CN103500813A - Elemental sulfur anode of secondary lithium-sulfur battery and preparation method of elemental sulfur anode - Google Patents
Elemental sulfur anode of secondary lithium-sulfur battery and preparation method of elemental sulfur anode Download PDFInfo
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Abstract
The invention provides an elemental sulfur anode of a secondary lithium-sulfur battery and a preparation method of the elemental sulfur anode. The method comprises the following steps: step 1, dissolving sublimed sulfur in a volatile solvent to prepare a sulfur solution; step 2, dispersing a composite conductive agent into an NMP (Nuclear Matrix Protein) solution of a binder PVDF (Polyvinylidene Fluoride) and stirring to prepare a finely-dispersed previous slurry; step 3, dropwise adding the sulfur solution into the previous slurry, and continuing to stir; step 4, opening a closed container, and continuing to stir for 0.5-1 hour to obtain slurry with uniformly-dispersed sulfur and carbon; step 5, coating the slurry onto a current collector; step 6, punching after vacuum drying, wherein the dosage rate of the sublimed sulfur, the conductive agent and the binder is (40-80):(50-10):10. The method uses functionalized aluminum foil as the current collector, the slurry with uniformly-dispersed and closely-connected sulfur and carbon prepared with a one-pot method is used as a coating layer, and therefore an electrode piece which has large possibility of caking and has large surface density is obtained. The preparation method has the advantages of simplicity, uniform dispersion of sulfur and carbon, high carrying capacity and high utilization rate of elemental sulfur.
Description
Technical field
The present invention relates to a kind of lithium-sulfur cell, relate in particular to a kind of lithium-sulfur cell elemental sulfur anode pole piece and preparation method thereof, belong to field of electrochemical batteries.
Background technology
Along with social high speed development and the raising of people's living standard, energy crisis seems and becomes increasingly conspicuous, and the diversified demand of the energy is also day by day urgent.The lithium battery cleaning chemistry power supply that particularly lithium ion battery of secondary is representative of take has obtained developing fast and applying, and is bringing into play indispensable effect.From portable electronic product as the iphone mobile phone to take the develop rapidly of aerospace craft, electric automobile, intelligent grid and energy-accumulating power station that power and energy storage be representative, to chemical power source used lithium battery particularly, have higher requirement: quality is light, volume is little, energy density is high, fail safe is good, long circulation life etc.
Current commercial anode material of lithium battery is mainly lithium transition-metal oxide stratiform or the spinelle shape, as LiCoCO
2, LiMn
2o
4, LiFePO
4deng.These materials have the advantages such as operating voltage is high, self-discharge rate is low, but weight energy density is not high enough, is limited at present 200-250Wh/Kg, can not meet the requirement of society to high-energy-density.Although can also improve to a certain extent the performance of battery by improving current material and battery preparation technique, if will improve significantly the energy density of battery, just must develop new material and new system.
The lithium-sulfur cell that the elemental sulfur of take is negative pole as anodal, lithium metal is a kind of new system battery that the high-energy-density of development potentiality is arranged very much.The electrochemistry overall reaction of its generation is: S
8+ LiLi
2s
x(1≤x≤8) Li
2s.According to final reduction reaction product Li
2s calculates, and the theoretical specific capacity of elemental sulfur is 1672mAh/g, and lithium metal has theoretical specific capacity 3860mAh/g, and the theoretical energy density of Li/S redox couple is up to 2600Wh/kg.In addition, sulphur also possesses the characteristics of aboundresources, cheap, nontoxic or low toxicity.
Because the electronic conductivity of elemental sulfur is extremely low, therefore need the activity of the conductive agent raising active material sulphur of a large amount of highly conductor phases of interpolation.Become a difficult point and how to prepare sulphur, carbon or sulphur, the uniform electrode slurry of distribution of polymer and electrode plates.The focus and emphasis of lithium-sulfur cell research at present is the preparation of sulphur/carbon or sulphur/polymer composite anode material, and its starting point and emphasis are all the preparations that is conceived to anode composite material, have often ignored the preparation of final dispersed electrode slurry.As, prepare the composite material of sulphur/carbon or sulphur/distribution of polymer homogeneous by heat treatment or chemical method, and then add other conductive agent, binding agent etc. and prepare electrode slurry and pole piece by dispersed with stirring, preparation process is more complicated all, and cost is high, be unfavorable for the production of large-scale industrialization.Secondly, the surface density of current reported elemental sulfur positive pole is all lower, far away apart from practical application.
