CN113213471A - Preparation method and application of graphitized mesoporous nano carbon material - Google Patents
Preparation method and application of graphitized mesoporous nano carbon material Download PDFInfo
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
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- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 32
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- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
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- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910001216 Li2S Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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Abstract
The invention relates to a preparation method and application of a graphitized mesoporous nano carbon material, and belongs to the technical field of porous carbon materials. Placing the porcelain boat containing the template powder into a tubular furnace, removing oxygen in the tubular furnace, leading nitrogen or inert gas to pass through an acetonitrile solvent at a flow rate of 50-100 mL/min, introducing the nitrogen or inert gas into the tubular furnace, heating the tubular furnace to 900-1100 ℃, and preserving the heat at 900-1100 ℃ for 1-30 h to obtain a carbonized precursor material; and soaking the carbonized precursor material in HF solution to remove the template agent, and then cleaning and drying to obtain the graphitized mesoporous nano carbon material. The method has the advantages of easily obtained raw materials and simple process, and the prepared mesoporous nano carbon material with a certain graphitization degree is used as a conductive carrier to be applied to the positive electrode material of the lithium-sulfur battery, thereby being beneficial to improving the multiplying power performance and the cycle performance of the battery and having good application prospect in the electrode material of the power battery.
Description
Technical Field
The invention relates to a preparation method and application of a graphitized mesoporous nano carbon material, and belongs to the technical field of porous carbon materials.
Background
Carbon materials are one of the basic materials that have been widely studied, and are widely used in various fields such as adsorbents, catalysts and conductive agents, electrode materials, and the like. Because the natural reserve volume of the carbon material is large, the variety, the appearance and the structure are various, the chemical property is strong, the conductivity is superior, and the stability is strong, the carbon material is one of the most common electrode materials in the research of novel energy storage devices. Some common energy storage devices are mainly fuel cells, lithium ion batteries, lithium sulfur batteries, sodium ion batteries, super capacitors and the like. The diversified applications of the carbon material in various fields depend on not only excellent electrical conductivity, thermal conductivity, chemical stability and low density, but also universality, easy synthesis of raw materials and easy realization of processing methods.
Among many carbon materials, activated carbon, nanoporous (microporous and mesoporous) carbon, carbon nanotubes, carbon nanospheres, carbon fibers, graphene sheets, and the like are more commonly used electrode materials. The porous carbon material has larger surface area and good chemical property, is convenient for electrolyte transmission and ion conduction, is a kind of electrode material which is researched more in the research of electrode materials of energy storage devices, and is applied to various energy storage devices. The pores in the porous carbon material may be classified into the following types according to the pore size: pore size <2nm, referred to as micropores; the pore size is not less than 2nm and not more than 50nm, and the mesoporous material is called mesoporous; pore size >50nm, called macropores. The mesoporous carbon material is convenient for electrolyte permeation and electron and ion transmission due to the unique aperture size, and is widely applied to electrode materials of power batteries.
In the new energy field, the lithium-sulfur battery has higher theoretical capacity (1675mAh g)-1) And theoretical specific energy (2600Wh kg)-1) The elemental sulfur is abundant in natural reserves, low in price and environment-friendly, so that the lithium sulfur battery is considered as one of new energy batteries which are most likely to realize large-scale industrial production in a new generation of energy storage system. In the lithium-sulfur battery, a sulfur simple substance is used as a positive electrode, lithium metal is used as a negative electrode, and the lithium-sulfur battery is realized through an electrochemical reaction with the sulfur simple substance. The specific reaction mechanism is as follows: upon discharge, the lithium metal negative electrode releases electrons to produce Li+Elemental sulfur (S)8) With Li+The reaction produces a series of polysulfides (Li)2SnN is more than or equal to 4 and less than or equal to 8); during charging, the electrochemical reaction is reversely carried out, polysulfide is dissolved, and elemental sulfur is generated. However, this reaction is not completely reversible, and the polysulfide produced is not completely dissolved when charged, resulting in the consumption of a part of the elemental sulfur of the positive electrode and the accumulation of polysulfide. Therefore, although the lithium-sulfur battery is well-regarded, further research and improvement are needed to realize mass production and application. The main problems of the current lithium-sulfur battery are as follows: (1) the conductivity of the sulfur is low (room temperature, 5.0 multiplied by 10)-30S·cm-1) End product of the reaction Li2S2And Li2S is an electronic insulator, and their presence is detrimental to the high rate performance of the cell. (2) Polysulfide generated by the reaction shuttles back and forth between the positive electrode and the negative electrode, so that the viscosity of the electrolyte is increased, and the ionic conductivity is reduced, namely the shuttle effect. The shuttle effect can cause a series of problems of diaphragm damage, sulfur simple substance consumption, low coulombic efficiency, short battery cycle life and the like. (3) During charging and discharging, there is a severe volumeThe expansion, volume expansion rate is up to 70%, which causes capacity attenuation and structural damage. Among them, the shuttling effect is the biggest problem existing in the lithium sulfur battery, so solving the problem of the shuttling effect of polysulfide is the key to improve the high rate performance of the lithium sulfur battery. For this reason, researchers have made a series of efforts, such as retarding or inhibiting the dissolution of polysulfides, increasing the conductivity of the positive electrode material, and seeking for a highly conductive separator and an effective electrolyte.
