CN108023062A - A kind of lithium sulfur battery anode material - Google Patents
A kind of lithium sulfur battery anode material Download PDFInfo
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- CN108023062A CN108023062A CN201711259805.8A CN201711259805A CN108023062A CN 108023062 A CN108023062 A CN 108023062A CN 201711259805 A CN201711259805 A CN 201711259805A CN 108023062 A CN108023062 A CN 108023062A
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- H01M4/00—Electrodes
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H01M4/0421—Methods of deposition of the material involving vapour deposition
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- 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
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- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of lithium sulfur battery anode material, and in particular to a kind of preparation and application based on sulfur vapor and nitrogen-doped carbon fiber lithium sulfur battery anode material, belong to lithium-sulfur cell field.A kind of lithium sulfur battery anode material, it is characterised in that：The positive electrode is that sheet nitrogen-doped carbon fiber is placed on deposition to have above the sheet form base of nano-sulfur particles obtained by lamination, wherein, the sheet form base that depositing has nano-sulfur particles is made as follows：After sulphur powder heating stirring is produced sulfur vapor to 120~300 DEG C, sulfur vapor is purged on sheet form base surface with the nitrogen or argon gas that flow velocity is 1~5L/min.The preparation method convenient material drawing of lithium sulfur battery anode material of the present invention and cheap and easy to get, without adhesive and coating process, preparation process is simply time saving, and energy consumption is low, has the prospect of large-scale industrial production and application.
Description
Technical field
The present invention relates to a kind of lithium sulfur battery anode material, and in particular to one kind is based on sulfur vapor and nitrogen-doped carbon fiber lithium
The preparation and application of sulphur cell positive electrode material, belong to lithium-sulfur cell field.
Background technology
With the continuous improvement of human living standards, the energy demand in living and produce also increases sharply, and traditional
Fossil resource not only face carrying out source problem and also causing serious problem of environmental pollution for increasingly depleted, therefore people compel to be essential
Find new green, safety, low cost, the energy of high-energy-density and replace fossil energy.The middle sulphur of lithium-sulfur cell is just
The theoretical specific capacity of pole is up to 1675mAh/g, theory is up to 2600Wh/kg than energy, and energy density is current lithium ion battery
6 times of theoretical value.In addition, sulphur simple substance as the accessory substance in industrial production, have it is environmental-friendly, cheap be easy to get etc. it is all
More advantages.Although lithium-sulfur cell have high-energy-density and it is cheap wait clear superiority, by more than 30 years research hair
Exhibition is still without obtaining practical application.
The main problem of lithium-sulfur cell practical application is hindered to have at present：1. the electrical conductivity of sulphur simple substance at normal temperatures is only 5 ×
10-30S/cm, is typical insulator.The sulphur that cannot be come into full contact with conductive network cannot be utilized effectively, and can cause to live
Property material utilization decline.2. the density of sulphur simple substance is 2.36g/cm3, and discharging product Li2The density of S is only 1.66g/cm3,
This means positive active material has 80% volume contraction after the completion of exoelectrical reaction, volume contraction may result in active matter
Matter comes off from collector or even causes battery structure to deform.3. negative material lithium metal is possible to have lithium in charging process
Ion irregularly reduces deposition in electrode surface and forms dendrite, and the presence of dendrite may penetrate membrane and cause short-circuit initiation
Catch fire or explosion danger.The more lithium sulfide Li of serious 4. " shuttle effect ", i.e. sulphur simple substance electric discharge intermediate product2Sn(n=3~8) meeting
It is being dissolved in electrolyte and is migrating, the more lithium sulfides being dissolved into electrolyte with conductive network because cannot contacts in charging
Reversible electrochemical reaction, which can not occur, causes active material to lose, and moves to more lithium sulfide meetings and the lithium simple substance of negative terminal surface
Generation self discharge reaction can equally cause battery capacity irreversible injury.
