CN108832098A - Lithium-sulphur cell positive electrode S@TiO2/ Pt/Polypyrrole composite material and preparation method - Google Patents
Lithium-sulphur cell positive electrode S@TiO2/ Pt/Polypyrrole composite material and preparation method Download PDFInfo
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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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- H—ELECTRICITY
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The present invention provides a kind of S@TiO with core-shell structure for lithium-sulphur cell positive electrode2The preparation method of/Pt/Polypyrrole composite material, this method specifically include：First using resorcinol-formaldehyde resin ball as sacrifice template, then use butyl titanate as raw material one layer of Ti (OH) of uniform fold on resorcinol-formaldehyde resin ball4, TiO is obtained by high-temperature calcination2Hollow ball, heat melting method obtain S@TiO after filling sulphur2Composite construction prepares polypyrrole nano line using chemical oxidization method, finally by ultrasonic agitation by S@TiO2It is compound uniformly with polypyrrole nano line, form S@TiO2The composite construction of polypyrrole nano line is wound outside hollow ball.The structure can effectively inhibit the volume expansion in the diffusion and charge and discharge process of polysulfide, and the polypyrrole nano line of high conductivity can carry out effective electronics conduction, and the two synergistic effect is to improve the chemical property of lithium-sulfur cell.
Description
Technical field
The present invention relates to a kind of S@TiO with core-shell structure for lithium-sulphur cell positive electrode2/ Pt/Polypyrrole composite material and
Preparation method belongs to battery material field.
Background technique
With energy and environmental problem become increasingly conspicuous and the fast development of electronic electric equipment, traditional lithium-ion electric
Pond is difficult to meet people to the requirement in terms of high power battery and high energy storage due to its lower energy density.Therefore how
Develop that a kind of novel specific capacity is high, have extended cycle life, the energy storage component that security performance is high is current urgent problem to be solved.
Lithium-sulfur cell theoretical specific capacity with higher using elemental sulfur as positive electrode（1675mAh/g）With theoretical ratio
Energy（2600Wh/kg）, it is 3-5 times of the lithium ion batteries such as cobalt acid lithium, LiFePO4 now.In addition, elemental sulfur also have it is low
The advantages that toxicity, reserves are big, cheap.Therefore using elemental sulfur as positive electrode, lithium sulphur electricity of the lithium metal as negative electrode material
Pond is a kind of very promising new energy devices.With high researching value and application prospect.
But there is also lot of challenges at present for lithium-sulfur cell：（1）The low electric conductivity of sulphur simple substance reduces active material
Electrochemical utilization rate seriously affects electronics in the transmission of anode；（2）Sulphur anode in the circulating cycle volume pattern variation influence anode
The stability and electron-transport of structure, so as to cause capacity attenuation；（3）The formation in the electrolytic solution of more lithium sulfides is dissolved and is moved
Shifting can seriously affect the electrochemical utilization rate of active material, high rate performance and cycle life in lithium-sulfur cell；（4）In cyclic process
Cathode of lithium surface, which generates Li dendrite, can destroy diaphragm so as to cause safety problem.
It is considered as solving sulphur list by surface cladding one layer of conducting polymer/polar metal oxide core-shell structure of sulphur
The low electric conductivity of matter, sulphur anode in the circulating cycle volume expansion the problems such as effective way.ZHOU Wencui et al. hydro-thermal legal system
Standby resorcinol-formaldehyde resin ball is a kind of sacrifice template of extensive application prospect.(Controllable
preparation and application of carbon spheres based on resorcinol-
formaldehyde resin. Journal of Zhejiang Sci-Tech University (Natural
), Sciences Vol.39, No.2, Mar. 2018) by the presoma uniform fold of metal oxide in resorcinol-first
The metal oxide nano ball with hollow structure can be obtained by calcining in urea formaldehyde ball surface.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of S@TiO with core-shell structure2/ polypyrrole is multiple
The preparation method of condensation material.The material structure can accommodate volume change of the sulphur in charge and discharge process, and can adsorb more
Sulfide alleviates shuttle effect, to improve the cyclical stability of lithium-sulfur cell.