In order to solve the problems of the lithium-sulfur battery, researchers have made a series of attempts and researches. At present, the effective and common method is to embed the elemental sulfur into the conductive carrier frame, compound the elemental sulfur with the microporous or mesoporous porous carbon material, and embed the elemental sulfur into the conductive carrier. The porous carbon material has porous inside, large specific surface area, strong adsorbability and proper size, and is the most used sulfur anode carrier in current research and exploration work. More common carbon materials include Carbon Nanofibers (CNF), carbon nanospheres, Carbon Nanotubes (CNT), graphene oxide, porous carbon materials, and the like. These materials have either a large surface area but low conductivity or a high conductivity but small surface area, not much of the same.
Conventional porous carbon materials, such as activated carbon and carbon molecular sieves, are mainly prepared by high temperature carbonization and activation of carbon-based organic polymers, mainly coal, wood, nutshells or polymers. However, the production process of the traditional porous carbon material is complex, and most importantly, although some of the existing producible carbon materials can be applied to electrode materials of power batteries, the electrochemical performance of the batteries is not obviously improved.
Disclosure of Invention
Aiming at the problems of the preparation of the existing porous carbon material and the lithium sulfur battery, the invention provides a preparation method and application of a graphitized mesoporous nano carbon material.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a graphitized mesoporous nano carbon material comprises the following steps:
placing the porcelain boat containing the template agent powder into a tube furnace, and connecting an anti-suck-back device containing the acetonitrile solvent between an air inlet of the tube furnace and an air source; removing oxygen in the tubular furnace, adjusting a gas source to enable the gas to continuously pass through an acetonitrile solvent at the flow rate of 50 mL/min-100 mL/min, introducing the gas into the tubular furnace, heating the tubular furnace to 900-1100 ℃, and preserving the heat at the temperature of 900-1100 ℃ for 1-30 h to obtain a carbonized precursor material; soaking the carbonized precursor material in HF solution to remove the template agent, and then cleaning and drying to obtain the graphitized mesoporous nano carbon material;
wherein the gas of the gas source is nitrogen or inert gas; the template powder is SBA-15 powder, the shape of the SBA-15 powder is not limited, and the template powder can be spherical, rod-shaped, sheet-shaped and irregular shapes).
Further, the mass ratio of the acetonitrile solvent to the template powder is preferably not less than 1175:1, more preferably (1175-1600): 1.
Further, it is preferable to heat the tube furnace to 900 to 1100 ℃ at a heating rate of 10 to 20 ℃/min.
Further, the temperature is preferably kept at 950 ℃ to 1050 ℃ for 18h to 22 h.
Further, the carbonized precursor material is preferably soaked in an HF solution with the mass fraction of 5-10% for not less than 10 hours, and the soaking time is more preferably 10-15 hours.
The positive electrode material of the lithium-sulfur battery comprises the graphitized mesoporous nano carbon material prepared by the method and sulfur, wherein the sulfur is loaded on the graphitized mesoporous nano carbon material.
