CN104037416A - Preparation method for electrode with three-dimensional structure formed by coating nickel sulfide by fold graphene through self-repairing - Google Patents

Preparation method for electrode with three-dimensional structure formed by coating nickel sulfide by fold graphene through self-repairing Download PDF

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CN104037416A
CN104037416A CN201410286560.8A CN201410286560A CN104037416A CN 104037416 A CN104037416 A CN 104037416A CN 201410286560 A CN201410286560 A CN 201410286560A CN 104037416 A CN104037416 A CN 104037416A
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CN104037416B (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

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  • General Chemical & Material Sciences (AREA)
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Abstract

The invention relates to a preparation method for an electrode with a three-dimensional structure formed by coating nickel sulfide by fold graphene through self-repairing. The preparation method comprises the following steps: (1) preparing NaOH solution, adding S and Na2S.9H2O into the NaOH solution, and stirring the mixture in a water bath; (2) adding a graphene dispersion liquid, and stirring by using magnetic force; (3) adding dilute hydrochloric acid, adjusting the pH of the solution, and stirring the solution by using the magnetic force; (4) performing suction and filtration to obtain graphene-coating sulfur particles, and drying the sulfur particles in air; (5) soaking the sulfur particles by using commercial nickel foam, and preserving for later use; (6) placing the soaked sulfur particles in a reaction kettle lining, adding de-ionized water into the sulfur particles, encapsulating and performing hydrothermal reaction on the mixture, and cooling a reaction product to room temperature; and (7) washing the reaction product by using alcohol and water once respectively, soaking the reaction product in hydrazine hydrate aqueous solution, and finally drying the soaked reaction product in the air. The preparation method has the beneficial effects that the electrode is prepared on the basis of a shrinkage strain drive mechanism; high-current fast charge and discharge can be realized; in addition, the cycling times can reach 1,000, and the capacity does not decay basically.

Description

The preparation method of the coated nickel sulfide structure electrode of three-dimensional fold 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 fold 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 is playing more and more important effect aspect 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 long circulation life more, higher reversible capacity, the lithium ion battery electrode material of low production cost more, is one of the forward position of research at present and focus.Transition metal oxide, sulfide, fluoride are because the theoretical specific capacity (part can reach 1000mAh/g) of its superelevation is subject to extensive concern and the research of scientists, nickel sulfide material is a kind of up-and-coming lithium ion battery electrode material as the typical transient metal sulfide material of one, but it is low that its development is limited by its conductivity, 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 material with carbon element additive of conductivity superhigh specific surface area super large also can greatly improve lithium ion battery chemical property.
In addition, the coated nickel sulfide structure electrode of three-dimensional fold Graphene selfreparing does not need any additive, can, directly as electrode, greatly reduce battery preparation flow, meets the requirement of Green Chemistry, is 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 fold Graphene selfreparing, its preparation process is simple, energy consumption is lower, and the coated nickel sulfide structure electrode of three-dimensional fold Graphene selfreparing 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 fold Graphene selfreparing, comprises the following steps:
1) the NaOH solution 50mL that preparation mass fraction is 10%, adds 0.25g S, 0.65g Na wherein 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 the watery hydrochloric acid that the mass fraction of 72mL is 5% in gained solution, regulator solution pH to 2, adularescent Precipitation, magnetic agitation 1 hour;
4) by step 3) gained suspension suction filtration obtains graphene coated sulfur granules, in 70 degrees Celsius of air, dries 24 hours;
5) use commercial nickel foam a slice, diameter is 18mm, soaks 15 minutes in the watery hydrochloric acid of 2mol/L, then in alcohol, soaks 10 minutes, then in deionized water, soaks 10 minutes, 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, after packaged, 180 degrees Celsius of lower hydro-thermal reactions 4 hours, be cooled to after completion of the reaction room temperature;
7) by step 6) the coated nickel sulfide structure electrode of the three-dimensional fold Graphene selfreparing that obtains uses alcohol and water is each rinses one time, then be in 0.048% hydrazine hydrate aqueous solution, to soak 3 hours at mass fraction, finally in 70 degrees Celsius of lower air, dry more than 24 hours.
