CN105161690A - Method for improving charge-discharge cycling capacity of molybdenum disulfide by doping graphene and titanium dioxide - Google Patents
Method for improving charge-discharge cycling capacity of molybdenum disulfide by doping graphene and titanium dioxide Download PDFInfo
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a method for improving the charge-discharge cycling capacity of molybdenum disulfide by doping graphene and titanium dioxide. According to a molybdenum disulfide/titanium dioxide/graphene composite, graphene is adopted as a conductive modified phase, and titanium dioxide is adopted as a support and collaborative phase, so that the charge-discharge cycling performance of the composite is enhanced. Sodium molybdate, thiourea, graphite oxide, titanium tetraisopropoxide, absolute ethyl alcohol, acetic acid, polyvinylpyrrolidone and deionized water are selected, and after electrostatic spinning and a hydrothermal reaction, the molybdenum disulfide/titanium dioxide/graphene composite is obtained through vacuum drying. The production process is simple, cost is low, and the prepared molybdenum disulfide/titanium dioxide/graphene composite has excellent electrochemical performance.
Description
Technical field
The present invention relates to a kind of preparation method of nano composite material, particularly relate to a kind of method being improved molybdenum bisuphide charge and discharge cycles ability by doped graphene and titanium dioxide, belong to advanced Nano-composite materials technology field.
Background technology
From Sony corporation of Japan nineteen nineties since lithium ion battery commercialization, lithium ion battery, due to advantages such as operating voltage are high, lightweight, specific energy is large, self discharge is little, have extended cycle life, becomes the ideal source of mobile phone, notebook computer, digital camera, video camera, electric automobile, hybrid vehicle and portable various instrument and equipment.In lithium ion battery, the positive electrode and the negative material that belong to lithium storage materials play conclusive effect as the part that battery is main to its chemical property.
The features such as at present, graphite is the negative material being widely used in commercial Li-ion battery, and simple, the long cycle life of electrochemical process is deviate from/embedded to this lithium ion having benefited from it, raw material supply is enriched and with low cost.However, the lithium storage content of graphite is confined to form LiC
6time the highest theoretical capacity 372 MAH every gram, and intercalation potential is low, and in charge and discharge process, graphite surface may cause the deposition of lithium metal, there is certain potential safety hazard.Therefore, explore novel negative material, improve its capacity further, become particularly necessary and important.Conventional lithium ion battery negative material has material with carbon element, alloy material and sulfide material, and wherein sulfide material account for greatly, is more promising negative material.
Molybdenum bisuphide, owing to having the layer structure the same with graphite, is very beneficial for the embedding of lithium ion and deviates from, and because having higher theoretical capacity (1063 MAH every gram), and in charge and discharge process, change in volume is little, thus enjoys the concern of people.But because molybdenum bisuphide self-conductive is poor, in charge and discharge process, capacity attenuation is fast and high-rate charge-discharge capability is poor, thus limits its Commercialization application.In order to improve the chemical property of molybdenum bisuphide, researcher has carried out a large amount of research work, mainly concentrate on the nanostructure of synthesis different-shape and carry out conducting particles doping on its surface and then form composite material etc., conducting particles is amorphous carbon, Graphene, CNT (carbon nano-tube) etc. mainly.As at prior art " " Facilesynthesisofcarbon-coatedMoS
2nanorodswithenhancedlithiumstorageproperties "; ChaofengZhangetal.; Electrochem.Commun.20 (2012) 7-10 " in mention " carbon coated after the specific discharge capacity of molybdenum bisuphide be significantly improved; the specific discharge capacity of 621 MAH every gram can be provided after 80 circles that circulate under 200 milliamperes of every gram of current densities ", but cyclical stability needs to improve further.As at prior art " " CTAB-assistedsynthesisofsingle-layerMoS
2-graphenecompositesasanodematerialsofLi-ionbatteries "; ZhenWangetal.; JMater.Chem.1 (2013) 2202-2210 ", publication number is mention in the Chinese patent of CN103904334A " in molybdenum bisuphide/graphene composite material, Graphene reduces contact resistance, facilitates electron transmission in electrode reaction ", but specific discharge capacity needs to improve further.At present, the cyclical stability solving molybdenum bisuphide and the specific discharge capacity improving molybdenum bisuphide are the technical barriers needing to solve, the present invention is directed to this problem, propose using Graphene as conductive modified phase, titanium dioxide as support and collaborative phase, strengthen the cyclical stability of molybdenum bisuphide/titanium dioxide/graphene composite material with this and improve its specific discharge capacity.
