CN102969481A - Sulfur/carbon composite material for lithium-sulfur secondary battery and preparation method thereof - Google Patents
Sulfur/carbon composite material for lithium-sulfur secondary battery and preparation method thereof Download PDFInfo
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- CN102969481A CN102969481A CN2012105308344A CN201210530834A CN102969481A CN 102969481 A CN102969481 A CN 102969481A CN 2012105308344 A CN2012105308344 A CN 2012105308344A CN 201210530834 A CN201210530834 A CN 201210530834A CN 102969481 A CN102969481 A CN 102969481A
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Abstract
The invention discloses a sulfur/carbon composite material for a lithium-sulfur secondary battery and a preparation method thereof. The composite material is formed by compositing a micro-pore carbon substrate with a lithium ion conduction property and elemental sulfur filled in the micro-pore structure. The carbon substrate is used as an electronic conductor in the composite material, and is further used as a lithium ion conductor, so that sulfur electrode reaction is directly carried out on a sulfur/carbon solid-solid interface in a conversion reaction manner without directly contacting with electrolyte. Therefore, the problem of circulation caused by that a polysulfide intermediate product is dissolved in the electrolyte can be solved. Compared with the other sulfur/carbon composite electrode, the composite material has the advantages of high electrochemical capacity, good circulation stability, high charging and discharging efficiency and the like; and meanwhile, the preparation method is simple and low in cost, and has a good application prospect.
Description
?
Technical field
The present invention relates to a kind of lithium-sulfur rechargeable battery with sulphur/carbon composite anode material and preparation method thereof, belong to technical field of chemical power.
Background technology
Along with the functional integration of portable type electronic product is more and more higher, and the fast development of electric automobile and energy-accumulating power station, people are to high-energy-density, the demand of secondary cell is day by day strong cheaply.Because lithium-sulfur rechargeable battery has the theoretical energy density up to 2600 watt-hour/kilograms, and have aboundresources, the advantage such as cheap as the elemental sulfur of positive electrode, therefore lithium-sulfur rechargeable battery is considered to the emphasis of high specific energy secondary cell development after the lithium ion battery.
Yet, because elemental sulfur (S) and reduction end product lithium sulfide (Li thereof
2S) be electronic body, cause the electro-chemical activity of sulfur electrode poor, the utilance of active material is low.And the electrode reaction of S is a multistep reaction, product (Li in the middle of it
2S
n, n=2-8) soluble in the common ethers electrolyte that adopts of lithium/sulphur battery causes a large amount of loss by dissolutions of active material.The loss by dissolution of sulphur not only causes the cycle performance of lithium/sulphur battery relatively poor, and produces " effect of shuttling back and forth " between the both positive and negative polarity of battery, low enclosed pasture efficient when causing the battery charging.The problems referred to above have seriously restricted development and the commercial applications of lithium-sulfur cell.
In order to improve the cycle life of Li-S battery, Chinese scholars is being carried out extensive work aspect the preparation of the apolegamy of sulfur electrode electrolyte and porous carbon matrix.In US Patent No. 5961672, US5523179,5814420 and 6030720, disclose and contained 1M LiSO
3CF
31, the mixed electrolytic solution system of 3-dioxane/diethylene glycol dimethyl ether/sulfolane/dimethoxy-ethane has been improved the cycle life of Li-S battery to a certain extent; U.S. Sion Power company proposes to add nitrate inhibitor (the US Patent 7 that shuttles back and forth in electrolyte, 352,680), nitrate by forming indissoluble on cathode of lithium surface-nitrite thin layer, and sulphur (Li-S-O) compound thin film of high price, make it passive metal lithium surface, thereby suppress shuttle and the reduction reaction of polysulfide on cathode of lithium, improve significantly the cyclical stability of sulfur electrode.But in above-mentioned patent, intermediate product (Li
2S
n, the loss by dissolution problem of n=2-8) is not effectively solved.