Press such scheme, step 2) described graphene dispersing solution prepared according to the following steps:
A) in 250ml conical flask, add 1g graphite powder and the 23ml concentrated sulfuric acid, at room temperature mix and blend 24 hours;
B) conical flask is put into thermostat water bath, 40 degrees Celsius of reaction temperatures, a) add 100mgNaNO in gained dispersion liquid to step 3, stir 5 minutes, slowly add subsequently 1500mgKMnO 4, and keep solution temperature below 45 degrees Celsius, stir 30 minutes;
C) b) in gained dispersion liquid, add 3ml deionized water to step, stir after 5 minutes, then add 3ml deionized water, stir subsequently 5 minutes, then add 40ml deionized water, stir 15 minutes;
D) conical flask is shifted out to water-bath, adding 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, subsequently with deionized water washing to neutral, be dispersed in 100ml deionized water ultrasonic 60 minutes;
F) by step, e) 8000 revs/min of gained suspension are 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 fold 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; increase the contact area of electrode material and electrolyte; improve the diffusion rate of lithium ion; adaptive deformation relaxation character has played good protection 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, prepare the coated nickel sulfide structure electrode of three-dimensional fold Graphene selfreparing based on contraction strain drive mechanism, can realize large electric current fast charging and discharging (under 20A/g current density, only need can complete charging in approximately 1 minute), it is substantially unattenuated that cycle-index can reach 1000 capacity in addition.
Brief description of the drawings
Fig. 1 is the XRD figure (Ni of fold graphene coated nickel sulfide particle on the coated nickel sulfide structure electrode of the three-dimensional fold Graphene selfreparing of the embodiment of the present invention 1 3s 2represent curing three nickel);
Fig. 2 is the SEM figure on the coated nickel sulfide structure electrode of the three-dimensional fold Graphene selfreparing surface of the embodiment of the present invention 1;
Fig. 3 is the TEM figure of fold graphene coated nickel sulfide particle on the coated nickel sulfide structure electrode of the three-dimensional fold Graphene selfreparing of the embodiment of the present invention 1;
Fig. 4 is the TEM figure of fold graphene coated nickel sulfide grain edges fold Graphene on the coated nickel sulfide structure electrode of the three-dimensional fold Graphene selfreparing of the embodiment of the present invention 1;
Fig. 5 is the bending lattice TEM figure of fold graphene coated nickel sulfide grain edges fold Graphene on the coated nickel sulfide structure electrode of the three-dimensional fold Graphene selfreparing of the embodiment of the present invention 1;
Fig. 6 is the coated nickel sulfide structure electrode synthesis mechanism figure of the three-dimensional fold Graphene selfreparing of the embodiment of the present invention 1;
Fig. 7 is the coated nickel sulfide structure electrode of the three-dimensional fold 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 better the present invention, further illustrate content of the present invention 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, add 1g graphite powder and the 23ml concentrated sulfuric acid, at room temperature mix and blend 24 hours;
B) conical flask is put into thermostat water bath, 40 degrees Celsius of reaction temperatures, a) add 100mgNaNO in gained dispersion liquid to step 3, stir 5 minutes, slowly add subsequently 1500mgKMnO 4, and keep solution temperature below 45 degrees Celsius, stir 30 minutes;
C) b) in gained dispersion liquid, add 3ml deionized water to step, stir after 5 minutes, then add 3ml deionized water, stir subsequently 5 minutes, then add 40ml deionized water, stir 15 minutes;
D) conical flask is shifted out to water-bath, adding 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, subsequently with deionized water washing to neutral, be dispersed in 100ml deionized water ultrasonic 60 minutes;
F) by step, e) 8000 revs/min of gained suspension are 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 fold Graphene selfreparing
1) the NaOH solution 50mL that preparation mass fraction is 10%, adds 0.25g S, 0.65g Na wherein 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 gained solution add the watery hydrochloric acid that the mass fraction of 72mL is 5%, regulator solution pH to 2, adularescent Precipitation, magnetic agitation 1 hour;
4) by step 3) gained suspension suction filtration obtains graphene coated sulfur granules, in 70 degrees Celsius of air, dries 24 hours;
5) use commercial nickel foam (in alcohol, acetone, to distinguish in advance ultrasonic cleaning 30 minutes, come again) a slice, disk diameter is 18mm, first in the watery hydrochloric acid of 2mol/L, soak 15 minutes, then in alcohol, soak 10 minutes, in deionized water, soak again 10 minutes, 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, after packaged, at 180 degrees Celsius of lower hydro-thermal reaction 4h, be cooled to after completion of the reaction room temperature;
7) by step 6) the coated nickel sulfide structure electrode of the three-dimensional fold Graphene selfreparing that obtains uses alcohol and water is each rinses one time, then be in 0.048% hydrazine hydrate aqueous solution, to soak 3 hours at mass fraction, finally in 70 degrees Celsius of lower air, dry more than 24 hours.
