CN104979100B - A kind of tungsten disulfide absorbent charcoal composite material and electrode material for super capacitor and preparation method thereof - Google Patents
A kind of tungsten disulfide absorbent charcoal composite material and electrode material for super capacitor and preparation method thereof Download PDFInfo
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- CN104979100B CN104979100B CN201510287069.1A CN201510287069A CN104979100B CN 104979100 B CN104979100 B CN 104979100B CN 201510287069 A CN201510287069 A CN 201510287069A CN 104979100 B CN104979100 B CN 104979100B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of tungsten disulfide absorbent charcoal composite material and electrode material for super capacitor and preparation method thereof, belong to field of new energy technologies.Described composite is combined by tungsten disulfide and activated carbon, and the mass ratio of tungsten disulfide and activated carbon is 5~10:1, described electrode material for super capacitor is prepared by above-mentioned tungsten disulfide absorbent charcoal composite material with carbon black, PTFE binder, and the mass ratio of tungsten disulfide absorbent charcoal composite material, carbon black and PTFE binder is 70~80:10~20:5~15.The electrode material for super capacitor of the present invention, there is big specific capacitance and high electrochemical stability, service life cycle length, and preparation method is easy, quick, and cost is low, environment-friendly, has preferable application prospect.
Description
Technical field
The invention belongs to field of new energy technologies, and in particular to a kind of tungsten disulfide-absorbent charcoal composite material and super electricity
Container electrode material and preparation method thereof.
Background technology
In energy field, ultracapacitor is a kind of in recent years emerging and quickly grown that performance is between traditional capacitance
Novel energy storage apparatus between device and secondary cell, the high specific power of traditional capacitor and the high ratio of secondary cell have been provided simultaneously with it
The advantages that energy, in addition, ultracapacitor also has, charge-discharge velocity is fast, have extended cycle life, operating temperature range is wide, security
The features such as energy is good and economic and environment-friendly, thus be all widely used in all fields.
Electrode material and electrolyte system determine the capacitive property of ultracapacitor, and the leading role of electrode material is especially
It is prominent.Transition metal dichalcogenide must have the characteristics that as the electrode material of ultracapacitor：1. in disulphide
Metal ion must have two or more oxidation state to coexist, but be unlikely to cause phase transformation；2. proton can be by also
The free disulphide lattice that comes in and goes out of original reaction.Tungsten disulfide（WS2）As the Typical Representative of transition metal dichalcogenide, be with
S-W-S sandwich of layers is basic structural unit.In sandwich of layers, each W atoms and 6 S atoms with Covalent bonding together, and layer with
Only combined between layer with weak model ylid bloom action power.Exactly this weak model ylid bloom action power between layers so that interlayer quilt
Expansion is opened, there is provided the possibility of the insertion of ion and other objects.Research shows, WS2Lamellar structure be advantageous to energy stores,
There is more preferable ionic conducting property than in general oxide, there is higher theoretical specific capacitance than carbon-based material.It is however, relative
In the materials such as graphene, CNT, activated carbon, WS2Electric conductivity it is poor, this make it that its specific capacitance is relatively low, shadow
The material further applying in energy field is rung.
Carbon material, particularly sp2The carbon material of hydridization（Such as activated carbon, graphene）, due to its special layer structure
It has been applied to the specific surface area of super large in ultracapacitor, activated carbon（Activated carbon, AC）It is super capacitor
One of the most frequently used electrode material of device, with specific surface area is big, electric conductivity is preferable, electrochemical stability is high, raw material sources enrich
The advantages that.But activated carbon itself pore-size distribution is unreasonable, the microcellular structure of activated carbon contribute to main specific surface area, and
Migration resistance of the ion in micropore is larger, causes its specific capacitance low, hinders its extensive use in ultracapacitor.
The content of the invention
In order to overcome drawbacks described above, it is an object of the invention to provide a kind of tungsten disulfide-absorbent charcoal composite material.
Another object of the present invention is to provide a kind of electrode material for super capacitor, by above-mentioned tungsten disulfide-activated carbon
Composite is prepared with carbon black, PTFE binder, and bulking value is high, service life cycle length.
Another object of the present invention, which also resides in, provides a kind of preparation method of above-mentioned electrode material for super capacitor, preparation side
Method is easy, and raw material is easy to get.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of tungsten disulfide-absorbent charcoal composite material, described composite are combined by tungsten disulfide and activated carbon,
The mass ratio of tungsten disulfide and activated carbon is 5~10:1.
