CN107946553A - High graphitization three dimensional carbon nanotubes graphene composite material and its preparation and application - Google Patents
High graphitization three dimensional carbon nanotubes graphene composite material and its preparation and application Download PDFInfo
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The present invention provides a kind of high graphitization three dimensional carbon nanotubes graphene composite material and its preparation and application, its preparation method：Carbon nanotubes and graphene are mixed, add ethanol, ultrasonic disperse is uniform, is placed in 50 DEG C of oven for drying, obtains the compound of carbon nanotubes and graphene；And the compound is placed in high temperature graphitization stove, under high-purity argon gas shielded, 2850 DEG C are risen to using programmed temperature method, and continue 2h, obtain high graphitization three dimensional carbon nanotubes graphene composite material.The invention preparation method is simple, easily large-scale production；High temperature graphitization processing at the same time can effectively repair the surface defect structure of carbon material and reject the oxygen-containing functional group on surface so that the conductance and thermal conductivity ability of the material are greatly improved；The load sulphur cathode obtained using the high-temperature material is showed great advantage in the charge and discharge cycles of high magnification high current and can effectively protect the integrality of membrane.
Description
Technical field
The invention mainly relates in carbon nanomaterial field, especially in high graphitization three dimensional carbon nanotubes graphene composite wood
In terms of material and its preparation and application.
Background technology
Lithium-sulfur cell is due to high-energy-density, 1675mAhg-1Theoretical capacity and cheap cost become large-scale energy storage field
In it is most desired can one of charge-discharge battery system.However, sulphur non-conductive property and polysulfide shuttle effect always
It is the shortcoming of lithium-sulfur cell.
For these shortcomings present in lithium-sulfur cell, people probe into its solution party since the sixties in last century
Case, proposes the compound cathode as lithium-sulfur cell of the conductive carbon material such as the sulphur and carbon nanotubes of insulating properties, graphene, porous carbon
Material, but these procedures are complicated, and the cumbersome and shuttle effect aspect for improving polysulfide is ineffective.In recent years,
The shuttle that people largely improve polysulfide by introducing the metal based compounds such as titanium dioxide, titanium carbide is imitated
Should, while excellent performance is also shown in terms of the chemical property of battery.But in order to further meet it in real life
In needs, meet to be indispensable requirement to the fast charging and discharging of large-scale carrying object.Therefore, the height electricity with three-dimensional structure
Lead, the material of thermal conductivity carries sulfur materials as cathode and is undoubtedly one of splendid selection.
The content of the invention
The purpose of the invention is to overcome shortcoming and defect existing in the prior art, and provide a kind of high graphitization degree
Three dimensional carbon nanotubes graphene composite material preparation method, synthetic method is simple, is easy to mass produce.
Second object of the present invention is to provide a kind of three dimensional carbon nanotubes graphene composite material of high graphitization degree.
Third object of the present invention is to provide a kind of three dimensional carbon nanotubes graphene composite material of high graphitization degree
The application of sulfur materials is carried as lithium-sulphur cell positive electrode, greatly improves the charge-discharge performance of lithium-sulfur cell high magnification high current.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of high graphitization three dimensional carbon nanotubes graphene composite material, its preparation method：
(1) by carbon nanotubes and graphene in mass ratio 0.5~3：After 1 mixing, ethanol is added, ultrasonic disperse is uniform, puts
In 50 DEG C of oven for drying, the compound of carbon nanotubes and graphene is obtained.
The carbon nanotubes is multi-walled carbon nanotube, single-walled carbon nanotube, array carbon nano tube；
Told graphene is single-layer graphene, bilayer graphene, multi-layer graphene；
The volumetric usage of the ethanol is calculated as 100~500mL/g with the quality of carbon nanotubes and the compound of graphene, excellent
Select 200~300mL/g；
(2) carbon nanotubes obtained by step (1) and the compound of graphene are placed in high temperature graphitization stove, are protected in argon gas
Under shield, using programmed temperature method, 1200 DEG C are warming up to 300~400 DEG C/0.5h first, afterwards with 200~300 DEG C/0.5h liters
2850 DEG C of temperature, and continue 1~5h under the conditions of 2850 DEG C, obtain the high graphitization three dimensional carbon nanotubes graphene composite wood
Material.
