CN105810915A - Preparation of graphene-coated sulfur-embedded ordered mesoporous carbon sphere composite material and application of ordered mesoporous carbon sphere composite material as lithium-sulfur battery positive electrode material - Google Patents
Preparation of graphene-coated sulfur-embedded ordered mesoporous carbon sphere composite material and application of ordered mesoporous carbon sphere composite material as lithium-sulfur battery positive electrode material Download PDFInfo
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Abstract
The invention provides preparation of a graphene-coated sulfur-embedded ordered mesoporous carbon sphere composite material and an application of the ordered mesoporous carbon sphere composite material as a lithium-sulfur battery positive electrode material, and belongs to the technical field of lithium-sulfur battery positive electrode materials. With a triblock copolymer F127 (polyoxyethylene-olyoxypropylene-polyoxyethylene) as a structure-directing agent and a carbon source, tetraethoxysilane as a template agent and glycerol as the carbon source, ordered mesoporous carbon spheres are prepared through a one-step method; the prepared ordered mesoporous carbon spheres are mixed with elemental sulfur and then are heated in vacuum; the elemental sulfur is embedded into the ordered mesoporous carbon spheres to prepare the sulfur-embedded ordered mesoporous carbon sphere composite material; and graphene coats the surface of the sulfur-embedded ordered mesoporous carbon sphere composite material through surface electrostatic interaction to prepare the graphene-coated sulfur-embedded ordered mesoporous carbon sphere lithium-sulfur battery positive electrode material. According to the technical scheme provided by the invention, the lithium-sulfur battery positive electrode material with excellent electrochemical properties is prepared; and the lithium-sulfur battery positive electrode material has a good application prospect.
Description
Technical field
The present invention relates to the preparation side of a kind of graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material
Method, a kind of prepares lithium-sulfur cell by the compound of ordered mesopore carbon ball, elemental sulfur and Graphene
The method of positive electrode, belongs to the technical field of lithium sulfur battery anode material.
Background technology
Lithium ion battery is widely used in portable electric appts, at electronic vapour owing to having higher energy density
The aspects such as car and power station energy storage also have application.But current lithium ion battery energy density can room for promotion
The least, it is difficult to meet the demand to heavy-duty battery that electronic product and electric automobile etc. are growing, therefore must
The battery material of high power capacity must be developed.Lithium-sulfur cell owing to having the theoretical specific capacity of up to 1675mAh/g,
And elemental sulfur rich reserves, cheap, environmental friendliness, therefore lithium-sulfur cell is the coming next generation
Heavy-duty battery.The but electric conductivity extreme difference of elemental sulfur and discharging product lithium sulfide, and discharge process can produce
The raw intermediate polysulfide being soluble in organic electrolyte, causes " effect of shuttling back and forth ", additionally in cyclic process
There is also serious change in volume, these factors cause lithium-sulfur cell active material utilization low and cycle performance
Difference, has had a strong impact on the application of lithium-sulfur cell.For solving the problems referred to above, what Recent study was most is with conduction
The material with carbon element carrier as sulfur and the sulfur carbon composite anode material of conducting matrix grain.Research shows that mesoporous carbon is due to tool
There is less pore passage structure, can effectively suppress dissolving and the migration of polysulfide.While it is true, mesoporous carbon
/ sulfur composite positive pole there are still the most serious effect of shuttling back and forth, and after experience repeatedly circulation, capacity attenuation compares
Severe, it is impossible to meet the requirement of heavy-duty battery.Therefore, just a kind of functional stable lithium-sulfur cell is being explored
The preparation method of pole material is significant, and the present invention uses one-step method to prepare ordered mesopore carbon ball, uses true
The way of empty heating makes elemental sulfur be embedded in ordered mesopore carbon ball, obtains embedding sulfur ordered mesopore carbon ball composite wood
Material, Graphene on embedding sulfur ordered mesopore carbon ball Surface coating, prepare the graphene coated of excellent electrochemical performance
Embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material.
