CN103178247A - Sulfur/carbon composite material and preparation method thereof - Google Patents
Sulfur/carbon composite material and preparation method thereof Download PDFInfo
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- CN103178247A CN103178247A CN201310094871XA CN201310094871A CN103178247A CN 103178247 A CN103178247 A CN 103178247A CN 201310094871X A CN201310094871X A CN 201310094871XA CN 201310094871 A CN201310094871 A CN 201310094871A CN 103178247 A CN103178247 A CN 103178247A
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 171
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 128
- 239000002131 composite material Substances 0.000 title claims abstract description 102
- 239000011593 sulfur Substances 0.000 title claims abstract description 36
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229920001021 polysulfide Polymers 0.000 claims abstract description 40
- 239000005077 polysulfide Substances 0.000 claims abstract description 40
- 150000008117 polysulfides Polymers 0.000 claims abstract description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 39
- 238000003756 stirring Methods 0.000 claims abstract description 28
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims abstract description 21
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 9
- 230000010355 oscillation Effects 0.000 claims abstract description 4
- 239000005864 Sulphur Substances 0.000 claims description 123
- 239000000463 material Substances 0.000 claims description 29
- 238000001914 filtration Methods 0.000 claims description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000013504 Triton X-100 Substances 0.000 claims description 5
- 229920004890 Triton X-100 Polymers 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 239000004964 aerogel Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims description 3
- 238000005352 clarification Methods 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 22
- 238000000151 deposition Methods 0.000 abstract description 14
- 238000011065 in-situ storage Methods 0.000 abstract description 14
- 230000008021 deposition Effects 0.000 abstract description 11
- 239000007789 gas Substances 0.000 abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003575 carbonaceous material Substances 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011149 active material Substances 0.000 abstract description 3
- 229910021529 ammonia Inorganic materials 0.000 abstract description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000007774 positive electrode material Substances 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 150000003463 sulfur Chemical class 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 230000004087 circulation Effects 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 238000005979 thermal decomposition reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- -1 carbon nano tube compound Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
一种硫/碳复合材料及其制备方法，所述硫/碳复合材料中的碳材料的孔道内均匀地填充了纳米硫，形成纳米硫粒子/碳复合材料；其制备方法包括以下步骤：（1）硫化铵溶液与硫源反应生成多硫化铵溶液；（2）向多硫化铵溶液中加入表面活性剂和碳材料，搅拌均匀后置于超声波清洗器中超声振荡，然后加热，使分解生成的硫原位沉积到碳材料孔道中得到硫/碳复合材料。本发明所得到的硫/碳复合材料，碳硫颗粒结合紧密，用作锂硫电池的正极材料有助于减少活性物质的溶解损失和抑制穿梭效应；多硫化铵分解产生的氨气与硫化氢气体通过冷凝器生成硫化铵循环使用，工艺过程污染小；制备方法工艺简单、成本低、时间短；硫含量高且可控，重复性强；易于规模化生产。
A sulfur/carbon composite material and a preparation method thereof, wherein the pores of the carbon material in the sulfur/carbon composite material are uniformly filled with nano-sulfur to form nano-sulfur particle/carbon composite materials; the preparation method comprises the following steps: ( 1) Ammonium sulfide solution reacts with sulfur source to form ammonium polysulfide solution; (2) Add surfactant and carbon material to ammonium polysulfide solution, stir evenly, place in ultrasonic cleaner for ultrasonic oscillation, and then heat to decompose and form In situ deposition of sulfur into the pores of carbon materials to obtain sulfur/carbon composites. The sulfur/carbon composite material obtained in the present invention has carbon and sulfur particles tightly combined, and is used as a positive electrode material for lithium-sulfur batteries to help reduce the dissolution loss of active materials and suppress the shuttle effect; the ammonia and hydrogen sulfide produced by the decomposition of ammonium polysulfide The gas passes through the condenser to generate ammonium sulfide for recycling, and the process has little pollution; the preparation method has simple process, low cost, and short time; the sulfur content is high and controllable, and the repeatability is strong; and it is easy for large-scale production.
Description
Technical field
The invention belongs to electrochemical field, be specifically related to a kind of sulphur/carbon composite and preparation method thereof.
