CN112786845A - VS4Hierarchical pore graphitized carbon composite material, preparation method thereof, positive electrode material, positive plate, lithium-sulfur battery cell and lithium-sulfur battery pack - Google Patents
VS4Hierarchical pore graphitized carbon composite material, preparation method thereof, positive electrode material, positive plate, lithium-sulfur battery cell and lithium-sulfur battery pack Download PDFInfo
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- CN112786845A CN112786845A CN201911085848.8A CN201911085848A CN112786845A CN 112786845 A CN112786845 A CN 112786845A CN 201911085848 A CN201911085848 A CN 201911085848A CN 112786845 A CN112786845 A CN 112786845A
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- 239000007774 positive electrode material Substances 0.000 title claims description 6
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 25
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 6
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- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical group [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
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- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- 229910052744 lithium Inorganic materials 0.000 description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 2
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- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- 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
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a VS4The preparation method comprises the following steps of: providing hierarchical porous graphitized carbon; dispersing the multi-stage porous graphitized carbon in a strong acid solution to increase the content of the carbonConnecting carboxyl on the hierarchical pore graphitized carbon or dispersing the hierarchical pore graphitized carbon in a strong alkaline solution to connect hydroxyl on the hierarchical pore graphitized carbon to obtain modified hierarchical pore graphitized carbon, and cleaning the modified hierarchical pore graphitized carbon to be neutral and then drying; and a load VS4Dispersing the modified hierarchical porous graphitized carbon in a solvent, adding a vanadium source and a sulfur source, and performing a second hydrothermal reaction to obtain VS4A hierarchical porous graphitized carbon composite material. Simple preparation steps and high yield, and has better electrochemical performance and VS when being applied to the lithium-sulfur battery4On one hand, the conductive material has good conductivity, and the reaction kinetics are accelerated; VS on the other hand4Can well inhibit the shuttling of polysulfide, thereby improving the cycle stability of the lithium-sulfur battery.
Description
Technical Field
The invention relates to the field of energy storage devices, in particular to a voltage VS switch4A/hierarchical pore graphitized carbon composite material, a preparation method thereof, a positive electrode material, a positive plate, a lithium-sulfur battery cell, a lithium-sulfur battery pack and application.
Background
The ever-increasing demand for emerging electric vehicles and renewable energy storage markets has led to the exploration of the next generation of energy storage devices. Rechargeable lithium-sulfur batteries are increasingly receiving attention due to their advantages of high theoretical energy density (2600Wh/kg), abundant sulfur reserves, low cost, environmental friendliness, and the like. Lithium sulfur batteries also face a number of challenges. First, sulfur can form polysulfide Li soluble in organic electrolyte with lithium during redox reaction2SX(2 < X < 8), and the 'shuttle effect' of polysulfide in the charging and discharging process causes poor coulombic efficiency and reduced cycle stability of the battery. Secondly, elemental sulfur has poor conductivity, is an insulator (10-30 s/cm) for ions and electrons, cannot be directly used as an electrode material, and a reduction product Li2S2And Li2S is an electronic insulator. Third, the reactant sulfur and the final product Li2The large difference of S density causes the lithium-sulfur battery to be accompanied with huge difference in charging and discharging processesThe volume changes, the electrode structure is easily pulverized and falls off from the current collector, thereby causing the significant attenuation of the battery capacity. The above problems result in low utilization of electrode active materials and poor cycle life of batteries, hindering the commercialization process of lithium sulfur secondary batteries.
Most studies have been made to solve the existing problems by using carbon materials having a high specific surface area and a well-designed pore structure as a sulfur carrier, such as mesoporous/microporous carbon, porous hollow carbon spheres, hollow carbon fiber spheres, carbide foams, and the like. The structure has the advantages that firstly, carbon has good conductivity, which is beneficial to improving the conductivity of the composite material; secondly, the porous structure design provides a buffering bed for sulfur, can relieve the influence of sulfur caused by volume change in the charging and discharging process, and finally, the carbon material with high specific surface area and special pore structure has physical adsorption effect on polysulfide generated in the reaction process, inhibits the loss of the polysulfide and slows down the shuttle effect of the polysulfide. Although electrochemical cells made with these carbonaceous materials exhibit a significant capacity increase over the first few tens of cycles, they suffer severe degradation over extended cycles, primarily because the carbon materials of this structure, although physisorbing polysulfides, are relatively weak.
