CN104953102A - Preparation method of lithium-sulfur battery applicable to industrialized production - Google Patents
Preparation method of lithium-sulfur battery applicable to industrialized production Download PDFInfo
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- CN104953102A CN104953102A CN201510369658.4A CN201510369658A CN104953102A CN 104953102 A CN104953102 A CN 104953102A CN 201510369658 A CN201510369658 A CN 201510369658A CN 104953102 A CN104953102 A CN 104953102A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a preparation method of a lithium-sulfur battery applicable to the industrialized production, and belongs to the field of an electrochemical battery. A battery positive electrode adopts a mixture obtained by simply processing a graphene material capable of being commercialized and realizing mass production and elemental sulfur. The graphene plays a role in mechanical isolation on one aspect, so that the volume variation of sulfur in the charging-discharging process can be inhibited; on the other aspect, the pass-through effect of polysulfide in electrolyte as well as corrosion of polysulfide on a lithium cathode can be prevented to a certain extent by virtue of good space structure, so that the specific discharge capacity of the charging and discharging of the lithium-sulfur battery can be improved. Under the 0.2C current density, the primary discharging capacity can reach 1370mAh.g<-1> or more. After the battery is cycled for 95 times, the capacity still can be maintained about 1000mAh.g<-1>. After the battery is cycled for 30 times, the capacity tends to be stable, and the capacity is maintained at 90 percent or more.
Description
Technical field
The present invention relates to a kind of preparation being applicable to the lithium-sulfur cell of suitability for industrialized production, belong to field of electrochemical batteries.
Background technology
At present, along with the development of science and technology, especially the appearance of power driven vehicle, require that the chemical power source used has lighter quality, less volume, larger capacity, longer life-span and higher fail safe etc., such as current commercial power driven vehicle, its Li-ion batteries piles used, for its flying power provided is only at 300 ~ 500 km, is difficult to meet the demand of people in driving.Lithium-sulfur cell is usually using lithium metal as negative pole, the battery system that elemental sulfur or sulphur carbon composite are constructed as positive pole, can realize the transfer of 2 electronics when there is complete conversion reaction, its theoretical specific capacity can reach 1685mAh/g, is 10 times of current commercial lithium-ion batteries.And element sulphur is as positive electrode active materials, and its rich reserves, environmental friendliness and cheap, these advantages all make lithium-sulfur cell become one of rising energy-storage battery of most.
But lithium-sulfur cell does not become commercialized always, but be in the state of research and development, mainly contain following reason and cause: due to the existence of negative pole Li dendrite, make the security performance of battery low; Polysulfide and lithium produce SEI film, owing to reacting the SEI film instability that complexity makes to generate; The change in volume of sulphur is comparatively large, and the density of sulphur is 2.03g/cm
3compare Li
2s (1.67g/cm
3) density exceed 20% nearly, during charge and discharge cycles, positive pole shrinks expansion, electrode structure is easily caved in, and capacitance loss is large; Chalcogen is in non-conductive material; The effect of shuttling back and forth of the many sulphions of positive pole intermediate product, limits the electrochemical efficiency of positive and negative polarities; The product that solubility is low can at positive and negative polarities surface deposition, and cause active sulfur to lose, capacity reduces gradually.In order to solve the problem for positive pole place, researcher is mainly diffused as thinking with what suppress many sulphions, expands a series of research.