Summary of the invention
The object of this invention is to provide a kind of method being improved molybdenum bisuphide charge and discharge cycles ability by doped graphene and titanium dioxide, preparation method is with low cost, technique is simple, molybdenum bisuphide/titanium dioxide/graphene composite material the excellent electrochemical performance of preparation, its specific discharge capacity can reach 718 MAH every gram after 100 circulations, the capacity attenuation rate of single cycle is 0.02%, operating temperature range is subzero 25 degrees Celsius ~ 60 degrees Celsius above freezing, memory-less effect, pollution-free, self-discharge rate is low, within 1st year, self-discharge rate is about 25%, average monthly self-discharge rate is at 2-2.5%.
Technical scheme of the present invention is:
1, improved a method for molybdenum bisuphide charge and discharge cycles ability by doped graphene and titanium dioxide, it is characterized in that:
By doping item obtain molybdenum bisuphide/titanium dioxide/graphene composite material using Graphene as conductive modified phase, titanium dioxide as support and collaborative phase, strengthen the charge-discharge performance of this composite material with this; The fibrous titanium oxide that this preparation method selects electrostatic spinning to prepare, sodium molybdate, thiocarbamide, graphite oxide are as the material that sets out, then after adopting hydro thermal method, obtain molybdenum bisuphide/titanium dioxide/graphene composite material through centrifugation, washing, vacuumize and heat treatment, concrete preparation process is as follows:
(1) adopt electrostatic spinning to prepare fibrous titanium oxide: by the acetic acid of the titanium tetraisopropylate of 0.5-5 milliliter, 0.4-4 milliliter, 0.05-0.6 gram polyvinylpyrrolidone or polyethylene glycol or softex kw or
dBSA sodiummix with absolute ethyl alcohol, oscillator vibrates 720-1680 minute; Then spinning under 5-30 kilovoltage, 0.1-2 milliliter fltting speed per hour and 4-20 centimetre of receiving range condition; Leave standstill 720-1680 minute, then roasting 120-640 minute under 400-600 degree Celsius of air atmosphere, obtains fibrous titanium oxide;
(2) 0.01-0.1 gram of graphite oxide is dissolved in 10-60 ml deionized water, and ultrasonic 15-60 minute, adds TiO
2with sodium molybdate or ammonium molybdate, stir 2-15 minute, then add thiocarbamide, stir 2-15 minute;
(3) above-mentioned solution to be transferred in reactor hydro-thermal reaction 720-1680 minute under 150-220 degrees celsius.
(4) after question response still is cooled to room temperature, take out material, with deionized water and washes of absolute alcohol, dry under 50-90 degree Celsius, roasting 60-270 minute under 600-950 degree Celsius of argon gas/hydrogen mixed gas concrete conditions in the establishment of a specific crime, obtains molybdenum bisuphide/titanium dioxide/graphene composite material;
Technical solutions according to the invention have following technique effect:
(1) molybdenum bisuphide/titanium dioxide/graphene composite material of the present invention is that substrate is depended on and formed with Graphene by generated in-situ molybdenum bisuphide, and thus molybdenum bisuphide has the feature large with Graphene contact area; Certain inhibitory action is had to the change in volume of molybdenum bisuphide in charge and discharge process.
(2) the graphite oxide in molybdenum bisuphide/titanium dioxide/graphene composite material of the present invention becomes after Graphene through reduction reaction, its conductivity increases, thus the conductivity of molybdenum bisuphide/titanium dioxide/graphene is increased, and then improve the cycle performance of molybdenum bisuphide/titanium dioxide/graphene.
(3) adding of the titanium dioxide in molybdenum bisuphide/titanium dioxide/graphene composite material of the present invention, it is made to play support effect, the two-phase of the molybdenum bisuphide/Graphene of sheet is propped, form a class loose structure, be beneficial to immersion and the delay of electrolyte in charge and discharge process, and be conducive to the diffusion of lithium ion, therefore it has higher cycle performance.