Summary of the invention
For overcoming the deficiencies in the prior art, the present invention provides a kind of graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur
Cell positive material preparation method, improves further the performance of positive electrode, such as cycle performance, and realizes big rule
Mould produces, and has more industrial value.
For achieving the above object, the present invention is by the following technical solutions:
The preparation method of a kind of graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material, includes successively
Following steps:
Step one: joined by concentrated sulphuric acid in deionized water, is heated to 36～40 DEG C, adds structure directing agent,
After it is completely dissolved, adds carbon source and stir 1.5～2.5 hours, adding template tetraethyl orthosilicate, continue
Continuous stirring 10min, then stands 28 hours at 36～40 DEG C, 105～115 DEG C of hydro-thermal reactions in a kettle.
26～30 hours, put into after filtration washing after baking oven is dried 7～9 hours in 110～120 DEG C, carry out pre-carbonization
Obtain complex, complex is put into retort and carries out carbonization, then by hydrofluoric acid dips more scrubbed, dry
Dry and grinding obtains ordered mesopore carbon ball；
Step 2: mixed with elemental sulfur by the ordered mesopore carbon ball of gained in step one, vacuum high-temperature heats one section
Time, then it is cooled to room temperature, prepares embedding sulfur ordered mesopore carbon ball.
Step 3: the embedding sulfur ordered mesopore carbon ball obtained in step 2 is scattered in the water of cationic surfactant
In solution, magnetic agitation 3～5 hours, after being centrifuged, product is joined the moisture of certain density graphene oxide
Dissipate in liquid, continue stirring 3～5 hours so that graphene oxide is coated with embedding sulfur ordered mesopore carbon ball completely, add
Reducing agent, after stirring 10 hours, is centrifuged, washs, is dried；Subsequently, in nitrogen atmosphere, will be dried
Product 300 DEG C process 1～3 hour, prepare graphene coated embedding sulfur ordered mesopore carbon ball lithium-sulphur cell positive electrode material
Material.
Preferably, the concentration of concentrated sulphuric acid is 98%.
Preferably, the volume ratio of concentrated sulphuric acid and deionized water is 1:15-25, it is furthermore preferred that concentrated sulphuric acid with go from
The volume ratio of sub-water is 1:20.
Preferably, after concentrated sulphuric acid is joined in deionized water by step one, heating-up temperature is 38 DEG C.
Preferably, the mixing time after step one adds carbon source 2 hours.
Preferably, step one dwell temperature is 38 DEG C.
Preferably, step one hydrothermal temperature is 110 DEG C, and the response time is 28 hours.
Preferably, in step one, baking temperature is 115 DEG C, and drying time is 8 hours.
Preferably, step one structure directing agent is F127.
Preferably, step one carbon source is glycerol.
Preferably, step one template is tetraethyl orthosilicate.
Preferably, step one carbon source is 1:1-3 with the mass ratio of structure directing agent, it is furthermore preferred that carbon source and knot
The mass ratio of structure directed agents is 1:2.The volume of the concentrated sulphuric acid that every 1g carbon source is corresponding is 1-5ml.
Preferably, carbon source is 1:3-5 with the mass ratio of template, it is furthermore preferred that carbon source and the quality of template
Ratio is 1:4.
Preferably, the pre-carburizing temperature of step one is 165～175 DEG C, and the time is 4.5～5.5 hours, it is furthermore preferred that
Pre-carburizing temperature is 170 DEG C, and the time is 5 hours.
Preferably, the step of step one carbonization includes: protecting with nitrogen atmosphere during whole, heating rate is
2 DEG C/min, after 875～975 DEG C of insulations 2.5～3.5 hours, stop heating natural cooling, it is furthermore preferred that
Carburizing temperature is 900 DEG C, and temperature retention time is 3 hours.
Preferably, step one hydrofluoric acid concentration is 15wt%.
Preferably, in step 2, ordered mesopore carbon ball is 1:1.5-2.5 with the mass ratio of elemental sulfur, it is furthermore preferred that
Ordered mesopore carbon ball is 1:2 with the mass ratio of elemental sulfur.
