CN105870417B - A kind of preparation method of sodium-ion battery tungsten disulfide/carbon nanometer tube negative pole composite - Google Patents
A kind of preparation method of sodium-ion battery tungsten disulfide/carbon nanometer tube negative pole composite Download PDFInfo
- Publication number
- CN105870417B CN105870417B CN201610269270.1A CN201610269270A CN105870417B CN 105870417 B CN105870417 B CN 105870417B CN 201610269270 A CN201610269270 A CN 201610269270A CN 105870417 B CN105870417 B CN 105870417B
- Authority
- CN
- China
- Prior art keywords
- tungsten
- tungsten disulfide
- area
- preparation
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of preparation method of sodium-ion battery tungsten disulfide/carbon nano tube compound material, tungsten source and CNT are respectively placed in the windward area of double temperature-area tubular furnaces first and leeward area is heated, tungsten source is decomposed at high temperature to be deposited on CNT, obtain tungsten oxide/carbon nanotube complex, then it is put into hydrothermal reaction kettle with elemental sulfur, reducing agent and reacted, reaction precipitate deionized water and absolute ethyl alcohol are filtered, wash, dried, calcining, that is, obtain high-purity tungsten disulfide/carbon nano tube compound material.Tungsten disulfide/carbon nano tube compound material prepared by this method, tungsten disulfide nano slices are evenly distributed on CNT, have excellent chemical property as anode material of lithium-ion battery, and its preparation method is simple, cost is cheap, has wide industrial applications prospect.
Description
Technical field
The present invention relates to a kind of anode material of lithium-ion battery and preparation method thereof, belongs to sodium-ion battery field.
Background technology
Lithium ion battery produces as a kind of electrochemical energy storing device for occupying social leading position in portable electronic
Achieved in product (notebook computer, intelligent mobile equipment, tablet personal computer etc.), electric automobile and instant-plugging hybrid-power electric vehicle
Good application prospect.However, due to the limitations such as the scarcity of metal lithium resource and the high cost of lithium ion battery because
The presence of element, the large-scale commercial application of lithium ion battery are faced with acid test.This means that research and development can be big
Scale commercial, the battery system of commercial application are imperative.Metallic sodium is in same main group with lithium in the periodic table of elements,
It has the physicochemical properties similar with lithium metal, meanwhile, sodium-ion battery is abundant, environment-friendly due to sodium resource reserves
Extensive concern is received, the research and development of sodium-ion battery can relax the battery hair triggered by lithium resource shortage to a certain extent
Open up limitation problem, it is considered to be substitute lithium ion battery and match somebody with somebody as electric powered motor power supply of future generation and extensive energy-accumulating power station
The ideal chose of stand-by power source.However, sodium-ion battery is also faced with many problems, for example, sodium ion ionic radius than lithium from
The ionic radius of son is big by 55% so that sodium ion is embedded in more difficult than lithium ion with abjection in electrode material.Therefore, at present
The ultimate challenge that sodium-ion battery development faces is the research and development of electrode material system.
In past tens year, researcher the positive electrode of sodium-ion battery has been carried out it is widely studied, but
Research to anode material of lithium-ion battery is still at an early stage.In existing negative material system, carbon material possesses good
Good cyclical stability, but its specific discharge capacity is relatively low (is less than 300mA hg-1), it is impossible to meet height ratio capacity sodium-ion battery business
The requirement of industryization application.The experimental results show that transient metal sulfide is in superconductor, infrared electro device, lithium-ion electric
The field such as pond negative material and solar cell is widely used, and tungsten disulfide is because it is with similar with graphene
Layer structure, synthesis technique is simple, even more causes the extensive concern of scientific worker.Meanwhile tungsten disulfide is as sodium ion
Cell negative electrode material also has higher initial specific capacities, but because itself electrons/ions electrical conductivity is relatively low, so as to reduce
Its high rate performance as electrode material；Further, since it can produce serious volumetric expansion during deintercalation sodium ion,
So as to significantly reduce its cyclical stability as electrode material.Therefore how to improve the high rate performance of tungsten disulfide and follow
Ring stability, the key issue studied into tungsten disulfide as anode material of lithium-ion battery.