Background technology
Along with portable type electronic product is universal, the fast development of energy storage technology and electric automobile, more and more higher to the requirement of lithium ion battery energy density and power density.There is prediction to claim, more than the energy density of following 4G mobile communication requirement battery reaches 500Wh/Kg.Lithium-sulfur cell has the characteristics of height ratio capacity (1675mAh/g) and high-energy-density (2600Wh/kg), and raw material elemental sulfur aboundresources, cheap, environmental friendliness; Therefore, lithium-sulfur cell is the high-energy density secondary battery that has development potentiality and application prospect.But there is the shortcoming of positive active material elemental sulfur poorly conductive, the intermediate product polysulfide of discharge process is soluble in electrolyte, and " effect of shuttling back and forth " occurs in electrolyte, causes irreversible loss and the capacity attenuation of active material; Simultaneously, final discharging product Li
2The indissolubility of S and electrical insulating property can cause the passivation of anodal and negative pole.At present, the sulphur positive electrode is mainly to have satisfactory electrical conductivity by elemental sulfur is adsorbed onto, on the carbon material of high-specific surface area and high porosity, form the sulphur carbon composite.The preparation method of existing sulphur/carbon composite has: ball-milling method, vapor phase method, liquid phase method etc.
Chung etc. (J.Power Sources, 2002,109,89-97) elemental sulfur is simply mixed rear preparation sulphur/carbon composite anode material with conductive carbon black with high energy ball mill.The method flow process is simple, but in the sulphur/carbon composite that makes with this method, the carbon sulfur granules is not in conjunction with tight.
(the Chem.Commun such as Shi; 2012; 48; 4106-4108.) the use vapor phase method; first with after material with carbon element and sulphur ball milling, 155 ℃ of heating a period of times under protective atmosphere, allow molten sulfur immerse in the pore space structure of material with carbon element; and then be warming up to the 300-350 ℃ of sulphur of removing carbon material surface, thereby prepare sulphur/carbon composite.The particle of sulphur/carbon composite that this method is prepared is in conjunction with very tight, but it is low to carry sulfur content.
Chinese patent net CN 101891930A discloses a kind of method for preparing the sulfur-based composite anode material of carbon nano-tube with vapor phase method, and this method is conducive to the dispersion of carbon nano-tube and the even distribution of sulphur, but in composite material, sulfur content is low and be difficult to control.
Chinese patent net CN 102832379A discloses a kind of method of Liquid preparation methods lithium sulfur battery anode material: elemental sulfur and organic solvent are mixed make elemental sulfur dissolve fully, Carbon Materials is added in sulphur-organic solution, stir, by naturally volatilizing or the method for heated volatile is removed solvent, make sulphur-carbon composite.This preparation method is simple, and composite material to carry sulfur content high; But have sulphur to be attached to the surface of carbon, and most of molten sulphur organic solvent is all toxic; In addition, by naturally volatilize or heated volatile to remove the solvent time long; Volatilization process is slow, and sulphur can slow crystallization, causes that the sulfur granules of separating out is large and granularity is inhomogeneous.
(the J.Mater.Chem.A.2013 such as Ho Suk Ryu, 1,1573 – 1578.) use the method for liquid impregnation, elemental sulfur is dissolved in dimethyl sulfoxide (DMSO) (DMSO), then add wherein active carbon, stir 3h and make the organic solvent of sulfur-bearing fully infiltrate active carbon, then be cooled to room temperature, elemental sulfur recrystallization in the hole of active carbon is separated out and is obtained active carbon/sulphur composite material.This method is simple to operate, but has sulphur to be attached to the surface of carbon, and most of molten sulphur organic solvent is all toxic.
Therefore, need a kind of carbon sulfur granules that can make of exploitation badly and combine closely, carry sulfur content high, controlled, and pollution-free, cost is low, and the preparation method of the simple sulphur/carbon composite of preparation technology is to improve its chemical property.
Summary of the invention
The object of the present invention is to provide a kind of sulphur/carbon composite and preparation method thereof, sulphur in sulphur/carbon composite/carbon combination is very tight, and simple by the method preparation technology; Cost is low; Time is short; Energy consumption is low; Sulfur content is high and controlled, and repeatability is strong; Be easy to large-scale production.
Purpose of the present invention is achieved through the following technical solutions:
A kind of sulphur/carbon composite has been filled nano-sulfur equably in the duct of the material with carbon element in described sulphur/carbon composite, form nano-sulfur particle/carbon composite, and in this sulphur/carbon composite, the mass percent of sulphur is 50%～90%.
