CN109742370A - A kind of self-supporting carried by nano carbon fiber molybdenum disulfide composite material and preparation method and application - Google Patents
A kind of self-supporting carried by nano carbon fiber molybdenum disulfide composite material and preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of self-supporting carried by nano carbon fiber molybdenum disulfide composite material and preparation method and applications, belong to aluminium ion field of batteries.The present invention directly utilizes (NH4)2MoS4Reduction generates MoS2, peculiar property with flexible self-supporting, it can be used directly as electrode, it avoids cumbersome technology for preparing electrode and is reduced using electric conductivity caused by binder, phenomena such as active material falls off in non-refractory and cyclic process, carbon nano-fiber can be used as the support substrate of molybdenum sulfide, during charge and discharge cycles, it can be destroyed to avoid structure of the molybdenum sulfide in cyclic process, stable cycle performance, there is mosaic texture of the unique molybdenum disulfide in carbon nano-fiber simultaneously, it is highly beneficial to insertion aluminum ions in battery charge and discharge process and deintercalation, it can satisfy practical application.
Description
Technical field
The invention belongs to aluminium ion battery technology field more particularly to a kind of self-supporting carried by nano carbon fiber molybdenum disulfide
Composite material and preparation method and application.
Background technique
The disadvantages of since the reserves of lithium metal are limited, price is high, inflammable and explosive fried, needs a kind of low cost, safe
Rechargeable battery replaces lithium ion battery.A kind of metal of the aluminium as rich reserves, price is well below lithium, and safety
Height, thus aluminium ion battery is promising instead of battery as lithium ion cell electrode.Since aluminium ion battery comes out, restrict
Factor is mainly the absence of suitable cathode material.Aluminium ion battery meets requirement of the practical application to cathode material: 1) it is inexpensive,
Process flow is simple.2) Fabrication of High Specific Capacitance.3) good cycling stability.4) good rate capability is suitable for high current charge-discharge.
Aluminium ion battery cathode material in the prior art be by binder by active material bonding on a current collector,
In cyclic process, it may appear that the case where falling off will result in battery performance decline, there is a problem of cyclical stability difference.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of self-supporting carried by nano carbon fiber molybdenum disulfide composite materials
And its preparation method and application.Carbon Nanowire in self-supporting carried by nano carbon fiber molybdenum disulfide composite material provided by the invention
The support substrate as molybdenum sulfide is tieed up, can be destroyed to avoid structure of the molybdenum sulfide in cyclic process, good cycling stability.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of self-supporting carried by nano carbon fiber molybdenum disulfide composite material, including with
Lower step:
By (NH4)2MoS4Powder adds polyacrylonitrile after being dissolved in n,N-Dimethylformamide, before obtaining electrostatic spinning
Drive body；
The electrostatic spinning presoma is subjected to spinning injection, obtains fiber；
The fiber is pre-oxidized in air atmosphere, obtains pre-oxidation product；
By the pre-oxidation product in Ar-H2Mixed atmosphere in restored, obtain reduzate；
The reduzate is carbonized in an inert atmosphere, obtains the self-supporting flexibility carried by nano carbon fiber two
Vulcanize molybdenum composite material.
Preferably, the described (NH4)2MoS4The partial size of powder is lower than 100 microns.
Preferably, the described (NH4)2MoS4The mass ratio of powder and polyacrylonitrile is 0.5~1:1.
Preferably, the mass concentration of the electrostatic spinning presoma is 8~10%.
Preferably, the spinning injection is carried out with injector for medical purpose, and the voltage of the spinning injection is preferably 18~20KV,
The Medical injection needle is 15~18cm at a distance from receiver board, and fltting speed is 10~12 μ L/min.
Preferably, the temperature of the pre-oxidation is 230~250 DEG C, and the time is 1~2h.
Preferably, the temperature of the reduction is 450~480 DEG C, and the time is 1~2h.
Preferably, the temperature of the carbonization is 830~850 DEG C, and the time is 1~2h.
The present invention also provides two sulphur of self-supporting carried by nano carbon fiber made from preparation method described in above-mentioned technical proposal
Change molybdenum composite material, the molybdenum disulfide is embedded in carbon nano-fiber.
The present invention also provides self-supporting carried by nano carbon fiber molybdenum disulfide composite materials described in above-mentioned technical proposal to make
For the application of aluminium ion battery cathode material.