The content of the invention
The invention provides a kind of technique is simple, cost of material is low, it is reproducible, workable, be advantageous to industrialize
Large-scale production, obtained product have the sodium ion electricity of high charge-discharge specific capacity, good high rate performance and stable circulation performance
The preparation method of the tungsten disulfide in pond/carbon nanometer tube negative pole composite.
By multiple by tungsten disulfide/carbon nanometer tube negative pole for sodium-ion battery obtained by the above method by the present invention
Condensation material composite, the composite are that the composite junction formed on CNT is evenly coated at by tungsten disulfide nano slices
Structure.
The method of the present invention：Comprise the following steps：
(1) tungsten source and CNT are respectively placed in the windward area of double temperature-area tubular furnaces and leeward area is heated, aoxidized
Tungsten/carbon nanotube precursor；Described windward area temperature is 800~1000 DEG C, 50~150 DEG C described of leeward area temperature.
(2) elemental sulfur, reducing agent and the compound obtained by above-mentioned (1) step are sufficiently stirred laggard water-filling thermal response；Hydro-thermal
Reaction temperature：180~250 DEG C；
(3) the hydro-thermal reaction product obtained by (2) step is uniformly wrapped through calcining except desulfuration produces tungsten disulfide nano slices
Sodium-ion battery tungsten disulfide/carbon nanometer tube negative pole composite of CNT is overlayed on, wherein, calcining heat is 250~350
℃。
The method for preparing tungsten disulfide/carbon nanometer tube negative pole composite of the present invention also includes following preferred scheme：
Heating is that CNT is placed in into leeward area, slumpability gas atmosphere in double temperature-area tubular furnaces in preferable scheme
Under enclosing, 50~100 DEG C are risen to 1~10 DEG C/min, tungsten source is placed in windward area, when when leeward area, temperature rises to setting value, with
10~20 DEG C/min heating rate rises to 900~1000 DEG C, is incubated 60~120min, 30~70sccm of gas flow rate.
Hydro-thermal reaction time control is in 18~36h, more preferably 24~36h in preferable scheme.
In preferred embodiments of the present invention in Muffle furnace calcining be by hydrothermal product in argon gas with 1~10 DEG C/min liter
Warm speed rises to 250~350 DEG C, is incubated 30~120min, is more preferably incubated 30~120min.
The mass ratio of tungsten source and CNT is 5 in preferable scheme:1~20:1, more preferably 10:1~20:1.
The mass ratio of sulphur powder and tungsten oxide/carbon nanotube complex is 3 in preferable scheme:1~10:1, more preferably 5:
1~10:1.
The concentration of tungsten oxide/carbon nanotube complex suspension is 1~3g/L in preferable scheme.
The time of sulphur source and tungsten oxide/carbon nanotube complex suspension ultrasound is 2~5h in preferable scheme.
Tungsten source is ammonium phosphotungstate or ammonium tungstate in further preferred scheme.
Tungsten disulfide/carbon nanometer tube negative pole composite that inventor's discovery is prepared by the method for the present invention has good
Good high charge-discharge specific capacity, good high rate performance and stable circulation performance
50~800nm of particle diameter of composite of the present invention, the thickness of tungsten disulfide nano slices is 5~15nm.
In preferable scheme in tungsten disulfide/carbon nano tube compound material, the weight/mass percentage composition of tungsten disulfide for 50~
80%.
Preparation method of the invention specific be by tungsten source and CNT be respectively placed in double temperature-area tubular furnaces windward area and
Leeward area is heated, and obtains tungsten oxide/carbon nanometer tube composite materials presoma；Then by excessive elemental sulfur, reducing agent and above-mentioned institute
The composite material precursor obtained carries out hydro-thermal reaction after being sufficiently stirred at 180~250 DEG C；Finally by resulting hydro-thermal reaction
It is compound except desulfuration produces high-purity sodium-ion battery tungsten disulfide/carbon nanometer tube negative pole that product is placed in low temperature calcination in Muffle furnace
Material.