The loss by dissolution that be to suppress the sulphur intermediate product, the technical scheme that generally adopts at present is: utilize the loose structure material with carbon element of high conductivity to be matrix, elemental sulfur is filled in the hole of porous carbon matrix or the pore passage structure forms the sulphur carbon composite.Realize mutually interior electron transport of body by carbon skeleton, realize the immobilization of sulphur by the capillary absorption power in hole or duct.The porous carbon matrix that adopts comprises: carbon hollow ball (the Angew. Chem. 2011 with macroporous structure, 123,1-6) with regular carbon pipe (Nano Lett. 2011,11,4462 – 4467), high oriented mesoporous carbon CMK-3(Nature Mater. with central hole structure, 2009,8,500) and multi-walled carbon nano-tubes (Electrochim.Acta 2006,51,1330), and the aperture is less than (J. Phys. Chem. C, 2009, the 113:4712 such as various microporous carbon of 2 nanometers; Energy ﹠amp; Environ. Sci., 2011,4,5053 – 5059).Studies show that rely on the strong suction-operated of porous carbon, the cyclical stability of sulphur-carbon composite anode material is significantly improved, but cycle life remains in big gap from application request.
Conventional sulfur electrode exists the main cause of cyclical stability problem to be: the electrochemical reaction process of sulfur electrode needs electronics (e
-), sulfur molecule (S
8) and lithium ion (Li
+) common participation, but because sulphur and the electrical conductivity of product and the insulating property (properties) of ionic conduction, existing sulfur electrode reaction all can only be in conductive carbon (solid phase), sulphur phase (solid phase) and crossing the consolidating of electrolyte (liquid phase)/solid-liquid triple point (or triple line) reaction, and in other zones, such as carbon/solution interface, carbon/sulphur interface, sulphur/solution interface, because lack one to two kind of reaction particle, in fact the reduction of sulphur can not be carried out.Therefore, such sulfur electrode reaction belongs to typical dissolution-deposition reaction mechanism, has inevitably the loss by dissolution problem of sulphur intermediate product.We are early stage patent (CN200610018830.2) and research paper (Electrochem. Commun. 2006,8,610) show, employing is electrolyte solvent to the quaternary ammonium salts ionic liquid that polysulfide has insoluble character, Gu the reactive mode of sulfur electrode can be solid-conversion reaction mechanism from traditional dissolution-deposition mechanism transformation, suppress the dissolving of sulfur electrode reaction intermediate in electrolyte fully, fundamentally solve the loss by dissolution problem of active material, thereby improve the cycle life of Li-S battery.But because in the discharge process of sulfur electrode, be insoluble to the sulphur intermediate product of such electrolyte immediately at the sulfur electrode surface deposition, sealing sulfur electrode surface, cutting off internal layer sulphur contacts with the direct of electrolyte, and the transmission channel of lithium ion, cause sulfur electrode in discharge process, to produce low electrochemistry capacitance because of inactivation.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of sulphur/carbon composite electrode material that has simultaneously high electro-chemical activity and good circulation stability and preparation method thereof.
Technical scheme of the present invention:
A kind of lithium-sulfur rechargeable battery sulphur/carbon composite anode material, be composited by porous carbon matrix and elemental sulfur, wherein elemental sulfur is filled in the micropore of porous carbon matrix, be distributed with carbon nano-fiber in the described porous carbon matrix, carbon ball in the porous carbon matrix connects by carbon nano-fiber, described carbon ball has lithium ion conduction character at the reaction electromotive force interval (3.0V-1.0V is with respect to metal lithium electrode) of elemental sulfur.
The carbon ball connects by the electrical-conductive nanometer carbon fiber in the described carbon base body, has the thyrsiform structure.Because this structure, so that electrode material not only has three-dimensional electronic conductive network structure, and interval at the electrochemical reaction electromotive force of sulfur electrode, can reversibly embed and deviate from lithium, have lithium ion conduction character.
