CN108666570B - Porous carbon nanobelt lithium-sulfur battery positive electrode material and preparation method and application thereof - Google Patents

Porous carbon nanobelt lithium-sulfur battery positive electrode material and preparation method and application thereof Download PDF

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CN108666570B
CN108666570B CN201810335294.1A CN201810335294A CN108666570B CN 108666570 B CN108666570 B CN 108666570B CN 201810335294 A CN201810335294 A CN 201810335294A CN 108666570 B CN108666570 B CN 108666570B
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lithium
sulfur
porous carbon
positive electrode
sulfur battery
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CN108666570A (en
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邹继兆
余良
曾燮榕
曾绍忠
黎晓华
姚跃超
刘世钰
涂文烜
陈双双
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Shenzhen University
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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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a porous carbon nanobelt lithium-sulfur battery positive electrode material, a preparation method thereof, a lithium-sulfur battery positive electrode and a lithium-sulfur battery. The preparation method of the porous carbon nanobelt lithium-sulfur battery positive electrode material comprises the following steps of: preparing a carbon nanobelt precursor; carbonizing and activating the carbon nanobelt precursor; and depositing a sulfur simple substance in the nitrogen-oxygen co-doped porous carbon nanoribbon. The porous carbon nanobelt lithium-sulfur battery positive electrode material prepared by the preparation method has the advantages of large specific surface area, good wettability and high elemental sulfur content, remarkably improves the sulfur fixation performance, and effectively inhibits the electrochemical performance such as shuttle effect of polysulfide. The lithium-sulfur battery positive electrode and the lithium-sulfur battery contain the lithium-sulfur battery positive electrode material prepared by the method.

Description

Porous carbon nanobelt lithium-sulfur battery positive electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrode materials, in particular to a porous carbon nanobelt lithium-sulfur battery positive electrode material and a preparation method and application thereof.
Background
The energy problem is the main problem facing human beings in the future, and resources such as petroleum, coal mine and the like are increasingly deficient at present, and the development process is large in consumption and serious in pollution, so that clean energy which can be continuously utilized is vigorously developed in all countries, and the storage and management of the energy cannot be left. And the energy storage material plays a very important role in energy storage and management. Secondary batteries are currently the most widely used energy storage devices, with lithium ion batteries occupying the major market due to their higher energy density (150-. However, as the actual energy density of the current lithium ion battery is very close to the theoretical energy density, huge breakthrough is difficult to generate.
The lithium-sulfur battery is a novel energy storage device, and is a lithium battery with sulfur as a battery anode and metal lithium as a cathode. The elemental sulfur has rich reserves in the earth, and has the characteristics of low price, environmental friendliness and the like. The lithium-sulfur battery using sulfur as the anode material has higher material theoretical specific capacity and battery theoretical specific energy which respectively reach 1675m Ah/g and 2600Wh/kg, and is far higher than the capacity (<150mAh/g) of a lithium cobaltate battery widely applied in commerce. And sulfur is an environment-friendly element, basically has no pollution to the environment, is a lithium battery with a very promising prospect, and has a wide application prospect in the fields of transportation, electronic information, national defense, military industry, aerospace and the like.
Despite the advantages of lithium-sulfur batteries, lithium-sulfur batteries currently face the following major problems compared to lithium-ion batteries: poor cycling performance and faster energy decay. The main points are as follows: sulfur itself is very poor in conductivity; the volume of sulfur changes during charge and discharge, and cracks are generated to fall off from the electrode; the shuttle effect of polysulfide is accompanied in the charging and discharging process, so that the service life of the battery is influenced; the self-discharge of polysulfides causes the cell capacity to decay faster. An ideal sulfur electrode should therefore contain four features: (1) sufficient space to accommodate the volumetric expansion of sulfur; (2) good electronic conductivity and lithium ion transmission channel; (3) the electrode has a high specific surface area so as to maintain the shape of the electrode; (4) polysulfides are efficiently captured by physical and chemical means.
Various materials are used to improve the performance of sulfur positive electrodes, and among them, carbon materials having good conductivity and large specific surface area and pore volume are considered as very promising positive electrode materials for lithium sulfur batteries. The carbon-based material, such as currently used relatively more activated carbon, carbon nanotubes, carbon nanofibers, graphene and the like, has excellent conductivity, and the conductivity of the lithium-sulfur battery positive electrode material can be greatly improved by compounding the carbon material with sulfur, and the dissolution of polysulfide can also be reduced due to the carbon adsorption. Among them, activated carbon is the most studied material and is the most widely used carbon material in a supercapacitor and the like because it is easy to prepare, has a high specific surface area and a low production cost, but activated carbon has too many micropores and has a relatively single pore size, so that the utilization rate of the specific surface area is very limited, which affects the diffusion and transmission of electrons and ions, and degrades the performance of, for example, a lithium sulfur battery. Carbon fibers have excellent conductivity and can be free of binders, but have a low apparent density, a low volumetric capacitance, and are expensive. Although the carbon nano tube has excellent conductivity and mechanical properties, if the pore diameter of the hierarchical pore structure is large, the size is easy to control, but the specific surface area is relatively small, and the production of the carbon nano tube is complicated and the production cost is high. Graphene is a material which is considered to have a good application prospect in recent years, has good conductivity, a large specific surface area and controllable pore size, but is easy to agglomerate, so that the performance of the graphene is greatly reduced.
