CN105489901B - A kind of preparation method and applications of lithium-sulfur cell three-dimensional carbon collector - Google Patents
A kind of preparation method and applications of lithium-sulfur cell three-dimensional carbon collector Download PDFInfo
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- CN105489901B CN105489901B CN201511025445.6A CN201511025445A CN105489901B CN 105489901 B CN105489901 B CN 105489901B CN 201511025445 A CN201511025445 A CN 201511025445A CN 105489901 B CN105489901 B CN 105489901B
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The present invention relates to field of electrochemical batteries, preparation method and the application of the lithium-sulfur cell three-dimensional carbon collector in lithium-sulfur cell more particularly to a kind of lithium-sulfur cell three-dimensional carbon collector.The preparation method of the lithium-sulfur cell three-dimensional carbon collector of the present invention includes：Organic foam material organic solvent is impregnated into 2 6h, is washed, it is dry, under inert gas shielding, 700 900 DEG C of 2 6h of heat preservation to get；The organic foam material is any one in polyurethane foam, melamine foamed plastic；The organic solvent is any one in ethyl alcohol, ethylene glycol, isopropanol, acetone.The preparation method of the lithium-sulfur cell three-dimensional carbon collector of the present invention is carbonized obtained collector at high temperature using organic foam material, the face that its three-dimensional structure can improve collector carries sulfur content, and with certain elasticity, the volume expansion of sulphur in charge and discharge process can be accommodated.
Description
Technical field
The present invention relates to field of electrochemical batteries, more particularly to a kind of preparation method of lithium-sulfur cell three-dimensional carbon collector
And the application of the lithium-sulfur cell three-dimensional carbon collector in lithium-sulfur cell.
Background technology
With the development that science and technology is with rapid changepl. never-ending changes and improvements, energy problem is more noticeable, and the development and utilization of novel energy will be
Following long-term hot spot.A kind of ripe, stable, safety energy storage system however the utilization of new energy needs to rely on.Lithium ion
Battery as a kind of new secondary cell, is acknowledged as one of energy-storage system being most potential.But it is than energy relatively
The shortcomings of low, at high price, limits its development.Therefore, low energy height, price, long lifespan, safe secure energy storage are developed
System is of great significance.
Lithium-sulfur cell be using elemental sulfur as anode, lithium metal as cathode secondary cell, as a positive electrode active material
Sulphur is widely present in the earth's crust, cheap, and has the characteristics that environmental-friendly.In addition, when sulphur is as active material,
Theoretical specific capacity is up to 1675mAh/g, and theory is 2600Wh/kg than energy, is equivalent to secondary cell market-oriented at present
3-5 times.But current lithium-sulfur cell also has the disadvantage that, and first, the insulating properties of sulphur simple substance；Second, polysulfide ion exists
It dissolves and migrates in electrolyte；3rd, the expansion of sulphur volume in electrochemical reaction.These shortcomings cause lithium-sulfur cell stable circulation
Property is poor, and coulombic efficiency is relatively low, seriously limits the extensive use of lithium-sulfur cell.
By the study found that the first cause for causing lithium-sulfur cell stable circulation difference low with coulombic efficiency is anti-in electrochemistry
The dissolving and migration of polysulfide ion in the electrolytic solution during answering, i.e. part element sulphur are present in electrolysis in the form of polysulfide
In liquid, so as to cause lithium-sulfur cell coulombic efficiency low.Diffuse further into cathode of lithium polysulfide can into being deposited on cathode of lithium,
The polysulfide corrosion that the very high cathode of lithium of activity can be migrated so as to cause the destruction of electrode slice, causes lithium sulphur electric
Tankage is decayed, and reduces its cycle performance.Further, since to add in some such as conductive agents during prepared by positive plate
Meets the needs of electrode slice with the non-active material of binding agent, these inert matters are largely that can occupy part body
Product and weight, so as to limit the specific capacity of lithium-sulfur cell.Therefore, inhibit dissolving and the migration problem of intermediate product, be to improve lithium
The key of the cycle performance of sulphur battery, meanwhile, it is also the weight for improving lithium-sulfur cell performance using suitable additive and collector
Want mode.
Construct conductive network frame, optimization battery structure design is the relatively effective method that solves the above problems.Application is public
The Chinese invention patent (data of publication of application is on 2 26th, 2014) that cloth number is CN103606646A discloses a kind of lithium-sulfur cell
Nickel sulphur anode and preparation method thereof, specifically disclose by anode of the nickel foam as mesh skeleton mechanism, under 0.2C multiplying powers,
Specific capacity reaches 1385mAh/g for the first time, and 1146mAh/g is still maintained after 10 Xun Huans.But the program is not improved lithium sulphur electricity
The stable circulation performance in pond.In addition, nickel foam density is relatively high, specific discharge capacity can be lost.Application publication number is
The Chinese invention patent (data of publication of application is on April 2nd, 2014) of CN103700818A discloses a kind of porous carbon of N doping
Carbon sulphur composite material of the netted structure of nanofiber and its preparation method and application, and specifically disclose being received by porous for its preparation
Rice carbon fiber net structure anode, specific capacity can reach 800mAh/g after the material 40 cycles.But the material makes work
Skill is complicated, and cost is higher, is unfavorable for large-scale production.The Chinese invention patent that for another example application publication number is CN103840167A is public
A kind of selenium based on graphene sponge/sulphur carbon electrode and preparation method and application has been opened, and has specifically disclosed a kind of graphene
Sponge electrode, the flexible electrode show more outstanding stable circulation performance, but because of its traditional two-dimensional structure, still not
Can solve the problems, such as that load sulfur content is low etc..It is higher to equipment requirement in addition, above method building-up process is more complicated, cause experiment into
This is higher.
