CN116000281B - Uniform and monodisperse FeCoNi medium-entropy alloy nanocrystalline composite material, preparation and application - Google Patents
Uniform and monodisperse FeCoNi medium-entropy alloy nanocrystalline composite material, preparation and application Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 57
- 239000000956 alloy Substances 0.000 title claims abstract description 57
- 229910002545 FeCoNi Inorganic materials 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 16
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 10
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007598 dipping method Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000004005 microsphere Substances 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 0.000 claims abstract description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 239000004743 Polypropylene Substances 0.000 claims description 14
- 229920001155 polypropylene Polymers 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000002159 nanocrystal Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- -1 polypropylene Polymers 0.000 claims description 5
- 239000006104 solid solution Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000010981 drying operation Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 239000013077 target material Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 238000001122 sequential pyrolysis Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 abstract description 17
- 239000011593 sulfur Substances 0.000 abstract description 17
- 239000002707 nanocrystalline material Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 229910052744 lithium Inorganic materials 0.000 abstract description 7
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- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 5
- 230000002441 reversible effect Effects 0.000 abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 229920001021 polysulfide Polymers 0.000 abstract description 2
- 239000005077 polysulfide Substances 0.000 abstract description 2
- 150000008117 polysulfides Polymers 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 7
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- 230000000052 comparative effect Effects 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 3
- 229910013553 LiNO Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
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- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- RZEQQEXIZXEASF-UHFFFAOYSA-N lithium trifluoro(sulfinato)methane Chemical compound [Li+].C(F)(F)(F)[S-](=O)=O RZEQQEXIZXEASF-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- 241001025261 Neoraja caerulea Species 0.000 description 1
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- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 239000002091 nanocage Substances 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
An even and monodisperse FeCoNi medium entropy alloy nanocrystalline composite material, a preparation method and an application thereof belong to the field of micro-nano functional materials and the field of electrochemical energy storage and conversion. The material takes graphene-like carbon with three-dimensional ordered macropores (3 DOM) as a carrier, and the form of monodisperse nano particles is uniformly embedded in the three-dimensional bicontinuous pore wall of the carbonaceous carrier. The preparation method comprises the following steps: (1) Preparing a precursor solution containing ferric nitrate, cobalt nitrate, nickel nitrate and citric acid; (2) Placing a hard template formed by self-assembly of polymethyl methacrylate microspheres in a precursor liquid for dipping, and obtaining a precursor through suction filtration and drying; (3) And (3) placing the precursor into a tube furnace for roasting in an inert atmosphere, and cooling to obtain the uniform and monodisperse FeCoNi medium entropy alloy nanocrystalline material. When the material is used as a lithium-sulfur battery diaphragm modification material, the material has excellent lithium polysulfide catalytic conversion activity, and can obviously improve the reversible specific capacity and the multiplying power performance of a sulfur anode.
Description
Technical Field
The invention belongs to the field of micro-nano functional materials and the field of electrochemical energy storage and conversion, and relates to a uniform and monodisperse FeCoNi medium-entropy alloy nanocrystalline composite material, a preparation method and application thereof.
Background
Traditional alloys based on a metal element can not meet the requirements of social technological development on the performance of metal materials. The high and medium entropy alloy composed of a plurality of main elements is likely to have more ideal physical and chemical properties and mechanical properties, and becomes one of the important points of attention and research of a plurality of subjects such as materiality, mechanics and the like in recent years. Among them, the high-entropy alloy is generally composed of five and more elements with equal or close atomic ratios, and the high-entropy alloy under the "cocktail" effect generally has the capability of catalyzing various reactions because different components tend to have different reaction catalysis preferences. Whereas medium entropy alloys are considered as derivative concepts of high entropy alloys, generally consisting of three or four elements and having a configurational entropy of between 1R and 1.5R. Both are solid solution structures and differ only in terms of the number of constituent elements and the configurational entropy, so they generally have very similar material properties. Nevertheless, the simpler composition structure enables the intermediate entropy alloy to realize relatively lower production cost while retaining the main property advantages of the high entropy alloy, and the clearer catalytic active site also enables the intermediate entropy alloy to have a larger application prospect in the catalysis related field.