In the defects of above lithium-sulfur cell, " shuttle effect " is because directly influencing the energy density of battery and using the longevity
Life, is one of current researchers institute key problems-solving.The approach for solving lithium-sulfur cell " shuttle effect " at present is functional
Layer stop, physical/chemical adsorption, porous material constraint etc., its purpose are that polysulfide is fixed among positive electrode to prevent
Only it, which is dissolved into electrolyte, migrates to anode side.But the above method is complicated often with there is preparation method, material expensive is not
Foot, and substantial amounts of pollution can be produced in practical operation and is wasted, it can not meet the practical requirement of lithium-sulfur cell
The content of the invention
For insufficient existing for lithium sulfur battery anode material, the object of the present invention is to provide a kind of using gas phase sulfur deposition
Method prepares nano-sulfur positive electrode, and provides electrochemical reaction place using the carbon fiber of N doping, which simplifies
The preparation process of electrode material, and improve the cycle performance of lithium-sulfur cell.In addition, sulfur vapor is petrochemistry industry sulphur removal
Common byproduct, cheap in device, and it is convenient to obtain.
A kind of lithium sulfur battery anode material, the positive electrode are that sheet nitrogen-doped carbon fiber is placed on deposition nanometer
Above the sheet form base of sulfur granules obtained by lamination, wherein,
The sheet form base that depositing has nano-sulfur particles is made as follows：By sulphur powder heating stirring to 120~300 DEG C of productions
After raw sulfur vapor, sulfur vapor is purged on sheet form base surface with the nitrogen or argon gas that flow velocity is 1~5L/min；
Sheet nitrogen-doped carbon fiber is made as follows：Sheet carbon fiber source material is taken, according to every gram of carbon fiber source material
Drop adds the ratio of 1~10ml to react 8 at 0~60 DEG C to the nitrogen source solution that concentration is 2mg/ml~100mg/ml is added dropwise thereon
~24h；After cleaning, dry 10~24h at 80~100 DEG C；Under inert atmosphere, carry out carbonization treatment, carburizing temperature for 500~
2000 DEG C, programming rate is 1~10 DEG C/min, and soaking time is 1~5h, cooling, up to sheet nitrogen-doped carbon fiber, is such as needed,
The aqueous solution of 1~10ml initiators is added dropwise according to every gram of carbon fiber source material before nitrogen source solution is added dropwise on carbon fiber source material
Ratio be added dropwise on carbon fiber source material concentration be 10~100mg/ml initiators aqueous solution,
Wherein, nitrogen source is aniline, pyridine, pyrroles, urea, melamine；The initiator is ammonium persulfate or persulfuric acid
Potassium.
The deposition obtained using the above method have nano-sulfur particles size in the sheet form base of nano-sulfur particles 1nm~
100nm。
In above-mentioned technical proposal, the inert atmosphere during carbonization treatment can be provided by nitrogen or argon gas.
In above-mentioned technical proposal, the positive electrode is that a piece of sheet nitrogen-doped carbon fiber is placed on a piece of deposition to receive
Above the sheet form base of rice sulfur granules obtained by lamination.
In above-mentioned technical proposal, when nitrogen source is aniline, pyridine or pyrroles, molten to dropwise addition nitrogen source on carbon fiber source material
Before liquid, the ratio that the aqueous solution of 1~10ml initiators is added dropwise according to every gram of carbon fiber source material is added dropwise on carbon fiber source material
Concentration is the aqueous solution of 10~100mg/ml initiators.
In above-mentioned technical proposal, when nitrogen source is urea and melamine, then the aqueous solution of initiator need not be added in advance,
Directly to dropwise addition urea or melamine solution on carbon fiber source material.
In lithium sulfur battery anode material of the present invention, the nitrogen source solution solvent for use is common dissolvable nitrogen source
The solvent of compound, such as ethanol.
In lithium sulfur battery anode material of the present invention, preferably described sheet form base is aluminium foil, aluminium net, nickel foil, nickel screen, iron
Paper tinsel, iron net, foamed aluminium, nickel foam, foamed iron, graphene film, carbon nano-tube film or carbon fiber paper.