The Chinese invention patent (data of publication of application is on July 8th, 2015) that application publication number is CN104766943A is open
A kind of preparation method and application of the lithium sulphur battery electrode of high-energy density, and specifically disclose a kind of three-dimensional conductive carbon fiber
Network is raw material by absorbent cotton, makes its carbonization, crystallization in 800-1200 DEG C of high-temperature process, obtains carbon fiber network structure.
But the rejection ability that the material dissolves polysulfide is poor, the cycle performance for the lithium-sulfur cell prepared is poor, Er Qie
It also needs to additionally incorporate conductive agent when preparing electrode, reduces the energy density of battery.
Organic foam material such as polyurethane foam etc. is largely used in the modern life, especially as packaging material, thermal insulating material
Material etc. is directly abandoned usually using rear, causes environmental pollution.But it there are no document or patent report utilize organic foam material material
Expect that polyurethane foam carbonization prepares three-dimensional carbon material as lithium-sulfur cell collector.
The content of the invention
It is an object of the invention to provide a kind of polysulfides that can inhibit to dissolve and can improve lithium-sulfur cell cycle performance
The preparation method of lithium-sulfur cell three-dimensional carbon collector.The present invention also aims to provide lithium sulphur electricity made from above-mentioned preparation method
Application of the pond three-dimensional carbon collector in lithium-sulfur cell.
In order to achieve the goal above, the technical solution of the preparation method of the lithium-sulfur cell three-dimensional carbon collector of the present invention is such as
Under：
A kind of preparation method of lithium-sulfur cell three-dimensional carbon collector, includes the following steps：By organic foam material with organic
Solvent soaking, it is washed, after dry, under inert gas shielding, it is warming up to 700-900 DEG C of heat preservation 2-6h and carries out high-temperature process,
To obtain the final product；The organic foam material is any one in polyurethane foam, melamine foamed plastic.
The preparation method of the lithium-sulfur cell three-dimensional carbon collector of the present invention is carbonized system at high temperature using organic foam material
Collector is obtained, has both the performance of conductive agent and adsorbent, the face that three-dimensional structure can improve collector carries sulfur content, and has
Certain elasticity in addition larger accommodation space, can offset the volume expansion of sulphur in charge and discharge process.Effectively inhibit more sulphur
Compound so as to play the role of effectively consolidating sulphur, improves the cyclical stability of lithium-sulfur cell in the migration of electrolyte.This method is grasped
Make simplicity, raw material sources are extensive and cost is relatively low, environmentally friendly, are suitable for large-scale production.
Organic foam material is to remove the impurity in organic foam material, organic solvent with the purpose that organic solvent impregnates
Ratio with organic foam material is so as to fully subject to cleaning organic foam material.
The organic solvent is any one in ethyl alcohol, ethylene glycol, isopropanol, acetone.
The time of the immersion is 2-6h.
The compression ratio of the organic foam material is 40-95%.
The drying is to be dried in vacuo 8-12h at 60-120 DEG C.
The inert gas is N2Gas or Ar gas.
With supersound process 0.5h after the immersion.The washing is distillation water washing 2-3 times.The heating rate of the heating
For 0.5 DEG C/min.
It is cut after the heat preservation.The size of cutting is determined according to specific battery specifications, such as collector is cut
For a diameter of 12-16mm, thickness 0.5-5.0mm.
The technical solution of application of the lithium-sulfur cell three-dimensional carbon collector of the present invention in lithium-sulfur cell is as follows：
Application of the lithium-sulfur cell three-dimensional carbon collector in lithium-sulfur cell made from above-mentioned preparation method.
The lithium-sulfur cell includes anode, cathode, electrolyte, and the anode includes lithium-sulfur cell three-dimensional carbon collector and bears
The positive active material being loaded on lithium-sulfur cell three-dimensional carbon collector, the positive active material is simple substance sulfur materials, carbon sulphur is answered
Any one in condensation material, metal sulfide material.
The sulphur is sublimed sulfur.
The carbon sulphur composite material is carbon nanotubes and sulphur composite material, hollow carbon and sulphur composite material, mesoporous carbon and sulphur
Composite material, activated carbon and sulphur composite material, graphite and sulphur composite material, graphene and sulphur composite material, carbide-derived carbon
It is answered with any one in sulphur composite material or the carbon nanotubes after acidifying with the hollow carbon after sulphur composite material, acidifying and sulphur
Mesoporous carbon and the activated carbon after sulphur composite material, acidifying and the graphite and sulphur after sulphur composite material, acidifying after condensation material, acidifying
After the acidifying after graphene and sulphur composite material, acidifying after composite material, acidifying in carbide-derived carbon and sulphur composite material
One or more.
Acid used in the acidifying is one or more of customary acids such as hydrochloric acid, sulfuric acid, nitric acid.
The carbon sulphur composite material is made with the following method：Mechanical attrition method, gas-protecting sintering method, solution chemistry are sunk
Area method or physical mixed combination low temperature liquid phase dipping method.Preferably physical mixed combination low temperature liquid phase dipping method, it is specific to walk
Suddenly it is：By carbon source and sulphur according to mass ratio 1:The mass ratio of 0.67-3 is uniformly mixed, in a nitrogen atmosphere, 155 DEG C of heat preservation 10h,
Raise the temperature to again 300 DEG C heat preservation 2h to get；The carbon source for carbon nanotubes, hollow carbon, mesoporous carbon, activated carbon, graphite,
The carbon nanotubes after any one or acidifying in graphene, carbide-derived carbon, the hollow carbon after acidifying, Jie after acidifying
The graphite after activated carbon, acidifying after hole carbon, acidifying, the graphene after acidifying, one kind in the carbide-derived carbon after acidifying
It is or a variety of.Acid used in the acidifying is one or more of customary acids such as hydrochloric acid, sulfuric acid, nitric acid.
The carbon source is ground after being mixed with sulphur, milling time 0.5-4h.
