CN105870417A - Preparation method for tungsten disulfide/carbon nanotube negative electrode composite material of sodium ion battery - Google Patents
Preparation method for tungsten disulfide/carbon nanotube negative electrode composite material of sodium ion battery Download PDFInfo
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- CN105870417A CN105870417A CN201610269270.1A CN201610269270A CN105870417A CN 105870417 A CN105870417 A CN 105870417A CN 201610269270 A CN201610269270 A CN 201610269270A CN 105870417 A CN105870417 A CN 105870417A
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- 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
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- 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
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- 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
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- 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
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- 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
Disclosed is a preparation method for a tungsten disulfide/carbon nanotube negative electrode composite material of a sodium ion battery. The preparation method comprises the steps of putting a tungsten source and the carbon nanotubes into an upper air region and a lower air region of a dual-temperature-region tubular furnace to be heated; enabling the tungsten source to be decomposed and deposited to the carbon nanotubes under a high temperature to obtain a tungsten oxide/carbon nanotube compound; then putting the tungsten oxide/carbon nanotube compound, an elementary sulfur, and a reducing agent into a hydrothermal reaction kettle to be reacted; and then carrying out suction filtration on the reaction precipitates by deionized water and absolute ethyl alcohol, and then washing, drying and calcining the processed reaction precipitates to obtain the high-purity tungsten disulfide/carbon nanotube composite material. According to the tungsten disulfide/carbon nanotube composite material prepared by the method, the tungsten disulfide nanosheets are uniformly distributed on the carbon nanotubes; the composite material has an excellent electrochemical performance when the composite material is used as the negative electrode material of the sodium ion battery; and in addition, the tungsten disulfide/carbon nanotube negative electrode composite material is simple in preparation method, low in cost and bright in industrial application prospect.
Description
Technical field
The present invention relates to a kind of anode material of lithium-ion battery and preparation method thereof, belong to sodium-ion battery field.
Background technology
Lithium ion battery is as a kind of electrochemical energy storing device occupying society's leading position, at portable electric
Sub-product (notebook computer, intelligent mobile equipment, panel computer etc.), electric automobile and instant-plugging mixing are dynamic
Power electric motor car achieves good application prospect.But, due to scarcity and the lithium-ion electric of lithium metal resource
The existence of the limiting factors such as the cost that pond is high, the large-scale commercial application of lithium ion battery is faced with tight
High test.This mean that research and development can large-scale commercial, the battery system gesture of commercial application is must
OK.Metallic sodium and lithium are in same main group in the periodic table of elements, and it has the physical chemistry similar with lithium metal
Character, meanwhile, sodium-ion battery is owing to sodium resource reserves are abundant, environmental friendliness receives extensive concern, sodium
The research and development of ion battery can relax the battery caused because of lithium resource shortage to a certain extent and develop limited asking
Topic is it is considered to be substitute lithium ion battery and join as electric powered motor power supply of future generation and extensive energy-accumulating power station
The ideal chose of stand-by power source.But, sodium-ion battery is also faced with the ion half of many problem, such as sodium ion
Footpath bigger than the ionic radius of lithium ion 55% so that sodium ion embeds in electrode material and compares lithium ion with abjection
More difficult.Therefore, the ultimate challenge that the development of current sodium-ion battery faces is the research of electrode material system
Exploitation.
In time decades in past, the positive electrode of sodium-ion battery has been carried out and has extensively been ground by researcher
Study carefully, but the research to anode material of lithium-ion battery is still at an early stage.In existing negative material system,
Material with carbon element has good cyclical stability, but its specific discharge capacity is relatively low (less than 300mAhg-1), it is impossible to
Meet the requirement of height ratio capacity sodium-ion battery commercial applications.The experimental results shows, transition metal vulcanizes
Thing obtains extensively in fields such as superconductor, infrared electro device, lithium ion battery negative material and solaodes
Application, and tungsten disulfide has the layer structure similar with Graphene due to it, and synthesis technique is simple, especially
Cause the extensive concern of scientist.Meanwhile, tungsten disulfide also has as anode material of lithium-ion battery
Higher initial specific capacities, but owing to itself electrons/ions electrical conductivity is relatively low, thus reduce its conduct
The high rate performance of electrode material；Additionally, due to it can produce serious volumetric expansion during deintercalation sodium ion,
Thus significantly reduce its cyclical stability as electrode material.The most how to improve the multiplying power of tungsten disulfide
Performance and stable circulation performance, become the key issue that tungsten disulfide is studied as anode material of lithium-ion battery.