The research of lithium sulfur battery anode material mainly contains two general orientation, and microcosmic isolation is isolated with macroscopic view.Microcosmic isolation mainly comprises following a few class: be that skeleton prepares carbon/sulphur composite material with conductive carbon material, be limited in by sulphur in the duct of material with carbon element; Adopt the coated elemental sulfur of conducting polymer; Conducting polymer network skeleton is utilized to adsorb elemental sulfur; Add oxide or carry out coated sulphur with oxide and prepare oxide/sulphur composite material.These methods can suppress the dissolving of many lithium sulfides to a certain extent, reduce the effect of effect of shuttling back and forth, and improve capacity and the cycle life of battery.But it is loaded down with trivial details that microcosmic isolates the large Alternative of method adopted, and related to HTHP etc., improve industrial danger coefficient.Macroscopic view isolation mainly adds separator, such as carbon paper, carbon cloth, conductive polymer membrane etc. between active material and barrier film, can play the dissolving suppressing product equally, improves capacity and the effect in life-span.But due to separator will be added in the battery, reduce specific energy and the volumetric specific energy of battery on the one hand, add the cost of battery on the other hand, and the suitability for industrialized production of separator is also a severe problem.
Summary of the invention
The object of this invention is to provide a kind of preparation method being applicable to the lithium sulfur battery anode material of mass industrialized production, solve with this problem that existing lithium-sulphur cell positive electrode prepares loaded down with trivial details difficulty.
The object of the invention is to be achieved through the following technical solutions.
Be applicable to a preparation for the lithium-sulfur cell of suitability for industrialized production, comprise the following steps:
Step one, prepare anode pole piece;
Graphene after cleaning is mixed with elemental sulfur 1:1 ~ 9, namely obtains Graphene/sulfur compound powder; Using Graphene/sulfur compound powder as positive active material, conductive agent, 1-METHYLPYRROLIDONE (NMP) solution of Kynoar (PVDF) is binding agent, mixes with mass ratio 6 ~ 9:0 ~ 3:1 ~ 2; Obtain thick slurry, by slurry even spread on a current collector, then dry in the vacuum drying chamber of 40 ~ 60 DEG C and obtain anode pole piece;
Step 2, battery are assembled:
According to the der group packed battery of anode cover, anode pole piece, barrier film (containing electrolyte), lithium anode sheet, negative electrode casing.
Described in step one, the method for cleaning is: Graphene is put into plasma cleaner and cleans;
Conductive agent described in step one is conductive black (Super-P) or acetylene black;
Collector described in step one comprises carbon cloth, aluminium foil, nickel screen;
Beneficial effect
1, the present invention adopts commercial graphite alkene to be matrix, and by simple process, preparation can the Graphene/sulphur composite active material of industrial mass production.Due to commercial graphite alkene conductivity better and the effect of its spatial network skeleton, polysulfide dissolving in the electrolytic solution and the Volumetric expansion of sulphur can be suppressed, while ensureing cycle-index, improve the actual capacity of battery.In addition, at present Graphene is carried to the research of sulphur composite material, its Graphene is prepared primarily of chemical method, this preparation method very loaded down with trivial details, reaction condition harshness very, is difficult to realize in industrialization, and Graphene of the present invention, be can suitability for industrialized production, and the compound of itself and sulphur has good performance on chemical property, and (after under 0.2C multiplying power, discharge and recharge 95 is enclosed, discharge capacity still remain on 1000mAhg
-1), there is significant commercial value.
2. the mode of plasma cleaning has quick, convenient, safe and harmless advantage.Graphene is after plasma cleaning activation, and the oiliness impurity on its surface is removed on the one hand.On the other hand, oxygen plasma bombardment can have an impact to the chemical property of graphenic surface, improves the functional group's character entrained by its amphipathic property and Graphene and quantity.
Accompanying drawing explanation
Fig. 1 is the Graphene/charge and discharge cycles figure of sulphur active material under 0.2C current density;
Fig. 2 is the charging and discharging curve figure of Graphene/sulphur active material under 0.2C, 0.5C, 1C, 2C, 3C, 4C, 0.2C different multiplying;
Fig. 3 is the Graphene/charge and discharge cycles figure of sulphur active material under 0.5C current density.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention will be further described.
