CN114472902B - Two-dimensional layered antimony cathode material, two-dimensional antimony alkene material, and preparation methods and applications thereof - Google Patents
Two-dimensional layered antimony cathode material, two-dimensional antimony alkene material, and preparation methods and applications thereof Download PDFInfo
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 94
- 239000000463 material Substances 0.000 title claims abstract description 44
- 239000010406 cathode material Substances 0.000 title claims description 6
- -1 antimony alkene Chemical class 0.000 title abstract description 10
- 238000002360 preparation method Methods 0.000 title description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 239000000843 powder Substances 0.000 claims abstract description 62
- 239000011777 magnesium Substances 0.000 claims abstract description 55
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000010410 layer Substances 0.000 claims abstract description 26
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 22
- 239000000956 alloy Substances 0.000 claims abstract description 22
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 239000002356 single layer Substances 0.000 claims abstract description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000005121 nitriding Methods 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000012467 final product Substances 0.000 claims description 18
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 16
- 238000000967 suction filtration Methods 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000005554 pickling Methods 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000010431 corundum Substances 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 239000007773 negative electrode material Substances 0.000 claims description 9
- 239000012495 reaction gas Substances 0.000 claims description 9
- 238000003892 spreading Methods 0.000 claims description 9
- 230000007480 spreading Effects 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims 1
- 239000010453 quartz Substances 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 abstract description 34
- 238000005275 alloying Methods 0.000 abstract description 21
- 239000010405 anode material Substances 0.000 abstract description 8
- 239000002243 precursor Substances 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- 239000012071 phase Substances 0.000 description 17
- 230000008569 process Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910021389 graphene Inorganic materials 0.000 description 8
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 7
- 230000000630 rising effect Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000009830 intercalation Methods 0.000 description 6
- 230000002687 intercalation Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004299 exfoliation Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 238000010587 phase diagram Methods 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- 229910006745 Li—Sb Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a method for preparing a micron-sized two-dimensional antimony anode material and a two-dimensional antimony alkene material in a large-scale controllable manner and application thereof. The invention takes magnesium powder and antimony powder as raw materials, and prepares the layered alpha-magnesium antimonide alloy precursor by controlling alloying reaction temperature, wherein the magnesium layers and the antimony layers are alternately arranged. By utilizing the difference of magnesium and antimony reactivity, magnesium is converted into magnesium nitride by adopting a nitrogen-containing atmosphere and serves as a two-dimensional template, so that a layered structure with alternately distributed simple substance antimony/magnesium nitride nano layers is generated. After removal of the magnesium nitride formed by subsequent acid washing, the unique layered two-dimensional antimony is finally formed and shows higher capacity and excellent rate capability and long cycling stability in subsequent testing of lithium ion batteries. The lamellar antimony is further subjected to ultrasonic dispersion treatment, so that the small-layer or single-layer antimonene with the size of microns can be obtained. The method is simple and feasible, has low cost, can be used for mass production, and provides reference for preparing large-size metal two-dimensional materials.
Description
Technical Field
The invention relates to a preparation method and application of a two-dimensional layered antimony material and a two-dimensional antimonene material, and provides a method and application for preparing a micron-sized two-dimensional antimonene anode material and a two-dimensional antimonene material in a large-scale controllable manner.
Background
After graphene was prepared by mechanical exfoliation from the uk scientist, geim et al, 2004, two-dimensional materials have initiated a research surge internationally. With the continuous and deep research of researchers on graphene in recent years, the graphene has unique physical properties such as Hall effect, quantum tunneling effect and the like, and the unique excellent properties of the graphene are found, so that the graphene has important application prospects in the aspects of materials science, micro-nano processing, energy sources, biomedicine, drug delivery and the like. However, the forbidden bandwidth of graphene is 0eV, which limits the application of graphene in the fields of semiconductor devices and photoelectrons and other wider fields, so that the research of graphene-like two-dimensional materials has become a very hot and far-reaching topic. The research in this field starts from graphene and expands gradually towards disulfides and groups four (silicon, germanium, tin) and then towards group five (phosphorus, arsenic, antimony, bismuth).