A kind of electrode material for super capacitor, by above-mentioned tungsten disulfide-absorbent charcoal composite material and carbon black, polytetrafluoroethylene (PTFE)
Adhesive is prepared, and the mass ratio of described tungsten disulfide-absorbent charcoal composite material, carbon black and PTFE binder is
70~80:10~20:5~15.
The preparation method of above-mentioned electrode material for super capacitor, comprises the following steps：
（1）By tungsten disulfide WS2Solid powder grinds 2~4 h in ball mill；
（2）By step（1）Middle WS20.1 ~ 0.3 g ultrasonic disperses obtain WS in 20 ~ 40 mL redistilled waters2It is scattered
Liquid；
（3）Take 0.01 ~ 0.03 g activated carbons AC to add 20 ~ 40 mL redistilled waters, obtained uniformly through ultrasonic disperse
Activated carbon dispersion liquid；
（4）By step（3）In activated carbon dispersion liquid be added slowly to step（2）WS2In dispersion liquid, second distillation is used
Water is diluted to 60~80 mL, persistently stirs 1~2 h；
（5）By above-mentioned steps（4）Obtained mixed solution, which is transferred in hydrothermal reaction kettle, carries out hydro-thermal reaction, reaction temperature
For 160 ~ 200 DEG C, the reaction time is 24 ~ 48 h；
（6）Treat step（5）After hydro-thermal reaction terminates, reaction solution is naturally cooled into room temperature, centrifugation, washing, dries, produces
To tungsten disulfide-activated carbon WS2- AC composites；
（7）Foam nickel sheet is cleaned up, dried, it is standby；
（8）By above-mentioned steps（6）Tungsten disulfide-absorbent charcoal composite material of preparation and carbon black, PTFE binder
It is 70~80 in mass ratio:10~20:5~15 is well mixed, after being ground into film, is coated in step（7）Standby foam nickel sheet
Surface, dry, produce combination electrode material.
According to the preparation method of above-mentioned electrode material for super capacitor, step（1）The WS2Solid powder particle diameter is
0.5~2 μm。
According to the preparation method of above-mentioned electrode material for super capacitor, step（1）Described drum's speed of rotation be 400~
800 r/min。
According to the preparation method of above-mentioned electrode material for super capacitor, step（2）With（3）Described ultrasonic frequency is
40~60 KHz.
According to the preparation method of above-mentioned electrode material for super capacitor, step（3）Described activated carbon specific surface area is
500~1000 m2/ g, apparent density are 0.08~0.45 g/mL.
According to the preparation method of above-mentioned electrode material for super capacitor, step（6）Described washing methods is：Secondary steaming
Distilled water and ethanol wash 2~4 times respectively.
According to the preparation method of above-mentioned electrode material for super capacitor, step（6）Described drying is vacuum drying, warm
Spend for 60 ~ 80 DEG C, drying time is 20 ~ 24 h.
According to the preparation method of above-mentioned electrode material for super capacitor, step（7）The specification of described foam nickel sheet is：
(4~8 cm)×(0.5~2 cm)×(0.1~0.5 cm）.
According to the preparation method of above-mentioned electrode material for super capacitor, step（8）Described drying is vacuum drying, warm
Spend for 60~100 DEG C, drying time is 6~10 h.
The positive effect of the present invention
The present invention is prepared for tungsten disulfide-activated carbon using simple step hydrothermal synthesis method（WS2-AC）Composite,
It has been effectively combined tungsten disulfide WS2The advantages of with activated carbon AC, i.e.,：WS2Easy intercalation and AC specific surface areas are big, conduct electricity very well
Advantage, be advantageous to improve the performance of electrode material for super capacitor.
The present invention uses tungsten disulfide-activated carbon（WS2-AC）Composite, carbon black and polytetrafluoroethylene (PTFE) are prepared super
Capacitance electrode material, there is big specific capacitance and high electrochemical stability, service life cycle length, and preparation method letter
Just, quickly, cost is low, environment-friendly, has preferable application prospect.
