CN111900405A - Graphene-based positive electrode material, preparation method thereof and lithium-sulfur battery - Google Patents

Graphene-based positive electrode material, preparation method thereof and lithium-sulfur battery Download PDF

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CN111900405A
CN111900405A CN202010760916.2A CN202010760916A CN111900405A CN 111900405 A CN111900405 A CN 111900405A CN 202010760916 A CN202010760916 A CN 202010760916A CN 111900405 A CN111900405 A CN 111900405A
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graphene
mxene
sulfur
positive electrode
electrode material
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CN111900405B (en
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黄国家
李悦
杨波
李茂东
郭华超
李仕平
***
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Guangzhou Special Pressure Equipment Inspection and Research Institute
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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
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
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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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a graphene-based positive electrode material, a preparation method thereof and a lithium-sulfur battery. The preparation method of the graphene-based cathode material comprises the following steps: dispersing MXene/graphene composite material, copper salt and a sulfur source in a solvent to obtain a first mixed solution; placing the first mixed solution in a closed pressure system, and carrying out solvothermal reaction for 18-24 h at 100-180 ℃ to prepare a copper sulfide/MXene/graphene nano composite material; mixing the copper sulfide/MXene/graphene nano composite material with elemental sulfur, grinding, and standing at 155-180 ℃ for 10-18 h to prepare a graphene-based positive electrode material; the MXene is Ti3C2. The cathode material prepared by the invention can improve the electrochemical performance of the lithium-sulfur battery.

Description

Graphene-based positive electrode material, preparation method thereof and lithium-sulfur battery
Technical Field
The invention relates to the technical field of nano materials, in particular to a graphene-based positive electrode material, a preparation method thereof and a lithium-sulfur battery.
Background
Nowadays, in order to meet the increasing large-scale energy storage requirements and sustainable use, the development of new electrochemical energy storage systems is urgent. In a new energy storage system, the theoretical specific energy of a lithium-sulfur battery taking metal lithium as a negative electrode and elemental sulfur as a positive electrode can reach 2600Wh/kg (the theoretical specific capacities of lithium and sulfur are 3860mAh/g and 1675mAh/g respectively), which is far greater than that of a commercial secondary battery used at the present stage. Moreover, the lithium-sulfur battery has attracted much attention because of its outstanding advantages of high specific energy, low raw material cost, environmental friendliness, etc., and is considered to be one of the most valuable research directions in the next-generation large-scale energy storage system.
However, the commercialization of the lithium sulfur battery still encounters technical obstacles such as low utilization of sulfur as a positive active material due to inefficient fixation of elemental sulfur, and in addition, shuttle effect caused by dissolution of polysulfide and change in volume of the lithium sulfur battery cause a decrease in utilization of elemental sulfur, so that cycle stability, conductivity and lifetime of the lithium sulfur battery are deteriorated, and even a series of safety problems are caused.
For the fixation of elemental sulfur of a lithium-sulfur battery, the existing sulfur-carrying method is generally low in carrying capacity or complicated in steps, for example, a continuous carbon-coating and solution-phase oxidation reaction method is adopted to synthesize a carbon-coated sulfur nanosheet, and when a pure zinc sulfide nanosheet is prepared, a zinc sulfide hybrid nanosheet needs to be calcined in a high-temperature inert environment. The method has certain requirements on equipment, complicated steps and unsuitability for large-scale production, and in addition, the method mixes sublimed sulfur and mesoporous silicon oxide, and the sulfur simple substance is embedded into the pore diameter through capillary force after secondary calcination to obtain the silicon oxide sulfur compound. The method can fix sulfur by capillary force, and the firmness is still poor.
Therefore, how to improve the sulfur carrying capacity, specific capacity and cycling stability of the lithium-sulfur battery becomes a technical problem to be solved urgently by the technical personnel in the field.
Disclosure of Invention
Based on the above, the invention provides a preparation method of a graphene-based positive electrode material, and the sulfur/copper sulfide/MXene/graphene composite material is prepared, and when the composite material is used for a lithium-sulfur battery, the elemental sulfur fixity can be improved, the sulfur carrying capacity can be improved, the conductivity of the positive electrode material can be further improved, and the specific capacity of the lithium-sulfur battery can be improved. Meanwhile, shuttle effect generated by sulfide dissolution is reduced, the volume of the lithium-sulfur battery is stabilized, and the cycle stability of the lithium-sulfur battery is improved.
The specific technical scheme is as follows:
a preparation method of a graphene-based positive electrode material comprises the following steps:
dispersing MXene/graphene composite material, copper salt and a sulfur source in a solvent to obtain a first mixed solution;
placing the first mixed solution in a closed pressure system, and carrying out solvothermal reaction for 18-24 h at 100-180 ℃ to prepare a copper sulfide/MXene/graphene nano composite material;
mixing the copper sulfide/MXene/graphene nano composite material with elemental sulfur, grinding, and standing at 155-180 ℃ for 10-18 h to prepare a graphene-based positive electrode material;
the MXene is Ti3C2。
In some preferred embodiments, the mixed solution is placed in a closed pressure system, and is subjected to solvothermal reaction for 20 to 24 hours at the temperature of between 150 and 180 ℃ to prepare the copper sulfide/MXene nanocomposite.