In lithium sulfur battery anode material of the present invention, preferably described carbon fiber source material is biomass carbon fiber, viscose glue
Fiber, phenolic fiber, polyacrylonitrile-based carbon fibre, asphalt base carbon fiber or carbon nanotubes.
Further, the biomass carbon fiber is bamboo fibre, silk, bacterial fibers.
Preferably, the sheet form base that deposition has nano-sulfur particles is made as follows：
1) sulphur powder is heated to 120~300 DEG C, nitrogen is passed through under stirring or argon gas bloats sulfur vapor, gas flow rate 1
~5L/min；
2) sheet form base is placed in sulfur vapor wind underside position to start to deposit sulphur；
3) stop ventilation after 2~30min, take out the substrate after deposition sulphur, up to the piece for depositing and there are nano-sulfur particles
Shape substrate.
Preferably, sheet nitrogen-doped carbon fiber is made as follows：
1) sheet carbon fiber source material is taken, is such as needed, the water-soluble of 1~10ml initiators is added dropwise according to every gram of carbon fiber source material
The aqueous solution that concentration is 10~100mg/ml initiators is added dropwise in the ratio of liquid on carbon fiber source material；
2) according to carbon obtained by the ratio to dropwise addition 1~10ml nitrogen source solution on every gram of carbon fiber source material to step 1) processing
The nitrogen source solution that concentration is 2mg/ml~100mg/ml is added dropwise on fiber source material, reacts 8~24h at 0~60 DEG C；
3) cleaning step 3) resulting materials are handled, dry 10~24h at 80~100 DEG C；
4) by dried material, carbonization treatment, carburizing temperature are 500~1000 DEG C in tube furnace, programming rate 1
~10 DEG C/min, soaking time is 1~5h, and protection gas is argon gas or nitrogen；Room temperature is naturally cooled to, it is fine up to nitrogen-doped carbon
Dimension.
The present invention advantageous effects be：Lithium sulphur positive electrode provided by the invention system by the way of sulfur vapor deposition
Standby nano-sulfur, sulfur vapor can largely be obtained from the desulfurizing device that petrochemical industry produces, and have cheap, easy scale metaplasia
The characteristics of production.And gas phase sulfur deposition also has the advantages that deposition substrate is various, deposition is controllable；The nitrogen-doped carbon fiber of use
Reacting environment can be not only provided for the electrochemical reaction of active material, also there is the work that absorption polysulfide suppresses shuttle effect
With.The preparation method convenient material drawing and cheap and easy to get, without adhesive and coating process, preparation process is simply time saving, energy consumption
It is low, there is the prospect of large-scale industrial production and application.
Brief description of the drawings
Fig. 1 is the photo of the nano-sulfur particles prepared in embodiment 1；
Fig. 2 is the N doping cotton base carbon fibre prepared in embodiment 1；
Fig. 3 is 100 discharge capacity curves that the lithium sulfur battery anode material prepared in embodiment 1 is assembled into lithium-sulfur cell
Figure；
Fig. 4 is the high rate performance curve map that the lithium sulfur battery anode material prepared in embodiment 1 is assembled into lithium-sulfur cell.
Embodiment
Following non-limiting examples can make those of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
Test method described in following embodiments, is conventional method unless otherwise specified；The reagent and material, such as
Without specified otherwise, commercially obtain.
Embodiment 1
Nano-sulfur is deposited in aluminum foil substrate：
Weigh 10.0g sulphur powders and be heated to 160 DEG C, import the nitrogen that flow velocity is 2L/min and bloat sulfur vapor.In sulfur vapor
Aluminium foil is placed above air-flow at 1cm as sulphur deposition substrate.It can be deposited after 3.5min on aluminium foil and obtain 2mg nano-sulfurs, Fig. 1
In it can be seen that prepare deposition sulphur by nanoscale little particle accumulate form.
