CN108767210A - A kind of electrochemical preparation method of self-supporting graphene/sulphur positive plate - Google Patents

A kind of electrochemical preparation method of self-supporting graphene/sulphur positive plate Download PDF

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CN108767210A
CN108767210A CN201810389128.XA CN201810389128A CN108767210A CN 108767210 A CN108767210 A CN 108767210A CN 201810389128 A CN201810389128 A CN 201810389128A CN 108767210 A CN108767210 A CN 108767210A
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graphene
electrochemical
self
positive plate
supporting
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杨蓉
陈利萍
许云华
燕映霖
邹鸣
邹一鸣
邓七九
樊潮江
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Xian University of Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

A kind of electrochemical preparation method of self-supporting graphene/sulphur positive plate disclosed by the invention, includes the following steps:By colloidal silica graphene drop Tu in pretreatment glassy carbon electrode surface, it is used as working electrode after freeze-drying, passes through electrochemical process redox graphene;Gained electrochemical reduction oxidation graphene is removed from glassy carbon electrode surface ultrasound, and sublimed sulfur is dissolved in carbon disulfide, drops evenly in electrochemical reduction oxidation graphene, self-supporting electrochemical reduction oxidation graphene/sulfur electrode piece is obtained after carbon disulfide volatilization.The present invention is prepared for self-supporting sulphur anode using electrochemical process, and gained electrochemical reduction oxidation graphene not chemical residue go back original reagent and efficient uniform, are a kind of comparatively ideal method for preparing anode material.

Description

A kind of electrochemical preparation method of self-supporting graphene/sulphur positive plate
Technical field
The invention belongs to lithium-sulfur cell technical fields, and in particular to a kind of electrochemistry of self-supporting graphene/sulphur positive plate Preparation method.
Background technology
Lithium-sulfur cell is a kind of extremely promising serondary lithium battery.But since the insulating properties of sulphur and its discharging product, sulphur exist Volume change is big in charge and discharge process and intermediate product polysulfide ease of solubility in the electrolytic solution so that lithium-sulfur cell exists The application bottleneck that active material utilization is low and cycle life is poor.Graphene has excellent electric conductivity and flexibility, is applied to Lithium-sulfur cell can effectively improve the utilization rate of active material, alleviate the sulphur damage of volume expansion to positive electrode in charge and discharge process It is bad.Using electrochemical process redox graphene not chemical residue go back original reagent and efficient uniform, be it is a kind of it is more satisfactory just Pole material preparation method.
Invention content
The purpose of the present invention is to provide a kind of electrochemical preparing methods of self-supporting graphene/sulphur positive plate, solve The low problem with cycle life difference of lithium-sulfur cell active material utilization made from existing method.
The technical solution adopted in the present invention is:A kind of electrochemical preparation method of self-supporting graphene/sulphur positive plate, packet Include following steps:
Step 1:Glass-carbon electrode is polished with alumina powder, is cleaned by ultrasonic in acetone, ethyl alcohol and nitric acid successively later, most It is activated in sulfuric acid solution afterwards, is repeatedly scanned with to cyclic voltammogram and stablizes;
Step 2:The glassy carbon electrode surface that colloidal silica graphene drop Tu is obtained in step 1, it is for use after freeze-drying;
Step 3:Using the glass-carbon electrode for being coated with graphene oxide obtained in step 2 as working electrode, pass through electrochemical process Redox graphene, it is for use after being rinsed with deionized water;
Step 4:The electrochemical reduction oxidation graphene obtained in step 3 is removed and freezed from glassy carbon electrode surface ultrasound It is dry;
Step 5:Sublimed sulfur is dissolved in carbon disulfide, the carbon disulfide solution of sublimed sulfur is taken to drop evenly in step later The electrochemical reduction oxidation graphene obtained in 4, after carbon disulfide volatilization to obtain the final product.
The features of the present invention also characterized in that
The glass-carbon electrode size used in step 1 is 15mm × 15mm.
A concentration of 6~8mg the mL of colloidal silica graphene used in step 2-1, drop Tu amount is 0.13~0.25mL.
The electrochemical process used in step 3 is potentiostatic method or cyclic voltammetry, and the recovery time is 2.5~4h, using perseverance Reduction potential is -1.0~-1.4V when potentiometry restores, and reduction potential is+0.9~(- 1.0 when cyclic voltammetry being used to restore ~-1.4) V.
Ultrasound stripping power is 10~20W in step 4, and the time is 1~2min.