Brief description of the drawings
Fig. 1 is WS prepared by the embodiment of the present invention 12The SEM figures of-AC composites；
Fig. 2 is WS prepared by the embodiment of the present invention 12The XRD of-AC composites；
Fig. 3 is charging and discharging curve figure of the electrode material for super capacitor of the embodiment of the present invention 1 under different current densities；
Fig. 4 be the electrode material for super capacitor of the embodiment of the present invention 1 cyclical stability test chart；
Fig. 5 is WS prepared by the embodiment of the present invention 22The SEM figures of-AC composites；
Fig. 6 is WS prepared by the embodiment of the present invention 22The XRD of-AC composites；
Fig. 7 is charging and discharging curve figure of the electrode material for super capacitor of the embodiment of the present invention 2 under different current densities；
Fig. 8 be the electrode material for super capacitor of the embodiment of the present invention 2 cyclical stability test chart；
Fig. 9 is WS prepared by the embodiment of the present invention 32The SEM figures of-AC composites；
Figure 10 is WS prepared by the embodiment of the present invention 32The XRD of-AC composites；
Figure 11 is charging and discharging curve figure of the electrode material for super capacitor of the embodiment of the present invention 3 under different current densities；
Figure 12 be the electrode material for super capacitor of the embodiment of the present invention 3 cyclical stability test chart.
Embodiment
With reference to some specific embodiments, the present invention is further described.
Embodiment 1
A kind of tungsten disulfide-absorbent charcoal composite material, described composite are combined by tungsten disulfide and activated carbon,
The mass ratio of tungsten disulfide and activated carbon is 5:1.
A kind of electrode material for super capacitor, by above-mentioned tungsten disulfide-absorbent charcoal composite material and carbon black, polytetrafluoroethylene (PTFE)
Adhesive is prepared, and the mass ratio of tungsten disulfide-absorbent charcoal composite material, carbon black and PTFE binder is 75:15:
10。
A kind of preparation method of super capacitance electrode material, comprises the following steps：
（1）By tungsten disulfide WS2Powder grinds 3 h in ball mill；
（2）By step（1）Middle WS20.1 g ultrasonic disperses obtain WS in 30 mL redistilled waters2Dispersion liquid；
（3）0.02 g activated carbons are taken, 30 mL redistilled waters is added, obtains uniform activated carbon through ultrasonic disperse and disperse
Liquid；
（4）By step（3）In activated carbon dispersion liquid be added slowly to step（2）WS2In dispersion liquid, second distillation is used
Water is diluted to 70 mL, persistently stirs 1 h；
（5）By above-mentioned steps（4）Obtained mixed solution is transferred in 100 mL hydrothermal reaction kettles and carries out hydro-thermal reaction, instead
It is 180 DEG C to answer temperature, and the reaction time is 48 h；
（6）Step（5）After hydro-thermal reaction terminates, reaction mixture is naturally cooled into room temperature, centrifugation, washing, dried,
Obtain WS2- AC composites；
（7）Foam nickel sheet is cleaned up, dried, it is standby；
（8）By above-mentioned steps（6）Tungsten disulfide-absorbent charcoal composite material of preparation and carbon black, PTFE binder
It is well mixed, after being ground into film, it is coated in step（6）Standby foam nickel sheet surface, dry, produce combination electrode material.
Step（1）Described drum's speed of rotation is 400 r/min.
Step（2）With（3）Described ultrasonic frequency is 40 KHz.
Step（6）Described washing methods is：Redistilled water and ethanol wash 3 times respectively.
Step（6）Described drying is vacuum drying, and temperature is 60 DEG C, and drying time is 24 h.
Step（7）The specification of described foam nickel sheet is：Length × width x thickness is the cm of the cm of 5 cm × 1 × 0.2.
Step（8）Described drying is vacuum drying, and temperature is 80 DEG C, and drying time is 8 h.
Performance test is made to 1 tungsten disulfide of the embodiment of the present invention-absorbent charcoal composite material, electrode material for super capacitor,
As a result Fig. 1~4 are seen.
From fig. 1, it can be seen that the AC of ellipsoid disperses and is attached to the WS of lamella2On.
As can be seen from Figure 2, in x-ray diffraction pattern（XRD）On, WS2There is WS simultaneously on the spectrogram of-AC composites2With
AC characteristic peak, show to be successfully prepared WS2- AC composites.