In some preferred embodiments, the method for preparing the MXene/graphene composite material comprises the following steps:
adding MAX phase precursor into hydrofluoric acid etching solution, and reacting at 35-45 ℃ for 24-48 h to obtain MXene, wherein the MAX phase precursor is Ti3AlC2；
Mixing 1-aminopyrene and bis-succinimide suberate in dimethylformamide, and stirring to prepare a second mixed solution;
and adding MXene and graphene into the second mixed solution, and performing ultrasonic treatment to prepare the MXene/graphene composite material.
In some preferred embodiments, the molar ratio of MXene to graphene is (0.5-4): 1.
In some preferred embodiments, the molar ratio of 1-aminopyrene to bis-succinimidyl suberate is (1.5-2.5): 1.
In some preferred embodiments, the hydrofluoric acid etching solution is selected from a mixed solution of HCl and lithium fluoride, HF and NH4HF2One or more of them.
In some preferred embodiments, the mass ratio of the MXene/graphene composite material to the copper salt to the sulfur source is (0.08-0.12): (0.2-2): (0.1-4).
In some preferred embodiments, the copper salt is selected from one or more of cuprous chloride dihydrate, copper nitrate trihydrate, copper nitrate hexahydrate, and copper nitrate dihydrate.
In some preferred embodiments, the sulfur source is selected from one or more of urea, thiourea and thioacetyl.
In some preferred embodiments, the sulfur source is selected from one or more of urea, thiourea and thioacetyl.
In some preferred embodiments, the solvent is selected from one or more of water, carbon disulfide, absolute ethanol, and ethylene glycol.
In some preferred embodiments, the elemental sulfur is sublimed sulfur.
In some preferred embodiments, the mass ratio of the elemental sulfur to the copper sulfide/MXene nanocomposite is (1-4): (0.25-1).
In some preferred embodiments, the mass percentage of elemental sulfur in the mixture obtained after grinding is between 60% and 90%.
The invention also provides the graphene-based positive electrode material prepared by the preparation method.
The invention also provides a lithium-sulfur battery.
The lithium-sulfur battery comprises the graphene-based positive electrode material.
Compared with the prior art, the invention has the following beneficial effects:
MXene (Ti) is prepared first3C2) The graphene/graphene composite material is taken as one of preparation raw materials of a lithium-sulfur battery positive electrode material, and MXene (Ti) is synthesized3C2) And the high specific surface area and the high conductivity of the graphene are favorable for improving the electrochemical performance of the lithium-sulfur battery. And, MXene (Ti)3C2) MXene (Ti) with a large number of active sites on the surface3C2) MXene (Ti) when copper sulfide/MXene/graphene nano composite material is prepared from/graphene composite material, copper salt and sulfur source by solvothermal method3C2) The surface of the material has a large amount of negative electrons which can generate coordination with copper ions, so that the copper ions can be uniformly adsorbed on MXene (Ti)3C2) On the surface, MXene (Ti)3C2) The surface evenly load nanocluster copper sulfide, simultaneously, the graphite alkene conductivity is high, and mechanical strength is high, and under its existence, not only can inhale negative copper ion, still helps promoting carrier material conductivity and grid structure stability. In this process of forming copper sulfide, nanocluster copper sulfide nanosheets are in MXene (Ti)3C2) The graphene grows in a two-dimensional direction on the surface, the copper sulfide sheet layer grows in a crossed mode without agglomeration, a nanocluster shape similar to a nanoflower is formed, the formed nanoscale copper sulfide cluster is small in size and large in surface energy, elemental sulfur can be effectively fixed and can play a role together with MXene and graphene, and when the nanoscale copper sulfide cluster is mixed with the elemental sulfur in a high-temperature melting diffusion mode, the loading capacity of the elemental sulfur is improved, the conductivity of a positive electrode material is improved, and the specific capacity of the lithium-sulfur battery is improved. At the same time, through the uniformly loaded nanocluster copper sulfide and MXene (Ti)3C2) The MXene (Ti) is effectively improved under the action of graphene3C2) The active sites on the surface of graphene have the adsorption effect on elemental sulfur and polysulfide. Moreover, the better the growth state of the copper sulfide nano cluster is, the larger the surface energy is, so that the copper sulfide nano cluster can better adsorb simple substancesThe action of sulfur with polysulfides.
The sulfur/copper sulfide/MXene/graphene battery positive electrode material prepared by the method disclosed by the invention can reduce the content of high sulfide in electrolyte, not only improves the conversion efficiency, but also buffers the volume change of the positive electrode material by adsorbing elemental sulfur and polysulfide, keeps the electrode structures of a conductive framework and active substances, improves the capacity stability, and thus greatly improves the electrochemical performance of a lithium-sulfur battery.
Drawings
FIG. 1 shows the sulfur/copper sulfide/MXene (Ti) prepared in example 13C2) SEM image of/graphene composite;
fig. 2 is the first three cyclic voltammograms of the sulfur/copper sulfide/MXene (Ti3C 2)/graphene composite prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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 this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a preparation method of a graphene-based positive electrode material, which can solve the technical problems of low sulfur-carrying capacity, poor conductivity, low specific capacity and poor cycling stability of a lithium-sulfur battery.