Taking the coated nickel sulfide structure electrode of three-dimensional fold Graphene of the present invention selfreparing as example, its structure and composition is determined by x-ray diffractometer.As Fig. 1, the coated nickel sulfide particle principal phase of three-dimensional fold Graphene selfreparing is curing three nickel, and dephasign is nickel sulfide, and curing three nickel peaks are very consistent with JCPDF card No.00-044-1418 contrast.
As shown in Figure 2, field emission scanning electron microscope figure shows that the coated nickel sulfide structure electrode surface three dimension fold Graphene of three-dimensional fold Graphene selfreparing is tightly wrapped in nickel sulfide surface.As shown in Figure 3, transmission electron microscope picture shows that Graphene is wrapped in nickel sulfide surface.As shown in Figure 4, high-resolution-ration transmission electric-lens Image Display fold Graphene is distributed in nickel sulfide edge.As shown in Figure 5, the lattice of high-resolution-ration transmission electric-lens Image Display fold Graphene bending.
Be coated nickel sulfide structure electrode as anodal taking the three-dimensional fold Graphene selfreparing of the present embodiment gained, LiTFSI with 1M is dissolved in 1, in 3-dioxolanes (DOL) and dimethyl second diether (DME) as electrolyte, taking lithium sheet as 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, be coated nickel sulfide structure electrode as example, at 8A g taking the three-dimensional fold Graphene selfreparing of the present embodiment gained -1under constant current charge-discharge, through 600 circles, with cocycle, battery still keeps 500mA h g -1capacity.At 10A g -1under constant current charge-discharge, through 650 circles, with cocycle, battery still keeps 450mA h g -1capacity. at 20A g -1under constant current charge-discharge, through 1000 circle circulations, battery still keeps 350mA h g -1capacity.Above result shows, the coated nickel sulfide structure electrode of three-dimensional fold 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 fold Graphene selfreparing
1) the NaOH solution 50mL that preparation mass fraction is 10%, adds 0.25g S, 0.65g Na wherein 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 gained solution add the watery hydrochloric acid that the mass fraction of about 72mL is 5%, regulator solution pH to 2, adularescent Precipitation, magnetic agitation 1 hour;
4) by step 3) gained suspension suction filtration obtains graphene coated sulfur granules, in 70 degrees Celsius of air, dries 24 hours;
5) use commercial nickel foam (in alcohol, acetone, to distinguish in advance ultrasonic cleaning 30 minutes, come again) a slice, disk diameter is 18mm, first in the watery hydrochloric acid of 2mol/L, soak 15 minutes, then in alcohol, soak 10 minutes, in deionized water, soak again 10 minutes, 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, after packaged, 180 degrees Celsius of lower hydro-thermal reactions 4 hours, be cooled to after completion of the reaction room temperature;
7) by step 6) the coated nickel sulfide structure electrode of the three-dimensional fold Graphene selfreparing that obtains uses alcohol and water is each rinses one time, then be in 0.048% hydrazine hydrate aqueous solution, to soak 3 hours at mass fraction, 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 fold Graphene selfreparing
1) the NaOH solution 50mL that preparation mass fraction is 10%, adds 0.25g S, 0.65g Na wherein 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 gained solution add the watery hydrochloric acid that the mass fraction of about 72mL is 5%, regulator solution pH to 2, adularescent Precipitation, magnetic agitation 1 hour;
4) by step 3) gained suspension suction filtration obtains graphene coated sulfur granules, in 70 degrees Celsius of air, dries 24 hours;
5) use commercial nickel foam (in alcohol, acetone, to distinguish in advance ultrasonic cleaning 30 minutes, come again) a slice, disk diameter is 18mm, first in the watery hydrochloric acid of 2mol/L, soak 15 minutes, then in alcohol, soak 10 minutes, in deionized water, soak again 10 minutes, 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, after packaged, 180 degrees Celsius of lower hydro-thermal reactions 4 hours, be cooled to after completion of the reaction room temperature;