Preferably, in step 2, in vacuum high-temperature heating process, heating rate is 5 DEG C/min, and holding temperature is
800～900 DEG C, temperature retention time is 6～8 hours, it is furthermore preferred that holding temperature is 850 DEG C, temperature retention time is 7
Hour.The preferred 40KPa-10Pa of vacuum.
Preferably, in step 3, aqueous solution of cationic surfactant active cationic surfactant concentration is
0.4wt%.
Preferably, cationic surfactant used is cetyl trimethylammonium bromide.
Preferably, reducing agent used is L-AA.
Preferably, in step 3,300 DEG C of process times of dried product are 2 hours.
As it is shown in figure 1, elemental sulfur is entered by heating in vacuum and forms embedding sulfur in the duct of spherical ordered mesoporous carbon and have
Sequence mesoporous carbon spheres, then makes embedding sulfur ordered mesopore carbon ball surface positively charged with cationic surfactant, makes embedding sulfur
Ordered mesopore carbon ball and electronegative graphene oxide self assembly, obtain graphene coated after redox graphene
Embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material.
Compared with immediate prior art, the technical scheme that the present invention provides has a following excellent effect:
Have employed one-step method to prepare ordered mesopore carbon ball in the technical scheme that the present invention provides, preparation technology is simple
Efficiently, obtained ordered mesopore carbon ball presents good spherical structure, has the mesoporous hole of orderly three-dimensional cubic
Road structure.Make elemental sulfur embed in the duct of orderly mesoporous carbon spheres by simple vaccum heating method, obtain electrification
Learn the embedding sulfur ordered mesopore carbon ball composite of excellent performance.By the upper graphite of simple electrostatic attraction effect cladding
After alkene, the graphene coated embedding sulfur ordered mesopore carbon ball lithium-sulphur cell positive electrode material that prepared chemical property is the most excellent
Material.
Accompanying drawing explanation
Accompanying drawing 1 graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material preparation flow schematic diagram.
Scanning electron microscope (SEM) photo of accompanying drawing 2 ordered mesopore carbon ball.
High-resolution-ration transmission electric-lens (HRTEM) photo of accompanying drawing 3 ordered mesopore carbon ball.
The scanning electron microscope (SEM) of accompanying drawing 4 graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material
Photo.
Accompanying drawing 5 embedding sulfur ordered mesopore carbon ball composite stable circulation linearity curve under 2.5C multiplying power.
The circulation curve of accompanying drawing 6 embedding sulfur ordered mesopore carbon ball composite.
Accompanying drawing 7 graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material following under 0.4C multiplying power
Ring stability curve.
The circulation under 4C multiplying power of the accompanying drawing 8 graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material
Stability curve.
The circulation curve of accompanying drawing 9 graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material.
Detailed description of the invention
The present invention is described in further detail with embodiment below in conjunction with the accompanying drawings, but the present invention be not limited to
Lower embodiment.
Embodiment 1
First 5mL concentrated sulphuric acid is joined in 100mL deionized water, be heated to 38 DEG C, add 4.0g tri-
Block copolymer F127 (polyoxyethylene-poly-oxypropylene polyoxyethylene), after it is completely dissolved, adds 2.0g
Glycerol also stirs 2 hours, adds the tetraethyl orthosilicate of 8g, continues stirring 10 minutes, then 38 DEG C
Stand 28 hours, in a kettle. 110 DEG C of hydro-thermal reactions 28 hours, put into after filtration washing in baking oven in
After 115 DEG C are dried 8 hours, homoiothermic to 170 DEG C pre-carbonization 5h obtains complex.Complex is put into retort
In nitrogen atmosphere protect under be warmed up to 900 DEG C with the heating rate of 2 DEG C/min, stop adding after being incubated 3 hours
Heat natural cooling, then by the hydrofluoric acid dips of 15wt% more scrubbed, dry and grinding obtains in order
Mesoporous carbon spheres.