Summary of the invention
The invention provides that a kind of technique is simple, cost of material is low, reproducible, workable, be conducive to
Industrialization large-scale production, the product obtained has high charge-discharge specific capacity, good high rate performance and stable circulation
The preparation method of the tungsten disulfide of the sodium-ion battery of performance/carbon nanometer tube negative pole composite.
By being born by the tungsten disulfide/CNT for sodium-ion battery obtained by said method by the present invention
Pole composite material, this composite is to be evenly coated at structure on CNT by tungsten disulfide nano slices
The composite construction become.
The method of the present invention: comprise the following steps:
(1) tungsten source and CNT are respectively placed in windward district and the heating of leeward district of double temperature-area tubular furnace, obtain oxygen
Change tungsten/carbon nanotube precursor；Described windward district temperature is 800～1000 DEG C, described leeward district temperature
50～150 DEG C.
(2) hydro-thermal reaction is carried out after being sufficiently stirred for by the complex of elemental sulfur, reducing agent and above-mentioned (1) step gained；
Hydrothermal temperature: 180～250 DEG C；
(3) the hydro-thermal reaction product obtained by (2) step is i.e. obtained tungsten disulfide nano slices through calcining removing sulfur uniform
It is coated on the sodium-ion battery tungsten disulfide/carbon nanometer tube negative pole composite of CNT, wherein, calcining temperature
Degree is 250～350 DEG C.
The method preparing tungsten disulfide/carbon nanometer tube negative pole composite of the present invention also includes following preferred side
Case:
Preferably in scheme, in double temperature-area tubular furnaces, heating is that CNT is placed in leeward district, slumpability gas
Under body atmosphere, rise to 50～100 DEG C with 1～10 DEG C/min, tungsten source is placed in windward district, treat leeward district temperature
When rising to setting value, rise to 900～1000 DEG C with the heating rate of 10～20 DEG C/min, be incubated 60～120min,
Gas flow rate 30～70sccm.
Preferably in scheme, the hydro-thermal reaction time controls 18～36h, more preferably 24～36h.
In preferred embodiments of the present invention in Muffle furnace calcining be by hydrothermal product in argon with 1～10 DEG C/min
Heating rate rise to 250～350 DEG C, be incubated 30～120min, more preferably insulation 30～120min.
Preferably in scheme, the mass ratio of tungsten source and CNT is 5:1～20:1, more preferably 10:1～20:1.
Preferably in scheme, the mass ratio of sulfur powder and tungsten oxide/carbon nanotube complex is 3:1～10:1, more preferably
For 5:1～10:1.
Preferably in scheme, the concentration of tungsten oxide/carbon nanotube complex suspension is 1～3g/L.
The time that preferably in scheme, sulfur source is ultrasonic with tungsten oxide/carbon nanotube complex suspension is 2～5h.
In further preferred scheme, tungsten source is ammonium phosphotungstate or ammonium tungstate.
Inventor finds that the tungsten disulfide/carbon nanometer tube negative pole composite prepared by the method for the present invention is had
There are good high charge-discharge specific capacity, good high rate performance and stable circulation performance
The diameter 50～800nm of composite of the present invention, the thickness of tungsten disulfide nano slices is 5～15
nm。
Preferably in scheme in tungsten disulfide/carbon nano tube compound material, the weight/mass percentage composition of tungsten disulfide is
50～80%.
The preparation method that the present invention is concrete is the windward that tungsten source and CNT are respectively placed in double temperature-area tubular furnace
District and the heating of leeward district, obtain tungsten oxide/carbon nanometer tube composite materials presoma；Subsequently by excess elemental sulfur,
It is anti-that reducing agent carries out hydro-thermal after being sufficiently stirred for the composite material precursor of above-mentioned gained at 180～250 DEG C
Should；Finally obtained hydro-thermal reaction product is placed in low temperature calcination removing sulfur in Muffle furnace and i.e. obtains high-purity sodium
Ion battery tungsten disulfide/carbon nanometer tube negative pole composite.