To achieve the above object, used technical solution is the present invention：
A kind of S@TiO with core-shell structure for lithium-sulphur cell positive electrode2The preparation method of/Pt/Polypyrrole composite material, including
Following steps：
（1）Using resorcinol-formaldehyde resin ball as template, cetyl trimethylammonium bromide is surfactant, is distributed to nothing
It is uniformly mixed, butyl titanate is slowly added into mixed solution, and be stirred at room temperature 8-12 hours in water-ethanol, is centrifuged
By product high-temperature calcination after separation, TiO is obtained2Hollow ball.
（2）Sublimed sulfur is dissolved in carbon disulfide solution, step is added after being completely dissolved to sulphur in stirring（1）Middle gained TiO2
Hollow ball is ultrasonically formed uniform mixing suspension, this suspension is stirred at room temperature to volatile dry, argon atmosphere is transferred to
Under polytetrafluoroethylene (PTFE) stainless steel cauldron in, 120-180 DEG C heat preservation 12-16 hours S@TiO2Hollow ball.
（3）Cetyl trimethylammonium bromide, pyrroles are distributed in deionized water and are uniformly mixed, ammonium persulfate is water-soluble
Liquid is slowly added into mixed solution, and ice-water bath stirs 1-4 hours, is dried product vacuum after centrifuge washing, is obtained polypyrrole
Nano wire.
（4）By step（2）Gained S@TiO2Hollow ball and step（3）Gained polypyrrole nano line is ultrasonic in dehydrated alcohol
It is uniformly dispersed, 50-90 DEG C of stirring is to being drying to obtain the S@TiO with core-shell structure2/ Pt/Polypyrrole composite material.
In above scheme, step（1）Described in resorcinol-formaldehyde resin ball diameter be 200nm-600nm.
In above scheme, step（1）Described in middle cetyl trimethylammonium bromide concentration be 0.2 mmol/L-1.5
mmol/L。
In above scheme, step（1）Described in resorcinol-formaldehyde resin ball and butyl titanate molar ratio be 1：
（0.1-1.0）.
In above scheme, step（1）Described in high-temperature calcination heating rate be 2-5 DEG C/min, holding temperature 400-600
DEG C, soaking time is 2-6 hours, and rate of temperature fall is 2-5 DEG C/min.
In above scheme, step（1）Described in TiO2Hollow bulb diameter is 100nm-500nm.
In above scheme, step（2）Described in TiO2Hollow ball, sublimed sulfur mass ratio be 1：（1-10）.
In above scheme, step（2）Described in sublimed sulfur carbon disulfide solution concentration be 1-5mg/ml.
In above scheme, step（3）Described in cetyl trimethylammonium bromide, pyrroles, ammonium persulfate molar ratio be 16：
（4-64）：（4-64）, wherein cetyl trimethylammonium bromide concentration is 1.6 × 10-2Mol/L, pyrroles and ammonium persulfate rub
You are than being 1:1.
In above scheme, step（3）Described in polypyrrole nano line diameter be 20-80nm, length be 1-5 μm.
The principle of the present invention is：The present invention uses hard template method, using resorcinol-formaldehyde resin ball as hard template, metatitanic acid
Four butyl esters are presoma, remove template by high-temperature calcination and obtain the TiO of uniform particle diameter2Hollow ball；After heat melting method fills sulphur
Obtain S@TiO2Composite construction；The present invention uses soft template method, using cetyl trimethylammonium bromide as soft template, ammonium persulfate
For oxidant, product vacuum is dried to obtain polypyrrole nano line；The present invention uses ultrasonic disperse by S@TiO2It is multiple with polypyrrole
It closes uniformly, obtains S@TiO2/ polypyrrole composite construction.
Beneficial effects of the present invention are：The present invention synthesizes the S@TiO with core-shell structure for the first time2/ polypyrrole composite construction,
TiO2Hollow ball effectively contains the volume expansion of sulphur in lithium-sulfur cell charge and discharge process, while polar material TiO2To more sulphur
Compound is dissolved with certain inhibiting effect.The conductive network that polypyrrole is formed effectively improves the electric conductivity of positive electrode,
Improve the cyclical stability of lithium-sulfur cell.