A kind of preparation method of sulphur/carbon composite mainly comprises the following steps:
Step 1: under normal temperature, certain density ammonium sulfide solution is mixed by a certain percentage with elemental sulfur, stir, standing 0.5～2h, the ammonium polysulfide solution ((NH that obtains clarifying
4)
2Sx (x=2～6)).
Step 2: a certain proportion of surfactant and material with carbon element are added in ammonium polysulfide solution successively, stir; Be placed in ultrasonic cleaner with 60～150W sonic oscillation, 0.5～2h, be heated to 80～120 ℃, ammonium polysulfide ((NH
4)
2Sx (x=2～6)) in the material with carbon element duct, through isolated by filtration or centrifugation, vacuumize obtains sulphur/carbon composite to the nano-sulfur that decompose to generate at 60～110 ℃ of temperature with in-situ deposition
In step 1, the mass concentration of ammonium sulfide solution used is 17～99%.
In step 1, the mol ratio of described ammonium sulfide and elemental sulfur is 1～5.
In step 1, described elemental sulfur is from one or more in sublimed sulfur, sedimentation sulphur, refining sulphur.
In step 2, surfactant used and material with carbon element mass percent are 1～20%.
In step 2, surfactant used is one or more in polyethylene glycol (PEG), softex kw (CTAB), neopelex (SDBS), Triton X-100 (TritonX-100).
In step 2, described material with carbon element is one or more in active carbon, mesoporous carbon, carbon black, carbon fiber, carbon nano-tube, charcoal-aero gel, Graphene.
In step 2, in described sulphur/carbon composite, the sulphur mass percent is 50%～90%, has filled uniformly the nano-sulfur particle in the hole of the material with carbon element in described sulphur/carbon composite, forms nano-sulfur particle/carbon composite.
With sulphur/carbon composite of finally obtaining positive electrode as lithium-sulfur cell.
The present invention utilizes under normal temperature elemental sulfur to be dissolved in ammonium sulfide solution can generate ammonium polysulfide ((NH
4)
2Sx (x=2～6)) solution, the ammonium polysulfide heating can decomposite this principle of elemental sulfur.Reaction equation is: (x-1) S+(NH
4)
2S=(NH
4)
2Sx, (NH
4)
2Sx=2NH
3+ H
2S+(x-1) S.Adopt inorganic solvent ammonium sulfide in situ deposition method, make material with carbon element be dispersed in fully in ammonium polysulfide solution by adding surfactant, under the Ultrasound-assisted effect, add thermal decomposition, the sulphur that generates will easier in-situ deposition in the material with carbon element duct, prepare carbon sulfur granules combination sulphur/carbon composite very closely.
Sulphur/carbon composite disclosed by the invention and preparation method thereof has the following advantages:
(1) the present invention adopts ammonium polysulfide directly to decompose the in situ deposition method that generates sulphur to prepare sulphur/carbon composite, make in the duct that ammonium polysulfide solution enters porous carbon by ultrasonic, ammonium polysulfide add nano-sulfur that thermal decomposition generates with in-situ deposition in the duct of porous carbon, thereby make the combination of carbon sulfur granules in the composite material of preparing very tight, reduced to a certain extent the solution loss of active material in the lithium-sulfur cell and suppressed the effect of shuttling back and forth.
(2) the present invention adopts ammonium polysulfide solution decomposition generation sulphur in situ deposition method to prepare sulphur/carbon composite, and sulfur content is high and controlled, can obtain the different sulphur/carbon composite of sulfur content by the material with carbon element of controlling in raw material from the elemental sulfur ratio.
(3) in the present invention, the ammonium polysulfide decomposition produces ammonia and hydrogen sulfide gas are easy to generate ammonium sulfide in industrialized condenser circulating device, can be recycled, and save cost, and whole technique is polluted little.
(4) the present invention adopts the sulphur source dissolving that ammonium sulfide solution is low with purity, particle is large to purify, generate ammonium polysulfide solution, ammonium polysulfide decomposes the highly purified nano-sulfur of generation, the preparation sulphur/the carbon composite impurity content is low, nano-sulfur particles size in sulphur/carbon composite is little, easily be embedded in the duct of porous carbon, make the combination of carbon sulfur granules very tight.
(5) the ammonium sulfide low price of the present invention's employing, can be recycled; And whole preparation technology is simple, and the time is short, and energy consumption is low, and is repeatable strong, is easy in industrial enforcement and production in enormous quantities.