Spherical ordered mesoporous for 1g Carbon Materials is mixed with 2g elemental sulfur, below vacuum 10KPa under the conditions of with
The heating rate of 5 DEG C/min is warmed up to 850 DEG C, is incubated 7 hours, is then cooled to room temperature, prepares embedding sulfur
Ordered mesopore carbon ball composite.
Weigh a certain amount of embedding sulfur ordered mesopore carbon ball composite and be scattered in the cetyl trimethyl of 0.4wt%
In the aqueous solution of ammonium bromide, magnetic agitation 4 hours, after being centrifuged, product is joined the finite concentration of previous preparation
Graphene oxide aqueous dispersions in, continue stirring 4 hours so that graphene oxide is coated with embedding sulfur completely to be had
Sequence mesoporous carbon spheres composite, adds appropriate L-AA reduction, after stirring 10 hours, is centrifuged, washes
Wash, be dried.Subsequently, in nitrogen atmosphere, dried product 300 DEG C is processed 2 hours, prepare graphite
Alkene is coated with embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material.
Fig. 2 is scanning electron microscope (SEM) photo of ordered mesopore carbon ball.As it can be seen, can find out intuitively,
Ordered mesopore carbon ball presents preferable spherical structure, and diameter is mainly distributed between 0.5～3 μm.
Fig. 3 is high-resolution-ration transmission electric-lens (HRTEM) photo of ordered mesopore carbon ball.As it can be seen, it is permissible
Finding out intuitively, ordered mesopore carbon ball has orderly three-dimensional cubic duct structure, and aperture is about 5～6nm.
Fig. 4 is the scanning electron microscope (SEM) of graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material
Photo.As it can be seen, can find out intuitively, graphene coated on the surface of embedding sulfur ordered mesopore carbon ball, and
And the surface smoother after cladding.
Fig. 5 is the stable circulation curve under the 2.5C multiplying power of embedding sulfur ordered mesopore carbon ball composite.As schemed
Show, it can be seen that embedding sulfur ordered mesopore carbon ball composite, when big electric current 2.5C rate charge-discharge, passes through
After 45 circulations, its specific discharge capacity still reaches 850mAh/g, and its capability retention reaches 89%, whole
During, coulombic efficiency is close to 100%.Electrochemical performance.
Fig. 6 is the circulation curve of embedding sulfur ordered mesopore carbon ball composite.As shown in the figure, it can be seen that
Embedding sulfur ordered mesopore carbon ball composite its specific discharge capacity when 0.5C, 1.25C, 2.5C and 5C discharge
Respectively may be about 930mAh/g, 830mAh/g, 750mAh/g and 660mAh/g, after 25 circulations, then
Secondary when 0.25C discharges, its specific discharge capacity still can reach about 860mAh/g, thus understands Jie in order
Hole carbon ball/sulfur nano composite material possesses quite excellent high rate performance.
Fig. 7 is graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material following under 0.4C multiplying power
The ring curve of stability.As shown in the figure, it can be seen that graphene coated embedding sulfur ordered mesopore carbon ball lithium-sulphur cell positive electrode
Material is when small area analysis 0.4C discharges, and its specific discharge capacity fluctuates up and down at 1230mAh/g, cyclic curve
Substantially present straight line, illustrate after graphene coated, graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur electricity
Specific discharge capacity and the cyclical stability of pond positive electrode are all significantly improved.
Fig. 8 is the circulation under 4C multiplying power of the graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material
The curve of stability.As shown in the figure, it can be seen that graphene coated embedding sulfur ordered mesopore carbon ball lithium-sulphur cell positive electrode material
Material when big electric current 4C discharge and recharge, have higher specific discharge capacity equally, through 99 times circulate after, its
Specific discharge capacity is still up to 827mAh/g, and has the efficiency for charge-discharge close to 100%, illustrates through stone
After ink alkene cladding, show the most excellent chemical property.