Most preferably scheme is that phosphotungstic acid amine and CNT that mass ratio is 10:1～20:1 are respectively placed in dual temperature
The windward district of district's tube furnace and leeward district, after leeward district temperature rises to 50～100 DEG C, windward district with
The speed of 10～20 DEG C/min rises to 900～1000 DEG C, is incubated 60～120min.Subsequently by sulfur powder with above-mentioned under
It is in the octylame of 1:1, alcoholic solution that wind district product is dispersed in volume ratio according to the mass ratio of 5:1-10:1, is placed in
Water heating kettle reacts at 200～250 DEG C 24～36h.Finally above-mentioned hydro-thermal reaction product is placed in Muffle furnace,
Sintering soak 60～120min at 250～350 DEG C.I.e. obtain highly purified sodium-ion battery tungsten disulfide/carbon to receive
Mitron anode material.
Tungsten disulfide/carbon nano tube compound material that the present invention prepares prepares negative pole: by tungsten disulfide/CNT
Composite is ground according to the mass ratio of 8:1:1 with conductive black and sodium alginate binding agent, the most mixed
Add deionized water after conjunction and form uniform pastel, be coated on Copper Foil as test electrode, make with metallic sodium
For electrode is made button cell, its electrolyte is 1M NaClO4/ EC:DMC (1:1)+5wt.%FEC,
Charging and discharging currents density used by test loop performance is 200mA/g.
Present invention have an advantage that
The present invention prepares that tungsten disulfide/operation is simple and reliable for carbon nano tube compound material method, reproducible,
It is workable, environmental friendliness, with low cost, products therefrom purity is high, has wide industrial applications
Prospect.Inventor is respectively placed in windward district and the heating of leeward district of double temperature-area tubular furnace by tungsten source and CNT
First prepare tungsten oxide/carbon precursor body of Nano tube, vulcanize through hydro-thermal method the most again, it is possible to make tungsten disulfide
Nanometer sheet is more uniformly coated on carbon nano tube surface, and the composite concordance simultaneously obtained is also more preferable, and
By can better control over the pattern of product with upper type, reproducible, it is suitable for industrialized production.It addition,
Inventor is when tungsten oxide/carbon precursor body of Nano tube is prepared in research, and begin to use is single temperature-area tubular furnace, tungsten
Source is placed in diamond heating district center, and CNT is placed in leeward district, it has been found that be subsequently generated Wolfram disulfide nano
Sheet is less, is unfavorable for the preparation of composite, employs double temperature-area tubular furnace by further improving and controls
The temperature in upper and lower wind district finds that gained composite of the present invention can uniform apposition growth.By the method institute of the present invention
The composite prepared, tungsten disulfide nano slices regular shape is uniform, and CNT is as matrix material, not only
Effectively increase the reaction active site of composite system, improve the electrons/ions electrical conductivity of electrode material,
And alleviate the change in volume that tungsten disulfide produces during deintercalation sodium ion to a great extent.By this
The composite of bright method gained is on the premise of ensureing height ratio capacity, hence it is evident that improve the most forthright of electrode material
Can prepare with stable circulation performance there is high specific discharge capacity, excellent high rate performance and circulation
The sodium-ion battery of stability.
Accompanying drawing explanation
[Fig. 1] is the X ray diffracting spectrum of tungsten disulfide/carbon nano tube compound material that embodiment 1 prepares
(XRD)；
[Fig. 2] is the scanning electron microscope (SEM) photograph (SEM) of the tungsten oxide/carbon precursor body of Nano tube that embodiment 1 prepares；
[Fig. 3] is the scanning electron microscope (SEM) photograph (SEM) of tungsten disulfide/carbon nano tube compound material that embodiment 1 prepares；
[Fig. 4] is the constant current of the sodium-ion battery that tungsten disulfide/carbon nano tube compound material that embodiment 1 prepares assembles
Charge-discharge performance figure；
[Fig. 5] is the multiplying power of the sodium-ion battery that tungsten disulfide/carbon nano tube compound material that embodiment 1 prepares assembles
Performance map.
