CN103606649B - A kind of electrolytic preparation method of sulphur/carbon composite - Google Patents

A kind of electrolytic preparation method of sulphur/carbon composite Download PDF

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CN103606649B
CN103606649B CN201310594046.6A CN201310594046A CN103606649B CN 103606649 B CN103606649 B CN 103606649B CN 201310594046 A CN201310594046 A CN 201310594046A CN 103606649 B CN103606649 B CN 103606649B
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sulphur
carbon composite
electrolyte
sulfuric acid
chemical pure
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CN103606649A (en
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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
    • 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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  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

The invention discloses a kind of electrolytic preparation method of sulphur/carbon composite, described sulphur/carbon composite is prepared as follows: (1) is by formulated electrolyte solution; (2) using graphite rod simultaneously as anode and carbon source, platinized platinum is negative electrode, carries out cell reaction under d.c. current; (3) sediment that cell reaction is formed gets filter cake by suction filtration, dry after washing, obtains sulphur/carbon composite; Sulphur/carbon composite obtained by the inventive method 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.

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 enriches, can change between-2 to+7, utilize the reversible change between Li2S and S, using lithium metal as negative pole, elemental sulfur or sulfenyl composite material are as the lithium-sulfur rechargeable battery of positive pole, there is higher theoretical energy density (2600Wh/kg), be considered to the most potential novel high-capacity reserve cell system.In addition, lithium-sulfur cell also has the advantages such as abundant raw material source, low price, environmental friendliness, battery security be 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 at room temperature poorly conductive, need add a large amount of conductive agent, thus cause maximum system energy density to reduce; (2) elemental sulfur can be reduced into the polysulfide being soluble in electrolyte in discharge process, causes active material to run off, and makes sulfur electrode material morphology that huge change occur; (3) polysulfide being dissolved in electrolyte can be that electrolyte viscosity increases, and also can shuttle back and forth to electrode metal lithium sheet simultaneously, self discharge reaction occurs.These problems seriously constrain the practical application of lithium-sulfur rechargeable battery.
At present, positive progress is achieved both at home and abroad in sulphur/carbon composite, find elemental sulfur to be filled into (as mesoporous carbon, active carbon, Graphene, carbon nano-tube etc.) in some cavernous structure material with carbon elements, effectively can solve the difficult problems such as the active material occurred in electrode charge and discharge process runs off, capacity attenuation is fast.The main method of synthesis sulphur/carbon composite is by heating sulphur powder, is spread, is adsorbed onto in the hole of porous carbon materials by elemental sulfur, obtain sulphur/carbon composite.As (LiwenJi such as YuegangZhang, MuminRao, HaimeiZheng, LiangZhang, YuanchangLi, YuegangZhang.GrapheneOxideasaSulfurImmobilizerinHighPerf ormanceLithium/SulfurCells.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 LyndenA.Archer of the U.S., J.Shen, SuryaS.Moganty, A.Corona, andL.A.Archer, PorousHollowCarbonSulfurCompositesforHigh-PowerLithium-S ulfurBatteries, Angew.Chem.Int.Ed., 2011,50:1-6) utilize the mode of repeatedly vapour deposition injection sulphur to prepare a kind of hollow ball-shape sulphur/carbon composite, it has higher cyclical stability and multiplying power property.The present invention adopts a kind of easy electrolysis first, be anode and carbon source simultaneously with graphite rod, in the electrolyte sulfuric acid solution being sulphur source containing thiocarbamide, carry out continued electrolysis reaction, the Simultaneous Electrodeposition that electrolysis stripping is occurring graphite goes out elemental sulfur, can obtain sulphur/carbon composite by a step in-situ electrolysis.
(3) summary of the invention
The object of the present invention is to provide a kind of simple to operate, the electrolytic preparation method of sulphur/carbon composite 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) configure 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 gets 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:
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 is joined in the aqueous sulfuric acid for preparing, mixes and obtains 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), preferred described direct current is the direct current of 3 ~ 15V, and the preferred described cell reaction time is 0.5 ~ 5 hour.
The present invention specifically recommends described sulphur/carbon composite to be prepared in accordance with the following steps:
(1) configure electrolyte, described electrolyte is mixed by the raw material of following percentage by weight:
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 is joined in the aqueous sulfuric acid for preparing, mixes and obtains 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 gets 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.
Can be applicable to the positive electrode of lithium-sulfur cell with sulphur/carbon composite that preparation method provided by the invention obtains, described lithium-sulfur cell can adopt conventional method to prepare.
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 sulphur/carbon composite prepared by embodiment 1.
Fig. 2 is the low power SEM figure of sulphur/carbon composite prepared by embodiment 1.
Fig. 3 is the XRD figure of sulphur/carbon composite prepared by embodiment 1.
Fig. 4 is first three discharge curve of simulated battery prepared by embodiment 1.
Fig. 5 is the cyclic voltammetry curve figure of simulated battery prepared by embodiment 1
Fig. 6 is the cycle performance curve chart of simulated battery prepared by embodiment 1.
(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 thereto.
Embodiment 1
First by 4.8g concentrated sulfuric acid dissolution in 100mL deionized water, then add the potassium hydroxide solution that 10mL mass fraction is 30%, thereupon, add a certain amount of thiocarbamide, make thiourea concentration in solution be 0.5mol/L.Transferred in electrolytic cell by the solution prepared, and with natural stone inker for anode, platinized platinum is negative electrode, electrolysis 5 hours under direct voltage 4.5V, by sediment suction filtration, washing and drying, obtains sulphur/carbon composite.Fig. 1, Fig. 2, Fig. 3 are respectively the SEM collection of illustrative plates of gained sulphur/carbon composite, low power SEM collection of illustrative plates and XRD collection of illustrative plates, can see after cell reaction, can a step obtain described in sulphur/carbon composite, its form is graininess.
Electrode is made as follows with the sulphur/carbon composite of embodiment 1 gained.
Sulphur/carbon composite, acetylene black and polyvinylidene fluoride is taken respectively with the mass ratio of 70:15:15, be coated on aluminium foil after grinding evenly and 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 0.1Ag -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, reach 1150mAhg -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 excellent cyclical stability, and after 35 circulations, specific capacity still can maintain 700mAhg -1, and coulombic efficiency can reach about 93%.
Embodiment 2
First by 4.8g concentrated sulfuric acid dissolution in 100mL deionized water, then add the potassium hydroxide solution that 10mL mass fraction is 30%, thereupon, add a certain amount of thiocarbamide, make thiourea concentration in solution be 1mol/L.The solution prepared is transferred in electrolytic cell, and with high purity graphite rod for anode, platinized platinum is negative electrode, and electrolysis 1 hour under direct voltage is 15V, by sediment suction filtration, washing and drying, obtains sulphur/carbon composite.
Electrode is made as follows with the sulphur/carbon composite of embodiment 2 gained.
Sulphur/carbon composite, acetylene black and polyvinylidene fluoride is taken respectively with the mass ratio of 70:20:10, be coated on aluminium foil after grinding evenly and 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 0.1Ag -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 620mAhg -1.
Embodiment 3
First by 4.8g concentrated sulfuric acid dissolution in 100mL deionized water, then add the potassium hydroxide solution that 10mL mass fraction is 30%, thereupon, add a certain amount of thiocarbamide, make the concentration of solution thiocarbamide be 0.8mol/L.Transferred in electrolytic cell by the solution prepared, and with artificial stone inker for anode, platinized platinum is negative electrode, electrolysis 2 hours under direct voltage is 7.5V, by sediment suction filtration, washing and drying, obtains sulphur/carbon composite.
Electrode is made as follows with the sulphur/carbon composite of embodiment 3 gained.
Sulphur/carbon composite, acetylene black and polyvinylidene fluoride is taken respectively with the mass ratio of 80:10:10, be coated on aluminium foil after grinding evenly and 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 0.1Ag -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 630mAhg -1.
Embodiment 4
First by 4.8g concentrated sulfuric acid dissolution in 100mL deionized water, then add the potassium hydroxide solution that 10mL mass fraction is 30%, thereupon, add a certain amount of thiocarbamide, make the concentration of solution thiocarbamide be 0.4mol/L.Transferred in electrolytic cell by the solution prepared, and with natural modified graphite rod for anode, platinized platinum is negative electrode, electrolysis 4 hours under direct voltage is 3V, by sediment suction filtration, washing and drying, obtains sulphur/carbon composite.
Electrode is made as follows with the sulphur/carbon composite of embodiment 4 gained.
Sulphur/carbon composite, acetylene black and polyvinylidene fluoride is taken respectively with the mass ratio of 80:5:15, be coated on aluminium foil after grinding evenly and 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 0.1Ag -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 600mAhg -1.
Embodiment 5
First by business material with carbon element and sublimed sulfur 1:3 Homogeneous phase mixing in mortar in mass ratio, then briquet in a mold.The module prepared is put in baking oven, and at 155 DEG C, thermal diffusion grind into powder after 24 hours, becomes sulphur/carbon composite for subsequent use.
Electrode is made as follows with the sulphur/carbon composite of the present embodiment gained.
Sulphur/carbon composite, acetylene black and polyvinylidene fluoride is taken respectively with the mass ratio of 80:5:15, be coated on aluminium foil after grinding evenly and 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 0.1Ag -1current density under, in 1.5-3.0V voltage range, this combination electrode material first discharge capacity is 600mAhg -1, after 35 circulations, specific capacity drops to 300mAhg -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 needs longer experimental period, and one-step synthesis of the present invention sulphur/carbon composite, simple to operate, more environmental protection, 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 (7)