The single-layer material formed by the V main group element is very suitable for being applied to next-generation electronic devices due to the characteristics of larger band gap, high carrier mobility, and 'non-mediocre' topological property. In recent years, single-layer Antimonene (Antimonene) is theoretically predicted to be a semiconductor material with a wide band gap, and has the characteristics of high carrier mobility, band gap adjustable with the number of layers (0-2.28 eV), high thermal conductivity, easy regulation of electrical properties and the like, so that the single-layer Antimonene (Antimonene) has been widely studied. However, at present, the work of preparing high-quality antimoney in experiments is rarely reported, and further realizing the regulation and control of the structure and physical properties of the material is more difficult.
Heretofore, the two-dimensional antimony production techniques can be classified into epitaxial growth, mechanical exfoliation, electrochemical exfoliation, liquid phase exfoliation, and the like. For example, a document "Two-dimensional antimonene single crystals grown by van der Waals epitaxy" adopts a van der Waals epitaxial growth method to successfully prepare a high-quality Two-dimensional antimoney film, commercial antimoney powder is used for carrying out gas-phase transportation, the commercial antimoney powder is deposited on a fluoromica substrate to prepare a plurality of layers of antimoney nano-sheets, and the thinnest nano-sheet is observed to be up to 4nm. Meanwhile, by means of experimental means such as Raman, AFM and the like and theoretical simulation, the excellent chemical stability of the antimoney is confirmed. However, this method has a great limitation, has extremely high requirements on equipment, is difficult to synthesize, and is not conducive to the development of extensive researches in this field. For example, the document 'Few-Layer anymonene: anisotropic Expansion and Reversible Crystalline-Phase Evolution Enable Large-Capacity and Long-Life Na-Ion Batteries' obtains an ultrathin two-dimensional few-Layer Antimonene material by a liquid phase stripping method, and the ultrathin two-dimensional few-Layer Antimonene material is applied to a negative electrode of a sodium Ion battery to obtain excellent electrochemical performance. The hexagonal lamellar (beta-Sb) antimony powder is subjected to ultrasonic stripping in a mixed solvent of alcohol and N-methylpyrrolidone, unpeeled blocks and thicker antimony nano sheets are removed by a gradient centrifugation method, and a high-quality few-layer antimoney material is obtained, so that high-quality few-layer antimoney is obtained, and the average thickness of the high-quality few-layer antimoney material is 8nm (about 18 atomic layer thickness). As another example, patent "a microwave-based stripping of antimones and its preparation method (CN 113333736A)" provides a microwave-based stripping of antimones, which is prepared as follows: firstly, pretreating antimony powder by a ball milling method to obtain micron-sized antimony powder; mixing the micron-sized antimony powder with an isopropanol solution, stirring, and performing ultrasonic dispersion to obtain a mixed solution; and then carrying out microwave treatment on the mixed solution, taking supernatant, centrifuging, washing and drying to obtain the antimoney based on microwave-assisted stripping. The invention adopts a microwave-assisted liquid phase rapid stripping technology to prepare the high-quality two-dimensional few-layer antimoney material with adjustable layers, modifiable surfaces and stable properties, but the method has the defects of time consumption, low yield, reduced transverse area of the obtained antimoney and the like. In the method, the porous two-dimensional antimonic is prepared by adopting a liquid phase dealloying mode, and the method takes Li-Sb alloy as a precursor, and can control the preparation of the two-dimensional porous antimonic by utilizing the reaction kinetics difference of different solvents in the liquid phase dealloying process. However, the method has the problems of higher preparation cost, unstable precursor, uneven thickness of the prepared antimoney, uneven morphology and the like. The method has the defects of unsatisfactory mechanical stripping effect, low yield, long time consumption, uneven thickness of the obtained two-dimensional antimony, reduced transverse area and the like.