The porous carbon matrix can adopt the hydro-thermal reaction method to make, and carbon source is sucrose, and carbon fiber is the gas-phase growth of carbon fibre (VGCF) of diameter 100-150 nanometer.For improving the hydrophily of conductive fiber, VGCF is in advance at dense HNO
3In boiled 2 hours under 120 ℃.Concrete preparation process is as follows: 200:1 takes by weighing respectively the VGCF after sucrose and the hydrophilic treated in mass ratio; Sucrose is dissolved in an amount of 6M H
2SO
4In the solution, be mixed with sucrose-H that concentration is 0.2M
2SO
4Solution adds through HNO
3The VGCF conductive carbon fibre of processing; This solution is transferred in the hydro-thermal reaction tank, behind heating 24h under 180 ℃ of temperature, with black product suction filtration, washing and at 100 ℃ of dry 12h.In order to improve the conductivity of end product, to be placed in the tube furnace that is full of Ar, heat up with 5 ℃/min, at 1000 ℃ of calcining 2h, obtain the carbosphere that carbon fiber connects.
The compound gas phase transfer method that can adopt of porous carbon matrix and elemental sulfur makes, concrete preparation process is as follows: 1:2～1:4 takes by weighing microporous carbon matrix and elemental sulfur in mass ratio, and place respectively two sample bottles, then they are sealed in the stainless steel cauldron that is full of Ar, 400 ℃ of heating 6h in Muffle furnace, the sulfur vapor that distillation produces shifts by gas phase and evenly is adsorbed onto in the microcellular structure of carbon base body.After it cools off naturally, obtain the sulphur carbon composite.Weigh by the poor of the material with carbon element before and after the heating, calculate the content of sulphur in the compound.
The carbon base body that sulphur/carbon composite of the present invention adopts has abundant microcellular structure, average pore size is less than 1 nanometer, elemental sulfur is to be close to unimolecule form uniform filling in microcellular structure, form abundant sulphur/carbon reaction interface, can greatly improve the reactivity of sulfur electrode, improve the utilance of sulphur; And the combination of nano-conductive fiber and microporous carbon ball, for carbon base body provides complete three-dimensional conductive network, avoided insulating properties sulphur simple substance and the many lithium sulfides of product thereof to cause poor electric contact between the carbon ball at microporous carbon ball surface deposition, for the sulfur electrode reaction provides good electron propagation ducts, guaranteed efficiently carrying out of sulfur electrode reaction.What is more important, the microporous carbon matrix that adopts (with respect to metal lithium electrode 1.0 V-3.0V), can reversibly embed and deviate from lithium, have the lithium ion conduction performance in that the electrochemical reaction electromotive force of sulfur electrode is interval.Therefore, carbon base body in composite material both as electronic conductor, again as lithium ion conductor, thereby the sulfur electrode reaction is directly carried out on carbon/sulphur solid-solid interface in the conversion reaction mode, do not need directly to contact with electrolyte, avoided the polysulfide intermediate product in electrolyte dissolving and the cyclicity problem that causes.Compare with the sulphur/carbon composite electrode of prior art, this composite material take organic carbonate class and quaternary ammonium salts ionic liquid in the electrolyte of solvent, have electrochemistry capacitance height, good cycling stability, efficiency for charge-discharge advantages of higher; The preparation method is simple, with low cost simultaneously, has a good application prospect.
Description of drawings
Fig. 1 is the SEM photo of micropore sulphur/carbon composite anode material.
Fig. 2 is the embedding lithium-Tuo lithium characteristic of microporous carbon matrix.
Fig. 3 is the electrode reaction schematic diagram of sulphur/carbon composite anode material.
Fig. 4 is the schematic diagram after local A amplifies among Fig. 3.
Fig. 5 is that sulfur content is 60% the cycle performance of sulphur/carbon composite anode material in organic carbonate class electrolyte.
Fig. 6 is that sulfur content is 70% the cycle performance of sulphur/carbon composite anode material in organic carbonate class electrolyte.
Fig. 7 is that sulfur content is 60% the cycle performance of sulphur/carbon composite anode material in the quaternary ammonium salts il electrolyte.