The present invention provides a kind of preparation methods of self-supporting carried by nano carbon fiber molybdenum disulfide composite material, including with
Lower step: by (NH4)2MoS4Powder adds polyacrylonitrile after being dissolved in n,N-Dimethylformamide, obtains electrostatic spinning forerunner
Body；The electrostatic spinning presoma is subjected to spinning injection, obtains fiber；The fiber is subjected to pre- oxygen in air atmosphere
Change, obtains pre-oxidation product；By the pre-oxidation product in Ar-H2Mixed atmosphere in restored, obtain reduzate；It will
The reduzate is carbonized in an inert atmosphere, and it is compound to obtain the self-supporting flexibility carried by nano carbon fiber molybdenum disulfide
Material.The present invention directly utilizes (NH4)2MoS4Reduction generates MoS2, there is the peculiar property of flexible self-supporting, can directly make
For electrode use, avoid cumbersome technology for preparing electrode and reduced using electric conductivity caused by binder, non-refractory and
Phenomena such as active material falls off in cyclic process, carbon nano-fiber can be used as the support substrate of molybdenum sulfide, in charge and discharge cycles
In the process, Al3+Insertion and abjection in molybdenum sulfide can generate stress to the structure of molybdenum sulfide and structure caused to be destroyed, carbon
The support protection of nanofiber substrate can destroy to avoid structure of the molybdenum sulfide in cyclic process, after 500 circulations still
It is able to maintain stable performance, while there is mosaic texture of the unique molybdenum disulfide in carbon nano-fiber, to battery charging and discharging
Aluminum ions insertion and deintercalation are highly beneficial in the process, and practical application is met for it requires guiding value.And due to
Carbon nano-fiber has excellent electric conductivity, compared to molybdenum sulfide, compound material molybdenum sulfide, electric conductivity with carbon nano-fiber
It is good, it is adapted to high current charge-discharge battery (100mAhg-1, 200mAhg-1, 300mAhg-1And 500mAhg-1), it is
Aluminium ion battery investment practical application provides feasibility.
Detailed description of the invention
Fig. 1 is 1 self-supporting flexibility carried by nano carbon fiber MoS of embodiment2The pictorial diagram of composite material；
Fig. 2 (a) is 1 self-supporting flexibility carried by nano carbon fiber MoS of embodiment2The LED lab diagram of composite material；2 (b) are
Open-circuit voltage test curve；
Fig. 3 is 1 self-supporting flexibility carried by nano carbon fiber MoS of embodiment2The constant current cycle charge-discharge ratio of composite material
Hold and coulombic efficiency curve；
Fig. 4 is 1 self-supporting flexibility carried by nano carbon fiber MoS of embodiment2Preceding voltage-the appearance recycled three times of composite material
Spirogram；
Fig. 5 is 1 self-supporting flexibility carried by nano carbon fiber MoS of embodiment2The high rate performance test curve of composite material；
Fig. 6 is 1 self-supporting flexibility carried by nano carbon fiber MoS of embodiment2The cyclic voltammetry curve of composite material；
Fig. 7 is 1 self-supporting flexibility carried by nano carbon fiber MoS of embodiment2Scanning electron under composite material different multiplying
Microscope tests spectrogram；
Fig. 8 is 1 self-supporting flexibility carried by nano carbon fiber MoS of embodiment2The transmission electron microscope image of composite material；
Fig. 9 is 1 self-supporting flexibility carried by nano carbon fiber MoS of embodiment2The Elemental redistribution of composite material C, Mo and S；
Figure 10 is the XRD diagram of 1 flexible self-supporting carried by nano carbon fiber molybdenum disulfide composite material of embodiment.
Specific embodiment
The present invention provides a kind of preparation methods of self-supporting carried by nano carbon fiber molybdenum disulfide composite material, including with
Lower step:
By (NH4)2MoS4Powder adds polyacrylonitrile after being dissolved in n,N-Dimethylformamide, before obtaining electrostatic spinning
Drive body；
The electrostatic spinning presoma is subjected to spinning injection, obtains fiber；
The fiber is pre-oxidized in air atmosphere, obtains pre-oxidation product；
By the pre-oxidation product in Ar-H2Mixed atmosphere in restored, obtain reduzate；
The reduzate is carbonized in an inert atmosphere, obtains the self-supporting flexibility carried by nano carbon fiber two
Vulcanize molybdenum composite material.
The present invention is by (NH4)2MoS4Powder adds polyacrylonitrile after being dissolved in n,N-Dimethylformamide, obtains electrostatic
Spinning presoma.(NH is first dissolved in the present invention4)2MoS4Powder adds polyacrylonitrile, and raw material can be made preferably to dissolve
It is even.