The carbon source is hollow carbon, and the hollow carbon is made with the following method：By glucose and lauryl sodium sulfate
According to mass ratio 30-60:1 mixing, adds water that solution is made, 16-24h is reacted at 160 DEG C, washs, and centrifuges, obtains hollow carbon
Presoma, by hollow carbon matrix precursor under nitrogen protection, 500-1000 DEG C calcining 1-6h to get.The reaction is in polytetrafluoro
It is carried out in ethylene liner reaction kettle.
The carbon source is mesoporous carbon, and the mesoporous carbon is made with the following method：By citric acid and ferric nitrate with molar ratio
1-4:1 is uniformly mixed in ethylene glycol, and 120 DEG C of dry 12-24h, obtain meso-porous carbon material presoma, will be situated between in air dry oven
Hole carbon matrix precursor under protection of argon gas, 500-1000 DEG C calcining 1-6h to get.
Above-mentioned lithium-sulphur cell positive electrode is made using the preparation method included the following steps：
1) positive active material is added in dispersant, uniformly dispersed, positive active material dispersion liquid or dispersion pulp is made
Material；
2) by the positive active material dispersed paste directly coated on obtained on the lithium-sulfur cell three-dimensional carbon collector
Carrier sheet；Or lithium-sulfur cell three-dimensional carbon collector in the positive active material dispersion liquid is impregnated, carrier sheet is made；Or
The positive active material dispersed paste is added dropwise on lithium-sulfur cell three-dimensional carbon collector and carries out vacuum or normal pressure suction filtration by person, is made
Carrier sheet；
3) by carrier sheet made from step 2) is dry, tabletting to get.
The preparation method of the lithium-sulphur cell positive electrode can improve the load sulfur content in collector, wherein, the immersion in step 2)
Mode, which is suitable for positive active material dispersion liquid is made, to be prepared, can be by controlling the concentration of dispersion liquid and impregnating number
Specific load sulfur content is controlled with the time；Direct coating method and the mode filtered are suitable for positive active material slurry is made
It prepares, direct coating method can control specific load sulfur content by controlling coating number and the time every time coated, make
With the mode that vacuum or normal pressure filter active material can be made to permeate in entire collector by the pressure difference of collector upper and lower surface.
After positive active material is added in dispersant in step 1), it is not added with conduction for bright sulfur as a positive electrode active material
Agent and binding agent；For sulphur carbon composite as a positive electrode active material, conductive agent and binding agent are added in.
Described filter uses Buchner funnel.
In the step 1) dispersant amount so as to by positive active material it is fully dispersed subject to, and be conducive to subsequent
It impregnates and either coats or filter.The dispersant is any one in carbon disulfide, toluene, NMP, isopropanol；It is described to lead
Electric agent is any one in conductive black, Ketjen black；Binding agent is Kynoar (PVDF), sodium alginate, carboxymethyl are fine
Tie up any one in plain (CMC), beta-cyclodextrin.
Uniformly dispersing in the step 1) is carried out by stirring or sonic oscillation.
The mode filtered in the step 2), which can be taken, is placed on lithium-sulfur cell three-dimensional carbon collector in Buchner funnel, to cloth
The lower end nozzle of family name's funnel is evacuated.
Soaking time is 5-30min in the step 2).
Dry in the step 3) is to be dried in vacuo 10-12h at 60-80 DEG C.
The pressure of tabletting is 0.5-1MPa in the step 3).
The electrolyte includes electrolyte and solvent, and the electrolyte is lithium perchlorate (LiClO4), lithium hexafluoro phosphate
(LiPF6), LiBF4 (LIBF4), one or more of double trifluoromethanesulfonimide lithiums (LiTFSI).The solvent
For one kind in ethylene carbonate (EC), dimethyl carbonate (DMC), 1,3- dioxolanes (DOL), glycol dimethyl ether (DME)
It is or several.
Collector at identical conditions, is made made from the preparation method of the lithium-sulfur cell three-dimensional carbon collector of the present invention
Lithium-sulfur cell cyclical stability it is better as the battery of collector than traditional aluminium foil, charging and discharging currents density 837.5mAh/g,
First discharge specific capacity is more than 1000mAh/g, and after 100 times cycle, specific discharge capacity remains at more than 800mAh/g, and highest can
Up to 920mAh/g, and this method is easy to operate, and cost is relatively low, is suitable for large-scale production, the extensive life to lithium-sulfur cell
Production is of great significance.
Description of the drawings
Fig. 1 is the structure diagram of the lithium-sulfur cell of embodiment 1；
Fig. 2 is the cycle performance curve of the lithium-sulfur cell of embodiment 1 and comparative example 1；
Fig. 3 is the cycle performance curve of the lithium-sulfur cell of embodiment 2 and comparative example 2；
Fig. 4 is the cycle performance curve of the lithium-sulfur cell of embodiment 4 and comparative example 2；
Fig. 5 is the cycle performance curve of the lithium-sulfur cell of embodiment 5 and comparative example 3；
Fig. 6 is the cycle performance curve of the lithium-sulfur cell of embodiment 6 and comparative example 4.
Specific embodiment
Technical scheme is further detailed with reference to specific embodiment.
Reagent used is ommercially available AR in embodiments below.
Embodiment 1
The preparation method of the lithium-sulfur cell three-dimensional carbon collector of the present embodiment, including step：By the poly- ammonia of organic foam material
Ester foamed material impregnates 6h with organic solvent ethylene glycol, is then ultrasonically treated 0.5h, is washed with distilled water 3 times, is placed on vacuum
In drying box, carbon matrix precursor is made in 60 DEG C of dry 12h.By carbon matrix precursor under nitrogen atmosphere protection, with the heating of 5 DEG C/min
Speed is warming up to 800 DEG C, keeps the temperature 2h, cooled to room temperature, is cut to slitter suitably sized after taking-up, is had
The lithium-sulfur cell three-dimensional carbon collector of elasticity.The compression ratio of above-mentioned polyurethane foamed material is 60%.
