CN109378475A - Three-dimensional grapheme carried metal compound composite material and its preparation method and application - Google Patents
Three-dimensional grapheme carried metal compound composite material and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to three-dimensional grapheme carried metal compound composite materials and its preparation method and application, it is uniformly dispersed in inside the three-dimensional redox graphene with a large amount of hole for metallic compound nano line, nanometer rods, nanometer sheet or nano particle, metallic compound nano line, nanometer rods, nanometer sheet or the nano particle is in contact with graphene film, forms a complete three dimensional composite structure.The beneficial effects of the present invention are: firstly, the three-dimensional grapheme frame of N doping can not only provide excellent electric conductivity for entire electrode material, while porous characteristic is able to achieve the positive electrode of more high-sulfur load;Secondly, polar metallic compound can effectively adsorb polysulfide, inhibits the shuttle effect in lithium-sulfur cell, improve the utilization rate of sulphur.When these excellent properties lead to the material as lithium sulfur battery anode material, excellent high rate performance and cyclical stability can be shown.
Description
Technical field
The present invention relates to the designs of lithium sulphur battery electrode material, multiple more particularly to three-dimensional grapheme carried metal compound
Condensation material and its preparation method and application.
Background technique
It is currently limited by the theoretical capacity of positive and negative pole material, the energy density of lithium ion battery, which is no longer satisfied, increasingly to be increased
The requirement for high-energy density energy storage device such as long electric car.Lithium-sulfur cell is due to very high theoretical capacity
(1675mAh/g) and energy density (2600Wh/Kg), it is considered to be the important development direction of next-generation electrochemical energy storing device it
One.However, the development of lithium-sulfur cell and the commercial applications in future are still limited by several factors, such as sulphur and its discharging product
The extremely low conductivity of lithium sulfide, in charge and discharge process among the performance degradation as caused by the volume change of sulphur and charge and discharge
Shuttle effect of product polysulfide etc..
In order to overcome the above problems, during prepared by sulfur electrode, a large amount of conductive additive etc. need to generally be introduced.Cause
It is non-electroactive for additives such as conductive additive and binders, therefore the introducing of these substances will certainly reduce battery
Integral energy density, to lose the advantage of lithium-sulfur cell high-energy density.Therefore, preparation has the compound of high sulfur content
Electrode material is most important.
Summary of the invention
The invention proposes a kind of three-dimensional grapheme carried metal compound composite materials and preparation method thereof, pass through oxidation
Metallic compound is supported on graphene monolithic by the process of graphene dispersing solution self assembly, improves the electric conductivity of integral material,
To enhance the transmission rate of electronics and ion in lithium-sulfur cell, the metallic compound being supported on graphene monolithic again can be effective
Inhibit the shuttle effect in lithium-sulfur cell, and then improves the chemical property of battery.
To achieve the goals above, the technical scheme is that three-dimensional grapheme carried metal compound composite material,
It is uniformly dispersed in the three-dimensional with a large amount of hole for metallic compound nano line, nanometer rods, nanometer sheet or nano particle
Inside redox graphene, metallic compound nano line, nanometer rods, nanometer sheet or the nano particle and graphene film phase
Contact forms a complete three dimensional composite structure.
According to the above scheme, the metallic compound nano linear diameter is 50-100nm, length 2-5um, the gold
Category compound nano rod diameter is 100-200nm, and length 1-3um, the metallic compound nano piece is with a thickness of 50-
100nm, length and width 50-200nm, the metal compound nanoparticles size are 100-200nm.
The preparation method of three-dimensional grapheme carried metal compound composite material, includes following steps:
1) the ultrasonic respectively, stirring by graphene oxide dispersion and metallic compound, continues to be stirred by ultrasonic after mixing;
2) reducing agent is added in the precursor solution obtained by step 1) and heats;
3) it will be freeze-dried, loaded after the washing of three-dimensional grapheme carried metal compound composite material obtained by step 2)
The three-dimensional graphene composite material of metallic compound.
According to the above scheme, the preparation method further includes by the three-dimensional grapheme of carried metal compound obtained by step 3)
Composite material is post-processed to obtain the three-dimensional graphene composite material of load different metal compound, the post-processing approach
For under ammonia atmosphere, 600-800 DEG C of nitridation 2-5h.
