CN103606649A - Electrolysis preparation method of sulfur/carbon composite material - Google Patents

Electrolysis preparation method of sulfur/carbon composite material Download PDF

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CN103606649A
CN103606649A CN201310594046.6A CN201310594046A CN103606649A CN 103606649 A CN103606649 A CN 103606649A CN 201310594046 A CN201310594046 A CN 201310594046A CN 103606649 A CN103606649 A CN 103606649A
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carbon composite
sulphur
electrolyte
sulfuric acid
sulfur
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黄辉
尹海林
夏阳
张文魁
陶新永
甘永平
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Zhejiang University of Technology ZJUT
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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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • 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
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Abstract

The invention discloses an electrolysis preparation method of a sulfur/carbon composite material. The sulfur/carbon composite material is prepared by the following steps: (1) preparing an electrolyte solution according to a formula; (2) performing an electrolysis reaction under direct current by taking a graphite rod as an anode and a carbon source at the same time and taking a platinum sheet as a cathode; and (3) performing suction filtration of the precipitate formed by the electrolysis reaction, fetching the filter cake, washing and drying to obtain the sulfur/carbon composite material. By adopting the method disclosed by the invention, the prepared sulfur/carbon composite material has good cycling stability and rate performance, can be used as an anode material of a lithium-sulfur battery and is widely applied to the field of high-performance lithium-sulfur secondary batteries.