The lithium-sulfur cell three-dimensional carbon collector of the present embodiment is lithium-sulfur cell three-dimensional carbon collector made from the above method.
The lithium-sulphur cell positive electrode of the present embodiment includes above-mentioned lithium-sulfur cell three-dimensional carbon collector and is supported on the lithium-sulfur cell
Positive active material on three-dimensional carbon collector, positive active material are carbon nanotubes and sulphur composite material, collector and activity
The mass ratio of substance is 1:0.4.
The carbon nanotubes is made with the following method with sulphur composite material：By sublimed sulfur and carbon nanotubes according to mass ratio
1:1.5 mixing, grind 1h, and in a nitrogen atmosphere, 155 DEG C of heat preservation 10h are cooled to room temperature to obtain the final product.
The preparation method of the lithium-sulphur cell positive electrode of the present embodiment includes the following steps：
1) by carbon and sulphur composite material, SP and PVDF according to 7:2:1 mass ratio adds in n-methyl-2-pyrrolidone
(NMP) in, 1h is ground, obtains dispersed paste；
2) dispersed paste made from step 1) is coated uniformly on above-mentioned lithium-sulfur cell three-dimensional collector, obtains carrier sheet；
3) carrier sheet that step 2) obtains is dried in vacuo 10h at 60 DEG C, with the pressure tabletting of 1MPa to get the sulphur
Anode.
The lithium-sulfur cell of the present embodiment includes anode, cathode, membrane, electrolyte, shell, and shell includes anode cover and cathode
Shell, cathode are lithium metal, and electrolyte is the solution for double (fluoroform sulphonyl) imine lithium LiTFSI that concentration is 1mol/L, solvent
It is dioxolane DOL and glycol dimethyl ether DME according to 1：The mixed solvent that 2 volume ratio is formulated, membrane are
Celgard2400 films.
Electro-chemical test carries out button cell manufactured in the present embodiment using simulated battery, battery is assembled in water oxygen point
Pressure is below carrying out in the environment of 0.1ppm：By anode, cathode, membrane, electrolyte, shell according to the prior art in glove box
In method assembling be made button cell, stand 2h to get as shown in Figure 1.
Electrochemical property test is carried out to battery using land test systems (Wuhan land Electronics Co., Ltd.s).Voltage model
Enclose 1.8-3.0V, charging and discharging currents density 837.5mAh/g.After optimization, battery first discharge specific capacity reaches 1175mAh/
G, after 100 times cycle, specific capacity can be maintained at 920mAh/g, and comparative example is for the first time 1356mAh/g, is protected after 100 cycles
625mAh/g is stayed, circulation volume is as shown in Figure 2.
Embodiment 2
The preparation method of the lithium-sulfur cell three-dimensional carbon collector of the present embodiment, including step：By the poly- ammonia of organic foam material
Ester foam impregnates 3h with organic solvent-acetone, is then ultrasonically treated 0.5h, is washed with distilled water 3 times, is placed on vacuum drying chamber
In, carbon matrix precursor is made in 120 DEG C of dry 8h.By carbon matrix precursor under nitrogen atmosphere protection, with the heating rate liter of 5 DEG C/min
Temperature keeps the temperature 4h to 900 DEG C, cooled to room temperature, is cut to slitter suitably sized after taking-up, obtains flexible
Lithium-sulfur cell three-dimensional carbon collector.The compression ratio of above-mentioned polyurethane foamed material is 90%.
The lithium-sulfur cell three-dimensional carbon collector of the present embodiment is lithium-sulfur cell three-dimensional carbon collector made from the above method.
The lithium-sulphur cell positive electrode of the present embodiment includes above-mentioned lithium-sulfur cell three-dimensional carbon collector and is supported on the lithium-sulfur cell
Positive active material on three-dimensional carbon collector, positive active material are bright sulfur material.In the embodiment, collector and active matter
The mass ratio of matter is 1:1.1.
The preparation method of the lithium-sulphur cell positive electrode of the present embodiment includes the following steps：
1) simple substance sulfur materials are added in toluene, is ultrasonically treated 0.5h, obtains dispersion liquid；
2) above-mentioned lithium-sulfur cell three-dimensional collector is immersed in dispersion liquid made from step 1), it is 2 times to impregnate number, often
The time of secondary immersion is 5min, takes out to obtain carrier sheet；
3) carrier sheet that step 2) obtains is dried in vacuo 11h at 70 DEG C, with the pressure tabletting of 1MPa to get the sulphur
Anode.
The lithium-sulfur cell of the present embodiment includes anode, cathode, membrane, electrolyte, shell, wherein just extremely above-mentioned lithium sulphur electricity
Pond anode, cathode are lithium metal, and electrolyte is the solution for double (fluoroform sulphonyl) imine lithium LiTFSI that concentration is 1mol/L,
Solvent is dioxolane DOL and glycol dimethyl ether DME according to 1：The mixed solvent that 2 volume ratio is formulated, membrane are
Celgard2400 films.
Electro-chemical test carries out button cell manufactured in the present embodiment using simulated battery, battery is assembled in water oxygen point
Pressure is below carrying out in the environment of 0.1ppm：By anode, cathode, membrane, electrolyte, shell according to the prior art in glove box
In method assembling be made button cell, stand 2h to get.
Electrochemical property test is carried out to battery using land test systems (Wuhan land Electronics Co., Ltd.s).Voltage model
Enclose 1.8-3.0V, charging and discharging currents density 167.5mAh/g.After optimization, battery first discharge specific capacity reaches 1125mAh/
G, after 100 times cycle, specific capacity 813mAh/g, comparative example is for the first time 1185mAh/g, retains 309mAh/ after 100 cycles
G, circulation volume are as shown in Figure 3.