Macroscopic blocks of medium/high entropy alloys are usually prepared by vacuum arc melting, mechanical alloying, etc., and the synthesis of nanocrystals is often dependent on carbon support materials, such as: the carbon nanofiber impregnated with the precursor solution is calcined by the Anbai steel and the like to prepare FeCoNi medium entropy alloy nano particles [ Small 19 (2022) 525] loaded on the surface of the carbon nanofiber. However, since the metal component is very liable to agglomerate during high temperature calcination, such a surface-based method is difficult to control the grain size of the resulting nano-crystalline medium entropy alloy. Hu Liangbing the carbon thermal shock method of the subject group invention can better overcome the problem [ Science 359 (2018) 1489], namely, the temperature is quickly raised to an extremely high temperature in an extremely short time and then is quickly lowered, but the technology has higher requirements on equipment. The popular preparation technology for developing and optimizing the high-quality medium/high-entropy alloy nanocrystalline has important significance for the industrialized application of the functional material.
The three-dimensional ordered macroporous (3 DOM) morphology has the advantages of uniform pore diameter, developed pore canal, large pore volume, large specific surface area and the like, so that the adsorption and diffusion of molecules are very favorable in the catalytic reaction, and the catalytic performance of the nano-crystalline medium-entropy alloy can be expected to be greatly exerted if the nano-crystalline medium-entropy alloy can be combined with the nano-crystalline medium-entropy alloy. To date, no literature reports on a medium-entropy alloy nanocrystalline material loaded by 3DOM structural carbon, and a preparation method and application thereof.
Disclosure of Invention
Aiming at the problems, the invention provides a uniform and monodisperse FeCoNi medium entropy alloy nanocrystalline composite material, and a preparation method and application thereof. The material takes graphene-like carbon with a 3DOM structure as a carrier, monodisperse FeCoNi nanocrystals are uniformly embedded in the three-dimensional bicontinuous pore wall of the carbonaceous carrier, and the particle size of the nanocrystals is uniform and can be regulated and controlled between 4 nm and 80 nm. Furthermore, the material is prepared by using a metal salt-polymethyl methacrylate co-sacrificial hard template sequential pyrolysis method, the whole preparation process is simple, economical and efficient, the graphene-like carbon coating generated in the low-temperature section can limit the agglomeration growth of the generated nanocrystalline at high temperature to a certain extent, and the particle size of the nano-crystalline material can be regulated and controlled by setting the final calcination temperature. When the material is used as a diaphragm modification layer of a lithium-sulfur battery, the output specific capacity and the rate capability of a sulfur anode can be obviously improved, which shows that the material has excellent catalytic conversion performance on a lithium polysulfide intermediate product.
The technical scheme adopted by the invention is as follows:
the invention provides a uniform and monodisperse FeCoNi medium entropy alloy nanocrystalline composite material, which is characterized in that the material takes graphene-like carbon with a 3DOM structure as a carrier, the monodisperse FeCoNi medium entropy alloy nanocrystalline is uniformly embedded in the three-dimensional bicontinuous pore wall of the carbon carrier, and the mass ratio of the FeCoNi medium entropy alloy nanocrystalline is 46-65wt%; the FeCoNi medium entropy alloy nanocrystalline is a single-phase solid solution with a face-centered cubic structure (FCC), and three elements of Fe, co and Ni forming the FeCoNi medium entropy alloy nanocrystalline are uniformly distributed in the whole particle; the grain diameter of the nanometer crystal is uniform and can be regulated and controlled between 4nm and 80 nm.
