CN116207222A - Aerogel microsphere material used for carrying lithium sulfide and preparation method thereof - Google Patents

Aerogel microsphere material used for carrying lithium sulfide and preparation method thereof Download PDF

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CN116207222A
CN116207222A CN202211579771.1A CN202211579771A CN116207222A CN 116207222 A CN116207222 A CN 116207222A CN 202211579771 A CN202211579771 A CN 202211579771A CN 116207222 A CN116207222 A CN 116207222A
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porous mxene
heteroatom
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刘立新
钟勇
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Changsha Xinli Silicon Material Technology Co ltd
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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
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    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/22—Alkali metal sulfides or polysulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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    • C01B32/182—Graphene
    • C01B32/198—Graphene oxide
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    • 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
    • H—ELECTRICITY
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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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    • 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
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Abstract

The invention discloses an aerogel microsphere material for carrying lithium sulfide and a preparation method thereof, wherein the aerogel microsphere is formed by compounding Graphene Oxide (GO) and an in-situ grown carbon nano tube composite heteroatom doped porous MXene material, and the mass ratio of the Graphene Oxide (GO) to the porous MXene material is (1:1) - (1:20).

Description

Aerogel microsphere material used for carrying lithium sulfide and preparation method thereof
Technical Field
The application relates to the technical field of material preparation, in particular to an aerogel microsphere material used for carrying lithium sulfide and a preparation method thereof.
Background
Lithium ion batteries have been rapidly developed in recent years, but the problems of low specific energy density, insufficient service life, environmental pollution and the like of the lithium ion batteries of the lithium iron phosphate/C and ternary material/C systems widely applied at present seriously restrict the deep application and development of the lithium ion batteries.
The lithium sulfur battery has high specific capacity and energy density, and at the same time, the sulfur element is stored in a rich amount, is environmentally friendly, and has no substantial pollution to the environment, so the lithium sulfur battery is considered as a very promising lithium battery. However, lithium sulfur batteries existCertain problems and disadvantages, such as the shuttle effect of polysulfide, low conductivity of sulfur element and volume expansion in the cycling process, and lithium dendrite generated by lithium metal in the cycling process, can cause the battery short circuit caused by the piercing of a diaphragm, and cause the battery safety problem, thereby limiting the practical application of a lithium-sulfur battery system. Lithium sulfide (Li) 2 S) is used as a lithiation product of sulfur and is used for a lithium ion battery anode material, lithium ions can be provided by the lithium ion battery anode material, and metal lithium is prevented from being used as a negative electrode, so that potential safety hazards can be effectively eliminated. However, lithium sulfide exhibits electron and ion insulation, and thus lithium sulfide cathode materials have low electrochemical activity. Moreover, during charge and discharge, the dissolution, diffusion and shuttle effects of polysulfide ions remain, and the battery still exhibits severe capacity fade.
Disclosure of Invention
The embodiment of the application aims to provide an aerogel microsphere material used for carrying lithium sulfide and a preparation method thereof. The aerogel microsphere material adopts a multi-element composite structure of graphene, carbon nano tubes and porous MXene, so that not only can the electronic conductivity, the load capacity and the utilization rate of a sulfur lithium positive electrode active substance be effectively improved, but also the problem of dissolution of an intermediate product polysulfide ion can be relieved, and the cycle stability of a battery can be improved, so that a high-performance lithium sulfur battery is possible.
According to a first aspect of the embodiments of the present application, there is provided an aerogel microsphere material for carrying lithium sulfide, where the aerogel microsphere is formed by compounding Graphene Oxide (GO) and an in-situ grown carbon nanotube composite heteroatom doped porous MXene material, and the mass ratio of the Graphene Oxide (GO) to the porous MXene material is (1:1) - (1:20).
According to a second aspect of embodiments of the present application, there is provided an aerogel microsphere material for carrying lithium sulfide, the preparation method comprising the steps of:
stirring and dispersing an MXene nano sheet into a hydrogen peroxide solution, stirring and etching, and centrifugally washing the reacted solution to obtain a porous MXene nano sheet solution by ultrasonic dispersion;
step two, preparing heteroatom dispersion liquid: adding a nitrogen source, a boron source and a phosphorus source into a dispersing agent, and fully stirring to uniformly disperse the components to obtain heteroatom dispersion liquid;
step three, adding the porous MXene nanosheet solution prepared in the step one into the heteroatom dispersion liquid prepared in the step two, fully stirring until the mixture is uniformly mixed, centrifuging the mixed liquid, and drying to obtain a precursor material;
step four, placing the precursor material into a corundum crucible, transferring the corundum crucible into a tube furnace, heating the corundum crucible to a preset temperature in a protective atmosphere, preserving heat, naturally cooling the corundum crucible to room temperature, and collecting solids in the corundum crucible to obtain the heteroatom-doped porous MXene material;
step five, taking ferrocene and the heteroatom doped porous MXene material prepared in the step four, placing the porous MXene material into a mortar, adding an organic dispersing agent, grinding the porous MXene material until the porous MXene material and the organic dispersing agent are fully mixed, and then drying the porous MXene material to obtain a mixture;
step six, placing the mixture prepared in the step five in a corundum crucible, uniformly laying an ignition agent on the top of the corundum crucible, placing the crucible in microwave equipment, and collecting products after microwave radiation to obtain the in-situ grown carbon nano tube composite heteroatom doped porous MXene material;
step seven, dissolving the porous MXene material doped with the in-situ grown carbon nano tube composite heteroatom prepared in the step six in deionized water, fully dissolving the porous MXene material by ultrasonic treatment, adding Graphene Oxide (GO), and fully dissolving the porous MXene material by ultrasonic treatment to obtain a porous MXene-graphene oxide composite dispersion liquid;
and step eight, atomizing the dispersion liquid prepared in the step seven into liquid drop microspheres by a spray method, forming porous MXene and graphene oxide composite ice microspheres in a cooling bath receiving liquid, and then freeze-drying the ice microspheres to obtain the aerogel microsphere material used for carrying lithium sulfide.
