CN105810915B - A kind of preparation of order mesoporous carbon ball composite material of the embedding sulphur of graphene coated and the application as lithium sulfur battery anode material - Google Patents
A kind of preparation of order mesoporous carbon ball composite material of the embedding sulphur of graphene coated and the application as lithium sulfur battery anode material Download PDFInfo
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- H—ELECTRICITY
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Abstract
A kind of preparation of order mesoporous carbon ball composite material of the embedding sulphur of graphene coated and the application as lithium sulfur battery anode material belong to the technical field of lithium sulfur battery anode material.Triblock copolymer F127 (polyoxyethylene polyoxypropylene polyoxyethylene) is structure directing agent and carbon source, ethyl orthosilicate are template, glycerine is that carbon source prepares order mesoporous carbon ball by one-step method, heating in vacuum after the order mesoporous carbon ball of preparation is mixed with elemental sulfur, elemental sulfur is embedded into order mesoporous carbon ball, the order mesoporous carbon ball composite material of embedding sulphur is prepared, then the order mesoporous carbon ball composite material surface coated graphite alkene of embedding sulphur is acted on by surface electrostatic and obtains the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated.The lithium sulfur battery anode material of electrochemical performance has been prepared in technical solution provided by the invention, has been had a good application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated, tools
Body, which is said, is related to a kind of compound side for preparing lithium sulfur battery anode material by order mesoporous carbon ball, elemental sulfur and graphene
Method belongs to the technical field of lithium sulfur battery anode material.
Background technology
Lithium ion battery due to having higher energy density to be widely used in portable electric appts, in electric vehicle and
Power station energy storage etc. also has application.But current lithium ion battery energy density can room for promotion very little, it is difficult to it is full
The growing demand to heavy-duty battery such as sufficient electronic product and electric vehicle, it is therefore necessary to develop the battery of high power capacity
Material.Lithium-sulfur cell is due to having the up to theoretical specific capacity of 1675mAh/g, and elemental sulfur rich reserves, cheap, ring
Border is friendly, therefore lithium-sulfur cell is coming next-generation heavy-duty battery.But elemental sulfur and discharging product lithium sulfide
Electric conductivity is very poor, and the intermediate polysulfide for being soluble in organic electrolyte can be generated in discharge process, causes and " shuttles and imitate
Should ", serious volume change is in addition there is also in cyclic process, these factors cause lithium-sulfur cell active material utilization
Low and poor circulation has seriously affected the application of lithium-sulfur cell.To solve the above problems, most studied in recent years is to lead
Electrical carbon material is as the carrier of sulphur and the sulphur carbon composite anode material of conducting matrix grain.Research shows that mesoporous carbon is smaller due to having
Pore passage structure, can effectively inhibit the dissolving and migration of polysulfide.Nevertheless, mesoporous carbon/sulphur composite positive pole
There are still more serious shuttle effects, and capacity attenuation is more severe after undergoing repeatedly Xun Huan, it is impossible to meet heavy-duty battery
Requirement.Therefore, explore a kind of preparation method of the lithium sulfur battery anode material of functional stabilization to be of great significance, this hair
It is bright that order mesoporous carbon ball is prepared using one-step method, using the method for heating in vacuum elemental sulfur is made to be embedded into order mesoporous carbon ball,
The order mesoporous carbon ball composite material of embedding sulphur is obtained, electrochemistry is made in the graphene in embedding sulphur ordered mesopore carbon ball surface cladding
The excellent order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated of energy.
The content of the invention
For overcome the deficiencies in the prior art, the present invention provides a kind of order mesoporous carbon ball lithium-sulfur cell of the embedding sulphur of graphene coated
Method for preparing anode material further improves the performance of positive electrode, such as cycle performance, and realizes large-scale production, has more
Industrial value.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated, successively including following
Step：
Step 1：The concentrated sulfuric acid is added in deionized water, is heated to 36~40 DEG C, structure directing agent is added in, treats that its is complete
After fully dissolved, when adding in carbon source and small stirring 1.5~2.5, template ethyl orthosilicate is added, continues to stir 10min, then
When 36~40 DEG C of standings 28 are small, when 105~115 DEG C of hydro-thermal reactions 26~30 are small in a kettle, baking is put into after filtration washing
In case in 110~120 DEG C it is dry 7~9 it is small when after, carry out pre- carbonization and obtain compound, compound is put into retort carries out charcoal
Change, then obtain order mesoporous carbon ball with hydrofluoric acid dips, then washed, dry and grinding；
Step 2：The order mesoporous carbon ball of gained in step 1 is mixed with elemental sulfur, vacuum high-temperature heating a period of time,
It is then cooled to room temperature, the embedding order mesoporous carbon ball of sulphur is made.
