CN105161690B - The method that molybdenum disulfide charge and discharge cycles ability is improved by doped graphene and titanium dioxide - Google Patents
The method that molybdenum disulfide charge and discharge cycles ability is improved by doped graphene and titanium dioxide Download PDFInfo
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Abstract
The invention discloses a kind of method for improving molybdenum disulfide charge and discharge cycles ability by doped graphene and titanium dioxide, described molybdenum disulfide/titanium dioxide/graphene composite material is using graphene as conductive modified phase, titanium dioxide as support and cooperates with phase, strengthens the charge-discharge performance of the composite with this.It is vacuum dried to obtain molybdenum disulfide/titanium dioxide/graphene composite material after electrostatic spinning, hydro-thermal reaction from sodium molybdate, thiocarbamide, graphite oxide, titanium tetraisopropylate, absolute ethyl alcohol, acetic acid, polyvinylpyrrolidone and deionized water.The low, obtained molybdenum disulfide/titanium dioxide/graphene of the method simple production process, cost has excellent chemical property.
Description
Technical field
The present invention relates to a kind of preparation method of nano composite material, pass through doped graphene and two more particularly to one kind
The method that titanium oxide improves molybdenum disulfide charge and discharge cycles ability, belongs to advanced nano composite material fabricating technology field.
Background technology
Since Sony corporation of Japan nineteen nineties are lithium ion battery commercialization, lithium ion battery is due to work
Make that voltage is high, in light weight, bigger than energy, self discharge is small, the advantages that having extended cycle life, turn into mobile phone, notebook computer, number
Code-phase machine, video camera, electric automobile, the ideal source of hybrid vehicle and portable various instrument and equipments.In lithium-ion electric
Chi Zhong, the positive electrode and the negative material part main as battery for belonging to lithium storage materials play to its chemical property
Conclusive effect.
At present, graphite is the negative material for being widely used in commercial Li-ion battery, and this lithium ion for having benefited from it takes off
Go out/be embedded in the features such as electrochemical process is simple and easy, long cycle life, raw material supply are abundant and cost is cheap.Although such as
This, the lithium storage content of graphite is confined to form LiC6When every gram of the MAH of highest theoretical capacity 372, and intercalation potential is low,
Graphite surface may cause the deposition of lithium metal in charge and discharge process, certain potential safety hazard be present.Therefore, explore new
Negative material, its capacity is further improved, become particularly necessary and important.Conventional lithium ion battery negative material has carbon materials
Material, alloy material and sulfide material, wherein sulfide material account for greatly, be more promising negative materials.
Insertion and abjection of the molybdenum disulfide due to the layer structure as graphite, being very beneficial for lithium ion, because
With higher theoretical capacity (1063 every gram of MAH), and Volume Changes are small in charge and discharge process, thus enjoy people's
Concern.But because molybdenum disulfide self-conductive is poor, capacity attenuation is fast in charge and discharge process and high-rate charge-discharge capability
Difference, thus limit its Commercialization application.In order to improve the chemical property of molybdenum disulfide, researcher has carried out substantial amounts of research
Work, it is concentrated mainly on the nanostructured of synthesis different-shape and then forms composite wood in its surface progress conducting particles doping
Material etc., conducting particles is mainly amorphous carbon, graphene, CNT etc..Such as in prior art " " Facile synthesis of
carbon-coated MoS2nanorods with enhanced lithium storage properties”,Chaofeng
" the electric discharge of the molybdenum disulfide after carbon coating is mentioned in Zhang et al., Electrochem.Commun.20 (2012) 7-10 "
Specific capacity is significantly improved, and putting for 621 every gram of MAHs can be provided after 80 circles are circulated under 200 milliamperes of every gram of current densities
Electric specific capacity ", but cyclical stability needs further to improve.Such as in prior art " " CTAB-assisted
synthesis of single-layer MoS2-graphene composites as anode materials of Li-
Ion batteries ", Zhen Wang et al., J Mater.Chem.1 (2013) 2202-2210 ", Publication No.