Preferably, the porous MXene nano-sheet is a ceramic material with a porous two-dimensional lamellar structure and has a chemical general formula of M n+1 X n T z WhereinM is a transition metal, X is C or/and N, N is 1-3, T z Refers to surface groups, preferably Ti 3 C 2 T x 。
Preferably, the heteroatom is one or more of N, B, P, a heteroatom: the molar ratio of the porous MXene nano-sheets is (1:10) - (1:1), wherein the molar ratio of B to N to P is (0-1): (0-4), and preferably 1:2:3.
preferably, the mass ratio of the MXene nano-sheet to the hydrogen peroxide solution is 0.1-1, and the mass concentration of the hydrogen peroxide solution is 0.01% -0.1%.
Preferably, the etching temperature is 20-80 ℃ and the etching time is 10-100 min.
Preferably, the nitrogen source is selected from one or more of ammonium sulfate, nitric acid, urea, 1-butyl-3-methylimidazole tetrafluoroborate (1-butyl-3-methylimidazolium tetrafluoroborate, BMI-TFB); the boron source is selected from sodium borohydride, boric acid and B 2 H 6 One or more of the following; the phosphorus source is selected from one or more of phosphoric acid, sodium hypophosphite, hexafluorophosphoric acid and ammonium dihydrogen phosphate.
Preferably, the dispersing agent is selected from one or more of deionized water and ethanol; the protective atmosphere is any one or two of argon and nitrogen.
Preferably, the ferrocene is dicyclopentadiene iron (of the formula Fe (C) 5 H 5 ) 2 ) The mass ratio of ferrocene to heteroatom doped porous MXene was (0.5: 1) (1.5: 1) Preferably 1:1.
preferably, the organic dispersing agent is one or more of toluene, acetone and dimethyl sulfoxide (dmso), preferably acetone; the mass ratio of the amount of the organic dispersant to the total amount of ferrocene and heteroatom doped porous MXene is (1:100) - (1:20).
Preferably, the ignition agent is selected from one or two of carbon powder or carbon fiber, preferably carbon fiber; the mass ratio of the ignition agent to the mixture is (1:300) - (1:100).
Preferably, in the fourth step, the precursor material is placed into a corundum crucible, then transferred into a tube furnace, heated to 200-500 ℃ at a heating rate of 3-6 ℃/min in a protective atmosphere, and naturally cooled to room temperature after heat preservation for 1-5 hours.
Preferably, the power of the microwave device is 400-1500W, preferably 900W; the microwave irradiation time is 20 s-80 s, preferably 40s each time; the number of microwave irradiation is 1 to 5, preferably 3.
Preferably, the concentration of the porous MXene and graphene oxide composite dispersion liquid is 1% -3%.
The technical scheme provided by the embodiment of the application can comprise the following beneficial effects:
the preparation method has the advantages of simple production process, easy control and low cost, is green and pollution-free from raw materials to the preparation process, and is beneficial to industrial mass production.
The aerogel microsphere prepared by the method is rich in pore channels, and is beneficial to increasing the specific surface area to adsorb a large amount of lithium sulfide active substances and improving the load rate. The two-dimensional porous MXene material layer can improve the ionic conductivity and the electronic conductivity, and the transmission speed of ions and electrons is accelerated, so that the reaction kinetic activity of the lithium-sulfur battery is improved. The intercalation and connection of the MXene/graphene oxide/carbon nanotubes in the aerogel microsphere structure will form a multi-layer network structure, which is also beneficial to electron transfer.
The carbon nano tube/graphene oxide has the advantages of good chemical stability, large elastic modulus and high mechanical strength, and forms a mutually staggered net structure in the electrode, so that a buffer area can be provided for the volume expansion of the positive electrode in the circulation process, the stress generated by the volume expansion of the electrode material in the charge and discharge process of the lithium-sulfur battery is effectively reduced, and the stability of the positive electrode material of the lithium-sulfur battery is improved.
The aerogel microsphere composite structure prepared by the invention can adsorb a large amount of active components, has better physical barrier and chemical adsorption effects on polysulfide generated in the charge and discharge process, thereby reducing the occurrence of the shuttle effect and improving the multiplying power performance and the cycle stability of the lithium-sulfur battery.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the application.
Detailed Description
The following examples are provided to clearly and fully describe the technical aspects of the present invention, and it is apparent that the described examples are only some, but not all, examples of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Exemplary embodiments will be described in detail herein.