Step 3：The order mesoporous carbon ball of embedding sulphur obtained in step 2 is scattered in the aqueous solution of cationic surfactant
In, when magnetic agitation 3~5 is small, product is added in the aqueous dispersions of certain density graphene oxide after centrifugation, continues to stir
Mix 3~5 it is small when so that graphene oxide coats the order mesoporous carbon ball of embedding sulphur completely, adds in reducing agent, when stirring 10 is small after, from
The heart, washing, drying；Then, in nitrogen atmosphere, by the 300 DEG C of processing 1~3 of dried product it is small when, graphene coated is made
The embedding order mesoporous carbon ball lithium sulfur battery anode material of sulphur.
Preferably, the concentration of the concentrated sulfuric acid is 98%.
Preferably, the volume ratio of the concentrated sulfuric acid and deionized water is 1:15-25, it is furthermore preferred that the concentrated sulfuric acid and deionized water
Volume ratio is 1:20.
Preferably, after the concentrated sulfuric acid is added in deionized water by step 1, heating temperature is 38 DEG C.
Preferably, when the mixing time 2 after step 1 addition carbon source is small.
Preferably, step 1 dwell temperature is 38 DEG C.
Preferably, step 1 hydrothermal temperature is 110 DEG C, when the reaction time is 28 small.
Preferably, in step 1, drying temperature is 115 DEG C, when drying time is 8 small.
Preferably, step 1 structure directing agent is F127.
Preferably, step 1 carbon source is glycerine.
Preferably, step 1 template is ethyl orthosilicate.
Preferably, the mass ratio of step 1 carbon source and structure directing agent is 1:1-3, it is furthermore preferred that carbon source and structure directing
The mass ratio of agent is 1:2.Volume per the corresponding concentrated sulfuric acid of 1g carbon sources is 1-5ml.
Preferably, the mass ratio of carbon source and template is 1:3-5, it is furthermore preferred that the mass ratio of carbon source and template is 1:
4。
Preferably, the pre- carburizing temperature of step 1 is 165~175 DEG C, when the time is 4.5~5.5 small, it is furthermore preferred that pre- carbon
It is 170 DEG C to change temperature, when the time is 5 small.
Preferably, the step of step 1 is carbonized includes：It is protected in whole process with nitrogen atmosphere, heating rate is 2 DEG C/minute
Clock, in 875~975 DEG C heat preservation 2.5~3.5 it is small when after, stop heating and natural cooling, it is furthermore preferred that carburizing temperature be 900
DEG C, when soaking time is 3 small.
Preferably, step 1 hydrofluoric acid concentration is 15wt%.
Preferably, in step 2, the mass ratio of order mesoporous carbon ball and elemental sulfur is 1:1.5-2.5 it is furthermore preferred that in order
The mass ratio of mesoporous carbon spheres and elemental sulfur is 1:2.
Preferably, in step 2, heating rate is 5 DEG C/min in vacuum high-temperature heating process, holding temperature for 800~
900 DEG C, when soaking time is 6~8 small, it is furthermore preferred that holding temperature is 850 DEG C, when soaking time is 7 small.Vacuum is preferred
40KPa-10Pa。
Preferably, in step 3, cationic surfactant concentration is in aqueous solution of cationic surfactant active
0.4wt%.
Preferably, cationic surfactant used is cetyl trimethylammonium bromide.
Preferably, reducing agent used is L-AA.
Preferably, in step 3, when dried 300 DEG C of processing times of product are 2 small.
As shown in Figure 1, elemental sulfur by heating in vacuum into forming embedding sulphur and be situated between in order in the duct of spherical ordered mesoporous carbon
Then hole carbon ball makes embedding sulphur ordered mesopore carbon ball surface positively charged with cationic surfactant, makes the order mesoporous carbon ball of embedding sulphur
With electronegative graphene oxide self assembly, the order mesoporous carbon ball lithium sulphur of the embedding sulphur of graphene coated is obtained after redox graphene
Cell positive material.