Description

A kind of electrolytic preparation method of sulphur/carbon composite
(1) technical field
The present invention relates to a kind of preparation method of sulphur/carbon composite, be specifically related to a kind of electrolytic preparation method of sulphur/carbon composite.
(2) background technology
The valence state of element sulphur is abundant, can between-2 to+7, change, utilize the reversible variation between Li2S and S, using lithium metal as negative pole, elemental sulfur or sulfenyl composite material are as anodal lithium-sulfur rechargeable battery, there is higher theoretical energy density (2600Wh/kg), be considered to the most potential novel high-capacity reserve cell system.In addition, the advantage such as lithium-sulfur cell also has that raw material sources are abundant, low price, environmental friendliness, battery security are good, has clear and definite market application foreground widely.
However, still there is following problem in the sulphur positive electrode as lithium-sulfur rechargeable battery critical material: (1) elemental sulfur is poorly conductive at room temperature, needs to add a large amount of conductive agents, thereby causes maximum system energy density to reduce; (2) elemental sulfur can be reduced into the polysulfide that is soluble in electrolyte in discharge process, causes active material to run off, and makes sulfur electrode material pattern that huge change occur; (3) polysulfide that is dissolved in electrolyte can be that electrolyte viscosity increases, and also can shuttle back and forth to electrode metal lithium sheet simultaneously, and self discharge reaction occurs.These problems have seriously restricted the practical application of lithium-sulfur rechargeable battery.
At present, aspect sulphur/carbon composite, obtained positive progress both at home and abroad, discovery is filled into (as mesoporous carbon, active carbon, Graphene, carbon nano-tube etc.) in some cavernous structure material with carbon elements by elemental sulfur, can effectively solve the difficult problems such as the active material occurring in electrode charge and discharge process runs off, capacity attenuation is fast.The main method of synthetic sulphur/carbon composite is by heating sulphur powder, and elemental sulfur is spread, is adsorbed onto in the hole of porous carbon materials, obtains sulphur/carbon composite.As (Liwen Ji such as Yuegang Zhang, Mumin Rao, Haimei Zheng, Liang Zhang, Yuanchang Li, Yuegang Zhang.Graphene Oxide as a Sulfur Immobilizer in High Performance Lithium/Sulfur Cells.J.Am.Chem.Soc.2011,133,18522-18525) elemental sulfur is filled into graphene oxide, obtains high-performance sulfenyl material; (the N.Jayaprakash such as the Lynden A.Archer of the U.S., J.Shen, Surya S.Moganty, A.Corona, and L.A.Archer, Porous Hollow Carbon@Sulfur Composites for High-Power Lithium-Sulfur Batteries, Angew.Chem.Int.Ed., 2011, the mode of 50:1-6) utilizing repeatedly vapour deposition to inject sulphur is prepared a kind of hollow ball-shape sulphur/carbon composite, and it has higher cyclical stability and multiplying power property.The present invention adopts a kind of easy electrolysis first, take graphite rod simultaneously as anode and carbon source, continue cell reaction in the electrolyte sulfuric acid solution that is sulphur source containing thiocarbamide, graphite goes out elemental sulfur at the Simultaneous Electrodeposition that electrolysis stripping occurs, and can make sulphur/carbon composite by a step in-situ electrolysis.
(3) summary of the invention
The object of the present invention is to provide the electrolytic preparation method of sulphur/carbon composite a kind of simple to operate, with low cost.
For achieving the above object, the technical solution used in the present invention is:
An electrolytic preparation method for sulphur/carbon composite, described preparation method carries out as follows:
(1) configuration electrolyte, described electrolyte is mixed by the raw material of following percentage by weight:
Figure BDA0000419659650000021
Figure BDA0000419659650000031
(2) take graphite rod as anode, platinized platinum is negative electrode, carries out cell reaction 0.1～10 hour under the direct current of 1～100V;
(3) sediment that cell reaction produces is got filter cake by suction filtration, dry after washing, obtains sulphur/carbon composite.
In the electrolytic preparation method step (1) of sulphur/carbon composite of the present invention, the purity of preferred described sulfuric acid, thiocarbamide and potassium hydroxide is chemical pure or higher than chemical pure; Preferred described water is deionized water.
In step of the present invention (1), preferred described electrolyte is mixed by the raw material of following percentage by weight:
Figure BDA0000419659650000032
In step of the present invention (1), the compound method of described electrolyte is: sulfuric acid and the water of getting formula ratio are mixed with aqueous sulfuric acid, then the thiocarbamide of formula ratio and potassium hydroxide are joined in the aqueous sulfuric acid preparing, and mixes and obtain electrolyte.
In the electrolytic preparation method step (2) of sulphur/carbon composite of the present invention, described graphite rod is selected from natural stone inker, artificial stone inker or high purity graphite rod, and preferably the purity of graphite rod is chemical pure or higher than chemical pure.