Comparative example 1:
The preliminary treatment of carbon cloth collector:
By carbon cloth (thickness 0.32 ~ 0.36mm, density 150 ~ 175g/cm
3) be laid in clean glass plate, put into plasma cleaner and clean it, in cleaning process, operating voltage is set to 600V, and oxygen gas flow rate is set to 500mL/min, and scavenging period is 5 minutes.After cleaning, Graphene is put into vacuum drying chamber, 50 DEG C save backup.
Prepared by anode pole piece:
Using elemental sulfur as positive active material, Super-P is conductive agent, and the nmp solution of PVDF is binding agent, mixes with mass ratio 7:2:1.Elemental sulfur needs to put into 50 DEG C of vacuum drying chambers dry 24 hours before use, then ground evenly, adding quantitative Super-P continuation grinding in proportion until mix, subsequently mixture being placed in glassware and proportionally adding binding agent (binder content 5%).Material is placed on medium speed on magnetic stirring apparatus and stirs 3h after adding.The thick slurry that will obtain after stirring, brushes on the carbon cloth (thickness is 0.34 ~ 0.38mm) after plasma cleaning uniformly by it, then in the vacuum drying chamber of 50 DEG C dry 24 hours for subsequent use.
Battery is assembled:
The carbon cloth being coated with electrode slurry is made the circular pole piece that diameter is 12mm, weigh pole piece weight and be placed in 50 DEG C of vacuum drying chambers and go out unnecessary moisture, obtain Graphene/sulphur positive pole; With diameter 12mm, the metal lithium sheet of thickness 1mm is negative pole, diameter is that the Celgard film of 18mm is as barrier film, choosing 1mol/L bis-(trifluoromethane sulfonic acid acyl) imine lithium is electrolyte, 0.4mol/L lithium nitrate does additive, and DOL (1,3-dioxolane), DME (glycol dimethyl ether) are solvent, solvent volume, than DOL:DME=1:1, is assembled into CR2032 type button cell.The addition of electrolyte is 50 times (mass ratioes) of sulphur.The assembling of whole battery all completes in glove box.
Electrochemical property test:
Use the indigo plant of Wuhan Lan Bo Electronics Co., Ltd. electricity LANDCT2001A discharge and recharge instrument to carry out charge-discharge test to battery, charging/discharging voltage scope is 1.6V to 2.8V, and front and back time of repose is 1min, and charging and discharging currents is 0.2C.Find that the initial capacity of the just very lithium-sulfur cell of elemental sulfur only has 800mAhg
-1, relative to its 1685mAhg
-1theoretical initial capacity differ greatly, at the 8th circulation time, its discharge capacity has decayed to 500mAhg
-1below.Describe in the process of shelving at battery on the one hand, the sulphur in positive plate is dissolved in electrolyte, causes capacity first not high.Show from the seriousness of battery capacity decay on the other hand, after front circulation several times, most active material lost efficacy.
Embodiment 1
Be applicable to a preparation for the lithium-sulfur cell of suitability for industrialized production, comprise the following steps:
The preliminary treatment of Graphene:
By Graphene, (at 10 ~ 20 microns, thickness is in 5 ~ 20 nanometers, and specific area is 34.193m in sheet footpath
2/ g) be evenly laid in clean glass plate, put into plasma cleaner and clean it, in cleaning process, operating voltage is set to 600V, and oxygen gas flow rate is set to 500mL/min, and scavenging period is 5 minutes.After cleaning, Graphene is put into vacuum drying chamber, 50 DEG C save backup.
The preliminary treatment of carbon cloth collector:
By carbon cloth (thickness 0.32 ~ 0.36mm, density 150 ~ 175g/cm
3) be laid in clean glass plate, put into oxygen plasma cleaning machine and clean it, in cleaning process, operating voltage is set to 600V, and oxygen gas flow rate is set to 500mL/min, and scavenging period is 5 minutes.After cleaning, Graphene is put into vacuum drying chamber 50 DEG C and save backup.