It by mass ratio is 10 that most preferred scheme, which is,:1~20:1 phosphotungstic acid amine and CNT is respectively placed in dual temperature area
The windward area and leeward area of tube furnace, after after leeward area, temperature rises to 50~100 DEG C, windward area is with 10~20 DEG C/min speed
900~1000 DEG C are risen to, is incubated 60~120min.Then by sulphur powder and above-mentioned leeward area product according to 5:1-10:1 mass ratio
Volume ratio is dispersed in as 1:In 1 octylame, alcoholic solution, 24~36h of reaction at 200~250 DEG C is placed in water heating kettle.Finally
Above-mentioned hydro-thermal reaction product is placed in Muffle furnace, 60~120min of sintering soak at 250~350 DEG C.Obtain high-purity
Sodium-ion battery tungsten disulfide/carbon nanometer tube negative pole composite.
Tungsten disulfide/carbon nano tube compound material produced by the present invention prepares negative pole：Tungsten disulfide/CNT is compound
Material is with conductive black and sodium alginate binding agent according to 8:1:1 mass ratio is ground, after being sufficiently mixed add go from
Sub- water forms uniform pastel, and coated in test electrode is used as on copper foil, button cell is made using metallic sodium as to electrode,
Its electrolyte is 1M NaClO4/EC:DMC(1:1)+5wt.%FEC, charging and discharging currents density is used in test loop performance
200mA/g。
Advantage of the invention is that：
The present invention's prepares tungsten disulfide/operation is simple and reliable for carbon nano tube compound material method, reproducible, operable
Property it is strong, environment-friendly, cost is cheap, products therefrom purity is high, has wide industrial applications prospect.Inventor passes through tungsten
Source is respectively placed in the windward area of double temperature-area tubular furnaces and leeward area with CNT and heated before first preparing tungsten oxide/carbon nanotube
Body is driven, is then vulcanized again through hydro-thermal method, tungsten disulfide nano slices can be made more to be uniformly coated on carbon nano tube surface,
The composite uniformity obtained simultaneously is also more preferable, and by the way that the pattern of product can be better controled over upper type, repeatability
It is good, it is adapted to industrialized production.In addition, what inventor when research prepares tungsten oxide/carbon precursor body of Nano tube, began to use is single
Temperature-area tubular furnace, tungsten source are placed in diamond heating district center, and CNT is placed in leeward area, it has been found that is subsequently generated tungsten disulfide
Nanometer sheet is less, is unfavorable for the preparation of composite, has used double temperature-area tubular furnaces by further improving and controls upper and lower
The temperature in wind area finds that present invention gained composite can uniform apposition growth.As the composite wood obtained by the method for the present invention
Material, tungsten disulfide nano slices regular shape is uniform, and CNT not only effectively increases composite bodies as matrix material
The reaction active site of system, improves the electrons/ions electrical conductivity of electrode material, and largely alleviates tungsten disulfide
The caused Volume Changes during deintercalation sodium ion.As the composite obtained by the inventive method before height ratio capacity is ensured
Put, hence it is evident that improve the high rate performance and stable circulation performance of electrode material, can be prepared with height electric discharge specific volume
The sodium-ion battery of amount, excellent high rate performance and stable circulation performance.
Brief description of the drawings
【Fig. 1】For the X ray diffracting spectrum (XRD) of tungsten disulfide/carbon nano tube compound material made from embodiment 1；
【Fig. 2】For the scanning electron microscope (SEM) photograph (SEM) of tungsten oxide/carbon precursor body of Nano tube made from embodiment 1；
【Fig. 3】For the scanning electron microscope (SEM) photograph (SEM) of tungsten disulfide/carbon nano tube compound material made from embodiment 1；
【Fig. 4】Constant current for the sodium-ion battery of tungsten disulfide made from embodiment 1/carbon nano tube compound material assembling is filled
Discharge performance figure；
【Fig. 5】For the assembling of tungsten disulfide made from embodiment 1/carbon nano tube compound material sodium-ion battery it is forthright again
Can figure.
Embodiment
Following examples are intended to be described in further details present invention；And the protection domain of the claims in the present invention
It is not limited by the example.