In step of the present invention (2), the direct current that preferred described direct current is 3～15V, the preferred described cell reaction time is 0.5～5 hour.
The present invention is concrete recommends described sulphur/carbon composite to be prepared in accordance with the following steps:
(1) configuration electrolyte, described electrolyte is mixed by the raw material of following percentage by weight:
Figure BDA0000419659650000041
The purity of described sulfuric acid, thiocarbamide and potassium hydroxide is chemical pure or higher than chemical pure;
The compound method of electrolyte is: sulfuric acid and the water of getting formula ratio are mixed with aqueous sulfuric acid, then the thiocarbamide of formula ratio and potassium hydroxide are joined in the aqueous sulfuric acid preparing, and mixes and obtain electrolyte;
(2) take graphite rod as anode, platinized platinum is negative electrode, carries out cell reaction 0.5～5 hour under 3～15V direct current; The purity of described graphite rod is chemical pure or higher than chemical pure;
(3) sediment that cell reaction produces is got filter cake by suction filtration, dry after washing, obtains sulphur/carbon composite.
The form of sulphur/carbon composite of the present invention is powder, fragment, particle.
With sulphur/carbon composite that preparation method provided by the invention makes, can be applicable to the positive electrode of lithium-sulfur cell, described lithium-sulfur cell can adopt conventional method preparation.
Compared with prior art, the inventive method is simple, is easy to control, with low cost, easily realizes industrialization; Sulphur/the carbon composite of gained has good cyclical stability and high rate performance, can be used as the positive electrode of lithium-sulfur cell, is widely used in high-performance lithium sulfur rechargeable battery field.
(4) accompanying drawing explanation
Fig. 1 is the SEM figure of the sulphur/carbon composite of embodiment 1 preparation.
Fig. 2 is the low power SEM figure of the sulphur/carbon composite of embodiment 1 preparation.
Fig. 3 is the XRD figure of the sulphur/carbon composite of embodiment 1 preparation.
Fig. 4 is first three discharge curve of the simulated battery of embodiment 1 preparation.
Fig. 5 is the cyclic voltammetry curve figure of the simulated battery of embodiment 1 preparation
Fig. 6 is the cycle performance curve chart of the simulated battery of embodiment 1 preparation.
(5) embodiment
With specific embodiment, technical scheme of the present invention is described further below, but protection scope of the present invention is not limited to this.
Embodiment 1
First by 4.8g concentrated sulfuric acid dissolution in 100mL deionized water, then adding 10mL mass fraction is 30% potassium hydroxide solution, thereupon, adds a certain amount of thiocarbamide, making thiourea concentration in solution is 0.5mol/L.The solution preparing is transferred in electrolytic cell, and be take natural stone inker as anode, platinized platinum is negative electrode, and under direct voltage 4.5V, electrolysis is 5 hours, by sediment suction filtration, washing and dry, obtains sulphur/carbon composite.Fig. 1, Fig. 2, Fig. 3 are respectively SEM collection of illustrative plates, low power SEM collection of illustrative plates and the XRD collection of illustrative plates of gained sulphur/carbon composite, can see after cell reaction, can a step obtain described sulphur/carbon composite, and its form is graininess.
With the sulphur/carbon composite of embodiment 1 gained, make as follows electrode.
Mass ratio with 70:15:15 takes respectively sulphur/carbon composite, acetylene black and polyvinylidene fluoride, after grinding evenly, be coated in and on aluminium foil, make electrode, employing metal lithium sheet is negative pole, electrolyte is 1mol/L1,3-dioxolanes (DOL)/glycol dimethyl ether (DME) base two (trifluoromethane sulfonic acid) imine lithium (LiTFSI) (volume ratio is 1:1), polypropylene microporous film is barrier film (Celgard2300), is assembled into simulated battery.Fig. 4 is that battery is at 0.1A g -1current density under, the discharge curve in 1.5～3.0V voltage range, can find that this combination electrode material has higher discharge capacity first, reaches 1150mAh g -1.Fig. 5 is that respective battery is at 0.1mVs -1cyclic voltammetry curve under sweep speed, wherein two reduction peak current potentials correspond respectively to the discharge platform of respective battery.Fig. 6 is the cycle performance figure of respective battery, can find that this combination electrode material has good cyclical stability, and after 35 circulations, specific capacity still can maintain 700mAh g -1, and coulomb efficiency can reach 93% left and right.
Embodiment 2
First by 4.8g concentrated sulfuric acid dissolution in 100mL deionized water, then adding 10mL mass fraction is 30% potassium hydroxide solution, thereupon, adds a certain amount of thiocarbamide, making thiourea concentration in solution is 1mol/L.The solution preparing is transferred in electrolytic cell, and be take high purity graphite rod as anode, platinized platinum is negative electrode, at direct voltage, is electrolysis 1 hour under 15V, by sediment suction filtration, washing and dry, obtains sulphur/carbon composite.