Disclosure of Invention
In order to solve the defects in the prior art, the invention has the advantages of simple whole preparation, short period, low energy consumption, green environment protection and mass production. Aiming at the problems of high cost and high synthesis difficulty in the synthesis process of the layered antimonic, a hexagonal layered alpha-antimonide magnesium alloy precursor is controllably prepared by utilizing a Mg-Sb alloy phase diagram, interlayer magnesium is selectively removed by phase separation in a gas phase dealloying mode, a two-dimensional layered antimonic material is obtained, and further, the two-dimensional layered antimonic material is further subjected to ultrasonic dispersion in an organic solvent, so that a large-sized single-layer or less-layer two-dimensional antimonic material can be finally obtained. The obtained two-dimensional layered antimony anode material has excellent electrochemical lithium storage performance, is favorable for rapid extraction/intercalation of lithium/sodium ions due to a unique layered structure, and sequentially undergoes intercalation reaction and alloying reaction, so that the two-dimensional layered antimony anode material has higher capacity and excellent rate capability, has higher commercial application potential, and has the following technical scheme:
a two-dimensional layered antimony cathode material and a preparation method of a two-dimensional antimony alkene material, in particular to a preparation method of a large-scale controllable preparation two-dimensional layered antimony cathode material, which is characterized in that: the method comprises the following steps:
step 1: placing antimony powder and magnesium powder in a certain mass ratio into a mixer for mixing, so that the antimony powder and the magnesium powder are uniformly mixed; preferably, it is: the atomic ratio of the antimony powder to the magnesium powder is 2:3, placing the materials into a mixer to mix for more than 1 h;
step 2: placing the powder uniformly mixed in the step 1 into a stainless steel reaction kettle, then placing the reaction kettle into an argon atmosphere tube furnace, heating to 500-700 ℃ at a heating rate of 1-10 ℃/min, preserving heat for 3-6 hours, and cooling along with the furnace after the heat preservation is finished and taking out; the heating rate of the conventional experimental furnace is generally within 20 ℃/min, so the default general heating rate in the general industry is controlled within 10 ℃/min, the resistance wire of the furnace can be damaged by the excessively fast heating rate, and the accuracy of temperature control is poorer as the heating rate is higher. The initial alloying temperature of the antimony powder and the magnesium powder is 500 ℃, and uniform Mg can not be formed below 500 DEG C 3 Sb 2 When the temperature of the alloy is higher than 700 ℃, magnesium is easier to evaporate, excessive loss of magnesium is easy to cause, and antimony does not participate in alloying reaction. The lowest time of the reaction is the standard when the time is selected, the time is related to more reaction materials, the less the materials are, and the shorter the alloying time is;
step 3: ball milling, crushing and screening the product obtained in the step 2 to obtain alloy powder with certain micron-sized particle size distribution; preferably, it is: alloy powder with the granularity distribution of 1-10 mu m, the small granularity can affect the tap density, and the excessive particle size can lead the inside of the particles not to be fully nitrided, thereby affecting the reaction dynamics in the dealloying process;
step 4: placing the powder sieved in the step 3 into a tube furnace, and introducing nitrogen to perform Mg 3 Sb 2 Is carried out by nitriding; preferably, it is: spreading the powder on the surface of corundum plate, ensuring sufficient contact with reaction gas to make reaction reach optimal effect, and introducing nitrogen-containing atmosphere (N) 2 、NH 3 NH3/Ar or N 2 /NH 3 Mixed gas) to carry out nitriding reaction of magnesium antimonide, wherein the gas flow rate is 0.1-0.3L/min, the temperature is kept for 3-6h at 400-900 ℃, the lowest occurrence temperature of nitriding is 400 ℃, the temperature in a furnace body cannot exceed 900 ℃, otherwise, antimony is volatilized in a large amount to reduce the yield), and the temperature rising rate is 5-10 ℃/min;
step 5: adding the product obtained in the step 4 into 1M hydrochloric acid, pickling for 3-6h, filtering to be neutral, and performing vacuum freeze drying to obtain a final product: two-dimensional layered antimony negative electrode material.
The invention also discloses a method for preparing the two-dimensional antimoney material by adopting gas phase dealloying, which comprises the method for preparing the two-dimensional layered antimoney anode material by adopting gas phase dealloying and is characterized in that: further comprising step 6: adding the product obtained in the step 5 into a certain amount of DMF (dimethylformamide), performing ultrasonic dispersion for a certain time, taking supernatant, performing suction filtration, cleaning, and performing vacuum freeze drying to obtain a final product: two-dimensional antimoney materials.
The invention also discloses a preparation method of the two-dimensional layered antimony anode material and the two-dimensional layered antimony anode material prepared by adopting the large-scale controllable preparation method.
The invention also discloses a preparation method of the large-scale controllable large-piece multi-layer or small-layer two-dimensional antimoney material and the large-piece multi-layer or small-layer two-dimensional antimoney material prepared by adopting the method.
The invention also discloses application of the two-dimensional layered antimony anode material to the anode of the lithium ion battery.