According to the above scheme, the graphene oxide dispersion concentration is 1mg/mL.
According to the above scheme, the reducing agent are as follows: sodium ascorbate or ascorbic acid.
According to the above scheme, the carried metal compound is metal nitride, metal oxide or metal sulfide.
According to the above scheme, the carried metal compound is TiN, Fe2N、VS2、V2O5、MoN、NiS2Or TiO2。
According to the above scheme, the heating reaction temperature is 95 DEG C, heating time 2h.
Application of the three-dimensional graphene composite material of the carried metal compound as lithium sulphur battery electrode material.
The assembling of three-dimensional grapheme of the invention derives from the effect of extremely strong reducing agent, under conditions of 95 DEG C, using also
Former agent and the interaction of graphene are so that graphene oxide loses rapidly a large amount of functional groups and is self-assembled into three-dimensional column structure;
It is a kind of physical action between the load and graphene of metallic compound, therefore the assembling and load of graphene are to metallic compound
Chemical composition and microscopic appearance there is no any change.Three-dimensional grapheme is formed by two dimensional oxidation graphene by self assembly,
And a large amount of hole is formed since self assembling process graphene oxide loses a large amount of functional group.Unique two-dimensional graphene
Piece provides the supporting substrate of large area for metallic compound, while porous three-dimensional grapheme can load a large amount of sulphur, and is whole
Body material provides excellent electric conductivity, such as attached drawing 5.And more vulcanizations can effectively be adsorbed by being supported on the metallic compound on graphene film
Object inhibits the shuttle effect in battery, improves the chemical property of battery.
The beneficial effects of the present invention are: proposing a kind of various metallic compounds are loaded using graphene self assembling process
Universal method can effectively improve the chemical property of lithium-sulfur cell.Firstly, the three-dimensional grapheme frame of N doping can not only be whole
A electrode material provides excellent electric conductivity, while porous characteristic is able to achieve the positive electrode of more high-sulfur load;Secondly, polarity
Metallic compound can effectively adsorb polysulfide, inhibit the shuttle effect in lithium-sulfur cell, improve the utilization rate of sulphur.These are excellent
When different property leads to the material as lithium sulfur battery anode material, excellent high rate performance and cyclical stability can be shown.
Detailed description of the invention
Fig. 1 is the N doping three-dimensional grapheme flow chart of the preparation load titanium nitride nano line of embodiment 1;
Fig. 2 is the morphology characterization figure of the N doping three-dimensional grapheme of the load titanium nitride nano line of embodiment 1;
Fig. 3 is the EDS distribution diagram of element of the N doping three-dimensional grapheme of the load titanium nitride nano line of embodiment 1;
Fig. 4 is the X-ray diffractogram of the N doping three-dimensional grapheme of the load titanium nitride nano line of embodiment 1;
Fig. 5 is the chemical property figure of the N doping three-dimensional grapheme of the load titanium nitride nano line of embodiment 1.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1:
N doping three-dimensional grapheme (3DNG/TiN) lithium sulphur battery electrode material of TiN nano wire is loaded, it includes as follows
Step:
1) graphene oxide dispersion of the 1mg/mL of 2mL, ultrasonic agitation are added in 10mL sample bottle;
2) by presoma H2Ti3O7Nano wire is stirred by ultrasonic in deionized water;
3) by scattered H2Ti3O7Nano wire is added in step 1) acquired solution and is stirred by ultrasonic;
4) sodium ascorbate is added in sample bottle, and shaken uniform;
5) sample bottle is put into 95 DEG C of baking ovens and heats 2h, so that graphene oxide dispersion is assembled into load H completely2Ti3O7
The three-dimensional redox graphene of nano wire;
6) H will be loaded2Ti3O7The three-dimensional redox graphene composite material of nano wire is washed, and then freezing is dry
It is dry;
7) it is freeze-dried back loading H2Ti3O7Under ammonia atmosphere, 800 DEG C of nitridation 2h are obtained the three-dimensional grapheme of nano wire
3DNG/TiN;
8) obtained 3DNG/TiN is used as self-supporting electrode material, the group of lithium-sulfur cell is carried out in argon gas glove box
Dress, and carry out electrochemical property test.