Embodiment 3
The preparation method of the lithium-sulfur cell three-dimensional carbon collector of the present embodiment, including step：By organic foam material trimerization
Cyanamide foam impregnates 6h with organic solvent ethylene glycol, is then ultrasonically treated 0.5h, is washed with distilled water 3 times, is placed on vacuum and does
In dry case, carbon matrix precursor is made in 60 DEG C of dry 12h.By carbon matrix precursor under nitrogen atmosphere protection, with the heating speed of 5 DEG C/min
Degree is warming up to 800 DEG C, keeps the temperature 2h, cooled to room temperature, is cut to slitter suitably sized after taking-up, obtains with bullet
The lithium-sulfur cell three-dimensional carbon collector of property.The compression ratio of above-mentioned melamine foam material is 90%.
The lithium-sulfur cell three-dimensional carbon collector of the present embodiment is lithium-sulfur cell three-dimensional carbon collector made from the above method.
The lithium-sulphur cell positive electrode of the present embodiment includes above-mentioned lithium-sulfur cell three-dimensional carbon collector and is supported on the lithium-sulfur cell
Positive active material on three-dimensional carbon collector, positive active material are commercialization Li2S4Material.In the embodiment, collector with
The mass ratio of active material is 1:0.8.
The preparation method of the lithium-sulphur cell positive electrode of the present embodiment includes the following steps：
1) Li will be commercialized2S4, conductive black and PVDF are 7 according to mass ratio:2:1 adds in n-methyl-2-pyrrolidone
(NMP) in, 1h is ground, obtains dispersed paste；
2) dispersed paste made from step 1) is coated uniformly on above-mentioned lithium-sulfur cell three-dimensional collector, obtains carrier sheet；
3) carrier sheet that step 2) obtains is dried in vacuo 10h at 60 DEG C, with the pressure tabletting of 1MPa to get the sulphur
Anode.
The lithium-sulfur cell of the present embodiment includes anode, cathode, membrane, electrolyte, shell, wherein just extremely above-mentioned lithium sulphur electricity
Pond anode, cathode are lithium metal, and electrolyte is the lithium tetrafluoroborate solution that concentration is 1mol/L, and solvent is methyl ethyl carbonate
(EMC), ethylene carbonate (EC), glycol dimethyl ether (DME) are according to volume ratio 1:1:1 mixed solvent being formulated, membrane
For GRE-20T membranes.
Electro-chemical test carries out button cell manufactured in the present embodiment using simulated battery, battery is assembled in water oxygen point
Pressure is below carrying out in the environment of 0.1ppm：By anode, cathode, membrane, electrolyte, shell according to the prior art in glove box
In method assembling be made button cell, stand 2h to get.
Electrochemical property test is carried out to battery using land test systems (Wuhan land Electronics Co., Ltd.s).Voltage model
Enclose 1.8-3.0V, charging and discharging currents density 167.5mAh/g.After optimization, battery first discharge specific capacity reaches 925mAh/
G, through overactivation, after 100 times cycle, specific capacity can be maintained at 730mAh/g, and comparative example is for the first time 844mAh/g, 100 times
Retain 629mAh/g after cycling, circulation volume is as shown in Figure 4.
Embodiment 4
The preparation method of the lithium-sulfur cell three-dimensional carbon collector of the present embodiment, including step：By the poly- ammonia of organic foam material
Ester foam impregnates 6h with organic solvent ethylene glycol, is then ultrasonically treated 0.5h, is washed with distilled water 3 times, is placed on vacuum drying
In case, carbon matrix precursor is made in 60 DEG C of dry 12h.By carbon matrix precursor under nitrogen atmosphere protection, with the heating rate of 5 DEG C/min
It is warming up to 800 DEG C, keeps the temperature 2h, cooled to room temperature is cut to slitter suitably sized after taking-up, obtain having elasticity
Lithium-sulfur cell three-dimensional carbon collector.
The lithium-sulfur cell three-dimensional carbon collector of the present embodiment is lithium-sulfur cell three-dimensional carbon collector made from the above method.
The lithium-sulphur cell positive electrode of the present embodiment includes above-mentioned lithium-sulfur cell three-dimensional carbon collector and is supported on the lithium-sulfur cell
Positive active material on three-dimensional carbon collector, positive active material are hollow carbon and sulphur composite material.In the embodiment, afflux
The mass ratio of body and active material is 1:0.5.
The hollow carbon sphere is made with the following method with sulphur composite material：By glucose and lauryl sodium sulfate
(SDS) according to 45:1 mass ratio mixing, adds deionized water wiring solution-forming, it is anti-to be transferred to polytetrafluoroethyllining lining after stirring evenly
It answers in kettle, reacts for 24 hours, be cooled to room temperature at 160 DEG C, the centrifugal treating after deionized water, ethyl alcohol washing, obtains hollow carbon successively
Ball presoma, by hollow carbon sphere presoma in a nitrogen atmosphere, 800 DEG C calcining 2h after obtain hollow carbon sphere, by hollow carbon sphere with
Sublimed sulfur is according to 1:1.5 mass ratio uniformly after mixing, 12h is kept the temperature at 155 DEG C, temperature then is risen to 300 DEG C of heat preservations
Up to hollow carbon sphere and sulphur composite material after 2h.
The preparation method of the lithium-sulphur cell positive electrode of the present embodiment includes the following steps：
1) using deionized water as solvent, isopropanol is dispersant, and the two is mixed and made into mixed solvent, by hollow carbon sphere and sulphur
Composite material, SP and sodium alginate are according to mass ratio 7:2:1 adds in the mixed solvent, grinds 1h, obtains dispersed paste；
2) dispersed paste made from step 1) is coated uniformly on above-mentioned lithium-sulfur cell three-dimensional collector, obtains carrier sheet；
3) carrier sheet that step 2) obtains is dried in vacuo 10h at 60 DEG C, with the pressure tabletting of 1MPa to get the sulphur
Anode.