The beneficial effects are that:
1. the innovation provides a novel synthesis mode of the lamellar antimoney, and provides a reference scheme for synthesizing lamellar metal;
2. the method can prepare the two-dimensional layered antimony with the accordion structure in a large scale, and has low cost and simple and easy mode;
3. the micron-sized layered antimony can realize rapid ion extraction/intercalation reaction, the intercalation reaction and the alloying reaction occur in sequence, so that excellent lithium storage performance is brought, and the method has good commercial application prospect;
4. the two-dimensional antimoney material prepared by the method has the advantages of high quality, large size, fewer and controllable layers, simple method and large-scale preparation.
Drawings
Fig. 1: and 2, preparing a hexagonal phase layered alpha-magnesium antimonide alloy reference phase diagram by adopting low-temperature (500-700 ℃) alloying.
Fig. 2: a crystal structure diagram of a hexagonal phase layered alpha-magnesium antimonide alloy is prepared in example 1. Wherein fig. 2 (a) is: a front view of a schematic diagram of the crystal structure of the alpha-magnesium antimonide alloy; fig. 2 (b) is: schematic top view of crystal structure of alpha-magnesium antimonide alloy.
Fig. 3: example 1 a scanning electron microscope image of a hexagonal phase layered alpha-magnesium antimonide alloy was prepared.
Fig. 4: example 1 a process phase change XRD pattern was prepared.
Fig. 5: example 1 in situ thermogravimetric TG-DTA plot of nitridation process.
Fig. 6: a scanning electron microscope image of the product prepared in example 1 after acid washing, wherein fig. 6 (a) is a scanning electron microscope image of two-dimensional layered antimony particles at a large size; (b) A partial magnified scanning electron microscope image of a single two-dimensional layered antimony particle.
Fig. 7: a graph of half-cell rate performance of the product package prepared in example 1.
Fig. 8: a half cell cycle performance profile for the product package prepared in example 1.
Fig. 9: preparation of the phase XRD pattern for part of the antimony unreacted during alloying for example 2
Fig. 10: preparation of example 3 to obtain a phase XRD pattern with substantial evaporation of antimony at too high a temperature of the nitriding process
Detailed Description
The preparation method of the two-dimensional layered antimony cathode material and the two-dimensional antimony alkene material is characterized in that: the method comprises the following steps:
step 1: placing antimony powder and magnesium powder in a certain mass ratio into a mixer for mixing, so that the antimony powder and the magnesium powder are uniformly mixed; preferably, it is: the atomic ratio of the antimony powder to the magnesium powder is 2:3, placing the materials into a mixer to mix for more than 1 h;
step 2: placing the powder uniformly mixed in the step 1 into a stainless steel reaction kettle, then placing the reaction kettle into an argon atmosphere tube furnace, heating to 500-700 ℃ at a heating rate of 1-10 ℃/min, preserving heat for 3-6 hours, and cooling along with the furnace after the heat preservation is finished and taking out; the heating rate of the conventional experimental furnace is generally within 20 ℃/min, so the default general heating rate in the general industry is controlled within 10 ℃/min, the resistance wire of the furnace can be damaged by the excessively fast heating rate, and the accuracy of temperature control is poorer as the heating rate is higher. The initial alloying temperature of the antimony powder and the magnesium powder is 500 ℃, and uniform Mg can not be formed below 500 DEG C 3 Sb 2 When the temperature of the alloy is higher than 700 ℃, magnesium is easier to evaporate, excessive loss of magnesium is easy to cause, and part of antimony does not participate in alloying reaction. The lowest time of the reaction is the standard when the time is selected, the time is related to more reaction materials, the less the materials are, and the shorter the alloying time is;
step 3: ball milling, crushing and screening the product obtained in the step 2 to obtain alloy powder with certain micron-sized particle size distribution; preferably, it is: alloy powder with the granularity distribution of 1-10 mu m has small granularity which can affect tap density and excessively increases dealloying reaction kinetics, so that the inside of the particles cannot be fully nitrided;
step 4: placing the powder sieved in the step 3 into a tube furnace, and introducing nitrogen to perform Mg 3 Sb 2 Is carried out by nitriding; preferably, it is: spreading the powder on the surface of corundum plate, ensuring sufficient contact with reaction gas to make reaction reach optimal effect, and introducing nitrogen-containing atmosphere (N) 2 、NH 3 NH3/Ar or N 2 /NH 3 Mixed gas) to carry out nitriding reaction of magnesium antimonide, the gas flow rate is 0.01-0.3L/min, and the temperature is 400-900 DEG CPreserving heat for 3-6h (the lowest nitriding temperature is 400 ℃, the temperature in the furnace body cannot exceed 900 ℃, otherwise, the antimony is volatilized in a large amount to reduce the yield), and the heating rate is 5-10 ℃/min;
step 5: adding the product obtained in the step 4 into 1M hydrochloric acid, pickling for 3-6h, filtering to be neutral, and performing vacuum freeze drying to obtain a final product: two-dimensional layered antimony negative electrode material;
step 6: adding the product obtained in the step 5 into 50ml of DMF solvent, performing ultrasonic dispersion for 2 hours, taking supernatant, performing suction filtration and cleaning, and performing vacuum freeze drying to obtain a final product: two-dimensional antimoney materials.