Therefore, a more strongly adsorbing material is desired to solve the existing problems.
Disclosure of Invention
The first purpose of the invention is to provide a VS4The composite material has strong adsorption effect and good conductivity and can contribute gram capacity.
It is a second object of the present invention to provide a VS4Preparation method of/hierarchical-pore graphitized carbon composite material and VS prepared by method4The/hierarchical pore graphitized carbon composite material has strong adsorption effect and good conductivity and can contribute gram capacity.
The third purpose of the invention is to provide a lithium-sulfur battery positive electrode material, which contains VS with strong adsorption effect, good conductive performance and capable of contributing gram capacity4A hierarchical porous graphitized carbon composite material.
The fourth object of the present invention is to provide a positive electrode sheet for a lithium-sulfur battery, which has a strong adsorption effect, a good conductivity and a capability of contributing to a gram volume of VS4A hierarchical porous graphitized carbon composite material.
It is a fifth object of the present invention to provide a lithium sulfur cell comprising VS which has strong adsorption, good conductivity and contributes to gram capacity4A hierarchical porous graphitized carbon composite material.
It is a sixth object of the present invention to provide a lithium sulfur battery pack comprising VS which has a strong adsorption effect and a good conductivity and can contribute to gram capacity4A hierarchical porous graphitized carbon composite material.
A seventh object of the present invention is to apply the lithium sulfur battery pack of the present invention.
To achieve the above object, the present invention provides a VS4A preparation method of a/hierarchical pore graphitized carbon composite material comprises the following steps: providing hierarchical porous graphitized carbon; modifying the hierarchical pore graphitized carbon, dispersing the hierarchical pore graphitized carbon in a strong acid solution, connecting carboxyl to the hierarchical pore graphitized carbon or dispersing the hierarchical pore graphitized carbon in a strong base solution, connecting hydroxyl to the hierarchical pore graphitized carbon to obtain modified hierarchical pore graphitized carbon, cleaning the modified hierarchical pore graphitized carbon to be neutral, and drying; and a load VS4Dispersing the modified hierarchical porous graphitized carbon in a solvent, adding a vanadium source and a sulfur source, and performing a second hydrothermal reaction to obtain VS4A hierarchical porous graphitized carbon composite material.
The method adopts cheap resin as a raw material, metal cobalt or nickel as a catalyst and an alkaline compound as a pore-forming agent, prepares the graphitized carbon with the high specific surface area and the hierarchical pores by a melt cracking method, has simple process and can be prepared in large batch, and for example, a patent with the publication number of CN106927451A discloses 'three-dimensional graphene and self-template catalytic pyrolysis of a carbon source thereof'. Due to the special structure of the carbon material, the carbon material can be applied to lithium-sulfur batteries and can be used for polysulfideThe compound has good physical adsorption effect. In order to better adsorb polysulfide, we further modify the carbon material, graft hydroxyl or carboxyl, and then load VS on the surface of the hydroxylated or carboxylated carbon4Nanoparticles, formation of VS4A hierarchical porous graphitized carbon composite material. The design of this structure has the following advantages: 1) the composite material has a large specific surface area and a porous structure, can load more sulfur, and improves the loading capacity of the sulfur; 2) nanoporous graphitized carbon and VS in the composite4The conductive performance of the electrode is improved; 3) the hierarchical porous graphitized carbon in the composite provides physical adsorption, VS4Providing chemical adsorption, which is combined to be beneficial to better adsorbing polysulfide and inhibiting the shuttling of polysulfide; 4) VS4Has the characteristic of 'iso-sulfur body', can contribute to capacity in the charging and discharging interval of the lithium-sulfur battery, can be used as an active material of an electrode, and can improve the occupation ratio of the electrode active material.
VS4Particles are uniformly loaded on the surface of the hierarchical porous graphitized carbon to form VS4A hierarchical porous graphitized carbon composite material. The composite material has simple preparation steps and high yield, has good electrochemical performance when being applied to a lithium-sulfur battery, and does not add VS4Compared with the anode material, the performance is obviously improved. Transition metal sulfide VS4On one hand, the conductive material has good conductivity, and the reaction kinetics are accelerated; VS on the other hand4Can well inhibit the shuttling of polysulfide, thereby improving the cycle stability of the lithium-sulfur battery.