(4) the electrospinning device that is applied to of the present invention and hydro thermal method make synthesis simple, eventually reduce cost and process complexity.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of molybdenum bisuphide (1,2), molybdenum bisuphide/Graphene (3,4), molybdenum bisuphide/titanium dioxide (5,6) and molybdenum bisuphide/titanium dioxide/graphene (7,8) prepared by the present invention.
Fig. 2 is the X-ray diffractogram of molybdenum bisuphide, molybdenum bisuphide/Graphene, molybdenum bisuphide/titanium dioxide and molybdenum bisuphide/titanium dioxide/graphene prepared by the present invention, in molybdenum bisuphide/titanium dioxide/graphene composite material, obvious titanium dioxide exists as seen from the figure, and Graphene does not exist obvious diffraction maximum less due to content.
Fig. 3 is the cyclic curve figure of molybdenum bisuphide/titanium dioxide/graphene prepared by the present invention, and after 100 circulations, specific discharge capacity still remains on 718 MAH every gram.
Fig. 4 is the curve of double curvature figure of molybdenum bisuphide/titanium dioxide/graphene prepared by the present invention, can find out that it has outstanding high rate performance in figure.
Embodiment
Embodiment one
(1) electrostatic spinning is adopted to prepare fibrous titanium oxide: the titanium tetraisopropylate of 3 milliliters, the acetic acid of 2 milliliters, 0.3 gram of polyvinylpyrrolidone and absolute ethyl alcohol to be mixed, oscillator vibrates 1440 minutes; Then spinning under 20 kilovoltages, 1 milliliter of fltting speed per hour and 10 centimetres of receiving range conditions; Leave standstill 1440 minutes, then roasting 360 minutes under 510 degrees Celsius of air atmospheres, obtains fibrous titanium oxide;
Described polyvinylpyrrolidone can select polyethylene glycol or softex kw or neopelex to substitute.
(2) 0.024 grams of graphite oxides are dissolved in 30 ml deionized water, ultrasonic 30 minutes, add titanium dioxide and sodium molybdate or ammonium molybdate, stir 5 minutes, then add thiocarbamide, stir 5 minutes.
(3) above-mentioned solution to be transferred in reactor under 200 degrees celsius hydro-thermal reaction 1440 minutes.
(4) after question response still is cooled to room temperature, take out material, with deionized water and washes of absolute alcohol, dry under 60 degrees Celsius, roasting 120 minutes under 800 degrees Celsius of argon gas/hydrogen mixed gas concrete conditions in the establishment of a specific crime, obtains molybdenum bisuphide/titanium dioxide/graphene composite material.
The performance of testing in accompanying drawing is that the present embodiment one is measured.
Embodiment two
(1) electrostatic spinning is adopted to prepare fibrous titanium oxide: the titanium tetraisopropylate of 0.5 milliliter, the acetic acid of 0.4 milliliter, 0.05 gram of polyvinylpyrrolidone and absolute ethyl alcohol to be mixed, oscillator vibrates 720 minutes; Then spinning under 5 kilovoltages, 0.1 milliliter of fltting speed per hour and 4 centimetres of receiving range conditions; Leave standstill 720 minutes, then roasting 120 minutes under 400 degrees Celsius of air atmospheres, obtains fibrous titanium oxide;
Described polyvinylpyrrolidone can select polyethylene glycol or softex kw or neopelex to substitute.
(2) 0.01 grams of graphite oxides are dissolved in 10 ml deionized water, ultrasonic 15 minutes, add titanium dioxide and sodium molybdate or ammonium molybdate, stir 2 minutes, then add thiocarbamide, stir 2 minutes.
(3) above-mentioned solution to be transferred in reactor under 150 degrees celsius hydro-thermal reaction 720 minutes.
(4) after question response still is cooled to room temperature, take out material, with deionized water and washes of absolute alcohol, dry under 50 degrees Celsius, roasting 60 minutes under 600 degrees Celsius of argon gas/hydrogen mixed gas concrete conditions in the establishment of a specific crime, obtains molybdenum bisuphide/titanium dioxide/graphene composite material.