Compared with the immediate prior art, technical solution provided by the invention has following excellent effect：
One-step method is employed in technical solution provided by the invention to prepare order mesoporous carbon ball, preparation process is simply high
Effect, obtained order mesoporous carbon ball are presented good spherical structure, possess orderly three-dimensional cubic mesopore orbit structure.Pass through
Simple vaccum heating method makes elemental sulfur be embedded in the duct of orderly mesoporous carbon spheres, and the embedding sulphur for obtaining electrochemical performance is orderly
Mesoporous carbon spheres composite material.After the upper graphene of simple electrostatic attraction effect cladding, it is more excellent that chemical property is made
The order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated.
Description of the drawings
The order mesoporous carbon ball lithium sulfur battery anode material preparation flow schematic diagram of the embedding sulphur of 1 graphene coated of attached drawing.
Scanning electron microscope (SEM) photo of 2 order mesoporous carbon ball of attached drawing.
High-resolution-ration transmission electric-lens (HRTEM) photo of 3 order mesoporous carbon ball of attached drawing.
Scanning electron microscope (SEM) photo of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of 4 graphene coated of attached drawing.
Stable circulation linearity curve of the order mesoporous carbon ball composite material of 5 embedding sulphur of attached drawing under 2.5C multiplying powers.
The circulation curve of the order mesoporous carbon ball composite material of 6 embedding sulphur of attached drawing.
Stable circulation of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of 7 graphene coated of attached drawing under 0.4C multiplying powers
Linearity curve.
Cyclical stability of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of 8 graphene coated of attached drawing under 4C multiplying powers
Curve.
The circulation curve of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of 9 graphene coated of attached drawing.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples, but the present invention is not limited to following realities
Apply example.
Embodiment 1
The 5mL concentrated sulfuric acids are added in 100mL deionized waters first, are heated to 38 DEG C, add in 4.0g triblock copolymers
F127 (polyoxyethylene-poly-oxypropylene polyoxyethylene), after it is completely dissolved, when adding in 2.0g glycerine and small stirring 2, then
Add in the ethyl orthosilicate of 8g, continue stirring 10 minutes, then 38 DEG C stand 28 it is small when, 110 DEG C of hydro-thermal reactions in a kettle
28 it is small when, be put into baking oven after filtration washing in 115 DEG C it is dry 8 it is small when after, temperature adjustment to 170 DEG C of pre- carbonization 5h obtains compound.
Compound is put into retort and is warming up to 900 DEG C, when heat preservation 3 is small under nitrogen atmosphere protection with 2 DEG C/min of heating rate
Stop heating and natural cooling afterwards, then with the hydrofluoric acid dips of 15wt%, then washed, dry and grinding obtain it is order mesoporous
Carbon ball.
The spherical ordered mesoporous Carbon Materials of 1g are mixed with 2g elemental sulfurs, with 5 DEG C/min under vacuum 10KPa the following conditions
Heating rate be warming up to 850 DEG C, heat preservation 7 it is small when, be then cooled to room temperature, be made the embedding order mesoporous carbon ball composite wood of sulphur
Material.
Weigh the cetyl trimethyl bromination that the order mesoporous carbon ball composite material of a certain amount of embedding sulphur is scattered in 0.4wt%
In the aqueous solution of ammonium, product is added to the certain density graphene oxide for preparing previously when magnetic agitation 4 is small, after centrifugation
In aqueous dispersions, continue stirring 4 it is small when so that graphene oxide coats the order mesoporous carbon ball composite material of embedding sulphur completely, add in
The reduction of suitable L-AA, when stirring 10 is small after, it is centrifugation, washing, dry.It then, will be dried in nitrogen atmosphere
When 300 DEG C of processing 2 of product are small, the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated is made.
Fig. 2 is scanning electron microscope (SEM) photo of order mesoporous carbon ball.As shown in the figure, can intuitively find out, it is order mesoporous
Preferable spherical structure is presented in carbon ball, and diameter is mainly distributed between 0.5~3 μm.
