CN105591077B - A kind of preparation method of molybdenum carbide/nitrogen sulphur codope sponge graphene anode material for sodium-ion battery - Google Patents
A kind of preparation method of molybdenum carbide/nitrogen sulphur codope sponge graphene anode material for sodium-ion battery Download PDFInfo
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- H—ELECTRICITY
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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
A kind of preparation method of molybdenum carbide/nitrogen sulphur codope sponge graphene anode material for sodium-ion battery.Molybdenum carbide/nitrogen sulphur codope sponge graphene composite material prepared by this method, molybdenum carbide nano particle are uniformly distributed in the more nitrogen sulphur codope spongy graphene with more active site and with three-dimensional structure of surface folding.The preparation method is by molybdenum source, and carbon source is dissolved in graphene oxide solution, and nitrogen source, sulphur source is added, obtained mixed solution is subjected to hydro-thermal reaction after adjusting ph, it is placed in silica crucible after product is freeze-dried and carries out high-temperature heat treatment, natural cooling is to get to composite material after the completion of reaction.Wherein in water-heat process, the doping and reduction of graphene, presoma forming and its being carried out with the composite sync of doped graphene.The composite material can be made by hydro-thermal method combination subsequent heat treatment technique, and the preparation method simple process and low cost is honest and clean, have preferable Research Prospects.
Description
Technical field
The present invention relates to a kind of preparation methods of anode material of lithium-ion battery, belong to sodium-ion battery field.
Background technology
With the quick change of information age, lithium ion battery is in portable electronic product (laptop, intelligence
Mobile Equipment, tablet computer etc.), achieve fast development in electric vehicle, and show good development prospect.However, by
In the scarcity of metal lithium resource, the presence of the limiting factors such as capacity of lithium ion battery of battery manufacture cost and maturation,
Development is inevitably challenged.Being in the sodium in same main group in the periodic table of elements with lithium has the physics similar with lithium
Chemical property, and compared with lithium, rich reserves.This makes sodium-ion battery become a kind of and most potential can be used for extensive quotient
The battery system of industryization application.However, the ionic radius due to sodium ion is bigger than the ionic radius of lithium ion so that sodium ion
It is embedded in electrode material more difficult than lithium ion with abjection.Therefore, the electrode material of sodium-ion battery grinds as its system
The emphasis studied carefully.
Past following period of time, researcher have carried out extensive research to the electrode material of sodium-ion battery, wherein
Carbon material, alloy material, sulfide, the materials such as oxide have correlative study report, but a variety of materials are being displayed one's respective advantages
While also show that capacity attenuation is fast, the defect of high rate performance difference etc..
Invention content
It is a kind of simple for process, reproducible present invention aims at providing, while environmentally friendly carrying out industrial metaplasia
Method of the preparation of production for molybdenum carbide/nitrogen sulphur codope sponge graphene of sodium-ion battery.
Technical scheme of the present invention includes the following steps：
(1) by thiocarbamide, fully dissolving is spread in graphene oxide solution under the conditions of magnetic agitation；
(2) molybdenum source and carbon source dissolving are spread in the solution of (1) step formation, ph is adjusted with three (methylol) aminomethanes
Value is 9~10；
(3) (2) step 180~220 DEG C of hydro-thermal reactions of progress in solution merging hydrothermal reaction kettle are formed to obtain containing forerunner
The graphene hydrogel of body；
(4) after being freeze-dried the obtained reaction product of (3) step, it is high at 800~900 DEG C to be passed through protective atmosphere
To get to molybdenum carbide/nitrogen sulphur codope sponge graphene composite material after warm processing；
In graphene adulterate N mass percentage be 4.0~10.0%, adulterate S mass percentage be 3.0~
8.0%；The particle size of molybdenum carbide is 20~100nm, and mass percentage is the composite material 30~70%.
The method for preparing molybdenum carbide/nitrogen sulphur codope sponge graphene composite material of the present invention further includes following preferred side
Case：
In preferred scheme the hydro-thermal reaction time be 10~for 24 hours.