Embodiment three
(1) electrostatic spinning is adopted to prepare fibrous titanium oxide: the titanium tetraisopropylate of 1 milliliter, the acetic acid of 0.8 milliliter, 0.1 gram of polyvinylpyrrolidone and absolute ethyl alcohol to be mixed, oscillator vibrates 960 minutes; Then spinning under 10 kilovoltages, 0.4 milliliter of fltting speed per hour and 6 centimetres of receiving range conditions; Leave standstill 960 minutes, then roasting 180 minutes under 450 degrees Celsius of air atmospheres, obtains fibrous titanium oxide;
Described polyvinylpyrrolidone can select polyethylene glycol or softex kw or neopelex to substitute.
(2) 0.015 grams of graphite oxides are dissolved in 15 ml deionized water, ultrasonic 20 minutes, add titanium dioxide and molybdenum or sour sodium ammonium molybdate or ammonium molybdate, stir 3 minutes, then add thiocarbamide, stir 3 minutes.
(3) above-mentioned solution to be transferred in reactor under 160 degrees celsius hydro-thermal reaction 780 minutes.
(4) after question response still is cooled to room temperature, take out material, with deionized water and washes of absolute alcohol, dry under 52 degrees Celsius, roasting 70 minutes under 650 degrees Celsius of argon gas/hydrogen mixed gas concrete conditions in the establishment of a specific crime, obtains molybdenum bisuphide/titanium dioxide/graphene composite material.
Embodiment four
(1) electrostatic spinning is adopted to prepare fibrous titanium oxide: the titanium tetraisopropylate of 3.5 milliliters, the acetic acid of 2.5 milliliters, 0.4 gram of polyvinylpyrrolidone and absolute ethyl alcohol to be mixed, oscillator vibrates 1500 minutes; Then spinning under 22 kilovoltages, 1.5 milliliters of fltting speeds per hour and 11 centimetres of receiving range conditions; Leave standstill 1500 minutes, then roasting 420 minutes under 530 degrees Celsius of air atmospheres, obtains fibrous titanium oxide;
Described polyvinylpyrrolidone can select polyethylene glycol or softex kw or neopelex to substitute.
(2) 0.028 grams of graphite oxides are dissolved in 35 ml deionized water, ultrasonic 40 minutes, add titanium dioxide and sodium molybdate or ammonium molybdate, stir 6 minutes, then add thiocarbamide, stir 6 minutes.
(3) above-mentioned solution to be transferred in reactor under 210 degrees celsius hydro-thermal reaction 1500 minutes.
(4) after question response still is cooled to room temperature, take out material, with deionized water and washes of absolute alcohol, dry under 65 degrees Celsius, roasting 150 minutes under 820 degrees Celsius of argon gas/hydrogen mixed gas concrete conditions in the establishment of a specific crime, obtains molybdenum bisuphide/titanium dioxide/graphene composite material.
Embodiment five
(1) electrostatic spinning is adopted to prepare fibrous titanium oxide: the titanium tetraisopropylate of 4 milliliters, the acetic acid of 3 milliliters, 0.45 gram of polyvinylpyrrolidone and absolute ethyl alcohol to be mixed, oscillator vibrates 1560 minutes; Then spinning under 25 kilovoltages, 1.8 milliliters of fltting speeds per hour and 13 centimetres of receiving range conditions; Leave standstill 1560 minutes, then roasting 480 minutes under 550 degrees Celsius of air atmospheres, obtains fibrous titanium oxide;
Described polyvinylpyrrolidone can select polyethylene glycol or softex kw or neopelex to substitute.
(2) 0.03 grams of graphite oxides are dissolved in 40 ml deionized water, ultrasonic 50 minutes, add titanium dioxide and sodium molybdate or ammonium molybdate, stir 10 minutes, then add thiocarbamide, stir 10 minutes.
(3) above-mentioned solution to be transferred in reactor under 215 degrees celsius hydro-thermal reaction 1560 minutes.