By taking product 3DNG/TiN lithium sulphur battery electrode material of the invention as an example, Fig. 1 is to prepare schematic diagram, finally obtained
It is the finely dispersed 3DNG/TiN composite construction of TiN nano wire.Corresponding microstructure such as Fig. 2, according to scanning electron microscope (SEM) photograph and thoroughly
Penetrating electron microscope can be seen that three-dimensional grapheme has a large amount of hole, while TiN nano wire is uniformly dispersed in inside graphene,
And with graphene film have one it is good contact, metallic compound TiN nanowire diameter be 50-100nm, length 2-5um, and
It is dispersed in three-dimensional grapheme, forms a complete three dimensional composite structure.
Fig. 3 is the distribution diagram of element of 3DNG/TiN, and what can be apparent finds out that C, N, Ti, O element are evenly distributed in
On 3DNG/TiN, it was demonstrated that TiN nano wire is uniformly dispersed in inside three-dimensional grapheme.
Fig. 4 is presoma H2Ti3O7The XRD spectrum of nano wire, TiN nano wire, 3DNG/TiN, it can be seen that presoma
H2Ti3O7Nano wire has obtained the preferable TiN nano wire of crystallinity after high-temperature ammonolysis, and with standard card number 01-087-0632
It is completely the same, it was demonstrated that regardless of whether have a presence of graphene, presoma H2Ti3O7Nano wire can be formed after high-temperature ammonolysis
TiN。
3DNG/TiN composite material manufactured in the present embodiment is as follows as the application of self-supporting lithium sulphur battery electrode material: will
The oven drying that obtained 3DNG/TiN composite material is placed in 70 DEG C in advance takes out afterwards for 24 hours, is directly used as electrode slice.Wherein it is electrolysed
Liquid is that DME (glycol dimethyl ether), the DOL (1,3- dioxolanes) of LiTFSI containing 1M (double trifluoromethanesulfonimide lithiums) are molten
Liquid, the volume ratio of two kinds of solvents is 1:1, and adds the LiNO of 1% mass ratio3As additive, protected in charge and discharge process
Cathode of lithium, Celgard2325 are diaphragm, and CR2025 type stainless steel is that battery case is assembled into button lithium-sulfur cell.Lithium-sulfur cell
Preparation method remaining step it is identical as common preparation method.
Fig. 5 is the electrochemical property test figure of 3DNG/TiN, no matter can be clearly seen that the combination electrode material of preparation
All considerably beyond comparative sample on capacity or on high rate performance, especially when the face carrying capacity of sulphur is up to 9.6mg cm-2When, electricity
Pond shows 12mAh cm-2Superelevation face amount.
Embodiment 2:
Load Fe2N doping three-dimensional grapheme (the 3DNG/Fe of N nano particle2N) lithium sulphur battery electrode material, it includes such as
Lower step:
1) graphene oxide dispersion of the 1mg/mL of 2mL, ultrasonic agitation are added in 10mL sample bottle;
2) by presoma Fe3O4Nano particle is stirred by ultrasonic in deionized water;
3) by scattered Fe3O4Nano particle is added in step 1) acquired solution and is stirred by ultrasonic;
4) sodium ascorbate is added in sample bottle, and shaken uniform;
5) sample bottle is put into 95 DEG C of baking ovens and heats 2h, so that graphene oxide dispersion is assembled into load Fe completely3O4It receives
The three-dimensional redox graphene of rice grain;
6) Fe will be loaded3O4The three-dimensional redox graphene composite material of nano particle is washed, and then freezing is dry
It is dry;
7) it is freeze-dried back loading Fe3O4Under ammonia atmosphere, 600 DEG C of nitridation 3h are obtained the three-dimensional grapheme of nano particle
3DNG/Fe2N;
8) 3DNG/Fe that will be obtained2N is used as self-supporting electrode material, and the group of lithium-sulfur cell is carried out in argon gas glove box
Dress, and carry out electrochemical property test.
Obtained 3DNG/Fe2The microscopic appearance of N composite material are as follows: Fe2N nano particle, which is uniformly dispersed in, to be had largely
Hole three-dimensional redox graphene inside, and with graphene film have one it is good contact, metallic compound Fe2N
The size of nano particle is 100-200nm, and is dispersed in three-dimensional grapheme, and a complete three-dimensional composite junction is formed
Structure.