Fig. 3 is high-resolution-ration transmission electric-lens (HRTEM) photo of order mesoporous carbon ball.As shown in the figure, can intuitively find out,
Order mesoporous carbon ball possesses orderly three-dimensional cubic duct structure, and aperture is about in 5~6nm.
Fig. 4 is scanning electron microscope (SEM) photo of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated.Such as
Shown in figure, can intuitively it find out, graphene coated is on the surface of the order mesoporous carbon ball of embedding sulphur, and the surface after cladding is compared
It is smooth.
Fig. 5 is the stable circulation curve under the 2.5C multiplying powers of the order mesoporous carbon ball composite material of embedding sulphur.As shown in the figure, can be with
Find out, the embedding order mesoporous carbon ball composite material of sulphur is in high current 2.5C rate charge-discharges, and after 45 Xun Huans, discharge ratio
Capacity still reaches 850mAh/g, and capacity retention ratio reaches 89%, and in whole process, coulombic efficiency is close to 100%.Electrochemistry
It can be excellent.
Fig. 6 is the circulation curve of the order mesoporous carbon ball composite material of embedding sulphur.As shown in the figure, it can be seen that embedding sulphur has
Sequence mesoporous carbon spheres composite material 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 times cycle, again when 0.25C discharges, specific discharge capacity still can reach
860mAh/g or so, so as to understand that ordered mesopore carbon ball/sulphur nanocomposite possesses quite excellent high rate performance.
Fig. 7 is stable circulation of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated under 0.4C multiplying powers
Curve.As shown in the figure, it can be seen that the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated is in low current 0.4C
During electric discharge, specific discharge capacity fluctuates above and below 1230mAh/g, and straight line is presented in cyclic curve substantially, illustrates through graphene
After cladding, the specific discharge capacity and cyclical stability of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated have
Apparent raising.
Fig. 8 is that stable circulation of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated under 4C multiplying powers is bent
Line.As shown in the figure, it can be seen that the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated is in high current 4C charge and discharges
When electric, equally there is higher specific discharge capacity, after 99 Xun Huans, specific discharge capacity is still up to 827mAh/g, and
And have the efficiency for charge-discharge close to 100%, illustrate after graphene coated, show more excellent chemical property.
Fig. 9 is the circulation curve of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated.As schemed
Show, it can be seen that the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated is filled in 0.4C, 0.8C, 2C, 4C, 8C
During electric discharge, 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 discharges, specific discharge capacity is still up to 1160mAh/g or so.It can thus be appreciated that the embedding sulphur of graphene coated
Order mesoporous carbon ball lithium sulfur battery anode material possesses superior high rate performance.
Embodiment 2
The 2mL concentrated sulfuric acids are added in 75mL deionized waters first, are heated to 36 DEG C, add in 2.0g F127, treat it completely
After dissolving, add in 2.0g glycerine and stir 1.5 it is small when, add the ethyl orthosilicate of 6g, continue stirring 10 minutes, then 36
DEG C stand 28 it is small when, when 105 DEG C of hydrothermal crystallizings 26 are small in a kettle, be put into baking oven after filtration washing in 110 DEG C dry 7 small
Shi Hou, temperature adjustment to 165 DEG C of pre- carbonization 4.5h obtain compound.Compound is put into retort under nitrogen atmosphere protection with 2
DEG C/min heating rate be warming up to 875 DEG C, when heat preservation 2.5 is small after stop heating and natural cooling, then with the hydrogen of 15wt%
Fluoric acid impregnates, then washed, dry and grinding obtains order mesoporous carbon ball.
The spherical ordered mesoporous Carbon Materials of 1g are mixed with 1.5g elemental sulfurs, with 5 DEG C/minute under vacuum 10KPa the following conditions
The heating rate of clock is warming up to 800 DEG C, when heat preservation 6 is small, is then cooled to room temperature, and the embedding order mesoporous carbon ball composite wood of sulphur is made
Material.
Weigh the cetyl trimethyl bromination that the order mesoporous carbon ball composite material of a certain amount of embedding sulphur is scattered in 0.4wt%
In the aqueous solution of ammonium, product is added to the certain density graphene oxide for preparing previously when magnetic agitation 3 is small, after centrifugation
In aqueous dispersions, continue stirring 3 it is small when so that graphene oxide coats the order mesoporous carbon ball composite material of embedding sulphur completely, add in
The reduction of suitable L-AA, when stirring 10 is small after, it is centrifugation, washing, dry.It then, will be dried in nitrogen atmosphere
When 300 DEG C of processing 1 of product are small, the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated is made.