Mentioned in CN103904334A Chinese patent " in molybdenum disulfide/graphene composite material graphene reduce contact resistance, promote
Enter electron transmission in electrode reaction ", but specific discharge capacity needs further to improve.At present, solves molybdenum disulfide
Cyclical stability and the specific discharge capacity for improving molybdenum disulfide are the technical barriers for needing to solve, and the present invention is directed to this problem,
It is proposed is using graphene as conductive modified phase, titanium dioxide as support and cooperates with phase, strengthens molybdenum disulfide/titanium dioxide with this
The cyclical stability of titanium/graphene composite material and improve its specific discharge capacity.
The content of the invention
Molybdenum disulfide charge and discharge cycles are improved by doped graphene and titanium dioxide it is an object of the invention to provide one kind
The method of ability, preparation method cost is cheap, technique is simple, the molybdenum disulfide of preparation/titanium dioxide/graphene composite material electricity
Chemical property is excellent, and its specific discharge capacity can reach 718 every gram of MAHs, the capacity attenuation of single cycle after 100 circulations
Rate is 0.02%, operating temperature range be subzero 25 degrees Celsius~it is above freezing 60 degrees Celsius, memory-less effect is pollution-free, self discharge
Rate is low, and self-discharge rate is about 25% within the 1st year, and average monthly self-discharge rate is in 2-2.5%.
The technical scheme is that：
1st, a kind of method that molybdenum disulfide charge and discharge cycles ability is improved by doped graphene and titanium dioxide, its feature
It is：
Molybdenum disulfide/the titanium dioxide/graphene composite material obtained by adulterating item is used as conductive modified using graphene
Phase, titanium dioxide as support and cooperate with phase, strengthen the charge-discharge performance of the composite with this；The preparation method is selected
Fibrous titanium oxide, sodium molybdate, thiocarbamide, the graphite oxide of electrostatic spinning preparation are used as the material that sets out, then using hydro-thermal method
Afterwards, molybdenum disulfide/titanium dioxide/graphene composite material is centrifuged, washs, is dried in vacuo and is thermally treated resulting in, specifically
Preparation process is as follows：
(1) fibrous titanium oxide is prepared using electrostatic spinning：By the titanium tetraisopropylate of 0.5-5 milliliters, 0.4-4 milliliters
Acetic acid, 0.05-0.6 grams of polyvinylpyrrolidone or polyethylene glycol or cetyl trimethylammonium bromide orDBSA SodiumMixed with absolute ethyl alcohol, oscillator vibration 720-1680 minutes；Then pushed away per hour in 5-30 kilovoltages, 0.1-2 milliliters
Enter speed and 4-20 centimetres receives spinning under distance condition；720-1680 minutes are stood, then in 400-600 degrees Celsius of air gas
120-640 minutes are calcined under atmosphere, obtain fibrous titanium oxide；
(2) 0.01-0.1 grams of graphite oxide is dissolved in 10-60 ml deionized waters, ultrasonic 15-60 minutes, adds TiO2With
Sodium molybdate or ammonium molybdate, 2-15 minutes are stirred, add thiocarbamide, stir 2-15 minutes；
(3) above-mentioned solution is transferred in reactor under 150-220 degrees celsius hydro-thermal reaction 720-1680 minutes.
(4) after question response kettle is cooled to room temperature, material is taken out, with deionized water and washes of absolute alcohol, under 50-90 degrees Celsius
Drying, 60-270 minutes are calcined under the conditions of 600-950 degrees Celsius of argon gas/hydrogen gas mixture, obtain molybdenum disulfide/titanium dioxide
Titanium/graphene composite material；
Technical solutions according to the invention have following technique effect：
Molybdenum disulfide/titanium dioxide/graphene composite material of the invention by generated in-situ molybdenum disulfide with graphite
Alkene depends on to be formed for substrate, thus molybdenum disulfide have with graphene contact area it is big the characteristics of；To in charge and discharge process two
The Volume Changes of molybdenum sulfide have certain inhibitory action.
(2) the graphite oxide in molybdenum disulfide/titanium dioxide/graphene composite material of the invention becomes through reduction reaction
After graphene, the increase of its electrical conductivity, so that the electrical conductivity increase of molybdenum disulfide/titanium dioxide/graphene, and then improve two sulphur
Change the cycle performance of molybdenum/titanium dioxide/graphene.
