CN103123966B - Method for preparing positive material of lithium-sulfur battery - Google Patents
Method for preparing positive material of lithium-sulfur battery Download PDFInfo
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- CN103123966B CN103123966B CN201310063527.4A CN201310063527A CN103123966B CN 103123966 B CN103123966 B CN 103123966B CN 201310063527 A CN201310063527 A CN 201310063527A CN 103123966 B CN103123966 B CN 103123966B
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- toluene
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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
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- 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
Abstract
The invention discloses a method for preparing a positive material of a lithium-sulfur battery. According to the technical scheme, the method is characterized in that a porous material is taken as a matrix, and elemental sulfur is uniformly dispersed in the porous structure of the matrix material through the processes of dissolving the elemental sulfur in toluene, soaking the matrix material in the toluene solution in vacuum manner, recovering the solvent toluene in the composite material, and the like, thus obtaining the high-activity positive material of the lithium-sulfur battery. The positive material is applied to the lithium-sulfur battery, and is excellent in electrochemical discharging activity and cycling stability.
Description
Technical field
The present invention relates to material chemistry technical field, be specifically related to a kind of preparation method of lithium sulfur battery anode material.
Background technology
Lithium-sulfur cell adopts elemental sulfur (or sulfur-containing compound) to be positive pole, and lithium metal is negative pole, realizes by the chemical reaction between lithium and sulphur the class lithium secondary battery that chemical energy and electric energy transform mutually.Compared with lithium rechargeable battery; lithium-sulfur cell has very high theoretical specific capacity; be up to 2600wh/kg; a kind of high-energy-density, environmental friendliness and secondary cell cheap and easy to get; therefore be considered to one of main representative of following electrokinetic cell application, have the using value of scale.
But, due to the electronics of sulphur and ionic conducting property all poor, and the serial polysulfide formed in charge and discharge process is soluble in the characteristic of electrolyte, causes lithium-sulfur cell to there is the problem of the low and cyclical stability difference of the utilization rate of sulphur, become the maximum bottleneck hindering lithium-sulfur cell practical application.If can be dispersed in the good porous material of electric conductivity with small granularity form by sulphur, the utilization rate of sulphur effectively can be improved on the one hand; Utilize the adsorption effect of porous material effectively can reduce the intermediate product of sulphur electric discharge from the loss positive plate and reunion on the other hand, better keep the stability of anode structure and excellent electric conductivity.Therefore, sulphur and the even compound of porous material can be prepared high power capacity and the lithium sulfur battery anode material of cycle performance excellence.
At present, people's many employings mechanical attrition method, gas-protecting sintering method and solution chemistry deposition method realize the compound of porous carbon materials and sulphur.But these methods all come with some shortcomings, mechanical attrition method is only the physical mixed of sulphur and carbon, and sulphur can not be realized to evenly spread in the microcellular structure of carbon base body; Atmosphere sintering method process is complicated, and with the distillation of sulphur in sintering process, therefore in composite, the content of sulphur can not accuracy controlling, and high temperature sintering to cause nano-carbon material to be reunited serious, be unfavorable for the dispersed of sulphur; Solution chemistry deposition method is by means of the sulphur produced when sodium thiosulfate or sodium persulfide and acid reaction and carbon compound, toxicity can be produced comparatively strong and electrode is had to sulfur dioxide or the hydrogen sulfide of poisoning effect in preparation process, and the sulfur content produced due to chemical reaction is less, can not realize the preparation of fairly large lithium sulfur battery anode material.
Summary of the invention
The technical problem that the present invention solves there is provided a kind of method that vacuum solution dipping method adopting toluene to make solvent prepares positive pole material for high-performance lithium-sulfur battery, mainly through at relatively high temperatures elemental sulfur being dissolved in toluene, under vacuum condition, the toluene solution being dissolved with elemental sulfur is drawn in the micropore of matrix material/mesoporous by means of the capillarity in matrix material hole, in temperature-fall period, sulphur crystallizes out from solution in the micropore that is deposited on matrix material/mesoporous, thus realizes the nanometer of sulfur granules and dispersed.Adopt the lithium sulfur battery anode material that this legal system is standby, because sulphur is dispersed in matrix material, achieve the nanometer of sulfur granules, effectively suppress the molten mistake of sulphur discharging product and the reunion at electrode surface in charge and discharge process, electric conductivity and the structural stability of sulfur electrode are kept all preferably.Therefore reactivity can be obtained high, good rate capability, the lithium sulfur battery anode material that cycle performance is good.
