CN107946553B - High-graphitization three-dimensional carbon nanotube graphene composite material and preparation and application thereof - Google Patents
High-graphitization three-dimensional carbon nanotube graphene composite material and preparation and application thereof Download PDFInfo
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Abstract
The invention provides a highly graphitized three-dimensional carbon nanotube graphene composite material and preparation and application thereof, wherein the preparation method comprises the following steps: mixing the carbon nano tube and the graphene, adding ethanol, performing ultrasonic dispersion uniformly, and drying in a 50 ℃ oven to obtain a compound of the carbon nano tube and the graphene; and placing the composite in a high-temperature graphitization furnace, heating to 2850 ℃ by using a programmed heating method under the protection of high-purity argon, and continuing for 2 hours to obtain the high-graphitization three-dimensional carbon nanotube graphene composite material. The preparation method is simple and is easy for large-scale production; meanwhile, the high-temperature graphitization treatment can effectively repair the surface defect structure of the carbon material and remove oxygen-containing functional groups on the surface, so that the electrical conductivity and the thermal conductivity of the material are greatly improved; the sulfur-carrying anode obtained by using the high-temperature material has great advantages in high-rate and high-current charge-discharge cycles and can effectively protect the integrity of the diaphragm.
Description
Technical Field
The invention mainly relates to the field of carbon nano materials, in particular to a high-graphitization three-dimensional carbon nano tube graphene composite material and preparation and application thereof.
Background
Lithium sulfur battery 1675mAhg due to high energy density-1Theoretical capacity and inexpensive cost ofBecomes one of the most promising rechargeable battery systems in the field of large-scale energy storage. However, sulfur non-conductivity and polysulfide shuttling effects have been deficiencies in lithium sulfur batteries.
Aiming at the defects of the lithium-sulfur battery, people explore solutions from the last 60 th century, and propose that the conductive carbon materials such as insulating sulfur, carbon nanotubes, graphene and porous carbon are compounded to be used as the anode material of the lithium-sulfur battery, but the methods are complex and fussy in process and have poor effect on improving the shuttle effect of polysulfide. In recent years, introduction of metal compounds such as titanium dioxide and titanium carbide has improved the shuttle effect of polysulfides to a great extent, and also has shown excellent performance in terms of electrochemical performance of batteries. However, in order to further meet the needs of the device in real life, it is indispensable to meet the requirements for rapid charge and discharge of a large-sized carrier fluid. Therefore, a material with high electrical and thermal conductivity and three-dimensional structure is undoubtedly an excellent choice as the sulfur-carrying material of the anode.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a preparation method of a three-dimensional carbon nanotube graphene composite material with high graphitization degree, which is simple in synthesis method and easy for large-scale production.
The second purpose of the invention is to provide a three-dimensional carbon nanotube graphene composite material with high graphitization degree.
The third purpose of the invention is to provide the application of the three-dimensional carbon nanotube graphene composite material with high graphitization degree as the sulfur-carrying material of the positive electrode of the lithium-sulfur battery, and the high-rate and high-current charge-discharge performance of the lithium-sulfur battery is greatly improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-graphitization three-dimensional carbon nanotube graphene composite material is prepared by the following steps:
(1) mixing a carbon nano tube and graphene according to a mass ratio of 0.5-3: 1, adding ethanol, performing ultrasonic dispersion uniformly, and drying in a 50 ℃ oven to obtain the compound of the carbon nano tube and the graphene.
The carbon nano tube is a multi-wall carbon nano tube, a single-wall carbon nano tube or an array carbon nano tube;
the graphene is single-layer graphene, double-layer graphene or multi-layer graphene;
the volume dosage of the ethanol is 100-500 mL/g, preferably 200-300 mL/g, based on the mass of the composite of the carbon nano tube and the graphene;
(2) and (2) placing the composite of the carbon nano tube and the graphene obtained in the step (1) in a high-temperature graphitization furnace, under the protection of argon, heating to 1200 ℃ at 300-400 ℃/0.5h by using a programmed heating method, then heating to 2850 ℃ at 200-300 ℃/0.5h, and continuing for 1-5 h at 2850 ℃ to obtain the high-graphitization three-dimensional carbon nano tube graphene composite material.