(3) the addition of the titanium dioxide in molybdenum disulfide/titanium dioxide/graphene composite material of the invention so that it rises
To support act on so that the two-phase of molybdenum disulfide/graphene of sheet is propped, formed a class loose structure, beneficial to
The immersion and delay of electrolyte in charge and discharge process, and be advantageous to the diffusion of lithium ion, therefore it has higher cyclicity
Energy.
(4) the electrospinning device that is applied to of the present invention and hydro-thermal method to synthesize simple and easy, eventually reduce cost
And process complexity.
Brief description of the drawings
Fig. 1 is molybdenum disulfide (1,2), molybdenum disulfide/graphene (3,4), molybdenum disulfide/titanium dioxide prepared by the present invention
(5,6) and the scanning electron microscope (SEM) photograph of molybdenum disulfide/titanium dioxide/graphene (7,8).
Fig. 2 is molybdenum disulfide, molybdenum disulfide/graphene, molybdenum disulfide/titanium dioxide and curing prepared by the present invention
The X-ray diffractogram of molybdenum/titanium dioxide/graphene, it is bright in molybdenum disulfide/titanium dioxide/graphene composite material as seen from the figure
Aobvious titanium dioxide is present, and obvious diffraction maximum is not present due to content in graphene less.
Fig. 3 is the cyclic curve figure of molybdenum disulfide/titanium dioxide/graphene prepared by the present invention, is discharged after 100 circulations
Specific capacity remains at 718 every gram of MAHs.
Fig. 4 is the curve of double curvature figure of molybdenum disulfide/titanium dioxide/graphene prepared by the present invention, it can be seen from the figure that its
With outstanding high rate performance.
Embodiment
Embodiment one
(1) fibrous titanium oxide is prepared using electrostatic spinning：By 3 milliliters of titanium tetraisopropylate, 2 milliliters of acetic acid, 0.3
Gram polyvinylpyrrolidone and absolute ethyl alcohol mixing, oscillator vibrate 1440 minutes；Then in 20 kilovoltages, 1 milliliter per small
When fltting speed and 10 centimetres receive distance conditions under spinning；1440 minutes are stood, is then roasted under 510 degrees Celsius of air atmospheres
Burn 360 minutes, obtain fibrous titanium oxide；
Described polyvinylpyrrolidone can select polyethylene glycol or cetyl trimethylammonium bromide or dodecyl
Benzene sulfonic acid sodium salt substitutes.
(2) 0.024 grams of graphite oxides are dissolved in 30 ml deionized waters, ultrasound 30 minutes, add titanium dioxide and molybdic acid
Sodium or ammonium molybdate, stir 5 minutes, add thiocarbamide, stir 5 minutes.
(3) above-mentioned solution is transferred in reactor hydro-thermal reaction 1440 minutes under 200 degrees celsius.
(4) after question response kettle is cooled to room temperature, material is taken out, with deionized water and washes of absolute alcohol, is dried under 60 degrees Celsius
It is dry, it is calcined 120 minutes under the conditions of 800 degrees Celsius of argon gas/hydrogen gas mixtures, obtains molybdenum disulfide/titanium dioxide/graphene
Composite.
The performance tested in accompanying drawing is that the present embodiment one is measured.
Embodiment two
(1) fibrous titanium oxide is prepared using electrostatic spinning：By 0.5 milliliter of titanium tetraisopropylate, 0.4 milliliter of vinegar
Acid, 0.05 gram of polyvinylpyrrolidone and absolute ethyl alcohol mixing, oscillator vibrate 720 minutes；Then in 5 kilovoltages, 0.1 milli
Liter per hour fltting speed and 4 centimetres receive spinning under distance conditions；720 minutes are stood, then in 400 degrees Celsius of air atmospheres
Lower roasting 120 minutes, obtains fibrous titanium oxide；
Described polyvinylpyrrolidone can select polyethylene glycol or cetyl trimethylammonium bromide or dodecyl
Benzene sulfonic acid sodium salt substitutes.