In preferred scheme sublimation drying be 12~for 24 hours.
The mass ratio of nitrogen source, sulphur source and graphene oxide is 4 in preferred scheme:1~10:1.
It is 2 to contain molybdenum source and carbon source molar ratio in preferred scheme:1~5:1.
Nitrogen source, sulphur source in further preferred scheme used in nitrogen sulphur codope sponge graphene are thiocarbamide, 2- neighbour's amino
Benzenethiol.
Molybdenum source is ammonium tetramolybdate ((NH in further preferred scheme4)2Mo4O13·2H2) or ammonium paramolybdate ((NH O4)6Mo7O24·4H2O)。
Carbon source is aniline or glucose in further preferred scheme.
Further preferably the nitrogen sulphur, which is co-doped with graphene oxide solution, is added in graphene oxide solution by thiocarbamide
By being stirred to obtain strongly.
Hydrothermal temperature further preferably in the step (3) is 180~200 DEG C.
Further preferably the high-temperature heat treatment time described in the step (4) is 5~12h.
In further preferred molybdenum carbide/nitrogen sulphur codope sponge graphene composite material molybdenum carbide be with ammonium paramolybdate,
Glucose is raw material, is made by hydro-thermal method combination subsequent heat treatment technique, the molybdenum carbide nanoparticle deposition of generation is grown in
In three-dimensional sponge shape graphene.
The most preferred scheme of the present invention is：First by thiocarbamide according to 4:1~10:1 mass ratio is in magnetic agitation condition
Lower fully dissolving is spread in the graphene oxide solution of Hummers methods preparation, and glucose, ammonium paramolybdate are fully secondly dissolved expansion
It dissipates in above-mentioned nitrogenous sulphur graphene oxide solution, is then allowed to fully dissolve under the conditions of magnetic agitation, mixed solution is used
It is 9~10 that three (methylol) aminomethanes, which adjust ph, and hydro-thermal reaction, the forerunner of synthesis are then carried out at a temperature of 180-200 DEG C
Body be embedded in graphene hydrogel in, finally, by reactant be freeze-dried 12~for 24 hours after, 800~900 DEG C progress high-temperature heat treatments,
Time is 5~12h, you can obtains molybdenum carbide/nitrogen sulphur codope sponge graphene composite material.
Graphene oxide solution used in the present invention is preferably to be prepared by improved Hummers methods.That is, by pure
Flaky graphite of the degree not less than 99.5% is added in the mixed solution of the concentrated sulfuric acid and phosphoric acid, after fully dispersed, maintains mixing molten
Between 0~5 DEG C potassium permanganate is added, and stir 2~4h, then 40~60 DEG C are warming up in water-bath in liquid temperature in batches,
10~16h of successive reaction under the conditions of magnetic agitation obtains mixed solution；Then, under condition of ice bath, slowly into mixture
Deionized water is added to be diluted, is carried out at the same time oxidation reaction, hydrogen peroxide, which is added, after the completion of reaction removes potassium permanganate, finally will
The mixing liquid of gained washes repeatedly with a large amount of deionized waters, centrifuge after be fitted into dialysis in dialysis bag obtain within 5~7 days it is pure
Graphene oxide solution.The concentration of graphene oxide in gained graphite oxide weak solution can be obtained by being calculated by heated drying.
The mass ratio of the flaky graphite and potassium permanganate is 1:6.
The volume ratio of the concentrated sulfuric acid and phosphoric acid is 7:1~5:1.
The solid-to-liquid ratio of the flaky graphite and the concentrated sulfuric acid is 2~5g:200~350mL.