The high-graphitization three-dimensional carbon nanotube graphene composite material can be used as a positive electrode sulfur-carrying material to be applied to a lithium-sulfur battery, and the application method comprises the following steps:
(1) preparation of high-graphitization three-dimensional carbon nanotube graphene/S composite material
Mixing a high-graphitization three-dimensional carbon nanotube graphene composite material with elemental sulfur according to a mass ratio of 1: 1-4, uniformly grinding, and then uniformly mixing the materials according to the mass ratio of the materials (namely the sum of the mass of the high-graphitization three-dimensional carbon nanotube graphene composite material and the mass of elemental sulfur and CS)21) 1: 10 to 20 portions of CS2Stirring, and then placing at 10-25 ℃ to CS2After complete volatilization, the residual substances are kept in an oven at 155 ℃ for 12h, and then cooled to room temperature, so as to obtain the highly graphitized three-dimensional carbon nanotube graphene/S composite material.
(2) Preparation of high-graphitization three-dimensional carbon nanotube graphene/S positive electrode material
Mixing the high-graphitization three-dimensional carbon nanotube graphene/S composite material obtained in the step (1), carbon black (conductive additive) and polyvinylidene fluoride (binder) according to a mass ratio of 1: 0.05-0.25: 0.05-0.15, adding N-methyl pyrrolidone (NMP), stirring and uniformly dispersing by ultrasonic, controlling the viscosity to be 1000-5000 cps to obtain slurry, uniformly coating the obtained slurry on a current collector aluminum foil with the thickness of 150-750 mm, transferring the aluminum foil to a 55 ℃ oven for drying to obtain the highly graphitized three-dimensional carbon nanotube graphene/S cathode material,
the thickness of mass flow body aluminium foil is 30um, washs with N-methyl pyrrolidone (NMP) and alcohol before the use, gets rid of surface oxide layer and impurity, uses after natural air-drying.
The invention has the beneficial effects that:
(1) the synthesis method for preparing the high-graphitization three-dimensional carbon nanotube graphene composite material is simple and is easy for large-scale production.
(2) The three-dimensional network structure provides an effective electron transmission channel and improves the conductivity of the anode of the lithium-sulfur battery.
(3) The surface defect structure of the three-dimensional carbon nanotube and graphene composite material is repaired and the oxygen-containing functional groups on the surface of the carbon material are removed by high-temperature graphitization treatment at 2850 ℃, so that the electric conductivity and the heat conductivity of the material are greatly improved.
(4) The sulfur-carrying anode obtained by using the high-temperature material has great advantages in high-rate and high-current charge-discharge cycles and can effectively protect the integrity of the diaphragm.
Drawings
Fig. 1 is a scanning electron microscope image of a highly graphitized three-dimensional carbon nanotube graphene composite;
FIG. 2 is a Raman characterization comparison graph of a carbon nanotube graphene composite material and a highly graphitized three-dimensional carbon nanotube graphene composite material;
FIG. 3 is a graph comparing the rate capability of 2 sulfur-carrying electrodes of a carbon nanotube graphene composite material and a highly graphitized three-dimensional carbon nanotube graphene composite material;
fig. 4 is a graph of the cycle performance of the carbon nanotube graphene composite material and the highly graphitized three-dimensional carbon nanotube graphene composite material sulfur-carrying electrode.
Detailed Description
The present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited thereto.
Example 1
A. Preparing a high-graphitization three-dimensional carbon nanotube graphene composite material:
(1) weighing 1000mg of multi-walled carbon nanotube and 500mg of multi-layer graphene, mixing and dissolving in 300ml of ethanol, violently stirring and carrying out ultrasound generation for 2h, and then placing in a 75 ℃ oven for drying to obtain a carbon nanotube graphene compound;
(2) placing the carbon nanotube graphene composite obtained in the step (1) in a high-temperature graphitization furnace body, under the protection of high-purity argon, heating to 1200 ℃ at 400 ℃/0.5h by using a programmed heating method, then heating to 2850 ℃ at 300 ℃/0.5h, and continuing for 2h at 2850 ℃ to obtain the high-graphitization three-dimensional carbon nanotube graphene composite material.
B. Preparing a lithium-sulfur secondary battery positive plate:
taking 300mg of highly graphitized three-dimensional carbon nanotube graphene composite material, fully grinding and mixing 700mg of elemental sulfur, then dissolving the highly graphitized three-dimensional carbon nanotube graphene composite material in 10mL of carbon disulfide, violently stirring for 12h, after the carbon disulfide is volatilized, transferring the mixture into a constant-temperature oven, heating to 155 ℃, keeping the temperature constant for 12h, cooling to obtain the highly graphitized three-dimensional carbon nanotube graphene/sulfur composite cathode material, and obtaining the actual sulfur content of 65% through thermogravimetric analysis test.