(4) after question response still is cooled to room temperature, take out material, with deionized water and washes of absolute alcohol, dry under 70 degrees Celsius, roasting 210 minutes under 850 degrees Celsius of argon gas/hydrogen mixed gas concrete conditions in the establishment of a specific crime, obtains molybdenum bisuphide/titanium dioxide/graphene composite material.
Embodiment six
(1) electrostatic spinning is adopted to prepare fibrous titanium oxide: the titanium tetraisopropylate of 5 milliliters, the acetic acid of 4 milliliters, 0.6 gram of polyvinylpyrrolidone and absolute ethyl alcohol to be mixed, oscillator vibrates 1680 minutes; Then spinning under 30 kilovoltages, 2 milliliters of fltting speeds per hour and 20 centimetres of receiving range conditions; Leave standstill 1680 minutes, then roasting 640 minutes under 600 degrees Celsius of air atmospheres, obtains fibrous titanium oxide;
Described polyvinylpyrrolidone can select polyethylene glycol or softex kw or neopelex to substitute.
(2) 0.1 grams of graphite oxides are dissolved in 60 ml deionized water, ultrasonic 60 minutes, add titanium dioxide and sodium molybdate or ammonium molybdate, stir 15 minutes, then add thiocarbamide, stir 15 minutes.
(3) above-mentioned solution to be transferred in reactor under 220 degrees celsius hydro-thermal reaction 1680 minutes.
(4) after question response still is cooled to room temperature, take out material, with deionized water and washes of absolute alcohol, dry under 90 degrees Celsius, roasting 270 minutes under 950 degrees Celsius of argon gas/hydrogen mixed gas concrete conditions in the establishment of a specific crime, obtains molybdenum bisuphide/titanium dioxide/graphene composite material.
Embodiments of the present invention are not limited only to above-described embodiment.
Claims (7)
1. improved a method for molybdenum bisuphide charge and discharge cycles ability by doped graphene and titanium dioxide, it is characterized in that:
By doping item obtain molybdenum bisuphide/titanium dioxide/graphene composite material using Graphene as conductive modified phase, titanium dioxide as support and collaborative phase, strengthen the charge-discharge performance of this composite material with this; The fibrous titanium oxide that this preparation method selects electrostatic spinning to prepare, sodium molybdate, thiocarbamide, graphite oxide are as the material that sets out, then after adopting hydro thermal method, obtain molybdenum bisuphide/titanium dioxide/graphene composite material through centrifugation, washing, vacuumize and heat treatment, concrete preparation process is as follows:
(1) adopt electrostatic spinning to prepare fibrous titanium oxide: by the acetic acid of the titanium tetraisopropylate of 0.5-5 milliliter, 0.4-4 milliliter, 0.05-0.6 gram polyvinylpyrrolidone or polyethylene glycol or softex kw or
neopelexmix with absolute ethyl alcohol, oscillator vibrates 720-1680 minute; Then spinning under 5-30 kilovoltage, 0.1-2 milliliter fltting speed per hour and 4-20 centimetre of receiving range condition; Leave standstill 720-1680 minute, then roasting 120-640 minute under 400-600 degree Celsius of air atmosphere, obtains fibrous titanium oxide;
(2) 0.01-0.1 gram of graphite oxide is dissolved in 10-60 ml deionized water, and ultrasonic 15-60 minute, adds TiO
2with sodium molybdate or ammonium molybdate, stir 2-15 minute, then add thiocarbamide, stir 2-15 minute;
(3) above-mentioned solution to be transferred in reactor hydro-thermal reaction 720-1680 minute under 150-220 degrees celsius.
(4) after question response still is cooled to room temperature, take out material, with deionized water and washes of absolute alcohol, dry under 50-90 degree Celsius, roasting 60-270 minute under 600-950 degree Celsius of argon gas/hydrogen mixed gas concrete conditions in the establishment of a specific crime, obtains molybdenum bisuphide/titanium dioxide/graphene composite material.
