CN107230560A - A kind of method that microwave radiation prepares titanium dioxide/stratiform carbon composite - Google Patents

A kind of method that microwave radiation prepares titanium dioxide/stratiform carbon composite Download PDF

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CN107230560A
CN107230560A CN201710566349.5A CN201710566349A CN107230560A CN 107230560 A CN107230560 A CN 107230560A CN 201710566349 A CN201710566349 A CN 201710566349A CN 107230560 A CN107230560 A CN 107230560A
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titanium dioxide
carbon composite
stratiform carbon
microwave
stratiform
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CN107230560B (en
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王庆涛
付春阳
张中浩
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Heze Smart New Material Technology Co ltd
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Northwest Normal University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/24Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/46Metal oxides
    • 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

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

It is by ternary MAX phase materials Ti the invention discloses a kind of preparation method of titanium dioxide/stratiform carbon composite3AlC2Powder is soaked ternary MAX phase materials Ti3AlC2Powder is soaked in a solution of hydrofluoric acid, and reaction is performed etching under continuous stirring;Reaction terminates rear suction filtration, and product is cleaned repeatedly with distilled water and absolute ethyl alcohol, obtains black powder product, dries, obtains depositing apertured Ti between synusia3C2TxStratified material;Again by Ti3C2TxWith conductive black mixed grinding it is uniform after, be put into microwave heating equipment, titanium dioxide/stratiform carbon composite obtained after microwave radiation.The method of titanium dioxide prepared by the present invention/stratiform carbon composite is simple, and reaction condition is gentle, and energy consumption is low;Preparation time is shorter, efficiency high.The titanium dioxide of acquisition/stratiform carbon composite has excellent chemical property, applies on ultracapacitor, possesses higher specific capacitance and excellent cyclical stability.