The invention provides a preparation method of a uniform and monodisperse FeCoNi medium entropy alloy nanocrystalline composite material, which is characterized by comprising the following steps of:
(1) Dissolving citric acid in deionized water, dissolving ferric nitrate, cobalt nitrate and nickel nitrate in a citric acid solution, stirring and carrying out ultrasonic treatment to uniformly disperse all substances to obtain a precursor solution;
(2) Dipping the PMMA microsphere colloidal crystal template in the precursor liquid obtained in the step (1), and performing suction filtration and drying operation after the dipping is finished to obtain a precursor for preparing a target material;
(3) And (3) placing the precursor obtained in the step (2) in a tube furnace, roasting under the protection of normal pressure and inert gas, and cooling to room temperature to obtain the FeCoNi medium entropy alloy nanocrystalline composite material uniformly embedded in the three-dimensional ordered macroporous graphene-like carbon carrier.
Preferably, the molar ratio of ferric nitrate, cobalt nitrate and nickel nitrate added in step (1) is 1:1:1, i.e. the metal nitrates are added in equimolar ratios.
Preferably, the total concentration of metal nitrate employed in step (1) is 2mol/L and the concentration of citric acid is 1mol/L, i.e. the total molar ratio of metal nitrate to citric acid is 2:1.
Preferably, the soaking time in the step (2) is 6-24 hours, and the soaking condition is room temperature and normal pressure.
Preferably, in the roasting process in the step (3), argon with the flow rate of 200sccm is selected as inert shielding gas, the temperature is raised to 300-310 ℃ at 1-2 ℃/min, the temperature is kept for 5-15 min, then the temperature is raised to the roasting final temperature at 10-15 ℃/min, the roasting final temperature is set to 750-1000 ℃, the temperature is kept for 0-4 h and is not 0, and the temperature is cooled to room temperature along with a tube furnace after the heat preservation is finished.
When the final roasting temperature is 750-1000 ℃, the average grain diameter of the entropy alloy grains in FeCoNi is 6-55 nm, and the average grain diameter of the entropy alloy grains in FeCoNi is relatively increased along with the increase of the final roasting temperature in the range of 750-1000 ℃.
The uniform and monodisperse FeCoNi medium entropy alloy nanocrystalline composite material is used for lithium-sulfur battery diaphragm modification materials.
For the application of the material as a lithium sulfur battery diaphragm modification material, mixing the material with polyvinylidene fluoride (PVDF) in a mass ratio of 9:1, adding a proper amount of N-methyl-2 pyrrolidone (NMP), uniformly stirring, coating the obtained slurry on a Celgard polypropylene (PP) diaphragm, and drying in a vacuum drying oven at 60 ℃ to obtain the modified lithium sulfur battery diaphragm. Subsequently, assembly of a button test cell of type 2032 was performed in a high purity argon protected glove box (H 2O<0.5ppm,O2 <0.5 ppm), wherein: a lithium bistrifluoromethylsulfonylimide (LiTFSI, 1 mol/L) solution dissolved in a mixed solution of 1, 3-Dioxolane (DOL), ethylene glycol dimethyl ether (DME; volume ratio 1:1) and LiNO 3 (mass percentage 1.0 wt%) is used as an electrolyte, sublimed sulfur, conductive carbon black and PVDF with a mass ratio of 6:3:1 are used for preparing a sulfur anode, and a lithium metal foil is used as a cathode. The assembled battery was subjected to a rate charge-discharge test at room temperature with a voltage range of 1.7 to 2.8V.
In addition, the invention utilizes Rigaku SmartLab type X-ray diffractometer (XRD), S4800 type Scanning Electron Microscope (SEM), JEOL JEM 2100F type high resolution electron transmission microscope (TEM), optosky ATR8300 type Raman spectrometer (Raman) and other instruments to measure the physical and chemical properties of the obtained material, such as crystal structure, morphology, element distribution, chemical composition and the like, and simultaneously utilizes a blue-ray battery test system to evaluate the electrochemical energy storage performance of the assembled lithium-sulfur battery.