Electrochemical results display load Fe2The three-dimensional grapheme of N nano particle recycles 200 times under the multiplying power of 1C,
Still there is up to 900mAh g-1Height ratio capacity, while showing excellent cyclical stability.
Embodiment 3:
Load vanadium disulfide (VS2) nano particle three-dimensional grapheme (3NG/VS2) lithium sulphur battery electrode material, it includes
Following steps:
1) graphene oxide dispersion of the 1mg/mL of 2mL, ultrasonic agitation are added in 10mL sample bottle;
2) by VS2Nano particle is stirred by ultrasonic in deionized water;
3) by scattered VS2Nano particle is added in step 1) acquired solution and is stirred by ultrasonic;
4) sodium ascorbate is added in sample bottle, and shaken uniform;
5) sample bottle is put into 95 DEG C of baking ovens and heats 2h, so that graphene oxide dispersion is assembled into supported V S completely2It receives
The three-dimensional redox graphene of rice grain;
6) by supported V S2The three-dimensional redox graphene composite material of nano particle is washed, and is then freeze-dried;
7) 3NG/VS that will be obtained2As self-supporting electrode material, the assembling of lithium-sulfur cell is carried out in argon gas glove box,
And carry out electrochemical property test.
Obtained 3NG/VS2The microscopic appearance of composite material are as follows: VS2Nano particle, which is uniformly dispersed in, to be had largely
Inside the three-dimensional redox graphene of hole, and with graphene film have one it is good contact, metallic compound VS2Nanometer
The size of particle is 100-200nm, and is dispersed in three-dimensional grapheme, and a complete three dimensional composite structure is formed.
Electrochemical results show supported V S2The three-dimensional grapheme of nano particle recycles 100 times under the multiplying power of 0.5C,
Still there is up to 1100mAh g-1Height ratio capacity, while showing excellent cyclical stability.
Embodiment 4:
Supported V2O5Three-dimensional grapheme (the 3NG/V of nanometer sheet2O5) lithium sulphur battery electrode material, it includes the following steps:
1) graphene oxide dispersion of the 1mg/mL of 2mL, ultrasonic agitation are added in 10mL sample bottle;
2) by V2O5Nanometer sheet is stirred by ultrasonic in deionized water;
3) by scattered V2O5Nanometer sheet is added in step 1) acquired solution and is stirred by ultrasonic;
4) sodium ascorbate is added in sample bottle, and shaken uniform;
5) sample bottle is put into 95 DEG C of baking ovens and heats 2h, so that graphene oxide dispersion is assembled into supported V completely2O5It receives
The three-dimensional redox graphene of rice piece;
6) by supported V2O5The three-dimensional redox graphene composite material of nanometer sheet is washed, and is then freeze-dried;
7) 3NG/V that will be obtained2O5As self-supporting electrode material, the assembling of lithium-sulfur cell is carried out in argon gas glove box,
And carry out electrochemical property test.
Obtained 3NG/V2O5The microscopic appearance of composite material are as follows: V2O5Nanometer sheet, which is uniformly dispersed in, to be had largely
Inside the three-dimensional redox graphene of hole, and with graphene film have one it is good contact, metallic compound V2O5Nanometer
Piece with a thickness of 50-100nm, length and width are about 50-200nm, and are dispersed in three-dimensional grapheme, formed one complete three
Tie up composite construction.
Electrochemical results show supported V2O5The three-dimensional grapheme of nanometer sheet recycles 100 times under the multiplying power of 0.2C, still
With up to 1150mAh g-1Height ratio capacity, while showing excellent cyclical stability.
Embodiment 5:
N doping three-dimensional grapheme (3DNG/MoN) lithium sulphur battery electrode material of Supported Nitrides nanometer rods, it includes such as
Lower step:
1) graphene oxide dispersion of the 1mg/mL of 2mL, ultrasonic agitation are added in 10mL sample bottle;
2) by presoma MoO3Nanometer rods are stirred by ultrasonic in deionized water;
3) by scattered MoO3Nanometer rods are added in step 1) acquired solution and are stirred by ultrasonic;
4) sodium ascorbate is added in sample bottle, and shaken uniform;
5) sample bottle is put into 95 DEG C of baking ovens and heats 2h, so that graphene oxide dispersion is assembled into load MoO completely3It receives
The three-dimensional redox graphene of rice stick;
6) MoO will be loaded3The three-dimensional redox graphene composite material of nanometer rods is washed, and is then freeze-dried;
7) it is freeze-dried back loading MoO3Under ammonia atmosphere, 600 or 700 DEG C of nitridation 5h are obtained the three-dimensional grapheme of nanometer rods
To 3DNG/MoN;
8) obtained 3DNG/MoN is used as self-supporting electrode material, the group of lithium-sulfur cell is carried out in argon gas glove box
Dress, and carry out electrochemical property test.