Example 1
The preparation method of the aerogel microsphere material used for carrying lithium sulfide specifically comprises the following steps:
step one, preparing a porous MXene nano-sheet solution: 30 parts by weight of Ti 3 C 2 T x Stirring and dispersing the nano-sheets to 300 parts by weight of hydrogen peroxide (H) with the mass concentration of 0.01 percent 2 O 2 ) And in the solution, stirring and etching for 10 minutes at 20 ℃, and then centrifugally washing the reacted solution, and performing ultrasonic dispersion to obtain the porous MXene nano-sheet solution.
Step two, preparing heteroatom dispersion liquid: preparation of heteroatom Dispersion: taking 100 parts by weight of boric acid with the concentration of 1%, wherein the boron source can alternatively use sodium borohydride and B 2 H 6 The method comprises the steps of carrying out a first treatment on the surface of the 100 parts by weight of phosphoric acid with the concentration of 1%, wherein sodium hypophosphite, hexafluorophosphoric acid and ammonium dihydrogen phosphate can be used as the phosphorus source alternatively; 100 parts by weight of nitric acid with the concentration of 1%, wherein the nitrogen source can be replaced by ammonium sulfate, urea and 1-butyl-3-methylimidazole tetrafluoroborate; 300 parts by weight of deionized water is added and fully and uniformly stirred to obtain heteroatom dispersion liquid.
Step three, preparing a precursor material: and (3) adding the porous MXene nano-sheet solution prepared in the step (I) into the heteroatom dispersion liquid prepared in the step (II), fully stirring until the mixture is uniformly mixed, centrifuging the mixed liquid, and drying to obtain the precursor material.
Step four, preparing a porous MXene material doped with hetero atoms: the precursor material is placed into a corundum crucible, transferred into a tube furnace, and heated to 200 ℃ at a heating rate of 3 ℃/min in a protective atmosphere of one-to-one ratio of argon and nitrogen. And (3) after heat preservation for 1 hour, naturally cooling to room temperature, and collecting solids in the corundum crucible to obtain the heteroatom doped porous MXene material.
Step five, preparing a ferrocene and porous MXene mixture: placing 10 parts by weight of ferrocene and 20 parts by weight of heteroatom doped porous MXene material prepared in the step four in a mortar, and adding 0.3 part by weight of acetone, wherein the acetone can be replaced by toluene or dimethyl sulfoxide (dmso); grinding for 5 minutes to fully mix, and then drying to obtain a ferrocene and porous MXene mixture;
step six, preparing a porous MXene material doped with carbon nano tube composite hetero atoms by in-situ growth: and (3) placing the mixture prepared in the step (V) into a corundum crucible, uniformly laying 0.1 part by weight of carbon fiber on the top of the corundum crucible, placing the crucible into microwave equipment, setting the power to be 400W and the time to be 20s, and collecting products after 1-time microwave radiation to obtain the in-situ grown carbon nano tube composite heteroatom doped porous MXene material.
Step seven, preparing a porous MXene and graphene oxide composite dispersion liquid: dissolving 1 part by weight of porous MXene material doped with the in-situ grown carbon nano tube composite heteroatom prepared in the step six in 200 parts by weight of deionized water, sufficiently dissolving the porous MXene material by ultrasonic treatment, adding 1 part by weight of Graphene Oxide (GO), and sufficiently dissolving the porous MXene material by ultrasonic treatment to obtain a porous MXene and graphene oxide composite dispersion liquid;
step eight, preparing an aerogel microsphere material used for carrying lithium sulfide: and atomizing the dispersion liquid prepared in the step seven into liquid drop microspheres by a spraying method, and forming porous MXene and graphene oxide composite ice microspheres in a cooling bath receiving liquid. And then freeze-drying the ice microspheres under the environment that the temperature is lower than 50 ℃ below zero and the pressure is lower than 50Pa, so that the porous MXene and graphene oxide composite aerogel microspheres used for carrying lithium sulfide can be obtained.
Example 2
The preparation method of the aerogel microsphere material used for carrying lithium sulfide specifically comprises the following steps:
step one, preparing a porous MXene nano-sheet solution: 30 parts by weight of Ti 3 C 2 T x Stirring and dispersing the nano-sheets to 60 parts by weight of hydrogen peroxide (H) with the mass concentration of 0.05 percent 2 O 2 ) And (3) in the solution, stirring and etching for 50 minutes at 50 ℃, and then centrifugally washing the reacted solution, and performing ultrasonic dispersion to obtain the porous MXene nano-sheet solution.
Step two, preparing heteroatom dispersion liquid: taking 100 parts by weight of boric acid with concentration of 1%, wherein the boron source can be sodium borohydride and B 2 H 6 Instead of one or more of the above, 100 parts by weight of deionized water is added, and the mixture is fully and uniformly stirred to obtain heteroatom dispersion.
Step three, preparing a precursor material: and (3) adding the porous MXene nano-sheet solution prepared in the step (I) into the heteroatom dispersion liquid prepared in the step (II), fully stirring until the mixture is uniformly mixed, centrifuging the mixed liquid, and drying to obtain the precursor material.
Step four, preparing a porous MXene material doped with hetero atoms: the precursor material is placed into a corundum crucible, transferred into a tube furnace and heated to 400 ℃ at a heating rate of 5 ℃/min in a nitrogen protection atmosphere. And (3) after heat preservation for 3 hours, naturally cooling to room temperature, and collecting solids in the corundum crucible to obtain the heteroatom doped porous MXene material.
