CN110336036A - Semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material and preparation method, lithium-sulphur cell positive electrode and battery - Google Patents
Semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material and preparation method, lithium-sulphur cell positive electrode and battery Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The invention discloses a kind of semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material and preparation methods, lithium-sulphur cell positive electrode and battery.Titanium dioxide is obtained by hydro-thermal method first, again by wrapping up carbon-coating by carbon source of dopamine, then in-situ polymerization grows polyaniline, loads sulfur granules finally by the mode of sulphuring, finally obtains titanium dioxide/carbon particle/Polyaniline-Supported sulphur semi-spherical hollow shape composite material.The material is applied to lithium sulfur battery anode material, has good cyclical stability and higher specific capacity.Compared with prior art, semi-spherical hollow shape is presented in material prepared by the present invention, and semi-spherical hollow shape structure large specific surface area can load more sulfur granules, be conducive to electron-transport, alleviates the volume expansion of charge and discharge process, improves battery performance.Also, experimentation is simple, the inexpensive easy acquisition of raw material.
Description
Technical field
The invention belongs to novel energy resource material technology fields, and in particular to a kind of semi-spherical hollow shape titanium dioxide/carbon particle/poly-
Composite material and preparation method, lithium-sulphur cell positive electrode and the battery of aniline sulfur loaded.
Background technique
Due to the exhaustion of environmental pollution and fossil fuel, non-renewable energy resources amount of storage increasingly reduces, climatic environment increasingly
Badly, the ecosystem is more and more fragile, and the demand of the cleanings such as solar energy and wind energy and renewable energy becomes more more and more urgent hair
Opening up, there is high-energy density, long circulation life, high security, environmentally protective and inexpensive secondary cell to have in new energy field
It is of great importance.
Lithium-sulfur cell is using element sulphur as anode, and a kind of lithium battery of the lithium metal as cathode, theory compares energy
Amount is up to (2600Wh/kg) and higher theoretical specific capacity (1675mAh/g), much higher than current commercialized lithium ion battery.
In recent years, lithium-sulfur cell is from a wealth of sources because having, and at low cost, the high advantage of biocompatibility becomes new research boom.And because
Its electrode material elemental sulfur is cheap and resourceful and environmental-friendly, so that lithium-sulfur cell system great commercial value.
However, intrinsic three challenges of lithium-sulfur cell restrict always its it is further develop, i.e. elemental sulfur and electric discharge produces
Object (Li2S electrical insulation property), volume expansion is serious in charge and discharge process and intermediate product polysulfide in the electrolyte molten
Solution, these problems cause that the low utilization rate of sulphur in battery, poor circulation, capacity attenuation are fast, high rate performance is poor.
Summary of the invention
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of semi-spherical hollow shape titanium dioxide/carbon particle/
The composite material of Polyaniline-Supported sulphur.Reasonable semi-spherical hollow shape structure has big specific surface area, is conducive to electron-transport, can
Load more active materials.
Another object of the present invention is to provide a kind of semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur and answers
Titanium dioxide is prepared using cheap raw material in the preparation method of condensation material, then by wrapping up by carbon source of dopamine
Carbon, then polyaniline is grown under ice bath environment, titanium dioxide/carbon particle/polyaniline nano material is obtained, sulfur loaded obtains later
Lithium sulfur battery anode material.Its preparation process is simple, yield is high, at low cost.
The present invention there are also being designed to provide a kind of lithium-sulphur cell positive electrode, using above-mentioned semi-spherical hollow shape titanium dioxide/
Carbon particle/Polyaniline-Supported sulphur composite material is made.
The present invention the last one be designed to provide a kind of battery, including above-mentioned lithium-sulphur cell positive electrode.