The preparation of N doping cotton base carbon fibre：
Cotton piece is cut into a diameter of 20mm, weight is the disk of 0.2g, and the mistake of 300 μ L 66.7mg/ml is added dropwise in cotton piece
Ammonium sulfate solution, after complete wetting, is added dropwise the aniline ethanol solution that 300 μ L volume fractions are 16.7%.24h is reacted at room temperature
Afterwards unreacted ammonium persulfate and aniline are washed away with ethanol and deionized water.Dry 5h is placed on carbon in tube furnace in 80 DEG C of baking ovens
Change is handled, and carburizing temperature is 800 DEG C, 5 DEG C/min of programming rate, and protection gas is argon gas.Naturally cool to after room temperature and mixed up to nitrogen
Miscellaneous cotton base carbon fibre, it can be seen that the nitrogen-doped carbon fiber prepared has the three-dimensional network for being connected with each other and forming in Fig. 2.
A piece of sheet nitrogen-doped carbon fiber is placed on a piece of sheet form base top lamination for depositing and there are nano-sulfur particles, is obtained
To positive electrode.
Above-mentioned gained positive electrode and lithium piece are assembled into lithium sulphur button cell, at room temperature in the voltage zone of 1.7~2.8V
Interior progress charge-discharge performance test.As shown in Figure 3 in 0.2C (335.0mA/g) constant current charge-discharge, first discharge specific capacity
Reach 1203mAh/g, capacity is maintained at 881.1mAh/g after 100 circulations.As shown in figure 4, in big multiplying power 1C (1675mA/g)
Lower positive discharge specific capacity is 952mAh/g, and positive discharge specific capacity is 876mAh/g under 2C (3350mA/g).
Embodiment 2
Sulphur sedimentation time is increased into 9min and obtains the nano-sulfur that deposition is 4mg, other conditions are consistent with embodiment 1.
Above-mentioned gained positive electrode and lithium piece are assembled into lithium sulphur button cell and carry out charge-discharge performance test, in 0.2C
During (335.0mA/g) constant current charge-discharge, first discharge specific capacity reaches 992mAh/g, and capacity is maintained at after 100 circulations
836mAh/g。
Embodiment 3
Sulphur sedimentation time is increased into 14.5min and obtains the nano-sulfur that deposition is 6mg, other conditions are consistent with embodiment 1.
Above-mentioned gained positive electrode and lithium piece are assembled into lithium sulphur button cell and carry out charge-discharge performance test, in 0.2C
During (335.0mA/g) constant current charge-discharge, first discharge specific capacity reaches 804mAh/g, and capacity is maintained at after 100 circulations
776mAh/g。
Embodiment 4
Nickel foil is consistent with embodiment 1~3 as sulphur deposition substrate, other conditions.Wherein the load capacity of sulphur is in cathode
6mg, gas phase sulfur can in nickel foil substrate uniform deposition, be conducive to contact of the active material with conductive agent and electrolyte so that
Improve active material utilization and then improve the specific discharge capacity and cyclical stability of positive electrode.
Embodiment 5
Iron foil is consistent with embodiment 1~3 as sulphur deposition substrate, other conditions.Wherein the load capacity of sulphur is in cathode
2mg, gas phase sulfur can in iron foil substrate uniform deposition, be conducive to contact of the active material with conductive agent and electrolyte so that
Improve active material utilization and then improve the specific discharge capacity and cyclical stability of positive electrode.
Embodiment 6
Aluminium net is consistent with embodiment 1~3 as sulphur deposition substrate, other conditions.Wherein the load capacity of sulphur is in cathode
6mg, gas phase sulfur can in aluminium net substrate uniform deposition, be conducive to contact of the active material with conductive agent and electrolyte so that
Improve active material utilization and then improve the specific discharge capacity and cyclical stability of positive electrode.
Embodiment 7
Nickel screen is consistent with embodiment 1~3 as sulphur deposition substrate, other conditions.Wherein the load capacity of sulphur is in cathode
6mg, gas phase sulfur can in nickel screen substrate uniform deposition, be conducive to contact of the active material with conductive agent and electrolyte so that
Improve active material utilization and then improve the specific discharge capacity and cyclical stability of positive electrode.