Molybdenum carbide produced by the present invention/nitrogen sulphur codope sponge graphene composite material prepares sodium-ion battery cathode pole piece
Method：
First by molybdenum carbide/nitrogen sulphur codope sponge graphene composite material according to 8:1:1 mass ratio and conductive charcoal
Black (conductive agent) and sodium alginate (binder) are fully ground mixing, and a small amount of deionized water is then added dropwise through being fully ground mixing
Homogeneous liquid paste is formed later, is coated on copper foil matrix as test electrode, with metallic sodium electrode system as a comparison
At button cell, electrolyte is 1M NaClO4/EC:DMC(1:1)+5wt%FEC.
Inventor for the first time attempts molybdenum carbide as anode material of lithium-ion battery, but inventor has found, molybdenum carbide
There is certain reunion in preparation process, is unfavorable for the performance of material property.Therefore, inventor consider be added graphene oxide into
Prepared by row, but since grapheme material itself cannot carry out sodium ion embedding de-, cause the performance of the material of the present invention without more
The promotion of few essence.Therefore, inventor needs to look for the preparation for more suitably preparing sodium-ion battery molybdenum carbide negative material
Method.The doped source that inventor uses thiocarbamide as graphene is improved doping to graphene, increases graphene carbon interlamellar spacing
Meanwhile by the doping and reduction of graphene, the formation of molybdenum carbide presoma and its it is compounded in water-heat process with doped graphene
In synchronously complete；So that molybdenum carbide forerunner's physical efficiency is grown on the active site of N doping generation of graphene, molybdenum carbide
In graphene hydrogel after presoma insertion reduction, it is tightly combined with doped graphene and uniformly；By stone after hydro-thermal reaction is complete
The freeze-drying of black alkene hydrogel, obtained graphene has three-dimensional sponge shape structure, and combines follow-up heat treatment process, from into
Work(by the growth of molybdenum carbide nano particle uniform deposition in nitrogen sulphur codope sponge graphene, method through the invention can be with
So that molybdenum carbide is disperseed the performance for being evenly effectively facilitated molybdenum carbide performance in sponge graphene, and then greatly improves
The specific discharge capacity of carbon matrix material.In addition, inventor also found that the present invention uses three (hydroxyl first before hydro-thermal reaction by experiment
Base) aminomethane adjust ph values be 9~10, be conducive to molybdenum carbide and be distributed evenly in spongy graphene.Through the invention
Preparation method, to obtain that there is the anode material of lithium-ion battery of good high rate performance and long circulation life.
Therefore, method of the invention successfully provides a kind of molybdenum carbide/nitrogen sulphur for sodium-ion battery and is co-doped with for the first time
Miscellaneous sponge graphene anode material, the composite material are to be dispersed in nitrogen sulphur codope sponge by molybdenum carbide nano particle
The three dimensional composite structure constituted in graphene.
Composite material made from method through the invention can largely reduce molybdenum carbide in deintercalation sodium ion
The volume expansion generated in the process improves the high rate performance and stable circulation of electrode material under the premise of ensureing specific capacity
Performance, to compensate for the deficiency of single carbonization molybdenum material well.Technical solution of the present invention molybdenum carbide/nitrogen sulphur codope sponge
The preparation method of graphene composite material is simple, and this method preparation process flow is short, reproducible, of low cost, environmental-friendly.
Description of the drawings
【Fig. 1】X-ray for molybdenum carbide made from embodiment 1/nitrogen sulphur codope sponge graphene anode material is spread out
Penetrate collection of illustrative plates (XRD).
【Fig. 2】For the scanning electron microscope of molybdenum carbide made from embodiment 1/nitrogen sulphur codope sponge graphene anode material
Scheme (SEM).
【Fig. 3】For the assembling of molybdenum carbide made from embodiment 1/nitrogen sulphur codope sponge graphene anode material sodium from
The constant current charge-discharge performance map of sub- battery.
【Fig. 4】For the assembling of molybdenum carbide made from embodiment 1/nitrogen sulphur codope sponge graphene anode material sodium from
The high rate performance figure of sub- battery.
【Fig. 5】For the scanning electron microscope of molybdenum carbide made from comparative example 1/nitrogen sulphur codope sponge graphene anode material
Scheme (SEM).