Step five, preparing a ferrocene and porous MXene mixture: placing 10 parts by weight of ferrocene and 10 parts by weight of heteroatom doped porous MXene material prepared in the step four into a mortar, and adding 0.4 part by weight of acetone, wherein the acetone can be replaced by toluene or dimethyl sulfoxide (dmso); grinding for 8 minutes to fully mix, and then drying to obtain a ferrocene and porous MXene mixture;
step six, preparing a porous MXene material doped with carbon nano tube composite hetero atoms by in-situ growth: placing the mixture prepared in the fifth step into a corundum crucible, uniformly laying 0.1 part by weight of carbon fibers on the top of the corundum crucible, placing the crucible into microwave equipment, setting the power to be 900W and the time to be 40s, and collecting products after 3 times of microwave radiation to obtain the in-situ grown carbon nano tube composite heteroatom doped porous MXene material.
Step seven, preparing a porous MXene and graphene oxide composite dispersion liquid: dissolving 10 parts by weight of porous MXene material doped with the in-situ grown carbon nano tube composite heteroatom prepared in the step six in 500 parts by weight of deionized water, fully dissolving the porous MXene material by ultrasonic treatment, adding 1 part by weight of Graphene Oxide (GO), and fully dissolving the porous MXene material by ultrasonic treatment to obtain a porous MXene and graphene oxide composite dispersion liquid;
step eight, preparing an aerogel microsphere material used for carrying lithium sulfide: and atomizing the dispersion liquid prepared in the step seven into liquid drop microspheres by a spraying method, and forming porous MXene and graphene oxide composite ice microspheres in a cooling bath receiving liquid. And then freeze-drying the ice microspheres under the environment that the temperature is lower than 50 ℃ below zero and the pressure is lower than 50Pa, so that the porous MXene and graphene oxide composite aerogel microspheres used for carrying lithium sulfide can be obtained.
Example 3
The preparation method of the aerogel microsphere material used for carrying lithium sulfide specifically comprises the following steps:
step one, preparing a porous MXene nano-sheet solution: 9 parts by weight of Ti 3 C 2 T x Stirring and dispersing the nano-sheets to 9 parts by weight of hydrogen peroxide (H) with the mass concentration of 0.1 percent 2 O 2 ) And in the solution, stirring and etching for 100 minutes at 80 ℃, and then centrifugally washing the reacted solution, and performing ultrasonic dispersion to obtain the porous MXene nano-sheet solution.
Step two, preparing heteroatom dispersion liquid: the nitrogen source can be replaced by ammonium sulfate, nitric acid, urea and 1-butyl-3-methylimidazole tetrafluoroborate, 100 parts by weight of deionized water is added, and the mixture is fully and uniformly stirred to obtain heteroatom dispersion liquid.
Step three, preparing a precursor material: and (3) adding the porous MXene nano-sheet solution prepared in the step (I) into the heteroatom dispersion liquid prepared in the step (II), fully stirring until the mixture is uniformly mixed, centrifuging the mixed liquid, and drying to obtain the precursor material.
Step four, preparing a porous MXene material doped with hetero atoms: the precursor material is placed into a corundum crucible, transferred into a tube furnace and heated to 500 ℃ at a heating rate of 6 ℃/min in an argon protective atmosphere. And (3) after heat preservation for 5 hours, naturally cooling to room temperature, and collecting solids in the corundum crucible to obtain the heteroatom doped porous MXene material.
Step five, preparing a ferrocene and porous MXene mixture: placing 10 parts by weight of ferrocene and 5 parts by weight of heteroatom-doped porous MXene material prepared in the step four into a mortar, adding 0.75 part by weight of acetone, alternatively toluene or dimethyl sulfoxide (dmso), grinding for 10 minutes to fully mix, and then drying to obtain a ferrocene and porous MXene mixture;
step six, preparing a porous MXene material doped with carbon nano tube composite hetero atoms by in-situ growth: and (3) placing the mixture prepared in the fifth step into a corundum crucible, uniformly laying 0.15 part by weight of carbon fibers on the top of the corundum crucible, placing the crucible into microwave equipment, setting the power to be 1500W and the time to be 80s, and collecting products after 5 times of microwave radiation to obtain the in-situ grown carbon nano tube composite heteroatom doped porous MXene material.
Step seven, preparing a porous MXene and graphene oxide composite dispersion liquid: dissolving 20 parts by weight of porous MXene material doped with in-situ grown carbon nano tube composite heteroatoms prepared in the step six in 150 parts by weight of deionized water, sufficiently dissolving the porous MXene material by ultrasonic treatment, adding 1 part by weight of Graphene Oxide (GO), and sufficiently dissolving the porous MXene material by ultrasonic treatment to obtain a porous MXene and graphene oxide composite dispersion liquid;
step eight, preparing an aerogel microsphere material used for carrying lithium sulfide: and atomizing the dispersion liquid prepared in the step seven into liquid drop microspheres by a spraying method, and forming porous MXene and graphene oxide composite ice microspheres in a cooling bath receiving liquid. And then freeze-drying the ice microspheres under the environment that the temperature is lower than 50 ℃ below zero and the pressure is lower than 50Pa, so that the porous MXene and graphene oxide composite aerogel microspheres used for carrying lithium sulfide can be obtained.