The carbon disulfide solution concentration of sublimed sulfur is 8~10mg mL in step 5-1, dripping quantity is 0.15~0.28mL.
The beneficial effects of the invention are as follows:(1) a kind of preparation method of self-supporting sulphur anode is provided using electrochemical process; (2) gained electrochemical reduction oxidation graphene has three-dimensional porous pattern flexible, this can not only provide continuous three-dimensional for sulphur Conductive network, moreover it is possible to alleviate the sulphur damage of volume expansion to anode in charge and discharge process.
Description of the drawings
Fig. 1 is the surface SEM figures of electrochemical reduction oxidation graphene prepared by embodiment 1;
Fig. 2 is the electrochemical reduction oxidation graphene cross section SEM figures prepared by embodiment 1;
Fig. 3 is the XRD spectrum of the electrochemical reduction oxidation graphene prepared by embodiment 1;
Fig. 4 is electrochemical reduction oxidation graphene/charging and discharging curve of the sulphur positive plate at 0.1C prepared by embodiment 1 Figure;
Fig. 5 is electrochemical reduction oxidation graphene/charging and discharging curve of the sulphur positive plate at 0.1C prepared by embodiment 2 Figure.
Specific implementation mode
Below in conjunction with the accompanying drawings and specific implementation mode the present invention is described in detail.
The present invention provides a kind of electrochemical preparing methods of self-supporting graphene/sulphur positive plate, include the following steps:
Step 1:After the glass-carbon electrode of 15mm × 15mm is polished with the alumina powder of 0.3 μm, 0.05 μm successively, exist successively Acetone, ethyl alcohol (VEthyl alcohol:VWater=1:And nitric acid (V 1)Nitric acid:VWater=1:1) it is cleaned by ultrasonic 5~10min in, finally uses cyclic voltammetry In 0.5~1mol L-1H2SO4It is activated in solution, is repeatedly scanned with to cyclic voltammogram and stablizes in -1.0~1.0V;
Step 2:By 0.13~0.25mL colloidal silicas graphene (6~8mg of concentration mL-1) drop Tu handled described in step 1 Glassy carbon electrode surface afterwards, it is for use after freeze-drying;
Step 3:Using the glass-carbon electrode for being coated with graphene oxide obtained in step 2 as working electrode, pass through electrochemical process Redox graphene, it is for use after being rinsed with deionized water;Wherein, the electrochemical process used is potentiostatic method or cyclic voltammetric Method, recovery time are 2.5~4h, and reduction potential is -1.0~-1.4V when potentiostatic method being used to restore, also using cyclic voltammetry Reduction potential is+0.9~(- 1.0~-1.4) V when former;
Step 4:By the electrochemical reduction oxidation obtained in step 3 graphene/glass-carbon electrode in deionized water with 10~ 20W power ultrasonics handle 1~2min, and electrochemical reduction oxidation graphene is removed and is freeze-dried from glassy carbon electrode surface;
Step 5:Sublimed sulfur is dissolved in carbon disulfide and obtains a concentration of 8~10mg mL-1Solution, take sublimed sulfur later 0.15~0.28mL of carbon disulfide solution drop evenly the electrochemical reduction oxidation graphene obtained in step 4, wait for two sulphur Change after carbon volatilizees to obtain the final product.
By the above-mentioned means, having prepared a kind of three-dimensional porous pattern graphene flexible, increase the surface of electrode material Product, solves the problems, such as the volume expansion of sulphur in charge and discharge process, and promote Li+Diffusion and electrolyte infiltration.
Embodiment 1
Step 1:By the glass-carbon electrode of 15mm × 15mm successively with 0.3 μm, 0.05 μm of Al2O3After powder polishing, exist successively Acetone, ethyl alcohol (VEthyl alcohol:VWater=1:And nitric acid (V 1)Nitric acid:VWater=1:1) it is cleaned by ultrasonic 10min in, is finally existed with cyclic voltammetry 0.8mol L-1H2SO4It is activated in solution, is repeatedly scanned with to cyclic voltammogram and stablizes in -1.0~1.0V;
Step 2:By 0.2mL colloidal silicas graphene (6.3mg mL-1) drop Tu glass-carbon electrode table is pre-processed described in step 1 Face, it is for use after freeze-drying;
Step 3:To be coated with the glass-carbon electrode of graphene oxide described in step 2 as working electrode, respectively with 15mm × 15mm Platinized platinum and saturated calomel electrode are to electrode and reference electrode, by potentiostatic method in -1.2V electrochemical reduction oxidation graphenes 3h is used in combination deionized water to rinse repeatedly;
Step 4:Step 3 gained electrochemical reduction oxidation graphene/glass-carbon electrode is surpassed with 20W power in deionized water Electrochemical reduction oxidation graphene is removed and is freeze-dried from glassy carbon electrode surface by sonication 2min;
Step 5:20mg sublimed sulfurs are dissolved in 2mL carbon disulfide, wherein 0.19mL is measured and drops evenly obtained by step 4 Electrochemical reduction oxidation graphene obtains self-supporting electrochemical reduction oxidation graphene/sulfur electrode piece after carbon disulfide volatilization.