The technical scheme is as follows:
a preparation method of a graphene-based positive electrode material comprises the following steps:
dispersing MXene/graphene composite material, copper salt and a sulfur source in a solvent to obtain a first mixed solution;
placing the first mixed solution in a closed pressure system, and carrying out solvothermal reaction for 18-24 h at 100-180 ℃ to prepare a copper sulfide/MXene/graphene nano composite material;
mixing the copper sulfide/MXene/graphene nano composite material with elemental sulfur, grinding, and standing at 155-180 ℃ for 10-18 h to prepare a graphene-based positive electrode material;
the MXene is Ti3C2。
In some preferred embodiments, MAX (Ti) may be used3AlC2) Preparing the graphene-like few-layer MXene (Ti) by taking a phase precursor as a raw material and adopting a hydrofluoric acid etching method3C2) Then a few layers of MXene (Ti)3C2) And compounding with graphene.
Preferably, the preparation method of the MXene/graphene composite material comprises the following steps:
adding MAX phase precursor into hydrofluoric acid etching solution, and reacting at 35-45 ℃ for 24-48 h to obtain MXene, wherein the MAX phase precursor is Ti3AlC2；
Mixing 1-aminopyrene and bis-succinimide suberate in dimethylformamide, and stirring to prepare a second mixed solution;
and adding MXene and graphene into the second mixed solution, and performing ultrasonic treatment to prepare the MXene/graphene composite material.
Understandably, after the reaction is carried out for 24 to 48 hours at the temperature of between 35 and 45 ℃, the reaction product can be subjected to centrifugation and ultrasonic treatment to prepare MXene (Ti) with few layers3C2)。
Preferably, the molar ratio of the 1-aminopyrene to the disuccinimidyl suberate is (1.5-2.5): 1. The stirring time is 20-28 h.
Preferably, the molar ratio of MXene to graphene is (0.5-4): 1, and after the MXene and graphene are added, ultrasonic treatment is carried out for 3-5 hours. The product can also be washed alternately with dimethylformamide and ethanol.
In some preferred embodiments, the hydrofluoric acid etching solution is selected from a mixed solution of HCl and lithium fluorideHF and NH4HF2One or more of them.
In some more preferred embodiments, the hydrofluoric acid etching is performed by using a mixed solution of HCl aqueous solution and lithium fluoride with the concentration of 6-12 mol/L, HF aqueous solution with the mass fraction of 30-50% or NH4HF2。
In some more preferred embodiments, the hydrofluoric acid etching solution is selected from a 40% HF aqueous solution or a 9mol/L HCl aqueous solution and lithium fluoride mixed solution.
Preferably, the temperature of the hydrofluoric acid etching reaction is 35 ℃ or 45 ℃.
Preferably, the time of the hydrofluoric acid etching reaction is 24h ℃ or 48 h.
MXene (Ti) obtained by the above method3C2) Graphene has high specific surface area and high conductivity, and MXene (Ti)3C2) Mixing it with copper salt and sulfur source, and solvothermal method to prepare copper sulfide/MXene (Ti)3C2) Graphene nanocomposites.
It should be understood that the MXene/graphene composite, the copper salt and the sulfur source are mixed in the solvent to uniformly disperse the components to obtain the mixed solution. And then placing the mixed solution in a closed pressure system for solvothermal reaction.
MXene (Ti) during the solvothermal reaction3C2) The surface of the material has a large amount of negative electrons which can generate coordination with copper ions, so that the copper ions can be uniformly adsorbed on MXene (Ti)3C2) On the surface, MXene (Ti)3C2) The surface of the nano-cluster copper sulfide nano-sheet is uniformly loaded with nano-cluster copper sulfide, and the nano-cluster copper sulfide nano-sheet is arranged on MXene (Ti)3C2) The copper sulfide layer grows in a two-dimensional direction on the surface, the copper sulfide layer grows in a cross mode without agglomeration, a nanocluster shape similar to a nanoflower is formed, the formed nanoscale copper sulfide cluster is small in size and large in surface energy, elemental sulfur can be effectively fixed, the copper sulfide cluster and the MXene and graphene composite material play a role together, and then the copper sulfide cluster and the elemental sulfur are mixed in a high-temperature melting diffusion mode to form a mixed effectDuring the process, the loading capacity of the elemental sulfur is improved, and the conductivity of the positive electrode material is improved. At the same time, through the uniformly loaded nanocluster copper sulfide and MXene (Ti)3C2) The effect of (2) effectively improves MXene (Ti)3C2) The adsorption of elemental sulphur and polysulphides by active sites of the surface.
Furthermore, the reaction temperature, the reaction time, the type and the amount of raw materials of the solvothermal reaction have influence on the growth state of the copper sulfide nano clusters, the better the growth state of the copper sulfide nano clusters is, the larger the surface energy is, and the better the effect of adsorbing elemental sulfur and polysulfide is exerted.