In the present invention, the described (NH4)2MoS4The partial size of powder is preferably shorter than 100 microns.The present invention is preferably by (NH4)2MoS4(the NH is ground into agate mortar4)2MoS4Powder.
In the present invention, the described (NH4)2MoS4The mass ratio of powder and polyacrylonitrile is preferably 0.5~1:1.
In the present invention, the Mw of the polyacrylonitrile is preferably 120000~150000.
In the present invention, the mass concentration of the electrostatic spinning presoma is preferably 8~10%.
In the present invention, the described (NH4)2MoS4Powder is dissolved in N,N-dimethylformamide and adds polyacrylonitrile
It is preferred that carrying out under magnetic stirring.In the present invention, the temperature of the magnetic agitation is preferably 50 DEG C, the magnetic agitation
Time is preferably 8h, and the present invention does not have special restriction to the power of the magnetic agitation.
After obtaining electrostatic spinning presoma, the electrostatic spinning presoma is carried out spinning injection by the present invention, obtains fiber.
In the present invention, the spinning injection is preferably carried out with injector for medical purpose, and the voltage of the spinning injection is preferably 18~20KV,
The Medical injection needle is preferably 15~18cm at a distance from receiver board, and fltting speed is preferably 10~12 μ L/min.
In the present invention, the diameter of the Medical injection needle is preferably 1.6mm.In the present invention, the medical injection
The volume of emitter is preferably 10mL.
After obtaining fiber, the present invention pre-oxidizes the fiber in air atmosphere, obtains pre-oxidation product.At this
In invention, the pre-oxidation can make fiber line shape molecule be converted into heat-resisting trapezium structure, make it in subsequent high temperature cabonization
Process keeps fibre morphology, avoids the occurrence of melting and and silk.In the present invention, the temperature of the pre-oxidation is preferably 230~250
DEG C, more preferably 235~245 DEG C, the time is preferably 1~2h.
In the present invention, it is preferred to by room temperature to the temperature of the pre-oxidation.In the present invention, it is warming up to the pre- oxygen
The heating rate of the temperature of change is preferably 3~5 DEG C/min.
After obtaining pre-oxidation product, the present invention is by the pre-oxidation product in Ar-H2Mixed atmosphere in restored, obtain
To reduzate.In the present invention, (NH occurs in the reduction4)2MoS4Reduction, obtain MoS2。
In the present invention, Ar-H in the mixed atmosphere2Volume ratio be preferably 93:7.
In the present invention, the temperature of the reduction is preferably 450~480 DEG C, and more preferably 460~470 DEG C, the time is preferred
For 1~2h.In the present invention, the heating rate for being warming up to the temperature of the reduction is preferably 3~5 DEG C/min.
After obtaining reduzate, the reduzate is carbonized by the present invention in an inert atmosphere, obtains described from branch
Support flexible carried by nano carbon fiber molybdenum disulfide composite material.
In the present invention, the inert atmosphere is preferably Ar.
In the present invention, the temperature of the carbonization is preferably 830~850 DEG C, and more preferably 835~845 DEG C, the time is preferred
For 1~2h.In the present invention, the heating rate for being warming up to the temperature of the carbonization is preferably 3~5 DEG C/min.
The present invention also provides two sulphur of self-supporting carried by nano carbon fiber made from preparation method described in above-mentioned technical proposal
Change molybdenum composite material, the molybdenum disulfide is embedded in carbon nano-fiber.
In the present invention, the quality of molybdenum disulfide contains in the self-supporting carried by nano carbon fiber molybdenum disulfide composite material
Amount preferably 55%~60%.
The present invention also provides self-supporting carried by nano carbon fiber molybdenum disulfide composite materials described in above-mentioned technical proposal to make
For the application of aluminium ion battery cathode material.Nano-fibre supported molybdenum disulfide composite material has flexible self-supporting in the present invention
Peculiar property, preferably used directly as electrode, avoid cumbersome technology for preparing electrode and use and led caused by binder
Phenomena such as active material falls off in non-refractory and cyclic process is electrically reduced, carbon nano-fiber can be used as the branch of molybdenum sulfide
Support group bottom, during charge and discharge cycles, Al3+Insertion and abjection in molybdenum sulfide, which can generate the structure of molybdenum sulfide, answers masterpiece
With and cause structure to be destroyed, the support of carbon nano-fiber substrate protection can be broken to avoid structure of the molybdenum sulfide in cyclic process
It is bad, it is still able to maintain stable performance after 500 circulations, while there is edge of the unique molybdenum disulfide in carbon nano-fiber
Embedding structure, it is highly beneficial to insertion aluminum ions in battery charge and discharge process and deintercalation, the requirement of practical application is met for it
With guiding value.It is compound with carbon nano-fiber compared to molybdenum sulfide and since carbon nano-fiber has excellent electric conductivity
Material molybdenum sulfide, good conductivity is adapted to high current charge-discharge battery, puts into practical application for aluminium ion battery and provides
Feasibility.