Technical scheme of the present invention is: a kind of preparation method of lithium sulfur battery anode material, it is characterized in that comprising the steps: that elemental sulfur is dissolved in the toluene solution of obtained elemental sulfur in toluene by (1); (2) pretreatment of matrix material, by matrix material vacuum drying 12-24h at the temperature of 110-120 DEG C, then transfers in container, vacuumizes, holding temperature 110 DEG C; (3) preparation of lithium sulfur battery anode material, under the condition of vacuum, is drawn into the toluene solution of obtained elemental sulfur and holds in the container of matrix material, after fully infiltrating, is down to room temperature, and toluene i.e. obtained lithium sulfur battery anode material is reclaimed in decompression distillation.
In step of the present invention (1), the consumption of toluene is every 4.0-7.0g elemental sulfur 16-42ml toluene.
In step of the present invention (1), elemental sulfur is fully dissolved in the temperature of toluene is 110 DEG C, and heating rate is 3-5 DEG C/min, and the speed of magnetic agitation is 300-500r/min, and elemental sulfur is incubated 30-50min after dissolving.
In step of the present invention (2), the consumption of matrix material and the consumption mass ratio of the middle elemental sulfur of step (1) are m(matrix material): m(elemental sulfur)=3:2-7.
In step of the present invention (2), matrix material is one or more in active carbon, mesoporous carbon, CNT, graphene oxide and superconduction graphite.
The vacuum degree control vacuumized in step of the present invention (2) is at-0.050--0.095MPa.
In step of the present invention (3), the toluene solution of elemental sulfur fully infiltrates the time of matrix material is 1-5h, and temperature-fall period is that 1-5 DEG C/min speed is down to room temperature.
In step of the present invention (3), the temperature of decompression distillation is 50-70 DEG C.
The present invention compared with prior art, there is following beneficial effect: active component sulphur is dispersed in Jie's micropore of matrix material by (1) the present invention, achieve the nanometer of simple substance sulphur granule, effectively can improve the electric conductivity of sulphur and carbon base body to solvable polysulfide adsorption capacity, and then play the utilization rate improving sulphur and the effect improving lithium-sulfur cell cycle performance; (2) the present invention can realize in lithium sulfur battery anode material, the accuracy controlling of sulphur load capacity, and solvent toluene can not poison lithium sulfur battery anode material simultaneously, and has catalytic action to the electro-chemical activity of sulfur electrode; (3) preparation method of the present invention is simple to operation, and in preparation process, sulphur can not distil loss, and do not produce toxic gas, solvent is recyclable to be recycled, and is applicable to the preparation of fairly large lithium sulfur battery anode material.
Accompanying drawing explanation
Fig. 1 is the SEM figure of CNT in the embodiment of the present invention 3/sulphur composite; Fig. 2 is the TG curve of CNT in the embodiment of the present invention 3/sulphur composite; Fig. 3 is CNT in the embodiment of the present invention 3/sulphur composite different multiplying charging and discharging curve figure; Fig. 4 is CNT in the embodiment of the present invention 3/sulphur composite different multiplying cycle performance figure; Fig. 5 is the specific discharge capacity of under lithium sulfur battery anode material different multiplying the 1st week and the 50th week.
Detailed description of the invention
Following examples contribute to understanding the present invention, but are not limited to content of the present invention.
Embodiment 1
The preparation of active carbon/sulphur composite: be transferred to after the active carbon of 4.0g first 110 DEG C of vacuum drying 12h in the glass container of band piston, then vacuumize, vacuum degree control at-0.050MPa, holding temperature 110 DEG C; Under room temperature, by the high purity sulphur of 6.0g, add in 24.0ml toluene, with 3 DEG C/min heating rate, be warmed up to 110 DEG C, under magnetic agitation (300r/min), form flaxen clear solution, insulation 30min; Then being incorporated into by the toluene solution of sulphur by conduit is equipped with in the glass container of active carbon, under vacuum condition, solution is inhaled in the micropore of active carbon instantaneously, maintenance system temperature 110 DEG C, abundant infiltration 1h, then be down to room temperature with 1 DEG C/min speed, then toluene is reclaimed in decompression distillation (50 DEG C), finally obtains active carbon/sulphur composite.