Embodiment 1
Take 2g phosphotungstic acid amine to be placed in the windward area of double temperature-area tubular furnaces first, take 0.2g CNTs to be placed in leeward area, control
Inert gas flow velocity processed is 50sccm, and leeward area rises to 50 DEG C with 10 DEG C/min speed, after temperature rises to rated temperature, on
Wind area rises to 900 DEG C with 10 DEG C/min speed, is incubated 120min, the product in leeward area is that tungsten oxide/carbon nanotube is compound
Material.0.5g tungsten oxide/carbons nanometer tube composite materials and 2.5g sulphur powders are taken, it is 1 to add 200ml volume ratios:1 octylame, alcohol
Mixed liquor, ultrasonic 5h, it is subsequently placed in 60ml hydrothermal reaction kettles, hydro-thermal reaction 24h, then anti-by hydro-thermal under the conditions of 250 DEG C
Product is answered to wash through filtering, tungsten disulfide/carbon nano tube compound material of high-purity is obtained after vacuum drying.Take 0.5g above-mentioned
Product, it is placed in Muffle furnace, 300 DEG C of insulation 2h is risen to 5 DEG C/min speed, you can obtain tungsten disulfide/carbon of high-purity
Nanometer tube composite materials.
Button cell is assembled into using sodium-ion battery composite negative pole material manufactured in the present embodiment and sodium piece, its material table
Chemical property seek peace as shown in drawings：
Can be seen that in Fig. 1 in tungsten disulfide/carbon nano tube compound material the position of each diffraction maximum and relative intensity with
JCPDS (Joint Committee on Powder Diffraction Standards) card (08-0237) matches, and shows the curing that product is six side's prismatic crystal systems
Tungsten crystal.
It can be seen that tungsten oxide uniform deposition in carbon nano tube surface in Fig. 2.
Tungsten disulfide nano slices are uniformly attached to carbon nanometer after the vulcanization of tungsten oxide/carbon nanotube complex is can be seen that in Fig. 3
Pipe surface, particle diameter about 50~500nm of composite.
Show to use electrode made of tungsten disulfide/carbon nano tube compound material in Fig. 4, it is permanent in 200mA/g at room temperature
When banishing electricity, the circle specific capacity of circulation 100 may remain in 290mA h/g；Show good cycle performance.
Show in Fig. 5 using the corresponding battery of electrode made of tungsten disulfide/carbon nano tube compound material in different electric discharges
High rate performance figure under multiplying power, it can be found that the composite has excellent high rate performance, under big multiplying power 2000mA/g, hold
Amount may remain in 200mA h/g, and capacity returns to 305mA h/ again after current density slowly returns to 100mA/g by high current
g。
Embodiment 2
Take 3g phosphotungstic acid amine to be placed in the windward area of double temperature-area tubular furnaces first, take 0.2g CNTs to be placed in leeward area, control
Inert gas flow velocity processed is 50sccm, and leeward area rises to 50 DEG C with 10 DEG C/min speed, after temperature rises to rated temperature, on
Wind area rises to 900 DEG C with 10 DEG C/min speed, is incubated 120min, the product in leeward area is that tungsten oxide/carbon nanotube is compound
Material.0.5g tungsten oxide/carbons nanometer tube composite materials and 4g sulphur powders are taken, it is 1 to add 200ml volume ratios:1 octylame, alcohol mix
Liquid is closed, ultrasonic 5h, is subsequently placed in 60ml hydrothermal reaction kettles, the hydro-thermal reaction 24h under the conditions of 250 DEG C, then by hydro-thermal reaction
Product is through filtering, washing, and tungsten disulfide/carbon nano tube compound material of high-purity is obtained after vacuum drying.Take the above-mentioned productions of 0.5g
Thing, it is placed in Muffle furnace, 300 DEG C of insulation 2h is risen to 5 DEG C/min speed, you can the tungsten disulfide/carbon for obtaining high-purity is received
Mitron composite.The diameter of composite is about 100~500nm, and the thickness of tungsten disulfide nano slices is about 5~10nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, in 200mA/
Under g constant-current discharge density, the circle specific discharge capacity of circulation 100 may remain in 265mAh/g.