Detailed description of the invention
Following example are intended to be described in further details present invention；And the protection of the claims in the present invention
Scope is not limited by the example.
Embodiment 1
First take 2g phosphotungstic acid amine and be placed in the windward district of double temperature-area tubular furnace, take 0.2g CNT and be placed in down
Wind district, controlling noble gas flow velocity is 50sccm, and leeward district rises to 50 DEG C with the speed of 10 DEG C/min,
After temperature rises to rated temperature, windward district rises to 900 DEG C with the speed of 10 DEG C/min, is incubated 120min,
The product in leeward district is tungsten oxide/carbon nanometer tube composite materials.Take 0.5g tungsten oxide/carbon nanometer tube composite materials
With 2.5g sulfur powder, adding 200ml volume ratio is the octylame of 1:1, alcohol blend, and ultrasonic 5h, with rearmounted
In 60ml hydrothermal reaction kettle, 250 DEG C of Water Under thermal responses 24h, then by hydro-thermal reaction product warp
Sucking filtration, washing, obtain highly purified tungsten disulfide/carbon nano tube compound material after vacuum drying.Take on 0.5g
State product, be placed in Muffle furnace, rise to 300 DEG C of insulation 2h with the speed of 5 DEG C/min, i.e. can get high-purity
Tungsten disulfide/the carbon nano tube compound material of degree.
The sodium-ion battery composite negative pole material using the present embodiment to prepare is assembled into button cell with sodium sheet, its material
Material characterizes with chemical property as shown in drawings:
Fig. 1 can be seen that, position and the relative intensity of each diffraction maximum in tungsten disulfide/carbon nano tube compound material are equal
Match with JCPDS (JCPDS) card (08-0237), show that product is six sides
The tungsten disulfide crystal of prismatic crystal system.
Fig. 2 can be seen that, tungsten oxide uniform deposition is in carbon nano tube surface.
After can be seen that the sulfuration of tungsten oxide/carbon nanotube complex in Fig. 3, tungsten disulfide nano slices is uniformly attached to carbon
Nanotube surface, the diameter of composite about 50～500nm, the thickness of tungsten disulfide nano slices is about 5-15
nm。
Fig. 4 shows the electrode using tungsten disulfide/carbon nano tube compound material to make, at room temperature 200
During mA/g constant-current discharge, circulation 100 circle specific capacity may remain in 290mA h/g；Show good
Cycle performance.
Fig. 5 showing, the corresponding battery of electrode using tungsten disulfide/carbon nano tube compound material to make is in difference
High rate performance figure under discharge-rate, it appeared that this composite has excellent high rate performance, in big multiplying power
Under 2000mA/g, capacity may remain in 200mA h/g, when electric current density is slowly returned to 100 by big electric current
After mA/g, capacity returns to again 305mA h/g.
Embodiment 2
First take 3g phosphotungstic acid amine and be placed in the windward district of double temperature-area tubular furnace, take 0.2g CNT and be placed in down
Wind district, controlling noble gas flow velocity is 50sccm, and leeward district rises to 50 DEG C with the speed of 10 DEG C/min,
After temperature rises to rated temperature, windward district rises to 900 DEG C with the speed of 10 DEG C/min, is incubated 120min,
The product in leeward district is tungsten oxide/carbon nanometer tube composite materials.Take 0.5g tungsten oxide/carbon nanometer tube composite materials
With 4g sulfur powder, adding 200ml volume ratio is the octylame of 1:1, alcohol blend, and ultrasonic 5h, with rearmounted
In 60ml hydrothermal reaction kettle, 250 DEG C of Water Under thermal responses 24h, then by hydro-thermal reaction product warp
Sucking filtration, washing, obtain highly purified tungsten disulfide/carbon nano tube compound material after vacuum drying.Take on 0.5g
State product, be placed in Muffle furnace, rise to 300 DEG C of insulation 2h with the speed of 5 DEG C/min, i.e. can get high-purity
Tungsten disulfide/the carbon nano tube compound material of degree.The diameter of composite is about 100～500nm, tungsten disulfide
The thickness of nanometer sheet is about 5～10nm.