Below with reference to embodiment to a kind of self-supporting carried by nano carbon fiber molybdenum disulfide composite material provided by the invention
And its preparation method and application be described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Step 1: self-supporting flexibility carried by nano carbon fiber MoS2The preparation of composite material
The preparation of electrostatic spinning presoma:
By (NH4)2MoS4After being ground into the powder of micron level (lower than 100 microns) with agate mortar, (NH is weighed4)2MoS4Be dissolved in n,N-Dimethylformamide solution, it is to be dissolved sufficiently after add polyacrylonitrile (Mw=120,000) and be configured to
Electrostatic spinning presoma, (NH4)2MoS4Mass ratio with polyacrylonitrile is 0.5:1, and the concentration of electrostatic spinning presoma is 8%,
After 50 DEG C of magnetic agitation 8h, electrostatic spinning presoma is obtained.
Electrostatic spinning process:
Electrostatic spinning presoma obtained is sucked into 10mL injector for medical purpose, carries out spinning with the syringe needle that diameter is 1.6mm
Injection.Electrostatic spinning voltage is 20KV, and syringe needle is 15cm at a distance from receiver board, and fltting speed is 10 μ L/min.
Heat treatment process:
Fiber obtained by electrostatic spinning is first pre-oxidized, with the heating of 3 DEG C/min since room temperature in air atmosphere
Rate is warming up to 230 DEG C, keeps the temperature 1h.After pre-oxidation, (NH is carried out4)2MoS4Reduction, in 93%Ar-7%H2It is risen in atmosphere
For temperature to 450 DEG C, heating rate is 5 DEG C/min, keeps the temperature 1h.It is carbonized finally, being warming up to 830 DEG C in an ar atmosphere to fiber,
Heating rate is 5 DEG C/min, keeps the temperature 1h, finally obtained self-supporting flexibility carried by nano carbon fiber MoS2Composite material.
Fig. 1 is the present embodiment self-supporting flexibility carried by nano carbon fiber MoS2The pictorial diagram of composite material, wherein Fig. 1 a be
Flexible self-supporting carried by nano carbon fiber molybdenum disulfide without loop test, Fig. 1 b are the flexible branch certainly after 200 circulations
Support carried by nano carbon fiber molybdenum disulfide.It can be read by Fig. 1, which is the structure of flexible self-supporting, can directly be cut
The electrode of required size, and after 200 circulations, electrode still keeps good integraty, and dusting and fragmentation do not occur
Problem illustrates that the composite material has excellent cyclical stability.
Step 2: battery system
Since aluminium ion used in battery electrolyte is acidic ion liquid, it is corrosive to stainless steel, therefore does not use button
Battery selects soft-package battery to be tested.
Using aluminium foil as anode, aluminum foil thickness 0.2mm, purity 99.999%.With the present embodiment self-supporting flexibility carbon
Nano-fibre supported vulcanization molybdenum composite material is directly as cathode.Using Whatman (GF/D) as diaphragm.Electrolyte is with anhydrous
Aluminium chloride and chlorination 1- ethyl-3-methylimidazole are formed with the molar ratio of 1.3:1.
Step 3: electro-chemical test
1) open-circuit voltage is tested
Open-circuit voltage is 1.5V or so.Two batteries are connected, LED small bulbs can be lighted.
Fig. 2 (a) is LED lab diagram；2 (b) be open-circuit voltage test curve.
2) constant current cycle is tested
Constant current loop test, current value 100mAg are carried out with LAND CT2001A battery test system-1, voltage model
It encloses for 0.1~2V.Fig. 3 is constant current cycle charge-discharge specific volume and coulombic efficiency curve.As seen from Figure 3, electric discharge specific volume is for the first time
293.2mAh·g-1, after 200 circulations, electric discharge specific volume can still keep 126.6mAhg-1, coulombic efficiency is higher than 95%.
As it can be seen that self-supporting flexibility carried by nano carbon fiber MoS2Composite material as aluminium ion battery cathode material have height ratio capacity and
Good cyclical stability.