In sum, preparation technology of the present invention is simple; Cost is low; Time is short; Energy consumption is low; Sulfur content is high and controlled; The ammonia that decomposition produces and hydrogen sulfide gas are easy to generate ammonium sulfide and recycle in circulating device, whole technical process is pollution-free; Repeatable strong; Be easy to large-scale production.The sulphur carbon composite of preparation is a kind of desirable lithium-sulfur cell positive electrode.
Description of drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the prepared sulphur/carbon composite of embodiment 1;
Fig. 2 is the scanning electron microscope (SEM) photograph of the prepared sulphur/carbon composite of embodiment 2;
Fig. 3 is the scanning electron microscope (SEM) photograph of the prepared sulphur/carbon composite of embodiment 3;
Fig. 4 is the scanning electron microscope (SEM) photograph of the prepared sulphur/carbon composite of embodiment 5;
Fig. 5 is the scanning electron microscope (SEM) photograph of the prepared sulphur/carbon composite of embodiment 6.
Fig. 6 is take the prepared sulphur/carbon composite of embodiment 1 as anodal 50 discharge capacity curve charts of lithium-sulfur cell;
Fig. 7 is that the prepared sulphur/carbon composite of embodiment 3 is anodal 50 discharge capacity curve charts of lithium-sulfur cell;
Fig. 8 is that the prepared sulphur/carbon composite of embodiment 4 is anodal 50 discharge capacity curve charts of lithium-sulfur cell;
Fig. 9 is that the prepared sulphur/carbon composite of embodiment 5 is anodal 50 discharge capacity curve charts of lithium-sulfur cell;
Figure 10 is that the prepared sulphur/carbon composite of embodiment 6 is anodal 50 discharge capacity curve charts of lithium-sulfur cell.
Figure 11 is the thermogravimetric curve figure of sulphur/carbon composite of obtaining by embodiment 1.
The composite material sulphur carbon dispersion that can find out preparation from the scanning electron microscope (SEM) photograph of accompanying drawing 1-5 is more even, and sulphur and carbon are in conjunction with tight.
Accompanying drawing 6 is that first discharge specific capacity is 1210mAh/g take the prepared sulphur/absorbent charcoal composite material of embodiment 1 as anodal 50 discharge capacity curve charts of lithium-sulfur cell, after 50 circulations greater than 550mAh/g;
Accompanying drawing 7 is that the prepared sulphur/Carbon Black Composites of embodiment 3 is anodal 50 discharge capacity curve charts of lithium-sulfur cell, and first discharge specific capacity is 980mAh/g, and 50 circulations are rear greater than 500mAh/g;
Accompanying drawing 8 is that the prepared sulphur/graphene composite material of embodiment 4 is anodal 50 discharge capacity curve charts of lithium-sulfur cell, and first discharge specific capacity is 1270mAh/g, and 50 circulations are rear greater than 800mAh/g;
Accompanying drawing 9 is that the prepared sulphur/carbon fibre composite of embodiment 5 is anodal 50 discharge capacity curve charts of lithium-sulfur cell, and first discharge specific capacity is 1320mAh/g, and 50 circulations are rear greater than 650mAh/g;
Accompanying drawing 10 is that the prepared sulphur/carbon nano tube compound material of embodiment 6 is anodal 50 discharge capacity curve charts of lithium-sulfur cell, and first discharge specific capacity is 1050mAh/g, and 50 circulations are rear greater than 600mAh/g.Prepared sulphur/carbon composite all shows for anodal lithium-sulfur cell the cycle performance that high first discharge specific capacity is become reconciled.
Accompanying drawing 11 is thermogravimetric curves of the prepared sulphur/carbon composite of embodiment 1.The thermogravimetric curve ordinate is sulphur quality percentage composition, and abscissa is the temperature of heating.Can find out that sulphur quality percentage composition is 79.6% from the thermogravimetric curve of accompanying drawing 11, sulfur content is high and consistent with the sulphur material with carbon element ratio that adds in embodiment, this shows that sulfur content is easy to control.
Embodiment
Below in conjunction with embodiment, the present invention will be further described in detail, but can not be regarded as the restriction to protection scope of the present invention.