With the sulphur/carbon composite of embodiment 2 gained, make as follows electrode.
Mass ratio with 70:20:10 takes respectively sulphur/carbon composite, acetylene black and polyvinylidene fluoride, after grinding evenly, be coated in and on aluminium foil, make electrode, employing metal lithium sheet is negative pole, electrolyte is 1mol/L1,3-dioxolanes (DOL)/glycol dimethyl ether (DME) base two (trifluoromethane sulfonic acid) imine lithium (LiTFSI) (volume ratio is 1:1), polypropylene microporous film is barrier film (Celgard2300), is assembled into simulated battery.At 0.1A g -1current density under, in 1.5～3.0V voltage range, this combination electrode material first discharge capacity reaches 1000mAhg -1, after 35 circulations, specific capacity is still higher than 620mAh g -1.
Embodiment 3
First by 4.8g concentrated sulfuric acid dissolution in 100mL deionized water, then adding 10mL mass fraction is 30% potassium hydroxide solution, thereupon, adds a certain amount of thiocarbamide, the concentration that makes solution thiocarbamide is 0.8mol/L.The solution preparing is transferred in electrolytic cell, and be take artificial stone inker as anode, platinized platinum is negative electrode, at direct voltage, is electrolysis 2 hours under 7.5V, by sediment suction filtration, washing and dry, obtains sulphur/carbon composite.
With the sulphur/carbon composite of embodiment 3 gained, make as follows electrode.
Mass ratio with 80:10:10 takes respectively sulphur/carbon composite, acetylene black and polyvinylidene fluoride, after grinding evenly, be coated in and on aluminium foil, make electrode, employing metal lithium sheet is negative pole, electrolyte is 1mol/L1,3-dioxolanes (DOL)/glycol dimethyl ether (DME) base two (trifluoromethane sulfonic acid) imine lithium (LiTFSI) (volume ratio is 1:1), polypropylene microporous film is barrier film (Celgard2300), is assembled into simulated battery.At 0.1A g -1current density under, in 1.5～3.0V voltage range, this combination electrode material first discharge capacity reaches 1050mAhg -1, after 35 circulations, specific capacity is still higher than 630mAh g -1.
Embodiment 4
First by 4.8g concentrated sulfuric acid dissolution in 100mL deionized water, then adding 10mL mass fraction is 30% potassium hydroxide solution, thereupon, adds a certain amount of thiocarbamide, the concentration that makes solution thiocarbamide is 0.4mol/L.The solution preparing is transferred in electrolytic cell, and be take natural modified graphite rod as anode, platinized platinum is negative electrode, at direct voltage, is electrolysis 4 hours under 3V, by sediment suction filtration, washing and dry, obtains sulphur/carbon composite.
With the sulphur/carbon composite of embodiment 4 gained, make as follows electrode.
Mass ratio with 80:5:15 takes respectively sulphur/carbon composite, acetylene black and polyvinylidene fluoride, after grinding evenly, be coated in and on aluminium foil, make electrode, employing metal lithium sheet is negative pole, electrolyte is 1mol/L1,3-dioxolanes (DOL)/glycol dimethyl ether (DME) base two (trifluoromethane sulfonic acid) imine lithium (LiTFSI) (volume ratio is 1:1), polypropylene microporous film is barrier film (Celgard2300), is assembled into simulated battery.At 0.1A g -1current density under, in 1.5～3.0V voltage range, this combination electrode material first discharge capacity reaches 900mAhg -1, after 35 circulations, specific capacity is still higher than 600mAh g -1.
Embodiment 5
First by business material with carbon element and sublimed sulfur in mass ratio 1:3 in mortar, evenly mix, briquet in mould then.The module preparing is put in baking oven, and at 155 ℃, thermal diffusion grind into powder after 24 hours, becomes standby sulphur/carbon composite.
With the sulphur/carbon composite of the present embodiment gained, make as follows electrode.
Mass ratio with 80:5:15 takes respectively sulphur/carbon composite, acetylene black and polyvinylidene fluoride, after grinding evenly, be coated in and on aluminium foil, make electrode, employing metal lithium sheet is negative pole, electrolyte is 1mol/L1,3-dioxolanes (DOL)/glycol dimethyl ether (DME) base two (trifluoromethane sulfonic acid) imine lithium (LiTFSI) (volume ratio is 1:1), polypropylene microporous film is barrier film (Celgard2300), is assembled into simulated battery.At 0.1A g -1current density under, in 1.5-3.0V voltage range, this combination electrode material first discharge capacity is 600mAh g -1, after 35 circulations, specific capacity drops to 300mAh g -1.
Comparative example 4 and embodiment 5, sulphur/carbon composite prepared by the present invention has electrochemistry cycle performance relatively preferably.In embodiment 5, thermal diffusion process not only consumes mass energy but also experimental period that need to be longer, and one-step synthesis sulphur/carbon composite of the present invention is simple to operate, and more environmental protection is more energy-conservation.
Sulphur/carbon composite prepared by the present invention possesses better chemical property, and its manufacturing cycle is short, and environmental protection and energy saving have good prospects for commercial application.