Description

A kind of method that microwave radiation prepares titanium dioxide/stratiform carbon composite
Technical field
The present invention relates to a kind of preparation method of titanium dioxide/stratiform carbon composite, more particularly to a kind of microwave radiation The method for preparing titanium dioxide/stratiform carbon composite, is mainly used as the electrode material of ultracapacitor.
Background technology
With developing rapidly for World Economics, energy crisis and problem of environmental pollution are very important, and development one kind can The energy and energy storage mode of lasting clean and effective are extremely urgent.Ultracapacitor is used as a kind of efficient, cleaning, sustainable energy Source device, is received significant attention.Ultracapacitor has good power density high and low temperature performance, service life length and high security The advantages of, electronic product and energy regenerating and field of storage can be widely applied to.
Two-dimensional layer titanium carbide, it is excellent due to its unique appearance structure, less particle size, larger specific surface area Different electric conductivity, big specific surface area and high magnification stability and with superpower chemical property, be widely used in electric capacity In device, lithium ion battery, solar cell etc..Nano titanium oxide not only have fabulous high rate capability, cyclical stability, Fast charging and discharging performance and higher capacity, nano titanium oxide can also effectively reduce the capacity attenuation of capacitor, increase electric capacity Device stability, improves chemical property.Titanium dioxide/stratiform carbon composite combines two-dimensional layer carbon and nano titanium oxide Characteristic, with good electric conductivity, chemical stability, heat endurance, nontoxicity etc., be widely used in capacitor, lithium from In sub- battery etc..
The method for preparing titanium dioxide/stratiform carbon material at present uses hydro-thermal method and in-situ method mostly, and hydro-thermal method needs height Temperature is reacted, and high energy consumption, cost is also high;In-situ method needs the longer reaction time, and efficiency is low;And mainly as lithium ion The electrode material of battery, sodium-ion battery.
The content of the invention
The purpose of the present invention is to be directed to hydro-thermal method and in-situ method high energy consumption, and there is provided a kind of microwave radiation for the problem of efficiency is low The method of synthesis of titanium dioxide/stratiform carbon composite;
First, the preparation of titanium dioxide/stratiform carbon composite
The method that microwave radiation of the present invention prepares titanium dioxide/stratiform carbon composite, is comprised the following steps that:
(1)Ti3C2TxThe preparation of stratified material:By ternary MAX phase materials Ti3AlC2Powder(Granularity is 500 ~ 2000 mesh)Immersion In 10 ~ 40 wt% hydrofluoric acid solutions, under continuous stirring in 20 ~ 50 °C of 2 ~ 24h of etching reaction;Reaction terminates rear suction filtration, produces Thing is cleaned repeatedly with distilled water and absolute ethyl alcohol, is obtained black powder product, is placed in drying box, in 40 ~ 80 °C of lower heat preservation and drynesses 8 ~ 24 h, obtain depositing apertured Ti between synusia3C2TxStratified material;
(2)The preparation of titanium dioxide/stratiform carbon composite:By Ti3C2TxWith conductive black with 1:0.01~1:0.1 mass ratio It is fully ground, is then placed in microwave heating equipment after mixing, in the case where power is 600 ~ 1200 W, the s of microwave radiation 10 ~ 60 is obtained To titanium dioxide/stratiform carbon composite.
Fig. 1(a)For the Ti after hf etching3AlC2Powder(Ti3C2TxStratified material)SEM figure, Fig. 1(b)For The SEM figures of titanium dioxide/stratiform carbon composite.By Fig. 1(b)And illustration can be seen that stratiform carbon material Ti3C2TxLamella Structure is substantially thinning, and the more uniform titanium dioxide granule of size is all generated in surface and lamellar structure, is grown in piece Obvious two lamellas of connection of nano particle in layer, which forms a more coarse three-dimensional structure, this structure is favourable In titanium dioxide/application of the stratiform carbon composite on ultracapacitor.
2nd, the chemical property of titanium dioxide/stratiform carbon composite
It is 8 by mass ratio to test the chemical property of titanium dioxide/stratiform carbon composite:1:1 titanium dioxide/stratiform Carbon nano-composite material, conductive black, polytetrafluoroethylene (PTFE)(PTFE)Electrode slurry is mixed into, slurry then is dispersed in into area is 1 cm2In foam nickel sheet, electrode is then dried into 8 ~ 24 h under 40 ~ 80 °C, titanium dioxide/stratiform carbon electricity has been finally given Pole.Electrode carries out electrochemical property test to it under three-electrode system using 3 mol/LKOH electrolyte, reference electrode and right Electrode is Hg/HgO and platinum plate electrode respectively.Electrode material is entered under 1 A/g current density respectively using electrochemical workstation Row constant current charge-discharge tests the specific capacitance for obtaining electrode material, is passed through using battery test system under 1 A/g current density 5000 circulations are crossed, its cyclical stability is investigated.Shown by the test result of chemical property, the electrode material is in 1 A/g Current density under specific capacitance up to 171 F/g, circulated by 5000 constant current charge-discharges, specific capacitance for 91 original % with On.
In summary, microwave radiation of the present invention prepare titanium dioxide/stratiform carbon composite method it is simple, reaction condition Gently, energy consumption is low;Preparation time is shorter, efficiency high.The titanium dioxide of acquisition/stratiform carbon composite has excellent electrochemistry Performance, is applied on ultracapacitor, with higher specific capacitance and excellent cyclical stability.
Brief description of the drawings
Fig. 1 is the Ti after over etching3AlC2Powder(a)And titanium dioxide/stratiform carbon composite(b)SEM figure.
Embodiment
It is following to pass through specific preparation method and performance of the specific embodiment to titanium dioxide of the present invention/stratiform carbon composite It is described further.
Embodiment 1
(1)Ti3C2TxThe preparation of stratified material:By 0.1946 g ternary MAX phase materials Ti3AlC2Powder(Granularity is 500 ~ 2000 Mesh)It is immersed in the wt% hydrofluoric acid solutions of 30 mL 20, continuing magnetic force is stirred in 20 DEG C of h of etching reaction 24, course of reaction; Suction filtration afterwards, product distilled water and each three times of washes of absolute alcohol, obtain black powder product, place into drying box in 50 DEG C dry 18 h, produce Ti3C2TxStratified material;
(2)The preparation of titanium dioxide/stratiform carbon composite:Take Ti3C2TxThe mg of stratified material 200, the mg of conductive black 20, puts Enter in agate mortar, 30 min are to uniform for grinding, be then placed in microwave reaction device, 60 are radiated under the W of microwave power 600 S, that is, obtain titanium dioxide/stratiform carbon composite.
(3)The chemical property of titanium dioxide/stratiform carbon composite:Take titanium dioxide/mg of stratiform carbon 40, conductive charcoal Black 5 mg and polytetrafluoroethylene (PTFE) 5 mg, is mixed into after uniform sizing material by ethanol and is dispersed in area for 1 cm2In foam nickel sheet, 60 12 h are dried at DEG C.By the test of chemical property, electrode material specific capacitance under 1 A/g current density is 171 F/g, Circulated by 5000 constant current charge-discharges, specific capacitance is original 93%.Therefore, with higher specific capacitance and excellent follow Ring stability.
Embodiment 2
(1)Ti3C2TxThe preparation of stratified material:By 0.5 g ternary MAX phase materials Ti3AlC2Powder(Granularity is 500 ~ 2000 mesh) It is immersed in the wt% hydrofluoric acid solutions of 50 mL 30, continuing magnetic force is stirred in 40 DEG C of h of etching reaction 12, course of reaction;Afterwards Suction filtration, product distilled water and each three times of washes of absolute alcohol, obtain black powder product, place into drying box dry in 60 DEG C Dry 24 h, produces Ti3C2TxStratified material;
(2)The preparation of titanium dioxide/stratiform carbon composite:Take Ti3C2TxThe mg of the stratified material 100 and mg of conductive black 1, puts Enter in agate mortar, 10 min are to uniform for grinding, are then placed in microwave reaction device, radiated in the case where microwave power is 700 W 10 s, that is, obtain titanium dioxide/stratiform carbon composite.
(3)The chemical property of titanium dioxide/stratiform carbon composite:Take titanium dioxide/mg of stratiform carbon 80, conductive charcoal Black 10 mg and polytetrafluoroethylene (PTFE) 10 mg, is mixed into after uniform sizing material by ethanol and is dispersed in area for 1 cm2In foam nickel sheet, 24 h are dried at 40 DEG C.By the test of chemical property, electrode material specific capacitance under 1 A/g current density is 162 F/g, is circulated by 5000 constant current charge-discharges, and specific capacitance is original 92%.Therefore, with higher specific capacitance and excellent Cyclical stability.
Embodiment 3
(1)Ti3C2TxThe preparation of stratified material
By 0.937 g ternary MAX phase materials Ti3AlC2Powder(Granularity is 500 ~ 2000 mesh)It is immersed in 40 mL, 40 wt% hydrogen In fluorspar acid solution, continuing magnetic force is stirred in 50 DEG C of h of etching reaction 18, course of reaction;Suction filtration afterwards, product distilled water and Each three times of washes of absolute alcohol, obtains black powder product, places into drying box in 40 DEG C of dry 12 h, produces Ti3C2TxLayer Shape material;
(2)The preparation of titanium dioxide/stratiform carbon composite:Take Ti3C2TxThe mg of the stratified material 200 and mg of conductive black 4, puts Enter in agate mortar, 20 min are to uniform for grinding, be then placed in microwave reaction device, 30 are radiated under the W of microwave power 800 S, that is, obtain titanium dioxide/stratiform carbon composite.
(3)The chemical property of titanium dioxide/stratiform carbon composite:Take titanium dioxide/mg of stratiform carbon 48, conductive charcoal Black 6 mg and polytetrafluoroethylene (PTFE) 6 mg, is mixed into after uniform sizing material by ethanol and is dispersed in area for 1 cm2In foam nickel sheet, 70 10 h are dried at DEG C.By the test of chemical property, electrode material specific capacitance under 1 A/g current density is 157 F/g, Circulated by 5000 constant current charge-discharges, specific capacitance is original 91%.Therefore, with higher specific capacitance and excellent follow Ring stability.