2. a kind of method being improved molybdenum bisuphide charge and discharge cycles ability by doped graphene and titanium dioxide according to claim 1, be is characterized in that:
(1) adopt electrostatic spinning to prepare fibrous titanium oxide: by the titanium tetraisopropylate of 3 milliliters, the acetic acid of 2 milliliters, 0.3 gram of polyvinylpyrrolidone or polyethylene glycol or softex kw or
neopelexmix with absolute ethyl alcohol, oscillator vibrates 1440 minutes; Then spinning under 20 kilovoltages, 1 milliliter of fltting speed per hour and 10 centimetres of receiving range conditions; Leave standstill 1440 minutes, then roasting 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 water, ultrasonic 30 minutes, add titanium dioxide and sodium molybdate or ammonium molybdate, stir 5 minutes, then add thiocarbamide, stir 5 minutes;
(3) above-mentioned solution to be transferred in reactor under 200 degrees celsius hydro-thermal reaction 1440 minutes;
(4) after question response still is cooled to room temperature, take out material, with deionized water and washes of absolute alcohol, dry under 60 degrees Celsius, roasting 120 minutes under 800 degrees Celsius of argon gas/hydrogen mixed gas concrete conditions in the establishment of a specific crime, obtains molybdenum bisuphide/titanium dioxide/graphene composite material.
3. a kind of method being improved molybdenum bisuphide charge and discharge cycles ability by doped graphene and titanium dioxide according to claim 1, be is characterized in that:
(1) adopt electrostatic spinning to prepare fibrous titanium oxide: by the titanium tetraisopropylate of 0.5 milliliter, the acetic acid of 0.4 milliliter, 0.05 gram of polyvinylpyrrolidone or polyethylene glycol or softex kw or
neopelexmix with absolute ethyl alcohol, oscillator vibrates 720 minutes; Then spinning under 5 kilovoltages, 0.1 milliliter of fltting speed per hour and 4 centimetres of receiving range conditions; Leave standstill 720 minutes, then roasting 120 minutes under 400 degrees Celsius of air atmospheres, obtains fibrous titanium oxide;
(2) 0.01 grams of graphite oxides are dissolved in 10 ml deionized water, ultrasonic 15 minutes, add titanium dioxide and sodium molybdate or ammonium molybdate, stir 2 minutes, then add thiocarbamide, stir 2 minutes;
(3) above-mentioned solution to be transferred in reactor under 150 degrees celsius hydro-thermal reaction 720 minutes;
(4) after question response still is cooled to room temperature, take out material, with deionized water and washes of absolute alcohol, dry under 50 degrees Celsius, to do under 600 degrees Celsius of argon gas/hydrogen mixed gas concrete conditions in the establishment of a specific crime roasting 60 minutes, obtain molybdenum bisuphide/titanium dioxide/graphene composite material.
4. a kind of method being improved molybdenum bisuphide charge and discharge cycles ability by doped graphene and titanium dioxide according to claim 1, be is characterized in that:
(1) adopt electrostatic spinning to prepare fibrous titanium oxide: by the titanium tetraisopropylate of 1 milliliter, the acetic acid of 0.8 milliliter, 0.1 gram of polyvinylpyrrolidone or polyethylene glycol or softex kw or
neopelexmix with absolute ethyl alcohol, oscillator vibrates 960 minutes; Then spinning under 10 kilovoltages, 0.4 milliliter of fltting speed per hour and 6 centimetres of receiving range conditions; Leave standstill 960 minutes, then roasting 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 water, ultrasonic 20 minutes, add titanium dioxide and sodium molybdate or ammonium molybdate, stir 3 minutes, then add thiocarbamide, stir 3 minutes;
(3) above-mentioned solution to be transferred in reactor under 160 degrees celsius hydro-thermal reaction 780 minutes;
(4) after question response still is cooled to room temperature, take out material, with deionized water and washes of absolute alcohol, dry under 52 degrees Celsius, roasting 70 minutes under 650 degrees Celsius of argon gas/hydrogen mixed gas concrete conditions in the establishment of a specific crime, obtains molybdenum bisuphide/titanium dioxide/graphene composite material.