Embodiment 8
Iron net is consistent with embodiment 1~3 as sulphur deposition substrate, other conditions.Wherein the load capacity of sulphur is in cathode
6mg, gas phase sulfur can in nickel screen substrate uniform deposition, be conducive to contact of the active material with conductive agent and electrolyte so that
Improve active material utilization and then improve the specific discharge capacity and cyclical stability of positive electrode.
Embodiment 9
Nickel foam is consistent with embodiment 1~3 as sulphur deposition substrate, other conditions.The load capacity of sulphur wherein in cathode
For 2mg, gas phase sulfur can in foam nickel base uniform deposition, be conducive to contact of the active material with conductive agent and electrolyte,
So as to improve active material utilization and then improve the specific discharge capacity and cyclical stability of positive electrode.
Embodiment 10
Foamed aluminium is consistent with embodiment 1~3 as sulphur deposition substrate, other conditions.The load capacity of sulphur wherein in cathode
For 6mg, gas phase sulfur can on foamed aluminium radical bottom uniform deposition, be conducive to contact of the active material with conductive agent and electrolyte,
So as to improve active material utilization and then improve the specific discharge capacity and cyclical stability of positive electrode.
Embodiment 11
Foamed iron is consistent with embodiment 1~3 as sulphur deposition substrate, other conditions.The load capacity of sulphur wherein in cathode
For 6mg, gas phase sulfur can on foamed aluminium radical bottom uniform deposition, be conducive to contact of the active material with conductive agent and electrolyte,
So as to improve active material utilization and then improve the specific discharge capacity and cyclical stability of positive electrode.
Embodiment 12
Graphene film is consistent with embodiment 1~3 as sulphur deposition substrate, other conditions.The load of sulphur wherein in cathode
Measure as 2mg, gas phase sulfur can on graphene film uniform deposition, be conducive to contact of the active material with conductive agent and electrolyte,
So as to improve active material utilization and then improve the specific discharge capacity and cyclical stability of positive electrode.
Embodiment 13
Carbon nano-tube film is consistent with embodiment 1~3 as sulphur deposition substrate, other conditions.Sulphur is negative wherein in cathode
Carrying capacity is 2mg, gas phase sulfur can uniform deposition over the carbon nanotube film, be conducive to connecing for active material and conductive agent and electrolyte
Touch, so as to improve active material utilization and then improve the specific discharge capacity and cyclical stability of positive electrode.
Embodiment 14
Carbon fiber paper is consistent with embodiment 1~3 as sulphur deposition substrate, other conditions.The load of sulphur wherein in cathode
Measure as 4mg, gas phase sulfur can on carbon fiber paper uniform deposition, be conducive to contact of the active material with conductive agent and electrolyte,
So as to improve active material utilization and then improve the specific discharge capacity and cyclical stability of positive electrode.
Embodiment 15
Bamboo fibre is made to the carbon material being made of a diameter of 2 μm of nitrogen-doped carbon fibers as carbon fiber source material, sulphur sinks
Product substrate uses one kind in embodiment 1~14, and the load capacity of sulphur is 4mg in cathode, and other conditions are consistent with embodiment 1~3.
More lithium sulfides can be by uniform adsorption on N doping carbonization bamboo fibre, and then is conducive to the fast charging and discharging row of active material
To improve active material utilization and cyclical stability.
Embodiment 16
Silk is made to the carbon material being made of a diameter of 5 μm of nitrogen-doped carbon fibers, sulphur deposition as carbon fiber source material
Substrate uses one kind in embodiment 1~14, and the load capacity of sulphur is 6mg in cathode, and other conditions are consistent with embodiment 1~3.It is micro-
The N doping carbonization silk fiber of meter level can be with the more lithium sulfides of uniform adsorption, and then are conducive to the fast charging and discharging row of active material
To improve active material utilization and cyclical stability.