Embodiment 3
Take 4g phosphotungstic acid amine to be placed in the windward area of double temperature-area tubular furnaces first, take 0.2g CNTs to be placed in leeward area, control
Inert gas flow velocity processed is 50sccm, and leeward area rises to 50 DEG C with 10 DEG C/min speed, after temperature rises to rated temperature, on
Wind area rises to 900 DEG C with 10 DEG C/min speed, is incubated 120min, the product in leeward area is that tungsten oxide/carbon nanotube is compound
Material.0.5g tungsten oxide/carbons nanometer tube composite materials and 5g sulphur powders are taken, it is 1 to add 200ml volume ratios:1 octylame, alcohol mix
Liquid is closed, ultrasonic 5h, is subsequently placed in 60ml hydrothermal reaction kettles, the hydro-thermal reaction 24h under the conditions of 250 DEG C, then by hydro-thermal reaction
Product is through filtering, washing, and tungsten disulfide/carbon nano tube compound material of high-purity is obtained after vacuum drying.Take the above-mentioned productions of 0.5g
Thing, it is placed in Muffle furnace, 300 DEG C of insulation 2h is risen to 5 DEG C/min speed, you can the tungsten disulfide/carbon for obtaining high-purity is received
Mitron composite.The diameter of composite is about 50~600nm, and the thickness of tungsten disulfide nano slices is about 5~15nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, in 200mA/
Under g constant-current discharge density, the circle specific discharge capacity of circulation 100 may remain in 260mAh/g.
Embodiment 4
Take 2g phosphotungstic acid amine to be placed in the windward area of double temperature-area tubular furnaces first, take 0.2g CNTs to be placed in leeward area, control
Inert gas flow velocity processed is 70sccm, and leeward area rises to 50 DEG C with 10 DEG C/min speed, after temperature rises to rated temperature, on
Wind area rises to 900 DEG C with 10 DEG C/min speed, is incubated 120min, the product in leeward area is that tungsten oxide/carbon nanotube is compound
Material.0.5g tungsten oxide/carbons nanometer tube composite materials and 2.5g sulphur powders are taken, it is 1 to add 200ml volume ratios:1 octylame, alcohol
Mixed liquor, ultrasonic 5h, it is subsequently placed in 60ml hydrothermal reaction kettles, hydro-thermal reaction 36h, then anti-by hydro-thermal under the conditions of 250 DEG C
Product is answered to wash through filtering, tungsten disulfide/carbon nano tube compound material of high-purity is obtained after vacuum drying.Take 0.5g above-mentioned
Product, it is placed in Muffle furnace, 300 DEG C of insulation 2h is risen to 5 DEG C/min speed, you can obtain tungsten disulfide/carbon of high-purity
Nanometer tube composite materials.The diameter of composite is about 70~600nm, and the thickness of tungsten disulfide nano slices is about 10~15nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, in 200mA/
Under g constant-current discharge density, the circle specific discharge capacity of circulation 100 may remain in 275mAh/g.
Embodiment 5
Take 2g phosphotungstic acid amine to be placed in the windward area of double temperature-area tubular furnaces first, take 0.2g CNTs to be placed in leeward area, control
Inert gas flow velocity processed is 70sccm, and leeward area rises to 50 DEG C with 10 DEG C/min speed, after temperature rises to rated temperature, on
Wind area rises to 1000 DEG C with 20 DEG C/min speed, is incubated 120min, the product in leeward area is that tungsten oxide/carbon nanotube is compound
Material.0.5g tungsten oxide/carbons nanometer tube composite materials and 2.5g sulphur powders are taken, it is 1 to add 200ml volume ratios:1 octylame, alcohol
Mixed liquor, ultrasonic 5h, it is subsequently placed in 60ml hydrothermal reaction kettles, hydro-thermal reaction 36h, then anti-by hydro-thermal under the conditions of 250 DEG C
Product is answered to wash through filtering, tungsten disulfide/carbon nano tube compound material of high-purity is obtained after vacuum drying.Take 0.5g above-mentioned
Product, it is placed in Muffle furnace, 300 DEG C of insulation 2h is risen to 5 DEG C/min speed, you can obtain tungsten disulfide/carbon of high-purity
Nanometer tube composite materials.The diameter of composite is about 500~550nm, and the thickness of tungsten disulfide nano slices is about 5~12nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, in 200mA/
Under g constant-current discharge density, the circle specific discharge capacity of circulation 100 may remain in 280mAh/g.