Embodiment 1:
At normal temperatures, be that 20% ammonium sulfide solution adds the 3.2g sublimed sulfur to the mass concentration of 17g, generate ammonium polysulfide solution; Then add 0.08g surfactant polyethylene octyl phenyl ether and 0.8g active carbon successively in ammonium polysulfide solution, stir 2h, after stirring, this mixed liquor is placed in ultrasonic cleaner and carries out sonic oscillation 1h with the power of 150W, and be placed in magnetic stirring apparatus and stir with certain rotating speed, be heated to 95 ℃, make ammonium polysulfide add sulphur in-situ deposition that thermal decomposition generates in the absorbent charcoal material duct, then by isolated by filtration, obtain sulphur/carbon composite and filtrate; Sulphur/the carbon composite that obtains is washed till neutrality with distilled water, then 80 ℃ of lower vacuumizes, obtains the sulfur-bearing mass percent and be sulphur/carbon composite of 79.6%.
The electrochemical property test of sulphur/carbon composite:
Preparation electrode slice and button cell: with the prepared sulphur/carbon composite of embodiment 1, binding agent (PVDF), conductive black in mass ratio 7:1:2 evenly mix, drip wherein appropriate 1-METHYLPYRROLIDONE (NMP) after mixing as solvent, then be ground into uniform sizing material, be coated on aluminum foil current collector, 60 ℃ of lower vacuumizes 12 hours.After drying, it is struck out the electrode slice that diameter is 10mm.Then take this electrode slice as anodal, take metal lithium sheet as negative pole, be assembled into the CR2025 button cell in being full of the glove box of argon gas, carry out the constant current charge-discharge test with 0.2C under room temperature (25 ℃), first discharge specific capacity is 1210mAh/g, and 50 circulations are rear greater than 550mAh/g.
Embodiment 2:
At normal temperatures, be to add the 3.2g sublimed sulfur in 20% ammonium sulfide solution to the mass concentration of 17g, generate ammonium polysulfide solution; Then add 0.32g surfactant polyethylene and 3.2g active carbon successively in ammonium polysulfide solution, stir 1h, after stirring, this mixed liquor is placed in ultrasonic cleaner with the power ultrasonic vibration 1h of 100W, and be placed in magnetic stirring apparatus and stir with certain rotating speed, and be heated to 95 ℃, make ammonium polysulfide add sulphur in-situ deposition that thermal decomposition generates in the material with carbon element duct, then by centrifugation, obtain sulphur/carbon composite and filtrate; Sulphur/the carbon composite that obtains is washed till neutrality with ethanol, then 70 ℃ of lower vacuumizes, obtains sulphur/carbon composite.
Embodiment 3:
At normal temperatures, be to add 3.2g sedimentation sulphur in 20% ammonium sulfide solution to the mass concentration of 6.8g, generate ammonium polysulfide solution; Then add 0.21g surfactant polyethylene and 1.37g carbon black successively in ammonium polysulfide solution, stir 1h, after stirring, this mixed liquor is placed in ultrasonic cleaner with the power ultrasonic vibration 1h of 60W, and be placed in magnetic stirring apparatus and stir with certain rotating speed, and be heated to 120 ℃, make ammonium polysulfide add sulphur in-situ deposition that thermal decomposition generates in the material with carbon element duct, isolated by filtration obtains sulphur/carbon composite and filtrate; Sulphur/the carbon composite that obtains is washed till neutrality with distilled water, then 80 ℃ of lower vacuumizes, obtains sulphur/carbon composite.
The electrochemical property test of sulphur/carbon composite:
With the prepared carbon of embodiment 3/sulphur composite material, binding agent (PVDF), conductive black in mass ratio 7:1:2 evenly mix, drip wherein appropriate solvent 1-METHYLPYRROLIDONE (NMP) after mixing, then be ground into uniform sizing material, be coated on aluminum foil current collector, 60 ℃ of lower vacuumizes 12 hours.After drying, it is struck out the electrode slice that diameter is 10mm.Then take this electrode slice as anodal, take metal lithium sheet as negative pole, be assembled into the CR2025 button cell in being full of the glove box of argon gas, carry out the constant current charge-discharge test with 0.2C under room temperature (25 ℃), first discharge specific capacity is 980mAh/g, after 50 circulations, greater than 500mAh/g, 50 discharge capacity curves as shown in Figure 7.。
Embodiment 4:
At normal temperatures, be to add 3.2g sedimentation sulphur in 30% ammonium sulfide solution to the mass concentration of 22.7g, generate ammonium polysulfide solution; Then add 0.16g surfactant softex kw and 3.2g Graphene successively in ammonium polysulfide solution, stir 0.5h, after stirring, this mixed liquor is placed in ultrasonic cleaner with the power ultrasonic vibration 1h of 60W, and be placed in magnetic stirring apparatus and stir with certain rotating speed, and be heated to 95 ℃, make ammonium polysulfide add sulphur in-situ deposition that thermal decomposition generates in the material with carbon element duct, isolated by filtration obtains sulphur/carbon composite and filtrate; Sulphur/the carbon composite that obtains is washed till neutrality with distilled water, 60 ℃ of lower vacuumizes, obtains sulphur/carbon composite.