Embodiment 2
The preparation of mesoporous carbon/sulphur composite: be transferred to after the mesoporous carbon of 5.0g first 110 DEG C of vacuum drying 16h in the glass container of band piston, then vacuumize, vacuum degree control at-0.070MPa, holding temperature 110 DEG C; Under room temperature, by the high purity sulphur of 5.0g, add in 25.0ml toluene, with 4 DEG C/min heating rate, be warmed up to 110 DEG C, under magnetic agitation (400r/min), form flaxen clear solution, insulation 40min; Then being incorporated into by the toluene solution of sulphur by conduit is equipped with in the glass container of mesoporous carbon, under vacuum condition, solution is inhaled in the micropore of mesoporous carbon instantaneously, maintenance system temperature 110 DEG C, abundant infiltration 2h, then be down to room temperature with 3 DEG C/min speed, then toluene is reclaimed in decompression distillation (60 DEG C), finally obtains mesoporous carbon/sulphur composite.
Embodiment 3
The preparation of CNT/sulphur composite: be transferred to after the CNT of 4.0g first 120 DEG C of vacuum drying 18h in the glass container of band piston, then vacuumize, vacuum degree control at-0.085MPa, holding temperature 110 DEG C; Under room temperature, by the high purity sulphur of 6.0g, add in 30.0ml toluene, with 4 DEG C/min heating rate, be warmed up to 110 DEG C, under magnetic agitation (400r/min), form flaxen clear solution, insulation 40min; Then being incorporated into by the toluene solution of sulphur by conduit is equipped with in the glass container of CNT, and under vacuum condition, solution is inhaled in the hole of CNT instantaneously, and maintenance system temperature 110 DEG C, fully infiltrates 3h, is then down to room temperature with 4 DEG C/min speed; Toluene is reclaimed in decompression distillation again (60 DEG C), finally obtains CNT/sulphur composite.
Fig. 1 is the SEM photo of CNT/sulphur composite.As can be seen from the figure, sulphur is evenly distributed in the conducting base of CNT, has no sulfur granules and the aggregate thereof of bulk, and meanwhile, the CNT of sulfur granules and conduction has good contact.
Fig. 2 is the thermogravimetric curve of CNT/sulphur composite.As can be seen from the figure, in composite, the weight-loss ratio of sulphur is 58.6%, very close with sulfur content 60% in desired composite, and when illustrating that the method prepares lithium sulfur battery anode material, the content of sulphur can regulate and control in advance more accurately.
Fig. 3 is the head week charging and discharging curve of CNT/sulphur composite under different charge-discharge magnification 0.1C, 0.2C, 0.5C.As can be seen from the rate charge-discharge curve of battery, under three kinds of different multiplying, specific discharge capacity reaches 1320mAh/g, 1210 mAh/g and 1080 mAh/g respectively, along with the change of multiplying power, the discharge platform of battery remains two (2.3V and 2.1V), illustrate that CNT/sulphur conductivity of composite material that the method is prepared can be excellent, the Stability Analysis of Structures of electrode in charge and discharge process, discharge performance is excellent.
Fig. 4 is the cycle performance figure of CNT/sulphur composite under different charge-discharge magnification.After circulating 50 weeks under the discharge-rate of 0.1C, 0.2C, 0.5C with the lithium sulfur battery anode material that this legal system is standby, its specific discharge capacity remains on 884 mAh/g, 832 mAh/g and 731 mAh/g respectively.This illustrates in lithium sulfur battery anode material prepared by the method, the carbon base body of conduction serves the effect of absorption elemental sulfur and electric discharge intermediate product thereof very well, the molten mistake of sulphur and the reunion at electrode surface thereof in effective suppression charge and discharge process, thus maintain the Stability Analysis of Structures of electrode and excellent electric conductivity, and then improve charging and discharging capacity and the cycle performance of lithium sulfur battery anode material.