Specific technical solution of the present invention is as follows:
A kind of preparation method of semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material, the system
Preparation Method the following steps are included:
1) dehydrated alcohol is uniformly mixed with isopropanol, adds butyl titanate, after mixing, hydro-thermal reaction obtains
To titanic oxide material；
2) titanic oxide material prepared by step 1) is dispersed in water, after trishydroxymethylaminomethane is added, is added
Dopamine hydrochloride is reacted, and after reaction, obtains titanium dioxide/carbon nanomaterial；
3) titanium dioxide/carbon nanomaterial prepared by step 2) is roasted under nitrogen atmosphere, naturally cools to room temperature, made
Obtain titanium dioxide/carbon particle；
4) in condition of ice bath, titanium dioxide/carbon particle prepared by step 3) is dispersed in sulfuric acid solution, aniline is added and stirs
It mixes uniformly, ammonium persulfate is then added and is reacted, semi-spherical hollow shape titanium dioxide/carbon particle/polyaniline is obtained；
5) semi-spherical hollow shape titanium dioxide/carbon particle/polyaniline prepared by step 4) is uniformly mixed with sulphur powder, in argon gas
Sulphuring under atmosphere obtains semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material.
In step 1), the ratio between the dehydrated alcohol, volume of isopropanol, butyl titanate are (10~30): (10~
20): (0.1~1.0)；
In step 1), the condition of the hydro-thermal reaction is 150~200 DEG C of 4~12h of reaction, and preferably 155~190 DEG C anti-
Answer 5~8h.
In step 1), after reaction, include thes steps that for product being cooled to room temperature, be centrifuged, wash, drying.
In step 2), the titanic oxide material, trishydroxymethylaminomethane, Dopamine hydrochloride mass ratio be 1:(1
~8): (0.2~0.5), preferably 1:(1.5~7.5): (0.225~0.45).
In step 2), the concentration of the titanic oxide material in water is 2~6g/L, preferably 3~5g/L.
In step 2) further include: be added trishydroxymethylaminomethane after regulation system pH be 6.5~10, preferably 8~
9.5。
In step 2), the time of the reaction is 18~30h, preferably 20~26h.
It after reaction further include that product is cooled to room temperature in step 2), the then step through centrifugation, washing, drying.
In step 3), the condition of the roasting is 500~800 DEG C of 2~8h of roasting, is 550~750 DEG C of roasting 3-6h.
In step 4), the titanium dioxide/carbon particle, aniline, ammonium persulfate amount ratio be 1g:(0.15~3.0)
ML:(2~4) g；Concentration of the titanium dioxide/carbon particle in sulfuric acid is 2~6g/L；The sulfuric acid concentration be 0.3~
1mol/L, preferably 0.5~0.8mol/L.
In step (4), the time of the reaction is 6~18h, preferably 8~15h.
In step 4), after reaction, include thes steps that for product being centrifuged, wash, is dry；The drying is dry for vacuum
Dry, vacuum drying condition is 45~85 DEG C of dry 4~18h, preferably 55~70 DEG C 6~8 h of drying.
In step 5), the semi-spherical hollow shape titanium dioxide/carbon particle/polyaniline and sulphur powder mass ratio are 1:1~5；Institute
The condition for stating sulphuring is 140~180 DEG C of 12~18h of sulphuring, preferably 145~175 DEG C of 14~16 h of sulphuring.
According to above-mentioned preparation method, semi-spherical hollow shape titanium dioxide/carbon particle/polyaniline that the present invention is prepared is negative
The composite gauge of sulphur is carried at 2~4 μm.
A kind of semi-spherical hollow shape titanium dioxide/carbon particle being prepared such as above-mentioned preparation method provided by the invention/poly-
Application of the composite material of aniline sulfur loaded as anode material for lithium-ion batteries.
A kind of lithium-sulphur cell positive electrode provided by the invention, the semi-spherical hollow shape dioxy being prepared using above-mentioned preparation method
Change titanium/carbon particle/Polyaniline-Supported sulphur composite material to be made.
A kind of battery provided by the invention, including the lithium-sulphur cell positive electrode, the battery has good cyclicity
Energy.