Prepared by anode pole piece:
Be that Graphene mixes with elemental sulfur by the ratio of 1:1 with mass ratio, with ethanol be subsequently solvent by mixture as in high speed ball mill, it is per minute that 400 circles are set, run 12 hours.Taken out from high speed ball mill by mixed liquor, be inverted in clean glass surface ware, vacuumize 24 hours at 50 DEG C, namely obtains Graphene/sulfur compound powder; Composite powder is placed in tube furnace; under the protection of inert gas; heat treatment 12 hours at 155 DEG C; Graphene after heat treatment/sulfur compound powder is placed in high speed ball mill and is solvent with ethanol; it is per minute that 400 circles are set; run 12 hours, mixed liquor is taken out from ball mill and puts into 50 DEG C of vacuum drying chamber dry for standby.
Using Graphene/sulfur compound as positive active material, Super-P is conductive agent, and the nmp solution of PVDF is binding agent, mixes with mass ratio 7:2:1.First by dried Graphene/sulfur compound grinding 5 ~ 10min, add quantitative Super-P after grinding evenly and continue grinding until mix, subsequently mixture be placed in container and proportionally add binding agent (binder content 5%).Container is placed in medium speed on magnetic stirring apparatus and stirs 3h.The thick slurry that will obtain after stirring, is uniformly coated on carbon cloth, then in the vacuum drying chamber of 50 DEG C dry 24 hours for subsequent use.
Battery is assembled:
The carbon cloth being coated with electrode slurry is made the circular pole piece that diameter is 12mm, weigh pole piece weight and be placed in 50 DEG C of vacuum drying chambers and go out unnecessary moisture, obtain Graphene/sulphur positive pole; With diameter 12mm, the metal lithium sheet of thickness 1mm is negative pole, and diameter is that the Celgard film of 18mm is as barrier film; Choosing 1mol/L bis-(trifluoromethane sulfonic acid acyl) imine lithium is electrolyte, 0.4mol/L lithium nitrate does additive, DOL (1,3-dioxolane), DME (glycol dimethyl ether) are solvent, and solvent volume compares DOL:DME=1:1; Be assembled into CR2032 type button cell.The addition of electrolyte is 50 times (mass ratioes) of sulphur.The assembling of whole battery all completes in glove box.
Data characterization:
Use the indigo plant of Wuhan Lan Bo Electronics Co., Ltd. electricity LANDCT2001A discharge and recharge instrument to carry out charge-discharge test to battery, charging/discharging voltage scope is 1.6V to 2.8V, and front and back time of repose is 1min.First, its charge-discharge performance is tested, as shown in Figure 1.Under 0.2C current density, capacity is at 1370mAhg first
-1left and right, after circulation 90 times, capacity still remains on 1000mAhg
-1above, be circulated to the 95th circulation at the 30th time, capability retention is more than 90%.
Next has carried out the test of high rate performance, and multiplying power is respectively 0.2C, 0.5C, 1C, 2C, 3C, 4C, 0.2C, as shown in Figure 2.Under different multiplying powers, its capacity mean value corresponds to 1300mAhg respectively
-1, 950mAhg
-1, 730mAhg
-1, 480mAhg
-1, 190mAhg
-1, 80mAhg
-1, 1100mAhg
-1.Find under little circulation, the capacity of battery is higher.
In sum, can find that the sulphur positive pole after Graphene doping obviously will be better than pure elemental sulfur positive pole in specific discharge capacity performance and cycle performance.
Comparative example 2:
The preliminary treatment of commercial graphite:
Evenly be laid in clean glass plate by graphite (3000 orders, purity 99.95%), put into plasma cleaner and clean it, in cleaning process, operating voltage is set to 600V, and oxygen gas flow rate is set to 500mL/min, and scavenging period is 5 minutes.After cleaning, Graphene is put into vacuum drying chamber, 50 DEG C save backup.