(2) 0.01 grams of graphite oxides are dissolved in 10 ml deionized waters, ultrasound 15 minutes, add titanium dioxide and sodium molybdate
Or ammonium molybdate, stir 2 minutes, add thiocarbamide, stir 2 minutes.
(3) above-mentioned solution is transferred in reactor hydro-thermal reaction 720 minutes under 150 degrees celsius.
(4) after question response kettle is cooled to room temperature, material is taken out, with deionized water and washes of absolute alcohol, is dried under 50 degrees Celsius
It is dry, it is calcined 60 minutes under the conditions of 600 degrees Celsius of argon gas/hydrogen gas mixtures, obtains molybdenum disulfide/titanium dioxide/graphene
Composite.
Embodiment three
(1) fibrous titanium oxide is prepared using electrostatic spinning：By 1 milliliter of titanium tetraisopropylate, 0.8 milliliter of acetic acid,
0.1 gram of polyvinylpyrrolidone and absolute ethyl alcohol mixing, oscillator vibrate 960 minutes；Then 10 kilovoltages, 0.4 milliliter
Fltting speed and 6 centimetres receive spinning under distance conditions per hour；960 minutes are stood, then under 450 degrees Celsius of air atmospheres
Roasting 180 minutes, obtains fibrous titanium oxide；
Described polyvinylpyrrolidone can select polyethylene glycol or cetyl trimethylammonium bromide or dodecyl
Benzene sulfonic acid sodium salt substitutes.
(2) 0.015 grams of graphite oxides are dissolved in 15 ml deionized waters, ultrasound 20 minutes, add titanium dioxide and molybdenum or
Sour sodium ammonium molybdate or ammonium molybdate, stir 3 minutes, add thiocarbamide, stir 3 minutes.
(3) above-mentioned solution is transferred in reactor hydro-thermal reaction 780 minutes under 160 degrees celsius.
(4) after question response kettle is cooled to room temperature, material is taken out, with deionized water and washes of absolute alcohol, is dried under 52 degrees Celsius
It is dry, it is calcined 70 minutes under the conditions of 650 degrees Celsius of argon gas/hydrogen gas mixtures, obtains molybdenum disulfide/titanium dioxide/graphene
Composite.
Example IV
(1) fibrous titanium oxide is prepared using electrostatic spinning：By 3.5 milliliters of titanium tetraisopropylate, 2.5 milliliters of vinegar
Acid, 0.4 gram of polyvinylpyrrolidone and absolute ethyl alcohol mixing, oscillator vibrate 1500 minutes；Then in 22 kilovoltages, 1.5
Fltting speed and 11 centimetres receive spinning under distance conditions to milliliter per hour；1500 minutes are stood, then in 530 degrees Celsius of air
It is calcined 420 minutes under atmosphere, obtains fibrous titanium oxide；
Described polyvinylpyrrolidone can select polyethylene glycol or cetyl trimethylammonium bromide or dodecyl
Benzene sulfonic acid sodium salt substitutes.
(2) 0.028 grams of graphite oxides are dissolved in 35 ml deionized waters, ultrasound 40 minutes, add titanium dioxide and molybdic acid
Sodium or ammonium molybdate, stir 6 minutes, add thiocarbamide, stir 6 minutes.
(3) above-mentioned solution is transferred in reactor hydro-thermal reaction 1500 minutes under 210 degrees celsius.
(4) after question response kettle is cooled to room temperature, material is taken out, with deionized water and washes of absolute alcohol, is dried under 65 degrees Celsius
It is dry, it is calcined 150 minutes under the conditions of 820 degrees Celsius of argon gas/hydrogen gas mixtures, obtains molybdenum disulfide/titanium dioxide/graphene
Composite.
Embodiment five
(1) fibrous titanium oxide is prepared using electrostatic spinning：By 4 milliliters of titanium tetraisopropylate, 3 milliliters of acetic acid,
0.45 gram of polyvinylpyrrolidone and absolute ethyl alcohol mixing, oscillator vibrate 1560 minutes；Then in 25 kilovoltages, 1.8 millis
Liter per hour fltting speed and 13 centimetres receive spinning under distance conditions；1560 minutes are stood, then in 550 degrees Celsius of air gas
It is calcined 480 minutes under atmosphere, obtains fibrous titanium oxide；
Described polyvinylpyrrolidone can select polyethylene glycol or cetyl trimethylammonium bromide or dodecyl
Benzene sulfonic acid sodium salt substitutes.