In order to improve the chemical property of lithium-sulfur cell, the invention discloses a kind of composite materials of semi-spherical hollow shape.If
Reasonable semi-spherical hollow shape composite material is counted with big specific surface area, is conducive to electron-transport, more active matters can be loaded
Matter.The generation of conductive polymer polyanaline can be improved sulphur anode overall conductivity, while also can inhibit to a certain extent more
The dissolution of sulfide, hollow shape are also that the sulphur chain of polysulfide forms more sulphate complex and works as a buffer, and alleviate and fill
Volume expansion problem in discharge process, and reduce active mass loss, it is suppressed that polysulfide shuttles, to improve
The chemical property of anode.
The present invention uses dehydrated alcohol and isopropanol to mix first, carries out transesterification with butyl titanate and is obtained by hydro-thermal method
Titanium dioxide is obtained, improves the volume ratio of dehydrated alcohol and isopropanol and the amount ratio of butyl titanate, then by improving temperature
Degree, reaction time obtain the semi-spherical hollow shape titanium dioxide of optimal pattern and optimum size；By using dopamine as carbon source
Carbon-coating is wrapped up on titanium dioxide again, then polyaniline is grown by in-situ polymerization, loads upper sulfur granules finally by the mode of sulphuring,
The final semi-spherical hollow shape composite material for obtaining carbon sulfur loaded.Semi-spherical hollow shape structure facilitates that sulphur is compound, and carbon can increase dioxy
The surface roughness for changing titanium, is conducive to the growth of polyaniline.The electric conductivity of sulphur anode, but also burr not only can be improved in polyaniline
Shape structure provides bigger specific surface area for the load of later period sulphur, obtains high sulphur load capacity.The material is applied to lithium sulphur electricity
Pond positive electrode has good cyclical stability and high specific capacity.
Compared with prior art, the present invention prepares presoma by hydro-thermal method, then wraps up carbon, and regrowth polyaniline, this two
Semi-spherical hollow shape is presented in titanium oxide/carbon/polyaniline material, and semi-spherical hollow shape structure large specific surface area can load more sulphur
Grain alleviates the volume expansion of charge and discharge process moreover, semi-spherical hollow shape structure is conducive to electron-transport, improves battery performance.And
And experimentation is simple, the inexpensive easy acquisition of raw material.
Detailed description of the invention
Fig. 1 is the SEM figure of the titanic oxide material of 3 step 1) of embodiment preparation；
Fig. 2 is titanium dioxide/carbon nanomaterial SEM figure of 3 step 2) of embodiment preparation；
Fig. 3 is semi-spherical hollow shape titanium dioxide/carbon particle/polyaniline SEM figure of 3 step 4) of embodiment preparation；
Fig. 4 is semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material prepared by embodiment 3
SEM figure.
Fig. 5 is semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material prepared by embodiment 3
TEM figure.
Fig. 6 is semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material prepared by embodiment 3
Mapping figure；
Fig. 7 is that semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material prepared by embodiment 3 closes
At the XRD diagram of process.
Fig. 8 is semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material prepared by embodiment 3
XPS figure.
Fig. 9 is that semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material prepared by embodiment 3 is made
The cyclical stability test chart for being lithium-sulfur cell under 0.1C current density.
Specific embodiment
The following describes the present invention in detail with reference to examples.
Embodiment 1
A kind of preparation method of semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material, including with
Lower step:
1) hydro-thermal process: the dehydrated alcohol of 10mL and the isopropanol of 20mL are uniformly mixed.Add 0.2mL metatitanic acid
After four butyl esters stir 10min, mixed solution is put into baking oven, anti-12 hours in 150 DEG C of constant temperature, after reaction, will be precipitated
It collects, centrifugation, cleaning, 40 DEG C are dried in vacuo 18 hours, obtain titanic oxide material；
2) compound working procedure: 0.3g tri- is added in 50mL deionized water in the titanic oxide material for taking 0.2g step 1) to prepare
Hydroxymethyl aminomethane (Tris) is added salt acid for adjusting pH to 6.5,45mg Dopamine hydrochloride is added, reacts 18 hours, reaction knot
Shu Hou takes out product, centrifugation, is alternately cleaned with deionized water, ethyl alcohol, and 40 DEG C of vacuum drying, 20 hours acquisition titanium dioxide/
Carbon nanomaterial.
