery still keeps 500mAhg -1capacity.At 10Ag -1under constant current charge-discharge, through 650 circles with cocycle, battery still keeps 450mAhg -1capacity. at 20Ag -1under constant current charge-discharge, through 1000 circle circulations, battery still keeps 350mAhg -1capacity.Above result shows, the coated nickel sulfide structure electrode of three-dimensional drape Graphene selfreparing can significantly improve battery charging and discharging performance, is the very potential structure electrode of one.
Embodiment 2:
One, the preparation of graphene dispersing solution: identical with embodiment 1;
Two, the coated nickel sulfide structure electrode preparation of three-dimensional drape Graphene selfreparing
1) preparing mass fraction is the NaOH solution 50mL of 10%, adds 0.25gS wherein, 0.65gNa 2s9H 2o, stirring in water bath is until form orange-yellow clear solution, and bath temperature is between 60 degrees Celsius;
2) to step 1) in add the graphene oxide solution (concentration is about 4.7mg/mL) of 10mL in gained solution, magnetic agitation stirs 1 hour;
3) to step 2) in the gained solution mass fraction that adds about 72mL be the watery hydrochloric acid of 5%, regulate pH value of solution to 2, adularescent Precipitation, magnetic agitation 1 hour;
4) by step 3) gained suspension suction filtration obtains graphene coated sulfur granules, dries 24 hours in 70 degrees Celsius of air;
5) Commercial foam nickel is used (in alcohol, acetone, to distinguish ultrasonic cleaning 30 minutes in advance, come again) a slice, disk diameter is 18mm, first soak 15 minutes in the watery hydrochloric acid of 2mol/L, then soak 10 minutes in alcohol, soak 10 minutes in deionized water again, reserved stand-by;
6) by step 4) the 40mg graphene coated sulfur granules that obtains, step 5) a slice nickel foam of obtaining, be placed in the polytetrafluoroethylene inner liner of reaction kettle of 100mL, add 40mL deionized water, 180 degrees Celsius of lower hydro-thermal reactions 4 hours after packaged, be cooled to room temperature after completion of the reaction;
7) by step 6) the coated nickel sulfide structure electrode of the three-dimensional drape Graphene selfreparing that obtains uses alcohol and water respectively to rinse one time, then mass fraction be in 0.048% hydrazine hydrate aqueous solution soak 3 hours, finally in 70 degrees Celsius of lower air dry more than 24 hours.
Embodiment 3:
One, the preparation of graphene dispersing solution: identical with embodiment 1;
Two, the coated nickel sulfide structure electrode preparation of three-dimensional drape Graphene selfreparing
1) preparing mass fraction is the NaOH solution 50mL of 10%, adds 0.25gS wherein, 0.65gNa 2s9H 2o, stirring in water bath is until form orange-yellow clear solution, and bath temperature is between 60 degrees Celsius;
2) to step 1) in add the graphene oxide solution (concentration is about 4.7mg/mL) of 5mL in gained solution, magnetic agitation stirs 1 hour;
3) to step 2) in the gained solution mass fraction that adds about 72mL be the watery hydrochloric acid of 5%, regulate pH value of solution to 2, adularescent Precipitation, magnetic agitation 1 hour;
4) by step 3) gained suspension suction filtration obtains graphene coated sulfur granules, dries 24 hours in 70 degrees Celsius of air;
5) Commercial foam nickel is used (in alcohol, acetone, to distinguish ultrasonic cleaning 30 minutes in advance, come again) a slice, disk diameter is 18mm, first soak 15 minutes in the watery hydrochloric acid of 2mol/L, then soak 10 minutes in alcohol, soak 10 minutes in deionized water again, reserved stand-by;
6) by step 4) the 40mg graphene coated sulfur granules that obtains, step 5) a slice nickel foam of obtaining, be placed in the polytetrafluoroethylene inner liner of reaction kettle of 100mL, add 40mL deionized water, 180 degrees Celsius of lower hydro-thermal reactions 4 hours after packaged, be cooled to room temperature after completion of the reaction;
7) by step 6) the coated nickel sulfide structure electrode of the three-dimensional drape Graphene selfreparing that obtains uses alcohol and water respectively to rinse one time, then mass fraction be in 0.048% hydrazine hydrate aqueous solution soak 3 hours, finally in 70 degrees Celsius of lower air dry more than 24 hours.