【Fig. 6】For the scanning electron microscope of molybdenum carbide made from comparative example 2/nitrogen sulphur codope sponge graphene anode material
Scheme (SEM).
Specific implementation mode
Following embodiment is intended to be described in further details the content of present invention；And the protection domain of the claims in the present invention
It is not limited by the example.
Embodiment 1
The flaky graphite for weighing 3g purity 99.5% first, be added to mass fraction containing 350mL be 98% the concentrated sulfuric acid and
In the mixed solution for the phosphoric acid that 50mL mass fractions are 85%, 18g potassium permanganate is added portionwise and is aoxidized, by the mixed solution
Be maintained under 0 DEG C of condition of ice bath and stir 2h, be then heated in water-bath 45 DEG C under the conditions of magnetic agitation reaction 12h obtain
Mixed solution；Then, 400mL deionized waters are slowly added into mixture under condition of ice bath, are slowly added after reacting balance
Enter 20mL hydrogen peroxide and remove the complete potassium permanganate of unreacted, mixed solution color becomes glassy yellow later；Finally by gained
Mixed solution washes repeatedly with a large amount of deionized waters, centrifuge after be fitted into dialysis in dialysis bag and obtain within 5~7 days pure oxidation stone
Black alkene solution.A concentration of 5mg/ of graphene oxide in obtained graphite oxide weak solution can be obtained by being calculated by heated drying
mL。
The above-mentioned graphene oxide solutions of 10mL (graphene oxide content is 10 × 5mg/mL=50mg) are measured with graduated cylinder to fall
Enter in the beaker of 150mL magnetic agitation at ambient temperature.Then according to nitrogen source, sulphur source and graphene oxide mass ratio 4:1
Thiocarbamide 0.2g is weighed, is added in the graphite oxide weak solution stirred, after thiocarbamide and graphene oxide solution are sufficiently mixed
Continue stirring 1h and can be obtained nitrogenous sulphur graphene oxide solution.
It is 4 according to molybdenum source and carbon source mass ratio:1, ammonium paramolybdate 1.0g, glucose 0.25g are weighed respectively, and are successively added
Enter into 40mL deionized waters, it is molten that mixed solution is slowly added into above-mentioned nitrogenous sulphur graphene oxide under the conditions of magnetic agitation
It in liquid, is sufficiently stirred after dispersion 1h, it is 10 that three (methylol) aminomethanes of mixed solution, which are adjusted ph, is then transferred to hydro-thermal
In reaction kettle, hydro-thermal reaction 10h is carried out at a temperature of 180 DEG C, after product is freeze-dried 12h, places it in silica crucible
In, it is passed through argon gas and carries out high-temperature heat treatment, time 6h, you can obtain molybdenum carbide/nitrogen sulphur codope sponge graphene in 800 DEG C
Composite material.
Using molybdenum carbide manufactured in the present embodiment/nitrogen sulphur codope sponge graphene composite material, molybdenum carbide nano particle
Evenly dispersed to be grown in nitrogen sulphur codope sponge graphene, granular size is 40~80nm.
Button cell, material table are assembled into using sodium-ion battery composite negative pole material manufactured in the present embodiment and sodium piece
Chemical property of seeking peace is as shown in the picture：
Can be seen that in Fig. 1 in molybdenum carbide/nitrogen sulphur codope sponge graphene anode material the position of each diffraction maximum and
Relative intensity matches with JCPDS (Joint Committee on Powder Diffraction Standards) card (35-0787), shows that product is hexagonal crystal
The Mo of system2C crystal.
It can be seen that molybdenum carbide nano particle homoepitaxial in nitrogen sulphur codope sponge graphene in Fig. 2.
Show, using electrode made of molybdenum carbide/nitrogen sulphur codope sponge graphene composite material, at room temperature to exist in Fig. 3
When 100mA/g constant-current discharges, 100 circle specific capacity of cycle may remain in 136mA h/g；Show good cycle performance.