Example 1
(1) Placing 0.3g of magnesium powder and 1g of antimony powder (the atomic ratio of the antimony powder to the magnesium powder is 1g of the antimony powder to 0.295g of the magnesium powder is 2:3, so that the magnesium powder is slightly excessive, namely the magnesium powder is finally determined to be 0.3g of the magnesium powder, thereby preventing the magnesium powder from evaporating out and causing the antimony to be unable to react completely to form a mixed phase), and mixing for 1h in a mixer, so that the antimony powder and the magnesium powder are fully and uniformly mixed;
(2) Placing the uniformly mixed powder in the step (1) into a stainless steel reaction kettle, then placing the reaction kettle into an argon atmosphere tube furnace, keeping the temperature at the temperature rising rate of 10 ℃/min for 2 hours at the temperature of 500 ℃, keeping the temperature at the temperature of 5 ℃/min to 600 ℃ for 1 hour, and keeping the temperature at the temperature of 5 ℃/min to 700 ℃ for 1 hour. As can be seen from the Mg-Sb phase diagram in FIG. 1, when the atomic ratio of Sb to Mg is 2 in the range of 500-900℃: alpha-Mg can be formed at 3 3 Sb 2 . FIG. 2 shows alpha-Mg 3 Sb 2 The magnesium layers and the antimony layers are alternately arranged for the intercalation alloy compound, which provides a theoretical feasible basis for subsequent dealloying. The alloying process is carried out in a closed stainless steel reaction kettle to reduce volatilization of Mg powder, firstly, the temperature is kept at 500 ℃ for 2 hours, at this time, the Mg powder and the Sb powder are both solid, the reaction of the Mg powder and the Sb powder is uniform by utilizing the diffusion process of the solid-solid reaction of the Mg powder and the Sb powder, the subsequent temperature is kept at 600 ℃ for 1 hour to ensure the complete reaction of the Mg powder and the Mg powder, and the temperature is kept at 700 ℃ to improve alpha-Mg 3 Sb 2 Is a crystal of (a) is a crystal of (b). Cooling and taking out along with the furnace after finishing; from the SEM image after alloying in FIG. 2, it can be seen that the alpha-Mg was prepared 3 Sb 2 Exhibiting a hexagonal layered structure. At the same time, XRD alloying results of FIG. 4 also show pure phase alpha-Mg 3 Sb 2 Without itOther impurities;
(3) Crushing and screening the product obtained in the step (2) to obtain alloy powder with the granularity distribution of 1-10 mu m;
(4) Spreading the powder screened in the step (3) on the surface of a corundum plate, ensuring full contact with reaction gas to ensure that the reaction achieves the optimal effect, introducing NH3/Ar mixed gas to carry out nitriding reaction of magnesium antimonide, keeping the temperature at 600 ℃ for 3h at a temperature rising rate of 10 ℃/min, and keeping the gas flow rate of 0.3L/min; from the XRD pattern of nitriding in FIG. 4, it can be seen that the nitriding sample contains Sb and Mg 3 N 2 And MgO; meanwhile, as can be seen from the in-situ TG-DTA diagram in the ammonia atmosphere in FIG. 5, magnesium antimonide starts to react at 400 ℃ and the reaction is most intense and the heat release is most intense when the temperature reaches 600 ℃. The mass is drastically reduced with the subsequent temperature rise, which is caused by volatilization of Sb (melting point 630 ℃), so the temperature needs to be about 600 ℃, and the volatilization of Sb is reduced as much as possible while ensuring sufficient nitridation of Mg.