The electrochemical property test of sulphur/carbon composite:
Preparation electrode slice and button cell: with the prepared carbon of embodiment 4/sulphur composite material, binding agent (PVDF), conductive black in mass ratio 7:1:2 evenly mix, drip wherein appropriate solvent 1-METHYLPYRROLIDONE (NMP) after mixing, then be coated on aluminum foil current collector after being ground into uniform sizing material, 60 ℃ of lower vacuumizes 12 hours.After drying, it is struck out the electrode slice that diameter is 10mm.Then take this electrode slice as anodal, take metal lithium sheet as negative pole, be assembled into the CR2025 button cell in being full of the glove box of argon gas, carry out the constant current charge-discharge test in room temperature (25 ℃) with 0.2C, first discharge specific capacity is 1270mAh/g, after 50 circulations, greater than 800mAh/g, 50 discharge capacity curves as shown in Figure 8.
Embodiment 5:
At normal temperatures, be to add 3.2g to make with extra care sulphur in 30% ammonium sulfide solution to the mass concentration of 22.7g, generate ammonium polysulfide solution; Then add 0.07g surfactant softex kw (CTAB) and 0.36 carbon fiber successively in ammonium polysulfide solution, stir 1h, after stirring, this mixed liquor is placed in ultrasonic cleaner with the power ultrasonic vibration 1h of 150W, and be placed in magnetic stirring apparatus and stir with certain rotating speed, and be heated to 95 ℃, make ammonium polysulfide add sulphur in-situ deposition that thermal decomposition generates in the material with carbon element duct, isolated by filtration obtains sulphur/carbon composite and filtrate; Sulphur/the carbon composite that obtains is washed till neutrality with distilled water, 90 ℃ of lower vacuumizes, obtains sulphur/carbon composite.
The electrochemical property test of sulphur/carbon composite:
With the prepared sulphur/carbon composite of embodiment 5, binding agent (PVDF), conductive black in mass ratio 7:1:2 evenly mix, drip wherein appropriate solvent 1-METHYLPYRROLIDONE (NMP) after mixing, then be coated on aluminum foil current collector after being ground into uniform sizing material, 60 ℃ of lower vacuumizes 12 hours.After drying, it is struck out the electrode slice that diameter is 10mm.Then take this electrode slice as anodal, take metal lithium sheet as negative pole, be assembled into the CR2025 button cell in being full of the glove box of argon gas, carry out the constant current charge-discharge test in room temperature (25 ℃) with 0.2C, first discharge specific capacity is 1320mAh/g, after 50 circulations, greater than 650mAh/g, 50 discharge capacity curves as shown in Figure 9.
Embodiment 6:
At normal temperatures, be to add 3.2g to make with extra care sulphur in 30% ammonium sulfide solution to the mass concentration of 7.56g, generate ammonium polysulfide solution; Then add 0.08g surfactant neopelex (SDBS) and 0.8g carbon nano-tube successively in ammonium polysulfide solution, stir 2h, after stirring, this mixed liquor is placed in ultrasonic cleaner with the power ultrasonic vibration 1h of 150W, and be placed in magnetic stirring apparatus and stir with certain rotating speed, and be heated to 95 ℃, make ammonium polysulfide add sulphur in-situ deposition that thermal decomposition generates in the material with carbon element duct, centrifugation obtains sulphur/carbon composite and filtrate; Sulphur/the carbon composite that obtains is washed till neutrality with distilled water, 90 ℃ of lower vacuumizes, obtains sulphur/carbon composite.