Show in Fig. 4 using the corresponding battery of electrode made of molybdenum carbide/nitrogen sulphur codope sponge graphene composite material
High rate performance figure under different discharge-rates, it can be found that the composite material has excellent high rate performance, in big multiplying power
Under 1000mA/g, capacity may remain in 120mA h/g, and capacity is restored to again after current density returns to 50mA/g by high current
180mAh/g。
Embodiment 2
The above-mentioned graphene oxide solutions of 10mL (graphene oxide content is 10 × 5mg/mL=50mg) are measured with graduated cylinder to fall
Enter in the beaker of 150mL magnetic agitation at ambient temperature.Then according to nitrogen source sulphur source and graphene oxide mass ratio 6:1 claims
Thiocarbamide 0.3g is taken, is added in the graphite oxide weak solution stirred, it is subsequent to wait for that thiocarbamide and graphene oxide solution are sufficiently mixed
Continuous stirring 1h can be obtained nitrogenous sulphur graphene oxide solution.
It is 4 according to molybdenum source and carbon source mass ratio:1, ammonium paramolybdate 1.0g, glucose 0.25g are weighed respectively, and are successively added
Enter into 40mL deionized waters, it is molten that mixed solution is slowly added into above-mentioned nitrogenous sulphur graphene oxide under the conditions of magnetic agitation
It in liquid, is sufficiently stirred after dispersion 1h, it is 10 that three (methylol) aminomethanes of mixed solution, which are adjusted ph, is then transferred to hydro-thermal
In reaction kettle, hydro-thermal reaction 10h is carried out at a temperature of 180 DEG C, after product is freeze-dried 12h, places it in silica crucible
In, it is passed through argon gas and carries out high-temperature heat treatment, time 12h, you can obtain molybdenum carbide/nitrogen sulphur codope sponge graphite in 800 DEG C
Alkene composite material.
Using molybdenum carbide manufactured in the present embodiment/nitrogen sulphur codope sponge graphene composite material, molybdenum carbide nano particle
Evenly dispersed to be grown in nitrogen sulphur codope sponge graphene, granular size is 40~90nm.
It is accordingly electric using electrode made of molybdenum carbide manufactured in the present embodiment/nitrogen sulphur codope sponge graphene composite material
At room temperature, when with 100mA/g constant-current discharges, 100 circle specific capacity of cycle may remain in 140mA h/g in pond；It shows good
Cycle performance.
Embodiment 3
The above-mentioned graphene oxide solutions of 10mL (graphene oxide content is 10 × 5mg/mL=50mg) are measured with graduated cylinder to fall
Enter in the beaker of 150mL magnetic agitation at ambient temperature.Then according to nitrogen source sulphur source and graphene oxide mass ratio 8:1 claims
Thiocarbamide 0.4g is taken, is added in the graphite oxide weak solution stirred, it is subsequent to wait for that thiocarbamide and graphene oxide solution are sufficiently mixed
Continuous stirring 1h can be obtained nitrogenous sulphur graphene oxide solution.
It is 2 according to molybdenum source and carbon source mass ratio:1, ammonium paramolybdate 1.0g, glucose 0.5g are weighed respectively, and are successively added
Enter into 40mL deionized waters, it is molten that mixed solution is slowly added into above-mentioned nitrogenous sulphur graphene oxide under the conditions of magnetic agitation
It in liquid, is sufficiently stirred after dispersion 1h, it is 10 that three (methylol) aminomethanes of mixed solution, which are adjusted ph, is then transferred to hydro-thermal
In reaction kettle, hydro-thermal reaction 15h is carried out at a temperature of 200 DEG C, after product is freeze-dried 12h, places it in silica crucible
In, it is passed through argon gas and carries out high-temperature heat treatment, time 6h, you can obtain molybdenum carbide/nitrogen sulphur codope sponge graphene in 800 DEG C
Composite material.
Using molybdenum carbide manufactured in the present embodiment/nitrogen sulphur codope sponge graphene composite material, molybdenum carbide nano particle
Evenly dispersed to be grown in nitrogen sulphur codope sponge graphene, granular size is 30~80nm.