Fig. 9 is the circulation curve of graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material.As
Figure shown in, it can be seen that graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material 0.4C,
During 0.8C, 2C, 4C, 8C discharge and recharge, its specific discharge capacity respectively may be about 1350mAh/g, 1210mAh/g,
1060mAh/g, 920mAh/g and 700mAh/g, and when again returning to 0.4C electric discharge, its ratio that discharges
Capacity is still up to about 1160mAh/g.It can thus be appreciated that graphene coated embedding sulfur ordered mesopore carbon ball lithium-sulfur cell
Positive electrode has more excellent high rate performance.
Embodiment 2
First 2mL concentrated sulphuric acid is joined in 75mL deionized water, is heated to 36 DEG C, add 2.0g F127,
After it is completely dissolved, adds 2.0g glycerol and stir 1.5 hours, adding the tetraethyl orthosilicate of 6g,
Continuing stirring 10 minutes, then 36 DEG C stand 28 hours, in a kettle. 105 DEG C of hydrothermal crystallizings 26 hours,
Putting into after filtration washing after being dried 7 hours in 110 DEG C in baking oven, homoiothermic to 165 DEG C pre-carbonization 4.5h is answered
Compound.Complex is put in retort and be warmed up to the heating rate of 2 DEG C/min under nitrogen atmosphere is protected
875 DEG C, after being incubated 2.5 hours, stop heating natural cooling, then by the hydrofluoric acid dips of 15wt%, then
Scrubbed, dry and grinding obtains ordered mesopore carbon ball.
Spherical ordered mesoporous for 1g Carbon Materials is mixed with 1.5g elemental sulfur, below vacuum 10KPa under the conditions of
It is warmed up to 800 DEG C with the heating rate of 5 DEG C/min, is incubated 6 hours, is then cooled to room temperature, prepare embedding
Sulfur ordered mesopore carbon ball composite.
Weigh a certain amount of embedding sulfur ordered mesopore carbon ball composite and be scattered in the cetyl trimethyl of 0.4wt%
In the aqueous solution of ammonium bromide, magnetic agitation 3 hours, after being centrifuged, product is joined the finite concentration of previous preparation
Graphene oxide aqueous dispersions in, continue stirring 3 hours so that graphene oxide is coated with embedding sulfur completely to be had
Sequence mesoporous carbon spheres composite, adds appropriate L-AA reduction, after stirring 10 hours, is centrifuged, washes
Wash, be dried.Subsequently, in nitrogen atmosphere, dried product 300 DEG C is processed 1 hour, prepare graphite
Alkene is coated with embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material.
Electrochemical results shows under 2.5C electric current density, and its specific discharge capacity is 1024mAh/g, i.e.
Making under high current density 8C, its capacity still has 617mAh/g.
Embodiment 3
First 10mL concentrated sulphuric acid is joined in 125mL deionized water, be heated to 40 DEG C, add 6.0g
F127, after it is completely dissolved, adds 2.0g glycerol and stirs 2.5 hours, adding the positive silicon of 10g
Acetoacetic ester, continues stirring 10 minutes, and then 40 DEG C stand 28 hours, 115 DEG C of hydro-thermal reactions in a kettle.
30 hours, put into after baking oven is dried 9 hours in 120 DEG C after filtration washing, homoiothermic to 175 DEG C pre-carbonization 5.5h
Obtain complex.Complex is put in retort under nitrogen atmosphere is protected with the heating rate liter of 2 DEG C/min
Temperature, to 975 DEG C, stops heating natural cooling after being incubated 3.5 hours, then by the hydrofluoric acid dips of 15wt%,
The most scrubbed, dry and grinding obtains ordered mesopore carbon ball.
Spherical ordered mesoporous for 1g Carbon Materials is mixed with 2.5g elemental sulfur, below vacuum 10KPa under the conditions of
It is warmed up to 900 DEG C with the heating rate of 5 DEG C/min, is incubated 8 hours, is then cooled to room temperature, prepare embedding
Sulfur ordered mesopore carbon ball composite.