(2) 0.03 grams of graphite oxides are dissolved in 40 ml deionized waters, ultrasound 50 minutes, add titanium dioxide and sodium molybdate
Or ammonium molybdate, stir 10 minutes, add thiocarbamide, stir 10 minutes.
(3) above-mentioned solution is transferred in reactor hydro-thermal reaction 1560 minutes under 215 degrees celsius.
(4) after question response kettle is cooled to room temperature, material is taken out, with deionized water and washes of absolute alcohol, is dried under 70 degrees Celsius
It is dry, it is calcined 210 minutes under the conditions of 850 degrees Celsius of argon gas/hydrogen gas mixtures, obtains molybdenum disulfide/titanium dioxide/graphene
Composite.
Embodiment six
(1) fibrous titanium oxide is prepared using electrostatic spinning：By 5 milliliters of titanium tetraisopropylate, 4 milliliters of acetic acid, 0.6
Gram polyvinylpyrrolidone and absolute ethyl alcohol mixing, oscillator vibrate 1680 minutes；Then in 30 kilovoltages, 2 milliliters per small
When fltting speed and 20 centimetres receive distance conditions under spinning；1680 minutes are stood, is then roasted under 600 degrees Celsius of air atmospheres
Burn 640 minutes, obtain fibrous titanium oxide；
Described polyvinylpyrrolidone can select polyethylene glycol or cetyl trimethylammonium bromide or dodecyl
Benzene sulfonic acid sodium salt substitutes.
(2) 0.1 grams of graphite oxides are dissolved in 60 ml deionized waters, ultrasound 60 minutes, add titanium dioxide and sodium molybdate
Or ammonium molybdate, stir 15 minutes, add thiocarbamide, stir 15 minutes.
(3) above-mentioned solution is transferred in reactor hydro-thermal reaction 1680 minutes under 220 degrees celsius.
(4) after question response kettle is cooled to room temperature, material is taken out, with deionized water and washes of absolute alcohol, is dried under 90 degrees Celsius
It is dry, it is calcined 270 minutes under the conditions of 950 degrees Celsius of argon gas/hydrogen gas mixtures, obtains molybdenum disulfide/titanium dioxide/graphene
Composite.
Embodiments of the present invention are not limited only to above-described embodiment.
Claims (7)
1. a kind of method for improving molybdenum disulfide charge and discharge cycles ability by doped graphene and titanium dioxide, its feature exist
In：
Molybdenum disulfide/the titanium dioxide/graphene composite material obtained by adulterating item is used as conductive modified phase, two using graphene
Titanium oxide is as support and cooperates with phase, strengthens the charge-discharge performance of the composite with this；Preparation method selects Static Spinning
Fibrous titanium oxide prepared by silk, sodium molybdate, thiocarbamide, graphite oxide as setting out material, then using hydro-thermal method after, through from
The heart separates, washs, is dried in vacuo and is thermally treated resulting in molybdenum disulfide/titanium dioxide/graphene composite material, specific preparation process
It is as follows：
(1) fibrous titanium oxide is prepared using electrostatic spinning：By the titanium tetraisopropylate of 0.5-5 milliliters, the vinegar of 0.4-4 milliliters
Acid, 0.05-0.6 grams of polyvinylpyrrolidone or polyethylene glycol or cetyl trimethylammonium bromide or neopelex
Mixed with absolute ethyl alcohol, oscillator vibration 720-1680 minutes；Then promoted per hour in 5-30 kilovoltages, 0.1-2 milliliters
Spinning under speed and 4-20 centimetres of reception distance condition；720-1680 minutes are stood, then in 400-600 degrees Celsius of air atmosphere
Lower roasting 120-640 minutes, obtain fibrous titanium oxide；
(2) 0.01-0.1 grams of graphite oxide is dissolved in 10-60 ml deionized waters, ultrasonic 15-60 minutes, adds step (1) system
Standby obtained fibrous titanium oxide and sodium molybdate or ammonium molybdate, stirs 2-15 minutes, adds thiocarbamide, stirs 2-15 minutes；
(3) solution that step (2) is prepared is transferred in reactor hydro-thermal reaction 720- under 150-220 degrees celsius
1680 minutes；
(4) after question response kettle is cooled to room temperature, material is taken out, with deionized water and washes of absolute alcohol, is dried under 50-90 degrees Celsius
It is dry, 60-270 minutes are calcined under the conditions of 600-950 degrees Celsius of argon gas/hydrogen gas mixture, obtain molybdenum disulfide/titanium dioxide
Titanium/graphene composite material.