It is accordingly electric using electrode made of molybdenum carbide manufactured in the present embodiment/nitrogen sulphur codope sponge graphene composite material
At room temperature, when with 100mA/g constant-current discharges, 100 circle specific capacity of cycle may remain in 126mA h/g in pond；It shows good
Cycle performance.
Embodiment 4
The above-mentioned graphene oxide solutions of 10mL (graphene oxide content is 10 × 5mg/mL=50mg) are measured with graduated cylinder to fall
Enter in the beaker of 150mL magnetic agitation at ambient temperature.Then according to nitrogen source sulphur source and graphene oxide mass ratio 10:1
Thiocarbamide 0.5g is weighed, is added in the graphite oxide weak solution stirred, after thiocarbamide and graphene oxide solution are sufficiently mixed
Continue stirring 1h and can be obtained nitrogenous sulphur graphene oxide solution.
It is 5 according to molybdenum source and carbon source mass ratio:1, ammonium paramolybdate 1.0g, glucose 0.2g are weighed respectively, and are successively added
Enter into 40mL deionized waters, it is molten that mixed solution is slowly added into above-mentioned nitrogenous sulphur graphene oxide under the conditions of magnetic agitation
It in liquid, is sufficiently stirred after dispersion 1h, it is 9 that three (methylol) aminomethanes of mixed solution, which are adjusted ph, is then transferred to hydro-thermal
In reaction kettle, hydro-thermal reaction 10h is carried out at a temperature of 200 DEG C, after the freeze-drying for 24 hours of anti-product, places it in quartzy earthenware
In crucible, it is passed through argon gas and carries out high-temperature heat treatment, time 6h, you can obtain molybdenum carbide/nitrogen sulphur codope sponge graphite in 900 DEG C
Alkene composite material.
Using molybdenum carbide manufactured in the present embodiment/nitrogen sulphur codope sponge graphene composite material, molybdenum carbide nano particle
Evenly dispersed to be grown in nitrogen sulphur codope sponge graphene, granular size is 30~100nm.
It is accordingly electric using electrode made of molybdenum carbide manufactured in the present embodiment/nitrogen sulphur codope sponge graphene composite material
At room temperature, when with 100mA/g constant-current discharges, 100 circle specific capacity of cycle may remain in 130mA h/g in pond；It shows good
Cycle performance.
Embodiment 5
The above-mentioned graphene oxide solutions of 10mL (graphene oxide content is 10 × 5mg/mL=50mg) are measured with graduated cylinder to fall
Enter in the beaker of 150mL magnetic agitation at ambient temperature.Then according to nitrogen source sulphur source and graphene oxide mass ratio 4:1 claims
Thiocarbamide 0.2g is taken, is added in the graphite oxide weak solution stirred, it is subsequent to wait for that thiocarbamide and graphene oxide solution are sufficiently mixed
Continuous stirring 1h can be obtained nitrogenous sulphur graphene oxide solution.
It is 2 according to molybdenum source and carbon source mass ratio:1, ammonium paramolybdate 1.0g, glucose 0.5g are weighed respectively, and are successively added
Enter into 40mL deionized waters, it is molten that mixed solution is slowly added into above-mentioned nitrogenous sulphur graphene oxide under the conditions of magnetic agitation
It in liquid, is sufficiently stirred after dispersion 1h, it is 9 that three (methylol) aminomethanes of mixed solution, which are adjusted ph, is then transferred to hydro-thermal
In reaction kettle, hydro-thermal reaction is carried out for 24 hours at a temperature of 180 DEG C, after product freeze-drying for 24 hours, places it in silica crucible
In, it is passed through argon gas and carries out high-temperature heat treatment, time 12h, you can obtain molybdenum carbide/nitrogen sulphur codope sponge graphite in 900 DEG C
Alkene composite material.