In addition, the utilization rate of the specific surface area is not high due to the inherent hydrophobicity of the existing carbon material. Therefore, it is still a great challenge to achieve good rate performance and excellent cycle performance of the current positive electrode material for lithium-sulfur batteries by compounding carbon material with sulfur.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a porous carbon nanobelt lithium-sulfur battery positive electrode material and a preparation method thereof, so as to solve the technical problem that the rate capability and the cycle performance of the conventional carbon-containing lithium-sulfur battery positive electrode material are not ideal.
Another object of the present invention is to provide a lithium sulfur battery positive electrode and a lithium sulfur battery, so as to solve the technical problem that the rate capability and cycle performance of the lithium sulfur battery are poor due to the lithium sulfur positive electrode material of the existing lithium sulfur battery positive electrode and lithium sulfur battery.
In order to achieve the above object, in one aspect of the present invention, a method for preparing a porous carbon nanoribbon lithium-sulfur battery cathode material is provided. The preparation method of the porous carbon nanobelt lithium-sulfur battery positive electrode material comprises the following steps of:
carrying out hydrothermal reaction on formaldehyde and hydroquinone in an acid solution to obtain a carbon nanobelt precursor;
carbonizing the carbon nanoribbon precursor and activating with ammonia water to obtain a nitrogen-oxygen co-doped porous carbon nanoribbon;
and (3) mixing the porous carbon nanoribbon with elemental sulfur, and then carrying out heat treatment in a closed environment to volatilize the elemental sulfur and deposit the elemental sulfur in the porous carbon nanoribbon.
In another aspect of the invention, a porous carbon nanoribbon lithium-sulfur battery cathode material is provided. The porous carbon nanobelt lithium-sulfur battery positive electrode material is prepared by the preparation method of the porous carbon nanobelt lithium-sulfur battery positive electrode material.
In yet another aspect of the present invention, a lithium sulfur battery positive electrode is provided. The positive electrode of the lithium-sulfur battery comprises a current collector and a positive active layer combined on the current collector, wherein the positive active layer comprises a sulfur positive electrode material, a conductive agent and a binder, and the sulfur positive electrode material is the lithium-sulfur positive electrode material.
In yet another aspect of the present invention, a lithium sulfur battery is provided. The lithium-sulfur battery comprises a positive electrode and a negative electrode, and the positive electrode is the positive electrode of the lithium-sulfur battery.
Compared with the prior art, the preparation method of the porous carbon nanoribbon lithium-sulfur battery cathode material carries out ammonia water activation treatment on the carbon nanoribbon generated by carbonization treatment, thereby introducing functional groups containing nitrogen and oxygen on the carbon nanoribbon, effectively improving the wettability of the carbon nanoribbon and improving the utilization rate of the specific surface area of the carbon nanoribbon. Meanwhile, the porous carbon nanoribbon lithium-sulfur battery positive electrode material obtained by ammonia activation contains a porous structure with multi-stage pore diameters, so that the specific surface area of the generated porous carbon nanoribbon lithium-sulfur battery positive electrode material is large, and the multi-stage pores with the porous structure can also achieve synergistic interaction, so that the content of elemental sulfur is increased. Therefore, the porous carbon nanobelt lithium-sulfur battery anode material prepared by the preparation method has the advantages of large specific surface area, good wettability and high elemental sulfur content, remarkably improves the sulfur fixation performance, and effectively inhibits the electrochemical performance such as shuttle effect of polysulfide and the like. In addition, the preparation method has the advantages of relatively simple process, easily controlled conditions, high efficiency and stable performance of the prepared porous carbon nanobelt lithium-sulfur battery anode material.
The porous carbon nanoribbon lithium-sulfur battery cathode material has a porous structure, and the surface of the porous carbon nanoribbon lithium-sulfur battery cathode material contains nitrogen functional groups and oxygen functional groups, and sulfur simple substances can be uniformly deposited inside and outside the porous structure of the nitrogen-oxygen doped hollow carbon nanoribbons. Therefore, the porous carbon nanobelt lithium-sulfur battery positive electrode material has a large specific surface area, good wettability and high elemental sulfur content, remarkably improves the sulfur fixation performance, and effectively inhibits the electrochemical performance such as shuttle effect of polysulfide.
The lithium-sulfur battery positive electrode and the lithium-sulfur battery contain the lithium-sulfur battery positive electrode material, so the lithium-sulfur battery positive electrode and the lithium-sulfur battery have high specific capacitance, and also have good rate performance and cycling stability.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) picture of the carbon nanobelt precursor prepared in example 1 of the present invention;
fig. 2 is a Scanning Electron Microscope (SEM) picture of the nitrogen-oxygen co-doped porous carbon nanoribbon prepared in example 1 of the present invention;
FIG. 3 is a physical adsorption curve (BET) of nitrogen-doped hollow carbon nanospheres prepared in example 1 of the present invention;
FIG. 4 is a pore size distribution curve of nitrogen-doped hollow carbon nanospheres prepared in example 1 of the present invention;
fig. 5 is an X-ray photoelectron spectroscopy (XPS) image of the nitrogen-doped hollow carbon nanosphere prepared in example 1 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the invention belong. If a definition set forth in this section is contrary to or otherwise inconsistent with a definition set forth in the patents, patent applications, published patent applications, and other publications that are herein incorporated by reference, the definition set forth in this section prevails over the definition that is incorporated herein by reference.
In addition, the mass of the related components mentioned in the description of the embodiment of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the mass between each component, and therefore, it is within the scope of the disclosure of the description of the embodiment of the present invention to scale up or down the content of the related components according to the description of the embodiment of the present invention. Specifically, the mass described in the description of the embodiments of the present invention may be a mass unit known in the chemical industry field, such as μ g, mg, g, and kg.