Electrochemical results show under 2.5C current densities, specific discharge capacity 1024mAh/g, even if in high electricity
Under current density 8C, capacity still has 617mAh/g.
Embodiment 3
The 10mL concentrated sulfuric acids are added in 125mL deionized waters first, are heated to 40 DEG C, 6.0g F127 is added in, treats that its is complete
After fully dissolved, when adding in 2.0g glycerine and small stirring 2.5, the ethyl orthosilicate of 10g is added, continues stirring 10 minutes, so
When 40 DEG C of standings 28 are small afterwards, when 115 DEG C of hydro-thermal reactions 30 are small in a kettle, it is put into after filtration washing in baking oven dry in 120 DEG C
It is dry 9 it is small when after, temperature adjustment to 175 DEG C of pre- carbonization 5.5h obtains compound.Compound is put into retort and is protected in nitrogen atmosphere
Under with 2 DEG C/min of heating rate be warming up to 975 DEG C, when heat preservation 3.5 is small after stop heating and natural cooling, Ran Houyong
The hydrofluoric acid dips of 15wt%, then washed, dry and grinding obtain order mesoporous carbon ball.
The spherical ordered mesoporous Carbon Materials of 1g are mixed with 2.5g elemental sulfurs, with 5 DEG C/minute under vacuum 10KPa the following conditions
The heating rate of clock is warming up to 900 DEG C, when heat preservation 8 is small, is then cooled to room temperature, and the embedding order mesoporous carbon ball composite wood of sulphur is made
Material.
Weigh the cetyl trimethyl bromination that the order mesoporous carbon ball composite material of a certain amount of embedding sulphur is scattered in 0.4wt%
In the aqueous solution of ammonium, product is added to the certain density graphene oxide for preparing previously when magnetic agitation 5 is small, after centrifugation
In aqueous dispersions, continue stirring 5 it is small when so that graphene oxide coats the order mesoporous carbon ball composite material of embedding sulphur completely, add in
The reduction of suitable L-AA, when stirring 10 is small after, it is centrifugation, washing, dry.It then, will be dried in nitrogen atmosphere
When 300 DEG C of processing 3 of product are small, the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated is made.
Electrochemical results show under 2.5C current densities, specific discharge capacity 962mAh/g, even if in high electricity
Under current density 8C, capacity still has 603mAh/g.
Finally it should be noted that：The above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof, this
After field technology personnel read description of the invention, it can modify to the specific embodiment of the present invention or equally replace
It changes, these are applying for pending claim guarantor without departing from any modification of spirit and scope of the invention or equivalent substitution
Within the scope of shield.
Claims (10)
1. a kind of preparation method of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated, successively including following step
Suddenly：
Step 1：The concentrated sulfuric acid is added in deionized water, is heated to 36~40 DEG C, adds in structure directing agent, treats that it is completely molten
Xie Hou when adding in carbon source and small stirring 1.5~2.5, adds template ethyl orthosilicate, continues to stir 10min, then 36
When~40 DEG C of standings 28 are small, when 105~115 DEG C of hydro-thermal reactions 26~30 are small in a kettle, it is put into after filtration washing in baking oven
After when 110~120 DEG C of dryings 7~9 are small, carry out pre- carbonization and obtain compound, compound is put into retort carbonizes, so
Afterwards order mesoporous carbon ball is obtained with hydrofluoric acid dips, then washed, dry and grinding；
Step 2：The order mesoporous carbon ball of gained in step 1 is mixed with elemental sulfur, vacuum high-temperature heating a period of time, then
Room temperature is cooled to, the embedding order mesoporous carbon ball of sulphur is made；
Step 3：The order mesoporous carbon ball of embedding sulphur obtained in step 2 is scattered in the aqueous solution of cationic surfactant,
When magnetic agitation 3~5 is small, product is added in the aqueous dispersions of certain density graphene oxide after centrifugation, continues stirring 3
~5 it is small when so that graphene oxide coats the order mesoporous carbon ball of embedding sulphur completely, adds in reducing agent, when stirring 10 is small after, centrifugation,
Washing, drying；Then, in nitrogen atmosphere, by the 300 DEG C of processing 1~3 of dried product it is small when, it is embedding that graphene coated is made
The order mesoporous carbon ball lithium sulfur battery anode material of sulphur；
Step 1 structure directing agent is F127.