2. one kind according to claim 1 passes through doped graphene and titanium dioxide improves molybdenum disulfide charge and discharge cycles energy
The method of power, it is characterised in that：
(1) fibrous titanium oxide is prepared using electrostatic spinning：3 milliliters of titanium tetraisopropylate, 2 milliliters of acetic acid, 0.3 gram are gathered
Vinylpyrrolidone or polyethylene glycol or cetyl trimethylammonium bromide or neopelex mix with absolute ethyl alcohol,
Oscillator vibrates 1440 minutes；Then in 20 kilovoltages, 1 milliliter fltting speed and 10 centimetres are received under distance conditions per hour
Spinning；1440 minutes are stood, is then calcined 360 minutes under 510 degrees Celsius of air atmospheres, obtains fibrous titanium oxide；
(2) 0.024 grams of graphite oxides are dissolved in 30 ml deionized waters, ultrasound 30 minutes, add the fibre that step (1) is prepared
Shape titanium dioxide and sodium molybdate or ammonium molybdate are tieed up, is stirred 5 minutes, adds thiocarbamide, is stirred 5 minutes；
(3) solution that step (2) is prepared is transferred in reactor hydro-thermal reaction 1440 minutes under 200 degrees celsius；
(4) after question response kettle is cooled to room temperature, material is taken out, with deionized water and washes of absolute alcohol, is dried under 60 degrees Celsius,
It is calcined 120 minutes under the conditions of 800 degrees Celsius of argon gas/hydrogen gas mixtures, it is compound obtains molybdenum disulfide/titanium dioxide/graphene
Material.
3. one kind according to claim 1 passes through doped graphene and titanium dioxide improves molybdenum disulfide charge and discharge cycles energy
The method of power, it is characterised in that：
(1) fibrous titanium oxide is prepared using electrostatic spinning：By 0.5 milliliter of titanium tetraisopropylate, 0.4 milliliter of acetic acid,
0.05 gram of polyvinylpyrrolidone or polyethylene glycol or cetyl trimethylammonium bromide or neopelex with it is anhydrous
Ethanol mixes, and oscillator vibrates 720 minutes；Then 5 kilovoltages, 0.1 milliliter per hour fltting speed and 4 centimetres receive away from
The spinning under the conditions of；720 minutes are stood, is then calcined 120 minutes under 400 degrees Celsius of air atmospheres, obtains fibrous dioxy
Change titanium；
(2) 0.01 grams of graphite oxides are dissolved in 10 ml deionized waters, ultrasound 15 minutes, add the fibre that step (1) is prepared
Shape titanium dioxide and sodium molybdate or ammonium molybdate are tieed up, is stirred 2 minutes, adds thiocarbamide, is stirred 2 minutes；
(3) solution that step (2) is prepared is transferred in reactor hydro-thermal reaction 720 minutes under 150 degrees celsius；
(4) after question response kettle is cooled to room temperature, take out material, with deionized water and washes of absolute alcohol, under 50 degrees Celsius drying exist
It is calcined 60 minutes under the conditions of 600 degrees Celsius of argon gas/hydrogen gas mixtures, obtains molybdenum disulfide/titanium dioxide/graphene composite wood
Material.