Further, the mass ratio of the graphitized mesoporous nano carbon material to sulfur is preferably 3: 2-2: 3.
Has the advantages that:
(1) the method has the advantages of simple and easily obtained raw materials, simple process flow, low production cost and easy realization of large-scale industrial production, and can be used as an adsorbent, a catalyst, a conductive agent and the like to be applied to the fields of medical treatment, construction, chemical industry, environmental protection, machinery and the like.
(2) The graphitized mesoporous carbon material has a large specific surface area, provides a large-area conductive carrier for a sulfur positive electrode, a mesoporous structure provides a convenient and fast transmission channel for lithium ions/electrons and electrolyte, the graphitized carbon material enhances the conductivity of the material, and the material is applied to the positive electrode material of the lithium-sulfur battery, so that the first-circle discharge specific capacity, the rate capability and the cycle performance of the battery can be improved, and the graphitized mesoporous carbon material has a good application prospect in an electrode material of a power battery.
(3) Graphitization of carbon materials is always a hotspot of research, and the prior graphitization has high temperature, high cost, difficult realization and huge potential safety hazard. Aiming at the problem, the invention uses common materials as carbon sources, adopts a unique and reasonable synthesis means, successfully realizes the graphitization of the carbon materials to a certain degree at a lower temperature, not only saves the cost, but also is easy to realize the industrialization and reduces the safety risk. The graphitization can not be formed in a short heat preservation time, the raw materials are wasted, the cost is increased, the formed mesopores are blocked, and the collapse of a graphitized carbon structure is caused, so the graphitization temperature and time are strictly regulated and controlled.
(4) The invention selects the template agent with a capillary and porous structure to provide a template for the graphitized mesoporous carbon material, thereby playing a role in forming.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the graphitized mesoporous nanocarbon material prepared in example 1.
Fig. 2 is a low Transmission Electron Microscope (TEM) image of the graphitized mesoporous nanocarbon material prepared in example 1.
Fig. 3 is a high-power transmission electron microscope image of the graphitized mesoporous nanocarbon material prepared in example 1.
Fig. 4 is a specific surface area test chart of the graphitized mesoporous nano carbon material prepared in example 1.
Fig. 5 is a distribution diagram of the pore size of the graphitized mesoporous nanocarbon material prepared in example 1.
Fig. 6 is a scanning electron microscope image of the graphitized mesoporous nanocarbon material prepared in example 2.
Fig. 7 is a low power transmission electron microscope image of the graphitized mesoporous nanocarbon material prepared in example 2.
Fig. 8 is a high-power transmission electron microscope image of the graphitized mesoporous nanocarbon material prepared in example 2.
Fig. 9 is a specific surface area test chart of the graphitized mesoporous nanocarbon material prepared in example 2.
Fig. 10 is a distribution diagram of the pore size of the graphitized mesoporous nanocarbon material prepared in example 2.
FIG. 11 is a graph comparing X-ray diffraction (XRD) patterns of graphitized mesoporous nanocarbon materials prepared in example 1 and example 2 with a commercial carbon material CMK-3.
Fig. 12 is a graph comparing the cycle performance of batteries assembled using the sulfur-loaded carbon materials of example 1, example 2, and comparative example 1, respectively.
Fig. 13 is a graph comparing rate performance of batteries assembled using the sulfur-loaded carbon materials of example 1, example 2, and comparative example 1, respectively.
Detailed Description
The present invention is further illustrated by the following figures and detailed description, wherein the processes are conventional unless otherwise specified, and the starting materials are commercially available from a public source without further specification.
In the following examples:
SBA-15 powder: purchased from Nanjing pioneer nano materials science and technology company;
acetonitrile solvent: GC purity is not less than 98.0%, and alatin is used;
and (3) testing by a scanning electron microscope: instrument model FESEM, Hitachi SU8020, japan;
testing a high-resolution transmission electron microscope: the model of the instrument is HRTEM, JEOL JEM-2010, Japan.