Detailed description of the invention
Fig. 1 is TiO made from embodiment 12The SEM of hollow ball schemes.
Fig. 2 is the SEM figure of polypyrrole nano line made from embodiment 1.
Fig. 3 is S@TiO made from embodiment 12The compound SEM figure of/polypyrrole nano line.
Fig. 4 is S@TiO made from embodiment 12/ Pt/Polypyrrole composite material is lithium-sulfur cell charge and discharge at 1C of positive electrode
The cycle performance figure that electricity is 200 times.
Specific embodiment
Following embodiment is described further the content of present invention, but is not limited to protection scope of the present invention.
S@TiO of the invention2/ Pt/Polypyrrole composite material is applied in lithium-sulfur cell, and specific test process is as follows：In argon gas
In the glove box of protection, the S@TiO of preparation2/ polypyrrole is anode, and Celgard 2300 is used as diaphragm, and metal lithium sheet is as negative
Pole, the LiTFSI (DOL/DME=1 of 1.0mol/L:1) LiNO of 0.1mol/L is added3As electrolyte assembled battery.In charge and discharge
In electrical measurement test system, charge-discharge test voltage is 1.5V-3.0V.
Embodiment 1
The resorcinol-formaldehyde resin ball of 300mg partial size 500nm is dispersed in 40ml dehydrated alcohol, takes 0.5 mmol/L's
Cetyl trimethylammonium bromide uses dehydrated alcohol centrifuge washing after stirring 2 hours as surfactant.
Modified resorcinol-formaldehyde resin ball is dispersed in 40ml dehydrated alcohol, four fourth of metatitanic acid of 240 μ L is measured
Ester is dissolved in 20ml dehydrated alcohol, and the ethanol solution of butyl titanate is added drop-wise to resorcinol-first according to the drop speed of 5ml/min
In urea formaldehyde ball dispersion liquid, stir 12 hours at room temperature.
The mixed solution centrifuge washing that will be stirred moves into Muffle furnace, 2 DEG C/min of heating rate after 60 DEG C of drying, protects
550 DEG C of temperature, soaking time 3 hours, 5 DEG C/min of rate of temperature fall.Obtain TiO2Hollow ball.
The sublimed sulfur of 70mg is dissolved in CS2In solution, the TiO of 20mg is added2Hollow ball is stirred at room temperature to drying.By sulphur
And TiO2The mixture of hollow ball moves into the polytetrafluoroethylene (PTFE) stainless steel cauldron under argon atmosphere protection, and 155 DEG C of heat preservations 12 are small
When, obtain S@TiO2Compound.
Take 500ml there-necked flask, sequentially add 200ml deionized water, 0.0032mol cetyl trimethylammonium bromide,
0.0032mol pyrroles, 0 DEG C is stirred 2 hours, and the ammonium persulfate aqueous solution with pyrroles's equimolar ratio is added, and 0 DEG C is stirred 2 hours.It will
60 DEG C of vacuum drying 12h obtain polypyrrole nano line after reacted mixed solution centrifugation, suction filtration.
By S@TiO2Compound and 10mg polypyrrole nano line are dispersed in ethanol solution, 60 DEG C of stirrings to drying,
Obtain S@TiO2/ Pt/Polypyrrole composite material.
By S@TiO2/ Pt/Polypyrrole composite material, Ketjen black, PVDF are according to mass ratio 7:2:1 is uniformly mixed, N- methylpyrrole
Alkanone adjusts concentration, stirs 4 hours production slurries.The slurry made knife coating is applied on a current collector, vacuum environment
Lower 60 DEG C dry 12 hours.It is cut into the round pole piece that diameter is 16mm and assembled battery test.