Using molybdenum carbide manufactured in the present embodiment/nitrogen sulphur codope sponge graphene composite material, molybdenum carbide nano particle
Evenly dispersed to be grown in nitrogen sulphur codope sponge graphene, granular size is 20~60nm.
It is accordingly electric using electrode made of molybdenum carbide manufactured in the present embodiment/nitrogen sulphur codope sponge graphene composite material
At room temperature, when with 100mA/g constant-current discharges, 100 circle specific capacity of cycle may remain in 130mA h/g in pond；It shows good
Cycle performance.
Comparative example 1
The above-mentioned graphene oxide solutions of 10mL (graphene oxide content is 10 × 5mg/mL=50mg) are measured with graduated cylinder to fall
Enter in the beaker of 150mL magnetic agitation at ambient temperature.Then according to nitrogen source, sulphur source and graphene oxide mass ratio 4:1
Thiocarbamide 0.2g is weighed, is added in the graphite oxide weak solution stirred, after thiocarbamide and graphene oxide solution are sufficiently mixed
Continue stirring 1h and can be obtained nitrogenous sulphur graphene oxide solution.
It is 4 according to molybdenum source and carbon source mass ratio:1, ammonium paramolybdate 1.0g, glucose 0.25g are weighed respectively, and are successively added
Enter into 40mL deionized waters, it is molten that mixed solution is slowly added into above-mentioned nitrogenous sulphur graphene oxide under the conditions of magnetic agitation
It in liquid, is sufficiently stirred after dispersion 1h, it is 10 that mixed solution ammonium hydroxide, which is adjusted ph, is then transferred in hydrothermal reaction kettle, 180
At a temperature of DEG C carry out hydro-thermal reaction 10h, by product freeze-drying for 24 hours after, product is placed in silica crucible, be passed through argon gas in
800 DEG C of progress high-temperature heat treatments, time 6h, you can obtain molybdenum carbide/nitrogen sulphur codope sponge graphene composite material.
Molybdenum carbide/nitrogen sulphur codope sponge the graphene composite material prepared using this comparative example, material characterization such as Fig. 5
It is shown：
It can be seen that spongy graphene pattern is uneven and more mixed and disorderly in Fig. 5.
Comparative example 2
The above-mentioned graphene oxide solutions of 10mL (graphene oxide content is 10 × 5mg/mL=50mg) are measured with graduated cylinder to fall
Enter in the beaker of 150mL magnetic agitation at ambient temperature.Then according to nitrogen source, sulphur source and graphene oxide mass ratio 4:1
Thiocarbamide 0.2g is weighed, is added in the graphite oxide weak solution stirred, after thiocarbamide and graphene oxide solution are sufficiently mixed
Continue stirring 1h and can be obtained nitrogenous sulphur graphene oxide solution.
It is 4 according to molybdenum source and carbon source mass ratio:1, ammonium paramolybdate 1.0g, glucose 0.25g are weighed respectively, and are successively added
Enter into 40mL deionized waters, it is molten that mixed solution is slowly added into above-mentioned nitrogenous sulphur graphene oxide under the conditions of magnetic agitation
In liquid, it is sufficiently stirred after dispersion 1h, mixed solution is transferred in hydrothermal reaction kettle, hydro-thermal reaction is carried out at a temperature of 180 DEG C
Product is placed in silica crucible by 10h after product freeze-drying for 24 hours, is passed through argon gas and is carried out high-temperature heat treatment in 800 DEG C,
Time is 6h, you can obtains molybdenum carbide/nitrogen sulphur codope sponge graphene composite material.
Molybdenum carbide/nitrogen sulphur codope sponge the graphene composite material prepared using this comparative example, material characterization such as Fig. 6
It is shown：
It can be seen that spongy graphene layer and interlayer spacing are smaller in Fig. 6, do not form spongelike structure well.