The lithium-sulfur cell of the present embodiment includes anode, cathode, membrane, electrolyte, shell, wherein just extremely above-mentioned lithium sulphur electricity
Pond anode, cathode are Li pieces, and electrolyte is the LiTFSI solution that concentration is 1mol/L, and solvent is dioxolane DOL and ethylene glycol
Dimethyl ether DME is according to 1：The mixed solvent that 2 volume ratio is formulated, the also LiNO containing 0.1mol/L in electrolyte3Addition
Agent, membrane are GRE-20T membranes.
Electro-chemical test carries out button cell manufactured in the present embodiment using simulated battery, battery is assembled in water oxygen point
Pressure is below carrying out in the environment of 0.1ppm：By anode, cathode, membrane, electrolyte, shell according to the prior art in glove box
In method assembling be made button cell, stand 2h to get.
Electrochemical property test is carried out to battery using land test systems (Wuhan land Electronics Co., Ltd.s).Voltage model
Enclose 1.8-3.0V, charging and discharging currents density 837.5mAh/g.After optimization, battery first discharge specific capacity reaches 1602mAh/
G, after 100 times cycle, specific capacity can be maintained at 802mAh/g, and comparative example is for the first time 1610mAh/g, is protected after 100 cycles
588mAh/g is stayed, circulation volume is as shown in Figure 5.
Embodiment 5
The preparation method of the lithium-sulfur cell three-dimensional carbon collector of the present embodiment, including step：By the poly- ammonia of organic foam material
Ester foam impregnates 6h with organic solvent ethylene glycol, is then ultrasonically treated 0.5h, is washed with distilled water 3 times, is placed on vacuum drying
In case, carbon matrix precursor is made in 60 DEG C of dry 12h.By carbon matrix precursor under nitrogen atmosphere protection, with the heating rate of 5 DEG C/min
It is warming up to 800 DEG C, keeps the temperature 2h, cooled to room temperature is cut to slitter suitably sized after taking-up, obtain having elasticity
Lithium-sulfur cell three-dimensional carbon collector.
The lithium-sulfur cell three-dimensional carbon collector of the present embodiment is lithium-sulfur cell three-dimensional carbon collector made from the above method.
The lithium-sulphur cell positive electrode of the present embodiment includes above-mentioned lithium-sulfur cell three-dimensional carbon collector and is supported on the lithium-sulfur cell
Positive active material on three-dimensional carbon collector, positive active material are mesoporous carbon and sulphur composite material.In the embodiment, afflux
The mass ratio of body and active material is 1:0.5.
The mesoporous carbon is made with the following method with sulphur composite material：Using citric acid as carbon source, ferric nitrate is crosslinking agent,
By the two according to 2:1 mixed in molar ratio is ultrasonically treated 0.5h, is placed in 120 DEG C of air dry oven dry 12h, obtains mesoporous
Carbon matrix precursor；By mesoporous carbon matrix precursor under argon gas atmosphere protection, 800 DEG C of carbonization 2h obtain meso-porous carbon material；By mesoporous carbon materials
Material is with sublimed sulfur according to mass ratio 1:2 mixing, grind 1h, 12h are kept the temperature at 155 DEG C, then heat to 300 DEG C, keep the temperature 2h, i.e.,
Obtain mesoporous carbon and sulphur composite material.
The preparation method of the lithium-sulphur cell positive electrode of the present embodiment includes the following steps：
1) using NMP as dispersant, by mesoporous carbon and sulphur composite material, SP and PVDF according to mass ratio 7:2:1 adds in mixing
In solvent, 1h is ground, obtains dispersed paste；
2) above-mentioned lithium-sulfur cell three-dimensional carbon collector is placed in Buchner funnel, Buchner funnel lower end side port is connected and is taken out
Device of air opens air extractor and dispersed paste made from step 1) is added dropwise on lithium-sulfur cell three-dimensional carbon collector, obtains negative
Slide glass；
3) carrier sheet that step 2) obtains is dried in vacuo 10h at 60 DEG C, with the pressure tabletting of 1MPa to get the sulphur
Anode.
The lithium-sulfur cell of the present embodiment includes anode, cathode, membrane, electrolyte, shell, wherein just extremely above-mentioned lithium sulphur electricity
Pond anode, cathode are lithium metal, and electrolyte is the LiClO that concentration is 1mol/L4Solution, solvent is dimethyl carbonate (DMC), carbon
Vinyl acetate (EC) is according to volume ratio 1:1 mixed solvent being formulated, membrane are PE monofilms.
Electro-chemical test carries out button cell manufactured in the present embodiment using simulated battery, battery is assembled in water oxygen point
Pressure is below carrying out in the environment of 0.1ppm：By anode, cathode, membrane, electrolyte, shell according to the prior art in glove box
In method assembling be made button cell, stand 2h to get.
Electrochemical property test is carried out to battery using land test systems (Wuhan land Electronics Co., Ltd.s).Voltage model
Enclose 1.8-3.0V, charging and discharging currents density 837.5mAh/g.After optimization, battery first discharge specific capacity reaches 1321mAh/
G, after 50 times cycle, specific capacity can be maintained at 920mAh/g, and comparative example is for the first time 902mAh/g, is retained after 50 cycles
597mAh/g, circulation volume are as shown in Figure 6.
Comparative example 1
Collector in this comparative example uses aluminium foil of the prior art.
The lithium-sulphur cell positive electrode of this comparative example is prepared with the following method：Carbon nanotubes in embodiment 1 and sulphur is compound
Material is with conductive black (SP), binding agent Kynoar (PVDF) according to mass ratio 7:2:1 adds in NMP, is uniformly mixed system
Into dispersed paste, coated on aluminium foil, dry, tabletting is to get lithium-sulphur cell positive electrode.