Fig. 4 is the preceding voltage-capacity figure recycled three times, from fig. 4, it can be seen that discharge voltage plateau be 0.7~0.8V and 0.5~
0.6V, charging voltage platform are 0.9~1.0V and 1.1~1.2V, self-supporting carried by nano carbon fiber molybdenum disulfide composite material
As the cathode material of aluminium ion battery, there is stable charging/discharging voltage platform.
3) high rate performance is tested
High rate performance test is carried out with LAND CT2001A battery test system.As seen from Figure 5, current density is
100mA·g-1When, specific volume is stablized in 146.2mAhg after 20 circulations-1Left and right, when current density progressively increases to
150mA·g-1, 200mAg-1And 250mAg-1When, specific volume reduces amplitude very little, respectively 128.4mAhg-1,
118.3mAh·g-1And 111.9mAhg-1, when electric current is restored to 100mAg-1Afterwards, capacity also restores completely, is
147.2mAh·g-1, illustrate cathode of the flexible self-supporting carried by nano carbon fiber molybdenum disulfide composite material as aluminium ion battery
Material has excellent high rate performance.
4) cyclic voltammetry
Cyclic voltammetry is carried out on Gamry Reference3000.Sweep speed is 5mV/s, surface sweeping voltage range
For 0.1~2V.Fig. 6 is cyclic voltammetry curve, and as seen from Figure 6, flexible self-supporting carried by nano carbon fiber molybdenum disulfide is multiple
There is cathodic peak current at 0.6V and 0.8V respectively as aluminium ion cell cathode in condensation material, occurs at 1.0V and 1.2V
Anodic peak current, it is very identical with charging/discharging voltage platform, and first three circle cyclic voltammetry scan curve essentially coincides, and illustrates battery
It is with good stability.
Step 4: morphology characterization
1) scanning electron microscope test under different multiplying (SEM) is as shown in fig. 7, wherein a, b are flexible self-supporting carbon
The surface sweeping sem image of nano-fibre supported molybdenum disulfide composite material, it is seen that its pattern is that the nanofiber of continuous uniform is constituted
Three-dimensional network.Fibrous external does not have visible substance, illustrates that molybdenum disulfide is supported on inside carbon nano-fiber, and c, d are by 200 times
The surface sweeping sem image of carried by nano carbon fiber molybdenum disulfide after circulation still maintains typical continuous uniform carbon after cycling
Nanofiber three-dimensional network has excellent structural stability.
2) transmission electron microscope test (TEM)
Fig. 8 is the transmission electron microscope image of flexible self-supporting carried by nano carbon fiber molybdenum disulfide.As it can be seen that molybdenum disulfide
It is evenly distributed in inside carbon nano-fiber.Fig. 8 c is high-resolution transmission electron microscope image, by between the visible lattice of lattice fringe
Away from for 0.62nm, corresponding MoS2(002) interplanar distance.
3) Auger electron spectroscopy test (EDS)
Fig. 9 is the Elemental redistribution of C, Mo and S.As seen from Figure 9, Mo and S are evenly distributed in carbon nano-fiber, with transmission
Electron micrograph image matches.
4) X-ray diffraction (XRD)
Figure 10 is the XRD diagram of flexible self-supporting carried by nano carbon fiber molybdenum disulfide composite material, as seen from Figure 10, flexible
There is diffraction maximum at 14 °, 32.5 ° and 58 ° in the XRD diagram of self-supporting carried by nano carbon fiber molybdenum disulfide composite material, with two
(002) of molybdenum sulfide, (100) and (110) are corresponding.24 ° of diffraction maximum corresponds to (002) crystal face of carbon nano-fiber.XRD is further
Demonstrate the successful preparation of flexible self-supporting carried by nano carbon fiber molybdenum disulfide composite material.