The invention has the following beneficial effects:
The method utilizes a metal salt-PMMA co-sacrificial hard template method, and can prepare the monodisperse FeCoNi medium entropy alloy nanocrystalline material which is uniformly embedded in the three-dimensional ordered macroporous graphene-like carbonaceous carrier in situ through a simple and efficient roasting pyrolysis mode. The technology creatively integrates the 3DOM graphene carbonaceous carrier and the FeCoNi medium entropy alloy nanocrystalline material in situ, the 3DOM structure provides a developed pore channel structure, a larger pore volume and a larger specific surface area, the adsorption and diffusion of reaction molecules can be greatly promoted, the mass transfer resistance of the reaction molecules can be reduced, the graphene carbon has excellent electric conduction, heat conduction and chemical stability, and the nano-crystalline material is very favorable for the entropy alloy nano-particles in the FeCoNi to fully play the catalytic role. Meanwhile, the graphene-like carbon layer generated in situ also successfully realizes good wrapping of the entropy alloy nano particles in FeCoNi, and the local core-shell structure characteristic can well inhibit agglomeration growth of the nano particles at high temperature, so that the nano crystal particles not only realize a good monodisperse state, but also can keep uniform and smaller particle sizes. In addition, the average grain diameter of the entropy alloy nanocrystalline in FeCoNi can be regulated and controlled only by changing the final roasting temperature. And the lithium sulfur battery taking the lithium sulfur battery as the diaphragm modification layer can show greatly improved reversible specific capacity and rate capability.
Drawings
In order to further explain the present invention, the following will explain in detail examples and comparative examples.
Wherein:
Fig. 1 is an XRD pattern of the entropy alloy nanocrystalline material in monodisperse FeCoNi embedded in a 3DOM grapheme carbonaceous carrier prepared in example 1 and example 2, where (a) is the XRD pattern of the FeCoNi-800 sample prepared in example 1 and (b) is the XRD pattern of the FeCoNi-1000 sample prepared in example 2.
Fig. 2 is a Raman graph of the entropy alloy nanocrystalline material in monodisperse FeCoNi embedded in a 3DOM grapheme carbonaceous carrier prepared in example 1 and example 2, where (a) is the Raman curve of the FeCoNi-800 sample prepared in example 1 and (b) is the Raman curve of the FeCoNi-1000 sample prepared in example 2.
FIG. 3 is a SEM photograph of a sample of FeCoNi-800 prepared in example 1; (b), (c) TEM photographs; (d) EDS element profile.
FIG. 4 is a SEM photograph of a sample of FeCoNi-1000 prepared in example 2; (b), (c) TEM photographs; (d) EDS element profile.
Fig. 5 is a graph of electrochemical energy storage performance of the assembled batteries of example 3, example 4 and comparative example 1.
Detailed Description
The present invention will be further illustrated by the following examples, which are provided to better understand the present invention and are not to be construed as limiting the scope of the present invention, and any product which is the same as or similar to the present invention, or which is obtained by combining the present invention with other features of the prior art, falls within the scope of the present invention.
Example 1
The nickel nitrate, the ferric nitrate and the cobalt nitrate which are equal in quantity are weighed and dissolved in deionized water (the total concentration is 2 mol/L), and a certain quantity of citric acid (the concentration is 1 mol/L) is added to stir to form a complexing solution. And (3) placing the PMMA microsphere template in the precursor liquid, soaking for 24 hours, and sufficiently drying at room temperature after vacuum suction filtration to obtain the precursor. And (3) placing the obtained precursor into a tubular furnace filled with argon inert shielding gas for roasting, heating from room temperature to 300 ℃ at 2 ℃/min, preserving heat for 5min, heating to 800 ℃ at 15 ℃/min, preserving heat for 30min, roasting, and naturally cooling to room temperature to obtain the monodisperse FeCoNi medium entropy alloy nanocrystalline material (marked as FeCoNi-800) embedded in the 3DOM grapheme carbonaceous carrier. The test result shows that the material is a single-phase solid solution with a face-centered cubic structure (FCC), and is uniformly distributed in the whole 3DOM carbonaceous frame in the form of monodisperse nano crystals, and the mass fraction is about 48.2%; the graphite-like grapheme carbon generated in situ wraps the entropy alloy nanocrystalline particles in the single FeCoNi by a carbon nano cage structure, three elements of Fe, co and Ni forming each nanocrystalline are uniformly distributed in the whole particle, the sizes of the particles are relatively similar, and the average particle size is about 7.5nm.