3) it calcining process: under nitrogen atmosphere by titanium dioxide/carbon nanomaterial of step 3) preparation, is roasted at 500 DEG C
It burns 3 hours, naturally cools to room temperature, titanium dioxide/carbon particle is made.
4) it grows process: weighing titanium dioxide/carbon particle of 0.2g step 3) preparation, be dispersed in 0.3 mol/L sulphur of 40mL
In acid solution, the aniline of 0.3mL is added, is stirred under ice bath environment, the ammonium persulfate of 0.4g is added, after reacting 6h, is centrifuged, is clear
It washes, 45 DEG C are dried in vacuo 18 hours, obtain semi-spherical hollow shape titanium dioxide/carbon particle/polyaniline.
5) sulphuring process: 0.5g semi-spherical hollow shape titanium dioxide/carbon particle/polyaniline is uniformly mixed with 0.5g sulphur powder and is put
Enter in polytetrafluoroethylplastic plastic bottle, argon gas is full of in bottle, 120 DEG C keep the temperature 18 hours, and natural cooling cooling obtains semi-spherical hollow shape
Titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material.
Embodiment 2
A kind of preparation method of semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material, including with
Lower step:
1) hydro-thermal process: the dehydrated alcohol of 15mL and the isopropanol of 20mL are uniformly mixed, add 0.4mL metatitanic acid
Four butyl esters stir 10min after, mixed solution is put into baking oven, 160 DEG C isothermal reaction 10 hours, after reaction, will sink
It forms sediment and collects, centrifugation, cleans, 50 DEG C are dried in vacuo 16 hours, obtain titanic oxide material；
2) compound working procedure: the titanic oxide material for taking 0.2g step 1) to prepare is dispersed in 50mL deionized water, is added
0.8g trishydroxymethylaminomethane (Tris) is added salt acid for adjusting pH to 7.5,55mg Dopamine hydrochloride is added, reaction 22 is small
When, after reaction, product is taken out, is centrifuged, is alternately cleaned with deionized water, ethyl alcohol, 55 DEG C obtain for vacuum drying 16 hours
Titanium dioxide/carbon nanomaterial；
3) it calcining process: under nitrogen atmosphere by titanium dioxide/carbon nanomaterial of step 2) preparation, is roasted at 550 DEG C
It burns 3 hours, naturally cools to room temperature, titanium dioxide/carbon particle is made；
4) it grows process: weighing titanium dioxide/carbon particle of 0.2g step 3) preparation, be dispersed in 0.4 mol/L sulphur of 50mL
In acid, the aniline of 0.4mL is added, is stirred under ice bath environment, the ammonium persulfate of 0.5g is added, after reacting 10h, centrifugation, cleaning,
55 DEG C are dried in vacuo 16 hours, obtain semi-spherical hollow shape titanium dioxide/carbon particle/polyaniline；
5) sulphuring process: 1.0g semi-spherical hollow shape titanium dioxide/carbon particle/polyaniline is uniformly mixed with 3.0g sulphur powder and is put
Enter in polytetrafluoroethylplastic plastic bottle, argon gas is full of in bottle, 135 DEG C keep the temperature 16 hours, and natural cooling cooling obtains semi-spherical hollow shape
Titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material.