Preferably, the temperature of the solvothermal reaction is from 150 ℃ to 180 ℃, more preferably 150 ℃ or 180 ℃.
Preferably, the solvothermal reaction time is 20h to 24h, more preferably 24 h.
Preferably, the mass ratio of the MXene/graphene composite material to the copper salt to the sulfur source is (0.08-0.12): (0.2-2): (0.1-4).
Wherein, the copper salt can be one or more selected from cuprous chloride dihydrate, copper nitrate trihydrate, copper nitrate hexahydrate and copper nitrate dihydrate. Preferably, the copper salt is selected from cuprous chloride dihydrate or cupric nitrate hexahydrate.
The sulfur source can be one or more selected from urea, thiourea and thioacetyl. Preferably, the sulfur source is thiourea.
The solvent is selected from one or more of water, carbon disulfide, absolute ethyl alcohol and glycol.
After the copper sulfide/MXene/graphene nano composite material is prepared, the copper sulfide/MXene nano composite material is compounded with elemental copper by adopting a high-temperature melting diffusion reaction.
In some preferred embodiments, the mass ratio of the elemental sulfur to the copper sulfide/MXene/graphene nanocomposite is (1-4): 0.25-1.
The elemental sulfur is sublimed sulfur.
Preferably, the mass percentage of the sulfur element in the mixture obtained after grinding is 60-90%. More preferably, the percentage by mass of elemental sulphur is controlled to be 60%, 70%, 80% or 90%.
The reaction conditions of the high-temperature melting diffusion reaction affect the compounding effect of the copper sulfide/MXene/graphene nano composite material and the elemental copper. Preferably, the temperature of the high temperature melt diffusion reaction is 155 ℃, 160 ℃ or 180 ℃; the time of the high-temperature melt diffusion reaction is 10h, 12h or 18 h.
The sulfur/copper sulfide/MXene/graphene positive electrode material prepared by the method can improve elemental sulfur immobilization and sulfur carrying capacity, further improve conductivity and specific capacity, reduce shuttle effect generated by polysulfide dissolution, stabilize the volume of the lithium-sulfur battery and improve the cycling stability of the lithium-sulfur battery.
The invention also provides a sulfur/copper sulfide/MXene/graphene positive electrode material prepared by the preparation method. The obtained positive electrode material can reduce the content of high sulfide in electrolyte, not only improves the conversion efficiency, but also buffers the volume change of the positive electrode material by adsorbing elemental sulfur and polysulfide, keeps the electrode structures of a conductive framework and active substances, improves the capacity stability, and thus greatly improves the electrochemical performance of the lithium-sulfur battery.
The invention also provides a lithium-sulfur battery.
The lithium-sulfur battery comprises the graphene-based positive electrode material.
The following specific examples are further illustrated by the following specific examples, and the raw materials referred to in the following specific examples are all derived from commercially available common products unless otherwise specified.
Example 1
The embodiment provides a graphene-based positive electrode material and a preparation method thereof, and the preparation method comprises the following specific steps:
step one, preparing MXene (Ti)3C2) Graphene composite material
a) Preparation of less layer MXene (Ti)3C2): weighing 2g of lithium fluoride by using an electronic balance, weighing 40ml of 9mol/L HCl aqueous solution by using a measuring cylinder, respectively placing the solution in a plastic beaker, stirring and dissolving the solution at the constant temperature of 35 ℃ for 30min, and then weighing MAX (Ti) of titanium system by using the electronic balance3AlC2) 2g of phase precursor is slowly addedContinuously stirring and reacting for 24 hours in a plastic beaker at the constant temperature of 35 ℃; adding distilled water into the product, centrifuging at 4000 rpm for 5 min, repeating for 5 times, performing ultrasonic treatment in ice bath for 1 hr until pH value is close to 7, and collecting supernatant as final product, namely, low-layer MXene (Ti)3C2) Finally, freeze-drying the suspension to obtain graphene-like few-layer MXene (Ti)3C2) And (3) solid powder.
b) 1-aminopyrene and bis (succinimidyl) suberate are mixed according to a molar ratio of 2:1 in dimethylformamide and stirring for 24 hours to obtain a second mixed solution.
c) The obtained small layer MXene (Ti)3C2) Adding graphene into the second mixed solution according to the mass ratio of 2:1, performing ultrasonic treatment for 4 hours, and then alternately cleaning the mixture for 5 times by using dimethylformamide and ethanol to obtain MXene (Ti)3C2) A graphene composite material.
Step two: preparation of copper sulfide/MXene (Ti)3C2) Graphene nanocomposite material
80mg of MXene (Ti) as described above were weighed out3C2) Placing the graphene solid powder in a beaker containing 60ml of ethylene glycol, carrying out stirring and ultrasonic treatment until the graphene solid powder is dispersed into a uniform suspension, then weighing 0.2416g of copper nitrate trihydrate and 0.1522g of thiourea into the suspension, stirring and ultrasonically dispersing for 2 hours, transferring the solution into a 100ml hydrothermal kettle liner, sealing, and carrying out constant-temperature reaction in an oven at 150 ℃ for 24 hours. After the reaction is naturally cooled, centrifugally cleaning the mixture for many times by using distilled water and ethanol, freezing and freeze-drying the mixture to obtain copper sulfide/MXene (Ti)3C2) Graphene nanocomposite powder.