Summary of the invention
The objective of the invention is that the anodal preparation technology of existing elemental sulfur is loaded down with trivial details in order to overcome, the defects such as active material sulphur and conductive agent skewness, a kind of preparation method of lithium-sulfur cell elemental sulfur positive pole is provided, utilize phase transformation, the one kettle way of sulphur to prepare the elemental sulfur positive pole, the preparation method is simple, sulphur carbon is uniformly dispersed, high carrying capacity, elemental sulfur utilance are high.
For achieving the above object, the invention provides a kind of preparation method of secondary lithium-sulfur cell elemental sulfur positive pole, the method comprises the steps:
Step 1, be dissolved in sublimed sulfur in easy volatile solvent, configuration sulphur solution;
Step 2, by microcosmic, be that the combined conductive agent that point, toe-in close is scattered in binding agent PVDF(Kynoar) the NMP(N-methyl pyrrolidone) solution (joins off-the-shelf binding agent by nmp solvent, stir and obtain) in, prepare slurry in finely disseminated early stage by magnetic agitation or mechanical agitation or ball milling;
Step 3, dropwise be added drop-wise to the sulphur solution of step 1 configuration in the good conductive agent slurry in finely disseminated early stage of the sealing of step 2 preparation, continues to stir 2～5 hours;
Step 4, closed container is uncovered, continue to stir 0.5～1 hour, obtain the slurry that sulphur carbon is finely dispersed, be suitable for coating;
Step 5, by finely dispersed slurry coating on the collector of functionalization; The collector of this functionalization refers to that collection liquid surface has passed through processing, and specifically collection liquid surface has applied one deck carbon-coating, and this functionalization collector is commercially available; The effect of this functionalization collector is mainly the roughness that has increased collection liquid surface, is conducive to slurry and applies, especially for the preparation of high areal density sulphur positive pole; Also having an effect is the contact resistance that reduces slurry coat and collection liquid surface;
Step 6, be placed in punching after 50 ℃ of vacuum dryings, weighing as positive plate; Lithium metal is that negative plate is assembled into battery and is tested in being full of the glove box of argon gas;
Wherein, sublimed sulfur: conductive agent: the usage ratio of binding agent is according to mass ratio 40～80:50～10:10.
The preparation method of above-mentioned secondary lithium-sulfur cell elemental sulfur positive pole, wherein, described sublimed sulfur is the sulfur granules that solvent evaporates is separated out, and particle diameter concentrates on 10 microns, and particle size range is the 6-12 micron, and the sulfur granules particle diameter of the percetage by weight of 60-95% is 10 microns.
The preparation method of above-mentioned secondary lithium-sulfur cell elemental sulfur positive pole, wherein, in step 1, more than any one in the solvent of described sublimed sulfur selection CS2, dimethylbenzene, toluene or DMSO; , these solvents are soluble sublimed sulfur not only, and solvent self is volatile.
The preparation method of above-mentioned secondary lithium-sulfur cell elemental sulfur positive pole, wherein, in step 1, the sulphur solution concentration is 5%～30%, preferably 10-30%.
The preparation method of above-mentioned secondary lithium-sulfur cell elemental sulfur positive pole, wherein, it is the graphite powder conductive agent that Japanese TIMCAL company produces that described point, line combined conductive agent are selected SP carbon black, XE2 carbon, KS6(KS6), acetylene black, activated carbon, mesoporous carbon, porous carbon, conductive carbon fibre VGCF (gas-phase growth of carbon fibre Vapor-grown carbon fiber is called for short VGCF) and CNT(carbon nano-tube, full name Carbon nanotube, be called for short CNT) in two or more arbitrarily.
The preparation method of above-mentioned secondary lithium-sulfur cell elemental sulfur positive pole, wherein, in step 5, described functionalization collector is corrosive aluminum foil or is coated with the carbon aluminium foil.
The preparation method of above-mentioned secondary lithium-sulfur cell elemental sulfur positive pole, wherein, in step 5, coating thickness is 50～150 microns, collector thickness is 18～22 microns.
The preparation method of above-mentioned secondary lithium-sulfur cell elemental sulfur positive pole, wherein, before step 1, the method also comprises the predrying step to sublimed sulfur and conductive agent; As dry 24h in the vacuum drying oven that sublimed sulfur, conductive agent is placed in respectively to 60 ℃ and 120 ℃, standby.
The present invention also provides a kind of secondary lithium-sulfur cell elemental sulfur positive pole prepared according to said method, and the coating thickness of this sulphur positive pole is 50～150 microns, and collector thickness is 18～22 microns, and the surface density of pole piece reaches 8 mg/cm
2.
