CN108766783A - A kind of preparation method of fiber/graphene/zinc sulphide flexible electrode material - Google Patents

A kind of preparation method of fiber/graphene/zinc sulphide flexible electrode material Download PDF

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Publication number
CN108766783A
CN108766783A CN201810605092.4A CN201810605092A CN108766783A CN 108766783 A CN108766783 A CN 108766783A CN 201810605092 A CN201810605092 A CN 201810605092A CN 108766783 A CN108766783 A CN 108766783A
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fiber
graphene
electrode material
graphene oxide
zinc sulphide
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王薇
张技术
何亚男
孙银银
陶金
吴建兵
穆红
郑宝伟
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Changshu Institute of Technology
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Changshu Institute of Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

Abstract

The invention discloses a kind of preparation methods of fiber/graphene/zinc sulphide flexible electrode material, include the following steps:A, pretreated fabric is impregnated in graphene oxide suspension and dried, repeated this step and obtain fiber/graphene oxide composite material several times, the graphene oxide suspension is that graphene oxide powder ultrasonic disperse is made in deionized water;B, in-situ reducing is carried out to fiber/graphene oxide composite material and obtains fiber/grapheme material;C, fiber/grapheme material that step B is obtained is immersed in the hydrothermal reaction kettle containing zinc salt and sulfur-bearing precursor solution, heating reaction synthesis obtains fiber/graphene/zinc sulphide flexible electrode material.Material made from the method for the present invention combines the zinc sulphide of the carbon material of good conductivity and specific capacitance height, poorly conductive, gives full play to the two advantage.It is superior with higher area specific capacitance and power characteristic, cycle performance.