7) by step 6) the coated nickel sulfide structure electrode of the three-dimensional fold Graphene selfreparing that obtains uses alcohol and water is each rinses one time, then be in 0.048% hydrazine hydrate aqueous solution, to soak 3 hours at mass fraction, 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 fold Graphene selfreparing
1) the NaOH solution 50mL that preparation mass fraction is 10%, adds 0.25g S, 0.65g Na wherein 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 gained solution add the watery hydrochloric acid that the mass fraction of about 72mL is 5%, regulator solution pH to 2, adularescent Precipitation, magnetic agitation 1 hour;
4) by step 3) gained suspension suction filtration obtains graphene coated sulfur granules, in 70 degrees Celsius of air, dries 24 hours;
5) use commercial nickel foam (in alcohol, acetone, to distinguish in advance ultrasonic cleaning 30 minutes, come again) a slice, disk diameter is 18mm, first in the watery hydrochloric acid of 2mol/L, soak 15 minutes, then in alcohol, soak 10 minutes, in deionized water, soak again 10 minutes, 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, after packaged, 180 degrees Celsius of lower hydro-thermal reactions 4 hours, be cooled to after completion of the reaction room temperature;
7) by step 6) the coated nickel sulfide structure electrode of the three-dimensional fold Graphene selfreparing that obtains uses alcohol and water is each rinses one time, then be in 0.048% hydrazine hydrate aqueous solution, to soak 3 hours at mass fraction, 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 fold Graphene selfreparing, comprises the following steps:
1) the NaOH solution 50mL that preparation mass fraction is 10%, adds 0.25g S, 0.65g Na wherein 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 5-20mL in gained solution, magnetic agitation stirs 1 hour;
3) to step 2) in add the watery hydrochloric acid that the mass fraction of 72mL is 5% in gained solution, regulator solution pH to 2, adularescent Precipitation, magnetic agitation 1 hour;
4) by step 3) gained suspension suction filtration obtains graphene coated sulfur granules, in 70 degrees Celsius of air, dries 24 hours;
5) use commercial nickel foam a slice, diameter is 18mm, soaks 15 minutes in the watery hydrochloric acid of 2mol/L, then in alcohol, soaks 10 minutes, then in deionized water, soaks 10 minutes, 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, after packaged, 180 degrees Celsius of lower hydro-thermal reactions 4 hours, be cooled to after completion of the reaction room temperature;
7) by step 6) the coated nickel sulfide structure electrode of the three-dimensional fold Graphene selfreparing that obtains uses alcohol and water is each rinses one time, then be in 0.048% hydrazine hydrate aqueous solution, to soak 3 hours at mass fraction, 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 fold Graphene claimed in claim 1 selfreparing, its step 2) described graphene dispersing solution prepared according to the following steps:
A) in 250ml conical flask, add 1g graphite powder and the 23ml concentrated sulfuric acid, at room temperature mix and blend 24 hours;
B) conical flask is put into thermostat water bath, 40 degrees Celsius of reaction temperatures, a) add 100mgNaNO in gained dispersion liquid to step 3, stir 5 minutes, slowly add subsequently 1500mgKMnO 4, and keep solution temperature below 45 degrees Celsius, stir 30 minutes;
C) b) in gained dispersion liquid, add 3ml deionized water to step, stir after 5 minutes, then add 3ml deionized water, stir subsequently 5 minutes, then add 40ml deionized water, stir 15 minutes;
D) conical flask is shifted out to water-bath, adding 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, subsequently with deionized water washing to neutral, be dispersed in 100ml deionized water ultrasonic 60 minutes;
F) by step, e) 8000 revs/min of gained suspension are 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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