(5) Pickling the product of the step (4) in 1M hydrochloric acid for 3-6 hours, filtering to neutrality, and performing vacuum freeze drying to obtain a final product; from the XRD results in FIG. 4, it can be seen that the final sample is pure phase beta-Sb free of other impurities. The SEM results in FIG. 6 show that the morphology of β -Sb is an accordion structure two-dimensional layered antimony. The micron-sized layered structure can bring about high tap density, can realize rapid ion extraction/intercalation reaction, and insertion reaction and alloying reaction occur in sequence, thereby bringing about excellent lithium storage performance.
(6) Adding the product obtained in the step (5) into 50ml of DMF solvent, performing ultrasonic dispersion for 2 hours, taking supernatant, performing suction filtration and cleaning, and performing vacuum freeze drying to obtain a final product: a two-dimensional antimoney material;
(7) FIG. 7 is a graph showing the rate capability of two-dimensional layered antimony at current densities of 0.1-3A/g, showing that the structure has excellent rate capability. FIG. 8 shows that the cycle stability of two-dimensional layered antimony under a high current density of 3A/g has a first coulomb efficiency of 86.4%, and a specific capacity of 450mAh/g still exists after 100 cycles, thus showing good cycle stability.
Example 2
(1) Mixing 0.3g of magnesium powder and 1g of antimony powder in a mixer to fully and uniformly mix the antimony powder and the magnesium powder;
(2) Placing the uniformly mixed powder in the step (1) in a stainless steel reaction kettle, then placing the reaction kettle in an argon atmosphere tube furnace, heating at a speed of 10 ℃/min, and preserving the heat at 800 ℃ for 2 hours, wherein the XRD pattern after alloying in figure 9 shows that the alloy is except alpha-Mg 3 Sb 2 Part of Sb can not participate in alloying, presumably because the Mg molten state at the temperature is subjected to alloying reaction with Sb, only part of the surface of antimony metal can be reacted, and the Sb in the inner layer can not be reacted, so that pure phase can not be prepared;
(3) Crushing and screening the product obtained in the step (2) to obtain alloy powder with the granularity distribution of 1-10 mu m;
(4) Spreading the powder screened in the step (3) on the surface of a corundum plate, ensuring full contact with reaction gas to ensure that the reaction achieves the optimal effect, introducing NH3/Ar mixed gas to carry out nitriding reaction of magnesium antimonide, keeping the temperature at 600 ℃ for 3h at a temperature rising rate of 10 ℃/min, and keeping the gas flow rate of 0.3L/min;
(5) Adding the product obtained in the step (4) into 1M hydrochloric acid, pickling for 3-6h, carrying out suction filtration to neutrality, and carrying out vacuum freeze drying to obtain a final product: a mixed product of two-dimensional layered antimony and bulk unreacted antimony;
(6) Adding the product obtained in the step (5) into 50ml of DMF solvent, performing ultrasonic dispersion for 2 hours, taking supernatant, performing suction filtration and cleaning, and performing vacuum freeze drying to obtain a final product: two-dimensional antimonees.
Example 3
(1) Mixing 0.3g of magnesium powder and 1g of antimony powder in a mixer to fully and uniformly mix the antimony powder and the magnesium powder;
(2) Placing the uniformly mixed powder in the step (1) into a stainless steel reaction kettle, then placing the reaction kettle into an argon atmosphere tube furnace, keeping the temperature at the temperature rising rate of 10 ℃/min for 2 hours at the temperature of 500 ℃, keeping the temperature at the temperature of 5 ℃/min to 600 ℃ for 1 hour, and keeping the temperature at the temperature of 5 ℃/min to 700 ℃ for 1 hour.
(3) Crushing and screening the product obtained in the step (2) to obtain alloy powder with the granularity distribution of 1-10 mu m;
(4) Spreading the powder screened in the step (3) on the surface of a corundum plate, ensuring full contact with reaction gas to ensure that the reaction achieves the optimal effect, introducing NH3/Ar mixed gas to carry out nitriding reaction of magnesium antimonide, keeping the temperature at 750 ℃ for 3h at a heating rate of 10 ℃/min, and keeping the temperature of the gas at 0.3L/min; the XRD results in fig. 10 show that the peak of Sb is significantly reduced because the temperature is too high to cause the Sb to volatilize in a large amount.