Embodiment 3
A kind of preparation method of semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material, including with
Lower step:
1) hydro-thermal process: the dehydrated alcohol of 20mL and the isopropanol of 10mL are uniformly mixed, add 0.5mL metatitanic acid
Four butyl esters stir 10min after, mixed solution is put into baking oven, 180 DEG C isothermal reaction 8 hours, after reaction, will precipitate
It collects, centrifugation, cleaning, 60 DEG C are dried in vacuo 12 hours, obtain titanic oxide material, and SEM is as shown in Figure 1, can be with from figure
Find out, is the semi-spherical hollow shape that the smooth partial size in surface is 2 μm；
2) compound working procedure: the titanic oxide material for taking 0.2g step 1) to prepare is dispersed in 50mL deionized water, is added
1.2g trishydroxymethylaminomethane (Tris) is added salt acid for adjusting pH to 8.5,60mg Dopamine hydrochloride is added, reaction 24 is small
When, after reaction, product is taken out, is centrifuged, is alternately cleaned with deionized water, ethyl alcohol, 60 DEG C obtain for vacuum drying 12 hours
Titanium dioxide/carbon nanomaterial, SEM is as shown in Fig. 2, it can be seen from the figure that it is 2 that it, which is the slightly scabrid partial size in surface,
~2.5 μm of semi-spherical hollow shape.
3) it calcining process: under nitrogen atmosphere by titanium dioxide/carbon nanomaterial of step 2) preparation, is roasted at 600 DEG C
It burns 4 hours, naturally cools to room temperature, titanium dioxide/carbon particle is made.
4) it grows process: weighing titanium dioxide/carbon particle of 0.2g step 3) preparation, be dispersed in 0.5 mol/L sulphur of 60mL
In acid, the aniline of 0.45mL is added, is stirred under ice bath environment, then the ammonium persulfate of 0.6g is dissolved in the sulfuric acid of 40mL,
After reacting 12h, centrifugation, cleaning, 60 DEG C are dried in vacuo 14 hours, obtain semi-spherical hollow shape titanium dioxide/carbon particle/polyaniline,
For its SEM as shown in figure 3, it can be seen from the figure that it grown burr shape polyaniline for surface, partial size is the half of 2.2~2.7 μm
Ball hollow shape.
5) sulphuring process: 1.0g semi-spherical hollow shape titanium dioxide/carbon particle/polyaniline is uniformly mixed with 2.0g sulphur powder and is put
Enter in polytetrafluoroethylplastic plastic bottle, argon gas is full of in bottle, 155 DEG C keep the temperature 15 hours, and natural cooling cooling obtains semi-spherical hollow shape
Titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material, SEM, TEM difference are as shown in Figure 4,5, can from figure
Semi-spherical hollow shape structure and burr shape keep complete out.
Fig. 6 is that the mapping of the present embodiment product schemes.Fig. 7 is that the XRD of each step products therefrom of the present embodiment schemes, Fig. 8
Scheme for semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material XPS in the present embodiment, from Fig. 4,5
In it can be seen that the present embodiment that semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur has successfully been prepared is compound
Material.
Embodiment 4
A kind of preparation method of semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material, including with
Lower step:
1) hydro-thermal process: the dehydrated alcohol of 20mL and the isopropanol of 15mL are uniformly mixed, add 0.7mL metatitanic acid
Four butyl esters stir 10min after, mixed solution is put into baking oven, 180 DEG C isothermal reaction 10 hours, after reaction, will sink
It forms sediment and collects, centrifugation, cleans, 70 DEG C are dried in vacuo 8 hours, obtain titanic oxide material；
2) compound working procedure: the titanic oxide material for taking 0.2g step 1) to prepare is dispersed in 50mL deionized water, is added
1.4g trishydroxymethylaminomethane (Tris) is added salt acid for adjusting pH to 9,70mg Dopamine hydrochloride is added, reacts 26 hours,
After reaction, product is taken out, is centrifuged, alternately cleaned with deionized water, ethyl alcohol, 70 DEG C of vacuum drying, 8 hours acquisition dioxies
Change titanium/carbon nanomaterial；
3) it calcining process: under nitrogen atmosphere by titanium dioxide/carbon nanomaterial of step 2) preparation, is roasted at 700 DEG C
It burns 6 hours, naturally cools to room temperature, titanium dioxide/carbon particle is made；
4) it grows process: weighing titanium dioxide/carbon particle of 0.2g step 3) preparation, be dispersed in 0.7 mol/L sulphur of 70mL
In acid, the aniline of 0.55mL is added, is stirred under ice bath environment, then the ammonium persulfate of 0.75g is dissolved in the sulfuric acid of 40mL,
After reacting 16h, centrifugation, cleaning, 80 DEG C are dried in vacuo 8 hours, obtain semi-spherical hollow shape titanium dioxide/carbon particle/polyaniline；
5) sulphuring process: 1.0g semi-spherical hollow shape titanium dioxide/carbon particle/polyaniline is uniformly mixed with 4.0g sulphur powder and is put
Enter in polytetrafluoroethylplastic plastic bottle, argon gas is full of in bottle, 170 DEG C keep the temperature 10 hours, and natural cooling cooling obtains semi-spherical hollow shape
Titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material.