Prepared by anode pole piece:
Elemental sulfur needs to put into the dry preliminary treatment in 24 hours of 50 DEG C of vacuum drying chambers before use, the graphite used is 400 order commercial graphite powder, by graphite and elemental sulfur in mass ratio 3:7 mix, then be placed in high speed ball mill and be solvent with ethanol, arranging rotating speed 500 encloses per minute, 24 hours time, after ball milling, mixed liquor is taken out and be placed in 50 DEG C of vacuum drying chambers and be dried into and obtain graphite/sulfur compound powder.Composite powder is placed in tube furnace; under the protection of inert gas; heat treatment 12 hours at 155 DEG C; mixture after heat treatment is placed in ball mill and is solvent with ethanol; it is per minute that 500 circles are set; run 24 hours, mixed liquor is taken out from ball mill and puts into 50 DEG C of vacuum drying chamber dry for standby.
Using graphite/sulphur as positive active material, Super-P is conductive agent, and the nmp solution of PVDF is binding agent, mixes with mass ratio 8:1:1.Then ground evenly, adding quantitative Super-P continuation grinding in proportion until mix, subsequently mixture being placed in glassware and proportionally adding binding agent (binder content 5%).Material is placed on medium speed on magnetic stirring apparatus and stirs 3h after adding.The thick slurry that will obtain after stirring, it be coated in uniformly on clean aluminium foil (thickness is 0.02mm), material bed thickness is 0.15mm, then in the vacuum drying chamber of 50 DEG C dry 24 hours for subsequent use.
Battery is assembled:
The aluminium foil being coated with sample is made the circular pole piece that diameter is 12mm, weigh pole piece weight and be placed in 50 DEG C of vacuum drying chambers and go out unnecessary moisture, obtain Graphene/sulphur positive pole; With diameter 12mm, the metal lithium sheet of thickness 1mm is negative pole, diameter is that the Celgard film of 18mm is as barrier film, choosing 1mol/L bis-(trifluoromethane sulfonic acid acyl) imine lithium is electrolyte, 0.4mol/L lithium nitrate does additive, and DOL (1,3-dioxolane), DME (glycol dimethyl ether) are solvent, solvent volume, than DOL:DME=1:1, is assembled into CR2032 type button cell.The addition of electrolyte is 50 times (mass ratioes) of sulphur.The assembling of whole battery all completes in glove box.
Data illness that has not attacked the vital organs of the human body:
Use the indigo plant of Wuhan Lan Bo Electronics Co., Ltd. electricity LANDCT2001A discharge and recharge instrument to carry out charge-discharge test to battery, charging/discharging voltage scope is 1.6V to 2.8V, and front and back time of repose is 1min, and charging and discharging currents is 0.5C.Find that the initial capacity of the just very lithium-sulfur cell of graphite/sulphur only has 942mAhg
-1, relative to its 1685mAhg
-1theoretical initial capacity differ greatly, at the 14th circulation time, its discharge capacity decays to 792mAhg
-1left and right, after the 100th circulation, discharge capacity only maintains 469mAhg
-1, capability retention is only 49.78%.
Embodiment 2
The preliminary treatment of Graphene:
By Graphene, (at 10 ~ 20 microns, thickness is in 5 ~ 20 nanometers, and specific area is 34.193m in sheet footpath
2/ g) be evenly laid in clean glass plate, put into plasma cleaner and clean it, in cleaning process, operating voltage is set to 600V, and oxygen gas flow rate is set to 500mL/min, and scavenging period is 5 minutes.After cleaning, Graphene is put into vacuum drying chamber, 50 DEG C save backup.