Further, the strong base is one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide and zinc hydroxide, the strong base is preferably sodium hydroxide, the strong acid is one or more of sulfuric acid, hydrochloric acid and nitric acid, the strong acid is preferably sulfuric acid, and the concentration of the strong acid and the strong base is 0.5-6 mol/L, preferably 2-6 mol/L.
Further, the way of connecting carboxyl or hydroxyl to the hierarchical porous graphitized carbon is as follows: dispersing the multi-stage hole graphitized carbon in a strong acid or strong base solution in an ultrasonic mode, and transferring the multi-stage hole graphitized carbon dispersed in the strong acid or strong base solution to a reaction kettle for a first hydrothermal reaction, so that the multi-stage hole graphitized carbon is connected with a carboxyl group or a hydroxyl group, the time of the first hydrothermal reaction is 3-48 h, preferably 6-12 h, and the temperature of the first hydrothermal reaction is 120-220 ℃, preferably 140-180 ℃. Under the preferred conditions, the hierarchical porous graphitized carbon is easier to be grafted with carboxyl or hydroxyl functional groups.
Further, the solvent is one or more of deionized water, ethylene glycol, methanol, ethanol and glycerol, preferably the solvent is an organic solvent, the modified hierarchical pore graphitized carbon is dispersed in the solvent in an ultrasonic manner, the ultrasonic time is 0.5-2 hours, preferably 1-2 hours, and the ultrasonic temperature is 25-45 ℃, preferably 35-45 ℃.
Further, the vanadium source is Na3VO4、NaVO3、NH4VO3、V2O5The sulfur source is one of thioacetamide and thiourea, the second hydrothermal reaction is carried out in a reaction kettle, the second hydrothermal reaction time is 3-24 hours, preferably 12-24 hours, the hydrothermal reaction temperature is 120-220 ℃, and preferably 140-180 ℃. Under preferred conditions, VS4Can be well loaded on the surface of the modified hierarchical pore graphitized carbon and has VS4The crystallinity of (a) will be good. After the second hydrothermal reaction, separating, cleaning and drying are carried out to obtain VS4A hierarchical porous graphitized carbon composite material.
The invention also provides a VS4Hierarchical porous graphitized carbon composites, said VS4The/hierarchical-pore graphitized carbon composite material is prepared by the preparation method.
The invention also provides a lithium-sulfur battery cathode material, which comprises the following components in percentage by mass: 10 to 39 wt% VS4The composite material comprises 60-80 wt% of sulfur, 5-10 wt% of a conductive agent and 5-10 wt% of an adhesive. The sulfur is sublimed sulfur. Further, the conductive agent is CNT, Super P, KB, acetylene black and stoneOne or two of graphene, and the adhesive is one of polyacrylonitrile, PVDF, CMC and LA-132.
VS according to the proportion4The preparation method comprises the steps of blending/multi-level hole graphitized carbon composite material, sublimed sulfur, conductive agent and adhesive, stirring and pulping, coating one or two surfaces of an aluminum foil by using a scraper, drying for a period of time in a blast oven, removing most of solvent, and then transferring to a vacuum oven for drying to be used as a positive plate of the lithium-sulfur battery.
The invention also provides a lithium-sulfur battery cell which comprises the positive plate, the negative plate, electrolyte, an isolating membrane and a packaging bag, wherein the isolating membrane is arranged between the negative plate and the positive plate, the packaging bag is made of an aluminum-plastic membrane composite material, and a bare battery cell made of the negative plate, the positive plate and the isolating membrane is arranged in the packaging bag.
The invention also provides a lithium-sulfur battery pack which comprises the lithium-sulfur battery cell.
The lithium-sulfur battery pack is also applied to the fields of unmanned aerial vehicles, portable equipment, new energy electric vehicles and the like.
Adding CoS2The load of the hierarchical porous graphitized carbon is also researched, and CoS is introduced2The gram capacity of the first and second circles of the lithium-sulfur battery reaches 1261mAh/g and 1181 mAh/g; the invention loads VS on the surface of the hierarchical porous graphitized carbon4Load VS4The gram capacity of the first circle and the gram capacity of the second circle of the lithium-sulfur battery can respectively reach 1451mAh/g and 1263mAh/g, the gram capacity is improved, and the energy density of the battery per unit area/mass is improved. In addition, for the hierarchical porous graphitized carbon, CoS is generated through hydrothermal reaction2And VS4The reaction mechanism of (a) is different, and CoS is generated on the hierarchical porous graphitized carbon2The functional group (-OH or-COOH) oxidized by grafting is only used for better dispersion in an aqueous solvent, so that the synthesized CoS2More uniform loading thereon to produce VS on the hierarchical porous graphitized carbon4Grafting functional groups on hierarchical porous graphitized carbon is also to enable the hierarchical porous graphitized carbon to be better in an aqueous solventOn the other hand, the functional groups (-OH or-COOH) and VS are grafted on4The reaction raw materials (such as sodium vanadate and thioacetamide) react to generate a reducing porous carbon material, so that the conductivity of the composite material is increased.