(5) Adding the product obtained in the step (4) into 1M hydrochloric acid, pickling for 3-6h, carrying out suction filtration to neutrality, and carrying out vacuum freeze drying to obtain a final product with greatly reduced yield: two-dimensional layered antimony negative electrode material;
(6) Adding the product obtained in the step (5) into 50ml of DMF solvent, performing ultrasonic dispersion for 2 hours, taking supernatant, performing suction filtration and cleaning, and performing vacuum freeze drying to obtain a final product: two-dimensional antimoney materials.
Example 4
(1) Mixing 0.3g of magnesium powder and 1g of antimony powder in a mixer to fully and uniformly mix the antimony powder and the magnesium powder;
(2) Placing the uniformly mixed powder in the step (1) into a stainless steel reaction kettle, then placing the reaction kettle into an argon atmosphere tube furnace, keeping the temperature at the temperature rising rate of 10 ℃/min for 2 hours at the temperature of 500 ℃, keeping the temperature at the temperature of 5 ℃/min to 600 ℃ for 1 hour, and keeping the temperature at the temperature of 5 ℃/min to 700 ℃ for 1 hour.
(3) Crushing and screening the product obtained in the step (2) to obtain alloy powder with the granularity distribution of 1-10 mu m;
(4) Spreading the powder screened in the step (3) on the surface of a corundum plate, and ensuring full contact with reaction gas so as to ensure that the reaction achieves an optimal effect; introducing N2/Ar mixed gas to carry out nitriding reaction of magnesium antimonide, wherein the gas flow rate is 0.3L/min, and the temperature is kept at 600 ℃ for 3 hours, and the heating rate is 10 ℃/min; nitrogen with low activity is used as a reaction gas, so that the nitriding reaction is incomplete, and magnesium antimonide still remains.
(5) Adding the product of the step (4) into 1M hydrochloric acid, and pickling for 3-6h, wherein in the pickling process, the product of the step (4) contains non-nitrided magnesium antimonide, the magnesium antimonide and hydrochloric acid undergo a severe reaction, so that the formed two-dimensional layered antimony is destroyed, and after suction filtration to be neutral, the final product can be obtained through vacuum freeze drying: large and broken small particles of non-morphological granular antimony;
(7): adding the product obtained in the step (6) into 50ml of DMF solvent, performing ultrasonic dispersion for 2 hours, taking supernatant, performing suction filtration and cleaning, and performing vacuum freeze drying to obtain the final product.
Example 5
(1) Mixing 0.3g of magnesium powder and 1g of antimony powder in a mixer to fully and uniformly mix the antimony powder and the magnesium powder;
(2) Placing the uniformly mixed powder in the step (1) into a stainless steel reaction kettle, then placing the reaction kettle into an argon atmosphere tube furnace, keeping the temperature at the temperature rising rate of 10 ℃/min for 2 hours at the temperature of 500 ℃, keeping the temperature at the temperature of 5 ℃/min to 600 ℃ for 1 hour, and keeping the temperature at the temperature of 5 ℃/min to 700 ℃ for 1 hour.
(3) Crushing and screening the product obtained in the step (2) to obtain alloy powder with the granularity distribution of 1-10 mu m;
(4) Spreading the powder screened in the step (3) on the surface of a corundum plate, ensuring full contact with reaction gas to ensure that the reaction achieves the optimal effect, introducing excessive NH3/Ar mixed gas into a tubular furnace to perform magnesium antimonide nitriding reaction with slight positive pressure, and preserving heat for 3 hours at 600 ℃ with the heating rate of 10 ℃/min; although positive pressure can inhibit evaporation of Sb, the total amount of internal NH3/Ar is insufficient for nitriding to be complete, and the exothermic reaction can lead to local excessive temperatures that lead to collapse of the product structure if no gas flow takes away heat.
(5) Adding the product obtained in the step (4) into 1M hydrochloric acid, pickling for 3-6h, carrying out suction filtration to neutrality, and carrying out vacuum freeze drying to obtain a final product: a mixed product of two-dimensional layered antimony and bulk antimony;
(6) Adding the product obtained in the step (5) into 50ml of DMF solvent, performing ultrasonic dispersion for 2 hours, taking supernatant, performing suction filtration and cleaning, and performing vacuum freeze drying to obtain a final product: two-dimensional antimoney materials.