Embodiment
Embodiment 1:
1) preparation of porous carbon: the H that 10 gram sucrose is dissolved in 200mL6M
2SO
4In, then, the VGCF carbon nano-fiber after the 0.05g nitric acid treatment is added wherein, vigorous stirring, behind 180 ℃ of lower hydro-thermal reaction 24h, suction filtration, washing, drying; At 1000 ℃ of lower high temperature cabonization 2h, obtain having the microporous carbon matrix (such as Fig. 1) of grape cluster structure at last.
2) preparation of sulphur/carbon composite anode material: 0.1g sublimed sulfur and 0.2g porous carbon are placed respectively different glass sample bottles, then it is sealed in the reactor that is full of Ar, in Muffle furnace, at 400 ℃ of lower heating 6h, prepare sulfur content and be sulphur-carbon composite of 60%.
3) prepare the circular pole piece that diameter is 1cm with sulphur-carbon composite: selecting acetylene black is conductive agent, the PTFE(polytetrafluoroethylene) is alite paste, after sulphur-carbon composite of making and acetylene black and PTFE mixed with the mass ratio of 8:1:1, add isopropyl alcohol, fully stirring mixes it, then, roll film, punching, and in 60 ℃ of dried overnight of vacuum.
Take the above-mentioned circular pole piece that makes as positive pole, lithium sheet as negative pole, organic electrolyte adopts the LiPF of 1mol/L
6Solution, solvent are the mixed solvent of propene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), and volume ratio is 1:4:5, and barrier film is polypropylene porous film, is assembled into battery in being full of the glove box of argon gas.
For understanding the embedding lithium characteristic of carbon base body, it is positive electrode that employing does not have the microporous carbon matrix of composite sulfur, has assembled battery according to identical mode.
Institute's packed battery is carried out charge-discharge test at ambient temperature, and voltage range is 1.0V-3.0V, and current density is 100mA/g.As shown in Figure 2, blank carbon base body has reversible embedding lithium-Tuo lithium character, thereby is sulfur electrode reaction conductive lithium ion, and the sulfur electrode reaction in the composite material is undertaken by mode shown in Fig. 3,4; As shown in Figure 5, sulphur/carbon composite anode circulated after 50 weeks, and capacity still remains on about 850 mAh/g, and coulomb efficient that discharge and recharge after 3 weeks remain on 100% always, showed that the loss by dissolution of sulphur has obtained suppressing fully.
Embodiment 2:
Prepared according to the method described above after the microporous carbon matrix, 0.1g sublimed sulfur and 0.4g porous carbon are placed respectively different glass sample bottles, then it is sealed in the reactor that is full of Ar, in Muffle furnace, under 400 ℃, heat 6h, prepare sulfur content and be sulphur-carbon composite of 70%, after being prepared into anode pole piece, adopt the in the same manner assembled battery of identical organic carbonate electrolyte.
Institute's packed battery is carried out charge-discharge test at ambient temperature, and voltage range is 1.0V-3.0V, and current density is 100mA/g.As shown in Figure 6, sulphur/carbon composite anode circulated after 50 weeks, and capacity still remains on about 450 mAh/g, and it discharges and recharges coulomb efficient and remain on 100% always, showed that the composite material of higher sulfur content also has good chemical property.
Embodiment 3:
After preparing sulfur content and be 60% sulphur/carbon composite and positive plate according to method described in the embodiment 1, employing contain 1M LiTFSI's (PP13) TFSI ionic liquid be electrolyte (wherein, PP13 represents N-methyl-N propyl group piperidines cation, and TFSI represents N(CF
3SO
2)
2-Anion), in the same manner assembled battery.
Institute's packed battery is carried out charge-discharge test at ambient temperature, and voltage range is 1.0V-3.0V, and current density is 100mA/g.As shown in Figure 7, first all charging capacitys of sulphur/carbon composite are 1200 mAh/g, and after 100 weeks of circulating, Capacitance reserve is more than 800mAh/g, and the enclosed pasture efficient after 3 weeks remains on 100% always.