Step three: preparation of Sulfur/copper sulfide/MXene (Ti)3C2) Graphene battery positive electrode material
Mixing sublimed sulfur with the above copper sulfide/MXene (Ti)3C2) Weighing the graphene nano composite material according to a mass ratio of 7:3, fully grinding the graphene nano composite material in a mortar until no obvious yellow particles exist, ensuring that the content of sulfur in the mixture is 70%, pouring the mixture into a sealed small glass tank, and putting the small glass tank into a glove boxSealing the glass bottle filled with the ground powder in an inert gas atmosphere, taking out the glass bottle, placing the glass bottle in an oven at 160 ℃ for 12 hours, naturally cooling to room temperature, taking out the material from the glass bottle, placing the glass bottle in a mortar, fully grinding the material, and sieving the ground material with a 200-mesh sieve to obtain sulfur/copper sulfide/MXene (Ti, Cu, Ni, Mn3C2) The Scanning Electron Microscope (SEM) of the graphene-based positive electrode material is shown in fig. 1, and it can be seen from fig. 1 that the copper sulfide nanosheets are uniformly distributed in MXene (Ti) as shown in fig. 13C2) A surface.
The graphene-based positive electrode material of the embodiment is used as a positive electrode material, and is prepared into a positive plate, and then the positive plate, a PP diaphragm and a lithium metal negative electrode are assembled into the lithium-sulfur button cell.
The lithium sulfur button cell of this example was tested for various properties and the results are shown in table 1.
FIG. 2 is a CV diagram of the assembled battery of this example, and it can be seen from FIG. 2 that the redox peaks at circles 1, 2 and 3 are well overlapped, and the assembled sulfur/copper sulfide/MXene (Ti) of the lithium-sulfur battery3C2) The graphene material has good cycling stability.
Example 2
The embodiment provides a graphene-based positive electrode material and a preparation method thereof, and the preparation method comprises the following specific steps:
step one, preparing MXene (Ti)3C2) Graphene composite material
a) Preparation of less layer MXene (Ti)3C2): measuring 40ml of HF aqueous solution with the mass fraction of 40% by using a measuring cylinder, pouring the HF aqueous solution into a plastic beaker, and then weighing MAX (Ti) of the titanium system by using an electronic balance3AlC2) 2g of phase precursor is slowly put into a plastic beaker under magnetic stirring to continuously react for 24 hours at constant temperature of 35 ℃; adding distilled water into the product, centrifuging at 4000 rpm for 5 min, repeating for 5 times, performing ultrasonic treatment in ice bath for 1 hr until pH value is close to 7, and collecting supernatant as final product, namely, low-layer MXene (Ti)3C2) Finally, freeze-drying the suspension to obtain graphene-like few-layer MXene (Ti)3C2) And (3) solid powder.
b) 1-aminopyrene and bis (succinimidyl) suberate are mixed according to a molar ratio of 2:1 in dimethylformamide and stirring for 24 hours to obtain a second mixed solution.
c) The obtained small layer MXene (Ti)3C2) Adding graphene into the second mixed solution according to the mass ratio of 2:1, performing ultrasonic treatment for 4 hours, and then alternately cleaning the mixture for 5 times by using dimethylformamide and ethanol to obtain MXene (Ti)3C2) A graphene composite material.
Step two: preparation of copper sulfide/MXene (Ti)3C2) Graphene nanocomposite material
120mg of MXene (Ti) as described above were weighed out3C2) Placing the graphene solid powder in a beaker containing 30ml of ethylene glycol and 30ml of distilled water, carrying out ultrasonic stirring until the graphene solid powder is dispersed into a uniform suspension, and then weighing 1.70g of CuCl2·2H2O and 3.04g of thiourea are put into the suspension, stirred and ultrasonically dispersed for 2 hours, and then the solution is transferred into a 100ml hydrothermal kettle liner, sealed and reacted in an oven at the constant temperature of 180 ℃ for 24 hours. After the reaction is naturally cooled, centrifugally cleaning the mixture for many times by using distilled water and ethanol, freezing and freeze-drying the mixture to obtain copper sulfide/MXene (Ti)3C2) Graphene nanocomposite powder.
Step three: preparation of Sulfur/copper sulfide/MXene (Ti)3C2) Graphene battery positive electrode material
Mixing sublimed sulfur with the above copper sulfide/MXene (Ti)3C2) Weighing the/graphene nano composite material according to a mass ratio of 6:4, placing the material in a mortar for fully grinding until no obvious yellow particles exist, ensuring that the content of sulfur element in the mixture is 60%, then pouring the material into a sealed small glass jar, placing the sealed small glass jar in a glove box, sealing the small glass jar filled with the ground powder, taking out the sealed small glass jar, placing the sealed small glass jar in a drying oven at 155 ℃ for 12 hours, naturally cooling to room temperature, taking out the material from the glass jar, placing the material in the mortar for fully grinding, and sieving (200 meshes) to obtain sulfur/copper sulfide/MXene (Ti/Cu sulfide/MXene) (Ti/Al3C2) Graphene battery positive electrode materials, namely graphene-based positive electrode materials.