Description

A kind of preparation method of fiber/graphene/zinc sulphide flexible electrode material
Technical field
The present invention relates to a kind of preparation methods of flexible electrode material, more particularly to a kind of fiber/graphene/zinc sulphide The preparation method of flexible electrode material.
Background technology
Electrochemical capacitor is based on the specific functions such as its high power capacity and high power density, is widely used in hybrid power vapour The fields such as vehicle, communication, national defence and wearable electronic.Become as current electronic equipment is just showing lightening and flexibility development Gesture, flexible display screen, distributed sensor, Electronic Paper and wearable multimedia device etc. be portable and wearable electronic day Benefit enters daily life.But traditional electrochemical capacitor volume is big, weight weight, shape are fixed, and far can not expire The demand for development of the current flexible electronic devices of foot.Urgent need develops that low with light weight and cost, small, chemical property is excellent Different and processing performance excellent flexible electrochemical capacitor and its electrode material.
Currently, the research and development of flexible electrochemical capacitor and electrode material have become international hot spot, have a large amount of close both at home and abroad In the wearing comfort for how improving wearable energy storage device and chemical property etc. research how is improved, but high system Make cost, poor flexibility, lower durability and environmental factor dependence etc. and limits their real application.Carry green wood Material, design new construction are the important methods for improving wearable energy storage device performance and improving its environmental suitability.
Textile material is natural wearable material, and there is excellent wearing comfort, selection generality and mechanics to stablize Property etc..The material and surface nature of textile material have particularity, therefore the conductive materials such as carbon are difficult to be formed on its surface three-dimensional Continuous conductive network often uses a large amount of crosslinking agent, table to increase the interaction between conductive material and fabric Activating agent even binder in face enables conductive material preferably to adhere on the fabric, on the one hand the addition of these substances can block up Hole on plug fabric is unfavorable for the diffusion of electrolyte ion, influences the performance of its chemical property, on the other hand can make material Building-up process is complicated, difficult, increases cost.
Invention content
In view of the above-mentioned defects in the prior art, the present invention provides a kind of fiber/graphene/zinc sulphide flexible electrode materials Preparation method, solve textile material surface and be difficult to shaped conductive network, hypodynamic problem is bonded between conductive material and fabric, The material that can be applied to super capacitor and wearable product is provided.
Technical solution of the present invention is as follows:A kind of preparation method of fiber/graphene/zinc sulphide flexible electrode material, including Following steps:
A, pretreated fabric is impregnated in graphene oxide suspension and dried, repeated this step and obtain several times To fiber/graphene oxide composite material, the graphene oxide suspension is by graphene oxide powder ultrasonic disperse in deionization It is made in water;
B, in-situ reducing is carried out to fiber/graphene oxide composite material and obtains fiber/grapheme material;
C, that fiber/grapheme material that step B is obtained is immersed in the hydro-thermal containing zinc salt and sulfur-bearing precursor solution is anti- It answers in kettle, heating reaction synthesis obtains fiber/graphene/zinc sulphide flexible electrode material.
Further, dip time is in a concentration of 0.5-3mg/mL of the graphene oxide suspension, the step A Drying temperature is 40-70 DEG C in 20-60min, the step A, drying time 2-3h.
Preferably, the number of repetition of the step A is 5-40 times.
Further, it is that fiber/graphene oxide composite material is immersed NaBH that the step B, which carries out in-situ reducing,4In solution Restore and dry after being cleaned with deionized water, or by fiber/graphene oxide composite material under inert gas protection into Row heating reduction.
Preferably, the NaBH4Solution concentration is 0.1-1mol/L, the immersion NaBH4The time of solution is 4-12h, institute It is 90-120 DEG C to state the drying temperature dried after deionized water cleaning, drying time 1-3h.
Preferably, 150-350 DEG C of the heating temperature of the heating reduction, heating time 0.5-5h, the inert gas He or N2
Further, the pretreated fabric is to pre-process fabric using aqueous slkali, then It is cleaned up, is dried with deionized water.
Preferably, the aqueous slkali is sodium hydroxide solution or sodium bicarbonate solution, a concentration of 0.5- of the aqueous slkali 2mol/L, the pretreatment temperature be 90-120 DEG C, pretreatment time 1-3h, in the pretreatment drying temperature be 80 DEG C- 130 DEG C, drying time 1-3h.
Further, the zinc salt and sulfur-bearing precursor solution be zinc chloride and thiocarbamide, zinc sulfate and thiocarbamide, zinc chloride and Carbon disulfide either zinc acetate and thioacetamide.
Preferably, the heating temperature that reaction is heated in the step C is 100 DEG C -180 DEG C, reaction time 4h-20h.
The advantages of technical solution provided by the present invention, is:
1, the present invention, which is combined using layer assembly with hydro-thermal method, is prepared for a kind of novel three-dimensional grown based on textile fabric Graphene/zinc sulphide super capacitance electrode material.The material high, poorly conductive sulphur by the carbon material of good conductivity and specific capacitance Change zinc to combine, gives full play to the two advantage.