Claims (9)
1. a kind of preparation method of molybdenum carbide/nitrogen sulphur codope sponge graphene anode material for sodium-ion battery,
It is characterized by comprising the following steps：
（1）By thiocarbamide, fully dissolving is spread in graphene oxide solution under the conditions of magnetic agitation；
（2）Molybdenum source and carbon source dissolving are spread in（1）It walks in the solution formed, with three（Methylol）Aminomethane adjusts pH value
It is 9 ~ 10；
（3）It will（2）Step forms 180 ~ 220 DEG C of hydro-thermal reactions of progress in solution merging hydrothermal reaction kettle and obtains containing presoma
Graphene hydrogel；
（4）It will（3）It walks after obtained reaction product is freeze-dried, is passed through protective atmosphere high temperature at 800 ~ 900 DEG C
To get to molybdenum carbide/nitrogen sulphur codope sponge graphene composite material after heat treatment；
The mass percentage that N is adulterated in graphene is 4.0 ~ 10.0 %, and the mass percentage for adulterating S is 3.0 ~ 8.0 %；Carbon
The particle size for changing molybdenum is 20 ~ 100 nm, and mass percentage is the 30 ~ 70% of the composite material.
2. preparation method according to claim 1, it is characterised in that：The mass ratio of the thiocarbamide and graphene oxide
It is 4:1~10:1.
3. preparation method according to claim 1, it is characterised in that：The step（2）Middle molybdenum source and carbon source molar ratio
It is 2:1~5:1.
4. preparation method according to claim 1, it is characterised in that：The step（3）In hydrothermal temperature be
180~200 ℃。
5. preparation method according to claim 1, it is characterised in that：The molybdenum source is ammonium tetramolybdate, ammonium paramolybdate, second
The one or more of acyl acetone molybdenum；The carbon source is one or more of aniline, o-phenylenediamine, glucose.
6. according to claim 1-5 any one of them preparation methods, the hydro-thermal reaction time is 10 ~ for 24 hours.
7. according to claim 1-5 any one of them preparation methods, it is characterised in that：The step（4）Described in freeze
Drying time be 12 ~ for 24 hours.
8. according to claim 1-5 any one of them preparation methods, it is characterised in that：The logical protective atmosphere of high-temperature heat treatment institute is
Argon gas, reaction time are 5 ~ 12h.
9. preparation method according to claim 1, it is characterised in that：（1）First by thiocarbamide according to 4:1~10:1 quality
Fully dissolving is spread in graphene oxide solution prepared by Hummers methods to ratio under the conditions of magnetic agitation；（2）Secondly by grape
Sugar, ammonium paramolybdate are fully dissolved and are spread in（1）It walks in the solution formed, is then allowed to fully dissolve under the conditions of magnetic agitation,
By mixed solution with three（Methylol）It is 9 ~ 10 that aminomethane, which adjusts pH,；（3）Then hydro-thermal is carried out at a temperature of 180-200 DEG C
Reaction 10 ~ for 24 hours, in the presoma insertion graphene hydrogel of synthesis；（4）Finally, by reactant be freeze-dried 12 ~ for 24 hours after,
800 ~ 900 DEG C of progress high-temperature heat treatments, time are 5 ~ 12h, you can it is compound to obtain molybdenum carbide/nitrogen sulphur codope sponge graphene
Material.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104409706A (en) * | 2014-12-22 | 2015-03-11 | 湖南大学 | Molybdenum disulfide/sulfur-and-nitrogen-doped graphene nanosheet composite material as well as preparation method and application thereof |
| CN104835945A (en) * | 2015-05-21 | 2015-08-12 | 哈尔滨理工大学 | Preparation method of graphene/molybdenum carbide composite cathode material |
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2015
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| CN104409706A (en) * | 2014-12-22 | 2015-03-11 | 湖南大学 | Molybdenum disulfide/sulfur-and-nitrogen-doped graphene nanosheet composite material as well as preparation method and application thereof |
| CN104835945A (en) * | 2015-05-21 | 2015-08-12 | 哈尔滨理工大学 | Preparation method of graphene/molybdenum carbide composite cathode material |
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