Embodiment 2
Step 1:By the glass-carbon electrode of 15mm × 15mm successively with 0.3 μm, 0.05 μm of Al2O3After powder polishing, exist successively Acetone, ethyl alcohol (VEthyl alcohol:VWater=1:And nitric acid (V 1)Nitric acid:VWater=1:1) it is cleaned by ultrasonic 8min in, is finally existed with cyclic voltammetry 0.5mol L-1H2SO4It is activated in solution, is repeatedly scanned with to cyclic voltammogram and stablizes in -1.0~1.0V;
Step 2:By 0.15mL colloidal silicas graphene (7.2mg mL-1) drop Tu glass-carbon electrode is pre-processed described in step 1 Surface, it is for use after freeze-drying;
Step 3:To be coated with the glass-carbon electrode of graphene oxide described in step 2 as working electrode, respectively with 15mm × 15mm Platinized platinum and saturated calomel electrode are to electrode and reference electrode, by cyclic voltammetry in+0.9~-1.4V reduction-oxidation graphite Alkene 3.2h, is used in combination deionized water to rinse repeatedly;
Step 4:Step 3 gained electrochemical reduction oxidation graphene is handled with 10W power ultrasonics in deionized water Electrochemical reduction oxidation graphene is removed and is freeze-dried from glassy carbon electrode surface by 2min;
Step 5:16mg sublimed sulfurs are dissolved in 2mL carbon disulfide, the carbon disulfide solution for measuring 0.2mL sulphur drops evenly In step 4 gained electrochemical reduction oxidation graphene, self-supporting electrochemical reduction oxidation graphite is obtained after carbon disulfide volatilization Alkene/sulfur electrode piece.
Embodiment 3
Step 1:By the glass-carbon electrode of 15mm × 15mm successively with 0.3 μm, 0.05 μm of Al2O3After powder polishing, exist successively Acetone, ethyl alcohol (VEthyl alcohol:VWater=1:And nitric acid (V 1)Nitric acid:VWater=1:1) it is cleaned by ultrasonic 5min in, is finally existed with cyclic voltammetry 1mol L-1H2SO4It is activated in solution, is repeatedly scanned with to cyclic voltammogram and stablizes in -1.0~1.0V;
Step 2:By 0.25mL colloidal silicas graphene (6mg mL-1) drop Tu glass-carbon electrode table is pre-processed described in step 1 Face, it is for use after freeze-drying;
Step 3:To be coated with the glass-carbon electrode of graphene oxide described in step 2 as working electrode, respectively with 15mm × 15mm Platinized platinum and saturated calomel electrode are to electrode and reference electrode, by cyclic voltammetry in+0.9~-1.0V reduction-oxidation graphite Alkene 4h, is used in combination deionized water to rinse repeatedly;
Step 4:Step 3 gained electrochemical reduction oxidation graphene is handled with 20W power ultrasonics in deionized water Electrochemical reduction oxidation graphene is removed and is freeze-dried from glassy carbon electrode surface by 2min;
Step 5:20mg sublimed sulfurs are dissolved in 2mL carbon disulfide, the carbon disulfide solution for measuring 0.15mL sulphur uniformly drips It is added on step 4 gained electrochemical reduction oxidation graphene, self-supporting electrochemical reduction oxidation stone is obtained after carbon disulfide volatilization Black alkene/sulfur electrode piece.