4. one kind according to claim 1 passes through doped graphene and titanium dioxide improves molybdenum disulfide charge and discharge cycles energy
The method of power, it is characterised in that：
(1) fibrous titanium oxide is prepared using electrostatic spinning：By 1 milliliter of titanium tetraisopropylate, 0.8 milliliter of acetic acid, 0.1 gram
Polyvinylpyrrolidone or polyethylene glycol or cetyl trimethylammonium bromide or neopelex mix with absolute ethyl alcohol
Close, oscillator vibrates 960 minutes；Then in 10 kilovoltages, 0.4 milliliter of fltting speed and 6 centimetres of reception per hour apart from bar
Spinning under part；960 minutes are stood, is then calcined 180 minutes under 450 degrees Celsius of air atmospheres, obtains fibrous titanium oxide；
(2) 0.015 grams of graphite oxides are dissolved in 15 ml deionized waters, ultrasound 20 minutes, add the fibre that step (1) is prepared
Shape titanium dioxide and sodium molybdate or ammonium molybdate are tieed up, is stirred 3 minutes, adds thiocarbamide, is stirred 3 minutes；
(3) solution that step (2) is prepared is transferred in reactor hydro-thermal reaction 780 minutes under 160 degrees celsius；
(4) after question response kettle is cooled to room temperature, material is taken out, with deionized water and washes of absolute alcohol, is dried under 52 degrees Celsius,
It is calcined 70 minutes under the conditions of 650 degrees Celsius of argon gas/hydrogen gas mixtures, obtains molybdenum disulfide/titanium dioxide/graphene composite wood
Material.
5. one kind according to claim 1 passes through doped graphene and titanium dioxide improves molybdenum disulfide charge and discharge cycles energy
The method of power, it is characterised in that：
(1) fibrous titanium oxide is prepared using electrostatic spinning：By 3.5 milliliters of titanium tetraisopropylate, 2.5 milliliters of acetic acid, 0.4
Gram polyvinylpyrrolidone or polyethylene glycol or cetyl trimethylammonium bromide or neopelex and absolute ethyl alcohol
Mixing, oscillator vibrate 1500 minutes；Then 22 kilovoltages, 1.5 milliliters per hour fltting speed and 11 centimetres receive away from
The spinning under the conditions of；1500 minutes are stood, is then calcined 420 minutes under 530 degrees Celsius of air atmospheres, obtains fibrous dioxy
Change titanium；
(2) 0.028 grams of graphite oxides are dissolved in 35 ml deionized waters, ultrasound 40 minutes, add the fibre that step (1) is prepared
Shape titanium dioxide and sodium molybdate or ammonium molybdate are tieed up, is stirred 6 minutes, adds thiocarbamide, is stirred 6 minutes；
(3) solution that step (2) is prepared is transferred in reactor hydro-thermal reaction 1500 minutes under 210 degrees celsius；
(4) after question response kettle is cooled to room temperature, material is taken out, with deionized water and washes of absolute alcohol, is dried under 65 degrees Celsius,
It is calcined 150 minutes under the conditions of 820 degrees Celsius of argon gas/hydrogen gas mixtures, it is compound obtains molybdenum disulfide/titanium dioxide/graphene
Material.
6. one kind according to claim 1 passes through doped graphene and titanium dioxide improves molybdenum disulfide charge and discharge cycles energy
The method of power, it is characterised in that：
(1) fibrous titanium oxide is prepared using electrostatic spinning：By 4 milliliters of titanium tetraisopropylate, 3 milliliters of acetic acid, 0.45 gram
Polyvinylpyrrolidone or polyethylene glycol or cetyl trimethylammonium bromide or neopelex mix with absolute ethyl alcohol
Close, oscillator vibrates 1560 minutes；Then 25 kilovoltages, 1.8 milliliters per hour fltting speed and 13 centimetres reception distances
Under the conditions of spinning；1560 minutes are stood, is then calcined 480 minutes under 550 degrees Celsius of air atmospheres, obtains fibrous titanium dioxide
Titanium；
(2) 0.03 grams of graphite oxides are dissolved in 40 ml deionized waters, ultrasound 50 minutes, add the fibre that step (1) is prepared
Shape titanium dioxide and sodium molybdate or ammonium molybdate are tieed up, is stirred 10 minutes, adds thiocarbamide, is stirred 10 minutes；
(3) solution that step (2) is prepared is transferred in reactor hydro-thermal reaction 1560 minutes under 215 degrees celsius；
(4) after question response kettle is cooled to room temperature, material is taken out, with deionized water and washes of absolute alcohol, is dried under 70 degrees Celsius,
It is calcined 210 minutes under the conditions of 850 degrees Celsius of argon gas/hydrogen gas mixtures, it is compound obtains molybdenum disulfide/titanium dioxide/graphene
Material.