In one aspect, embodiments of the present invention provide a preparation method of a porous carbon nanoribbon lithium-sulfur battery positive electrode material. The preparation method of the porous carbon nanoribbon lithium-sulfur battery positive electrode material comprises the following steps:
step S01, preparing a carbon nanobelt precursor:
carrying out hydrothermal reaction on formaldehyde and hydroquinone in an acid solution to obtain a carbon nanobelt precursor;
s02, carbonizing and activating the carbon nanobelt precursor:
carbonizing the carbon nanoribbon precursor and activating with ammonia water to obtain a nitrogen-oxygen co-doped porous carbon nanoribbon;
s03, depositing a sulfur simple substance in the nitrogen-oxygen co-doped porous carbon nanoribbon:
and mixing the nitrogen-oxygen co-doped porous carbon nanoribbon with elemental sulfur, and then carrying out heat treatment in a closed environment to volatilize the elemental sulfur and deposit the elemental sulfur in the porous carbon nanoribbon.
In step S01, the reaction formaldehyde and hydroquinone are subjected to a polymerization reaction in an acidic solution to form a ladder-shaped polymer. The chemical formula of the hydrothermal reaction between formaldehyde and hydroquinone is as follows:
Figure BDA0001626926740000061
in the reaction system, the produced product appeared to have a nano-ribbon shape as shown in FIG. 1.
In one embodiment, the temperature of the hydrothermal reaction in step S01 is 120-200 ℃, and the reaction time is 8-16 h. In another embodiment, the mass ratio of the formaldehyde to the hydroquinone is (1-5): (1-4); the mass ratio of the acid solution to the hydroquinone is (50-150): (1-4). Preferably, the mass ratio of the acid solution to formaldehyde and hydroquinone is (50-100): (1-4): (1-3). In a specific embodiment, the acid solution is diluted hydrochloric acid with a mass concentration of 5% -20%, and the concentration of the formaldehyde solution may also be 30% -40%, such as 37%. Therefore, by controlling and adjusting the hydrothermal reaction system, such as the concentration ratio of reactants, the reaction solvent, the hydrothermal reaction temperature, the hydrothermal reaction time and other factors, on one hand, the reaction efficiency of the reactants is improved, and the yield of the product is improved; on the other hand, the product is allowed to crystallize out a band-shaped carbon nanobelt precursor.
In the step S02, the carbonization treatment may be a conventional carbonization treatment, that is, the carbon nanoribbon precursor prepared in the step S01 is thermally cracked, so that the organic material is cracked into carbon. In one embodiment, the temperature of the carbonization treatment may be 700-1000 ℃. In addition, the carbonization treatment should be sufficient, such as in one embodiment, the heat treatment time at 700-. In addition, the heat treatment temperature is controlled to be raised to 700-1000 ℃ at a temperature raising rate of 2-10 ℃/min. Thus, the completeness of the form of the carbon nanobelt generated by carbonization is ensured by controlling the temperature rise rate, and the carbon nanobelt has a porous structure.
In one embodiment, the ammonia activation treatment is to perform heat treatment on the carbon nanoribbon with the porous structure generated by carbonization in a protective atmosphere at the temperature of 700-1000 ℃; and the protective atmosphere contains a mixed gas of ammonia and water vapor generated by thermal decomposition of ammonia water. The porous carbon nanobelts are activated by ammonia gas, so that rich nitrogen-containing functional groups and oxygen-containing functional groups are generated on the porous carbon nanobelts generated by carbonization, extra Faraday pseudo-capacitance can be increased by the existence of the nitrogen-containing functional groups and the oxygen-containing functional groups, the wettability of the porous carbon nanobelts on electrolyte is improved, the specific surface utilization rate of the porous carbon nanobelts is improved, the diffusion resistance of ions in the electrolyte in material pores is reduced, lone-pair electrons can be provided, the transmission rate of the electrons in the material is increased, the ions in the electrolyte are attracted to improve the concentration of an electric double layer, and the electrochemical performance of the material is improved.
In a preferred embodiment, the carbonization treatment and the ammonia activation treatment are carried out by the following methods:
in protective atmosphere, carrying out heat treatment on the carbon nanobelt precursor subjected to pulverization treatment at the temperature of 700-1000 ℃; and the protective atmosphere contains a mixed gas of ammonia and water vapor generated by thermal decomposition of ammonia water.
Thus, the carbonization treatment and the activation treatment are arranged in the same atmosphere for treatment, so that not only can rich nitrogen-containing and oxygen-containing functional groups be generated on the porous carbon nano-belt generated by the carbonization treatment, but also the wettability and the related electrochemical performance of the porous carbon nano-belt are improved; on the other hand, the porous structure on the surface of the lithium-sulfur battery can be effectively improved, so that the pores of the porous structure have gradient pore diameters, such as a multi-level pore structure containing micropores, mesopores and macropores, certainly, the porous structures with different pore diameters are randomly distributed, and the porous structure with the porous pore diameter distribution can improve the electrochemical performance of the porous carbon nanobelt lithium-sulfur battery anode material by a synergistic effect, such as when the porous carbon nanobelt lithium-sulfur battery anode material is used as a supercapacitor electrode material, the performances of specific capacity, rate capability, cycling stability and the like can be improved.
In addition, the protective atmosphere for the carbonization or activation treatment may be provided by argon, and ammonia gas and water vapor volatilized by heating by introducing ammonia gas into the protective atmosphere may be introduced with the argon gas. In one embodiment, the flow rate of the argon gas may be set to 20-150ml/min, and the volatilized ammonia and water vapor of the ammonia water should be sufficient, for example, the ammonia water may be heated, specifically, at 20-80 ℃, so that the volatilized ammonia and water vapor are brought together with the protective gas.