Embodiment 6
Take 2g phosphotungstic acid amine to be placed in the windward area of double temperature-area tubular furnaces first, take 0.2g CNTs to be placed in leeward area, control
Inert gas flow velocity processed is 70sccm, and leeward area rises to 50 DEG C with 10 DEG C/min speed, after temperature rises to rated temperature, on
Wind area rises to 1000 DEG C with 10 DEG C/min speed, is incubated 60min, the product in leeward area is that tungsten oxide/carbon nanotube is compound
Material.0.5g tungsten oxide/carbons nanometer tube composite materials and 2.5g sulphur powders are taken, it is 1 to add 200ml volume ratios:1 octylame, alcohol
Mixed liquor, ultrasonic 5h, it is subsequently placed in 60ml hydrothermal reaction kettles, hydro-thermal reaction 36h, then anti-by hydro-thermal under the conditions of 200 DEG C
Product is answered washing, tungsten disulfide/carbon nano tube compound material to be obtained after vacuum drying through filtering.The above-mentioned products of 0.5g are taken, are placed in
In Muffle furnace, 300 DEG C of insulation 2h are risen to 5 DEG C/min speed, you can the tungsten disulfide/CNT for obtaining high-purity is compound
Material.The diameter of composite is about 60~600nm, and the thickness of tungsten disulfide nano slices is about 7~13nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, in 200mA/
Under g constant-current discharge density, the circle specific discharge capacity of circulation 100 may remain in 255mAh/g.
Comparative example 1
Take 3g phosphotungstic acid amine to be placed in the center of single warm formula tube furnace first, take 0.2g CNTs to be placed in single warm formula tube furnace
Leeward area, it is 50sccm to control inert gas flow velocity, rises to 900 DEG C with 10 DEG C/min speed, is incubated 120min, leeward area
Product be tungsten oxide/carbon nanometer tube composite materials.0.5g tungsten oxide/carbons nanometer tube composite materials and 4g sulphur powders are taken, are added
200ml volume ratios are 1:1 octylame, alcohol blend, ultrasonic 5h, are subsequently placed in 60ml hydrothermal reaction kettles, in 250 DEG C of conditions
Lower hydro-thermal reaction 24h, then by hydro-thermal reaction product through filtering, washing, the curing containing sulphur simple substance is obtained after vacuum drying
Tungsten/carbon nano tube compound material.The above-mentioned products of 0.5g are taken, are placed in Muffle furnace, 300 DEG C of insulations are risen to 5 DEG C/min speed
2h, obtain tungsten disulfide/carbon nano tube compound material.Through thermogravimetric analysis, the load capacity of tungsten disulfide is only 20% in compound.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, in 200mA/
Under g constant-current discharge density, the circle specific discharge capacity of circulation 100 is only 160mAh/g.
Claims (8)
- A kind of 1. preparation method of tungsten disulfide/carbon nanometer tube negative pole composite, it is characterised in that：Comprise the following steps：(1) tungsten source and CNT are respectively placed in the windward area and leeward area of double temperature-area tubular furnaces, slumpability atmosphere Under, heating, obtain tungsten oxide/carbon nanometer tube composite materials presoma；Wherein described windward area temperature is 800~1000 DEG C, under 50~150 DEG C of wind area temperature；Described tungsten source is phosphotungstic acid amine, ammonium tungstate, ammonium paratungstate, one kind in primary ammonium tungstate or several Kind；(2) presoma obtained by above-mentioned (1) step and sulphur powder, reducing agent are sufficiently stirred scattered laggard water-filling thermal response；Water Hot temperature is 180~250 DEG C；(3) by the product that above-mentioned hydro-thermal reaction obtains through filtering, wash, dry after calcining to can obtain tungsten disulfide nano slices equal Even tungsten disulfide/carbon nanometer tube negative pole the composite for being coated on CNT；Wherein described calcining heat is 250~350 ℃。
- 2. the method according to claim 1 for preparing tungsten disulfide/carbon nanometer tube negative pole composite, it is characterised in that： The mass ratio of tungsten source and CNT is 5 in described step (1):1~20:1.