2. a kind of preparation of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated described in accordance with the claim 1
Method, which is characterized in that step 1, the concentration of the concentrated sulfuric acid is 98%, and the volume ratio of the concentrated sulfuric acid and deionized water is 1:15-25；
After the concentrated sulfuric acid is added in deionized water, heating temperature is 38 DEG C；When mixing time 2 after addition carbon source is small；Dwell temperature
For 38 DEG C.
3. a kind of preparation of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated described in accordance with the claim 1
Method, which is characterized in that step 1 hydrothermal temperature is 110 DEG C, when the reaction time is 28 small.
4. a kind of preparation of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated described in accordance with the claim 1
Method, which is characterized in that step 1 carbon source is glycerine；Step 1 template is ethyl orthosilicate；Carbon source and structure directing agent
Mass ratio be 1:1-3, the volume per the corresponding concentrated sulfuric acid of 1g carbon sources are 1-5mL；The mass ratio of carbon source and template is 1:3-
5。
5. a kind of preparation of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated described in accordance with the claim 1
Method, which is characterized in that the pre- carburizing temperature of step 1 is 165~175 DEG C, when the time is 4.5~5.5 small；Step 1 carbonization
Step includes：It is protected in whole process with nitrogen atmosphere, heating rate is 2 DEG C/min, and 2.5~3.5 are kept the temperature in 875~975 DEG C
After hour, stop heating and natural cooling.
6. a kind of preparation of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated described in accordance with the claim 1
Method, which is characterized in that in step 2, the mass ratio of order mesoporous carbon ball and elemental sulfur is 1:1.5-2.5.
7. a kind of preparation of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated described in accordance with the claim 1
Method, which is characterized in that in step 2, heating rate is 5 DEG C/min in vacuum high-temperature heating process, holding temperature for 800~
900 DEG C, when soaking time is 6~8 small.
8. according to a kind of preparation of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated described in claim 7
Method, which is characterized in that holding temperature is 850 DEG C, when soaking time is 7 small.
9. a kind of preparation of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated described in accordance with the claim 1
Method, which is characterized in that in step 3, cationic surfactant concentration is in aqueous solution of cationic surfactant active
0.4wt%；Cationic surfactant used is cetyl trimethylammonium bromide；Reducing agent used is L- Vitamin Cs
Acid.
10. a kind of system of the order mesoporous carbon ball lithium sulfur battery anode material of the embedding sulphur of graphene coated described in accordance with the claim 1
Preparation Method, which is characterized in that in step 3, when dried 300 DEG C of processing times of product are 2 small.
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|---|---|---|---|
| CN201610323865.0A CN105810915B (en) | 2016-05-16 | 2016-05-16 | A kind of preparation of order mesoporous carbon ball composite material of the embedding sulphur of graphene coated and the application as lithium sulfur battery anode material |
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| CN105810915B true CN105810915B (en) | 2018-05-25 |
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| 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 |
| 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 |
| CN109205594B (en) * | 2017-06-29 | 2022-04-05 | 中国科学院金属研究所 | Preparation method and application of graphene conductive microspheres |
| CN107768643B (en) * | 2017-10-19 | 2020-10-09 | 山东大学 | Carbon sphere/sulfur/reduced graphene oxide composite material for lithium-sulfur battery and preparation method thereof |
| CN107640758B (en) * | 2017-10-30 | 2019-10-15 | 福州大学 | A kind of preparation method of mesoporous carbon/graphene oxide compound |
| CN108054377B (en) * | 2017-12-27 | 2020-08-04 | 湖南工业大学 | Preparation method of wool spherical carbon/sulfur composite microsphere material and lithium-sulfur battery |
| 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 |
| CN108448086B (en) * | 2018-03-14 | 2020-09-15 | 吉林大学 | Sulfurized lithium-sulfur battery positive electrode composite material rich in polythiol 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 |
| 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 |
| 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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