Embodiment 5
A kind of preparation method of semi-spherical hollow shape titanium dioxide/carbon/Polyaniline-Supported sulphur composite material, including following step
It is rapid:
1) hydro-thermal process: the dehydrated alcohol of 20mL and the isopropanol of 15mL are uniformly mixed, add 1mL metatitanic acid four
Butyl ester stir 10min after, mixed solution is put into baking oven, 180 DEG C isothermal reaction 12 hours, after reaction, will precipitate
It collects, centrifugation, cleaning, 80 DEG C are dried in vacuo 6 hours, obtain titanic oxide material.
2) compound working procedure: the titanic oxide material for taking 0.2g step 1) to prepare is dispersed in 50mL deionized water, is added
1.5g trishydroxymethylaminomethane (Tris) is added salt acid for adjusting pH to 10,90mg Dopamine hydrochloride is added, reacts 30 hours,
After reaction, product is taken out, is centrifuged, alternately cleaned with deionized water, ethyl alcohol, 80 DEG C of vacuum drying, 4 hours acquisition dioxies
Change titanium/carbon nanomaterial.
3) it calcining process: under nitrogen atmosphere by titanium dioxide/carbon nanomaterial of step 2) preparation, is roasted at 800 DEG C
It burns 7 hours, naturally cools to room temperature, titanium dioxide/carbon particle is made.
4) it grows process: weighing titanium dioxide/carbon particle of 0.2g step 3) preparation, be dispersed in 0.8 mol/L sulphur of 80mL
In acid solution, the aniline of 0.6mL is added, is stirred under ice bath environment, then the ammonium persulfate of 0.8g is dissolved in the sulfuric acid of 40mL
In, after reacting 18h, centrifugation, cleaning, 80 DEG C are dried in vacuo 4 hours, obtain semi-spherical hollow shape titanium dioxide/carbon particle/polyphenyl
Amine.
5) sulphuring process: 1.0g semi-spherical hollow shape titanium dioxide/carbon particle/polyaniline is uniformly mixed with 5.0g sulphur powder and is put
Enter in polytetrafluoroethylplastic plastic bottle, argon gas is full of in bottle, 180 DEG C keep the temperature 12 hours, and natural cooling cooling obtains semi-spherical hollow shape
Titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material.
Embodiment 6
Semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material is as lithium ion cell positive material
The application of material.
Using 3 gained final product titanium dioxide of embodiment/carbon particle/Polyaniline-Supported sulphur composite material as lithium sulphur electricity
The active material of pond anode is mixed gained active material, with the mass ratio of 7:2:1 with superconducting carbon black, PVDF with N- methyl pyrrole
Pyrrolidone (NMP) solvent is modulated into uniform sizing material, is coated on aluminium foil, manufactured coating is put in baking oven later, with 60 DEG C
Drying 4 hours；It moves into vacuum oven after the completion of drying, is dried in vacuo 12 hours with 60 DEG C；Again by the composite wood after drying
Expect that coating carries out tabletting, cut-parts processing using tablet press machine etc..