With reference to the same procedure as in example 1, the above-mentioned sulfur/copper sulfide/MXene (Ti)3C2) The graphene battery positive electrode material is assembled into a lithium-sulfur battery. The lithium sulfur button cell of this example was tested for various properties and the results are shown in table 1.
Example 3
The embodiment provides a graphene-based positive electrode material and a preparation method thereof, and the preparation method comprises the following specific steps:
step one, preparing MXene (Ti)3C2) Graphene composite material
a) Preparation of less layer MXene (Ti)3C2): weighing 2g of lithium fluoride by using an electronic balance, weighing 40ml of 9mol/L HCl aqueous solution by using a measuring cylinder, respectively placing the solution in a plastic beaker, stirring and dissolving the solution at the constant temperature of 35 ℃ for 30min, then weighing 2g of a titanium system MAX phase precursor by using the electronic balance, slowly placing the precursor in the plastic beaker, and continuously stirring and reacting the precursor at the constant temperature of 35 ℃ for 24 h; adding distilled water into the product, centrifuging at 4000 rpm for 5 min, repeating for 5 times, performing ultrasonic treatment in ice bath for 1 hr until pH value is close to 7, and collecting supernatant as final product, namely, low-layer MXene (Ti)3C2) Finally, freeze-drying the suspension to obtain graphene-like few-layer MXene (Ti)3C2) And (3) solid powder.
b) 1-aminopyrene and bis (succinimidyl) suberate are mixed according to a molar ratio of 2:1 in dimethylformamide and stirring for 24 hours to obtain a second mixed solution.
c) The obtained small layer MXene (Ti)3C2) Adding graphene into the second mixed solution according to the mass ratio of 2:1, performing ultrasonic treatment for 4 hours, and then alternately cleaning the mixture for 5 times by using dimethylformamide and ethanol to obtain MXene (Ti)3C2) A graphene composite material.
Step two: preparation of copper sulfide/MXene (Ti)3C2) Graphene nanocomposite material
120mg of MXene (Ti) as described above were weighed out3C2) Placing the graphene solid powder in a beaker containing 10ml of glycol and 30ml of distilled water, and performing ultrasonic stirring until the graphene solid powder is uniformly dispersedThe suspension was then weighed 0.483g of Cu (NO)3)2·2H2O and 0.38g of thiourea are put into the suspension, stirred and ultrasonically dispersed for 1.5h, and then the solution is transferred into a 50ml hydrothermal kettle liner, sealed and reacted in an oven at 100 ℃ for 18h at constant temperature. After the reaction is naturally cooled, centrifugally cleaning the mixture for many times by using distilled water and ethanol, freezing and freeze-drying the mixture to obtain copper sulfide/MXene (Ti)3C2) Graphene nanocomposite powder.
Step three: preparation of Sulfur/copper sulfide/MXene (Ti)3C2) Graphene battery positive electrode material
Mixing sublimed sulfur with copper sulfide/MXene (Ti)3C2) The graphene nano composite material is weighed according to the mass ratio of 9:1, and then is placed in a mortar for full grinding until no obvious yellow particles exist, so that the content of sulfur in the mixture is ensured to be 90%; pouring the powder into a sealed small glass jar, placing the glass jar into a glove box, sealing the small glass jar filled with the ground powder in an inert gas atmosphere, taking out the glove box, placing the glove box into an oven at 180 ℃ for 18h, naturally cooling to room temperature, taking out the material from the glass jar, placing the material into a mortar for full grinding, and sieving (100 meshes) to obtain sulfur/copper sulfide/MXene (Ti/Cu sulfide/MXene)3C2) Graphene battery positive electrode materials, namely graphene-based positive electrode materials.
With reference to the same procedure as in example 1, the above-mentioned sulfur/copper sulfide/MXene (Ti)3C2) The graphene battery positive electrode material is assembled into a lithium-sulfur battery. The lithium sulfur button cell of this example was tested for various properties and the results are shown in table 1.
Example 4
The embodiment provides a graphene-based cathode material and a preparation method thereof, which are basically the same as those in embodiment 1, and are different only in that the solvothermal reaction conditions are different, and the specific steps are as follows:
step one, preparing MXene (Ti)3C2) Graphene composite material
a) Preparation of less layer MXene (Ti)3C2): 2g of lithium fluoride is weighed by an electronic balance, 40ml of HCl water solution with the concentration of 9mol/L is measured by a measuring cylinderRespectively placing the solution in a plastic beaker, stirring and dissolving at constant temperature of 35 deg.C for 30min, and then weighing the MAX (Ti) of titanium system with an electronic balance3AlC2) 2g of phase precursor is slowly put into a plastic beaker, and the mixture is continuously stirred and reacted for 24 hours at the constant temperature of 35 ℃; adding distilled water into the product, centrifuging at 4000 rpm for 5 min, repeating for 5 times, performing ultrasonic treatment in ice bath for 1 hr until pH value is close to 7, and collecting supernatant as final product, namely, low-layer MXene (Ti)3C2) Finally, freeze-drying the suspension to obtain graphene-like few-layer MXene (Ti)3C2) And (3) solid powder.
b) 1-aminopyrene and bis (succinimidyl) suberate are mixed according to a molar ratio of 2:1 in dimethylformamide and stirring for 24 hours to obtain a second mixed solution.
c) The obtained small layer MXene (Ti)3C2) Adding graphene into the second mixed solution according to the mass ratio of 2:1, performing ultrasonic treatment for 4 hours, and then alternately cleaning the mixture for 5 times by using dimethylformamide and ethanol to obtain MXene (Ti)3C2) A graphene composite material.