Before the carbonization treatment and the ammonia water activation treatment are carried out on the carbon nanobelt precursor, the method also comprises the treatment steps of washing, pulverizing and the like on the carbon nanobelt precursor. In the present invention, the carbon nanoribbon precursor is washed by any washing method capable of removing the unreacted reactant and the solvent residue, without affecting the carbon nanoribbon precursor, and the carbon nanoribbon precursor is washed with water, filtered until the filtrate is nearly neutral, and then dried.
The pulverization treatment of the washed carbon nanoribbon precursor may be performed by a conventional method, such as pulverization treatment of the carbon nanoribbon precursor according to the particle size requirement.
In the step S03, the elemental sulfur may volatilize after being heated, and then may deposit on the surface of the nitrogen-oxygen co-doped porous carbon nanoribbon and in the porous structure thereof, so that the elemental sulfur may be uniformly re-nucleated with the nitrogen-oxygen co-doped porous carbon nanoribbon, thereby improving the electrochemical performance of the porous carbon nanoribbon lithium-sulfur battery cathode material. In one embodiment, the weight ratio of the nitrogen-oxygen co-doped porous carbon nanoribbon to elemental sulfur is controlled to be (3-8): (4-8); in another embodiment, the temperature of the heat treatment, i.e. the temperature for controlling the volatilization of the elemental sulfur is 150-.
In a specific embodiment, the nitrogen-oxygen co-doped porous carbon nanoribbon and elemental sulfur are added into CS2Fully grinding and uniformly mixing the solution, placing the solution in a closed container, and volatilizing sulfur at high temperature such as 150-250 ℃ to fully enter pores of the hollow carbon nano microspheres.
Therefore, the preparation method of the porous carbon nanobelt lithium sulfur battery anode material has the advantages that the prepared porous carbon nanobelt lithium sulfur battery anode material has large specific surface area, good wettability and high elemental sulfur content by setting the process steps and conditions, the sulfur fixation performance is obviously improved, and the electrochemical performance such as shuttle effect of polysulfide and the like is effectively inhibited. In addition, the preparation method has the advantages of relatively simple process, easily controlled conditions, high efficiency and stable performance of the prepared porous carbon nanobelt lithium-sulfur battery anode material.
Based on the preparation method of the porous carbon nanoribbon lithium-sulfur battery cathode material, the embodiment of the invention also provides a porous carbon nanoribbon lithium-sulfur battery cathode material, and specifically, the porous carbon nanoribbon lithium-sulfur battery cathode material is prepared by the preparation method of the porous carbon nanoribbon lithium-sulfur battery cathode material. Therefore, the porous carbon nanobelt lithium-sulfur battery cathode material has a porous structure on one hand, and the porous structure can be a multi-level pore structure with randomly distributed unequal pore diameters, such as a multi-level pore structure containing micropores, mesopores and macropores (according to IUPAC (International Union of Pure and applied Chemistry), wherein pore channels in the carbon material can be divided into macropores (> 50nm), mesopores (2-50nm) and micropores (< 2nm)) according to the pore diameter, and the specific surface area of the porous carbon nanobelt lithium-sulfur battery cathode material is detected to be as high as 3000m2(ii)/g; on the other hand, the porous carbon nanoribbon lithium-sulfur battery positive electrode material is bonded with abundant nitrogen-containing functional groups and oxygen-containing functional groups on the surface, has good wettability and high elemental sulfur content, remarkably improves the sulfur fixation performance, and effectively inhibits the electrochemical performance such as shuttle effect of polysulfide and the like. The porous carbon nanobelt lithium-sulfur battery positive electrode material has the structural characteristics, so that the porous carbon nanobelt lithium-sulfur battery positive electrode material has electrochemical properties such as high rate performance, cycling stability and the like. Through determination, the thickness of the porous carbon nanoribbon lithium-sulfur battery anode material is 10-30nm, the width is 50-200nm, and the length is micron-sized, for example, the length is tens of microns.
On the other hand, based on the lithium-sulfur battery positive electrode material and the preparation method thereof, the embodiment of the invention also provides a lithium-sulfur battery positive electrode. The lithium sulfur battery positive electrode may include necessary components of the lithium sulfur battery positive electrode, such as a current collector and a positive active layer bonded on the current collector.
The current collector may be a commonly used positive current collector material, such as aluminum foil.
The positive electrode active layer may include a sulfur positive electrode material, a conductive agent, and a binder. Wherein, the weight ratio of the sulfur anode material, the conductive agent and the binder can be (60-90): (5-20): (5-20), further (70-90): (5-15): (5:20). The binder may be, but is not limited to PVDF, and the conductive agent may be, but is not limited to acetylene black. The sulfur positive electrode material is the porous carbon nanoribbon lithium sulfur battery positive electrode material. Therefore, based on the characteristics of the porous carbon nanoribbon lithium sulfur battery cathode material described above. The lithium-sulfur battery positive electrode has larger specific capacity, higher rate performance and good cycling stability. In one embodiment, the positive active layer is formed by coating a slurry containing the sulfur positive electrode material, a conductive agent, and a binder on a current collector to a thickness of 50 to 300 μm, and then performing a drying process (e.g., vacuum, 40 to 100 ℃).
On the basis of the lithium-sulfur battery positive electrode, the embodiment of the invention also provides a lithium-sulfur battery. The lithium sulfur battery comprises necessary components, such as a positive electrode and a negative electrode, wherein the positive electrode is the positive electrode of the lithium sulfur battery of the embodiment of the invention. Thus, the lithium-sulfur battery has specific capacity, higher rate performance and good cycling stability.