Assembling the lithium-sulfur battery: the carbon material loaded with sulfur, a conductive agent Super P and a binder polytetrafluoroethyleneUniformly mixing ethylene according to the mass ratio of 80:10:10, coating the mixture on a current collector aluminum foil, putting the current collector aluminum foil into a 60 ℃ drying oven for drying for 12 hours, and then cutting pieces to be used as positive pole pieces; taking a lithium plate as a negative pole piece; the electrolyte is 1M lithium bistrifluoromethanesulfonimide (LiTFSI, Sigma Aldrich,99.99 percent), wherein the solvent is a mixed solvent of 1, 3 dioxolane and ethylene glycol dimethyl ether with the volume ratio of 1:1, and 1 to 5 weight percent of 0.5M LiNO is added3To properly mitigate the shuttling effect of polysulfides; celgard 2500 as battery separator was assembled under argon atmosphere to 2032 type button cells.
Example 1
(1) Firstly, drying SBA-15 powder in a 60 ℃ oven, then weighing 0.2g of the dried SBA-15 powder and putting the powder into a porcelain boat, and then putting the porcelain boat containing the SBA-15 powder into a tube furnace; the anti-suck-back device filled with 400mL of acetonitrile solvent is connected between an air inlet of the tube furnace and a nitrogen gas source, wherein two ends of the anti-suck-back device are both provided with three-way connecting valves, and a deoxygenation pipeline is connected between the two three-way connecting valves;
(2) adjusting a three-way connecting valve switch on the suck-back prevention device to communicate the nitrogen gas source, the deoxygenation pipeline and the tubular furnace, and introducing nitrogen into the tubular furnace at the flow rate of (150 +/-10) mL/min for 30min to remove oxygen in the tubular furnace; then adjusting a three-way connecting valve switch on the suck-back prevention device to communicate a nitrogen gas source, the suck-back prevention device and the tubular furnace, introducing the nitrogen gas into the tubular furnace after continuously passing through the acetonitrile solvent at the flow rate of (95 +/-5) mL/min, heating the tubular furnace to 900 ℃ at the heating rate of 20 ℃/min, and preserving the heat at 900 ℃ for 3 hours to obtain a carbonized precursor material;
(3) and soaking the carbonized precursor material in a 10% HF solution for 12h to fully etch away the template agent, then washing the template agent for three times by using distilled water, and then drying the template agent in a vacuum drying oven at 60 ℃ for 12h to obtain the graphitized mesoporous nano carbon material (abbreviated as CVD-C-1).
As can be seen from the SEM image of FIG. 1, the prepared carbon material has a nanorod structure with a length of 5-20 μm and a diameter of 5-20 nm, and has uniform size distribution and high order.
According to FIG. 4 and the drawing5, the prepared carbon material has larger specific surface area (464 m)2The pore diameter is mostly distributed between 2nm and 10nm, which indicates that the interior is mesoporous. As can be seen by combining the TEM image of FIG. 2, the interior of the prepared carbon material is of an ordered mesoporous structure, and the mesoporous morphology is complete.
The apparent lattice fringes in fig. 3 indicate and the diffraction signature peaks in fig. 11 indicate that the carbon material produced exhibits a graphitization transition.
Mixing sulfur powder and the prepared material in a ratio of 60: 40, putting the mixture into a sealing tube in an argon environment, putting the sealing tube into a heating incubator, and heating the sealing tube at 155 ℃ for 15 hours to obtain the sulfur/graphitized mesoporous nano carbon cathode material (abbreviated as S/CVD-C-1) with 53 wt% of sulfur loading. The obtained sulfur/graphitized mesoporous nano carbon cathode material is assembled into a lithium sulfur battery to be subjected to electrochemical performance test, the test voltage interval is 1.7V-2.8V, and the test temperature is 25 ℃.
When the assembled lithium-sulfur battery is subjected to a constant-current charge-discharge cycle performance test at a 5C (1C: 1675mA/g) rate, due to the generation of SEI, the discharge specific capacity of the first circle of the lithium-sulfur battery is 320mAh/g, the cycle is stable after 2 circles of activation, the discharge capacity of the 3 rd circle reaches 430mAh/g, and the discharge specific capacity can still be maintained at 328.7mAh/g after 100 circles of cycle, as shown in FIG. 12.