Fig. 1 is the TiO prepared in the present embodiment2The SEM of hollow ball schemes, it can be seen that we are successfully prepared from this figure
Diameter is the TiO of 200nm2Hollow ball.Fig. 2 is the SEM figure of the polypyrrole nano line prepared in the present embodiment, can be with from this figure
Find out, polypyrrole nano line diameter is 40nm, and length is 2 μm.Fig. 3 is S@TiO in the present embodiment2The compound SEM of/polypyrrole
Figure, it can be seen that polypyrrole nano line uniform winding is in S TiO from this figure2Surface forms core-shell structure.Fig. 4 is this implementation
Sulphur@TiO obtained in example2/ polypyrrole is the lithium-sulfur cell of positive electrode with 1C charge and discharge 200 times charging and discharging capacities and library
Human relations efficiency curve.
Electrochemical property test is the result shows that the S@TiO prepared in the present embodiment2/ Pt/Polypyrrole composite material at 1C for the first time
Specific discharge capacity reaches 1014.6mAh/g, still possesses 516.3mAh/g after circulation 200 times.Effectively raise lithium-sulfur cell
Cyclical stability.
Embodiment 2
The resorcinol-formaldehyde resin ball that 300mg partial size is 250nm is dispersed in 40ml dehydrated alcohol, 0.5 mmol/L is taken
Cetyl trimethylammonium bromide as surfactant, use dehydrated alcohol centrifuge washing after stirring 2 hours.
Modified resorcinol-formaldehyde resin ball is dispersed in 40ml dehydrated alcohol, four fourth of metatitanic acid of 400 μ L is measured
Ester is dissolved in 20ml dehydrated alcohol, and the ethanol solution of butyl titanate is added drop-wise to resorcinol-first according to the drop speed of 5ml/min
In urea formaldehyde ball dispersion liquid, stir 12 hours at room temperature.
The mixed solution centrifuge washing that will be stirred moves into Muffle furnace, 2 DEG C/min of heating rate after 60 DEG C of drying, protects
550 DEG C of temperature, soaking time 3 hours, 5 DEG C/min of rate of temperature fall.Obtain TiO2Hollow ball.
The sublimed sulfur of 70mg is dissolved in CS2In solution, the TiO of 20mg is added2Hollow ball is stirred at room temperature to drying.By sulphur
And TiO2The mixture of hollow ball moves into the polytetrafluoroethylene (PTFE) stainless steel cauldron under argon atmosphere protection, and 155 DEG C of heat preservations 12 are small
When, obtain S@TiO2Compound.
Take 500ml there-necked flask, sequentially add 200ml deionized water, 0.0032mol cetyl trimethylammonium bromide,
0.0032mol pyrroles, 0 DEG C is stirred 2 hours, and the ammonium persulfate aqueous solution with pyrroles's equimolar ratio is added, and 0 DEG C is stirred 2 hours.It will
Reacted mixed solution centrifugation, suction filtration obtain polypyrrole nano line.
By S@TiO2Compound and 10mg polypyrrole nano line are dispersed in ethanol solution, 60 DEG C of stirrings to drying,
Obtain S@TiO2/ Pt/Polypyrrole composite material.
By S@TiO2/ Pt/Polypyrrole composite material, Ketjen black, PVDF are according to mass ratio 7:2:1 is uniformly mixed, N- methylpyrrole
Alkanone adjusts concentration, stirs 4 hours production slurries.The slurry made knife coating is applied on a current collector, vacuum environment
Lower 60 DEG C dry 12 hours.It is cut into the round pole piece that diameter is 16mm and assembled battery test.
Comparative example 1
Take 500ml there-necked flask, sequentially add 200ml deionized water, 0.0032mol cetyl trimethylammonium bromide,
0.0032mol pyrroles, 0 DEG C is stirred 2 hours, and the ammonium persulfate aqueous solution with pyrroles's equimolar ratio is added, and 0 DEG C is stirred 2 hours.It will
Reacted mixed solution centrifugation, suction filtration obtain polypyrrole nano line.
The sublimed sulfur of 70mg is dissolved in CS2In solution, the polypyrrole nano line of 20mg is added, is stirred at room temperature to drying.
The mixture of sulphur and polypyrrole nano line is moved into the polytetrafluoroethylene (PTFE) stainless steel cauldron under argon atmosphere protection, 155 DEG C of guarantors
Temperature 12 hours, obtains S/ polypyrrole nano line compound.