The high graphitization three dimensional carbon nanotubes graphene composite material can be used as cathode to carry sulfur materials applied to lithium sulphur electricity
Chi Zhong, the method for the application are：
(1) preparation of high graphitization three dimensional carbon nanotubes graphene/S composite materials
By high graphitization three dimensional carbon nanotubes graphene composite material and elemental sulfur in mass ratio 1：1~4 mixing, grinding are equal
With feed liquid mass ratio (i.e. high graphitization three dimensional carbon nanotubes graphene composite material and elemental sulfur quality sum and CS after even2's
Mass ratio) 1：10~20 add CS2Middle stirring, is subsequently placed in 10~25 DEG C down toward CS2After volatilization completely, surplus materials is in 155
12h is kept the temperature in DEG C baking oven, is cooled to room temperature afterwards, up to high graphitization three dimensional carbon nanotubes graphene/S composite materials.
(2) preparation of high graphitization three dimensional carbon nanotubes graphene/S positive electrodes
By high graphitization three dimensional carbon nanotubes graphene/S composite materials obtained by step (1) and carbon black (conductive additive),
Kynoar (binding agent) in mass ratio 1：0.05~0.25：0.05~0.15 mixing, then adds 1-methyl-2-pyrrolidinone
(NMP), stirring and ultrasonic disperse is uniform, control viscosity obtains slurry in 1000~5000cps, by gained slurry with 150~
The thickness of 750mm is coated uniformly in current collector aluminum foil, aluminium foil then is transferred to 55 DEG C of drying in oven, up to high graphitization
Three dimensional carbon nanotubes graphene/S positive electrodes,
The thickness of the current collector aluminum foil is 30um, before use with 1-methyl-2-pyrrolidinone (NMP) and alcohol washes, is gone
Except surface oxide layer and impurity, used after natural air drying.
The beneficial effects of the present invention are：
(1) it is simple to prepare high graphitization three dimensional carbon nanotubes graphene composite material synthetic method by the present invention, easily extensive
Production.
(2) three-dimensional net structure provides effective electron propagation ducts, improves the electric conductivity of lithium-sulphur cell positive electrode.
(3) 2850 DEG C of high temperature graphitization processings surface defect knot of three dimensional carbon nanotubes and graphene composite material
Structure and the oxygen-containing functional group for eliminating carbon material surface so that the conductance and thermal conductivity ability of the material are greatly improved.
(4) the load sulphur cathode obtained using the high-temperature material shows greatly excellent in the charge and discharge cycles of high magnification high current
Gesture and the integrality that can effectively protect membrane.
Brief description of the drawings
The scanning electron microscope diagram of Fig. 1 high graphitization three dimensional carbon nanotubes graphene composite materials；
The Raman table of Fig. 2 carbon nanotubes graphene composite material and high graphitization three dimensional carbon nanotubes graphene composite material
Levy comparison diagram；
2 kinds of load sulphur of Fig. 3 carbon nanotubes graphene composite material and high graphitization three dimensional carbon nanotubes graphene composite material
The high rate performance comparison diagram of electrode；
Fig. 4 carbon nanotubes graphene composite material and high graphitization three dimensional carbon nanotubes graphene composite material carry sulfur electrode
Cycle performance figure.
Embodiment
The present invention is further detailed below by specific embodiment, but protection scope of the present invention and is not only limited
In this.
Embodiment 1
A, the preparation of high graphitization three dimensional carbon nanotubes graphene composite material：
(1) multi-walled carbon nanotube 1000mg, multi-layer graphene 500mg are weighed, mixing is dissolved in 300ml ethanol, acutely stirs
Mix and have children outside the state plan 2h, be placed in 75 DEG C of baking ovens and dry, obtain carbon nanotubes graphene complex；
(2) the obtained carbon nanotubes graphene complex of step (1) is placed in high temperature graphitization furnace body, in high-purity argon
Under the protection of gas, using programmed temperature method, 1200 DEG C are warming up to 400 DEG C/0.5h first, is heated up afterwards with 300 DEG C/0.5h
2850 DEG C, and continue 2h under the conditions of 2850 DEG C, obtain the high graphitization three dimensional carbon nanotubes graphene composite material.