Embodiment 4
Step 1:By the glass-carbon electrode of 15mm × 15mm successively with 0.3 μm, 0.05 μm of Al2O3After powder polishing, exist successively Acetone, ethyl alcohol (VEthyl alcohol:VWater=1:And nitric acid (V 1)Nitric acid:VWater=1:1) it is cleaned by ultrasonic 10min in, is finally existed with cyclic voltammetry 0.6mol L-1H2SO4It is activated in solution, is repeatedly scanned with to cyclic voltammogram and stablizes in -1.0~1.0V;
Step 2:By 0.13mL colloidal silicas graphene (8mg mL-1) drop Tu glass-carbon electrode table is pre-processed described in step 1 Face, it is for use after freeze-drying;
Step 3:To be coated with the glass-carbon electrode of graphene oxide described in step 2 as working electrode, respectively with 15mm × 15mm Platinized platinum and saturated calomel electrode are to electrode and reference electrode, by potentiostatic method in -1.0V electrochemical reduction oxidation graphenes 2.5h is used in combination deionized water to rinse repeatedly;
Step 4:Step 3 gained electrochemical reduction oxidation graphene is handled with 20W power ultrasonics in deionized water Electrochemical reduction oxidation graphene is removed and is freeze-dried from glassy carbon electrode surface by 1min;
Step 5:16mg sublimed sulfurs are dissolved in 2mL carbon disulfide, the carbon disulfide solution for measuring 0.25mL sulphur uniformly drips It is added on step 4 gained electrochemical reduction oxidation graphene, self-supporting electrochemical reduction oxidation stone is obtained after carbon disulfide volatilization Black alkene/sulfur electrode piece.
Embodiment 5
Step 1:By the glass-carbon electrode of 15mm × 15mm successively with 0.3 μm, 0.05 μm of Al2O3After powder polishing, exist successively Acetone, ethyl alcohol (VEthyl alcohol:VWater=1:And nitric acid (V 1)Nitric acid:VWater=1:1) it is cleaned by ultrasonic 8min in, is finally existed with cyclic voltammetry 0.8mol L-1H2SO4It is activated in solution, is repeatedly scanned with to cyclic voltammogram and stablizes in -1.0~1.0V;
Step 2:By 0.2mL colloidal silicas graphene (7.2mg mL-1) drop Tu glass-carbon electrode table is pre-processed described in step 1 Face, it is for use after freeze-drying;
Step 3:To be coated with the glass-carbon electrode of graphene oxide described in step 2 as working electrode, respectively with 15mm × 15mm Platinized platinum and saturated calomel electrode are to electrode and reference electrode, by potentiostatic method in -1.4V electrochemical reduction oxidation graphenes 3.5h is used in combination deionized water to rinse repeatedly;
Step 4:Step 3 gained electrochemical reduction oxidation graphene is handled with 20W power ultrasonics in deionized water Electrochemical reduction oxidation graphene is removed and is freeze-dried from glassy carbon electrode surface by 2min;
Step 5:18mg sublimed sulfurs are dissolved in 2mL carbon disulfide, the carbon disulfide solution for measuring 0.28mL sulphur uniformly drips It is added on step 4 gained electrochemical reduction oxidation graphene, self-supporting electrochemical reduction oxidation stone is obtained after carbon disulfide volatilization Black alkene/sulfur electrode piece.
Embodiment 6
Step 1:By the glass-carbon electrode of 15mm × 15mm successively with 0.3 μm, 0.05 μm of Al2O3After powder polishing, exist successively Acetone, ethyl alcohol (VEthyl alcohol:VWater=1:And nitric acid (V 1)Nitric acid:VWater=1:1) it is cleaned by ultrasonic 8min in, is finally existed with cyclic voltammetry 0.8mol L-1H2SO4It is activated in solution, is repeatedly scanned with to cyclic voltammogram and stablizes in -1.0~1.0V;
Step 2:By 0.2mL colloidal silicas graphene (7.2mg mL-1) drop Tu glass-carbon electrode table is pre-processed described in step 1 Face, it is for use after freeze-drying;
Step 3:To be coated with the glass-carbon electrode of graphene oxide described in step 2 as working electrode, respectively with 15mm × 15mm Platinized platinum and saturated calomel electrode are to electrode and reference electrode, by cyclic voltammetry in+0.9~-1.2V reduction-oxidation graphite Alkene 3h, is used in combination deionized water to rinse repeatedly;
Step 4:Step 3 gained electrochemical reduction oxidation graphene is handled with 20W power ultrasonics in deionized water Electrochemical reduction oxidation graphene is removed and is freeze-dried from glassy carbon electrode surface by 1min;
Step 5:16mg sublimed sulfurs are dissolved in 2mL carbon disulfide, the carbon disulfide solution for measuring 0.25mL sulphur uniformly drips It is added on step 4 gained electrochemical reduction oxidation graphene, self-supporting electrochemical reduction oxidation stone is obtained after carbon disulfide volatilization Black alkene/sulfur electrode piece.