By S/ polypyrrole nano line composite material, Ketjen black, PVDF according to mass ratio 7:2:1 is uniformly mixed, N- methyl pyrrole
Pyrrolidone adjusts concentration, stirs 4 hours production slurries.The slurry made knife coating is applied on a current collector, vacuum ring
It dries 12 hours in lower 60 DEG C of border.It is cut into the round pole piece that diameter is 16mm and assembled battery test.
Comparative example 2
The resorcinol-formaldehyde resin ball that 300mg partial size is 500nm is dispersed in 40ml dehydrated alcohol, 0.5 mmol/L is taken
Cetyl trimethylammonium bromide as surfactant, use dehydrated alcohol centrifuge washing after stirring 2 hours.
Modified resorcinol-formaldehyde resin ball is dispersed in 40ml dehydrated alcohol, four fourth of metatitanic acid of 240 μ L is measured
Ester is dissolved in 20ml dehydrated alcohol, and the ethanol solution of butyl titanate is added drop-wise to resorcinol-first according to the drop speed of 5ml/min
In urea formaldehyde ball dispersion liquid, stir 12 hours at room temperature.
The mixed solution centrifuge washing that will be stirred moves into Muffle furnace, 2 DEG C/min of heating rate after 60 DEG C of drying, protects
550 DEG C of temperature, soaking time 3 hours, 5 DEG C/min of rate of temperature fall.Obtain TiO2Hollow ball.
The sublimed sulfur of 70mg is dissolved in CS2In solution, the TiO of 20mg is added2Hollow ball is stirred at room temperature to drying.By sulphur
And TiO2The mixture of hollow ball moves into the polytetrafluoroethylene (PTFE) stainless steel cauldron under argon atmosphere protection, and 155 DEG C of heat preservations 12 are small
When, obtain S@TiO2Compound.
By S@TiO2Composite material, Ketjen black, PVDF are according to mass ratio 7:2:1 is uniformly mixed, N-Methyl pyrrolidone tune
Concentration is saved, 4 hours production slurries are stirred.The slurry made knife coating is applied on a current collector, lower 60 DEG C of vacuum environment
Drying 12 hours.It is cut into the round pole piece that diameter is 16mm and assembled battery test.
Claims (10)
1. a kind of S@TiO with core-shell structure for lithium-sulphur cell positive electrode2The preparation method of/Pt/Polypyrrole composite material, it is special
Sign is that this approach includes the following steps：
（1）Using resorcinol-formaldehyde resin ball as template, cetyl trimethylammonium bromide is surfactant, is distributed to nothing
It is uniformly mixed, butyl titanate is slowly added into mixed solution, and be stirred at room temperature 8-12 hours in water-ethanol, is centrifuged
By product high-temperature calcination after separation, TiO is obtained2Hollow ball；
（2）Sublimed sulfur is dissolved in carbon disulfide solution, step is added after being completely dissolved to sulphur in stirring（1）Middle gained TiO2It is hollow
Ball is ultrasonically formed uniform mixing suspension, this suspension is stirred at room temperature to volatile dry, is transferred under argon atmosphere
In polytetrafluoroethylene (PTFE) stainless steel cauldron, 120-180 DEG C obtains S@TiO in heat preservation 12-16 hours2Hollow ball；
（3）Cetyl trimethylammonium bromide, pyrroles are distributed in deionized water and are uniformly mixed, ammonium persulfate aqueous solution is delayed
Slowly it is added in mixed solution, ice-water bath stirs 1-4 hours, dries product vacuum after centrifuge washing, obtains polypyrrole nanometer
Line；
（4）By step（2）Gained S@TiO2Hollow ball and step（3）Gained polypyrrole nano line ultrasonic disperse in dehydrated alcohol
Uniformly, 50-90 DEG C of stirring is to being drying to obtain the S@TiO with core-shell structure2/ Pt/Polypyrrole composite material.
2. preparation method according to claim 1, which is characterized in that the step（1）Middle resorcinol-formaldehyde resin ball
Diameter is 200 nm-600 nm.