B, lithium-sulfur rechargeable battery anode piece is prepared：
300mg high graphitization three dimensional carbon nanotubes graphene composite materials are taken, 700mg elemental sulfurs are fully ground mixing, it
After be dissolved in 10mL carbon disulfide, be vigorously stirred 12h, treat that carbon disulfide is evaporated completely, by mixture transfer put in constant temperature oven,
Be warming up to 155 DEG C, constant temperature 12h, cool down after obtain high graphitization three dimensional carbon nanotubes graphene/sulfur composite positive electrode material, lead to
Cross thermogravimetric analysis test its actual sulfur content be 65%.
By high graphitization three dimensional carbon nanotubes graphene/sulphur composite material 300mg and conductive additive carbon black 35.3mg, glue
Agent Kynoar 17.6mg mixing is connect, 3mL NMP and ultrasonic disperse is then added, is sufficiently stirred, control the viscosity of slurry
In 1000cps, then with the thickness of 200mm with scraper coated in current collector aluminum foil (aluminium foil NMP and alcohol washes three times,
To remove surface oxide layer and impurity, natural air drying, aluminum foil thickness 30um).Then aluminium foil is transferred in 45 DEG C of baking ovens, dried
It is dry, that is, obtain high graphitization three dimensional carbon nanotubes graphene/sulphur positive plate.
C, the assembling and test of battery：
By high graphitization three dimensional carbon nanotubes graphene/sulphur positive plate after twin-roll machine rolling is closely knit, it is cut into a diameter of
The circular piece of 14mm, weighs under dry environment, and deducts blank aluminium flake quality, and anode pole piece is made, stand-by；As control
Experiment, same treatment is done by the carbon nanotubes graphene composite material handled without high temperature graphitization；Full of argon gas, water and
Oxygen content is respectively less than the assembling that battery is carried out in the glove box of lppm；Using commercial metals lithium piece as reference electrode and to electrode,
Using LiTFSI/DOL.DMC (1：1) and dissolved with 1%LiNO3Liquid electrolyte, membrane uses Celgard2400, is assembled into
After CR2025 button cells, 12h is stood, battery charging and discharging survey is then carried out under 10C multiplying powers with new prestige battery test system
Examination, test condition is room temperature environment, and window starting voltage is 1.5V, final voltage 2.8V；Time of repose is 10s.
Fig. 4 is at high graphitization three dimensional carbon nanotubes graphene composite material made from the present embodiment and non-high temperature graphitization
Load sulphur cathode circulation comparison diagram under 10C of the carbon nanotubes graphene composite material of reason as lithium-sulfur cell, can from figure
To find out, the capacity with the lithium-sulfur cell of high graphitization three dimensional carbon nanotubes graphene composite material is substantially better than not high fire stons
The carbon nanotubes graphene composite material of inkization processing.-
Embodiment 2
A, the preparation of high graphitization three dimensional carbon nanotubes graphene composite material：
(1) array carbon nano tube 500mg, multi-layer graphene 500mg are weighed, mixing is dissolved in 200ml ethanol, is vigorously stirred
And have children outside the state plan 2h, be placed in 75 DEG C of baking ovens and dry, obtain carbon nanotubes graphene complex.
(2) the obtained carbon nanotubes graphene complex of step (1) is placed in high temperature graphitization furnace body, in high-purity argon
Under the protection of gas, using programmed temperature method, 1200 DEG C are warming up to 400 DEG C/0.5h first, is heated up afterwards with 300 DEG C/0.5h
2850 DEG C, and continue 2h under the conditions of 2850 DEG C, obtain the high graphitization three dimensional carbon nanotubes graphene composite material.
B, lithium-sulfur rechargeable battery anode piece is prepared：
300mg high graphitization three dimensional carbon nanotubes graphene composite materials are taken, 700mg elemental sulfurs are fully ground mixing, it
After be dissolved in 12mL carbon disulfide, be vigorously stirred 12h, treat that carbon disulfide is evaporated completely, by mixture transfer put in constant temperature oven,
155 DEG C, constant temperature 12h are warming up to, high graphitization three dimensional carbon nanotubes graphene/sulfur composite positive electrode material is obtained after cooling, is passed through
Thermogravimetric analysis test its actual sulfur content be 63%.