2, material prepared by the present invention can be as the electrode material of ultracapacitor, the material use flexible textile fiber Between the porous structure structure that has promote the diffusion of electrolyte ion, while also giving full play to the high-ratio surface of graphene and height is led Electrical property is effectively increased the contact interface of zinc sulphide/graphene, and effective dispersed sulfur zinc carries for its fake capacitance redox reaction For more reactivity points, the advantage of the capacitance of zinc sulphide is played, and ensures quick transmission of the electronics in electrode material, from And obtain high specific capacitance, high power density and high-energy density.
3, electrode material lightweight obtained, softness have higher area specific capacitance and power characteristic, cycle performance excellent More, synthesis is simple, and cost is relatively low, and durability is good, it is made to play making for bigger in wearable electronic product energy storage etc. With value.
Specific implementation mode
With reference to embodiment, the invention will be further described, but not as a limitation of the invention.
Oxygen in each embodiment of the preparation method of fiber/graphene/zinc sulphide flexible electrode material of the present invention Graphite alkene powder is prepared by the following method:Graphene oxide is prepared using improved Hummers synthetic methods.It will 1.5g powdered graphites are added to be mixed by what 98% concentrated sulfuric acids of 10mL, 1.25g potassium thiosulfates and 1.25g phosphorus pentoxides formed It closes in object, 4.5h is stirred under the conditions of 80 DEG C.Then obtained product is cleaned with deionized water, in 50 in vacuum drying chamber It is dried under the conditions of DEG C.Product after drying is added in 98% concentrated sulfuric acids of 60mL, is slowly added into 7.5g permanganic acid again later Potassium, temperature is maintained at 20 DEG C hereinafter, then adding the deionized water of 125mL in the adition process of potassium permanganate.After 2h again The hydrogen peroxide of 200mL deionized waters and 10mL a concentration of 30% is added, solution becomes glassy yellow after 10min.It is bright what is obtained The solution of yellow is centrifuged, and is then cleaned, is removed with diluted hydrochloric acid solution (concentrated hydrochloric acid/deionized water volume ratio is 1/10) Then metal ion and sulfate ion are cleaned with deionized water to weakly acidic pH again, finally in 50 DEG C of bakings in vacuum drying chamber It is dry to obtain graphene oxide.
Embodiment 1
Graphene oxide powder is add to deionized water, the graphite oxide of a concentration of 1.5mg/L is made in ultrasonic 60min Alkene suspension.Cotton fabric handles 2h with the sodium hydroxide solution of 1mol/L in 100 DEG C, is then cleaned up with deionized water, in 2h is dried in 110 DEG C of drying boxes.Pretreated cotton fabric is impregnated into the graphene oxide suspension prepared, in room temperature After lower stirring 30min, dry 2h, repeated impregnations-drying course 20 times are placed in 50 DEG C of vacuum drying ovens.By cotton/graphite oxide Alkene compound fabric is immersed in the NaBH of a concentration of 0.5mol/L4In solution, in room temperature condition stir 12h, then take out spend from Sub- water cleans 3 times, and 2h is dried in 100 DEG C, and reduction obtains cotton/graphene composite material.
It is 1 ︰ 1 that cotton/graphene composite material, which is immersed in containing zinc chloride and thiourea solution (Xin ︰ sulphur molar ratios) water In thermal response kettle, 160 DEG C of reaction 6h, synthesis obtains fiber/graphene/zinc sulphide electrode material, and 80 DEG C of bakings are carried out to the material Dry 2h, it is 206 Ω/sq to measure sheet resistance, and when sweep speed is 2m V/s, specific capacitance has good up to 530F/g Flex capability.
Embodiment 2
Graphene oxide powder is add to deionized water, the graphene oxide of a concentration of 2mg/L is made in ultrasonic 30min Suspension.Cotton fabric handles 3h with the sodium bicarbonate solution of 0.5mol/L in 90 DEG C, is then cleaned up with deionized water, in 2.5h is dried in 100 DEG C of drying boxes.Pretreated cotton fabric is impregnated into the graphene oxide suspension prepared, in room After the lower stirring 20min of temperature, dry 3h, repeated impregnations-drying course 30 times are placed in 50 DEG C of vacuum drying ovens.By cotton/oxidation stone Black alkene compound fabric is immersed in the NaBH of a concentration of 0.1mol/L4In solution, 12h is stirred in room temperature condition, then takes out and spends Ionized water cleans 3 times, and 2h is dried in 100 DEG C, and reduction obtains cotton/graphene composite material.
Cotton/graphene composite material is immersed in the ethylene glycol solution (Xin ︰ sulphur mole containing zinc chloride and carbon disulfide Than for 1 ︰ 1) hydrothermal reaction kettle in, 130 DEG C of reaction 8h, synthesis obtains fiber/graphene/zinc sulphide electrode material, to the material Material carries out 80 DEG C of drying 2h, and it is 183 Ω/sq to measure sheet resistance, and when sweep speed is 2mV/s, specific capacitance has up to 565F/g There is good flex capability.
Embodiment 3
Graphene oxide powder is add to deionized water, the graphite oxide of a concentration of 2.5mg/L is made in ultrasonic 60min Alkene suspension.Cotton fabric handles 1h with the sodium hydroxide solution of 1mol/L in 110 DEG C, is then cleaned up with deionized water, in 3h is dried in 90 DEG C of drying boxes.Pretreated cotton fabric is impregnated into the graphene oxide suspension prepared, in room temperature After lower stirring 40min, dry 2.5h, repeated impregnations-drying course 20 times are placed in 40 DEG C of vacuum drying ovens.By cotton/oxidation stone Black alkene compound fabric is placed in high temperature process furnances, and heating rate is 2 DEG C/min, in 250 DEG C, N2It is anti-by high temperature under atmospheric condition 3h, reduction is answered to obtain cotton/graphene composite material.