The present invention, in preparing the process of slurry, utilizes the phase change (Gu solid-liquid-) of active material sulphur to reduce the particle of sulphur, realizes dispersed, the close contact of active material and conductive agent; Increase the contact area of conductive agent and sulphur by the combined conductive agent that adds Joint of Line and Dot, and finally synchronously prepare the slurry that is suitable for coating; Realize the pole piece technology of stable mechanical performance, thick coating by the collector of functionalization.Have that the preparation method is simple, the remarkable advantages such as sulphur carbon is uniformly dispersed, high carrying capacity, elemental sulfur utilance height.
Compared with prior art, the present invention has following beneficial effect:
1, phase transformation of the present invention, one kettle way prepare the preparation method of elemental sulfur positive pole, do not need to prepare the sulphur carbon composite by high-temperature heating or more complicated chemical reaction in advance, simple, quick, energy savings;
2, the present invention passes through the transformation mutually of active material sulphur: solid phase-liquid phase-solid phase, making conductive agent originally is that solid-liquid contacts with the microcosmic solid-solid interface changes in contact between sulphur, effectively increase the contact area between the two, thereby can increase to a great extent dispersing uniformity and the compactness of sulphur carbon; In addition, changing mutually of active material sulphur also can not affect itself and the contacting of binder solution, dispersion; Finally improve activity and the utilance of active material sulphur, improved the cyclical stability of lithium-sulfur cell;
3, the present invention is by the combined conductive agent that adopts Joint of Line and Dot and contact area, the increase conductivity that the functionalization collector can improve sulphur carbon in whole electrode, strengthen the mechanical strength of whole electrode, realize the anodal technology of preparing of elemental sulfur of high carrying capacity, the surface density of pole piece can reach 8 mg/cm
2, increase the practical possibility of lithium-sulfur cell.
The accompanying drawing explanation
The scanning electron microscope sem photo of the positive plate that Fig. 1 is the final preparation in embodiment 1.
The charging and discharging curve that Fig. 2 is in lithium-sulfur rechargeable battery first twice of prepared anode pole piece in embodiment 1 (for the first time and for the second time).
Fig. 3 is the cycle performance curve of prepared anode pole piece in lithium-sulfur rechargeable battery in embodiment 1, Comparative Examples 1,2.
Embodiment
Below in conjunction with accompanying drawing, embodiment of the present invention is described in detail: embodiments of the invention are implemented take technical scheme of the present invention under prerequisite; and provided detailed execution mode and concrete operating process, but protection scope of the present invention not only is confined to following embodiment.
Embodiment 1
(1) take in mass ratio sublimed sulfur: SP carbon black (hereinafter to be referred as SP): VGCF:PVDF=60:22:8:10, SP, VGCF and PVDF are mixed and be placed in airtight vial, and add a certain amount of NMP, magnetic agitation 60min makes the slurry in early stage that conductive agent mixes, and sublimed sulfur gives over to next step use;
(2) measure a certain amount of CS
2liquid, be configured to by the sublimed sulfur powder S-CS that mass fraction is 10%
2solution;
(3) by S-CS
2solution dropwise joins and in slurry, stirs 3h by peristaltic pump the prepared early stage mixed in step (1); Then the open container continuation is stirred 30min and is made the final slurry mixed;
(4) final slurry is coated on corrosive aluminum foil with scraper, 50 ℃ of vacuumize 24h, obtain final pole piece.
The final pole piece that embodiment 1 is prepared has carried out the SEM test, can find out that the dispersion of active material sulphur, SP and VGCF is very even.
Resulting electrode plates is assembled into to 2016 type button cells to be tested.As shown in Figure 2, discharge capacity can be up to 1218 mAh/g first for charging and discharging curve under room temperature, and discharge capacity still can reach 1080 mAh/g for the second time.
Comparative Examples 1
(1) take in mass ratio sublimed sulfur: SP:VGCF:PVDF=60:22:8:10, SP, VGCF and PVDF are mixed and be placed in airtight vial, and adding a certain amount of NMP, magnetic agitation 60min makes the slurry in early stage that conductive agent mixes, and sublimed sulfur gives over to next step use;
(2) the sublimed sulfur powder taken is added to step (1) prepared early stage in slurry, continue to stir 2h, prepare final slurry;
(3) final slurry is coated on corrosive aluminum foil with scraper, 50 ℃ of vacuumize 24h, obtain final pole piece.