The lithium-sulfur cell of this comparative example is prepared with the following method：In glove box by anode, cathode, membrane, electrolyte,
Shell is assembled into button cell according to method of the prior art, stand 2h to get.Wherein, cathode, electrolyte, membrane, shell
It is identical in embodiment 1.
Comparative example 2
Collector in this comparative example uses aluminium foil of the prior art.
The lithium-sulphur cell positive electrode of this comparative example is prepared with the following method：By the elemental sulfur in embodiment 2 and conductive agent charcoal
Black (SP), binding agent Kynoar (PVDF) in mass ratio 7：2：1 mixing, with -2 pyrrolidones of N- methyl (NMP) for solvent,
It is uniformly mixed and slurry is made, coated in current collector aluminum foil, then when 60 DEG C of vacuum drying 6 are small, tabletting is to get lithium-sulfur cell
Anode.
The lithium-sulfur cell of this comparative example is prepared with the following method：In glove box by anode, cathode, membrane, electrolyte,
Shell is assembled into button cell according to method of the prior art, stand 2h to get.Wherein, cathode, electrolyte, membrane, shell
It is identical in embodiment 2.
Comparative example 3
Collector in this comparative example uses aluminium foil of the prior art.
The lithium-sulphur cell positive electrode of this comparative example is prepared with the following method：By the commercialization Li in embodiment 32S4With conduction
Carbon black (SP), binding agent Kynoar (PVDF) are according to mass ratio 7:2:1 adds in NMP, is uniformly mixed and dispersed paste is made,
Coated on aluminium foil, dry, tabletting is to get lithium-sulphur cell positive electrode.
The lithium-sulfur cell of this comparative example is prepared with the following method：In glove box by anode, cathode, membrane, electrolyte,
Shell is assembled into button cell according to method of the prior art, stand 2h to get.Wherein, cathode, electrolyte, membrane, shell
It is identical in embodiment 3.
Comparative example 4
Collector in this comparative example uses aluminium foil of the prior art.
The lithium-sulphur cell positive electrode of this comparative example is prepared with the following method：Hollow carbon sphere in embodiment 4 and sulphur is compound
Material is with conductive black (SP), sodium alginate according to mass ratio 7:2:1 adds in deionized water, is uniformly mixed and dispersion pulp is made
Material, coated on aluminium foil, dry, tabletting is to get lithium-sulphur cell positive electrode.
The lithium-sulfur cell of this comparative example is prepared with the following method：In glove box by anode, cathode, membrane, electrolyte,
Shell is assembled into button cell according to method of the prior art, stand 2h to get.Wherein, cathode, electrolyte, membrane, shell
It is identical in embodiment 4.
Comparative example 5
Collector in this comparative example uses aluminium foil of the prior art.
The lithium-sulphur cell positive electrode of this comparative example is prepared with the following method：By the mesoporous carbon in embodiment 5 and sulphur composite wood
Material is with conductive black (SP), binding agent Kynoar (PVDF) according to mass ratio 7:2:1 adds in NMP, is uniformly mixed and is made
Dispersed paste, coated on aluminium foil, dry, tabletting is to get lithium-sulphur cell positive electrode.
The lithium-sulfur cell of this comparative example is prepared with the following method：In glove box by anode, cathode, membrane, electrolyte,
Shell is assembled into button cell according to method of the prior art, stand 2h to get.Wherein, cathode, electrolyte, membrane, shell
It is identical in embodiment 5.
Experimental example
Lithium-sulfur cell in embodiment 1-5 and comparative example 1-5 is surveyed in LADN test systems according to following condition
Examination：
Charging or discharging current density corresponds to the test charging or discharging current density in embodiment 1-5 respectively, except 3 charge and discharge of embodiment end
Voltage is outside 1.5-2.5, other embodiment charge and discharge blanking voltage is 1.8-3.0V (vs.Li/Li+), test result is respectively such as
Shown in Fig. 2-6.
The lithium-sulfur cell of wherein embodiment 1-5 is respectively labeled as ECF-CNT/S, ECF-S, ECF-Li2S4、ECF-CS/S、
ECF-MS/S, the lithium-sulfur cell of comparative example 1-5 are respectively labeled as Al-CNT/S, Al-S, Al-Li2S4、Al-CS/S、Al-MS/S。
From Fig. 2-6, lithium-sulfur cell that technical solution using the present invention obtains, specific capacity, cyclical stability have
It increases substantially.More sulphur in charge and discharge process can effectively be inhibited by illustrating the lithium-sulfur cell three-dimensional carbon current collector material of the present invention
The dissolving of compound in the electrolytic solution reduces corrosion of the polysulfide to lithium anode, steady so as to improve the cycling of lithium-sulfur cell
It is qualitative, to realizing that lithium-sulfur cell industrialized production is significant.
Claims (8)
1. a kind of preparation method of lithium-sulfur cell three-dimensional carbon collector, which is characterized in that including：By organic foam material with organic
Solvent soaking, after washed, dry, under inert gas shielding, kept the temperature at 700-900 DEG C 2-6h carry out high-temperature process to get；
The organic foam material is any one in polyurethane foam, melamine foamed plastic；The organic solvent is ethyl alcohol, second two
Any one in alcohol, isopropanol, acetone；The time of the immersion is 2-6h；
The compression ratio of the organic foam material is 40-95%.
2. the preparation method of lithium-sulfur cell three-dimensional carbon collector as described in claim 1, which is characterized in that the drying is
8-12h is dried in vacuo at 60-120 DEG C.
3. application of a kind of lithium-sulfur cell three-dimensional carbon collector in lithium-sulfur cell, which is characterized in that the lithium-sulfur cell is three-dimensional
Carbon collector is made by preparation method as described in claim 1.