As can be seen from Figure 3, using 6.0 mol/L KOH as electrolyte, in different current densities（1、1.5、3、5、10、20
A/g）Under, the constant current charge-discharge figure of electrode material for super capacitor, obtain in different current densities（1、1.5、3、5、10、
20 A/g）Quality specific capacitance corresponding to lower is respectively 909.3,843.6,776.46,719.1,673.1,607.6 F/g.
As can be seen from Figure 4, super capacitance electrode material circulates 1000 circles, the ratio of electrode material under 5 A/g current density
Electric capacity keeps original 102%, illustrates that prepared electrode material for super capacitor has good stability, suitable for length
The capacitor in life-span.
Embodiment 2
A kind of tungsten disulfide-absorbent charcoal composite material, described composite are combined by tungsten disulfide and activated carbon,
The mass ratio of tungsten disulfide and activated carbon is 10:1.
A kind of electrode material for super capacitor, by above-mentioned tungsten disulfide-absorbent charcoal composite material and carbon black, polytetrafluoroethylene (PTFE)
Adhesive is prepared, and the mass ratio of tungsten disulfide-absorbent charcoal composite material, carbon black and PTFE binder is 70:10:
5。
A kind of preparation method of electrode material for super capacitor, comprises the following steps：
（1）By tungsten disulfide WS2Powder grinds 2 h in ball mill；
（2）By step（1）Middle WS20.2 g ultrasonic disperses obtain WS in 40 mL redistilled waters2Dispersion liquid；
（3）0.02 g activated carbons are taken, 30 mL redistilled waters is added, obtains uniform activated carbon through ultrasonic disperse and disperse
Liquid；
（4）By step（3）In activated carbon dispersion liquid be added slowly to step（2）WS2In dispersion liquid, second distillation is used
Water is diluted to 80 mL, persistently stirs 2 h；
（5）By above-mentioned steps（4）Obtained mixed solution is transferred in 100 mL hydrothermal reaction kettles and carries out hydro-thermal reaction, instead
It is 200 DEG C to answer temperature, and the reaction time is 24 h；
（6）Step（5）After hydro-thermal reaction terminates, reaction mixture is naturally cooled into room temperature, centrifugation, washing, dried,
Obtain WS2- AC composites；
（7）Foam nickel sheet is cleaned up, dried, it is standby；
（8）By above-mentioned steps（6）Tungsten disulfide-absorbent charcoal composite material of preparation and carbon black, PTFE binder
It is well mixed, after being ground into film, it is coated in step（7）Standby foam nickel sheet surface, dry, produce combination electrode material.
Step（1）Described drum's speed of rotation is 600 r/min.
Step（2）With（3）Described ultrasonic frequency is 50 KHz.
Step（6）Described washing methods is：Redistilled water and ethanol wash 4,2 times respectively.
Step（6）Described drying is vacuum drying, and temperature is 70 DEG C, and drying time is 23 h.
Step（7）The specification of described foam nickel sheet is：The cm of the cm of the cm of length × width x thickness 6 × 1 × 0.2.
Step（8）Described drying is vacuum drying, and temperature is 100 DEG C, and drying time is 6 h.
Performance test is made to 2 tungsten disulfides of the embodiment of the present invention-absorbent charcoal composite material, electrode material for super capacitor,
As a result Fig. 5~8 are seen.
As can be seen from Figure 5, the AC of larger particles is attached to the WS of lamella2On.
As can be seen from Figure 6, in x-ray diffraction pattern（XRD）On, WS2There is WS simultaneously on the spectrogram of-AC composites2With
AC characteristic peak, show to be successfully prepared WS2- AC composites.
As can be seen from Figure 7, using 6.0 mol/L KOH as electrolyte, in different current densities（1、1.5、3、5、10、20
A/g）Under, the constant current charge-discharge figure of electrode material for super capacitor, obtain in different current densities（1、1.5、3、5、10、
20 A/g）Quality specific capacitance corresponding to lower is respectively 700.4,582.5,530.1,485.3,431.2,397.6 F/g.
As it can be observed in the picture that super capacitance electrode material circulates 1000 circles, the ratio of electrode material under 5 A/g current density
Electric capacity keeps original 88.8%, illustrates that prepared electrode material for super capacitor has preferable stability.
Embodiment 3
A kind of tungsten disulfide-absorbent charcoal composite material, described composite are combined by tungsten disulfide and activated carbon,
The mass ratio of tungsten disulfide and activated carbon is 7.5:1.