It should be noted that the hierarchical porous graphitized carbon used in the present invention is different from Graphene, (1) although the hierarchical porous graphitized carbon and Graphene are allotropes each other, both are simple substances composed of carbon atoms, but the arrangement of carbon atoms are different, and Graphene (Graphene) is a honeycomb-shaped planar thin film formed by carbon atoms in an sp2 hybridization manner, and is a quasi-two-dimensional material with a thickness of only one atomic layer, and is also called monoatomic layer graphite. The porous carbon belongs to multi-layer graphitized carbon and has micropores, mesopores and macropores, the specific surface area of the multi-level porous carbon is 1981-2400 m2/g, the total pore volume is 1.72-2.24 cm3/g, compared with the surface of single-layer graphene, the material transportation efficiency is improved due to the existence of the pores, and particularly, the pores of different levels can play a role in screening ions/molecules of different sizes. More importantly, the introduction of the holes also effectively opens the energy band gap and increases more reactive active points; (2) the property of the hierarchical porous graphitized carbon different from that of the two-dimensional graphene is derived from the introduction of nano-pores. Taking a redox method for preparing graphene as an example, in the reduction process, oxygen-containing functional groups on the surface are removed, electrostatic repulsion between sheet layers is reduced, so that graphene is easy to agglomerate, the agglomeration not only reduces the specific surface area, but also can prevent other substances such as electrolyte ions from entering the graphene sheet layers, and the material of a two-dimensional plane has no inhibition effect on the dissolution of sulfur or the volume change of sulfur in the charging and discharging process. The introduction of pores with different sizes in the surface of the multi-level pore graphitized carbon avoids adverse effects caused by agglomeration, the mesopores and the macropores can promote the permeation and transportation of substances, the micropores are favorable for improving the specific surface area, and the introduction of a nanopore structure enables the multi-level pore graphitized carbon to have the characteristics of high specific surface area, rich mass transfer channels, adjustable energy band gap, high pore edge activity, air permeability, good mechanical stability, biochemical sensing and the like. In summary, although both substances are composed of carbon elements, the structures of the two substances are completely different. It is well known to those skilled in the art that the structure determines the nature, and that different structures may perform differently in electrochemical reactions.
A large number of experiments have shown that the transition metal sulfide VS4It is used by many scholars to improve the performance of lithium sulfur batteries due to its higher conductivity and stronger chemisorption to polysulfides, but currently VS4The problems of complex preparation process, low yield, high impurity content and the like generally exist, so that the lithium-sulfur battery anode can not be widely used. The invention can obtain VS with higher S content by grafting oxidized functional group (-OH or-COOH) and performing hydrothermal reaction under the auxiliary action of the grafted oxidized functional group (-OH or-COOH)4The functionalized material is reduced into reductive carbon in the process, the conductivity of the composite material is increased, and the structural design combines the advantages of the two materials, so that the electrode material obtains better capacity in the conversion reaction and shows better lithium storage capacity.
Drawings
FIG. 1 is VS prepared in example 1 of the present invention4XRD pattern of the/hierarchical pore graphitized carbon composite material.
FIG. 2 is VS prepared in example 1 of the present invention4SEM photographs of/hierarchical porous graphitized carbon composites.
FIG. 3 is VS prepared in example 1 of the present invention4First circle and second circle charge-discharge curve diagrams of the/hierarchical pore graphitized carbon composite material anode.
FIG. 4 is VS prepared in example 1 of the present invention4Cycle performance graphs of the/hierarchical pore graphitized carbon composite anode and the comparative example 1 at 0.5C.
FIG. 5 is VS prepared in example 1 of the present invention4Performance graphs of the/hierarchical porous graphitized carbon composite anode and the comparative example 1 under different current densities.