The electrochemical property test of sulphur/carbon composite:
With the prepared sulphur/carbon composite of embodiment 6, binding agent (PVDF), conductive black in mass ratio 7:1:2 evenly mix, drip wherein appropriate solvent (NMP) after mixing, then be coated on aluminum foil current collector after being ground into uniform sizing material, 60 ℃ of lower vacuumizes 12 hours.After drying, it is struck out the electrode slice that diameter is 10mm.Take metal lithium sheet as negative pole, be assembled into the CR2025 button cell in being full of the glove box of argon gas, carrying out the constant current charge-discharge test in room temperature (25 ℃) with 0.2C, first discharge specific capacity is 1050mAh/g, after 50 circulations, greater than 600mAh/g, 50 discharge capacity curves as shown in figure 10.
Embodiment 7:
At normal temperatures, be that to add elemental sulfur content in 20% ammonium sulfide solution be 70% mixture 4.6g to the mass concentration of 17g, after reaction, the clarification ammonium polysulfide solution is got in centrifugation; Then add 0.1g surfactant polyethylene octyl phenyl ether (TritonX-100) and 2.13g charcoal-aero gel successively in ammonium polysulfide solution, stir 2h, after stirring, this mixed liquor is placed in ultrasonic cleaner with the power ultrasonic vibration 1h of 120W, and be placed in magnetic stirring apparatus and stir with certain rotating speed, and be heated to 95 ℃, make ammonium polysulfide add sulphur in-situ deposition that thermal decomposition generates in the material with carbon element duct, isolated by filtration obtains sulphur/carbon composite and filtrate; Sulphur/the carbon composite that obtains is washed till neutrality with distilled water, 90 ℃ of lower vacuumizes, obtains sulphur/carbon composite.
Claims (10)
1. a sulphur/carbon composite, is characterized in that: filled equably nano-sulfur in the duct of the material with carbon element in described sulphur/carbon composite, form nano-sulfur particle/carbon composite, and in this sulphur/carbon composite, the mass percent of sulphur has been 50%～90%.
2. the preparation method of a sulphur/carbon composite, is characterized in that, described preparation method comprises the following steps:
Step 1: at normal temperatures, ammonium sulfide solution is mixed the ammonium polysulfide solution ((NH that obtains clarifying after the rear standing 0.5～2h that stirs with elemental sulfur
4)
2Sx (x=2～6));
Step 2: add surfactant and material with carbon element in the ammonium polysulfide solution of prepared clarification in the step 1, be placed on sonic oscillation 0.5～2h in ultrasonic cleaner after stirring, be heated to 80～120 ℃, then separate, obtain sulphur/carbon composite and raffinate, with the sulphur/carbon composite vacuumize at 60～110 ℃ of temperature that obtains.
3. the preparation method of sulphur/carbon composite according to claim 2, is characterized in that, in step 1, the mass concentration of ammonium sulfide solution used is 17～99%.
4. the preparation method of according to claim 2 or 3 described sulphur/carbon composites, it is characterized in that: the mol ratio of the ammonium sulfide described in step 1 and elemental sulfur is 1～5.
5. the preparation method of sulphur/carbon composite according to claim 2 is characterized in that: the elemental sulfur described in step 1 is selected from one or more in sublimed sulfur, sedimentation sulphur, refining sulphur.
6. the preparation method of according to claim 2 or 5 described sulphur/carbon composites, it is characterized in that: the surfactant that adds in step 2 is one or more in polyethylene glycol (PEG), softex kw (CTAB), neopelex (SDBS), Triton X-100 (TritonX-100).
7. the preparation method of sulphur/carbon composite according to claim 6, it is characterized in that: the surfactant that adds in step 2 and the mass percent of material with carbon element are 1～20%.
8. the preparation method of sulphur/carbon composite according to claim 7, it is characterized in that: the material with carbon element that adds in step 2 is selected from one or more in active carbon, mesoporous carbon, carbon black, carbon fiber, carbon nano-tube, charcoal-aero gel, Graphene.
9. the preparation method of sulphur/carbon composite according to claim 2, it is characterized in that: the mode of the separation in step 2 is isolated by filtration or centrifugation.