Claims (4)
1. a lithium-sulfur rechargeable battery is with sulphur/carbon composite, be composited by porous carbon matrix and elemental sulfur, wherein elemental sulfur is filled in the micropore of porous carbon matrix, be distributed with carbon nano-fiber in the described porous carbon matrix, carbon ball in the porous carbon matrix connects by carbon nano-fiber, described carbon ball is interval at the reaction electromotive force of elemental sulfur, has lithium ion conduction character.
2. sulphur/carbon composite according to claim 1, it is characterized in that: described carbon nano-fiber is the gas-phase growth of carbon fibre of diameter 100-150 nanometer.
3. sulphur/carbon composite according to claim 1 and 2 is characterized in that: described porous carbon matrix adopting following steps preparation:
1), 200:1 takes by weighing respectively gas-phase growth of carbon fibre after sucrose and the hydrophilic treated in mass ratio;
2), sucrose is dissolved in an amount of 6M H
2SO
4In the solution, be mixed with sucrose-H that concentration is 0.2M
2SO
4Solution, and the carbon fiber after the adding hydrophilic treated;
3), with mentioned solution in the hydro-thermal reaction tank behind 180 ℃ of lower heating 26h, suction filtration, washing and at 100 ℃ of dry 12h;
4), solid product is placed the tube furnace that is full of argon gas, be warming up to 1000 ℃ with 5 ℃/min speed, and insulation 2h, the carbosphere that carbon fiber connects obtained.
4. the preparation method of sulphur/carbon composite claimed in claim 1 is characterized in that, comprises the steps:
1), 200:1 takes by weighing respectively gas-phase growth of carbon fibre after sucrose and the hydrophilic treated in mass ratio;
2), sucrose is dissolved in an amount of 6M H
2SO
4In the solution, be mixed with sucrose-H that concentration is 0.2M
2SO
4Solution, and the carbon fiber after the adding hydrophilic treated;
3), with mentioned solution in the hydro-thermal reaction tank behind 180 ℃ of lower heating 26h, suction filtration, washing and at 100 ℃ of dry 12h;
4), solid product is placed the tube furnace that is full of argon gas, be warming up to 1000 ℃ with 5 ℃/min speed, and insulation 2h, the carbosphere that carbon fiber connects obtained;
5), 1:2～1:4 takes by weighing microporous carbon matrix and elemental sulfur in mass ratio, and place respectively two sample bottles, then they are sealed in the stainless steel cauldron that is full of Ar;
6), reactor is placed Muffle furnace, heat 6h under 400 ℃ of temperature, the sulfur vapor that distillation is produced shifts by gas phase and evenly is adsorbed onto in the microcellular structure of carbon base body;
7), after it cools off naturally, take out, obtain the sulphur carbon composite.
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|---|---|---|---|---|
| CN103531759A (en) * | 2013-09-23 | 2014-01-22 | 广州市香港科大***研究院 | Two-step adsorption preparation method of high magnification sulphur/mesoporous and microporous carbon HAC (honeycomb activated carbon) lithium sulphur battery anode composite material |
| CN103806276A (en) * | 2014-01-27 | 2014-05-21 | 天津水泥工业设计研究院有限公司 | Carbon fiber composite material and preparation method thereof |
| CN104179003A (en) * | 2014-08-11 | 2014-12-03 | 中北大学 | Preparation method of carbon nanosphere-carbon fiber multi-scale reinforcement |
| CN104362320A (en) * | 2014-12-05 | 2015-02-18 | 上海空间电源研究所 | Positive electrode material of lithium-sulfur battery and preparation method of positive electrode material |
| CN104538602A (en) * | 2015-01-16 | 2015-04-22 | 中国计量学院 | Preparation device and production method for sulfur electrode material |
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| WO2018127124A1 (en) * | 2017-01-06 | 2018-07-12 | The Hong Kong University Of Science And Technology | Synthesis of porous carbon microspheres and their application in lithium-sulfur batteries |
| CN108288697A (en) * | 2018-01-16 | 2018-07-17 | 湖南国盛石墨科技有限公司 | A kind of preparation method of the lithium-sulfur cell of graphene/activated carbon microballon as positive electrode |
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Application publication date: 20130313 |