Embodiment 4
The preparation of graphene oxide/sulphur composite: be transferred to after the graphene oxide of 3.0g first 120 DEG C of vacuum drying 24h in the glass container of band piston, then vacuumize, vacuum degree control at-0.095MPa, holding temperature 110 DEG C; Under room temperature, by the high purity sulphur of 7.0g, add in 42.0ml toluene, with 5 DEG C/min heating rate, be warmed up to 110 DEG C, under magnetic agitation (500r/min), form flaxen clear solution, insulation 50min; Then being incorporated into by the toluene solution of sulphur by conduit is equipped with in the glass container of graphene oxide, and under vacuum condition, solution is inhaled in the micropore of graphene oxide instantaneously, and maintenance system temperature 110 DEG C, fully infiltrates 5h, is then down to room temperature with 5 DEG C/min speed; Toluene is reclaimed in decompression distillation again (70 DEG C), finally obtains graphene oxide/sulphur composite.
Embodiment 5
The preparation of superconduction graphite/sulphur composite: be transferred to after the superconduction graphite of 6.0g first 120 DEG C of vacuum drying 24h in the glass container of band piston, then vacuumize, vacuum degree control at-0.075MPa, holding temperature 110 DEG C; Under room temperature, by the high purity sulphur of 4.0g, add in 16.0ml toluene, with 3 DEG C/min heating rate, be warmed up to 110 DEG C, under magnetic agitation (500r/min), form flaxen clear solution, insulation 50min; Then to be incorporated into by the toluene solution of sulphur by conduit in the glass container that superconduction graphite is housed, under vacuum condition, solution is inhaled in the micropore of superconduction graphite instantaneously, and maintenance system temperature 110 DEG C, fully infiltrates 3h, is then down to room temperature with 3 DEG C/min speed; Toluene is reclaimed in decompression distillation again (70 DEG C), finally obtains superconduction graphite/sulphur composite.
The ratio of the lithium sulfur battery anode material of preparation, binding agent PVDF, superconduction carbon black 7:2:1 in mass ratio mixed, add solvent NMP and fully stir and obtain slurry, be then coated on aluminium foil, after dry, compressing tablet obtains a kind of lithium-sulphur cell positive electrode.
Battery Integration Assembly And Checkout: adopt lithium metal to be that negative pole is assembled into lithium-sulfur rechargeable battery, electrolyte is the LiTFSI/DOL:DME (1:2 volume ratio, DOL: dioxolane, DME: glycol dimethyl ether) of 1M; Discharge and recharge blanking voltage is: 1-3V(vs.Li/Li
+).Fig. 5 shows the specific discharge capacity of under lithium sulfur battery anode material different multiplying the 1st week and the 50th week.
Claims (3)
1. the preparation method of a lithium sulfur battery anode material, it is characterized in that comprising the steps: that elemental sulfur is dissolved in the toluene solution of obtained elemental sulfur in toluene by (1), wherein the consumption of toluene is every 4.0-7.0g elemental sulfur 16-42ml toluene, the temperature that elemental sulfur is fully dissolved in toluene is 110 DEG C, heating rate is 3-5 DEG C/min, the speed of magnetic agitation is 300-500r/min, and elemental sulfur is incubated 30-50min after dissolving; (2) pretreatment of matrix material, by matrix material vacuum drying 12-24h at the temperature of 110-120 DEG C, then transfer in container, vacuumize, vacuum degree control is at-0.050--0.095MPa, holding temperature 110 DEG C, described matrix material is one or more in active carbon, mesoporous carbon, CNT, graphene oxide and superconduction graphite; (3) preparation of lithium sulfur battery anode material, under the condition of vacuum, being drawn into by the toluene solution of obtained elemental sulfur holds in the container of matrix material, abundant infiltration 1-5h, then be down to room temperature with the rate of temperature fall of 1-5 DEG C/min, toluene i.e. obtained lithium sulfur battery anode material is reclaimed in decompression distillation.
2. the preparation method of lithium sulfur battery anode material according to claim 1, is characterized in that: in described step (2), the consumption of matrix material and the consumption mass ratio of the middle elemental sulfur of step (1) are m(matrix material): m(elemental sulfur)=3:2-7.
3. the preparation method of lithium sulfur battery anode material according to claim 1, is characterized in that: in described step (3), the temperature of decompression distillation is 50-70 DEG C.
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| CN107591254A (en) * | 2017-09-08 | 2018-01-16 | 南陵县生产力促进中心 | A kind of ultracapacitor graphene/Na2S composite nano materials and preparation method thereof |
| CN107768636A (en) * | 2017-10-18 | 2018-03-06 | 中南大学 | A kind of preparation method of high power capacity fluoride/porous carbon composite anode material |
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