Example 4
The preparation method of the aerogel microsphere material used for carrying lithium sulfide specifically comprises the following steps:
step one, preparing a porous MXene nano-sheet solution: taking 20 parts by weight of Ti 3 C 2 T x Stirring and dispersing the nano-sheets to 200 parts by weight of hydrogen peroxide (H) with the mass concentration of 0.01 percent 2 O 2 ) In the solution, stirring and etching are carried out for 10 minutes at 20 ℃, and then the reacted solution is subjected to the reactionAnd (3) centrifugally washing the solution, and performing ultrasonic dispersion to obtain the porous MXene nano-sheet solution.
Step two, preparing heteroatom dispersion liquid: 100 parts by weight of phosphoric acid with the concentration of 1% is taken, sodium hypophosphite, hexafluorophosphoric acid and ammonium dihydrogen phosphate can be used as the phosphorus source instead, 100 parts by weight of deionized water is added, and the mixture is fully and uniformly stirred to obtain heteroatom dispersion liquid.
Step three, preparing a precursor material: and (3) adding the porous MXene nano-sheet solution prepared in the step (I) into the heteroatom dispersion liquid prepared in the step (II), fully stirring until the mixture is uniformly mixed, centrifuging the mixed liquid, and drying to obtain the precursor material.
Step four, preparing a porous MXene material doped with hetero atoms: the precursor material is placed into a corundum crucible, transferred into a tube furnace and heated to 200 ℃ at a heating rate of 3 ℃/min in a nitrogen protection atmosphere. And (3) after heat preservation for 1 hour, naturally cooling to room temperature, and collecting solids in the corundum crucible to obtain the heteroatom doped porous MXene material.
Step five, preparing a ferrocene and porous MXene mixture: placing 10 parts by weight of ferrocene and 20 parts by weight of heteroatom doped porous MXene material prepared in the step four into a mortar, adding 0.3 part by weight of acetone, alternatively toluene or dimethyl sulfoxide (dmso), grinding for 5 minutes to fully mix, and then drying to obtain a ferrocene and porous MXene mixture;
step six, preparing a porous MXene material doped with carbon nano tube composite hetero atoms by in-situ growth: and (3) placing the mixture prepared in the step (V) into a corundum crucible, uniformly laying 0.1 part by weight of carbon fiber on the top of the corundum crucible, placing the crucible into microwave equipment, setting the power to be 400W and the time to be 20s, and collecting products after 1-time microwave radiation to obtain the in-situ grown carbon nano tube composite heteroatom doped porous MXene material.
Step seven, preparing a porous MXene and graphene oxide composite dispersion liquid: dissolving 1 part by weight of porous MXene material doped with the in-situ grown carbon nano tube composite heteroatom prepared in the step six in 200 parts by weight of deionized water, sufficiently dissolving the porous MXene material by ultrasonic treatment, adding 1 part by weight of Graphene Oxide (GO), and sufficiently dissolving the porous MXene material by ultrasonic treatment to obtain a porous MXene and graphene oxide composite dispersion liquid;
step eight, preparing an aerogel microsphere material used for carrying lithium sulfide: and atomizing the dispersion liquid prepared in the step seven into liquid drop microspheres by a spraying method, and forming porous MXene and graphene oxide composite ice microspheres in a cooling bath receiving liquid. And then freeze-drying the ice microspheres under the environment that the temperature is lower than 50 ℃ below zero and the pressure is lower than 50Pa, so that the porous MXene and graphene oxide composite aerogel microspheres used for carrying lithium sulfide can be obtained.
Example 5
The preparation method of the aerogel microsphere material used for carrying lithium sulfide specifically comprises the following steps:
step one, preparing a porous MXene nano-sheet solution: taking 20 parts by weight of Ti 3 C 2 T x Stirring and dispersing the nano-sheets to 40 parts by weight of hydrogen peroxide (H) with the mass concentration of 0.05 percent 2 O 2 ) And (3) in the solution, stirring and etching for 50 minutes at 50 ℃, and then centrifugally washing the reacted solution, and performing ultrasonic dispersion to obtain the porous MXene nano-sheet solution.
Step two, preparing heteroatom dispersion liquid:
taking 100 parts by weight of boric acid with the concentration of 1%, wherein the boron source can alternatively use sodium borohydride and B 2 H 6 The method comprises the steps of carrying out a first treatment on the surface of the 100 parts by weight of phosphoric acid with the concentration of 1%, wherein sodium hypophosphite, hexafluorophosphoric acid and ammonium dihydrogen phosphate can be used as the phosphorus source alternatively; 200 parts by weight of deionized water is added and fully and uniformly stirred to obtain heteroatom dispersion liquid.
Step three, preparing a precursor material: and (3) adding the porous MXene nano-sheet solution prepared in the step (I) into the heteroatom dispersion liquid prepared in the step (II), fully stirring until the mixture is uniformly mixed, centrifuging the mixed liquid, and drying to obtain the precursor material.
Step four, preparing a porous MXene material doped with hetero atoms: the precursor material is placed into a corundum crucible, transferred into a tube furnace and heated to 400 ℃ at a heating rate of 5 ℃/min in an argon protective atmosphere. And (3) after heat preservation for 3 hours, naturally cooling to room temperature, and collecting solids in the corundum crucible to obtain the heteroatom doped porous MXene material.