By high graphitization three dimensional carbon nanotubes graphene/sulphur composite material 300mg and conductive additive carbon black 16.7mg, glue
Agent Kynoar 16.7mg mixing is connect, 4mL NMP and ultrasonic disperse is then added, is sufficiently stirred, control the viscosity of slurry
In 1000cps, then with the thickness of 200mm with scraper coated in current collector aluminum foil (aluminium foil NMP and alcohol washes three times,
To remove surface oxide layer and impurity, natural air drying, aluminum foil thickness 30um).Then aluminium foil is transferred in 45 DEG C of baking ovens, dried
It is dry, that is, obtain high graphitization three dimensional carbon nanotubes graphene/sulphur positive plate.
C, the assembling and test of battery：
By high graphitization three dimensional carbon nanotubes graphene/sulphur positive plate after twin-roll machine rolling is closely knit, it is cut into a diameter of
The circular piece of 14mm, weighs under dry environment, and deducts blank aluminium flake quality, and anode pole piece is made, stand-by.Full of argon
Gas, water and oxygen content are respectively less than the assembling that battery is carried out in the glove box of lppm；Using commercial metals lithium piece as reference electrode and
To electrode, using LiTFSI/DOL.DMC (1：1) and dissolved with 1%LiNO3Liquid electrolyte, membrane uses Celgard2400,
It is assembled into after CR2025 button cells, stands 12h, battery charging and discharging is then carried out under 10C with new prestige battery test system
Test, test condition is room temperature environment, and window starting voltage is 1.5V, final voltage 2.8V；Time of repose is 10s.With original
Begin to enclose also surplus 250mAh/g, efficiency for charge-discharge after charge and discharge cycles for the composite material contrast of high-temperature heat treatment, circulation 1000
99%.
Embodiment 3
A, the preparation of high graphitization three dimensional carbon nanotubes graphene composite material：
(1) array carbon nano tube 1000mg, single-layer graphene 500mg are weighed, mixing is dissolved in 300ml ethanol, acutely stirs
Mix and have children outside the state plan 3h, be placed in 75 DEG C of baking ovens and dry, obtain carbon nanotubes graphene complex.
(2) the obtained carbon nanotubes graphene complex of step (1) is placed in high temperature graphitization furnace body, in high-purity argon
Under the protection of gas, using programmed temperature method, 1200 DEG C are warming up to 400 DEG C/0.5h first, is heated up afterwards with 300 DEG C/0.5h
2850 DEG C, and continue 3h under the conditions of 2850 DEG C, obtain the high graphitization three dimensional carbon nanotubes graphene composite material.
B, lithium-sulfur rechargeable battery anode piece is prepared：
300mg high graphitization three dimensional carbon nanotubes graphene composite materials are taken, 700mg elemental sulfurs are fully ground mixing, it
After be dissolved in 12mL carbon disulfide, be vigorously stirred 12h, treat that carbon disulfide is evaporated completely, by mixture transfer put in constant temperature oven,
155 DEG C, constant temperature 12h are warming up to, high graphitization three dimensional carbon nanotubes graphene/sulfur composite positive electrode material is obtained after cooling, is passed through
Thermogravimetric analysis test its actual sulfur content be 67%.
By high graphitization three dimensional carbon nanotubes graphene/sulphur composite material 300mg and conductive additive carbon black 56.3mg, glue
Agent Kynoar 18.8mg mixing is connect, 3.5mL NMP and ultrasonic disperse is then added, is sufficiently stirred, controls the viscous of slurry
Spend in 1000cps, (aluminium foil NMP and alcohol washes three in current collector aluminum foil are then coated in the thickness of 200mm scraper
Time, to remove surface oxide layer and impurity, natural air drying, aluminum foil thickness 30um).Then aluminium foil is transferred to 45 DEG C of baking ovens
Interior, drying, that is, obtain high graphitization three dimensional carbon nanotubes graphene/sulphur positive plate.
C, the assembling and test of battery：
By high graphitization three dimensional carbon nanotubes graphene/sulphur positive plate after twin-roll machine rolling is closely knit, it is cut into a diameter of
The circular piece of 14mm, weighs under dry environment, and deducts blank aluminium flake quality, and anode pole piece is made, stand-by.Full of argon
Gas, water and oxygen content are respectively less than the assembling that battery is carried out in the glove box of lppm.Using commercial metals lithium piece as reference electrode and
To electrode, using LiTFSI/DOL.DMC (1：1) and dissolved with 1%LiNO3Liquid electrolyte, membrane uses Celgard2400,
It is assembled into after CR2025 button cells, stands 12h, battery charging and discharging is then carried out under 15C with new prestige battery test system
Test, test condition is room temperature environment, and window starting voltage is 1.5V, final voltage 2.8V；Time of repose is 5s.With it is original
Also surplus 273mAh/g, efficiency for charge-discharge 99% after charge and discharge cycles are enclosed in the composite material contrast of non-high-temperature heat treatment, circulation 1500.