The microscopic appearance of obtained 3DNG/MoN composite material are as follows: MoN nanometer rods, which are uniformly dispersed in, to be had largely
Inside the three-dimensional redox graphene of hole, and with graphene film have one it is good contact, MoN nanometers of metallic compound
The diameter of stick is 100-200nm, and length is about 1-3um, and is dispersed in three-dimensional grapheme, forms a complete three-dimensional
Composite construction.
Even if the three-dimensional grapheme of Electrochemical results display load MoN nanometer rods remains to open up under the up to multiplying power of 3C
Reveal up to 612mAh g-1Reversible capacity, show excellent high rate performance and cyclical stability.
Embodiment 6:
Three-dimensional grapheme loads curing nickel (3NG/NiS2) lithium sulphur battery electrode material, it includes the following steps:
1) graphene oxide dispersion of the 1mg/mL of 2mL, ultrasonic agitation are added in 10mL sample bottle;
2) by NiS2Nano particle is stirred by ultrasonic in deionized water;
3) by scattered NiS2Nano particle is added in step 1) acquired solution and is stirred by ultrasonic;
4) sodium ascorbate is added in sample bottle, and shaken uniform;
5) sample bottle is put into 95 DEG C of baking ovens and heats 2h, so that graphene oxide dispersion is assembled into load NiS completely2It receives
The three-dimensional redox graphene of rice grain;
6) three-dimensional grapheme is loaded into NiS2Nano particle composite material (3NG/NiS2) be freeze-dried;
7) 3NG/NiS that will be obtained2As self-supporting electrode material, the group of lithium-sulfur cell is carried out in argon gas glove box
Dress, and carry out electrochemical property test.
Obtained 3NG/NiS2The microscopic appearance of composite material are as follows: NiS2Nano particle, which is uniformly dispersed in, to be had largely
Hole three-dimensional redox graphene inside, and with graphene film have one it is good contact, metallic compound NiS2
The size of nano particle is about 100nm, and is dispersed in three-dimensional grapheme, and a complete three dimensional composite structure is formed.
Electrochemical results display load NiS2The three-dimensional grapheme of nano particle recycles 300 times under the multiplying power of 1C,
Still there is up to 795mAh g-1Height ratio capacity, while showing excellent cyclical stability.
Embodiment 7:
Three-dimensional grapheme carried titanium dioxide nano wire (3NG/TiO2) lithium sulphur battery electrode material, it includes following step
It is rapid:
1) graphene oxide dispersion of the 1mg/mL of 2mL, ultrasonic agitation are added in 10mL sample bottle;
2) by TiO2Nano wire grain is stirred by ultrasonic in deionized water;
3) by scattered TiO2Nano wire is added in step 1) acquired solution and is stirred by ultrasonic;
4) sodium ascorbate is added in sample bottle, and shaken uniform;
5) sample bottle is put into 95 DEG C of baking ovens and heats 2h, so that graphene oxide dispersion is assembled into load TiO completely2It receives
The three-dimensional redox graphene of rice noodles;
6) three-dimensional grapheme is loaded into TiO2Nanowire composite (3NG/TiO2) be freeze-dried;
7) 3NG/TiO that will be obtained2As self-supporting electrode material, the group of lithium-sulfur cell is carried out in argon gas glove box
Dress, and carry out electrochemical property test.
Obtained 3NG/TiO2The microscopic appearance of composite material are as follows: TiO2Nano wire, which is uniformly dispersed in, to be had largely
Inside the three-dimensional redox graphene of hole, and with graphene film have one it is good contact, metallic compound TiO2It receives
The diameter of rice noodles is about 50-100nm, and is dispersed in three-dimensional grapheme, and a complete three dimensional composite structure is formed.