A kind of electrode material for super capacitor, by above-mentioned tungsten disulfide-absorbent charcoal composite material and carbon black, polytetrafluoroethylene (PTFE)
Adhesive is prepared, and the mass ratio of tungsten disulfide-absorbent charcoal composite material, carbon black and PTFE binder is 80:20:
15。
A kind of preparation method of super capacitance electrode material, comprises the following steps：
（1）By tungsten disulfide WS2Powder grinds 4 h in ball mill；
（2）By step（1）Middle WS20.15 g ultrasonic disperses obtain WS in 20 mL redistilled waters2Dispersion liquid；
（3）0.02 g activated carbons are taken, 20 mL redistilled waters is added, obtains uniform activated carbon through ultrasonic disperse and disperse
Liquid；
（4）By step（3）In activated carbon dispersion liquid be added slowly to step（2）WS2In dispersion liquid, second distillation is used
Water is diluted to 60 mL, persistently stirs 1.5 h；
（5）By above-mentioned steps（4）Obtained mixed solution is transferred in 100 mL hydrothermal reaction kettles and carries out hydro-thermal reaction, instead
It is 160 DEG C to answer temperature, and the reaction time is 40 h；
（6）Step（5）After hydro-thermal reaction terminates, reaction mixture is naturally cooled into room temperature, centrifugation, washing, dried,
Obtain WS2- AC composites；
（7）Foam nickel sheet is cleaned up, dried, it is standby；
（8）By above-mentioned steps（6）Tungsten disulfide-absorbent charcoal composite material of preparation and carbon black, PTFE binder
It is well mixed, after being ground into film, it is well mixed, is coated in step（6）Standby foam nickel sheet surface, dry, produce compound electric
Pole material.
Step（1）Described drum's speed of rotation is 800 r/min.
Step（2）With（3）Described ultrasonic frequency is 60 KHz.
Step（6）Described washing methods is：Redistilled water and ethanol wash 2,4 times respectively.
Step（6）Described drying is vacuum drying, and temperature is 80 DEG C, and drying time is 20 h.
Step（7）The specification of described foam nickel sheet is：The cm of the cm of the cm of length × width x thickness 5 × 1.2 × 0.3.
Step（8）Described drying is vacuum drying, and temperature is 60 DEG C, and drying time is 10 h.
Performance test is made to 3 tungsten disulfides of the embodiment of the present invention-absorbent charcoal composite material, electrode material for super capacitor,
As a result Fig. 9~12 are seen.
As can be seen from Figure 9, the AC of bulky grain ellipsoid disperses and is attached to the WS of lamella2On.
As can be seen from Figure 10, in x-ray diffraction pattern（XRD）On, WS2There is WS simultaneously on the spectrogram of-AC composites2With
AC characteristic peak, show to be successfully prepared WS2- AC composites.
As can be seen from Figure 11, using 6.0 mol/L KOH as electrolyte, in different current densities（1、1.5、3、5、10、20
A/g）Under, the constant current charge-discharge figure of electrode material for super capacitor, obtain in different current densities（1、1.5、3、5、10、
20 A/g）Quality specific capacitance corresponding to lower is respectively 875.6,780.3,645.1,586.5,523.7,481.2 F/g.
As can be seen from Figure 12, electrode material for super capacitor circulates 1000 circles under 5 A/g current density, electrode material
Specific capacitance keeps original 86.7%, illustrates that prepared electrode material for super capacitor has preferable stability.