Cotton/graphene composite material is immersed in containing PEG-400 (0.1%), zinc acetate and thioacetyl amine aqueous solution In the hydrothermal reaction kettle of (zinc ︰ sulphur molar ratios are 1 ︰ 1), 140 DEG C of reaction 4h, synthesis obtains fiber/graphene/vulcanization zinc electrode material Material carries out 80 DEG C of drying 2h to the material, and it is 172 Ω/sq to measure sheet resistance, and when sweep speed is 2mV/s, specific capacitance is reachable 590F/g, and there is good flex capability.
Embodiment 4
Graphene oxide powder is add to deionized water, the graphene oxide of a concentration of 3mg/L is made in ultrasonic 30min Suspension.Dacron handles 1.5h with the sodium bicarbonate solution of 2mol/L in 120 DEG C, is then cleaned up with deionized water, 3h is dried in 80 DEG C of drying boxes.Pretreated dacron is impregnated into the graphene oxide suspension prepared, in After stirring 50min at room temperature, dry 2.5h, repeated impregnations-drying course 40 times are placed in 60 DEG C of vacuum drying ovens.Terylene is knitted Object/graphene oxide compound fabric is immersed in the NaBH of a concentration of 1mol/L4In solution, 12h is stirred in room temperature condition, is then taken Go out and cleaned 3 times with deionized water, 2h is dried in 100 DEG C, reduction obtains dacron/graphene composite material.
Dacron/graphene composite material is immersed in the ethylene glycol solution (Xin ︰ sulphur containing zinc chloride and carbon disulfide Molar ratio be 1 ︰ 1) hydrothermal reaction kettle in, 100 DEG C reaction 20h, synthesis obtain fiber/graphene/zinc sulphide electrode material, it is right The material carries out 80 DEG C of drying 2h, and it is 358 Ω/sq to measure sheet resistance, when sweep speed is 2mV/s, specific capacitance up to 462F/g, And there is good flex capability.
Embodiment 5
Graphene oxide powder is add to deionized water, the graphite oxide of a concentration of 0.5mg/L is made in ultrasonic 30min Alkene suspension.The sodium hydroxide solution of cotton/wash blended fabric 1.5mol/L handles 2.5h in 120 DEG C, then uses deionized water It cleans up, 1.5h is dried in 130 DEG C of drying boxes.Pretreated cotton/wash blended fabric is impregnated into the oxidation prepared In graphene suspension, after stirring 60min at room temperature, dry 2h, repeated impregnations-drying course are placed in 70 DEG C of vacuum drying ovens 10 times.The NaBH that cotton/wash blended fabric/graphene oxide compound fabric is immersed in a concentration of 0.5mol/L4In solution, in room Warm condition stirs 12h, then takes out and clean 3 times with deionized water, and 2h are dried in 100 DEG C, restore obtain cotton/wash blended fabric/ Graphene composite material.
Cotton/wash blended fabric/graphene composite material is immersed in containing zinc chloride and thiourea solution (Xin ︰ sulphur molar ratios For 1 ︰ 1) hydrothermal reaction kettle in, 110 DEG C reaction 15h, synthesis obtain fiber/graphene/zinc sulphide electrode material, to the material 80 DEG C of drying 2h are carried out, it is 265 Ω/sq to measure sheet resistance, and when sweep speed is 2mV/s, specific capacitance has up to 492F/g Good flex capability.
Embodiment 6
Graphene oxide powder is add to deionized water, the graphene oxide of a concentration of 1mg/L is made in ultrasonic 30min Suspension.Nylon fabric handles 3h with the sodium hydroxide solution of 0.5mol/L in 100 DEG C, is then cleaned up with deionized water, 1h is dried in 120 DEG C of drying boxes.Pretreated nylon fabric is impregnated into the graphene oxide suspension prepared, in After stirring 30min at room temperature, dry 3h, repeated impregnations-drying course 5 times are placed in 40 DEG C of vacuum drying ovens.By nylon fabric/oxygen Graphite alkene compound fabric is placed in high temperature process furnances, and heating rate is 2 DEG C/min, passes through height under 350 DEG C, He atmospheric conditions Temperature reaction 0.5h, reduction obtain nylon fabric/graphene composite material.
Nylon fabric/graphene composite material is immersed in the ethylene glycol solution (Xin ︰ sulphur containing zinc chloride and carbon disulfide Molar ratio be 1 ︰ 1) hydrothermal reaction kettle in, 120 DEG C reaction 10h, synthesis obtain fiber/graphene/zinc sulphide electrode material, it is right The material carries out 80 DEG C of drying 2h, and it is 416 Ω/sq to measure sheet resistance, when sweep speed is 2mV/s, specific capacitance up to 403F/g, And there is good flex capability.
Embodiment 7
Graphene oxide powder is add to deionized water, the graphene oxide of a concentration of 1mg/L is made in ultrasonic 30min Suspension.Non-woven fabrics handles 3h with the sodium hydroxide solution of 0.5mol/L in 100 DEG C, is then cleaned up with deionized water, in 1h is dried in 120 DEG C of drying boxes.Pretreated non-woven fabrics is impregnated into the graphene oxide suspension prepared, in room temperature After lower stirring 30min, dry 3h, repeated impregnations-drying course 5 times are placed in 40 DEG C of vacuum drying ovens.By non-woven fabrics/graphite oxide Alkene compound fabric is placed in high temperature process furnances, and heating rate is 2 DEG C/min, passes through pyroreaction under 150 DEG C, He atmospheric conditions 5h, reduction obtain non-woven fabrics/graphene composite material.
It is 1 ︰ 1 that non-woven fabrics/graphene composite material, which is immersed in containing zinc chloride and thiourea solution (Xin ︰ sulphur molar ratios) In hydrothermal reaction kettle, 130 DEG C of reaction 12h, synthesis obtains fiber/graphene/zinc sulphide electrode material, and 80 DEG C are carried out to the material 2h is dried, it is 440 Ω/sq to measure sheet resistance, and when sweep speed is 2mV/s, specific capacitance has good soft up to 389F/g Property performance.