- 3. the method according to claim 1 for preparing tungsten disulfide/carbon nanometer tube negative pole composite, it is characterised in that： The mass ratio of sulphur powder and tungsten oxide/carbon nanotube complex is 3 in described step (2):1~10:1.
- 4. preparation method according to claim 1, it is characterised in that：In step (1), in double temperature-area tubular furnaces heating be by CNT is placed in leeward area, under slumpability atmosphere, rises to 50~100 DEG C with 1~10 DEG C/min, tungsten source is placed in Wind area, when temperature rises to setting value when leeward area, 900~1000 DEG C are risen to 10~20 DEG C/min heating rate, insulation 60 ~120min, 30~70sccm of gas flow rate.
- 5. preparation method according to claim 1, it is characterised in that：The hydro-thermal reaction time 18 in described step (2)~ 36h；In described step (3) step, 30~120min of calcination time.
- 6. according to the preparation method described in any one of Claims 1 to 5, it is characterised in that：Described reducing agent is octylame, second two One or more in amine, hydrazine hydrate.
- 7. preparation method according to claim 1, it is characterised in that：Described composite particle diameter is 50-800nm, The thickness of tungsten disulfide nano slices is 5-15nm.
- 8. preparation method according to claim 1, it is characterised in that：Described tungsten disulfide/carbon nanotube composite In material, weight/mass percentage composition shared by tungsten disulfide is 50~80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610269270.1A CN105870417B (en) | 2016-04-27 | 2016-04-27 | A kind of preparation method of sodium-ion battery tungsten disulfide/carbon nanometer tube negative pole composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610269270.1A CN105870417B (en) | 2016-04-27 | 2016-04-27 | A kind of preparation method of sodium-ion battery tungsten disulfide/carbon nanometer tube negative pole composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105870417A CN105870417A (en) | 2016-08-17 |
| CN105870417B true CN105870417B (en) | 2018-02-23 |
Family
ID=56629406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610269270.1A Expired - Fee Related CN105870417B (en) | 2016-04-27 | 2016-04-27 | A kind of preparation method of sodium-ion battery tungsten disulfide/carbon nanometer tube negative pole composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105870417B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106744820B (en) * | 2016-12-26 | 2019-03-29 | 中国科学院金属研究所 | Laminated metal chalcogenide/carbon nano tube flexible composite film material of higher order structures and preparation |
| CN106981626B (en) * | 2017-04-20 | 2019-07-02 | 陕西科技大学 | A kind of preparation method of tungsten disulfide/Super P sodium-ion battery self-supporting cathode |
| CN109449411B (en) * | 2018-10-30 | 2020-12-01 | 陕西科技大学 | Method for synthesizing tungsten disulfide @ C composite electrode material in limited domain |
| CN109326787B (en) * | 2018-10-30 | 2021-08-10 | 陕西科技大学 | Preparation method of tungsten disulfide/GO composite electrode material |
| CN110526296A (en) * | 2019-09-26 | 2019-12-03 | 东华大学 | A kind of preparation method of the tungsten disulfide composite film electrode of doped carbon nanometer pipe |
| CN110880597A (en) * | 2019-11-28 | 2020-03-13 | 陕西科技大学 | Tungsten sulfide/CNTs @ C composite electrode material and preparation method thereof |
| CN111540889B (en) * | 2020-05-08 | 2022-04-08 | 珠海冠宇电池股份有限公司 | Silicon negative electrode material coated by double-layer coating layer and preparation method and application thereof |
| CN112125339B (en) * | 2020-09-17 | 2022-08-26 | 江西师范大学 | Method for forming tungsten oxide and carbon nanosheet composite sodium storage material with single crystal face |
| CN114628673A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Three-dimensional macroporous tungsten disulfide/carbon composite material and preparation method and application thereof |