Comparative Examples 2
(1) the standby sulphur carbon composite of exchange of solvent legal system: will take in mass ratio sublimed sulfur: SP:VGCF:PVDF=60:22:8:10, PVDF gives over to next step use.Sulphur is configured to the S-CS that mass fraction is 10%
2solution; SP, VGCF are distributed in a certain amount of ethanol, and ultrasonic processing 1h is prepared into the carbon gel; Then the carbon gel of preparation is dropwise joined to S-CS
2the ultrasonic 2h of solution for continuous is placed on 50 ℃ of dry 10h, finally prepares and disperses sulphur carbon composite preferably.
(2) sulphur carbon composite and PVDF mix a certain amount of NMP of rear interpolation, make final slurry after magnetic agitation 3h;
(3) final slurry is coated on corrosive aluminum foil with scraper, 50 ℃ of vacuumize 24h, obtain final pole piece.
Above resulting electrode plates is assembled into to 2016 type button cells to be tested, its stable circulation linearity curve is as Fig. 3, contrast shows: electrode plates prepared by phase transformation of the present invention, one kettle way (embodiment 1) has extraordinary cycle performance, and 50 circulations can be stabilized in 815 mAh/g.
Embodiment 2
(1) take in mass ratio sublimed sulfur: SP:CNT:PVDF=66:16:8:10, SP, VGCF and PVDF are mixed and be placed in airtight vial, and adding a certain amount of NMP, magnetic agitation 60min makes the slurry in early stage that conductive agent mixes, and sublimed sulfur gives over to next step use;
(2) measure a certain amount of dimethylbenzene liquid, the sublimed sulfur powder is configured to the S-xylene solution that mass fraction is 10%;
(3) the S-xylene solution is dropwise joined and in slurry, stirs 3h by peristaltic pump the prepared early stage mixed in step (1); Then the open container continuation is stirred 30min and is made the final slurry mixed;
(4) final slurry is coated on the carbon aluminium foil with scraper, 50 ℃ of vacuumize 24h, obtain final pole piece.
Embodiment 3
(1) take in mass ratio sublimed sulfur: SP:VGCF:PVDF=60:22:8:10, SP, VGCF and PVDF are mixed and be placed in airtight vial, and adding a certain amount of NMP, magnetic agitation 60min makes the slurry in early stage that conductive agent mixes, and sublimed sulfur gives over to next step use;
(2) measure a certain amount of DMSO liquid, the sublimed sulfur powder is configured to the S-DMSO solution that mass fraction is 10%;
(3) the S-xylene solution is dropwise joined in step (1) to the prepared early stage mixed in slurry by peristaltic pump, and be heated to 115 ℃, stir 3h; Then open container stop heating, continue to stir 30min and make the final slurry mixed;
(4) final slurry is coated on the carbon aluminium foil with scraper, 50 ℃ of vacuumize 24h, obtain final pole piece.
Preparation method's key provided by the invention is to utilize the reduction of the transformation mutually particle of sulphur less, increases combining closely of sulphur carbon, obtain the slurry that sulphur carbon disperses simultaneously, the solution that is about to sulphur joins in the initial stage slurry of prior finely dispersed conductive agent-PVDF-NMP, elemental sulfur is separated out in the slow volatilization of recycling solvent, thereby reach, obtains the slurry purpose that sulphur carbon is finely dispersed, be suitable for coating.One kettle way of the present invention prepares the elemental sulfur positive pole, and the preparation method is simple, sulphur carbon is uniformly dispersed, high carrying capacity, elemental sulfur utilance are high.
The elemental sulfur positive pole and the lithium metal that adopt preparation method of the present invention to obtain form lithium-sulfur cell, and the reversible specific capacity first of electrode is up to 1218 mAh/g at normal temperatures, and 50 circulations still remain on 815 mAh/g, have good cyclical stability.
Although content of the present invention has been done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple modification of the present invention with to substitute will be all apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. the preparation method of a secondary lithium-sulfur cell elemental sulfur positive pole, is characterized in that, the method comprises the steps:
Step 1, be dissolved in sublimed sulfur in easy volatile solvent, configuration sulphur solution;
Step 2, be that the combined conductive agent that point, toe-in close is scattered in the nmp solution of binding agent PVDF by microcosmic, by magnetic agitation or mechanical agitation or ball milling, prepares slurry in finely disseminated early stage;
Step 3, in closed container, dropwise be added drop-wise to the sulphur solution of step 1 configuration in the conductive agent slurry in finely disseminated early stage of step 2 preparation, continues to stir 2～5 hours;
Step 4, closed container is uncovered, continue to stir 0.5～1 hour, obtain the slurry that sulphur carbon is finely dispersed, be suitable for coating;
Step 5, by finely dispersed slurry coating on the collector of functionalization;
Step 6, be placed in punching after 50 ℃ of vacuum dryings, weighing as positive plate;
Wherein, sublimed sulfur: conductive agent: the usage ratio of binding agent is according to mass ratio 40～80:50～10:10.