Claims (8)
- A kind of 1. preparation method of electrode material for super capacitor, it is characterised in that by tungsten disulfide-absorbent charcoal composite material with Carbon black, PTFE binder are prepared, described tungsten disulfide-absorbent charcoal composite material, carbon black and polytetrafluoroethylene (PTFE) The mass ratio of adhesive is 70~80:10~20:5~15；Described tungsten disulfide-absorbent charcoal composite material by tungsten disulfide and Activated carbon is combined, and the mass ratio of described tungsten disulfide and activated carbon is 5~10:1；The preparation method of the electrode material for super capacitor, specifically includes following steps：（1）By tungsten disulfide WS2Solid powder grinds 2~4 h in ball mill；（2）By step（1）In 0.1 ~ 0.3 g WS2Ultrasonic disperse obtains WS in 20 ~ 40 mL redistilled waters2Dispersion liquid；（3）Take 0.01 ~ 0.03 g activated carbons AC to add 20 ~ 40 mL redistilled waters, uniform activity is obtained through ultrasonic disperse Charcoal dispersion liquid；（4）By step（3）In activated carbon dispersion liquid be added slowly to step（2）WS2It is dilute with redistilled water in dispersion liquid Release to 60~80 mL, persistently stir 1~2 h；（5）By above-mentioned steps（4）Obtained mixed solution, which is transferred in hydrothermal reaction kettle, carries out hydro-thermal reaction, and reaction temperature is 160 ~ 200 DEG C, the reaction time is 24 ~ 48 h；（6）Treat step（5）After hydro-thermal reaction terminates, reaction solution is naturally cooled into room temperature, centrifugation, washing, dries, that is, obtains two Tungsten sulfide-activated carbon WS2- AC composites；（7）Foam nickel sheet is cleaned up, dried, it is standby；（8）By above-mentioned steps（6）Tungsten disulfide-absorbent charcoal composite material of preparation mixes with carbon black, PTFE binder Uniformly, after being ground into film, it is coated in step（7）Standby foam nickel sheet surface, dry, produce combination electrode material.
- 2. the preparation method of electrode material for super capacitor according to claim 1, it is characterised in that step（1）It is described WS2Solid powder particle diameter is 0.5 ~ 2 μm.
- 3. the preparation method of electrode material for super capacitor according to claim 1, it is characterised in that step（1）It is described Drum's speed of rotation be 400~800 r/min.
- 4. the preparation method of electrode material for super capacitor according to claim 1, it is characterised in that step（2）With（3） Described ultrasonic frequency is 40~60 KHz.
- 5. the preparation method of electrode material for super capacitor according to claim 1, it is characterised in that step（3）It is described Activated carbon specific surface area be 500~1000 m2/ g, apparent density are 0.08~0.45 g/mL.
- 6. the preparation method of electrode material for super capacitor according to claim 1, it is characterised in that step（6）It is described Washing methods be：Redistilled water and ethanol wash 2~4 times respectively.
- 7. the preparation method of electrode material for super capacitor according to claim 1, it is characterised in that step（6）It is described Drying for vacuum drying, temperature be 60 ~ 80 DEG C, drying time is 20 ~ 24 h.
- 8. the preparation method of electrode material for super capacitor according to claim 1, it is characterised in that step（8）It is described Drying for vacuum drying, temperature be 60~100 DEG C, drying time is 6~10 h.
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| CN105719845B (en) * | 2015-12-22 | 2018-02-13 | 信阳师范学院 | A kind of electrode material for super capacitor tungsten sulfide charcoal-aero gel and preparation method thereof |
| CN106356202A (en) * | 2016-09-28 | 2017-01-25 | 上海电力学院 | Graphene/tungsten disulfide film flexible super capacitor and manufacturing method and application thereof |
| CN108039289A (en) * | 2017-12-15 | 2018-05-15 | 陕西科技大学 | A kind of WS of macroreticular structure2Preparation method of nano material |
| CN110890226A (en) * | 2019-11-21 | 2020-03-17 | 北京协同创新研究院 | Tungsten sulfide supercapacitor electrode and preparation method thereof |
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| CN102214816A (en) * | 2011-02-25 | 2011-10-12 | 浙江振龙电源股份有限公司 | Grapheme/WS2 nanocomposite electrode of lithium ion battery and manufacturing method thereof |
| CN103769167A (en) * | 2014-01-28 | 2014-05-07 | 陕西科技大学 | Method for preparing photocatalytic material with graphene-covered cadmium sulfide nuclear shell structure |
| CN104577047A (en) * | 2014-12-15 | 2015-04-29 | 安泰科技股份有限公司 | Binary sulfide and C nano-composite negative pole material and preparation method thereof |
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| CN102214816A (en) * | 2011-02-25 | 2011-10-12 | 浙江振龙电源股份有限公司 | Grapheme/WS2 nanocomposite electrode of lithium ion battery and manufacturing method thereof |
| CN103769167A (en) * | 2014-01-28 | 2014-05-07 | 陕西科技大学 | Method for preparing photocatalytic material with graphene-covered cadmium sulfide nuclear shell structure |
| CN104577047A (en) * | 2014-12-15 | 2015-04-29 | 安泰科技股份有限公司 | Binary sulfide and C nano-composite negative pole material and preparation method thereof |
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