4. application of the lithium-sulfur cell three-dimensional carbon collector as claimed in claim 3 in lithium-sulfur cell, which is characterized in that described
Lithium-sulfur cell includes anode, cathode, electrolyte, and the anode includes lithium-sulfur cell three-dimensional carbon collector and is supported on lithium-sulfur cell
Positive active material on three-dimensional carbon collector, the positive active material is simple substance sulfur materials, carbon sulphur composite material, metal sulphur
Any one in compound material.
5. application of the lithium-sulfur cell three-dimensional carbon collector as claimed in claim 4 in lithium-sulfur cell, which is characterized in that described
Carbon sulphur composite material is carbon nanotubes and sulphur composite material, hollow carbon and sulphur composite material, mesoporous carbon and sulphur composite material, activity
In charcoal and sulphur composite material, graphite and sulphur composite material, graphene and sulphur composite material, carbide-derived carbon and sulphur composite material
Any one or acidifying after carbon nanotubes and the hollow carbon after sulphur composite material, acidifying with after sulphur composite material, acidifying
Activated carbon after mesoporous carbon and sulphur composite material, acidifying and the graphite after sulphur composite material, acidifying and sulphur composite material, after being acidified
Graphene and sulphur composite material, one or more of the carbide-derived carbon after acidifying and sulphur composite material.
6. application of the lithium-sulfur cell three-dimensional carbon collector as claimed in claim 4 in lithium-sulfur cell, which is characterized in that described
Anode is made using the preparation method included the following steps：
1）Positive active material is added in dispersant, is uniformly dispersed, positive active material dispersion liquid or dispersed paste is made；
2）By the positive active material dispersed paste coated on obtained carrier sheet on the lithium-sulfur cell three-dimensional carbon collector；Or
Person impregnates lithium-sulfur cell three-dimensional carbon collector in the positive active material dispersion liquid is made carrier sheet；Or to lithium sulphur electricity
One surface of pond three-dimensional carbon collector is filtered, another surface dropwise addition to lithium-sulfur cell three-dimensional carbon collector is described just
Carrier sheet is made in pole active material dispersed paste；
3）By step 2）Carrier sheet obtained is dry, tabletting to get.
7. application of the lithium-sulfur cell three-dimensional carbon collector as claimed in claim 6 in lithium-sulfur cell, which is characterized in that described
Dispersant is any one in carbon disulfide, toluene, NMP, isopropanol；The positive active material is sulphur carbon composite,
Step 1）After middle positive active material is added in dispersant, conductive agent and binding agent are added in；The conductive agent is conductive black, section
Any one during qin is black；Binding agent is any one in Kynoar, sodium alginate, carboxymethyl cellulose.
8. application of the lithium-sulfur cell three-dimensional carbon collector as claimed in claim 4 in lithium-sulfur cell, which is characterized in that described
Electrolyte includes electrolyte and solvent, and the electrolyte is lithium perchlorate, lithium hexafluoro phosphate, LiBF4, double fluoroforms
One or more of sulfimide lithium, the solvent is ethylene carbonate, dimethyl carbonate, 1,3-dioxolane, ethylene glycol
One or more of dimethyl ether.
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| CN105826540B (en) * | 2016-06-03 | 2018-10-02 | 合肥工业大学 | A kind of lithium-sulfur cell composite positive pole and the preparation method and application thereof |
| CN106450191A (en) * | 2016-10-11 | 2017-02-22 | 天津工业大学 | Positive electrode material of lithium-sulfur battery |
| CN106848250B (en) * | 2017-03-15 | 2020-05-22 | 清华大学深圳国际研究生院 | Carbon-sulfur material with high sulfur content and preparation method thereof |
| CN106972156A (en) * | 2017-03-22 | 2017-07-21 | 陕西科技大学 | Flexible nitrogen-doped carbon sponge of a kind of self-supporting and its preparation method and application |
| CN107895786B (en) * | 2017-11-15 | 2021-04-27 | 晋中学院 | Flexible self-supporting SnS/carbon foam composite material and preparation method and application thereof |
| EP3557676A1 (en) * | 2018-04-18 | 2019-10-23 | Brno University Of Technology | Alkali and/or alkaline earth ion - monoclinic sulfur allotrope battery with self-supporting electrodes |
| CN110407165B (en) * | 2018-04-27 | 2023-05-09 | 宝山钢铁股份有限公司 | Selenium-doped covalent organic framework-sulfur positive electrode composite material for lithium-sulfur battery and synthesis method thereof |
| CN108862275B (en) * | 2018-06-20 | 2020-03-27 | 厦门理工学院 | Carrier of lithium-sulfur battery positive electrode material and application thereof |
| CN108847503A (en) * | 2018-06-22 | 2018-11-20 | 宇东箔材科技南通有限公司 | A kind of preparation method of novel microporous carbon-coated aluminum foils |
| CN111048782A (en) * | 2019-12-23 | 2020-04-21 | 北京理工大学重庆创新中心 | Preparation method and calcination temperature optimization method of nitrogen-doped conductive carbon material for lithium-sulfur battery |
| CN112479176B (en) * | 2020-10-26 | 2022-11-22 | 温州大学 | 3D carbon foam material, preparation method and application thereof |
| CN113551814A (en) * | 2021-06-23 | 2021-10-26 | 浙江工业大学 | Preparation method and application of electrode material with carbon/MOF three-dimensional continuum structure |
| CN114204128A (en) * | 2021-11-18 | 2022-03-18 | 华中科技大学 | Lithium-sulfur battery capable of monitoring internal state change in real time and preparation and monitoring methods thereof |
| CN114229823B (en) * | 2021-12-03 | 2023-05-23 | 四川轻化工大学 | Preparation of cobalt-nickel catalyzed melamine foam synthesized porous carbon and application of porous carbon in lithium-sulfur battery |
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