Using lithium piece as to electrode, 1M LiTFSI/DME+DOL solution is electrolyte, the packed battery under argon atmosphere, most
Charge-discharge performance test is carried out using cell tester afterwards, products therefrom is as lithium sulfur battery anode material in 0.1C current density
Under cyclical stability test result it is as shown in Fig. 9.By attached drawing 9 as it can be seen that the good cycling stability of battery, electricity after recycling 50 times
Tankage is still higher than 1200mAh g-1。
It is above-mentioned referring to embodiment to hemisphere hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material and its
The detailed description that preparation method, lithium-sulphur cell positive electrode and battery carry out, is illustrative without being restrictive, can be according to being limited
Determine range and enumerate several embodiments, therefore the change and modification in the case where not departing from present general inventive concept, the present invention should be belonged to
Protection scope within.
Claims (10)
1. a kind of semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material preparation method, feature exist
In the preparation method comprises the following steps:
1) dehydrated alcohol is uniformly mixed with isopropanol, adds butyl titanate, after mixing, hydro-thermal reaction obtains two
Titania meterial；
2) titanic oxide material prepared by step 1) is dispersed in water, after trishydroxymethylaminomethane is added, adds hydrochloric acid
Dopamine is reacted, and after reaction, obtains titanium dioxide/carbon nanomaterial；
3) titanium dioxide/carbon nanomaterial prepared by step 2) is roasted under nitrogen atmosphere, naturally cools to room temperature, be made two
Titanium oxide/carbon particle；
4) in condition of ice bath, titanium dioxide/carbon particle prepared by step 3) is dispersed in sulfuric acid solution, it is equal that aniline stirring is added
It is even, ammonium persulfate is then added and is reacted, semi-spherical hollow shape titanium dioxide/carbon particle/polyaniline is obtained；
5) semi-spherical hollow shape titanium dioxide/carbon particle/polyaniline prepared by step 4) is uniformly mixed with sulphur powder, in argon atmosphere
Lower sulphuring obtains semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material.
2. preparation method according to claim 1, which is characterized in that in step 1), the dehydrated alcohol, isopropanol, titanium
The ratio between the volume of sour four butyl esters is (10~30): (10~20): (0.1~1.0)；The condition of the hydro-thermal reaction is 150~200
DEG C reaction 4~12h.
3. preparation method according to claim 1, which is characterized in that in step 2), the titanic oxide material, three hydroxyl first
Base aminomethane, Dopamine hydrochloride mass ratio be 1:(1~8): (0.2~0.5)；The titanic oxide material is in water
Concentration is 2~6g/L.
4. preparation method according to claim 1, which is characterized in that in step 2) further include: trihydroxy methyl amino is added
The pH of regulation system is 6.5~10 after methane；The time of the reaction is 18~30h.
5. preparation method according to claim 1, which is characterized in that in step 3), the condition of the roasting is 500~
800 DEG C of 2~8h of roasting.
6. preparation method according to claim 1, which is characterized in that in step 4), the titanium dioxide/carbon particle, benzene
Amine, ammonium persulfate amount ratio be 1g:(0.15~3.0) mL:(2~4) g；Titanium dioxide/the carbon particle is dense in sulfuric acid
Degree is 2~6g/L；The sulfuric acid concentration is 0.3~1mol/L.
7. preparation method according to claim 1, which is characterized in that in step 5), the semi-spherical hollow shape titanium dioxide/
Carbon particle/polyaniline and sulphur powder mass ratio are 1:1~5；The condition of the sulphuring is 140~180 DEG C of 12~18h of sulphuring.
8. a kind of semi-spherical hollow shape titanium dioxide/carbon that the preparation method as described in claim 1-7 any one is prepared
Application of particle/Polyaniline-Supported sulphur composite material as anode material for lithium-ion batteries.
9. a kind of lithium-sulphur cell positive electrode, which is characterized in that be prepared into using preparation method described in claim 1-7 any one
To semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material be made.
10. a kind of battery, which is characterized in that including lithium-sulphur cell positive electrode as claimed in claim 9.
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