2. the preparation method of secondary lithium-sulfur cell elemental sulfur positive pole as claimed in claim 1, is characterized in that, described sublimed sulfur is the sulfur granules that solvent evaporates is separated out, and particle diameter concentrates on 10 microns.
3. the preparation method of secondary lithium-sulfur cell elemental sulfur positive pole as claimed in claim 1, is characterized in that, in step 1, the solvent of described sublimed sulfur is selected CS
2, more than any one in dimethylbenzene, toluene or DMSO.
4. the preparation method of secondary lithium-sulfur cell elemental sulfur positive pole as claimed in claim 1, is characterized in that, in step 1, the sulphur solution concentration is 5%～30%.
5. the preparation method of secondary lithium-sulfur cell elemental sulfur positive pole as claimed in claim 4, is characterized in that, in step 1, the sulphur solution concentration is 10%～30%.
6. the preparation method of secondary lithium-sulfur cell elemental sulfur positive pole as claimed in claim 1, it is characterized in that, described point, line combined conductive agent are respectively: SP carbon black, XE2 carbon, KS6, acetylene black, activated carbon, mesoporous carbon, carbon nano-tube, porous carbon and conductive carbon fibre VGCF.
7. the preparation method of secondary lithium-sulfur cell elemental sulfur positive pole as claimed in claim 1, is characterized in that, in step 5, described functionalization collector is corrosive aluminum foil or is coated with the carbon aluminium foil.
8. the preparation method of secondary lithium-sulfur cell elemental sulfur positive pole as claimed in claim 1, is characterized in that, in step 5, coating thickness is 50～150 microns, and collector thickness is 18～22 microns.
9. the preparation method of secondary lithium-sulfur cell elemental sulfur positive pole as claimed in claim 1, is characterized in that, before step 1, the method also comprises the predrying step to sublimed sulfur and conductive agent.
10. the secondary lithium-sulfur cell elemental sulfur positive pole prepared according to the method for claim 1, is characterized in that, the coating thickness of this sulphur positive pole is 50～150 microns, and collector thickness is 18～22 microns, and the surface density of pole piece reaches 8 mg/cm
2.
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| CN104282914A (en) * | 2014-10-24 | 2015-01-14 | 北京化工大学 | Composite conductive agent for lithium-sulfur battery positive material and preparation method of composite conductive agent |
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| CN104282914A (en) * | 2014-10-24 | 2015-01-14 | 北京化工大学 | Composite conductive agent for lithium-sulfur battery positive material and preparation method of composite conductive agent |
| CN104362294A (en) * | 2014-12-05 | 2015-02-18 | 上海空间电源研究所 | Porous sulfur anode used for lithium-sulfur battery and preparation method thereof as well as lithium-sulfur battery |
| CN106410283B (en) * | 2016-02-03 | 2018-11-16 | 宁波设会物联网科技有限公司 | A kind of preparation method of lithium-sulfur cell |
| CN105702944A (en) * | 2016-02-03 | 2016-06-22 | 宁波良能新材料有限公司 | Lithium-sulfur battery |
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| CN105932265B (en) * | 2016-07-11 | 2019-04-23 | 大连理工大学 | A kind of lithium-sulphur cell positive electrode, preparation method and applications |
| CN105932265A (en) * | 2016-07-11 | 2016-09-07 | 大连理工大学 | Lithium sulfur battery anode, preparation method and application thereof |
| US11919770B2 (en) | 2017-08-10 | 2024-03-05 | Suzhou Canastar New-Materials Technology Corporation | Nano-sulfur containing composition and application thereof |
| CN107910535A (en) * | 2017-11-22 | 2018-04-13 | 哈尔滨工业大学 | A kind of preparation method of the high carrying capacity sulfur electrode of fibre reinforced |
| CN108975280A (en) * | 2018-06-27 | 2018-12-11 | 天津大学 | A kind of nano-sulfur particles dispersion liquid and preparation method thereof, nano-sulfur particles and lithium-sulfur cell |
| CN112687863A (en) * | 2020-12-25 | 2021-04-20 | 惠州亿纬锂能股份有限公司 | Lithium-sulfur battery positive electrode slurry, homogenizing method and application thereof |
| CN113130892A (en) * | 2021-04-20 | 2021-07-16 | 郑州大学 | Sulfur-carbon composite emulsion and preparation method and application thereof |
| CN113130892B (en) * | 2021-04-20 | 2022-06-03 | 郑州大学 | Sulfur-carbon composite emulsion and preparation method and application thereof |
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