The invention will now be described in further detail by taking specific porous carbon nanoribbon lithium-sulfur battery positive electrode materials, and a preparation method and application thereof as examples.
1. Porous carbon nanoribbon lithium-sulfur battery positive electrode material and preparation method embodiment thereof
Example 1
The embodiment provides a porous carbon nanoribbon lithium-sulfur battery cathode material and a preparation method thereof. The preparation method of the porous carbon nanobelt lithium-sulfur battery positive electrode material comprises the following steps of:
s11: weighing 120g of 10% diluted hydrochloric acid, 2.5g of 37% formaldehyde solution and 1.65g of hydroquinone, and stirring the three for 30min until a uniform and transparent solution is formed;
s12: pouring the solution prepared in the step into a hydrothermal reaction kettle with polytetrafluoroethylene as a lining, sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a drying oven at 180 ℃, reacting for 12 hours, and naturally cooling to room temperature;
s13: filtering the product obtained in the step, washing the product for 5 times by using deionized water, and then placing the product in a vacuum drying oven to dry the product for 24 hours at the temperature of 60 ℃;
s14: grinding the dried product (carbon nanobelt precursor) into powder, sealing and storing for later use;
s15: placing 1.5g of carbon nanobelt in a corundum crucible, placing the crucible in a tubular furnace, introducing ammonia gas decomposed by heated ammonia water (50 ℃) and steam into the tubular furnace by using argon gas with the flow rate of 50ml/min, wherein the tubular furnace is filled with mixed gas of the argon gas, the steam and the ammonia gas;
s16: heating the tubular furnace from room temperature at a heating rate of 5 ℃/min to 950 ℃, preserving the heat for 40min, and then cooling to room temperature to obtain the nitrogen-oxygen co-doped porous carbon nanoribbon;
s17: grinding 160mg of nitrogen-oxygen co-doped porous carbon nanoribbons and 240mg of sulfur uniformly, and adding 4ml of CS2Further grinding until CS2And after complete volatilization, placing the mixture in a closed container, keeping the temperature at 155 ℃ for 12h to volatilize sulfur to enter pores of the nitrogen-oxygen co-doped porous carbon nanoribbon, and cooling to room temperature to obtain the sulfur-loaded nitrogen-oxygen co-doped porous carbon nanoribbon, namely the porous carbon nanoribbon lithium-sulfur battery positive electrode material.
Example 2
The embodiment provides a porous carbon nanoribbon lithium-sulfur battery cathode material and a preparation method thereof. The preparation method of the porous carbon nanobelt lithium-sulfur battery positive electrode material comprises the following steps of:
s11: weighing 125g of 10% diluted hydrochloric acid, 2.8g of 37% formaldehyde solution and 1.5g of hydroquinone, and stirring the three for 20 min;
s12: pouring the solution prepared in the step into a hydrothermal reaction kettle with polytetrafluoroethylene as a lining, sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a drying oven at 150 ℃, reacting for 15h, and naturally cooling to room temperature;
s13: filtering the product obtained in the step, washing the product for 6 times by using deionized water, and then placing the product in a common drying oven to dry the product for 15 hours at the temperature of 80 ℃;
s14: grinding the dried product (carbon nanobelt precursor) into powder, sealing and storing for later use;
s15: putting 1.0g of carbon nanobelt in a corundum crucible, putting the crucible in a tubular furnace, and introducing ammonia gas decomposed by heated ammonia water (40 ℃) and steam into the tubular furnace by using argon gas with the flow rate of 80ml/min, wherein the tubular furnace is filled with mixed gas of the argon gas, the steam and the ammonia gas;
s16: heating the tube furnace from room temperature at a heating rate of 5 ℃/min to 800 ℃, preserving the heat for 90min, and then cooling to room temperature to obtain the nitrogen-oxygen co-doped porous carbon nanoribbon;
s17: grinding 200mg of nitrogen-oxygen co-doped porous carbon nanoribbon and 200mg of sulfur uniformly, and adding 5ml of CS2Further grinding until CS2And after complete volatilization, placing the mixture in a closed container, keeping the temperature at 160 ℃ for 10h to volatilize sulfur to enter pores of the nitrogen-oxygen co-doped porous carbon nanoribbon, and cooling to room temperature to obtain the sulfur-loaded nitrogen-oxygen co-doped porous carbon nanoribbon, namely the porous carbon nanoribbon lithium-sulfur battery positive electrode material.
Example 3
The embodiment provides a porous carbon nanoribbon lithium-sulfur battery cathode material and a preparation method thereof. The preparation method of the porous carbon nanobelt lithium-sulfur battery positive electrode material comprises the following steps of:
s11: weighing 100g of 15% diluted hydrochloric acid, 2.0g of 37% formaldehyde solution and 1.2g of hydroquinone, and stirring the three for 60 min;
s12: pouring the solution prepared in the step into a hydrothermal reaction kettle with polytetrafluoroethylene as a lining, sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a baking oven at 190 ℃, reacting for 8 hours, and naturally cooling to room temperature;
s13: filtering the product obtained in the step, washing the product for 5 times by using deionized water, and then placing the product in a common drying oven to dry the product for 12 hours at the temperature of 100 ℃;
s14: grinding the dried product (carbon nanobelt precursor) into powder, sealing and storing for later use;
s15: putting 1.2g of the carbon nanobelt in a corundum crucible, putting the crucible in a tubular furnace, and introducing ammonia gas decomposed by heated ammonia water (60 ℃) and steam into the tubular furnace by using argon gas with the flow rate of 40ml/min, wherein the tubular furnace is filled with mixed gas of the argon gas, the steam and the ammonia gas;
s16: heating the tube furnace from room temperature at a heating rate of 10 ℃/min to 900 ℃, preserving heat for 30min, and then cooling to room temperature to obtain the nitrogen-oxygen co-doped porous carbon nanoribbon;
s17: grinding 150mg of nitrogen-oxygen co-doped porous carbon nanoribbon and 250mg of sulfur uniformly, and adding 3ml of CS2Further grinding until CS2And after complete volatilization, placing the mixture in a closed container, keeping the temperature at 160 ℃ for 10h to volatilize sulfur to enter pores of the nitrogen-oxygen co-doped porous carbon nanoribbon, and cooling to room temperature to obtain the sulfur-loaded nitrogen-oxygen co-doped porous carbon nanoribbon, namely the porous carbon nanoribbon lithium-sulfur battery positive electrode material.