10. the preparation method of according to claim 2 or 9 described sulphur/carbon composites, it is characterized in that: the sulphur/carbon composite that makes is as the positive electrode of lithium-sulfur cell.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103746095A (en) * | 2013-12-18 | 2014-04-23 | 广西科技大学 | Carbon-sulfur composite positive pole material and preparation method thereof |
| CN103746101A (en) * | 2013-12-18 | 2014-04-23 | 广西科技大学 | Carbon-sulfur composite positive pole material and preparation method thereof |
| CN104078661A (en) * | 2014-05-23 | 2014-10-01 | 南京中储新能源有限公司 | Carbon nanotube-nanosulfur composite material and secondary aluminium battery using same |
| CN106058208A (en) * | 2016-07-29 | 2016-10-26 | 天津巴莫科技股份有限公司 | Sulfur-carbon positive pole material for lithium-sulfur secondary battery and preparation method of sulfur-carbon positive pole material |
| CN106450510A (en) * | 2015-08-05 | 2017-02-22 | 苏州宝时得电动工具有限公司 | Electrolyte and battery |
| CN108039457A (en) * | 2017-11-08 | 2018-05-15 | 西安理工大学 | A kind of preparation method of lithium sulfur battery anode material |
| CN109378466A (en) * | 2018-12-08 | 2019-02-22 | 河南师范大学 | A kind of preparation method and product of spherical lithium-sulfur battery cathode material |
| CN111065600A (en) * | 2017-10-30 | 2020-04-24 | 株式会社Lg化学 | Sulfur-carbon composite material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040043291A1 (en) * | 2002-09-04 | 2004-03-04 | Kim Nam In | Cathode containing muticomponent binder mixture and lithium-sulfur battery using the same |
| CN101562244A (en) * | 2009-06-02 | 2009-10-21 | 北京理工大学 | Method for preparing elemental sulfur composite material used by lithium secondary battery |
| CN102231439A (en) * | 2011-05-17 | 2011-11-02 | 奇瑞汽车股份有限公司 | Sulfur-carbon composite material for cathode of lithium ion battery, preparation method and lithium ion battery |
-
2013
- 2013-03-22 CN CN201310094871.XA patent/CN103178247B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040043291A1 (en) * | 2002-09-04 | 2004-03-04 | Kim Nam In | Cathode containing muticomponent binder mixture and lithium-sulfur battery using the same |
| CN101562244A (en) * | 2009-06-02 | 2009-10-21 | 北京理工大学 | Method for preparing elemental sulfur composite material used by lithium secondary battery |
| CN102231439A (en) * | 2011-05-17 | 2011-11-02 | 奇瑞汽车股份有限公司 | Sulfur-carbon composite material for cathode of lithium ion battery, preparation method and lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| J.L.WANG，ET AL.: "Sulfur–carbon nano-composite as cathode for rechargeable lithium battery based on gel electrolyte", 《ELECTROCHEMISTRY COMMUNICATIONS》 * |
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| CN103746095A (en) * | 2013-12-18 | 2014-04-23 | 广西科技大学 | Carbon-sulfur composite positive pole material and preparation method thereof |
| CN103746101A (en) * | 2013-12-18 | 2014-04-23 | 广西科技大学 | Carbon-sulfur composite positive pole material and preparation method thereof |
| CN103746101B (en) * | 2013-12-18 | 2016-03-30 | 广西科技大学 | A kind of carbon sulphur composite positive pole and preparation method thereof |
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| CN106450510A (en) * | 2015-08-05 | 2017-02-22 | 苏州宝时得电动工具有限公司 | Electrolyte and battery |
| CN106058208A (en) * | 2016-07-29 | 2016-10-26 | 天津巴莫科技股份有限公司 | Sulfur-carbon positive pole material for lithium-sulfur secondary battery and preparation method of sulfur-carbon positive pole material |
| CN106058208B (en) * | 2016-07-29 | 2019-01-25 | 天津巴莫科技股份有限公司 | Sulphur carbon positive electrode and preparation method thereof for lithium-sulfur rechargeable battery |
| CN111065600A (en) * | 2017-10-30 | 2020-04-24 | 株式会社Lg化学 | Sulfur-carbon composite material and preparation method thereof |
| US20200152971A1 (en) * | 2017-10-30 | 2020-05-14 | Lg Chem, Ltd. | Sulfur-carbon composite and method for preparing same |
| US11611066B2 (en) * | 2017-10-30 | 2023-03-21 | Lg Energy Solution, Ltd. | Sulfur-carbon composite and method for preparing same |
| CN108039457A (en) * | 2017-11-08 | 2018-05-15 | 西安理工大学 | A kind of preparation method of lithium sulfur battery anode material |
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