Claims (7)

1. a kind of method that microwave method prepares titanium dioxide/stratiform carbon composite, comprises the following steps:
(1)Ti3C2TxThe preparation of stratified material:By ternary MAX phase materials Ti3AlC2Powder soaks in a solution of hydrofluoric acid, is holding Reaction is performed etching under continuous stirring;Reaction terminates rear suction filtration, and product is cleaned repeatedly with distilled water and absolute ethyl alcohol, obtains black powder Last product, dries, obtains depositing apertured Ti between synusia3C2TxStratified material;
(2)The preparation of titanium dioxide/stratiform carbon composite:By Ti3C2TxWith conductive black mixed grinding it is uniform after, be put into micro- Titanium dioxide/stratiform carbon composite is obtained in Wave heating device, after microwave radiation.
2. the method that microwave method as claimed in claim 1 prepares titanium dioxide/stratiform carbon composite, it is characterised in that:Ternary MAX phase materials Ti3AlC2Powder size is 500 ~ 2000 mesh.
3. the method that microwave method as claimed in claim 1 prepares titanium dioxide/stratiform carbon composite, it is characterised in that:Hydrogen fluorine Acid concentration is 10 ~ 40 wt%.
4. the method that microwave method as claimed in claim 3 prepares titanium dioxide/stratiform carbon composite, it is characterised in that:Ternary MAX phase materials Ti3AlC2Time in powder immersion hydrofluoric acid is 2 ~ 24h, and its etching temperature is 20 ~ 50 °C.
5. the method that microwave method as claimed in claim 1 prepares titanium dioxide/stratiform carbon composite, it is characterised in that:It is described Ti3C2TxStratified material is dried, and is that 8 ~ 24 h are dried under 40 ~ 80 °C.
6. the method that microwave method as claimed in claim 1 prepares titanium dioxide/stratiform carbon composite, it is characterised in that:It is described Conductive black and Ti3C2TxThe mass ratio of stratified material is 1:0.01~1:0.1.
7. the method that microwave method as claimed in claim 1 prepares titanium dioxide/stratiform carbon composite, it is characterised in that:Microwave The power of radiation is 600 ~ 1200 W, and microwave irradiation time is 10 ~ 60 s.
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Cited By (9)