Example 4
The embodiment provides a porous carbon nanoribbon lithium-sulfur battery cathode material and a preparation method thereof. The preparation method of the porous carbon nanobelt lithium-sulfur battery positive electrode material comprises the following steps of:
s11: weighing 150g of 8% diluted hydrochloric acid, 3.0g of 37% formaldehyde solution and 2g of hydroquinone, and uniformly mixing and stirring the three for 35 min;
s12: pouring the solution prepared in the step into a hydrothermal reaction kettle with polytetrafluoroethylene as a lining, sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an oven at 170 ℃, reacting for 14h, and naturally cooling to room temperature;
s13: filtering the product obtained in the step, washing the product for 5 times by using deionized water, and then placing the product in a hollow drying box for drying for 20 hours at 70 ℃;
s14: grinding the dried product (carbon nanobelt precursor) into powder, sealing and storing for later use;
s15: putting 1.0g of carbon nanobelt in a corundum crucible, putting the crucible in a tubular furnace, and introducing ammonia gas decomposed by heated ammonia water (30 ℃) and steam into the tubular furnace by using argon gas with the flow rate of 60ml/min, wherein the tubular furnace is filled with mixed gas of the argon gas, the steam and the ammonia gas;
s16: heating the tubular furnace from room temperature at a heating rate of 4 ℃/min to 850 ℃, keeping the temperature for 70min, and then cooling to room temperature to obtain the nitrogen-oxygen co-doped porous carbon nanoribbon;
s17: grinding 100mg of nitrogen-oxygen co-doped porous carbon nanoribbon and 120mg of sulfur uniformly, and adding 2ml of CS2Further grinding until CS2And after complete volatilization, placing the mixture in a closed container, keeping the temperature at 200 ℃ for 8h to volatilize sulfur and enable the sulfur to enter pores of the carbon nanoribbon, and cooling to room temperature to obtain the sulfur-loaded nitrogen-oxygen co-doped porous carbon nanoribbon, namely the porous carbon nanoribbon lithium-sulfur battery positive electrode material.
Example 5
The embodiment provides a porous carbon nanoribbon lithium-sulfur battery cathode material and a preparation method thereof. The preparation method of the porous carbon nanobelt lithium-sulfur battery positive electrode material comprises the following steps of:
s11: weighing 80g of 15% diluted hydrochloric acid, 2.4g of 37% formaldehyde solution and 1.2g of hydroquinone, and stirring the three for 30 min;
s12: pouring the solution prepared in the step into a hydrothermal reaction kettle with polytetrafluoroethylene as a lining, sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a 175-DEG C drying oven, reacting for 10h, and naturally cooling to room temperature;
s13: filtering the product obtained in the step, washing the product for 5 times by using deionized water, and then placing the product in a common drying box to dry the product for 12 hours at the temperature of 120 ℃;
s14: grinding the dried product (carbon nanobelt precursor) into powder, sealing and storing for later use;
s15: placing 2.0g of carbon nanobelt in a corundum crucible, placing the crucible in a tubular furnace, introducing ammonia gas decomposed by heated ammonia water (55 ℃) and steam into the tubular furnace by using argon gas with the flow rate of 30ml/min, wherein the tubular furnace is filled with mixed gas of the argon gas, the steam and the ammonia gas;
s16: heating the tube furnace from room temperature at the heating rate of 6 ℃/min to 750 ℃, preserving the heat for 120min, and then cooling to room temperature to obtain the nitrogen-oxygen co-doped porous carbon nanoribbon;
s17: grinding 100mg of nitrogen-oxygen co-doped porous carbon nanoribbon and 80mg of sulfur uniformly, and adding 2ml of CS2Further grinding until CS2And after complete volatilization, placing the mixture in a closed container, keeping the temperature at 165 ℃ for 12h to volatilize sulfur to enter pores of the nitrogen-oxygen co-doped porous carbon nanoribbons, and cooling to room temperature to obtain the nitrogen-oxygen co-doped porous carbon nanoribbons loaded with sulfur, namely the porous carbon nanoribbons lithium-sulfur battery positive electrode material.
Further, the carbon nanoribbon precursor, the nitrogen-oxygen co-doped porous carbon nanoribbon and the porous carbon nanoribbon lithium-sulfur battery cathode material prepared in embodiments 1 to 5 are subjected to scanning electron microscopy, respectively, wherein a scanning electron microscopy picture of the carbon nanoribbon precursor provided in embodiment 1 is shown in fig. 1, and a scanning electron microscopy picture of the nitrogen-oxygen co-doped porous carbon nanoribbon is shown in fig. 2. As can be seen from fig. 1 and 2, the carbon nanoribbon precursor and the nitrogen-oxygen co-doped porous carbon nanoribbon are both in a ribbon structure, and the ribbon structure has dimensions such as length and span in a nanoscale and is uniform in size distribution. Scanning electron microscope scanning is carried out on the porous carbon nanoribbon lithium-sulfur battery cathode material prepared in the example 1, and the shape and the size of the porous carbon nanoribbon are basically the same as those of the nitrogen-oxygen co-doped porous carbon nanoribbon in the example 1. In the examples 2-5, scanning electron microscope images of the carbon nanoribbon precursor, the nitrogen-oxygen co-doped porous carbon nanoribbon and the porous carbon nanoribbon lithium-sulfur battery positive electrode material are similar to those in the example 1.