Claims (8)

1. an electrolytic preparation method for sulphur/carbon composite, is characterized in that described preparation method is:
(1) configuration electrolyte, described electrolyte is mixed by the raw material of following percentage by weight:
(2) take graphite rod as anode, platinized platinum is negative electrode, carries out cell reaction 0.1～10 hour under the direct current of 1～100V;
(3) sediment that cell reaction produces is got filter cake by suction filtration, dry after washing, obtains sulphur/carbon composite.
2. the electrolytic preparation method of sulphur/carbon composite as claimed in claim 1, is characterized in that in step (1), and the purity of described sulfuric acid, thiocarbamide and potassium hydroxide is chemical pure or higher than chemical pure; Described water is deionized water.
3. the electrolytic preparation method of sulphur/carbon composite as claimed in claim 1, is characterized in that in step (1), described electrolyte is mixed by the raw material of following percentage by weight:
Figure FDA0000419659640000012
4. the electrolytic preparation method of sulphur/carbon composite as claimed in claim 1, is characterized in that in step (2), and described graphite rod is natural stone inker, artificial stone inker or high purity graphite rod.
5. the electrolytic preparation method of sulphur/carbon composite as claimed in claim 1, is characterized in that in step (2), and the purity of described graphite rod is chemical pure or higher than chemical pure.
6. the electrolytic preparation method of the sulphur/carbon composite as described in one of claim 1～5, is characterized in that in step (2), the direct current that described direct current is 3～15V, and the described cell reaction time is 0.5～5 hour.
7. the electrolytic preparation method of the sulphur/carbon composite as described in one of claim 1～5, it is characterized in that in step (1), described electrolyte is prepared as follows: sulfuric acid and the water of getting formula ratio are mixed with aqueous sulfuric acid, again the thiocarbamide of formula ratio and potassium hydroxide are joined in the aqueous sulfuric acid preparing, mix and obtain electrolyte.
8. the electrolytic preparation method of sulphur/carbon composite as claimed in claim 1, is characterized in that described preparation method is:
(1) configuration electrolyte, described electrolyte is mixed by the raw material of following percentage by weight:
Figure FDA0000419659640000021
The purity of described sulfuric acid, thiocarbamide and potassium hydroxide is chemical pure or higher than chemical pure;
The compound method of electrolyte is: sulfuric acid and the water of getting formula ratio are mixed with aqueous sulfuric acid, then the thiocarbamide of formula ratio and potassium hydroxide are joined in the aqueous sulfuric acid preparing, and mixes and obtain electrolyte;
(2) take graphite rod as anode, platinized platinum is negative electrode, carries out cell reaction 0.5～5 hour under 3～15V direct current; The purity of described graphite rod is chemical pure or higher than chemical pure;
(3) sediment that cell reaction produces is got filter cake by suction filtration, dry after washing, obtains sulphur/carbon composite.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104617253A (en) * 2015-02-02 2015-05-13 吉林大学 Method for preparing sulfur composite electrodes
CN105070893A (en) * 2015-07-07 2015-11-18 大连理工大学 Porous carbon/sulfur cathode material of lithium-sulfur battery and preparation method for cathode material

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107302079A (en) * 2017-07-31 2017-10-27 安阳工学院 A kind of electrochemical method prepares titanium carbide sulphur nano composite material

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CN101478061B (en) * 2008-12-16 2011-09-28 南开大学 Lithium battery using sulfur/carbon composite material as positive pole and preparation thereof
CN102820456A (en) * 2012-08-20 2012-12-12 中国科学院化学研究所 Porous carbon/sulfur composite material, its preparation method and application
WO2013109807A1 (en) * 2012-01-18 2013-07-25 E. I. Du Pont De Nemours And Company Compositions, layerings, electrodes and methods for making
JP2013214503A (en) * 2012-03-09 2013-10-17 Toray Ind Inc Carbon-sulfur complex, electrochemical element using the same, and lithium ion battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101478061B (en) * 2008-12-16 2011-09-28 南开大学 Lithium battery using sulfur/carbon composite material as positive pole and preparation thereof
WO2013109807A1 (en) * 2012-01-18 2013-07-25 E. I. Du Pont De Nemours And Company Compositions, layerings, electrodes and methods for making
JP2013214503A (en) * 2012-03-09 2013-10-17 Toray Ind Inc Carbon-sulfur complex, electrochemical element using the same, and lithium ion battery
CN102820456A (en) * 2012-08-20 2012-12-12 中国科学院化学研究所 Porous carbon/sulfur composite material, its preparation method and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104617253A (en) * 2015-02-02 2015-05-13 吉林大学 Method for preparing sulfur composite electrodes
CN105070893A (en) * 2015-07-07 2015-11-18 大连理工大学 Porous carbon/sulfur cathode material of lithium-sulfur battery and preparation method for cathode material

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