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CN108461300A (en) * 2018-05-11 2018-08-28 西北师范大学 A kind of stratiform titanium carbide-carbon pipe composite material and its preparation and application
CN109647464A (en) * 2019-01-09 2019-04-19 青岛大学 A kind of electrocatalysis material converting nitrogen to ammonia
CN110098391A (en) * 2019-04-18 2019-08-06 北京化工大学 Titanium dioxide/carbon-coated nano silicon trielement composite material derived from a kind of MXene and preparation method thereof
CN110817875A (en) * 2019-12-20 2020-02-21 武汉科技大学 Ti3AlC2Powder and preparation method thereof
CN111151276A (en) * 2020-01-19 2020-05-15 中南大学 Full-spectrum photocatalytic synthesis of ammonia Ti3C2Tx/TiO2Composite material and preparation method and application thereof
TWI711584B (en) * 2018-12-28 2020-12-01 日商亞都瑪科技股份有限公司 MXene particle material, slurry, secondary battery, transparent electrode, manufacturing method of MXene particle material
CN112599762A (en) * 2020-12-15 2021-04-02 南京国轩电池有限公司 TiO 22Negative electrode material of CNF battery and preparation method thereof
CN113410454A (en) * 2021-06-09 2021-09-17 昆明理工大学 Preparation method and application of porous layered titanium dioxide
CN113690066A (en) * 2021-08-10 2021-11-23 太原理工大学 Graphene quantum dot/few-layer Ti3C2TxPreparation method and application of composite material

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108461300A (en) * 2018-05-11 2018-08-28 西北师范大学 A kind of stratiform titanium carbide-carbon pipe composite material and its preparation and application
CN108461300B (en) * 2018-05-11 2020-05-12 西北师范大学 Layered titanium carbide-carbon tube composite material and preparation and application thereof
TWI711584B (en) * 2018-12-28 2020-12-01 日商亞都瑪科技股份有限公司 MXene particle material, slurry, secondary battery, transparent electrode, manufacturing method of MXene particle material
US10981835B2 (en) 2018-12-28 2021-04-20 Admatechs Co., Ltd. “MXene” particulate material, slurry, secondary battery, transparent electrode and production process for “MXene” particulate material
CN109647464A (en) * 2019-01-09 2019-04-19 青岛大学 A kind of electrocatalysis material converting nitrogen to ammonia
CN110098391B (en) * 2019-04-18 2021-06-01 北京化工大学 MXene-derived titanium dioxide/carbon-coated nano-silicon ternary composite material and preparation method thereof
CN110098391A (en) * 2019-04-18 2019-08-06 北京化工大学 Titanium dioxide/carbon-coated nano silicon trielement composite material derived from a kind of MXene and preparation method thereof
CN110817875A (en) * 2019-12-20 2020-02-21 武汉科技大学 Ti3AlC2Powder and preparation method thereof
CN111151276A (en) * 2020-01-19 2020-05-15 中南大学 Full-spectrum photocatalytic synthesis of ammonia Ti3C2Tx/TiO2Composite material and preparation method and application thereof
CN112599762A (en) * 2020-12-15 2021-04-02 南京国轩电池有限公司 TiO 22Negative electrode material of CNF battery and preparation method thereof
CN113410454A (en) * 2021-06-09 2021-09-17 昆明理工大学 Preparation method and application of porous layered titanium dioxide
CN113690066A (en) * 2021-08-10 2021-11-23 太原理工大学 Graphene quantum dot/few-layer Ti3C2TxPreparation method and application of composite material
CN113690066B (en) * 2021-08-10 2022-11-25 太原理工大学 Graphene quantum dot/few-layer Ti 3 C 2 T x Preparation method and application of composite material

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