Prepared by anode pole piece:
Be that Graphene mixes with elemental sulfur by the ratio of 3:7 with mass ratio, with ethanol be subsequently solvent by mixture as in high speed ball mill, it is per minute that 500 circles are set, run 24 hours.Taken out from ball mill by mixed liquor, be inverted in clean glass surface ware, vacuumize 24 hours at 50 DEG C, namely obtains Graphene/sulfur compound powder; Composite powder is placed in tube furnace; under the protection of inert gas; heat treatment 12 hours at 155 DEG C; mixture after heat treatment is placed in ball mill and is solvent with ethanol; it is per minute that 500 circles are set; run 24 hours, mixed liquor is taken out from ball mill and puts into 50 DEG C of vacuum drying chamber dry for standby.
Using Graphene/sulfur compound as positive active material, Super-P is conductive agent, and the nmp solution of PVDF is binding agent, mixes with mass ratio 8:1:1.First by dried Graphene/sulfur compound grinding 5 ~ 10min, add quantitative Super-P after grinding evenly and continue grinding until mix, subsequently mixture be placed in container and proportionally add binding agent (binder content 5%).Container is placed in medium speed on magnetic stirring apparatus and stirs 3h.The thick slurry that will obtain after stirring, it be coated in uniformly on clean aluminium foil (thickness is 0.02mm), material bed thickness is 0.15mm, then in the vacuum drying chamber of 50 DEG C dry 24 hours for subsequent use.
Battery is assembled:
The aluminium foil being coated with sample is made the circular pole piece that diameter is 12mm, weigh pole piece weight and be placed in 50 DEG C of vacuum drying chambers and go out unnecessary moisture, obtain Graphene/sulphur positive pole; With diameter 12mm, the metal lithium sheet of thickness 1mm is negative pole, diameter is that the Celgard film of 18mm is as barrier film, choosing 1mol/L bis-(trifluoromethane sulfonic acid acyl) imine lithium is electrolyte, 0.4mol/L lithium nitrate does additive, and DOL (1,3-dioxolane), DME (glycol dimethyl ether) are solvent, solvent volume, than DOL:DME=1:1, is assembled into CR2032 type button cell.The addition of electrolyte is 50 times (mass ratioes) of sulphur.The assembling of whole battery all completes in glove box.
Data characterization:
Use the indigo plant of Wuhan Lan Bo Electronics Co., Ltd. electricity LANDCT2001A discharge and recharge instrument to carry out charge-discharge test to battery, charging/discharging voltage scope is 1.6V to 2.8V, and front and back time of repose is 1min.First, its charge-discharge performance is tested, as shown in Figure 3.Under 0.5C current density, capacity is at 1194mAhg first
-1left and right, after circulation 100 times, capacity still remains on 800mAhg
-1above, tend towards stability the 30th circulation backlash discharge capacity, be recycled to the 100th circulation from the 30th time, capability retention, more than 90.35%, on average often encloses decay 0.14%.
Found by this group contrast test, when condition is identical, by the positive pole prepared by Graphene/sulphur composite material, its specific discharge capacity and cycle performance will be superior to graphite/sulphur composite material positive pole.
Claims (9)
1. be applicable to a preparation for the lithium-sulfur cell of suitability for industrialized production, it is characterized in that: comprise the following steps:
Step one, prepare anode pole piece;
Graphene after cleaning is mixed with elemental sulfur 1:1 ~ 9, namely obtains Graphene/sulfur compound powder; Using Graphene/sulfur compound powder as positive active material, conductive agent, the 1-METHYLPYRROLIDONE solution of Kynoar is binding agent, mixes with mass ratio 6 ~ 9:0 ~ 3:1 ~ 2; Obtain thick slurry, slurry is evenly applied on a current collector, then dry in the vacuum drying chamber of 40 ~ 60 DEG C and obtain anode pole piece;
Step 2, battery are assembled:
According to the der group packed battery of anode cover, anode pole piece, barrier film (containing electrolyte), lithium anode sheet, negative electrode casing.
2. a kind of preparation being applicable to the lithium-sulfur cell of suitability for industrialized production as claimed in claim 1, is characterized in that: described in step one, the method for cleaning is: Graphene is put into plasma cleaner and cleans.