Step five, preparing a ferrocene and porous MXene mixture: taking 10 parts by weight of ferrocene and 10 parts by weight of heteroatom doped porous MXene material prepared in the step four, placing the materials into a mortar, and adding 0.4 part by weight of dimethyl sulfoxide, wherein the dimethyl sulfoxide can be replaced by acetone or toluene; grinding for 8 minutes to fully mix, and then drying to obtain a ferrocene and porous MXene mixture;
step six, preparing a porous MXene material doped with carbon nano tube composite hetero atoms by in-situ growth: placing the mixture prepared in the fifth step into a corundum crucible, uniformly laying 0.1 part by weight of carbon fibers on the top of the corundum crucible, placing the crucible into microwave equipment, setting the power to be 900W and the time to be 40s, and collecting products after 3 times of microwave radiation to obtain the in-situ grown carbon nano tube composite heteroatom doped porous MXene material.
Step seven, preparing a porous MXene and graphene oxide composite dispersion liquid: dissolving 10 parts by weight of porous MXene material doped with the in-situ grown carbon nano tube composite heteroatom prepared in the step six in 500 parts by weight of deionized water, fully dissolving the porous MXene material by ultrasonic treatment, adding 1 part by weight of Graphene Oxide (GO), and fully dissolving the porous MXene material by ultrasonic treatment to obtain a porous MXene and graphene oxide composite dispersion liquid;
step eight, preparing an aerogel microsphere material used for carrying lithium sulfide: and atomizing the dispersion liquid prepared in the step seven into liquid drop microspheres by a spraying method, and forming porous MXene and graphene oxide composite ice microspheres in a cooling bath receiving liquid. And then freeze-drying the ice microspheres under the environment that the temperature is lower than 50 ℃ below zero and the pressure is lower than 50Pa, so that the porous MXene and graphene oxide composite aerogel microspheres used for carrying lithium sulfide can be obtained.
Example 6
The preparation method of the aerogel microsphere material used for carrying lithium sulfide specifically comprises the following steps:
step one, preparing a porous MXene nano-sheet solution: taking 5 parts by weight of Ti 3 C 2 T x Stirring and dispersing the nano-sheets to 5 parts by weight of hydrogen peroxide (H) with the mass concentration of 0.1 percent 2 O 2 ) Stirring and etching for 100 minutes at 80 ℃ in the solution, and then centrifugally washing the reacted solution, and performing ultrasonic dispersion to obtainPorous MXene nanoplatelet solutions.
Step two, preparing heteroatom dispersion liquid: taking 100 parts by weight of phosphoric acid with the concentration of 1%, wherein the phosphorus source can be replaced by sodium hypophosphite, hexafluorophosphoric acid and ammonium dihydrogen phosphate; 100 parts by weight of nitric acid with the concentration of 1%, wherein the nitrogen source can be replaced by ammonium sulfate, urea and 1-butyl-3-methylimidazole tetrafluoroborate; 200 parts by weight of deionized water is added and fully and uniformly stirred to obtain heteroatom dispersion liquid. Step three, preparing a precursor material: and (3) adding the porous MXene nano-sheet solution prepared in the step (I) into the heteroatom dispersion liquid prepared in the step (II), fully stirring until the mixture is uniformly mixed, centrifuging the mixed liquid, and drying to obtain the precursor material.
Step four, preparing a porous MXene material doped with hetero atoms: the precursor material is placed into a corundum crucible, transferred into a tube furnace and heated to 500 ℃ at a heating rate of 6 ℃/min in an argon protective atmosphere. And (3) after heat preservation for 5 hours, naturally cooling to room temperature, and collecting solids in the corundum crucible to obtain the heteroatom doped porous MXene material.
Step five, preparing a ferrocene and porous MXene mixture: placing 10 parts by weight of ferrocene and 5 parts by weight of heteroatom-doped porous MXene material prepared in the step four into a mortar, adding 0.75 part by weight of toluene which can be replaced by acetone or dimethyl sulfoxide, grinding for 10 minutes to fully mix, and then drying to obtain a ferrocene and porous MXene mixture;
step six, preparing a porous MXene material doped with carbon nano tube composite hetero atoms by in-situ growth: and (3) placing the mixture prepared in the fifth step into a corundum crucible, uniformly laying 0.15 part by weight of carbon fibers on the top of the corundum crucible, placing the crucible into microwave equipment, setting the power to be 1500W and the time to be 80s, and collecting products after 5 times of microwave radiation to obtain the in-situ grown carbon nano tube composite heteroatom doped porous MXene material.
Step seven, preparing a porous MXene and graphene oxide composite dispersion liquid: dissolving 20 parts by weight of porous MXene material doped with in-situ grown carbon nano tube composite heteroatoms prepared in the step six in 150 parts by weight of deionized water, sufficiently dissolving the porous MXene material by ultrasonic treatment, adding 1 part by weight of Graphene Oxide (GO), and sufficiently dissolving the porous MXene material by ultrasonic treatment to obtain a porous MXene and graphene oxide composite dispersion liquid;
step eight, preparing an aerogel microsphere material used for carrying lithium sulfide: and atomizing the dispersion liquid prepared in the step seven into liquid drop microspheres by a spraying method, and forming porous MXene and graphene oxide composite ice microspheres in a cooling bath receiving liquid. And then freeze-drying the ice microspheres under the environment that the temperature is lower than 50 ℃ below zero and the pressure is lower than 50Pa, so that the porous MXene and graphene oxide composite aerogel microspheres used for carrying lithium sulfide can be obtained.