Embodiment 17
Bacterial fibers are made to the carbon material being made of a diameter of 7 μm of nitrogen-doped carbon fibers, sulphur as carbon fiber source material
Deposition substrate uses one kind in embodiment 1~14, and other conditions are consistent with embodiment 1~3.
Embodiment 18
Polyacrylonitrile fibre is made to the carbon materials being made of a diameter of 100nm nitrogen-doped carbons fiber as carbon fiber source material
Material, sulphur deposition substrate use one kind in embodiment 1~14, and the load capacity of sulphur be 6mg, other conditions and embodiment 1 in cathode
~3 is consistent.Nano level N doping carbonized polyacrylonitrile fibre can be with the more lithium sulfides of uniform adsorption, and then are conducive to active material
Fast charging and discharging behavior, improve active material utilization and cyclical stability.
Embodiment 19
Pitch fibers are made to the carbon material being made of a diameter of 100nm nitrogen-doped carbons fiber as carbon fiber source material,
Sulphur deposition substrate uses one kind in embodiment 1~14, and the load capacity of sulphur be 6mg, other conditions and embodiment 1~3 in cathode
Unanimously.Nano level N doping carbonized pitch fibers can be with the more lithium sulfides of uniform adsorption, and then are conducive to the quick of active material
Discharge and recharge behavior, improves active material utilization and cyclical stability.
Embodiment 20
Viscose rayon is made to the carbon material being made of a diameter of 10 μm of nitrogen-doped carbon fibers, sulphur as carbon fiber source material
Deposition substrate uses one kind in embodiment 1~14, and the load capacity of sulphur be 6mg, other conditions and embodiment 1~3 one in cathode
Cause.Micron-sized N doping carbonization viscose rayon can be with the more lithium sulfides of uniform adsorption, and then are conducive to the quick of active material and fill
Electric discharge behavior, improves active material utilization and cyclical stability.
Embodiment 21
Phenolic fiber is made to the carbon materials being made of a diameter of 100nm nitrogen-doped carbons fiber as carbon fiber source material
Material, sulphur deposition substrate use one kind in embodiment 1~14, and the load capacity of sulphur be 6mg, other conditions and embodiment 1 in cathode
~3 is consistent.The specific surface area that nano level N doping carbonization phenolic fiber enriches can with the more lithium sulfides of uniform adsorption, and then
Be conducive to the fast charging and discharging behavior of active material, improve active material utilization and cyclical stability.
Embodiment 22
Using carbon nano-tube film as carbon source material, nitrogen source before processing is being carried out, is being handled first with normal pressure gas plasma
100s carries out hydrophilic treated to carbon nano-tube film and carries out N doping again, and final be made is made of a diameter of 50nm nitrogen-doped carbons fiber
Carbon material, sulphur deposition substrate uses one kind in embodiment 1~14, and the load capacity of sulphur is 6mg, other conditions and reality in cathode
It is consistent to apply example 1~3.The micro-nano structure and the nitrogen-doped carbon of polarity that carbon nano-tube film enriches can largely adsorb more lithium sulfides, suppression
System " shuttle effect " simultaneously improves the cycle performance of battery.
Embodiment 23
Using graphene film as carbon source material, nitrogen source before processing is being carried out, is being handled first with normal pressure gas plasma
100s carries out graphene membrane surface hydrophilic treated, final that the nitrogen-doped carbon material being made of the superposition of flake graphite alkene, sulphur is made
Deposition substrate uses one kind in embodiment 1~14, and the load capacity of sulphur be 6mg, other conditions and embodiment 1~3 one in cathode
Cause.Nitrogen-doped graphene, which can not only utilize nonpolar nature to adsorb more lithium sulfides, can also utilize the more sulphur of lamellar structure physical barrier
Change lithium to be lost in, so as to improve the cycle performance of battery.
Embodiment 24
One kind in embodiment 1~14 is used using pyrroles as N doping nitrogen source, sulphur deposition substrate, carbon source material material is adopted
With one kind in embodiment 15~23, the load capacity of sulphur is 6mg in cathode, and other conditions are consistent with embodiment 1~3.Pyrroles gathers
Carbon source material surface is coated on after conjunction, the nitrogen-doped carbon material of preparation can effectively adsorb more lithium sulfides, so as to improve battery
Cycle performance.