Weigh a certain amount of embedding sulfur ordered mesopore carbon ball composite and be scattered in the cetyl trimethyl of 0.4wt%
In the aqueous solution of ammonium bromide, magnetic agitation 5 hours, after being centrifuged, product is joined the finite concentration of previous preparation
Graphene oxide aqueous dispersions in, continue stirring 5 hours so that graphene oxide is coated with embedding sulfur completely to be had
Sequence mesoporous carbon spheres composite, adds appropriate L-AA reduction, after stirring 10 hours, is centrifuged, washes
Wash, be dried.Subsequently, in nitrogen atmosphere, dried product 300 DEG C is processed 3 hours, prepare graphite
Alkene is coated with embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material.
Electrochemical results shows under 2.5C electric current density, and its specific discharge capacity is 962mAh/g, i.e.
Making under high current density 8C, its capacity still has 603mAh/g.
Finally should be noted that: it is only limited by above example in order to technical scheme to be described
System, after those skilled in the art read description of the invention, can repair the detailed description of the invention of the present invention
Changing or equivalent, these, without departing from any amendment of spirit and scope of the invention or equivalent, all exist
Within the claims that application is awaited the reply.
Claims (10)
1. a preparation method for graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material, comprises the following steps successively:
Step one: concentrated sulphuric acid is joined in deionized water, it is heated to 36～40 DEG C, add structure directing agent, after it is completely dissolved, add carbon source and stir 1.5～2.5 hours, add template tetraethyl orthosilicate, continue stirring 10min, then 28 hours are stood at 36～40 DEG C, 105～115 DEG C of hydro-thermal reactions 26～30 hours in a kettle., put into after baking oven is dried 7～9 hours in 110～120 DEG C after filtration washing, carry out pre-carbonization and obtain complex, complex is put into retort and carries out carbonization, then by hydrofluoric acid dips, the most scrubbed, it is dried and grinds and obtain ordered mesopore carbon ball；
Step 2: being mixed with elemental sulfur by the ordered mesopore carbon ball of gained in step one, vacuum high-temperature heats a period of time, is then cooled to room temperature, prepares embedding sulfur ordered mesopore carbon ball；
Step 3: the embedding sulfur ordered mesopore carbon ball obtained in step 2 is scattered in the aqueous solution of cationic surfactant, magnetic agitation 3～5 hours, after Li Xin, product is joined in the aqueous dispersions of certain density graphene oxide, continue stirring 3～5 hours, graphene oxide is made to be coated with embedding sulfur ordered mesopore carbon ball completely, add reducing agent, after stirring 10 hours, be centrifuged, wash, be dried；Subsequently, in nitrogen atmosphere, dried product 300 DEG C is processed 1～3 hour, prepare graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material.
2. according to the preparation method of a kind of graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material described in claim 1, it is characterised in that step one, the concentration of concentrated sulphuric acid is 98%, and concentrated sulphuric acid is 1:15-25 with the volume ratio of deionized water；After being joined in deionized water by concentrated sulphuric acid, heating-up temperature is 38 DEG C；Mixing time after addition carbon source 2 hours；Dwell temperature is 38 DEG C.
3. according to the preparation method of a kind of graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material described in claim 1, it is characterised in that step one hydrothermal temperature is 110 DEG C, and the response time is 28 hours.
4. according to the preparation method of a kind of graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material described in claim 1, it is characterised in that step one structure directing agent is F127；Step one carbon source is glycerol；Step one template is tetraethyl orthosilicate；Carbon source is 1:1-3 with the mass ratio of structure directing agent, and the volume of the concentrated sulphuric acid that every 1g carbon source is corresponding is 1-5ml；Carbon source is 1:3-5 with the mass ratio of template.
5. according to the preparation method of a kind of graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material described in claim 1, it is characterised in that the pre-carburizing temperature of step one is 165～175 DEG C, and the time is 4.5～5.5 hours；The step of step one carbonization includes: protecting with nitrogen atmosphere during whole, heating rate is 2 DEG C/min, after 875～975 DEG C of insulations 2.5～3.5 hours, stops heating natural cooling.
6., according to the preparation method of a kind of graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material described in claim 1, it is characterised in that in step 2, ordered mesopore carbon ball is 1:1.5-2.5 with the mass ratio of elemental sulfur.