Example 2
The nickel nitrate, the ferric nitrate and the cobalt nitrate which are equal in quantity are weighed and dissolved in deionized water (the total concentration is 2 mol/L), and a certain quantity of citric acid (the concentration is1 mol/L) is added to stir to form a complexing solution. And (3) placing the PMMA microsphere template in the precursor liquid, soaking for 24 hours, and sufficiently drying at room temperature after vacuum suction filtration to obtain the precursor. And (3) placing the obtained precursor into a tubular furnace filled with argon inert shielding gas for roasting, heating from room temperature to 300 ℃ at 2 ℃/min, preserving heat for 5min, heating to 1000 ℃ at 15 ℃/min, preserving heat for 30min, roasting, and naturally cooling to room temperature to obtain the monodisperse FeCoNi medium entropy alloy nanocrystalline material (marked as FeCoNi-1000) embedded in the 3DOM grapheme carbonaceous carrier. Test results show that the material is still a single-phase solid solution with a face-centered cubic structure (FCC), but compared with FeCoNi-800, the crystallinity of an in-situ generated graphene-like carbon carrier and the crystallinity of an entropy alloy in FeCoNi are greatly enhanced, the size of the entropy alloy nanocrystalline particles in single FeCoNi is also greatly increased, and the average particle size is increased to 53.7nm; nevertheless, it is uniformly distributed throughout the 3DOM carbonaceous framework in a monodisperse form, with a mass fraction of about 52.3%, and still surrounded by a graphene-like carbon layer, the three elements Fe, co, ni constituting each nanocrystal are still uniformly distributed throughout the particle.
Example 3
FeCoNi-800 prepared in example 1 is mixed with polyvinylidene fluoride (PVDF) according to a mass ratio of 9:1, a proper amount of N-methyl-2 pyrrolidone (NMP) is added dropwise and stirred uniformly, the obtained slurry is coated on a Celgard polypropylene (PP) diaphragm, and the diaphragm is dried in a vacuum drying oven at 60 ℃ to obtain the modified diaphragm material. Mixing sublimed sulfur, conductive carbon black (Super P) and PVDF according to a mass ratio of 6:3:1, dripping an appropriate amount of NMP, uniformly stirring, coating the obtained slurry on aluminum foil, and drying at 80 ℃ to obtain the sulfur electrode. In a glove box (H 2O<0.5ppm,O2 <0.5 ppm) protected by high purity argon, a sulfur electrode prepared by the method is taken as a positive electrode, a lithium metal foil is taken as a negative electrode, a PP diaphragm modified by FeCoNi-800 is taken as a battery diaphragm, a 1mol/L bis (trifluoromethanesulfonyl) Lithium (LiTFSI) solution which is dissolved in 1, 3-dioxolane/ethylene glycol dimethyl ether with a volume ratio of 1:1 is taken as an electrolyte (containing 1.0wt% of LiNO 3), and a 2032 type button battery is assembled. The assembled battery was subjected to constant current charge and discharge test at room temperature with a voltage range of 1.7 to 2.8V. The result shows that when the current density is 0.2C, 0.5C, 1C, 2C, 3C, 4C and 5C, the reversible specific capacity of the battery sulfur positive electrode respectively reaches 1362mAh/g, 1262mAh/g, 1116mAh/g, 934mAh/g, 771mAh/g, 678mAh/g and 549mAh/g, and compared with the performance realized based on the original PP diaphragm sulfur positive electrode in comparative example 1, the specific capacity and the multiplying power performance are greatly improved; and when the current density was returned to 0.2C again, the capacity of the sulfur cathode used could be restored to 1314mAh/g, exhibiting excellent reversibility.