The above disclosure is only the preferred embodiments of the present invention, cannot limit the right model of the present invention with this certainly
Enclose, therefore equivalent variations made according to the claims of the present invention, it is still within the scope of the present invention.
Claims (6)
1. a kind of preparation method of high graphitization three dimensional carbon nanotubes graphene composite material, it is characterised in that as follows
Prepare：
(1) by carbon nanotubes and graphene in mass ratio 1~3：After 1 mixing, ethanol is added, ultrasonic disperse is uniform, it is placed in 50~
60 DEG C of oven for drying, obtain the compound of carbon nanotubes and graphene；
(2) carbon nanotubes obtained by step (1) and the compound of graphene are placed in high temperature graphitization stove, are protected in argon gas
Under, using programmed temperature method, 1200 DEG C are warming up to 300~400 DEG C/0.5h first, is heated up afterwards with 200~300 DEG C/0.5h
2850 DEG C, and continue 1~5h under the conditions of 2850 DEG C, obtain the high graphitization three dimensional carbon nanotubes graphene composite wood
Material.
2. according to claim 1 preparation method, it is characterised in that in step (1), the carbon nanotubes is multi-wall carbon nano-tube
One or more combinations in pipe, single-walled carbon nanotube, array carbon nano tube；Graphene for single-layer graphene, bilayer graphene,
One or more combinations in multi-layer graphene.
3. preparation method according to claim 1, it is characterised in that in step (1), the volumetric usage of the ethanol is with carbon
The quality of the compound of nanotube and graphene is calculated as 100~500mL/g.
A kind of 4. high graphitization three dimensional carbon nanotubes graphene prepared according to claim 1-3 any one of them preparation method
Composite material.
5. a kind of high graphitization three dimensional carbon nanotubes graphene composite material according to claim 4 as lithium-sulfur cell just
Pole carries the application of sulfur materials, it is characterised in that the method for application is：
(1) preparation of high graphitization three dimensional carbon nanotubes graphene/S composite materials
By high graphitization three dimensional carbon nanotubes graphene composite material and elemental sulfur in mass ratio 1：1~4 mixing, after grinding uniformly
With feed liquid mass ratio 1：10~20 add CS2Middle stirring, is subsequently placed in 10~25 DEG C down toward CS2Volatilization completely after, surplus materials in
12h is kept the temperature in 155 DEG C of baking ovens, is cooled to room temperature afterwards, up to high graphitization three dimensional carbon nanotubes graphene/S composite materials；
The feed liquid mass ratio is high graphitization three dimensional carbon nanotubes graphene composite material and elemental sulfur quality sum and CS2
Mass ratio；
(2) preparation of high graphitization three dimensional carbon nanotubes graphene/S positive electrodes
High graphitization three dimensional carbon nanotubes graphene/S composite materials obtained by step (1) are pressed into quality with carbon black, Kynoar
Than 1：0.05~0.25：0.05~0.15 mixing, then adds 1-methyl-2-pyrrolidinone, stirs and ultrasonic disperse is uniform, control
Viscosity obtains slurry, gained slurry is coated uniformly on current collector aluminum foil with the thickness of 150~750mm in 1000~5000cps
On, aluminium foil is then transferred to 55 DEG C of drying in oven, up to high graphitization three dimensional carbon nanotubes graphene/S positive electrodes.
6. application according to claim 5, it is characterised in that：The thickness of the current collector aluminum foil is 30um, before use
With 1-methyl-2-pyrrolidinone and alcohol washes, surface oxide layer and impurity are removed, is used after natural air drying.
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| CN112820857A (en) * | 2019-11-15 | 2021-05-18 | 中国科学院成都有机化学有限公司 | Nano carbon composite lithium metal cathode and preparation method thereof |
| CN112436114A (en) * | 2020-11-16 | 2021-03-02 | 扬州大学 | Three-dimensional graphene/carbon nanotube/phosphotungstic acid/sulfur composite material, preparation method and application thereof |
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