7. according to the preparation method of a kind of graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material described in claim 1, it is characterized in that, in step 2, in vacuum high-temperature heating process, heating rate is 5 DEG C/min, holding temperature is 800～900 DEG C, and temperature retention time is 6～8 hours.
8. according to the preparation method of a kind of graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material described in claim 7, it is characterised in that holding temperature is 850 DEG C, and temperature retention time is 7 hours.
9. according to the preparation method of a kind of graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material described in claim 1, it is characterised in that in step 3, aqueous solution of cationic surfactant active cationic surfactant concentration is 0.4wt%；Cationic surfactant used is cetyl trimethylammonium bromide；Reducing agent used is L-AA.
10., according to the preparation method of a kind of graphene coated embedding sulfur ordered mesopore carbon ball lithium sulfur battery anode material described in claim 1, it is characterised in that in step 3,300 DEG C of process times of dried product are 2 hours.
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Cited By (11)
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| CN106450190A (en) * | 2016-10-11 | 2017-02-22 | 武汉理工大学 | Method for high-current density fast filling of microporous sulfur in lithium-sulfur battery |
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| CN108448086A (en) * | 2018-03-14 | 2018-08-24 | 吉林大学 | The anode composite material of lithium sulfur battery and preparation method thereof rich in polymercaptan of vulcanization |
| CN109205594A (en) * | 2017-06-29 | 2019-01-15 | 中国科学院金属研究所 | A kind of preparation method and applications of graphene conductive microballoon |
| CN109920985A (en) * | 2019-01-28 | 2019-06-21 | 四川大学 | A kind of lithium sulfur battery anode material and preparation method thereof |
| CN114512657A (en) * | 2022-02-16 | 2022-05-17 | 太原理工大学 | Graphene oxide/sulfur nanoparticle composite microsphere and preparation method thereof, prepared battery anode and preparation method thereof |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103050702A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Application of carbon material containing in-situ doped component with catalytic activity to lithium-air battery |
| CN103253740A (en) * | 2013-05-14 | 2013-08-21 | 上海大学 | Preparation method of three-dimensional hierarchical graphene/porous carbon composite capacitive type desalination electrode |
| CN103474633A (en) * | 2012-06-07 | 2013-12-25 | 中国人民解放军63971部队 | Carbon-sulfur-shell matter composite material having network dual-core shell structure and preparation method thereof |
| CN103560235A (en) * | 2013-11-15 | 2014-02-05 | 哈尔滨工业大学 | Graphene-coated sulfur/porous carbon composite positive electrode material and preparation method thereof |
| CN103825000A (en) * | 2014-03-03 | 2014-05-28 | 东南大学 | Mesoporous carbon loaded sulfur/selenium flexible electrode based on three-dimensional graphite alkene self-supporting structure as well as preparation method and application thereof |
| CN104157849A (en) * | 2013-05-14 | 2014-11-19 | 深圳华粤宝电池有限公司 | Method for preparing elemental sulfur and mesoporous carbon composite material |
| CN104269538A (en) * | 2014-09-29 | 2015-01-07 | 南京中储新能源有限公司 | Graphene-coated carbon nanofiber/sulphur composite material, preparation and application thereof |
| CN104269543A (en) * | 2014-10-09 | 2015-01-07 | 南京中储新能源有限公司 | Graphene-cladded sulfur/microporous carbon sphere composite cathode material |
| CN204243132U (en) * | 2014-09-05 | 2015-04-01 | 南京中储新能源有限公司 | A kind of carbon sulphur combination electrode of graphene coated and secondary aluminium cell |
| CN104916828A (en) * | 2015-04-16 | 2015-09-16 | 中国人民解放军国防科学技术大学 | Three dimensional graphene/hollow carbon sphere/sulfur composite material, preparation method thereof, and application in lithium-sulfur batteries |
-
2016