When the assembled lithium-sulfur battery is subjected to constant current charging and discharging for 5 circles under the multiplying power of 0.5C, 1C, 2C and 5C in sequence and subjected to multiplying power performance test, the average specific discharge capacity of the lithium-sulfur battery under each multiplying power of 0.5C, 1C, 2C and 5C for 5 circles is 1081.6mAh/g, 970.2mAh/g, 649.5mAh/g and 226.6mAh/g in sequence, as shown in FIG. 13.
Example 2
(1) Firstly, drying SBA-15 powder in a 60 ℃ oven, then weighing 0.2g of the dried SBA-15 powder and putting the powder into a porcelain boat, and then putting the porcelain boat containing the SBA-15 powder into a tube furnace; the anti-suck-back device filled with 400mL of acetonitrile solvent is connected between an air inlet of the tube furnace and a nitrogen gas source, wherein two ends of the anti-suck-back device are both provided with three-way connecting valves, and a deoxygenation pipeline is connected between the two three-way connecting valves;
(2) adjusting a three-way connecting valve switch on the suck-back prevention device to communicate the nitrogen gas source, the deoxygenation pipeline and the tubular furnace, and introducing nitrogen into the tubular furnace at the flow rate of (150 +/-10) mL/min for 30min to remove oxygen in the tubular furnace; then adjusting a three-way connecting valve switch on the suck-back prevention device to communicate a nitrogen gas source, the suck-back prevention device and the tubular furnace, introducing the nitrogen gas into the tubular furnace after continuously passing through the acetonitrile solvent at the flow rate of (95 +/-5) mL/min, heating the tubular furnace to 1000 ℃ at the heating rate of 20 ℃/min, and preserving the heat for 20 hours at 1000 ℃ to obtain a carbonized precursor material;
(3) and soaking the carbonized precursor material in a 10% HF solution for 12h to fully etch away the template agent, then washing the template agent for three times by using distilled water, and then drying the template agent in a vacuum drying oven at 60 ℃ for 12h to obtain the graphitized mesoporous nano carbon material (abbreviated as CVD-C-2).
As can be seen from the SEM image of FIG. 6, the prepared carbon material has a nanorod structure with a length of 5-20 μm and a diameter of 5-20 nm, and has uniform size distribution.
As can be seen from the results of the test of FIG. 9, the prepared carbon material has a large specific surface area (47.4 m)2The reason for the reduction in specific surface area relative to the carbon material prepared in example 1 is: as the holding time is prolonged, the graphitization degree is increased, but the material structural framework is inevitably collapsed, and partial pores are blocked, so that partial surface area is sacrificed. According to the test results in FIG. 10, the pore diameter of the prepared carbon material is mostly distributed between 2nm and 10nm, which indicates that the interior is mesoporous; as can be seen from the TEM image of FIG. 7, the interior of the prepared carbon material is of an ordered mesoporous structure, the mesopores are slightly collapsed, and the pore order is slightly reduced.
The lattice fringes are more pronounced in fig. 8 compared to fig. 3; the characteristic peak intensity of the carbon material prepared in example 2 in fig. 11 is significantly stronger than that of the carbon material prepared in example 1, indicating that the carbon material prepared in example 2 exhibits graphitization and the degree of graphitization is higher than that of the carbon material prepared in example 1.
Mixing sulfur powder and the prepared material in a ratio of 60: 40, putting the mixture into a sealed tube in an argon environment, putting the sealed tube into a heating incubator, and heating the sealed tube at 155 ℃ for 15 hours to obtain the sulfur/graphitized mesoporous nano carbon cathode material (abbreviated as S/CVD-C-2) with 53 wt% of sulfur loading. The obtained sulfur/graphitized mesoporous nano carbon cathode material is assembled into a lithium sulfur battery to be subjected to electrochemical performance test, the test voltage interval is 1.7V-2.8V, and the test temperature is 25 ℃.
When the assembled lithium-sulfur battery is subjected to a constant-current charge-discharge cycle performance test at a 5C (1C: 1675mA/g) rate, the discharge specific capacity of the first circle of the lithium-sulfur battery reaches 777mAh/g, the discharge specific capacity can still be kept at 598mAh/g after 100 circles of cycle, and the discharge specific capacity can still be kept at 439.7mAh/g after 300 circles of cycle, as shown in FIG. 12.