Step two: preparation of copper sulfide/MXene (Ti)3C2) Graphene nanocomposite material
80mg of MXene (Ti) as described above were weighed out3C2) Placing the graphene solid powder in a beaker containing 60ml of ethylene glycol, carrying out stirring and ultrasonic treatment until the graphene solid powder is dispersed into a uniform suspension, then weighing 0.2416g of copper nitrate trihydrate and 0.1522g of thiourea into the suspension, stirring and ultrasonically dispersing for 2 hours, transferring the solution into a 100ml hydrothermal kettle liner, sealing, and carrying out constant-temperature reaction in an oven at 150 ℃ for 24 hours. After the reaction is naturally cooled, centrifugally cleaning the mixture for many times by using distilled water and ethanol, freezing and freeze-drying the mixture to obtain copper sulfide/MXene (Ti)3C2) Graphene nanocomposite powder.
Step three: preparation of Sulfur/copper sulfide/MXene (Ti)3C2) Graphene battery positive electrode material
Mixing sublimed sulfur with the above copper sulfide/MXene (Ti)3C2) Weighing the graphene nano composite material according to the mass ratio of 7:3, and placing the material in a mortarFully grinding until no obvious yellow particles exist, ensuring that the content of sulfur in the mixture is 70%, pouring the mixture into a sealed small glass jar, putting the small glass jar into a glove box, sealing the small glass jar filled with the ground powder in an inert gas atmosphere, taking out the glove box, putting the glove box into an oven at 100 ℃ for 18 hours, naturally cooling to room temperature, taking the material out of the glass jar, putting the material into a mortar, fully grinding the material, and sieving the material (200 meshes) to obtain sulfur/copper sulfide/MXene (Ti/Cu sulfide/MXene)3C2) Graphene battery positive electrode materials, namely graphene-based positive electrode materials.
With reference to the same procedure as in example 1, the above-mentioned sulfur/copper sulfide/MXene (Ti)3C2) The graphene battery positive electrode material is assembled into a lithium-sulfur battery. The lithium sulfur button cell of this example was tested for various properties and the results are shown in table 1.
Comparative example 1
The comparative example provides a graphene-based cathode material and a preparation method thereof, which are basically the same as those in example 1, and are different only in the preparation method of MXene, and the specific steps are as follows:
step one, preparing MXene (Ti)4N3) Graphene composite material
a) Preparation of less layer MXene (Ti)4N3): weighing 2g of lithium fluoride by using an electronic balance, weighing 40ml of 9mol/L HCl aqueous solution by using a measuring cylinder, respectively placing the solution in a plastic beaker, stirring and dissolving the solution at the constant temperature of 35 ℃ for 30min, and then weighing MAX (Ti) of titanium system by using the electronic balance4AlN3) 2g of phase precursor is slowly put into a plastic beaker, and the mixture is continuously stirred and reacted for 24 hours at the constant temperature of 35 ℃; adding distilled water into the product, centrifuging at 4000 rpm for 5 min, repeating for 5 times, performing ultrasonic treatment in ice bath for 1 hr until pH value is close to 7, and collecting supernatant as final product, namely, low-layer MXene (Ti)4N3) Finally, freeze-drying the suspension to obtain graphene-like few-layer MXene (Ti)4N3) And (3) solid powder.
b) 1-aminopyrene and bis (succinimidyl) suberate are mixed according to a molar ratio of 2:1 in dimethylformamide and stirring for 24 hours to obtain a second mixed solution.
c) The obtained small layer MXene (Ti)4N3) Adding graphene into the second mixed solution according to the mass ratio of 2:1, performing ultrasonic treatment for 4 hours, and then alternately cleaning the mixture for 5 times by using dimethylformamide and ethanol to obtain MXene (Ti)4N3) A graphene composite material.
Step two: preparation of copper sulfide/MXene (Ti)4N3) Graphene nanocomposite material
80mg of MXene (Ti) as described above were weighed out4N3) Placing the graphene solid powder in a beaker containing 60ml of ethylene glycol, carrying out stirring and ultrasonic treatment until the graphene solid powder is dispersed into a uniform suspension, then weighing 0.2416g of copper nitrate trihydrate and 0.1522g of thiourea into the suspension, stirring and ultrasonically dispersing for 2 hours, transferring the solution into a 100ml hydrothermal kettle liner, sealing, and carrying out constant-temperature reaction in an oven at 150 ℃ for 24 hours. After the reaction is naturally cooled, centrifugally cleaning the mixture for many times by using distilled water and ethanol, freezing and freeze-drying the mixture to obtain copper sulfide/MXene (Ti)4N3) Graphene nanocomposite powder.