- 2016-05-16 CN CN201610323865.0A patent/CN105810915B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103050702A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Application of carbon material containing in-situ doped component with catalytic activity to lithium-air battery |
| CN103474633A (en) * | 2012-06-07 | 2013-12-25 | 中国人民解放军63971部队 | Carbon-sulfur-shell matter composite material having network dual-core shell structure and preparation method thereof |
| CN103253740A (en) * | 2013-05-14 | 2013-08-21 | 上海大学 | Preparation method of three-dimensional hierarchical graphene/porous carbon composite capacitive type desalination electrode |
| CN104157849A (en) * | 2013-05-14 | 2014-11-19 | 深圳华粤宝电池有限公司 | Method for preparing elemental sulfur and mesoporous carbon composite material |
| CN103560235A (en) * | 2013-11-15 | 2014-02-05 | 哈尔滨工业大学 | Graphene-coated sulfur/porous carbon composite positive electrode material and preparation method thereof |
| CN103825000A (en) * | 2014-03-03 | 2014-05-28 | 东南大学 | Mesoporous carbon loaded sulfur/selenium flexible electrode based on three-dimensional graphite alkene self-supporting structure as well as preparation method and application thereof |
| CN204243132U (en) * | 2014-09-05 | 2015-04-01 | 南京中储新能源有限公司 | A kind of carbon sulphur combination electrode of graphene coated and secondary aluminium cell |
| CN104269538A (en) * | 2014-09-29 | 2015-01-07 | 南京中储新能源有限公司 | Graphene-coated carbon nanofiber/sulphur composite material, preparation and application thereof |
| CN104269543A (en) * | 2014-10-09 | 2015-01-07 | 南京中储新能源有限公司 | Graphene-cladded sulfur/microporous carbon sphere composite cathode material |
| CN104916828A (en) * | 2015-04-16 | 2015-09-16 | 中国人民解放军国防科学技术大学 | Three dimensional graphene/hollow carbon sphere/sulfur composite material, preparation method thereof, and application in lithium-sulfur batteries |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450190B (en) * | 2016-10-11 | 2019-06-28 | 武汉理工大学 | The method of high current density Fast Filling micropore sulphur in lithium-sulfur cell |
| CN106450190A (en) * | 2016-10-11 | 2017-02-22 | 武汉理工大学 | Method for high-current density fast filling of microporous sulfur in lithium-sulfur battery |
| CN106784851A (en) * | 2017-03-08 | 2017-05-31 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method and applications of graphene quantum dot/mesoporous carbon composite material |
| CN106784851B (en) * | 2017-03-08 | 2019-12-06 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of graphene quantum dot/mesoporous carbon composite material |
| CN109205594A (en) * | 2017-06-29 | 2019-01-15 | 中国科学院金属研究所 | A kind of preparation method and applications of graphene conductive microballoon |
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| CN108249418B (en) * | 2018-01-16 | 2023-07-21 | 南京农业大学 | High specific surface area myrica rubra nuclear-based graphene/ordered mesoporous carbon composite material and preparation method thereof |
| CN108448086A (en) * | 2018-03-14 | 2018-08-24 | 吉林大学 | The anode composite material of lithium sulfur battery and preparation method thereof rich in polymercaptan of vulcanization |
| CN109920985A (en) * | 2019-01-28 | 2019-06-21 | 四川大学 | A kind of lithium sulfur battery anode material and preparation method thereof |
| CN109920985B (en) * | 2019-01-28 | 2021-04-20 | 四川大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| CN114512657A (en) * | 2022-02-16 | 2022-05-17 | 太原理工大学 | Graphene oxide/sulfur nanoparticle composite microsphere and preparation method thereof, prepared battery anode and preparation method thereof |
| CN114512657B (en) * | 2022-02-16 | 2024-03-08 | 太原理工大学 | Graphene oxide/sulfur nanoparticle composite microsphere and preparation method thereof, prepared battery anode and preparation method thereof |
| CN114735673A (en) * | 2022-05-05 | 2022-07-12 | 贵州大学 | Preparation method and application of crosslinked mesoporous carbon composite material |
| CN114735673B (en) * | 2022-05-05 | 2024-03-01 | 贵州大学 | Preparation method and application of crosslinked micro-mesoporous carbon composite material |
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