Embodiment 4:
One, the preparation of graphene dispersing solution: identical with embodiment 1;
Two, the coated nickel sulfide structure electrode preparation of three-dimensional drape Graphene selfreparing
1) preparing mass fraction is the NaOH solution 50mL of 10%, adds 0.25gS wherein, 0.65gNa 2s9H 2o, stirring in water bath is until form orange-yellow clear solution, and bath temperature is between 70 degrees Celsius;
2) to step 1) in add the graphene oxide solution (concentration is about 4.7mg/mL) of 20mL in gained solution, magnetic agitation stirs 1 hour;
3) to step 2) in the gained solution mass fraction that adds about 72mL be the watery hydrochloric acid of 5%, regulate pH value of solution to 2, adularescent Precipitation, magnetic agitation 1 hour;
4) by step 3) gained suspension suction filtration obtains graphene coated sulfur granules, dries 24 hours in 70 degrees Celsius of air;
5) Commercial foam nickel is used (in alcohol, acetone, to distinguish ultrasonic cleaning 30 minutes in advance, come again) a slice, disk diameter is 18mm, first soak 15 minutes in the watery hydrochloric acid of 2mol/L, then soak 10 minutes in alcohol, soak 10 minutes in deionized water again, reserved stand-by;
6) by step 4) the 40mg graphene coated sulfur granules that obtains, step 5) a slice nickel foam of obtaining, be placed in the polytetrafluoroethylene inner liner of reaction kettle of 100mL, add 40mL deionized water, 180 degrees Celsius of lower hydro-thermal reactions 4 hours after packaged, be cooled to room temperature after completion of the reaction;
7) by step 6) the coated nickel sulfide structure electrode of the three-dimensional drape Graphene selfreparing that obtains uses alcohol and water respectively to rinse one time, then mass fraction be in 0.048% hydrazine hydrate aqueous solution soak 3 hours, finally in 70 degrees Celsius of lower air dry more than 24 hours.

Claims (2)

1. the preparation method of the coated nickel sulfide structure electrode of three-dimensional drape Graphene selfreparing, comprises the following steps:
1) preparing mass fraction is the NaOH solution 50mL of 10%, adds 0.25gS wherein, 0.65gNa 2s9H 2o, stirring in water bath is until form orange-yellow clear solution, and bath temperature is between 60-80 degree Celsius;
2) to step 1) in add 5-20mL in gained solution concentration be 4.7mg/mL graphene dispersing solution, magnetic agitation 1 hour;
3) to step 2) in add 72mL in gained solution mass fraction be the watery hydrochloric acid of 5%, regulate pH value of solution to 2, adularescent Precipitation, magnetic agitation 1 hour;
4) by step 3) gained suspension suction filtration obtains graphene coated sulfur granules, dries 24 hours in 70 degrees Celsius of air;
5) use Commercial foam nickel a slice, diameter is 18mm, soaks 15 minutes in the watery hydrochloric acid of 2mol/L, then soaks 10 minutes in alcohol, then soaks 10 minutes in deionized water, reserved stand-by;
6) by step 4) the 40mg graphene coated sulfur granules that obtains, step 5) a slice nickel foam of obtaining, be placed in the polytetrafluoroethylene inner liner of reaction kettle of 100mL, add 40mL deionized water, 180 degrees Celsius of lower hydro-thermal reactions 4 hours after packaged, be cooled to room temperature after completion of the reaction;
7) by step 6) the coated nickel sulfide structure electrode of the three-dimensional drape Graphene selfreparing that obtains uses alcohol and water respectively to rinse one time, then mass fraction be in 0.048% hydrazine hydrate aqueous solution soak 3 hours, finally in 70 degrees Celsius of lower air dry more than 24 hours.
2. according to the preparation method of the coated nickel sulfide structure electrode of three-dimensional drape Graphene according to claim 1 selfreparing, its step 2) described in graphene dispersing solution preparation according to the following steps:
A) in 250mL conical flask, 1g graphite powder and the 23mL concentrated sulfuric acid is added, at room temperature mix and blend 24 hours;
B) conical flask is put into thermostat water bath, reaction temperature 40 degrees Celsius, in step a) gained dispersion liquid, add 100mgNaNO 3, stir 5 minutes, slowly add 1500mgKMnO subsequently 4, and keep solution temperature below 45 degrees Celsius, stir 30 minutes;
C) to step b) in gained dispersion liquid, add 3mL deionized water, stir after 5 minutes, then add 3mL deionized water, stir 5 minutes subsequently, then add 40mL deionized water, stir 15 minutes;
D) conical flask is shifted out water-bath, add 140mL deionized water and 10mL mass fraction is 30%H 2o 2to stop oxidation reaction;
E) by steps d) gained suspension service quality mark is 5%HCl solution washing twice, spends deionized water subsequently to neutral, is dispersed in 100mL deionized water, ultrasonic 60 minutes;
F) by step e) gained suspension 8000 revs/min is centrifugal, and the time is 5 minutes, repeatedly gets supernatant liquor, until isolate uniform graphene dispersing solution, concentration is 4.7mg/mL.
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