Example 4
FeCoNi-1000 prepared in example 2 and polyvinylidene fluoride (PVDF) are mixed according to a mass ratio of 9:1, a proper amount of N-methyl-2 pyrrolidone (NMP) is added dropwise and stirred uniformly, the obtained slurry is coated on a Celgard polypropylene (PP) diaphragm, and the diaphragm is dried in a vacuum drying oven at 60 ℃ to obtain the modified diaphragm material. Mixing sublimed sulfur, conductive carbon black (Super P) and PVDF according to a mass ratio of 6:3:1, dripping an appropriate amount of NMP, uniformly stirring, coating the obtained slurry on aluminum foil, and drying at 80 ℃ to obtain the sulfur electrode. In a glove box (H 2O<0.5ppm,O2 <0.5 ppm) protected by high purity argon, a sulfur electrode prepared by the method is taken as a positive electrode, a lithium metal foil is taken as a negative electrode, a PP diaphragm modified by FeCoNi-1000 is taken as a battery diaphragm, a 1mol/L bis (trifluoromethanesulfonyl) Lithium (LiTFSI) solution which is dissolved in 1, 3-dioxolane/ethylene glycol dimethyl ether with a volume ratio of 1:1 is taken as an electrolyte (containing 1.0wt% of LiNO 3), and a 2032 type button battery is assembled. The assembled battery was subjected to constant current charge and discharge test at room temperature with a voltage range of 1.7 to 2.8V. The result shows that when the current density is 0.2C, 0.5C, 1C, 2C, 3C, 4C and 5C, the reversible specific capacity of the battery sulfur positive electrode respectively reaches 1024mAh/g, 912mAh/g, 820mAh/g, 707mAh/g, 630mAh/g, 579mAh/g and 528mAh/g, and compared with the performance realized by the original PP diaphragm sulfur positive electrode in comparative example 1, the specific capacity and the rate performance are greatly improved; and when the current density is returned to 0.2C again, most of the capacity of the sulfur positive electrode used can be recovered, and the reversibility is good.
Comparative example 1
In a high purity argon protected glove box (H 2O<0.5ppm,O2 <0.5 ppm), the same sulfur positive electrode, electrolyte and lithium metal foil negative electrode as in examples 3 and 4 were used, except that unmodified Celgard polypropylene (PP) separator was used as battery separator, assembling a type 2032 coin cell. The assembled battery was subjected to a rate charge-discharge test at room temperature with a voltage range of 1.7 to 2.8V. The results show that the reversible specific capacity of the battery sulfur positive electrode is lower in all current densities compared with that of the battery sulfur positive electrode in the example 1 and the example 2, when the current densities are 0.2C and 0.5C, the initial specific capacity is only 663mAh/g and 425mAh/g, the capacity decays rapidly at high multiplying power, and the specific capacity is smaller than 100mAh/g at the multiplying power of 3C and higher, so that the electrochemical energy storage performance of the sulfur positive electrode in the lithium sulfur battery assembled by the unmodified diaphragm is poor.
Claims (10)
1. The uniform and monodisperse FeCoNi medium entropy alloy nanocrystalline composite material is characterized in that the material takes graphene-like carbon with a 3DOM structure as a carrier, and the monodisperse FeCoNi medium entropy alloy nanocrystalline is uniformly embedded in the three-dimensional bicontinuous pore wall of the carbon carrier; is prepared by a metal salt-polymethyl methacrylate PMMA co-sacrificial hard template sequential pyrolysis method, and specifically comprises the following steps:
(1) Dissolving citric acid in deionized water, dissolving ferric nitrate, cobalt nitrate and nickel nitrate in a citric acid solution, stirring and carrying out ultrasonic treatment to uniformly disperse all substances to obtain a precursor solution;
(2) Dipping the PMMA microsphere colloidal crystal template in the precursor liquid obtained in the step (1), and performing suction filtration and drying operation after the dipping is finished to obtain a precursor for preparing a target material;
(3) And (3) placing the precursor obtained in the step (2) in a tube furnace, roasting under the protection of normal pressure and inert gas, and cooling to room temperature to obtain the FeCoNi medium entropy alloy nanocrystalline composite material uniformly embedded in the three-dimensional ordered macroporous graphene-like carbon carrier.