The alloying reaction temperature is controlled to prevent the complete alloying reaction, so that the final product phase is impure, and the product phase contains large blocks of unreacted antimony and lamellar two-dimensional antimony; by controlling the nitriding temperature, volatilization of antimony in the nitriding process is effectively inhibited, and the final product is prevented from being greatly reduced; the NH3/Ar with higher activity is used for participating in the nitriding reaction, so that the magnesium antimonide in the sample is ensured to be completely reacted into magnesium nitride and antimony, and the severe reaction of the magnesium antimonide in the pickling process is restrained, and the uniform and stable appearance of the two-dimensional layered antimony is ensured.
The foregoing shows and describes the basic principles, principal features and advantages of the invention: the gradient heat preservation can effectively ensure the complete reaction in the alloying process and prevent byproducts from being generated; the low nitriding temperature can inhibit volatilization of antimony accompanied by formation of magnesium nitride in the nitriding process, and finally the layered two-dimensional antimony material with higher purity and a large piece of single-layer or few-layer two-dimensional antimonic material are obtained. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. The method for preparing the two-dimensional layered antimony cathode material by adopting gas phase dealloying is characterized by comprising the following steps of: the method comprises the following steps:
step 1: placing magnesium powder and antimony powder in a mixer according to a certain mass ratio, and mixing the antimony powder and the magnesium powder fully and uniformly;
step 2: placing the uniformly mixed powder in the step 1 into a stainless steel reaction kettle, then placing the stainless steel reaction kettle into an inert atmosphere tube furnace, heating to 500-700 ℃ at a heating rate of 1-10 ℃/min, preserving heat for 3-6h, and cooling along with the furnace after the heat preservation is finished and taking out;
step 3: ball milling, crushing and screening the product obtained in the step 2 to obtain alloy powder with certain micron particle size distribution;
step 4: spreading the powder screened in the step 3 on a corundum plate, introducing a nitrogen-containing atmosphere into a tube furnace, heating to 400-900 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 3-6h, and carrying out Mg 3 Sb 2 Is taken out along with furnace cooling after heat preservation is finished;
step 5: adding the product obtained in the step 4 into hydrochloric acid with a certain concentration, pickling for a certain time, filtering to be neutral, and performing vacuum freeze drying to obtain a final product: two-dimensional layered antimony negative electrode material.
2. The method for preparing a two-dimensional layered antimony negative electrode material by gas phase dealloying according to claim 1, wherein the method comprises the steps of: the step 1 further comprises the steps of mixing antimony powder and magnesium powder according to an atomic ratio of 2:3, placing the mixture in a mixer for mixing for 1h.
3. The method for preparing a two-dimensional layered antimony negative electrode material by gas phase dealloying according to claim 1, wherein the method comprises the steps of: the step 2 further comprises the step of placing the stainless steel reaction kettle in an inert atmosphere N 2 Or Ar tube furnace, the heating rate is 1-10 ℃/min to 500-700 ℃, and the temperature is kept for 3-6h.
4. The method for preparing a two-dimensional layered antimony negative electrode material by gas phase dealloying according to claim 1, wherein the method comprises the steps of: the step 3 further comprises alloy powder with the particle size distribution of 1-10 mu m.
5. The method for preparing a two-dimensional layered antimony negative electrode material by gas phase dealloying according to claim 1, wherein the method comprises the steps of: step 4 further comprises spreading the sample on the surface of the corundum plate to ensure sufficient contact with the reaction gas, firstly exhausting air in the quartz tube, and then introducing nitrogen-containing atmosphere to perform Mg 2 Nitriding Si at gas flow rate of 0.1-0.3L/min, maintaining at 400-900 deg.c for 3-6 hr at heating rate of 5-10 deg.c/min; the nitrogen-containing atmosphere comprises N2, NH3/Ar.
6. The method for preparing a two-dimensional layered antimony negative electrode material by gas phase dealloying according to claim 1, wherein the method comprises the steps of: step 5 further comprises slowly adding the sample into a hydrochloric acid solution with the concentration of 1M, and pickling for 3-6h.
7. A method for preparing a two-dimensional antimoney material using gas phase dealloying, comprising the method of claim 1, characterized by: further comprising step 6: adding the product obtained in the step 5 into a certain amount of dimethylformamide DMF, performing ultrasonic dispersion for a certain time, taking supernatant, performing suction filtration, cleaning, and performing vacuum freeze drying to obtain a final product: two-dimensional antimoney materials.
8. A two-dimensional antimoney material is characterized in that: a bulk two-dimensional antimoney material having a single layer or a few layers prepared by the method of claim 7.
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