1. an electrolytic preparation method for sulphur/carbon composite, is characterized in that described preparation method is:
(1) configure 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 0.5 ~ 5 hour under the direct current of 3 ~ 15V;
(3) sediment that cell reaction produces gets 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:
4. the electrolytic preparation method of sulphur/carbon composite as claimed in claim 1, it is characterized in that in step (2), described graphite rod is natural stone inker or artificial stone inker.
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 Claims 1 to 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, the thiocarbamide of formula ratio and potassium hydroxide are joined in the aqueous sulfuric acid prepared again, mix and obtain electrolyte.
7. the electrolytic preparation method of sulphur/carbon composite as claimed in claim 1, is characterized in that described preparation method is:
(1) configure electrolyte, described electrolyte is mixed by the raw material of following percentage by weight:
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 is joined in the aqueous sulfuric acid for preparing, mixes and obtains 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 gets filter cake by suction filtration, dry after washing, obtains sulphur/carbon composite.
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Cited By (1)

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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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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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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
US20130183548A1 (en) * 2012-01-18 2013-07-18 E I Du Pont De Nemours And Company Compositions, layerings, electrodes and methods for making
JP6167561B2 (en) * 2012-03-09 2017-07-26 東レ株式会社 Carbon sulfur composite, electrochemical device using the same, and lithium ion battery
CN102820456B (en) * 2012-08-20 2014-10-29 中国科学院化学研究所 Porous carbon/sulfur composite material, its preparation method and application

Cited By (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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