Detailed Description
The "ranges" disclosed herein are in the form of lower and upper limits. There may be one or more lower limits, and one or more upper limits, respectively. The given range is defined by the selection of a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular range. All ranges that can be defined in this manner are inclusive and combinable, i.e., any lower limit can be combined with any upper limit to form a range. For example, ranges of 60-120 and 80-110 are listed for particular parameters, with the understanding that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present invention, all embodiments and preferred embodiments mentioned herein may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the steps mentioned herein may be performed sequentially or randomly, if not specifically stated, but preferably sequentially.
In the examples, unless otherwise specified, the technical means used are those conventional in the art.
In examples 1 to 8 and comparative examples 1 to 3:
the preparation method of the hierarchical pore graphitized carbon mainly refers to the preparation method of patent CN106927451A, and the specific operation steps are as follows:
1. adding 50g of pretreated ion exchange resin into 200ml of 0.2mol/L cobalt chloride aqueous solution, stirring for 2 hours, putting into 80 ℃ water bath, stirring, evaporating to dryness, drying by blowing at 80 ℃ for 12 hours, and crushing to obtain resin for adsorbing cobalt ions;
2. dissolving 100g of potassium hydroxide in 400ml of absolute ethanol to form a potassium hydroxide/ethanol solution, adding the product obtained in the step 1 into the potassium hydroxide/ethanol and calcium hydroxide/water solution, putting the mixture into an oil bath at 80 ℃, stirring and evaporating the mixture until the mixture is pasty, drying the mixture at 80 ℃, and then crushing the mixture again;
3. heating the product obtained in the step 2 to 800 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, preserving the heat for 2 hours, and naturally cooling to room temperature;
4. and (3) soaking the product obtained in the step (3) in 1mol/L hydrochloric acid solution for 36 hours, filtering, drying at 60 ℃ for 36 hours, and continuing to dry at 150 ℃ for 8 hours to obtain the hierarchical porous graphitized carbon.
Example 1:
weighing 150mg of hierarchical porous graphitized carbon, transferring the hierarchical porous graphitized carbon into 160mL of 2mol/L sodium hydroxide solution, ultrasonically dispersing for 1h, transferring the hierarchical porous graphitized carbon into a 200mL hydrothermal reaction kettle, reacting for 3h in a vacuum oven at 140 ℃, cleaning the obtained substance with deionized water until the pH value is 7, putting the substance into an oven at 80 ℃, and drying to obtain the modified hierarchical porous graphitized carbon.
100mg of the modified hierarchical porous graphitized carbon is taken and dispersed in 40ml of glycol solution, ultrasonic treatment is carried out for 1h at the temperature of 45 ℃, sodium orthovanadate and thioacetamide are sequentially added, the molar ratio S/V of sulfur element to vanadium element is 5, the obtained product is transferred to a 50ml reaction kettle, the hydrothermal temperature is 160 ℃, and the reaction is carried out for 12 h. And (3) carrying out suction filtration and cleaning on the obtained substance for three times by using deionized water and ethanol, and baking for 12 hours in a vacuum oven at the temperature of 80 ℃.
Homogenizing the obtained material with sublimed sulfur, SuperP and adhesive PAN at a ratio (wt%: 25:60:5:10), and coating the prepared slurry on aluminum foil with the loading amount controlled at 1.0-2.0mg/cm2And drying in a vacuum oven at 55 ℃, assembling the obtained positive plate into a button cell in a glove box, and carrying out electrochemical test.
For the above VS4Performing structure and morphology analysis on the/hierarchical pore graphitized carbon composite material, and performing 1VS on the embodiment4The/hierarchical porous graphitized carbon composite material is characterized. The XRD pattern (FIG. 1) indicates that the composite contains VS4XRD peak of crystal. From the SEM photograph (FIG. 2), it can be seen that VS having a diameter of 100 to 200nm is uniformly distributed on the matrix of the hierarchical porous graphitized carbon4The particles of (1). The above characterization results show that the VS is on the nanometer scale4Successfully and uniformly loaded on the hierarchical porous graphitized carbon matrix.
Example 1VS prepared4The/hierarchical porous graphitized carbon composite material used as a sulfur carrier applied to a lithium-sulfur battery cell shows excellent electrochemical performance. The positive electrode is 0.1C (1C ═ C)1675mAh/g) current density the first and second discharge specific capacities were 1451mAh/g and 1263mAh/g, respectively (FIG. 3).