The nitrogen and oxygen co-doped porous carbon nanoribbons prepared in examples 1 to 5 were further subjected to physical adsorption property and pore size distribution and X-ray photoelectron spectroscopy analysis, wherein the physical adsorption curve (BET) of the nitrogen and oxygen co-doped porous carbon nanoribbons of example 1 is shown in fig. 3, the pore size distribution curve is shown in fig. 4, and the X-ray photoelectron spectroscopy analysis image is shown in fig. 5. As can be seen from FIG. 3, the nitrogen absorption and desorption curve of the nitrogen-oxygen co-doped porous carbon nanoribbon is a typical I/IV type absorption curveLines, all at low relative pressure (P/P)0<0.05)N2The adsorption capacity rises sharply and then reaches the equilibrium rapidly, which shows that all the nitrogen-oxygen co-doped porous carbon nanoribbons including the porous carbon nanoribbons exist a large number of micropores (< 2nm) in the positive electrode material of the lithium-sulfur battery, and the structure is P/P0In the area with the range of 0.9-1, desorption curves of all the nitrogen-oxygen co-doped porous carbon nanoribbons and the porous carbon nanoribbon lithium-sulfur battery positive electrode material are obviously lagged behind adsorption curves, so that a lagging loop is formed, which shows that numerous mesopores (2-50nm) and macropores (more than 50nm) exist in the nitrogen-oxygen co-doped porous carbon nanoribbons and the porous carbon nanoribbon lithium-sulfur battery positive electrode material. As can be seen from fig. 4, the nitrogen-oxygen co-doped porous carbon nanoribbons are distributed in micropores, mesopores and macropores, and have a hierarchical pore structure; as can be seen from fig. 5, the nitrogen-oxygen co-doped porous carbon nanoribbon contains C, N, O elements, and thus, it contains hydrophilic groups, nitrogen groups and oxygen groups.
Examples 2-5 nitrogen and oxygen co-doped porous carbon nanoribbons were separately subjected to physical adsorption performance test results similar to those of example 1.
2. Supercapacitor electrode and supercapacitor embodiments
Example 6
The embodiment provides a supercapacitor electrode and a supercapacitor.
The super capacitor comprises electrodes and other necessary components, wherein the electrodes are prepared according to the following method:
the nitrogen-doped carbon nanobelt loaded with sulfur, PVDF powder, and acetylene black were uniformly ground in a mortar with 2ml of N-methylpyrrolidone (NMP) and then coated on an aluminum foil to a thickness of 200 μm. Wherein the nitrogen-doped carbon nanobelt loaded with sulfur: PVDF and acetylene black are mixed according to the weight ratio of 8:1: 1; then the aluminum foil coated with the electrode material is placed in a vacuum drying oven, hollow drying is carried out for 12 hours at the temperature of 60 ℃, and then a sheet punching machine is used for punching the aluminum foil containing the electrode material into an electrode sheet.
Example 7
The embodiment provides a supercapacitor electrode and a supercapacitor.
The super capacitor comprises an electrode and other necessary components, wherein the electrode is prepared according to the following method:
the nitrogen-doped carbon nanobelt loaded with sulfur, PVDF powder, and acetylene black were uniformly ground in a mortar with 2ml of N-methylpyrrolidone (NMP) and then coated on an aluminum foil to a thickness of 100 μm. Wherein the nitrogen-doped carbon nanobelt loaded with sulfur: PVDF and acetylene black in a weight ratio of 85:7: 8; and then placing the aluminum foil coated with the electrode material in a vacuum drying oven, drying in the air at 50 ℃ for 15h, and then punching the aluminum foil containing the electrode material into an electrode plate by using a punching machine.
The supercapacitor of example 7 was subjected to relevant electrochemical performance tests, and the test results are close to the performance of the supercapacitor of example 6.
Example 8
The embodiment provides a supercapacitor electrode and a supercapacitor.
The super capacitor comprises an electrode and other necessary components, wherein the electrode is prepared according to the following method:
the nitrogen-doped carbon nanobelt loaded with sulfur, PVDF powder, and acetylene black were uniformly ground in a mortar with 1.5ml of N-methylpyrrolidone (NMP) and then coated on an aluminum foil to a thickness of 50 μm. Wherein the nitrogen-doped carbon nanobelt loaded with sulfur: PVDF and acetylene black in a weight ratio of 80:8: 12; then the aluminum foil coated with the electrode material is placed in a vacuum drying oven, hollow drying is carried out for 10 hours at 70 ℃, and then a sheet punching machine is used for punching the aluminum foil containing the electrode material into an electrode sheet.
The super capacitor of the example 8 is subjected to relevant electrochemical performance tests, and the test result is close to the performance of the super capacitor of the example 6.
Example 9
The embodiment provides a supercapacitor electrode and a supercapacitor.