Mixing 300mg of high-graphitization three-dimensional carbon nanotube graphene/sulfur composite material with 35.3mg of conductive additive carbon black and 17.6mg of adhesive polyvinylidene fluoride, then adding 3mL of NMP, performing ultrasonic dispersion and full stirring, controlling the viscosity of the slurry to be 1000cps, and then coating the slurry on a current collector aluminum foil with the thickness of 200mm by using a scraper (the aluminum foil is cleaned for three times by using NMP and alcohol to remove a surface oxide layer and impurities, and is naturally air-dried, wherein the thickness of the aluminum foil is 30 um). And then transferring the aluminum foil into a 45 ℃ oven, and drying to obtain the high-graphitization three-dimensional carbon nanotube graphene/sulfur positive plate.
C. Assembling and testing the battery:
after the highly graphitized three-dimensional carbon nanotube graphene/sulfur positive plate is rolled and compacted by a double-roller machine, the highly graphitized three-dimensional carbon nanotube graphene/sulfur positive plate is cut into a circular plate with the diameter of 14mm, the circular plate is weighed in a dry environment, and the mass of a blank aluminum sheet is deducted to prepare a positive plate for later use; as a control experiment, carbon nanotube graphite without high temperature graphitization treatment was usedCarrying out the same treatment on the alkene composite material; assembling the battery in a glove box filled with argon and with water and oxygen contents less than lpm; commercial lithium metal sheets were used as reference and counter electrodes, and LiTFSI/DOL.DMC (1: 1) was used with 1% LiNO dissolved3After a diaphragm of the liquid electrolyte is assembled into a CR2025 button cell by adopting Celgard2400, standing for 12 hours, and then carrying out battery charge and discharge test by using a Xinwei battery test system under 10C multiplying power, wherein the test condition is a room-temperature environment, the window initial voltage is 1.5V, and the termination voltage is 2.8V; the standing time was 10 s.
Fig. 4 is a cycle comparison graph of the high-graphitization three-dimensional carbon nanotube graphene composite material prepared in the embodiment and the carbon nanotube graphene composite material which is not subjected to high-temperature graphitization treatment as the sulfur-carrying positive electrode of the lithium sulfur battery under 10C, and it can be seen from the graph that the capacity of the lithium sulfur battery with the high-graphitization three-dimensional carbon nanotube graphene composite material is obviously better than that of the carbon nanotube graphene composite material which is not subjected to high-temperature graphitization treatment. -
Example 2
A. Preparing a high-graphitization three-dimensional carbon nanotube graphene composite material:
(1) weighing 500mg of array carbon nanotube and 500mg of multilayer graphene, mixing and dissolving in 200ml of ethanol, violently stirring and carrying out ultrasound generation for 2h, and then placing in a 75 ℃ oven for drying to obtain the carbon nanotube graphene compound.
(2) Placing the carbon nanotube graphene composite obtained in the step (1) in a high-temperature graphitization furnace body, under the protection of high-purity argon, heating to 1200 ℃ at 400 ℃/0.5h by using a programmed heating method, then heating to 2850 ℃ at 300 ℃/0.5h, and continuing for 2h at 2850 ℃ to obtain the high-graphitization three-dimensional carbon nanotube graphene composite material.
B. Preparing a lithium-sulfur secondary battery positive plate:
taking 300mg of highly graphitized three-dimensional carbon nanotube graphene composite material, fully grinding and mixing 700mg of elemental sulfur, then dissolving the highly graphitized three-dimensional carbon nanotube graphene composite material in 12mL of carbon disulfide, violently stirring for 12h, after the carbon disulfide is volatilized, transferring the mixture into a constant-temperature oven, heating to 155 ℃, keeping the temperature constant for 12h, cooling to obtain the highly graphitized three-dimensional carbon nanotube graphene/sulfur composite cathode material, and obtaining the actual sulfur content of 63% through thermogravimetric analysis test.