Example 2:
compared with the embodiment 1, the difference is that sulfuric acid is selected for the functionalization of the hierarchical porous graphitized carbon, and other steps are consistent with the embodiment 1.
Example 3:
compared with the embodiment 1, the difference is that the multi-stage pore graphitized carbon/VS is synthesized4The solvent used in the composite material was deionized water, and the other steps were the same as in example 1.
Example 4:
compared with the embodiment 1, the difference is that the adhesive used for preparing the positive pole piece is LA-132, and other steps are consistent with the embodiment 1.
Example 5:
compared with the embodiment 1, the difference is that the multi-stage pore graphitized carbon/VS is synthesized4The reaction temperature required for the composite was 220 ℃ and the other steps were in accordance with example 1.
Example 6:
compared with the embodiment 1, the difference is that the multi-stage pore graphitized carbon/VS is synthesized4The reaction temperature required for the composite was 120 ℃ and the other steps were in accordance with example 1.
Example 7:
compared with the embodiment 1, the difference is that the multi-stage pore graphitized carbon/VS is synthesized4The reaction time required for the composite was 3h, and the other steps were identical to those of example 1.
Example 8:
compared with the embodiment 1, the difference is that the multi-stage pore graphitized carbon/VS is synthesized4The reaction time required for the composite was 24h, and the other steps were identical to those of example 1.
The excellent performances of the embodiments 2-8 are not significantly different from the embodiment 1.
Meanwhile, in order to illustrate the advantages of the composite electrode structure design of the present invention, the inventors also conducted the following comparative tests:
comparative example 1:
the positive plate is prepared by the ratio of the hierarchical pore graphitized carbon to the embodiment 1, and the test is carried out. The performance of the pole piece is shown in figures 4 and 5, and the load VS is the performance under the conditions of cycle stability and different current densities4The battery of (2) is better than the battery without load. The reason for this is attributed to the fact that the hierarchical porous graphitized carbon material without any treatment has a weak adsorption effect on polysulfides and is insufficient in physical adsorption.
Comparative example 2:
and (3) preparing the positive plate according to the proportion which is consistent with that of the embodiment 1 after the multi-level hole graphitized carbon is modified, and testing. The conclusion is that the cycle stability is better under low multiplying power and still is not higher than VS4The gram capacity of the positive plate prepared from the/hierarchical-pore graphitized carbon composite material is lower under high multiplying power. The reason can be summarized as that the modified hierarchical porous graphitized carbon has poor conductivity, the capacity exertion is influenced, and meanwhile, the adsorption effect of hydroxyl carboxyl on polysulfide is weak.
Comparative example 3:
compared with the embodiment 1, VS is directly synthesized without adding hierarchical porous graphitized carbon4And preparing and testing the positive plate according to the same proportion. The test capacity is lower, and the cycling stability is better. The reason can be summarized as that the graphitized carbon without the large specific surface area hierarchical pores is used as a carrier, VS4The lithium sulfide is easy to agglomerate in the synthesis process, the specific surface area of large particles is too small, reaction interfaces are few, and the deposition and volume expansion of the lithium sulfide are not facilitated. But VS4Has better adsorbability, so the cycle performance is better under low capacity.
Compared with the prior art, VS4The/hierarchical pore graphitized carbon composite material has the following advantages: 1) the composite material has a large specific surface area and a porous structure, can load more sulfur, and improves the loading capacity of the sulfur; 2) nanoporous graphitized carbon and VS in the composite4The conductive performance of the electrode is improved; 3) the hierarchical porous graphitized carbon in the composite provides physical adsorption, VS4Provide chemical adsorption, and the combination of the chemical adsorption and the chemical adsorption is favorable for better adsorbing polysulfide and inhibiting polysulfideShuttling of the compound; 4) VS4Has the characteristic of 'iso-sulfur body', can contribute to capacity in the charging and discharging interval of the lithium-sulfur battery, can be used as an active material of an electrode, and can improve the occupation ratio of the electrode active material. VS4Particles are uniformly loaded on the surface of the hierarchical porous graphitized carbon to form VS4A hierarchical porous graphitized carbon composite material. The composite material has simple preparation steps and high yield, has good electrochemical performance when being applied to a lithium-sulfur battery, and does not add VS4Compared with the anode material, the performance is obviously improved. Transition metal sulfide VS4On one hand, the conductive material has good conductivity, and the reaction kinetics are accelerated; VS on the other hand4Can well inhibit the shuttling of polysulfide, thereby improving the cycle stability of the lithium-sulfur battery.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the scope of the present invention, therefore, the present invention is not limited by the appended claims.