Interpretation of result
The electrochemical reduction oxidation graphene prepared using 1 scheme of embodiment is analyzed:As depicted in figs. 1 and 2, with It is in three-dimensional porous pattern that sem analysis, which obtains surface and cross section, and pole piece thickness is about 150 μm.To graphene oxide and gained Electrochemical reduction oxidation graphene carries out XRD analysis respectively, as shown in figure 3, by electrochemical reduction, the feature of graphene oxide Peak disappears, and the characteristic peak of graphene occurs at 25 ° or so.The disk that above-mentioned gained pole piece is cut to diameter 12.5mm is made For anode, lithium metal is cathode, electrolyte is 1mol L-1[LiTFSI, two (trimethyl fluoride sulfonyl) imine lithiums]/(DOL, 1,3- Dioxolanes)+(DME, glycol dimethyl ether) (v:V=1:1) (contain 1% (quality) LiNO3), in the glove box full of argon gas It is assembled into CR2025 button cells.Charge-discharge test (Neware BTS types, the new prestige in Shenzhen are carried out at room temperature to institute's packed battery Battery detection equipment Co., Ltd), charging/discharging voltage ranging from 1.5~3.0V.It is filled as shown in figure 4, sample can keep good Discharge cycles stability, and discharge platform does not reduce after recycling 50 times, without apparent polarization.As shown in figure 5, made from embodiment 2 Standby electrochemical reduction oxidation graphene/charging and discharging curve figure of the sulphur positive plate at 0.1C can be seen that similarly, sample energy Good charge and discharge cycles stability is kept, and discharge platform does not reduce after recycling 50 times, without apparent polarization.

Claims (6)

1. a kind of electrochemical preparation method of self-supporting graphene/sulphur positive plate, which is characterized in that include the following steps:
Step 1:Glass-carbon electrode is polished with alumina powder, is cleaned by ultrasonic in acetone, ethyl alcohol and nitric acid successively later, finally exists It is activated in sulfuric acid solution, is repeatedly scanned with to cyclic voltammogram and stablizes;
Step 2:The glassy carbon electrode surface that colloidal silica graphene drop Tu is obtained in step 1, it is for use after freeze-drying;
Step 3:Using the glass-carbon electrode for being coated with graphene oxide obtained in step 2 as working electrode, restored by electrochemical process Graphene oxide, it is for use after being rinsed with deionized water;
Step 4:The electrochemical reduction oxidation graphene obtained in step 3 is removed from glassy carbon electrode surface ultrasound and freezed dry It is dry;
Step 5:Sublimed sulfur is dissolved in carbon disulfide, the carbon disulfide solution of sublimed sulfur is taken to drop evenly in step 4 later Obtained electrochemical reduction oxidation graphene, after carbon disulfide volatilization to obtain the final product.
2. a kind of electrochemical preparation method of self-supporting graphene/sulphur positive plate as described in claim 1, which is characterized in that The glass-carbon electrode size used in the step 1 is 15mm × 15mm.
3. a kind of electrochemical preparation method of self-supporting graphene/sulphur positive plate as described in claim 1, which is characterized in that A concentration of 6~8mg the mL of colloidal silica graphene used in the step 2-1, drop Tu amount is 0.13~0.25mL.
4. a kind of electrochemical preparation method of self-supporting graphene/sulphur positive plate as described in claim 1, which is characterized in that The electrochemical process used in the step 3 is potentiostatic method or cyclic voltammetry, and the recovery time is 2.5~4h, using constant potential Reduction potential is -1.0~-1.4V when method restores, when cyclic voltammetry being used to restore reduction potential for+0.9~(- 1.0~- 1.4)V。
5. a kind of electrochemical preparation method of self-supporting graphene/sulphur positive plate as described in claim 1, which is characterized in that Ultrasound stripping power is 10~20W in the step 4, and the time is 1~2min.
6. a kind of electrochemical preparation method of self-supporting graphene/sulphur positive plate as described in claim 1, which is characterized in that The carbon disulfide solution concentration of sublimed sulfur is 8~10mg mL in the step 5-1, dripping quantity is 0.15~0.28mL.
CN201810389128.XA 2018-04-27 2018-04-27 A kind of electrochemical preparation method of self-supporting graphene/sulphur positive plate Pending CN108767210A (en)

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Application publication date: 20181106