3. preparation method according to claim 1, which is characterized in that the step（1）Middle cetyl trimethyl bromination
Ammonium concentration is 0.2 mmol/l-1.5 mmol/l.
4. preparation method according to claim 1, which is characterized in that the step（1）Middle resorcinol-formaldehyde resin ball
It is 1 with butyl titanate molar ratio：（0.1-1.0）.
5. preparation method according to claim 1, which is characterized in that the step（1）High temperature calcines heating rate
2-5 DEG C/min, holding temperature is 400-600 DEG C, and soaking time is 2-6 hours, and rate of temperature fall is 2-5 DEG C/min.
6. preparation method according to claim 1, which is characterized in that the step（1）Obtained in TiO2Hollow ball it is straight
Diameter is 100nm-500nm.
7. preparation method according to claim 1, which is characterized in that the step（2）Middle TiO2Hollow ball and sublimed sulfur
Mass ratio is 1：1-10；The carbon disulfide solution concentration of sublimed sulfur is 1-5mg/ml.
8. preparation method according to claim 1, which is characterized in that the step（3）Middle cetyl trimethyl bromination
Ammonium, pyrroles, ammonium persulfate molar ratio are 16：（4-64）：（4-64）, wherein cetyl trimethylammonium bromide concentration be 1.6 ×
10-2The molar ratio of mol/l, pyrroles and ammonium persulfate is 1:1.
9. preparation method according to claim 1, which is characterized in that the step（3）Obtained in polypyrrole nano line
Diameter is 20-80 nm, and length is 1-5 μm.
10. the S@TiO with core-shell structure that preparation method according to claim 1 states preparation2/ Pt/Polypyrrole composite material
Application in the energy storages such as lithium-sulphur cell positive electrode and switching device.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109473659A (en) * | 2018-12-07 | 2019-03-15 | 杭州电子科技大学 | A kind of polypyrrole nanotube/Co3O4Particulate composite and preparation method |
| CN109698333A (en) * | 2018-12-17 | 2019-04-30 | 中国空间技术研究院 | A kind of Lithium-sulphur battery anode material and its preparation method and application |
| CN110620235A (en) * | 2019-09-16 | 2019-12-27 | 安徽师范大学 | Polypyrrole-coated hollow porous cobalt manganate-loaded sulfur composite material, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
| CN110752355A (en) * | 2019-10-09 | 2020-02-04 | 天津大学 | Method for preparing high-sulfur-content electrode material sulfur-titanium dioxide-polypyrrole |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103247788A (en) * | 2012-02-13 | 2013-08-14 | 苏州宝时得电动工具有限公司 | Preparation method of electrode composite material |
-
2018
- 2018-06-14 CN CN201810614877.8A patent/CN108832098B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103247788A (en) * | 2012-02-13 | 2013-08-14 | 苏州宝时得电动工具有限公司 | Preparation method of electrode composite material |
Non-Patent Citations (2)
| Title |
|---|
| GUOGANG TANG ET AL.: "Template-assisted hydrothermal synthesis and photocatalytic activity of novel TiO2 hollow nanostructures", 《CERAMICS INTERNATIONAL》 * |
| YONG LI ET AL.: "Hollow polypyrrole@MnO2 spheres as nano-sulfur hosts for improved lithium-sulfur batteries", 《ELECTROCHIMICA ACTA》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109473659A (en) * | 2018-12-07 | 2019-03-15 | 杭州电子科技大学 | A kind of polypyrrole nanotube/Co3O4Particulate composite and preparation method |
| CN109698333A (en) * | 2018-12-17 | 2019-04-30 | 中国空间技术研究院 | A kind of Lithium-sulphur battery anode material and its preparation method and application |
| CN110620235A (en) * | 2019-09-16 | 2019-12-27 | 安徽师范大学 | Polypyrrole-coated hollow porous cobalt manganate-loaded sulfur composite material, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
| CN110752355A (en) * | 2019-10-09 | 2020-02-04 | 天津大学 | Method for preparing high-sulfur-content electrode material sulfur-titanium dioxide-polypyrrole |
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