Mixing 300mg of high-graphitization three-dimensional carbon nanotube graphene/sulfur composite material with 16.7mg of conductive additive carbon black and 16.7mg of adhesive polyvinylidene fluoride, then adding 4mL of NMP, performing ultrasonic dispersion and full stirring, controlling the viscosity of the slurry to be 1000cps, and then coating the slurry on a current collector aluminum foil with the thickness of 200mm by using a scraper (the aluminum foil is cleaned for three times by using NMP and alcohol to remove a surface oxide layer and impurities, and is naturally air-dried, wherein the thickness of the aluminum foil is 30 um). And then transferring the aluminum foil into a 45 ℃ oven, and drying to obtain the high-graphitization three-dimensional carbon nanotube graphene/sulfur positive plate.
C. Assembling and testing the battery:
the high-graphitization three-dimensional carbon nanotube graphene/sulfur positive plate is rolled and compacted by a double-roller machine, then cut into circular sheets with the diameter of 14mm, weighed in a dry environment, and the mass of blank aluminum sheets is deducted to prepare the positive plate for later use. Assembling the battery in a glove box filled with argon and with water and oxygen contents less than lpm; commercial lithium metal sheets were used as reference and counter electrodes, and LiTFSI/DOL.DMC (1: 1) was used with 1% LiNO dissolved3After a diaphragm of the liquid electrolyte is assembled into a CR2025 button cell by adopting Celgard2400, standing for 12 hours, and then carrying out battery charging and discharging tests by using a Xinwei battery testing system at 10 ℃, wherein the testing conditions are room-temperature environment, the window initial voltage is 1.5V, and the termination voltage is 2.8V; the standing time was 10 s. Compared with the original composite material subjected to high-temperature heat treatment, 250mAh/g is remained after 1000 cycles of charge-discharge cycle, and the charge-discharge efficiency is 99%.
Example 3
A. Preparing a high-graphitization three-dimensional carbon nanotube graphene composite material:
(1) weighing 1000mg of array carbon nanotube and 500mg of single-layer graphene, mixing and dissolving in 300ml of ethanol, violently stirring and carrying out ultrasound generation for 3h, and then placing in a 75 ℃ oven for drying to obtain the carbon nanotube graphene compound.
(2) Placing the carbon nanotube graphene composite obtained in the step (1) in a high-temperature graphitization furnace body, under the protection of high-purity argon, heating to 1200 ℃ at 400 ℃/0.5h by using a programmed heating method, then heating to 2850 ℃ at 300 ℃/0.5h, and continuing for 3h at 2850 ℃ to obtain the high-graphitization three-dimensional carbon nanotube graphene composite material.
B. Preparing a lithium-sulfur secondary battery positive plate:
taking 300mg of highly graphitized three-dimensional carbon nanotube graphene composite material, fully grinding and mixing 700mg of elemental sulfur, then dissolving the highly graphitized three-dimensional carbon nanotube graphene composite material in 12mL of carbon disulfide, violently stirring for 12h, after the carbon disulfide is volatilized, transferring the mixture into a constant-temperature oven, heating to 155 ℃, keeping the temperature constant for 12h, cooling to obtain the highly graphitized three-dimensional carbon nanotube graphene/sulfur composite cathode material, and obtaining the actual sulfur content of 67% through thermogravimetric analysis test.
Mixing 300mg of high-graphitization three-dimensional carbon nanotube graphene/sulfur composite material with 56.3mg of conductive additive carbon black and 18.8mg of adhesive polyvinylidene fluoride, then adding 3.5mL of NMP, performing ultrasonic dispersion and full stirring, controlling the viscosity of the slurry to be 1000cps, and then coating the slurry on a current collector aluminum foil with the thickness of 200mm by using a scraper (the aluminum foil is cleaned for three times by using NMP and alcohol to remove a surface oxide layer and impurities, and is naturally dried, wherein the thickness of the aluminum foil is 30 um). And then transferring the aluminum foil into a 45 ℃ oven, and drying to obtain the high-graphitization three-dimensional carbon nanotube graphene/sulfur positive plate.