Example 7
The preparation method of the aerogel microsphere material used for carrying lithium sulfide specifically comprises the following steps:
step one, preparing a porous MXene nano-sheet solution: taking 10 parts by weight of Ti 3 C 2 T x Stirring and dispersing the nano-sheets to 100 parts by weight of hydrogen peroxide (H) with the mass concentration of 0.01 percent 2 O 2 ) And in the solution, stirring and etching for 10 minutes at 20 ℃, and then centrifugally washing the reacted solution, and performing ultrasonic dispersion to obtain the porous MXene nano-sheet solution.
Step two, preparing heteroatom dispersion liquid: taking 100 parts by weight of boric acid with the concentration of 1%, wherein the boron source can alternatively use sodium borohydride and B 2 H 6 The method comprises the steps of carrying out a first treatment on the surface of the 100 parts by weight of nitric acid with the concentration of 1%, wherein the nitrogen source can be replaced by ammonium sulfate, urea and 1-butyl-3-methylimidazole tetrafluoroborate; 200 parts by weight of deionized water is added and fully and uniformly stirred to obtain heteroatom dispersion liquid. Step three, preparing a precursor material: and (3) adding the porous MXene nano-sheet solution prepared in the step (I) into the heteroatom dispersion liquid prepared in the step (II), fully stirring until the mixture is uniformly mixed, centrifuging the mixed liquid, and drying to obtain the precursor material.
Step four, preparing a porous MXene material doped with hetero atoms: the precursor material is placed into a corundum crucible, transferred into a tube furnace and heated to 200 ℃ at a heating rate of 3 ℃/min in a nitrogen protection atmosphere. And (3) after heat preservation for 1 hour, naturally cooling to room temperature, and collecting solids in the corundum crucible to obtain the heteroatom doped porous MXene material.
Step five, preparing a ferrocene and porous MXene mixture: placing 10 parts by weight of ferrocene and 20 parts by weight of heteroatom-doped porous MXene material prepared in the step four into a mortar, adding 0.3 part by weight of acetone which can be replaced by toluene or dimethyl sulfoxide, grinding for 5 minutes to fully mix, and then drying to obtain a ferrocene and porous MXene mixture;
step six, preparing a porous MXene material doped with carbon nano tube composite hetero atoms by in-situ growth: and (3) placing the mixture prepared in the step (V) into a corundum crucible, uniformly laying 0.1 part by weight of carbon fiber on the top of the corundum crucible, placing the crucible into microwave equipment, setting the power to be 400W and the time to be 20s, and collecting products after 1-time microwave radiation to obtain the in-situ grown carbon nano tube composite heteroatom doped porous MXene material.
Step seven, preparing a porous MXene and graphene oxide composite dispersion liquid: dissolving 1 part by weight of porous MXene material doped with the in-situ grown carbon nano tube composite heteroatom prepared in the step six in 200 parts by weight of deionized water, sufficiently dissolving the porous MXene material by ultrasonic treatment, adding 1 part by weight of Graphene Oxide (GO), and sufficiently dissolving the porous MXene material by ultrasonic treatment to obtain a porous MXene and graphene oxide composite dispersion liquid;
step eight, preparing an aerogel microsphere material used for carrying lithium sulfide: and atomizing the dispersion liquid prepared in the step seven into liquid drop microspheres by a spraying method, and forming porous MXene and graphene oxide composite ice microspheres in a cooling bath receiving liquid. And then freeze-drying the ice microspheres under the environment that the temperature is lower than 50 ℃ below zero and the pressure is lower than 50Pa, so that the porous MXene and graphene oxide composite aerogel microspheres used for carrying lithium sulfide can be obtained.
Other embodiments of the present application will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure herein. This application is intended to cover any variations, uses, or adaptations of the application following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the application pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the application being indicated by the following claims.
It is to be understood that the present application is not limited to the precise construction set forth above, and that various modifications and changes may be made without departing from the scope thereof. The scope of the application is limited only by the appended claims.

Claims (13)

1. An aerogel microsphere material for carrying lithium sulfide, which is characterized in that: the aerogel microspheres are formed by compounding Graphene Oxide (GO) and in-situ grown carbon nano tube composite heteroatom doped porous MXene material, and the mass ratio of the Graphene Oxide (GO) to the porous MXene material is (1:1) - (1:20).