The sodium-ion battery anode material using the present embodiment to prepare is assembled into button cell with sodium sheet,
Under the constant-current discharge density of 200mA/g, circulation 100 circle specific discharge capacity may remain in 265mAh/g.
Embodiment 3
First take 4g phosphotungstic acid amine and be placed in the windward district of double temperature-area tubular furnace, take 0.2g CNT and be placed in down
Wind district, controlling noble gas flow velocity is 50sccm, and leeward district rises to 50 DEG C with the speed of 10 DEG C/min,
After temperature rises to rated temperature, windward district rises to 900 DEG C with the speed of 10 DEG C/min, is incubated 120min,
The product in leeward district is tungsten oxide/carbon nanometer tube composite materials.Take 0.5g tungsten oxide/carbon nanometer tube composite materials
With 5g sulfur powder, adding 200ml volume ratio is the octylame of 1:1, alcohol blend, and ultrasonic 5h, with rearmounted
In 60ml hydrothermal reaction kettle, 250 DEG C of Water Under thermal responses 24h, then by hydro-thermal reaction product warp
Sucking filtration, washing, obtain highly purified tungsten disulfide/carbon nano tube compound material after vacuum drying.Take on 0.5g
State product, be placed in Muffle furnace, rise to 300 DEG C of insulation 2h with the speed of 5 DEG C/min, i.e. can get high-purity
Tungsten disulfide/the carbon nano tube compound material of degree.The diameter of composite is about 50～600nm, and tungsten disulfide is received
The thickness of rice sheet is about 5～15nm.
The sodium-ion battery anode material using the present embodiment to prepare is assembled into button cell with sodium sheet,
Under the constant-current discharge density of 200mA/g, circulation 100 circle specific discharge capacity may remain in 260mAh/g.
Embodiment 4
First take 2g phosphotungstic acid amine and be placed in the windward district of double temperature-area tubular furnace, take 0.2g CNT and be placed in down
Wind district, controlling noble gas flow velocity is 70sccm, and leeward district rises to 50 DEG C with the speed of 10 DEG C/min,
After temperature rises to rated temperature, windward district rises to 900 DEG C with the speed of 10 DEG C/min, is incubated 120min,
The product in leeward district is tungsten oxide/carbon nanometer tube composite materials.Take 0.5g tungsten oxide/carbon nanometer tube composite materials
With 2.5g sulfur powder, adding 200ml volume ratio is the octylame of 1:1, alcohol blend, and ultrasonic 5h, with rearmounted
In 60ml hydrothermal reaction kettle, 250 DEG C of Water Under thermal responses 36h, then by hydro-thermal reaction product warp
Sucking filtration, washing, obtain highly purified tungsten disulfide/carbon nano tube compound material after vacuum drying.Take on 0.5g
State product, be placed in Muffle furnace, rise to 300 DEG C of insulation 2h with the speed of 5 DEG C/min, i.e. can get high-purity
Tungsten disulfide/the carbon nano tube compound material of degree.The diameter of composite is about 70～600nm, and tungsten disulfide is received
The thickness of rice sheet is about 10～15nm.
The sodium-ion battery anode material using the present embodiment to prepare is assembled into button cell with sodium sheet,
Under the constant-current discharge density of 200mA/g, circulation 100 circle specific discharge capacity may remain in 275mAh/g.
Embodiment 5
First take 2g phosphotungstic acid amine and be placed in the windward district of double temperature-area tubular furnace, take 0.2g CNT and be placed in down
Wind district, controlling noble gas flow velocity is 70sccm, and leeward district rises to 50 DEG C with the speed of 10 DEG C/min,
After temperature rises to rated temperature, windward district rises to 1000 DEG C with the speed of 20 DEG C/min, is incubated 120min,
The product in leeward district is tungsten oxide/carbon nanometer tube composite materials.Take 0.5g tungsten oxide/carbon nanometer tube composite materials
With 2.5g sulfur powder, adding 200ml volume ratio is the octylame of 1:1, alcohol blend, and ultrasonic 5h, with rearmounted
In 60ml hydrothermal reaction kettle, 250 DEG C of Water Under thermal responses 36h, then by hydro-thermal reaction product warp
Sucking filtration, washing, obtain highly purified tungsten disulfide/carbon nano tube compound material after vacuum drying.Take on 0.5g
State product, be placed in Muffle furnace, rise to 300 DEG C of insulation 2h with the speed of 5 DEG C/min, i.e. can get high-purity
Tungsten disulfide/the carbon nano tube compound material of degree.The diameter of composite is about 500～550nm, tungsten disulfide
The thickness of nanometer sheet is about 5～12nm.