The present invention has prepared flexible self-supporting carried by nano carbon fiber molybdenum disulfide composite material, can be directly as aluminium
The cathode of ion battery, simplify battery preparation work technique and shown excellent chemical property: 1) open-circuit voltage is higher than
1.5V；2) electric discharge specific volume is 293.2mAhg for the first time-1；3) after 200 circulations, capacity is stably held in 126.6mAhg-1,
Coulombic efficiency is higher than 95%；4) in high rate performance test, 100mAg-1, 150mAg-1, 200mAg-1, 250mAg-1
Current density under after charge and discharge cycles, electric current is restored to 100mAg-1Afterwards, specific volume almost restores.5) have stable
Charging/discharging voltage platform, discharge voltage plateau be 0.7~0.8V and 0.5~0.6V, charging voltage platform be 0.9~1.0V and
1.1~1.2V.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of self-supporting carried by nano carbon fiber molybdenum disulfide composite material, which is characterized in that including following
Step:
By (NH4)2MoS4Powder adds polyacrylonitrile after being dissolved in n,N-Dimethylformamide, obtains electrostatic spinning presoma；
The electrostatic spinning presoma is subjected to spinning injection, obtains fiber；
The fiber is pre-oxidized in air atmosphere, obtains pre-oxidation product；
By the pre-oxidation product in Ar-H2Mixed atmosphere in restored, obtain reduzate；
The reduzate is carbonized in an inert atmosphere, obtains the self-supporting flexibility carried by nano carbon fiber curing
Molybdenum composite material.
2. preparation method described in claim 1, which is characterized in that (the NH4)2MoS4The partial size of powder is lower than 100 microns.
3. preparation method according to claim 1 or 2, which is characterized in that (the NH4)2MoS4Powder and polyacrylonitrile
Mass ratio is 0.5~1:1.
4. preparation method according to claim 1, which is characterized in that the mass concentration of the electrostatic spinning presoma is 8
~10%.
5. preparation method according to claim 1, which is characterized in that the spinning injection is carried out with injector for medical purpose, institute
The voltage for stating spinning injection is preferably 18~20KV, and the Medical injection needle is 15~18cm at a distance from receiver board, is pushed away
It is 10~12 μ L/min into speed.
6. preparation method according to claim 1, which is characterized in that the temperature of the pre-oxidation is 230~250 DEG C, when
Between be 1~2h.
7. preparation method according to claim 1, which is characterized in that the temperature of the reduction is 450~480 DEG C, the time
For 1~2h.
8. preparation method according to claim 1, which is characterized in that the temperature of the carbonization is 830~850 DEG C, the time
For 1~2h.
9. self-supporting carried by nano carbon fiber molybdenum disulfide composite wood made from any one of claim 1~8 preparation method
Material, which is characterized in that in the molybdenum disulfide insertion carbon nano-fiber.
10. self-supporting carried by nano carbon fiber molybdenum disulfide composite material described in claim 9 is as aluminium ion cell cathode material
The application of material.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111463508.1A CN114142014A (en) | 2019-01-11 | 2019-01-11 | Self-supporting carbon nanofiber loaded molybdenum disulfide composite material and preparation method and application thereof |
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| CN113097466A (en) * | 2021-04-02 | 2021-07-09 | 宁波润锦环保科技有限公司 | Lithium ion battery negative electrode material MoS2Preparation method of @ CFs |
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| CN113998740A (en) * | 2021-10-25 | 2022-02-01 | 同济大学 | C-FeOOH lossless deformation self-supporting electrode with wolf tooth rod structure and preparation method |
| CN114300676A (en) * | 2021-11-01 | 2022-04-08 | 北京航空航天大学 | Flexible sodium-ion battery negative electrode material, preparation method thereof and battery negative electrode |
| CN114944476A (en) * | 2022-05-09 | 2022-08-26 | 桂林理工大学 | MoS 2 /Fe 2 O 3 Heterostructure @ porous carbon fiber composite material and preparation method and application thereof |
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| CN113998740A (en) * | 2021-10-25 | 2022-02-01 | 同济大学 | C-FeOOH lossless deformation self-supporting electrode with wolf tooth rod structure and preparation method |
| CN114300676A (en) * | 2021-11-01 | 2022-04-08 | 北京航空航天大学 | Flexible sodium-ion battery negative electrode material, preparation method thereof and battery negative electrode |
| CN114944476A (en) * | 2022-05-09 | 2022-08-26 | 桂林理工大学 | MoS 2 /Fe 2 O 3 Heterostructure @ porous carbon fiber composite material and preparation method and application thereof |
| CN114944476B (en) * | 2022-05-09 | 2023-10-13 | 桂林理工大学 | MoS (MoS) 2 /Fe 2 O 3 Heterostructure @ porous carbon fiber composite material and preparation method and application thereof |
| CN115537973A (en) * | 2022-09-27 | 2022-12-30 | 河北师范大学 | Molybdenum sulfide/porous carbon nanofiber composite electrode material and preparation method and application thereof |
| CN115537973B (en) * | 2022-09-27 | 2024-04-30 | 河北师范大学 | Molybdenum sulfide/porous carbon nanofiber composite electrode material and preparation method and application thereof |
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