Embodiment 25
One kind in embodiment 1~14 is used using pyridine as N doping nitrogen source, sulphur deposition substrate, carbon source material material is adopted
With one kind in embodiment 15~23, the load capacity of sulphur is 6mg in cathode, and other conditions are consistent with embodiment 1~3.Pyrroles gathers
Carbon source material surface is coated on after conjunction, the nitrogen-doped carbon material of preparation can effectively adsorb more lithium sulfides, so as to improve battery
Cycle performance.
Embodiment 26
Using urea as N doping nitrogen source, during impregnated carbon fiber is dried to will be taken out after 2h in urea liquid, sulphur
Deposition substrate uses one kind in embodiment 1~14, and carbon source material material uses one kind in embodiment 15~23, sulphur in cathode
Load capacity be 6mg, other conditions are consistent with embodiment 1~3.The nitrogen-doped carbon material of preparation can effectively adsorb more vulcanizations
Lithium, so as to improve the cycle performance of battery.
Embodiment 27
Using melamine as N doping nitrogen source, during directly impregnated carbon fiber is taken out to after by 2h in urea liquid
Drying, sulphur deposition substrate use one kind in embodiment 1~14, and carbon source material material uses one kind in embodiment 15~23,
The load capacity of sulphur is 6mg in cathode, and other conditions are consistent with embodiment 1~3.The nitrogen-doped carbon material of preparation can be adsorbed effectively
More lithium sulfides, so as to improve the cycle performance of battery.
Embodiment 28
Using ethylenediamine as N doping nitrogen source, during directly impregnated carbon fiber is taken out into ethylenediamine after 2h, sulphur sinks
Product substrate uses one kind in embodiment 1~14, and carbon source material material uses one kind in embodiment 15~23, sulphur in cathode
Load capacity is 6mg, and other conditions are consistent with embodiment 1~3.The nitrogen-doped carbon material of preparation can effectively adsorb more lithium sulfides,
So as to improve the cycle performance of battery.
Embodiment 29
Using ammonia as N doping nitrogen source, during heat directly by carbon fiber in ammonia atmosphere and carry out nitrogen and mix
Miscellaneous, sulphur deposition substrate uses one kind in embodiment 1~14, and carbon source material material uses one kind in embodiment 15~23, just
The load capacity of extremely middle sulphur is 6mg, and other conditions are consistent with embodiment 1~3.The nitrogen-doped carbon material of preparation can effectively adsorb more
Lithium sulfide, so as to improve the cycle performance of battery.
Embodiment 30
Using lithium nitride as N doping nitrogen source, during directly impregnated carbon fiber is taken out into lithium nitride solution after 2h,
Sulphur deposition substrate uses one kind in embodiment 1~14, and carbon source material material uses one kind in embodiment 15~23, in cathode
The load capacity of sulphur is 6mg, and other conditions are consistent with embodiment 1~3.The nitrogen-doped carbon material of preparation can effectively adsorb more vulcanizations
Lithium, so as to improve the cycle performance of battery.
Embodiment 31
Using cyanuryl chloride as N doping nitrogen source, during directly by impregnated carbon fiber into cyanuryl chloride solution 2h
After take out, sulphur deposition substrate use embodiment 1~14 in one kind, carbon source material material use embodiment 15~23 in one
Kind, the load capacity of sulphur is 6mg in cathode, and other conditions are consistent with embodiment 1~3.The nitrogen-doped carbon material of preparation can be effective
More lithium sulfides are adsorbed, so as to improve the cycle performance of battery.
Embodiment 32
Using hydrazine hydrate as N doping nitrogen source, during directly impregnated carbon fiber is taken out into hydrazine hydrate solution after 2h,
Sulphur deposition substrate uses one kind in embodiment 1~14, and carbon source material material uses one kind in embodiment 15~23, in cathode
The load capacity of sulphur is 6mg, and other conditions are consistent with embodiment 1~3.The nitrogen-doped carbon material of preparation can effectively adsorb more vulcanizations
Lithium, so as to improve the cycle performance of battery.