2. The uniform and monodisperse FeCoNi medium entropy alloy nanocrystalline composite material according to claim 1, wherein the mass ratio of the FeCoNi medium entropy alloy nanocrystalline is 46-65wt%; the FeCoNi medium entropy alloy nanocrystalline is a single-phase solid solution of FCC with a face-centered cubic structure, and three elements of Fe, co and Ni forming the FeCoNi medium entropy alloy nanocrystalline are uniformly distributed in the whole particle; the grain diameter of the nano-crystal is uniform and is adjustable and controllable between 4 nm and 80 nm.
3. The method for preparing the uniform and monodisperse FeCoNi medium entropy alloy nanocrystalline composite material according to claim 1 or 2, which is characterized by comprising the following steps of:
(1) Dissolving citric acid in deionized water, dissolving ferric nitrate, cobalt nitrate and nickel nitrate in a citric acid solution, stirring and carrying out ultrasonic treatment to uniformly disperse all substances to obtain a precursor solution;
(2) Dipping the PMMA microsphere colloidal crystal template in the precursor liquid obtained in the step (1), and performing suction filtration and drying operation after the dipping is finished to obtain a precursor for preparing a target material;
(3) And (3) placing the precursor obtained in the step (2) in a tube furnace, roasting under the protection of normal pressure and inert gas, and cooling to room temperature to obtain the FeCoNi medium entropy alloy nanocrystalline composite material uniformly embedded in the three-dimensional ordered macroporous graphene-like carbon carrier.
4. A method according to claim 3, wherein the molar ratio of ferric nitrate, cobalt nitrate and nickel nitrate added in step (1) is 1:1:1, i.e. the metal nitrates are added in equimolar ratios.
5. A method according to claim 3, characterized in that the total concentration of metal nitrate used in step (1) is 2mol/L and the concentration of citric acid is 1mol/L, i.e. the total molar ratio of metal nitrate to citric acid is 2:1.
6. A method according to claim 3, wherein the impregnation time in step (2) is from 6 to 24 hours and the impregnation conditions are room temperature and atmospheric pressure.
7. A method according to claim 3, wherein in the roasting in step (3), argon gas with a flow rate of 200 seem is selected as an inert shielding gas, the temperature is raised to 300-310 ℃ at 1-2 ℃/min, the temperature is kept for 5-15 min, then the temperature is raised to the roasting final temperature at 10-15 ℃/min, the roasting final temperature is set to 750-1000 ℃, the temperature is kept for 0-4 h and is not 0, and the temperature is cooled to room temperature along with a tube furnace after the end of the heat preservation.
8. The method of claim 7, wherein the average particle size of the entropy alloy particles in FeCoNi is 6 to 55nm when the final baking temperature is 750 to 1000 ℃, and the average particle size of the entropy alloy particles in FeCoNi is relatively increased with an increase in the final baking temperature in the range of 750 to 1000 ℃.
9. The use of the uniform, monodisperse FeCoNi medium entropy alloy nanocrystalline composite material according to claim 1 or 2 for lithium-sulfur battery separator modification materials.
10. The method according to claim 9, wherein the composite material is mixed with polyvinylidene fluoride PVDF according to a mass ratio of 9:1, N-methyl-2 pyrrolidone NMP is added, the mixture is stirred uniformly, the obtained slurry is coated on a Celgard polypropylene PP diaphragm, and the mixture is dried in a vacuum drying oven to obtain the lithium-sulfur battery diaphragm.
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