7. one kind according to claim 1 passes through doped graphene and titanium dioxide improves molybdenum disulfide charge and discharge cycles energy
The method of power, it is characterised in that：
(1) fibrous titanium oxide is prepared using electrostatic spinning：5 milliliters of titanium tetraisopropylate, 4 milliliters of acetic acid, 0.6 gram are gathered
Vinylpyrrolidone or polyethylene glycol or cetyl trimethylammonium bromide or neopelex mix with absolute ethyl alcohol,
Oscillator vibrates 1680 minutes；Then in 30 kilovoltages, 2 milliliters fltting speed and 20 centimetres are received under distance conditions per hour
Spinning；1680 minutes are stood, is then calcined 640 minutes under 600 degrees Celsius of air atmospheres, obtains fibrous titanium oxide；
(2) 0.1 grams of graphite oxides are dissolved in 60 ml deionized waters, ultrasound 60 minutes, add the fiber that step (1) is prepared
Shape titanium dioxide and sodium molybdate or ammonium molybdate, stir 15 minutes, add thiocarbamide, stir 15 minutes；
(3) solution that step (2) is prepared is transferred in reactor hydro-thermal reaction 1680 minutes under 220 degrees celsius；
(4) after question response kettle is cooled to room temperature, material is taken out, with deionized water and washes of absolute alcohol, is dried under 90 degrees Celsius,
It is calcined 270 minutes under the conditions of 950 degrees Celsius of argon gas/hydrogen gas mixtures, it is compound obtains molybdenum disulfide/titanium dioxide/graphene
Material.
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| CN107978742B (en) * | 2017-11-17 | 2020-11-06 | 齐鲁工业大学 | C-doped flower spherical titanium dioxide/molybdenum disulfide composite material formed by nanosheets and preparation method thereof |
| CN108183269A (en) * | 2018-01-09 | 2018-06-19 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of water system high magnification sodium-ion battery |
| CN110252345B (en) * | 2019-05-10 | 2021-07-20 | 吉林大学 | Preparation method and application of graphene-molybdenum disulfide/titanium dioxide composite material with accordion structure |
| CN112750992B (en) * | 2019-10-31 | 2022-05-03 | 中国石油化工股份有限公司 | Molybdenum disulfide/titanium dioxide/graphene composite material |
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| CN102683710A (en) * | 2012-05-21 | 2012-09-19 | 北京化工大学 | Carbon nanofiber load titanium dioxide thin film anode material and preparation method thereof |
| CN104022260A (en) * | 2014-06-24 | 2014-09-03 | 中国第一汽车股份有限公司 | Preparation method of titanium dioxide composite carbon nano-fiber negative material of lithium ion battery |
| CN104393254A (en) * | 2014-09-30 | 2015-03-04 | 上海交通大学 | Nitrogen-doped graphene/molybdenum disulfide composite material, and preparation method and application thereof |
| CN104835654A (en) * | 2015-05-29 | 2015-08-12 | 青岛大学 | 3D nitrogen-doped graphene/molybdenum disulfide compound and preparation method thereof |
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| CN102683710A (en) * | 2012-05-21 | 2012-09-19 | 北京化工大学 | Carbon nanofiber load titanium dioxide thin film anode material and preparation method thereof |
| CN104022260A (en) * | 2014-06-24 | 2014-09-03 | 中国第一汽车股份有限公司 | Preparation method of titanium dioxide composite carbon nano-fiber negative material of lithium ion battery |
| CN104393254A (en) * | 2014-09-30 | 2015-03-04 | 上海交通大学 | Nitrogen-doped graphene/molybdenum disulfide composite material, and preparation method and application thereof |
| CN104835654A (en) * | 2015-05-29 | 2015-08-12 | 青岛大学 | 3D nitrogen-doped graphene/molybdenum disulfide compound and preparation method thereof |
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