Claims (12)
1. VS (virtual switch)4The preparation method of the/hierarchical-pore graphitized carbon composite material is characterized by comprising the following steps:
providing hierarchical porous graphitized carbon;
modifying the hierarchical pore graphitized carbon, dispersing the hierarchical pore graphitized carbon in a strong acid solution, connecting carboxyl to the hierarchical pore graphitized carbon or dispersing the hierarchical pore graphitized carbon in a strong base solution, connecting hydroxyl to the hierarchical pore graphitized carbon to obtain modified hierarchical pore graphitized carbon, cleaning the modified hierarchical pore graphitized carbon to be neutral, and drying; and
load VS4Dispersing the modified hierarchical porous graphitized carbon in a solvent, adding a vanadium source and a sulfur source, and performing a second hydrothermal reaction to obtain VS4A hierarchical porous graphitized carbon composite material.
2. The VS of claim 14The preparation method of the/hierarchical pore graphitized carbon composite material is characterized in thatThe strong base is one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide and zinc hydroxide, the strong base is preferably sodium hydroxide, the strong acid is one or more of sulfuric acid, hydrochloric acid and nitric acid, the strong acid is preferably sulfuric acid, and the concentration of the strong acid and the strong base is 0.5-6 mol/L, preferably 2-6 mol/L.
3. The VS of claim 14The preparation method of the/hierarchical-pore graphitized carbon composite material is characterized in that the way of connecting carboxyl or hydroxyl on the hierarchical-pore graphitized carbon is as follows: transferring the hierarchical pore graphitized carbon dispersed in the strong acid or strong base solution to a reaction kettle for a first hydrothermal reaction, so that carboxyl or hydroxyl is connected to the hierarchical pore graphitized carbon, wherein the first hydrothermal reaction time is 3-48 h, preferably 6-12 h, and the first hydrothermal reaction temperature is 120-220 ℃, preferably 140-180 ℃.
4. The VS of claim 14The preparation method of the/hierarchical-pore graphitized carbon composite material is characterized in that the solvent is one or more of deionized water, ethylene glycol, methanol, ethanol and glycerol, the modified hierarchical-pore graphitized carbon is dispersed in the solvent in an ultrasonic mode, the ultrasonic time is 0.5-2 hours, preferably 1-2 hours, and the ultrasonic temperature is 25-45 ℃, preferably 35-45 ℃.
5. The VS of claim 14The preparation method of the/hierarchical pore graphitized carbon composite material is characterized in that the vanadium source is Na3VO4、NaVO3、NH4VO3、V2O5The sulfur source is one of thioacetamide and thiourea, the second hydrothermal reaction is carried out in a reaction kettle, the second hydrothermal reaction time is 3-24 hours, preferably 12-24 hours, the hydrothermal reaction temperature is 120-220 ℃, and preferably 140-180 ℃.
6. AVS4A/hierarchical porous graphitized carbon composite characterized in that said VS4The/hierarchical pore graphitized carbon composite material is prepared by the preparation method of any one of claims 1 to 5.
7. A positive electrode material for a lithium-sulfur battery, comprising, in mass percent:
8. the positive electrode material for lithium-sulfur batteries according to claim 7, wherein the conductive agent is one or two of CNT, Super P, KB, acetylene black and graphene, and the binder is one of polyacrylonitrile, PVDF, CMC and LA-132.
9. A positive plate of a lithium-sulfur battery is characterized by comprising a positive current collector and a positive material of the lithium-sulfur battery, wherein the positive material of the lithium-sulfur battery is arranged on one surface or two surfaces of the positive current collector, and the positive material of the lithium-sulfur battery is as defined in any one of claims 7 to 8.
10. A lithium sulfur cell, comprising:
the positive electrode sheet according to claim 9;
a negative plate;
the isolating film is arranged between the negative plate and the positive plate; and
the packaging bag is made of an aluminum-plastic film composite material, and the negative pole piece, the positive pole piece and the bare cell made of the isolating film are arranged in the packaging bag.
11. A lithium sulfur battery pack, comprising the lithium sulfur cell of claim 10.
12. The lithium sulfur battery pack according to claim 11 is applied to unmanned aerial vehicles, portable equipment, and new energy electric vehicles.
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