The super capacitor comprises an electrode and other necessary components, wherein the electrode is prepared according to the following method:
the nitrogen-doped carbon nanobelt loaded with sulfur, PVDF powder, and acetylene black were uniformly ground in a mortar with 2ml of N-methylpyrrolidone (NMP) and then coated on an aluminum foil to a 150 μm thick coating layer. Wherein the nitrogen-doped carbon nanobelt loaded with sulfur: PVDF and acetylene black in a weight ratio of 78:11: 11; and then placing the aluminum foil coated with the electrode material in a vacuum drying oven, drying in the air at 55 ℃ for 15h, and then punching the aluminum foil containing the electrode material into an electrode plate by using a punching machine.
The supercapacitor of the example 9 is subjected to relevant electrochemical performance tests, and the test result is close to the performance of the supercapacitor of the example 6.
Example 10
The embodiment provides a supercapacitor electrode and a supercapacitor.
The super capacitor comprises an electrode and other necessary components, wherein the electrode is prepared according to the following method:
the nitrogen-doped carbon nanobelt loaded with sulfur, PVDF powder, and acetylene black were uniformly ground in a mortar with 2ml of N-methylpyrrolidone (NMP) and then coated on an aluminum foil to a thickness of 100 μm. Wherein the nitrogen-doped carbon nanobelt loaded with sulfur: PVDF and acetylene black in a weight ratio of 75:10: 15; then the aluminum foil coated with the electrode material is placed in a vacuum drying oven, hollow drying is carried out for 10 hours at the temperature of 80 ℃, and then a sheet punching machine is used for punching the aluminum foil containing the electrode material into an electrode sheet.
The supercapacitor of the example 10 was subjected to relevant electrochemical performance tests, and the test results are close to the performance of the supercapacitor of the example 6.
The lithium sulfur batteries provided in examples 6 to 10 and the lithium sulfur batteries provided in comparative examples were subjected to the relevant electrochemical performance tests, respectively, according to the following measurement methods and results:
the determination method comprises the following steps: the voltage capacity curve of the cathode material at 0.1C rate and the cycle performance of the lithium-sulfur battery containing the cathode material at 1C rate were measured.
And (3) measuring results: example 6 provides a lithium sulfur battery with an initial discharge capacity of 1361mA · h · g of the electrode at 0.1C rate－1The initial discharge capacity of the electrode can reach 770 mA.h.g at the multiplying power of 1C－1And passed 300 times at 1C magnificationThe charging and discharging cycle of the battery can still maintain 475 mA.h.g－1The capacity of (c).
The prepared lithium-sulfur battery positive electrode material has high capacity, high nitrogen content and a hierarchical pore structure, so that the lithium-sulfur battery positive electrode material has high capacity and good rate capability, can effectively inhibit shuttle effect in the charge and discharge process, and has higher capacity, excellent rate capability and good cycle stability compared with the lithium-sulfur battery positive electrode materials with publication numbers of CN106981649A and CN 106654231.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (9)

1. A preparation method of a porous carbon nanobelt lithium-sulfur battery positive electrode material is characterized by comprising the following steps of:
carrying out hydrothermal reaction on formaldehyde and hydroquinone in an acid solution to obtain a carbon nanobelt precursor;
carbonizing the carbon nanoribbon precursor and activating with ammonia water to make the pores of the porous structure be gradient pore diameters containing microporous, mesoporous and macroporous hierarchical pore structures, so as to obtain the nitrogen-oxygen co-doped porous carbon nanoribbon; the carbonization treatment and ammonia water activation treatment method comprises the following steps: in protective atmosphere, carrying out heat treatment on the carbon nanobelt precursor at the temperature of 700-1000 ℃; the protective atmosphere contains a mixed gas of ammonia and water vapor generated by heating and decomposing ammonia water;
and mixing the porous carbon nanoribbon with elemental sulfur, and then carrying out heat treatment in a closed environment to volatilize the elemental sulfur and deposit the elemental sulfur in the porous carbon nanoribbon.
2. The preparation method as claimed in claim 1, wherein the hydrothermal reaction temperature is 120-200 ℃ and the reaction time is 8-16 h.
3. The process according to claim 1 or 2, wherein the mass ratio of the formaldehyde to the hydroquinone is (1-5): (1-4); and/or
The mass ratio of the acid solution to the hydroquinone is (50-150): (1-4); and/or
The acid solution is dilute hydrochloric acid with the mass concentration of 5-20%.
4. The method of claim 1, wherein: the time of the heat treatment is 20-120 min; and/or
The heat treatment temperature is raised to 700-1000 ℃ at a temperature raising rate of 2-10 ℃/min.
5. The production method according to any one of claims 1, 2 and 4, characterized in that: the weight ratio of the porous carbon nanoribbon to the elemental sulfur is (3-8): (4-8); and/or
The temperature for volatilizing the elemental sulfur is 150-250 ℃.
6. A porous carbon nanoribbon lithium-sulfur battery cathode material, which is prepared by the preparation method of any one of claims 1 to 5.
7. The porous carbon nanoribbon lithium-sulfur battery cathode material as claimed in claim 6, wherein the thickness of the porous carbon nanoribbon lithium-sulfur battery cathode material is 10-30nm, the width is 50-200nm, and the length is in micron order; and/or
The porous carbon nanoribbon lithium-sulfur battery positive electrode material contains a porous structure.
8. A lithium sulfur battery positive electrode comprising a current collector and a positive active layer bonded on the current collector, characterized in that the positive active layer comprises a sulfur positive electrode material, a conductive agent and a binder, wherein the sulfur positive electrode material is the lithium sulfur battery positive electrode material according to claim 6 or 7.
9. A lithium sulfur battery comprising a positive electrode and a negative electrode, wherein the positive electrode is the lithium sulfur battery positive electrode of claim 8.
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