3. a kind of preparation being applicable to the lithium-sulfur cell of suitability for industrialized production as claimed in claim 1, is characterized in that: conductive agent described in step one is conductive black or acetylene black.
4. a kind of preparation being applicable to the lithium-sulfur cell of suitability for industrialized production as claimed in claim 1, is characterized in that: collector described in step one comprises carbon cloth, aluminium foil, nickel screen.
5. a kind of preparation being applicable to the lithium-sulfur cell of suitability for industrialized production as claimed in claim 1, is characterized in that: the Graphene described in step one, and its sheet footpath is at 10 ~ 20 microns, and thickness is in 5 ~ 20 nanometers, and specific area is 34.193m
2/ g.
6. a kind of preparation being applicable to the lithium-sulfur cell of suitability for industrialized production as described in claim 1 or 4, is characterized in that: the carbon cloth collector described in step one, its thickness is 0.32 ~ 0.36mm.
7. a kind of preparation being applicable to the lithium-sulfur cell of suitability for industrialized production as described in claim 1 or 4, is characterized in that: the carbon cloth collector described in step one, its density is 150 ~ 175g/cm
3.
8. a kind of preparation being applicable to the lithium-sulfur cell of suitability for industrialized production as described in claim 1 or 4, is characterized in that: the carbon cloth collector described in step one is cleaned by plasma cleaner.
9. a kind of preparation being applicable to the lithium-sulfur cell of suitability for industrialized production as claimed in claim 1, is characterized in that: Graphene/sulphur is mixed by high speed ball mill, rotating speed 300 ~ 500 enclose per minute, running time 12 ~ 48h.
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Cited By (5)
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CN106602063A (en) * | 2016-12-30 | 2017-04-26 | 浙江大学 | Preparation method for graphene spray and application of graphene spray in lithium-sulfur battery |
CN107611395A (en) * | 2017-09-08 | 2018-01-19 | 中国科学院山西煤炭化学研究所 | Small size graphene lithium sulfur battery anode material, its lithium-sulfur cell prepared and preparation method |
CN107611396A (en) * | 2017-09-08 | 2018-01-19 | 中国科学院山西煤炭化学研究所 | A kind of quisqueite base/graphene composite material and its preparation method and application |
CN108630890A (en) * | 2018-04-28 | 2018-10-09 | 四川华昆能源有限责任公司 | A kind of multi-layer electrode structure and preparation method thereof for lithium-sulfur cell |
CN109950473A (en) * | 2019-03-29 | 2019-06-28 | 柯良节 | A kind of lithium-sulphur cell positive electrode and preparation method thereof |
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CN106602063A (en) * | 2016-12-30 | 2017-04-26 | 浙江大学 | Preparation method for graphene spray and application of graphene spray in lithium-sulfur battery |
CN107611395A (en) * | 2017-09-08 | 2018-01-19 | 中国科学院山西煤炭化学研究所 | Small size graphene lithium sulfur battery anode material, its lithium-sulfur cell prepared and preparation method |
CN107611396A (en) * | 2017-09-08 | 2018-01-19 | 中国科学院山西煤炭化学研究所 | A kind of quisqueite base/graphene composite material and its preparation method and application |
CN107611395B (en) * | 2017-09-08 | 2020-10-27 | 中国科学院山西煤炭化学研究所 | Small-size graphene lithium-sulfur battery positive electrode material, lithium-sulfur battery prepared from small-size graphene lithium-sulfur battery positive electrode material and preparation method of small-size graphene lithium-sulfur battery positive electrode material |
CN108630890A (en) * | 2018-04-28 | 2018-10-09 | 四川华昆能源有限责任公司 | A kind of multi-layer electrode structure and preparation method thereof for lithium-sulfur cell |
CN109950473A (en) * | 2019-03-29 | 2019-06-28 | 柯良节 | A kind of lithium-sulphur cell positive electrode and preparation method thereof |
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