Electrochemical results display load TiO2The three-dimensional grapheme of nano wire recycles 100 times under the multiplying power of 0.5C,
Still there is up to 968mAh g-1Height ratio capacity, while showing excellent cyclical stability.
Claims (10)
1. three-dimensional grapheme carried metal compound composite material for metallic compound nano line, nanometer rods, nanometer sheet or is received
Rice grain is uniformly dispersed in inside the three-dimensional redox graphene with a large amount of hole, the metallic compound nano
Line, nanometer rods, nanometer sheet or nano particle are in contact with graphene film, form a complete three dimensional composite structure.
2. three-dimensional grapheme carried metal compound composite material according to claim 1, it is characterised in that the metal
Compound nano linear diameter is 50-100nm, and length 2-5um, the metallic compound nano stick diameter is 100-200nm,
Length is 1-3um, and the metallic compound nano piece is with a thickness of 50-100nm, length and width 50-200nm, the metallization
Conjunction object nano particle size is 100-200nm.
3. the preparation method of three-dimensional grapheme carried metal compound composite material, includes following steps:
1) the ultrasonic respectively, stirring by graphene oxide dispersion and metallic compound, continues to be stirred by ultrasonic after mixing;
2) reducing agent is added in the precursor solution obtained by step 1) and heats;
3) it will be freeze-dried after the washing of three-dimensional grapheme carried metal compound composite material obtained by step 2), obtain carried metal
The three-dimensional graphene composite material of compound.
4. the preparation method of the three-dimensional graphene composite material of carried metal compound according to claim 3, feature exist
After the preparation method further includes carrying out the three-dimensional graphene composite material of carried metal compound obtained by step 3)
Reason obtain load different metal compound three-dimensional graphene composite material, the post-processing approach be under ammonia atmosphere,
600-800 DEG C of nitridation 2-5h.
5. the preparation method of three-dimensional grapheme carried metal compound composite material according to claim 3, it is characterised in that
The graphene oxide dispersion concentration is 1mg/mL.
6. the preparation method of three-dimensional grapheme carried metal compound composite material according to claim 3, it is characterised in that
The reducing agent are as follows: sodium ascorbate or ascorbic acid.
7. the preparation method of three-dimensional grapheme carried metal compound composite material according to claim 3, it is characterised in that
The carried metal compound is metal nitride, metal oxide or metal sulfide.
8. the preparation method of three-dimensional grapheme carried metal compound composite material according to claim 7, it is characterised in that
The carried metal compound is TiN, Fe2N、VS2、V2O5、MoN、NiS2Or TiO2。
9. the preparation method of three-dimensional grapheme carried metal compound composite material according to claim 3, it is characterised in that
The heating reaction temperature is 95 DEG C, heating time 2h.
10. the three-dimensional graphene composite material of carried metal compound described in claim 1 is as lithium sulphur battery electrode material
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CN110137456A (en) * | 2019-05-08 | 2019-08-16 | 陕西科技大学 | A kind of Ag/SnS2@rGO, preparation method and application |
CN110797514A (en) * | 2019-09-30 | 2020-02-14 | 温州大学 | Molybdenum-nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material, preparation method thereof and application of composite material in positive electrode of lithium-sulfur battery |
CN113066979A (en) * | 2021-03-17 | 2021-07-02 | 攀枝花学院 | S @ VxSy composite positive electrode material, preparation method thereof and lithium-sulfur battery |
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CN110137456A (en) * | 2019-05-08 | 2019-08-16 | 陕西科技大学 | A kind of Ag/SnS2@rGO, preparation method and application |
CN110120516A (en) * | 2019-06-20 | 2019-08-13 | 西北师范大学 | A kind of preparation method of antimony/redox graphene composite material |
CN110797514A (en) * | 2019-09-30 | 2020-02-14 | 温州大学 | Molybdenum-nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material, preparation method thereof and application of composite material in positive electrode of lithium-sulfur battery |
CN110797514B (en) * | 2019-09-30 | 2022-08-30 | 温州大学 | Molybdenum-nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material, preparation method thereof and application of composite material in positive electrode of lithium-sulfur battery |
CN113066979A (en) * | 2021-03-17 | 2021-07-02 | 攀枝花学院 | S @ VxSy composite positive electrode material, preparation method thereof and lithium-sulfur battery |
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