The sodium-ion battery anode material using the present embodiment to prepare is assembled into button cell with sodium sheet,
Under the constant-current discharge density of 200mA/g, circulation 100 circle specific discharge capacity may remain in 280mAh/g.
Embodiment 6
First take 2g phosphotungstic acid amine and be placed in the windward district of double temperature-area tubular furnace, take 0.2g CNT and be placed in down
Wind district, controlling noble gas flow velocity is 70sccm, and leeward district rises to 50 DEG C with the speed of 10 DEG C/min,
After temperature rises to rated temperature, windward district rises to 1000 DEG C with the speed of 10 DEG C/min, is incubated 60min,
The product in leeward district is tungsten oxide/carbon nanometer tube composite materials.Take 0.5g tungsten oxide/carbon nanometer tube composite materials
With 2.5g sulfur powder, adding 200ml volume ratio is the octylame of 1:1, alcohol blend, and ultrasonic 5h, with rearmounted
In 60ml hydrothermal reaction kettle, 200 DEG C of Water Under thermal responses 36h, then by hydro-thermal reaction product warp
Sucking filtration, washing, obtain tungsten disulfide/carbon nano tube compound material after vacuum drying.Take the above-mentioned product of 0.5g,
It is placed in Muffle furnace, rises to 300 DEG C of insulation 2h with the speed of 5 DEG C/min, i.e. can get highly purified two sulfur
Change tungsten/carbon nano tube compound material.The diameter of composite is about 60～600nm, the thickness of tungsten disulfide nano slices
Degree is about 7～13nm.
The sodium-ion battery anode material using the present embodiment to prepare is assembled into button cell with sodium sheet,
Under the constant-current discharge density of 200mA/g, circulation 100 circle specific discharge capacity may remain in 255mAh/g.
Comparative example 1
First take 3g phosphotungstic acid amine and be placed in the central authorities of single temperature formula tube furnace, take 0.2g CNT and be placed in Dan Wen
The leeward district of formula tube furnace, controlling noble gas flow velocity is 50sccm, rises to the speed of 10 DEG C/min
900 DEG C, being incubated 120min, the product in leeward district is tungsten oxide/carbon nanometer tube composite materials.Take 0.5g
Tungsten oxide/carbon nanometer tube composite materials and 4g sulfur powder, adding 200ml volume ratio is the octylame of 1:1, ethanol
Mixed liquor, ultrasonic 5h, it is subsequently placed in 60ml hydrothermal reaction kettle, 250 DEG C of Water Under thermal responses 24
H, then by hydro-thermal reaction product through sucking filtration, washing, obtain after vacuum drying the tungsten disulfide containing sulfur simple substance/
Carbon nano tube compound material.Take the above-mentioned product of 0.5g, be placed in Muffle furnace, rise to the speed of 5 DEG C/min
300 DEG C of insulation 2h, obtain tungsten disulfide/carbon nano tube compound material.Two sulfur in thermogravimetric analysis, complex
The load capacity changing tungsten is only 20%.
The sodium-ion battery anode material using the present embodiment to prepare is assembled into button cell with sodium sheet,
Under the constant-current discharge density of 200mA/g, circulation 100 circle specific discharge capacity is only 160mAh/g.