Embodiment 33
Using nitrogen as N doping nitrogen source, during directly carbon fiber is taken out after nitrogen plasma treatment 2h,
Sulphur deposition substrate uses one kind in embodiment 1~14, and carbon source material material uses one kind in embodiment 15~23, in cathode
The load capacity of sulphur is 6mg, and other conditions are consistent with embodiment 1~3.The nitrogen-doped carbon material of preparation can effectively adsorb more vulcanizations
Lithium, so as to improve the cycle performance of battery.
Claims (4)
- A kind of 1. lithium sulfur battery anode material, it is characterised in that：The positive electrode is to be placed on sheet nitrogen-doped carbon fiber Deposition has above the sheet form base of nano-sulfur particles obtained by lamination, wherein,The sheet form base that depositing has nano-sulfur particles is made as follows：By sulphur powder heating stirring to 120~300 DEG C of generation sulphur After steam, sulfur vapor is purged on sheet form base surface with the nitrogen or argon gas that flow velocity is 1~5L/min；Sheet nitrogen-doped carbon fiber is made as follows：Sheet carbon fiber source material is taken, is dripped according to every gram of carbon fiber source material Add the ratio of 1~10ml to being added dropwise the nitrogen source solution that concentration is 2mg/ml~100mg/ml thereon, reaction 8 at 0~60 DEG C~ 24h；After cleaning, dry 10~24h at 80~100 DEG C；Under inert atmosphere, carbonization treatment is carried out, carburizing temperature is 500~2000 DEG C, programming rate is 1~10 DEG C/min, and soaking time is 1~5h, cooling, up to sheet nitrogen-doped carbon fiber；As need, to The ratio of the aqueous solution of 1~10ml initiators is added dropwise on carbon fiber source material before dropwise addition nitrogen source solution according to every gram of carbon fiber source material The aqueous solution that concentration is 10~100mg/ml initiators is added dropwise in example on carbon fiber source material,Wherein, nitrogen source is aniline, pyridine, pyrroles, urea, melamine；The initiator is ammonium persulfate or potassium peroxydisulfate.
- 2. material according to claim 1, it is characterised in that：The sheet form base is aluminium foil, aluminium net, nickel foil, nickel screen, iron Paper tinsel, iron net, foamed aluminium, nickel foam, foamed iron, graphene film, carbon nano-tube film or carbon fiber paper.
- 3. material according to claim 1, it is characterised in that：The carbon fiber source material is biomass carbon fiber, viscose glue Fiber, phenolic fiber, polyacrylonitrile-based carbon fibre, asphalt base carbon fiber or carbon nanotubes.
- 4. material according to claim 1, it is characterised in that：Deposition has the nano-sulfur in the sheet form base of nano-sulfur particles Particle size is in 1nm~100nm.
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| CN111403719B (en) * | 2020-03-31 | 2021-10-08 | 浙江大学 | Sponge nickel material, preparation method thereof and application of sponge nickel material in preparation of flexible lithium-sulfur battery |
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| CN112875681A (en) * | 2021-01-27 | 2021-06-01 | 常州大学 | Preparation method of modified carbon nanotube film/sulfur composite flexible positive electrode material and application of modified carbon nanotube film/sulfur composite flexible positive electrode material in flexible lithium-sulfur battery |
| CN112875681B (en) * | 2021-01-27 | 2023-08-22 | 常州大学 | Preparation method of modified carbon nanotube film/sulfur composite flexible positive electrode material and application of modified carbon nanotube film/sulfur composite flexible positive electrode material in flexible lithium sulfur battery |
| CN113036104A (en) * | 2021-03-04 | 2021-06-25 | 浙江大学 | Sulfur-rhizopus filamentous carbon/metal oxide composite material and preparation method and application thereof |
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