C. Assembling and testing the battery:
the high-graphitization three-dimensional carbon nanotube graphene/sulfur positive plate is rolled and compacted by a double-roller machine, then cut into circular sheets with the diameter of 14mm, weighed in a dry environment, and the mass of blank aluminum sheets is deducted to prepare the positive plate for later use. The cell assembly was carried out in a glove box filled with argon, water and oxygen, each less than lpm. Commercial lithium metal sheets were used as reference and counter electrodes, and LiTFSI/DOL.DMC (1: 1) was used with 1% LiNO dissolved3After a diaphragm of the liquid electrolyte is assembled into a CR2025 button cell by adopting Celgard2400, standing for 12 hours, and then carrying out battery charging and discharging tests by using a Xinwei battery test system under 15C, wherein the test conditions are room-temperature environment, the window initial voltage is 1.5V, and the termination voltage is 2.8V; the standing time was 5 s. And original hasCompared with the composite material subjected to high-temperature heat treatment, 273mAh/g is remained after 1500 cycles of charge and discharge, and the charge and discharge efficiency is 99%.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (2)
1. The application of the high-graphitization three-dimensional carbon nanotube graphene composite material as the positive electrode of the lithium-sulfur battery is characterized in that the preparation method of the high-graphitization three-dimensional carbon nanotube graphene composite material is as follows:
(a) weighing 1000mg of array carbon nanotube and 500mg of single-layer graphene, mixing and dissolving in 300ml of ethanol, violently stirring and ultrasonically treating for 3 hours, and then placing in a 75 ℃ oven for drying to obtain a carbon nanotube graphene compound;
(b) placing the carbon nanotube graphene composite obtained in the step (a) in a high-temperature graphitization furnace body, under the protection of high-purity argon, heating to 1200 ℃ at 400 ℃/0.5h by using a programmed heating method, then heating to 2850 ℃ at 300 ℃/0.5h, and continuing for 3h at 2850 ℃ to obtain the high-graphitization three-dimensional carbon nanotube graphene composite material;
the method for applying the high-graphitization three-dimensional carbon nanotube graphene composite material as the positive electrode of the lithium-sulfur battery comprises the following steps:
(1) preparation of high-graphitization three-dimensional carbon nanotube graphene/S composite material
Taking 300mg of highly graphitized three-dimensional carbon nanotube graphene composite material, fully grinding and mixing 700mg of elemental sulfur, then dissolving the highly graphitized three-dimensional carbon nanotube graphene composite material in 12mL of carbon disulfide, violently stirring for 12h, transferring the mixture into a constant-temperature oven after the carbon disulfide is volatilized, heating to 155 ℃, keeping the temperature constant for 12h, cooling to obtain a highly graphitized three-dimensional carbon nanotube graphene/sulfur composite cathode material, and obtaining the actual sulfur content of 67% through thermogravimetric analysis test;
(2) preparation of high-graphitization three-dimensional carbon nanotube graphene/S positive electrode material
Mixing 300mg of high-graphitization three-dimensional carbon nanotube graphene/sulfur composite material with 56.3mg of conductive additive carbon black and 18.8mg of adhesive polyvinylidene fluoride, then adding 3.5mL of NMP, performing ultrasonic dispersion and full stirring, controlling the viscosity of the slurry to be 1000cps, and then coating the slurry on a current collector aluminum foil by a scraper with the thickness of 200 mu m; then transferring the aluminum foil into a 45 ℃ oven, and drying to obtain a highly graphitized three-dimensional carbon nanotube graphene/sulfur positive plate;
(3) after the highly graphitized three-dimensional carbon nanotube graphene/sulfur positive plate is rolled and compacted by a double-roller machine, the highly graphitized three-dimensional carbon nanotube graphene/sulfur positive plate is cut into a circular plate with the diameter of 14mm, the circular plate is weighed in a dry environment, and the mass of a blank aluminum sheet is deducted to prepare a positive plate for later use; assembling the battery in a glove box filled with argon and with water and oxygen contents less than lpm; commercial lithium metal sheets are used as a reference electrode and a counter electrode, and the mass ratio of the commercial lithium metal sheets is 1: 1 LiTFSI/DOL + DMC and 1% LiNO dissolved3The liquid electrolyte and the diaphragm are Celgard2400, and are assembled into a CR2025 button cell.
2. Use according to claim 1, characterized in that: the thickness of the current collector aluminum foil is 30 micrometers, the current collector aluminum foil is cleaned by N-methyl pyrrolidone and alcohol before use, a surface oxidation layer and impurities are removed, and the current collector aluminum foil is used after being naturally dried.
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| CN109686953B (en) * | 2018-12-27 | 2020-10-27 | 杭州电子科技大学 | Lithium-sulfur battery composite positive electrode material and preparation method thereof |
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