Claims (10)

1. a kind of preparation method of fiber/graphene/zinc sulphide flexible electrode material, which is characterized in that include the following steps:
A, pretreated fabric is impregnated in graphene oxide suspension and dried, repeated this step and obtain fibre several times Dimension/graphene oxide composite material, the graphene oxide suspension be by graphene oxide powder ultrasonic disperse in deionized water It is made;
B, in-situ reducing is carried out to fiber/graphene oxide composite material and obtains fiber/grapheme material;
C, fiber/grapheme material that step B is obtained is immersed in the hydrothermal reaction kettle containing zinc salt and sulfur-bearing precursor solution In, heating reaction synthesis obtains fiber/graphene/zinc sulphide flexible electrode material.
2. the preparation method of fiber/graphene/zinc sulphide flexible electrode material according to claim 1, which is characterized in that Dip time is 20-60min, the step in a concentration of 0.5-3mg/mL of the graphene oxide suspension, the step A Drying temperature is 40-70 DEG C in A, drying time 2-3h.
3. the preparation method of fiber/graphene/zinc sulphide flexible electrode material according to claim 1, which is characterized in that The number of repetition of the step A is 5-40 times.
4. the preparation method of fiber/graphene/zinc sulphide flexible electrode material according to claim 1, which is characterized in that It is that fiber/graphene oxide composite material is immersed NaBH that the step B, which carries out in-situ reducing,4It is restored in solution and uses deionization It is dried after water cleaning, or fiber/graphene oxide composite material is subjected to heating reduction under inert gas protection.
5. the preparation method of fiber/graphene/zinc sulphide flexible electrode material according to claim 4, which is characterized in that The NaBH4Solution concentration is 0.1-1mol/L, the immersion NaBH4The time of solution is 4-12h, the deionized water cleaning The drying temperature dried afterwards is 90-120 DEG C, drying time 1-3h.
6. the preparation method of fiber/graphene/zinc sulphide flexible electrode material according to claim 4, which is characterized in that 150-350 DEG C of the heating temperature of the heating reduction, heating time 0.5-5h, the inert gas He or N2
7. the preparation method of fiber/graphene/zinc sulphide flexible electrode material according to claim 1, which is characterized in that The pretreated fabric is to pre-process fabric using aqueous slkali, is then cleaned with deionized water dry Only, it dries.
8. the preparation method of fiber/graphene/zinc sulphide flexible electrode material according to claim 7, which is characterized in that The aqueous slkali is sodium hydroxide solution or sodium bicarbonate solution, a concentration of 0.5-2mol/L of the aqueous slkali, the pre- place It is 90-120 DEG C, pretreatment time 1-3h to manage temperature, and drying temperature is 80 DEG C -130 DEG C in the pretreatment, and drying time is 1-3h。
9. the preparation method of fiber/graphene/zinc sulphide flexible electrode material according to claim 1, which is characterized in that The zinc salt and sulfur-bearing precursor solution are zinc chloride and thiocarbamide, zinc sulfate and thiocarbamide, zinc chloride and carbon disulfide either vinegar Sour zinc and thioacetamide.
10. the preparation method of fiber/graphene/zinc sulphide flexible electrode material according to claim 1, feature exist In the heating temperature for heating reaction in the step C is 100 DEG C -180 DEG C, reaction time 4h-20h.
CN201810605092.4A 2018-06-13 2018-06-13 A kind of preparation method of fiber/graphene/zinc sulphide flexible electrode material Pending CN108766783A (en)

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CN110136976A (en) * 2019-05-20 2019-08-16 常熟理工学院 A kind of fiber/graphene/carbon quantum dot/FeOF flexible electrode material preparation method
CN110164709A (en) * 2019-05-20 2019-08-23 常熟理工学院 A kind of preparation method of fiber/graphene/carbon quantum dot/cobalt sulfide nickel flexible electrode material
CN111293295A (en) * 2020-01-13 2020-06-16 宁夏博尔特科技有限公司 Electrode material for waste rubber material-based secondary battery and preparation method thereof
CN111293295B (en) * 2020-01-13 2021-08-03 博尔特新材料(银川)有限公司 Electrode material for waste rubber material-based secondary battery and preparation method thereof

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