When the assembled lithium-sulfur battery is subjected to constant current charging and discharging for 5 circles under the multiplying power of 0.5C, 1C, 2C and 5C in sequence to carry out a multiplying power performance test, the average specific discharge capacity of the lithium-sulfur battery under each multiplying power of 0.5C, 1C, 2C and 5C for 5 circles is 939.4mAh/g, 861.9mAh/g, 773.2mAh/g and 601.9mAh/g in sequence, as shown in FIG. 13.
Comparative example 1
A commercial carbon material CMK-3 (pioneer nanotechnology Co., Ltd.) was used to load the same sulfur loading as in example 1, and a sulfur/CMK-3 positive electrode material was obtained accordingly. And electrochemical performance tests were performed under the same conditions.
As can be seen from the test results in fig. 12, when the assembled lithium-sulfur battery is subjected to a constant current charge-discharge cycle performance test at a 5C (1C — 1675mA/g) rate, the discharge specific capacity of the first coil of the lithium-sulfur battery is 113.9mAh/g, and the discharge specific capacity after 100 cycles is 62.8 mAh/g.
According to the test results of fig. 13, when the assembled lithium-sulfur battery is subjected to a rate performance test for 5 cycles of constant current charging and discharging at 0.5C, 1C, 2C and 5C rates in sequence, the average specific discharge capacities of the lithium-sulfur battery at 0.5C, 1C, 2C and 5C at 5 cycles are 1351.5mAh/g, 834.9mAh/g, 718.8mAh/g and 181.5mAh/g in sequence.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of a graphitized mesoporous nano carbon material is characterized by comprising the following steps: the steps of the method are as follows,
placing the porcelain boat containing the template agent powder into a tube furnace, and connecting an anti-suck-back device containing the acetonitrile solvent between an air inlet of the tube furnace and an air source; removing oxygen in the tubular furnace, adjusting a gas source to enable the gas to continuously pass through an acetonitrile solvent at the flow rate of 50 mL/min-100 mL/min, introducing the gas into the tubular furnace, heating the tubular furnace to 900-1100 ℃, and preserving the heat at the temperature of 900-1100 ℃ for 1-30 h to obtain a carbonized precursor material; soaking the carbonized precursor material in HF solution to remove the template agent, and then cleaning and drying to obtain the graphitized mesoporous nano carbon material;
wherein the gas of the gas source is nitrogen or inert gas; the template agent powder is SBA-15 powder.
2. The method for preparing a graphitized mesoporous nano carbon material according to claim 1, wherein: the mass ratio of the acetonitrile solvent to the template powder is not less than 1175: 1.
3. The method for preparing a graphitized mesoporous nano carbon material as claimed in claim 2, wherein: the mass ratio of the acetonitrile solvent to the template powder is (1175-1600): 1.
4. The method for preparing a graphitized mesoporous nano carbon material according to claim 1, wherein: heating the tubular furnace to 900-1100 ℃ at a heating rate of 10-20 ℃/min.
5. The method for preparing a graphitized mesoporous nano carbon material according to claim 1, wherein: preserving the heat for 18 to 22 hours at 950 to 1050 ℃ to obtain the carbonized precursor material.
6. The method for preparing a graphitized mesoporous nano carbon material according to claim 1, wherein: the carbonized precursor material is soaked in 5-10 wt% HF solution for at least 10 hr.
7. The method for preparing a graphitized mesoporous nano carbon material according to claim 6, wherein: the carbonized precursor material is soaked in 5 to 10 mass percent of HF solution for 10 to 15 hours.
8. A positive electrode material for a lithium-sulfur battery, characterized in that: the cathode material comprises a graphitized mesoporous nanocarbon material prepared by the method of any one of claims 1 to 7 and sulfur, wherein the sulfur is supported on the graphitized mesoporous nanocarbon material.
9. The positive electrode material for a lithium-sulfur battery according to claim 8, wherein: the mass ratio of the graphitized mesoporous nano carbon material to sulfur is 3: 2-2: 3.
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