2. The method for preparing aerogel microspheres according to claim 1, wherein: the preparation method comprises the following steps:
stirring and dispersing an MXene nano sheet into a hydrogen peroxide solution, stirring and etching, and centrifugally washing the reacted solution to obtain a porous MXene nano sheet solution by ultrasonic dispersion;
step two, preparing heteroatom dispersion liquid: adding a nitrogen source, a boron source and a phosphorus source into a dispersing agent, and fully stirring to uniformly disperse the components to obtain heteroatom dispersion liquid;
step three, adding the porous MXene nanosheet solution prepared in the step one into the heteroatom dispersion liquid prepared in the step two, fully stirring until the mixture is uniformly mixed, centrifuging the mixed liquid, and drying to obtain a precursor material;
step four, placing the precursor material into a corundum crucible, transferring the corundum crucible into a tube furnace, heating the corundum crucible to a preset temperature in a protective atmosphere, preserving heat, naturally cooling the corundum crucible to room temperature, and collecting solids in the corundum crucible to obtain the heteroatom-doped porous MXene material;
step five, taking ferrocene and the heteroatom doped porous MXene material prepared in the step four, placing the porous MXene material into a mortar, adding an organic dispersing agent, grinding the porous MXene material until the porous MXene material and the organic dispersing agent are fully mixed, and then drying the porous MXene material to obtain a mixture;
step six, placing the mixture prepared in the step five in a corundum crucible, uniformly laying an ignition agent on the top of the corundum crucible, placing the crucible in microwave equipment, and collecting products after microwave radiation to obtain the in-situ grown carbon nano tube composite heteroatom doped porous MXene material;
step seven, dissolving the porous MXene material doped with the in-situ grown carbon nano tube composite heteroatom prepared in the step six in deionized water, fully dissolving the porous MXene material by ultrasonic treatment, adding Graphene Oxide (GO), and fully dissolving the porous MXene material by ultrasonic treatment to obtain a porous MXene-graphene oxide composite dispersion liquid;
and step eight, atomizing the dispersion liquid prepared in the step seven into liquid drop microspheres by a spray method, forming porous MXene and graphene oxide composite ice microspheres in a cooling bath receiving liquid, and then freeze-drying the ice microspheres to obtain the aerogel microsphere material used for carrying lithium sulfide.
3. The preparation method according to claim 2, characterized in that: the porous MXene nano-sheet is a ceramic material with a porous two-dimensional lamellar structure, and the chemical general formula is M n+1 X n T z Wherein M is a transition metal, X is C or/and N, N is 1-3, T z Refers to surface groups, preferably Ti 3 C 2 T x 。
4. The preparation method according to claim 2, characterized in that: the heteroatom is one or more of N, B, P, heteroatom: the molar ratio of the porous MXene nano-sheets is (1:10) - (1:1), wherein the molar ratio of B to N to P is (0-1): (0-4), and preferably 1:2:3.
5. the preparation method according to claim 2, characterized in that: the mass ratio of the MXene nano-sheet to the hydrogen peroxide solution is 0.1-1, and the mass concentration of the hydrogen peroxide solution is 0.01% -0.1%.
6. The preparation method according to claim 2, characterized in that: the etching temperature is 20-80 ℃, and the etching time is 10-100 min.
7. The preparation method according to claim 2, characterized in that: the nitrogen source is selected from sulfurOne or more of ammonium acid, nitric acid, urea, 1-butyl-3-methylimidazolium tetrafluoroborate (1-butyl-3-methylimidazolium tetrafluoroborate, BMI-TFB); the boron source is selected from sodium borohydride, boric acid and B 2 H 6 One or more of the following; the phosphorus source is selected from one or more of phosphoric acid, sodium hypophosphite, hexafluorophosphoric acid and ammonium dihydrogen phosphate.
8. The preparation method according to claim 2, characterized in that: the dispersing agent is one or more selected from deionized water and ethanol; the protective atmosphere is any one or two of argon and nitrogen.
9. The preparation method according to claim 2, characterized in that: the ferrocene is dicyclopentadiene iron (the chemical formula is Fe (C) 5 H 5 ) 2 ) The mass ratio of ferrocene to heteroatom doped porous MXene was (0.5: 1) (1.5: 1) Preferably 1:1.
10. the preparation method according to claim 2, characterized in that: the organic dispersing agent is one or more of toluene, acetone and dimethyl sulfoxide (dmso), preferably acetone; the mass ratio of the amount of the organic dispersant to the total amount of ferrocene and heteroatom doped porous MXene is (1:100) - (1:20).
11. The preparation method according to claim 2, characterized in that: the ignition agent is selected from one or two of carbon powder or carbon fiber, preferably carbon fiber; the mass ratio of the ignition agent to the mixture is (1:300) - (1:100).
12. The preparation method according to claim 2, characterized in that: step four, placing the precursor material into a corundum crucible, transferring the corundum crucible into a tube furnace, heating to 200-500 ℃ at a heating rate of 3-6 ℃/min in a protective atmosphere, preserving heat for 1-5 hours, and naturally cooling to room temperature;
the power of the microwave equipment is 400-1500W, preferably 900W; the microwave irradiation time is 20 s-80 s, preferably 40s each time; the number of microwave irradiation is 1 to 5, preferably 3.
13. The preparation method according to claim 2, characterized in that: the concentration of the porous MXene and graphene oxide composite dispersion liquid is 1% -3%.
CN202211579771.1A 2022-12-06 2022-12-06 Aerogel microsphere material used for carrying lithium sulfide and preparation method thereof Pending CN116207222A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117410479A (en) * 2023-12-13 2024-01-16 河南鑫泉能源科技有限公司 Lithium ion battery composite positive electrode material, preparation method thereof and assembled battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117410479A (en) * 2023-12-13 2024-01-16 河南鑫泉能源科技有限公司 Lithium ion battery composite positive electrode material, preparation method thereof and assembled battery
CN117410479B (en) * 2023-12-13 2024-03-01 河南鑫泉能源科技有限公司 Lithium ion battery composite positive electrode material, preparation method thereof and assembled battery

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