5. a kind of method being improved molybdenum bisuphide charge and discharge cycles ability by doped graphene and titanium dioxide according to claim 1, be is characterized in that:
(1) adopt electrostatic spinning to prepare fibrous titanium oxide: by the titanium tetraisopropylate of 3.5 milliliters, the acetic acid of 2.5 milliliters, 0.4 gram of polyvinylpyrrolidone or polyethylene glycol or softex kw or
neopelexmix with absolute ethyl alcohol, oscillator vibrates 1500 minutes; Then spinning under 22 kilovoltages, 1.5 milliliters of fltting speeds per hour and 11 centimetres of receiving range conditions; Leave standstill 1500 minutes, then roasting 420 minutes under 530 degrees Celsius of air atmospheres, obtains fibrous titanium oxide;
(2) 0.028 grams of graphite oxides are dissolved in 35 ml deionized water, ultrasonic 40 minutes, add titanium dioxide and sodium molybdate or ammonium molybdate, stir 6 minutes, then add thiocarbamide, stir 6 minutes;
(3) above-mentioned solution to be transferred in reactor under 210 degrees celsius hydro-thermal reaction 1500 minutes;
(4) after question response still is cooled to room temperature, take out material, with deionized water and washes of absolute alcohol, dry under 65 degrees Celsius, roasting 150 minutes under 820 degrees Celsius of argon gas/hydrogen mixed gas concrete conditions in the establishment of a specific crime, obtains molybdenum bisuphide/titanium dioxide/graphene composite material.
6. a kind of method being improved molybdenum bisuphide charge and discharge cycles ability by doped graphene and titanium dioxide according to claim 1, be is characterized in that:
(1) adopt electrostatic spinning to prepare fibrous titanium oxide: by the titanium tetraisopropylate of 4 milliliters, the acetic acid of 3 milliliters, 0.45 gram of polyvinylpyrrolidone or polyethylene glycol or softex kw or
neopelexmix with absolute ethyl alcohol, oscillator vibrates 1560 minutes; Then spinning under 25 kilovoltages, 1.8 milliliters of fltting speeds per hour and 13 centimetres of receiving range conditions; Leave standstill 1560 minutes, then roasting 480 minutes under 550 degrees Celsius of air atmospheres, obtains fibrous titanium oxide;
(2) 0.03 grams of graphite oxides are dissolved in 40 ml deionized water, ultrasonic 50 minutes, add titanium dioxide and sodium molybdate or ammonium molybdate, stir 10 minutes, then add thiocarbamide, stir 10 minutes;
(3) above-mentioned solution to be transferred in reactor under 215 degrees celsius hydro-thermal reaction 1560 minutes;
(4) after question response still is cooled to room temperature, take out material, with deionized water and washes of absolute alcohol, dry under 70 degrees Celsius, roasting 210 minutes under 850 degrees Celsius of argon gas/hydrogen mixed gas concrete conditions in the establishment of a specific crime, obtains molybdenum bisuphide/titanium dioxide/graphene composite material.
7. a kind of method being improved molybdenum bisuphide charge and discharge cycles ability by doped graphene and titanium dioxide according to claim 1, be is characterized in that:
(1) adopt electrostatic spinning to prepare fibrous titanium oxide: by the titanium tetraisopropylate of 5 milliliters, the acetic acid of 4 milliliters, 0.6 gram of polyvinylpyrrolidone or polyethylene glycol or softex kw or
neopelexmix with absolute ethyl alcohol, oscillator vibrates 1680 minutes; Then spinning under 30 kilovoltages, 2 milliliters of fltting speeds per hour and 20 centimetres of receiving range conditions; Leave standstill 1680 minutes, then roasting 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 water, ultrasonic 60 minutes, add titanium dioxide and sodium molybdate or ammonium molybdate, stir 15 minutes, then add thiocarbamide, stir 15 minutes;
(3) above-mentioned solution to be transferred in reactor under 220 degrees celsius hydro-thermal reaction 1680 minutes;
(4) after question response still is cooled to room temperature, take out material, with deionized water and washes of absolute alcohol, dry under 90 degrees Celsius, roasting 270 minutes under 950 degrees Celsius of argon gas/hydrogen mixed gas concrete conditions in the establishment of a specific crime, obtains molybdenum bisuphide/titanium dioxide/graphene composite material.
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| CN110252345A (en) * | 2019-05-10 | 2019-09-20 | 吉林大学 | Graphene with accordion structure-molybdenum disulfide/composite titania material preparation method and applications |
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