Step three: preparation of Sulfur/copper sulfide/MXene (Ti)4N3) Graphene battery positive electrode material
Mixing sublimed sulfur with the above copper sulfide/MXene (Ti)4N3) Weighing the/graphene nano composite material according to a mass ratio of 7:3, placing the material in a mortar for fully grinding until no obvious yellow particles exist, ensuring that the content of sulfur element in the mixture is 70%, then pouring the material into a sealed small glass jar, placing the sealed small glass jar in a glove box, sealing the small glass jar filled with the ground powder, taking out the sealed small glass jar, placing the sealed small glass jar in a 160 ℃ oven for 12 hours, naturally cooling to room temperature, taking out the material from the glass jar, placing the material in the mortar for fully grinding, and sieving (200 meshes) to obtain sulfur/copper sulfide/MXene (Ti/Cu sulfide/MXene) (Ti/MXene)4N3) Graphene battery positive electrode materials, namely graphene-based positive electrode materials.
With reference to the same procedure as in example 1, the above-mentioned sulfur/copper sulfide/MXene (Ti)4N3) The battery cathode material was assembled into a lithium sulfur battery. For the lithium-sulfur battery of this comparative exampleThe latter properties were tested and the results are shown in table 1.
TABLE 1
Figure BDA0002613044760000161
Figure BDA0002613044760000171
As can be seen from table 1, in the lithium sulfur batteries of examples 1 to 4, the current-carrying capacity is maintained between 60% and 90%, the elemental sulfur can be effectively fixed, the conductivity of the positive electrode material is improved, and meanwhile, the lithium sulfur batteries have high specific capacity and good coulombic efficiency (discharge capacity/charge capacity × 100%).
Comparative example 1 MXene (Ti)3C2) Replacement by MXene (Ti)4N3) After that, the specific discharge capacity of the battery is reduced, and the coulombic efficiency is also reduced, which shows that MXene (Ti)4N3) The lithium-ion battery is applied to the anode material of the sulfur lithium battery, and has a limited effect of improving the comparative capacity.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A preparation method of a graphene-based positive electrode material is characterized by comprising the following steps:
dispersing MXene/graphene composite material, copper salt and a sulfur source in a solvent to obtain a first mixed solution;
placing the first mixed solution in a closed pressure system, and carrying out solvothermal reaction for 18-24 h at 100-180 ℃ to prepare a copper sulfide/MXene/graphene nano composite material;
mixing the copper sulfide/MXene/graphene nano composite material with elemental sulfur, grinding, and standing at 155-180 ℃ for 10-18 h to prepare a graphene-based positive electrode material;
the MXene is Ti3C2。
2. The preparation method of the graphene-based cathode material according to claim 1, wherein the preparation method of the MXene/graphene composite material comprises the following steps:
adding MAX phase precursor into hydrofluoric acid etching solution, and reacting at 35-45 ℃ for 24-48 h to obtain MXene, wherein the MAX phase precursor is Ti3AlC2；
Mixing 1-aminopyrene and bis-succinimide suberate in dimethylformamide, and stirring to prepare a second mixed solution;
and adding MXene and graphene into the second mixed solution, and performing ultrasonic treatment to prepare the MXene/graphene composite material.
3. The preparation method of the graphene-based positive electrode material according to claim 2, wherein the molar ratio of MXene to graphene is (0.5-4): 1.
4. The preparation method of the graphene-based positive electrode material according to claim 2, wherein the molar ratio of the 1-aminopyrene to the disuccinimidyl suberate is (1.5-2.5): 1.
5. The method for preparing the graphene-based positive electrode material according to claim 2, wherein the hydrofluoric acid etching solution is selected from a mixed solution of HCl and lithium fluoride, HF and NH4HF2One or more of them.
6. The preparation method of the graphene-based positive electrode material according to any one of claims 1 to 5, wherein the mass ratio of the MXene/graphene composite material to the copper salt to the sulfur source is (0.08-0.12): (0.2-2): (0.1-4).
7. The method for preparing the graphene-based positive electrode material as claimed in any one of claims 1 to 5, wherein the mass ratio of the elemental sulfur to the copper sulfide/MXene/graphene nanocomposite material is (1-4): 0.25-1.
8. The method for preparing the graphene-based positive electrode material according to any one of claims 1 to 5, wherein the copper salt is selected from one or more of cuprous chloride dihydrate, cupric nitrate trihydrate, cupric nitrate hexahydrate, and cupric nitrate dihydrate; and/or the presence of a catalyst in the reaction mixture,
the sulfur source is selected from one or more of urea, thiourea and thioacetyl; and/or the presence of a catalyst in the reaction mixture,
the solvent is selected from one or more of water, carbon disulfide, absolute ethyl alcohol and glycol; and/or the presence of a catalyst in the reaction mixture,
the elemental sulfur is sublimed sulfur.
9. A graphene-based positive electrode material produced by the production method according to any one of claims 1 to 8.
10. A lithium-sulfur battery comprising the graphene-based positive electrode material according to claim 9.
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