| CN114639815A (en) * | 2022-04-08 | 2022-06-17 | 东莞市沃泰通新能源有限公司 | Preparation method of sodium ion battery negative electrode material, negative electrode sheet and sodium ion battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723464A (en) * | 2009-12-11 | 2010-06-09 | 中南大学 | Method for preparing mono-disperse tungsten disulfide nano slices |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201302798D0 (en) * | 2013-02-18 | 2013-04-03 | Univ Exeter | Manufacture of carbon nano-particles |
-
2016
- 2016-04-27 CN CN201610269270.1A patent/CN105870417B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723464A (en) * | 2009-12-11 | 2010-06-09 | 中南大学 | Method for preparing mono-disperse tungsten disulfide nano slices |
Non-Patent Citations (1)
| Title |
|---|
| Carbon nanotube hybrids with MoS2 and WS2 synthesized with control of crystal structure and morphology;Xin Li等;《CARBON》;20141230;第85卷;第168-175页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105870417A (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105870417B (en) | A kind of preparation method of sodium-ion battery tungsten disulfide/carbon nanometer tube negative pole composite | |
| CN103682302B (en) | The method of the nano-electrode material of atomization drying synchronized compound porous graphene parcel | |
| CN105762360A (en) | Graphene-silicon-coated composite negative electrode material and preparing method and application thereof | |
| CN103682327B (en) | Based on the lithium ion battery and preparation method thereof of the hollow porous nickel oxide composite material of N doping carbon-coating parcel | |
| CN108658119B (en) | Method for preparing copper sulfide nanosheet and compound thereof by low-temperature vulcanization technology and application | |
| WO2022021643A1 (en) | Novel lithium-ion battery negative electrode material and preparation method therefor | |
| CN108199011B (en) | Preparation method of lithium titanate negative electrode material | |
| CN102623677A (en) | Process for producing high capacity molybdenum dioxide/carbon cathode materials | |
| CN105789615A (en) | Modified lithium nickel cobalt manganese cathode material and preparation method thereof | |
| CN104733714B (en) | Modification method of lithium ion battery cathode material | |
| CN109148859A (en) | A kind of preparation method of double carbon-coating coated manganese oxide composite materials | |
| CN109616331A (en) | A kind of hud typed nickel hydroxide nano piece/manganese cobalt/cobalt oxide combination electrode material and preparation method thereof | |
| WO2022021641A1 (en) | Battery negative electrode material and preparation method therefor | |
| CN105609772A (en) | Method for preparing N, S-codoped graphene cathode material for lithium-sulfur battery by microwave method | |
| CN106410153A (en) | Titanium nitride-cladded nickel titanate composite material as well as preparation method and application thereof | |
| CN106115785B (en) | A kind of pure phase MoO2Anode material of lithium-ion battery and preparation method thereof | |
| CN104157858A (en) | Hierarchical porous ferroferric oxide / graphene nano wire and preparation method and application thereof | |
| CN103682277B (en) | Hollow porous nickel oxide composite material of N doping carbon-coating parcel and preparation method thereof | |
| CN109767928A (en) | The synthetic method and its application of Fluorin doped carbon coating silica nano particle@carbon nano tube compound material | |
| CN107819125A (en) | A kind of preparation method of straw bundle shape cobaltosic oxide and its application in lithium ion battery | |
| CN107732175A (en) | A kind of graphene and the common coated porous lithium titanate of nitrogen-doped carbon and preparation method thereof | |
| CN104803423A (en) | Preparation method and application of porous cobaltosic oxide material | |
| CN104810515A (en) | Preparation method of doped Li4Ti5O12 anode material | |
| CN104393275A (en) | Preparation method of carbon-coated lithium titanate battery material | |
| CN104577126A (en) | Method for preparing MWCNT@a-C@Co9S8 composite electrode material with uniform morphology and application of material in lithium electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180223 Termination date: 20210427 |