Claims (9)
1. the 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 windward district and the heating of leeward district of double temperature-area tubular furnace, obtain oxygen
Change tungsten/carbon nano tube compound material presoma；Wherein said windward district temperature is 800～1000 DEG C, leeward district temperature
Spend 50～150 DEG C；
(2) water is carried out after the described presoma of above-mentioned (1) step gained and sulfur powder, reducing agent being sufficiently stirred for dispersion
Thermal response；Hydrothermal temperature is 180～250 DEG C；
(3) product above-mentioned hydro-thermal reaction obtained i.e. can get tungsten disulfide through sucking filtration, washing, dried calcining
Nanometer sheet is evenly coated at the tungsten disulfide/carbon nanometer tube negative pole composite of CNT；Wherein said forges
Burning temperature is 250～350 DEG C.
The method preparing tungsten disulfide/carbon nanometer tube negative pole composite the most according to claim 1, its feature
It is: in described step (1), tungsten source is 5:1～20:1 with the mass ratio of CNT.
The method preparing tungsten disulfide/carbon nanometer tube negative pole composite the most according to claim 1, its feature
It is: in described step (2), sulfur powder is 3:1～10:1 with the mass ratio of tungsten oxide/carbon nanotube complex.
Preparation method the most according to claim 1, it is characterised in that: in step (1), double temperature-area tubular furnaces
Middle heating is that CNT is placed in leeward district, under slumpability atmosphere, rises to 1～10 DEG C/min
50～100 DEG C, tungsten source is placed in windward district, when leeward district temperature rises to setting value, with 10～20 DEG C/min
Heating rate rise to 900～1000 DEG C, be incubated 60～120min, gas flow rate 30～70sccm.
Preparation method the most according to claim 1, it is characterised in that: in described step (2), hydro-thermal is anti-
Between Ying Shi 18～36h；In described step (3) step, calcination time 30～120min.
6. according to the preparation method described in any one of Claims 1 to 5, it is characterised in that: described tungsten source is phosphotungstic acid
One or more in amine, ammonium tungstate, ammonium paratungstate, primary ammonium tungstate.
7. according to the preparation method described in any one of Claims 1 to 5, it is characterised in that: described reducing agent be octylame,
One or more in ethylenediamine, hydrazine hydrate.
Preparation method the most according to claim 1, it is characterised in that: a diameter of 50-800 of described composite
Nm, the thickness of tungsten disulfide nano slices is 5-15nm.
Preparation method the most according to claim 1, it is characterised in that: described tungsten disulfide/CNT
In composite, 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 |
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| 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 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106744820A (en) * | 2016-12-26 | 2017-05-31 | 中国科学院金属研究所 | Laminated metal chalcogenide/carbon nano tube flexible the composite film material of higher order structures and preparation |
| CN106981626A (en) * | 2017-04-20 | 2017-07-25 | 陕西科技大学 | A kind of preparation method of tungsten disulfide/SuperP sodium-ion battery self-supporting negative poles |
| CN109326787A (en) * | 2018-10-30 | 2019-02-12 | 陕西科技大学 | A kind of preparation method of tungsten disulfide/GO combination electrode material |
| CN109449411A (en) * | 2018-10-30 | 2019-03-08 | 陕西科技大学 | A kind of method of confinement synthesis tungsten disulfide@C combination 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 |
| CN111540889A (en) * | 2020-05-08 | 2020-08-14 | 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 |
| CN112125339A (en) * | 2020-09-17 | 2020-12-25 | 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 |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN106744820A (en) * | 2016-12-26 | 2017-05-31 | 中国科学院金属研究所 | Laminated metal chalcogenide/carbon nano tube flexible the composite film material of higher order structures and preparation |
| CN106981626A (en) * | 2017-04-20 | 2017-07-25 | 陕西科技大学 | A kind of preparation method of tungsten disulfide/SuperP sodium-ion battery self-supporting negative poles |
| 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 |
| CN109449411A (en) * | 2018-10-30 | 2019-03-08 | 陕西科技大学 | A kind of method of confinement synthesis tungsten disulfide@C combination electrode material |
| CN109326787A (en) * | 2018-10-30 | 2019-02-12 | 陕西科技大学 | A kind of preparation method of tungsten disulfide/GO combination electrode material |
| 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 |
| CN111540889A (en) * | 2020-05-08 | 2020-08-14 | 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 |
| 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 |
| CN112125339A (en) * | 2020-09-17 | 2020-12-25 | 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 |
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