CN115522244B - Preparation method of high-safety sodium storage material based on antimony-bismuth nano array - Google Patents
Preparation method of high-safety sodium storage material based on antimony-bismuth nano array Download PDFInfo
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- CN115522244B CN115522244B CN202211219479.9A CN202211219479A CN115522244B CN 115522244 B CN115522244 B CN 115522244B CN 202211219479 A CN202211219479 A CN 202211219479A CN 115522244 B CN115522244 B CN 115522244B
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 17
- 239000011734 sodium Substances 0.000 title claims abstract description 17
- PEEDYJQEMCKDDX-UHFFFAOYSA-N antimony bismuth Chemical compound [Sb].[Bi] PEEDYJQEMCKDDX-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011232 storage material Substances 0.000 title claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000010949 copper Substances 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 4
- 238000000151 deposition Methods 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910001415 sodium ion Inorganic materials 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- OQRNKLRIQBVZHK-UHFFFAOYSA-N selanylideneantimony Chemical compound [Sb]=[Se] OQRNKLRIQBVZHK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001152 Bi alloy Inorganic materials 0.000 claims description 3
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical group Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical group Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- HCFPRFJJTHMING-UHFFFAOYSA-N ethane-1,2-diamine;hydron;chloride Chemical compound [Cl-].NCC[NH3+] HCFPRFJJTHMING-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 2
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical group O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims 2
- 150000001462 antimony Chemical class 0.000 claims 2
- 150000001621 bismuth Chemical class 0.000 claims 2
- 239000011669 selenium Substances 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 8
- 229910018289 SbBi Inorganic materials 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 235000007164 Oryza sativa Nutrition 0.000 abstract description 3
- 238000004070 electrodeposition Methods 0.000 abstract description 3
- 239000007773 negative electrode material Substances 0.000 abstract description 3
- 235000009566 rice Nutrition 0.000 abstract description 3
- 150000003346 selenoethers Chemical class 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 240000007594 Oryza sativa Species 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 12
- 229910052787 antimony Inorganic materials 0.000 description 9
- 238000003860 storage Methods 0.000 description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- CUNAJIREFWUWGY-UHFFFAOYSA-N [Sb].[C] Chemical compound [Sb].[C] CUNAJIREFWUWGY-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 229910002056 binary alloy Inorganic materials 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910018143 SeO3 Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- -1 antimony bismuth selenide-selenide Chemical compound 0.000 description 1
- XDMXNXNLJCQUHV-UHFFFAOYSA-N antimony;copper(1+) Chemical compound [Cu+].[Cu+].[Cu+].[Sb] XDMXNXNLJCQUHV-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- GNZJTRGEKSBAAS-UHFFFAOYSA-N selanylideneantimony;selenium Chemical compound [Se].[Sb]=[Se].[Sb]=[Se] GNZJTRGEKSBAAS-UHFFFAOYSA-N 0.000 description 1
- OMEPJWROJCQMMU-UHFFFAOYSA-N selanylidenebismuth;selenium Chemical compound [Se].[Bi]=[Se].[Bi]=[Se] OMEPJWROJCQMMU-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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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- 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 Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention provides a preparation method of a high-safety sodium storage material based on an antimony-bismuth nano array, and belongs to the field of novel chemical power sources. The main point is to solve the practical problem that the existing negative electrode material cannot achieve both high capacity and long-cycle stability. The main scheme includes that a rice spike-shaped nano wall array structure with uniform heterogeneous interface distribution grows on a copper substrate, bi, sb and Se are simultaneously combined into the nano wall in the electrodeposition process, so that an array structure of SbBi alloy with uniform dispersed phases and metal selenide Bi 2Se3 and Sb 2Se3 is formed, the heterogeneous interfaces among different phases are uniformly distributed in the whole structure, na + diffusion is facilitated, electron conduction is promoted, and the rate capability of the material is improved. The self-supporting three-dimensional structure brings extra buffer space, can alleviate side effects brought by severe volume expansion, and greatly improves the structural stability of the whole nano array, thereby effectively prolonging the cycle life of the material.
Description
Technical Field
The invention belongs to the field of preparation of negative electrode materials of sodium ion batteries and novel chemical power supplies applied to batteries, and particularly relates to a preparation method of a high-safety sodium storage material based on an antimony-bismuth nano array.
Background
With the proposal of the dual-carbon target (carbon peak and carbon neutralization) of the climate change in China, the search for renewable green clean energy is increasingly important. Lithium ion batteries are considered as one of the most successful energy storage devices at present, and as the demand in recent years is continuously increased, the problem of lithium resource exhaustion is brought, so that searching for an alternative energy storage battery system with richer reserves, low price and similar working principle as that of lithium ion batteries is a problem to be solved urgently, and sodium ions are a potential choice. Despite the cost and resource advantages of sodium ions, its practical application faces many challenges due to its large ionic radius and high potential, one of which is the lack of high capacity, high stability anode materials.
Among the numerous negative electrode materials, materials that alloy sodium storage mechanisms, such as antimony-based (Sb: 660 mAh g -1, Sb2Se3: 670 mAh g-1), are of great interest because of their relatively high theoretical capacity and suitable sodium storage potential (0.4: V). However, due to the alloying/dealloying reaction mechanism of multiple electron transfer, the antimony material has serious volume change (390 percent to 390 percent) in the charge and discharge process, and larger structural stress is easily generated to cause pulverization and falling of the active material and electrical contact with a current collector to cause deactivation of the electrode material. In addition, pulverization exposes more active interfaces and causes continuous formation of an SEI film, thereby consuming sodium ions and degrading cycle performance.
The conventional method for relieving the volume expansion of the antimony-based material in the sodium storage process and improving the circulation stability is to compound antimony with conductive carbon, but the method is complex in process and poor in capacity performance. As in the Chinese patent (application No. 201911110217.7), a nitrogen-doped antimony-carbon composite material is prepared, and the discharge capacity of the nitrogen-doped antimony-carbon composite material is only 325 mAh g -1 after the nitrogen-doped antimony-carbon composite material is cycled for 100 times under the current of 0.5A mg -1. In addition to being composited with carbon materials, binary alloys in combination with other elements are also one of the methods of improving the stability of antimony-based materials. The introduction of the second metal may act as a buffer layer, mitigating volume changes during cycling of the electrode. For example, chinese patent (CN 201611002285.8) introduced the formation of binary alloys of inactive Cu and antimony to form in situ unbonded copper antimonide on the surface of a copper foil. Although the material did not significantly decay after 100 cycles, its reversible capacity was low. Chinese patent (CN 201680005500.1) discloses a bismuth-antimony negative electrode for rechargeable sodium ion batteries, which has a first de-sodifying capacity of 428 mAh g -1, a capacity decay to 113 mAh g -1 after 50 cycles, and poor performance of stability.
Disclosure of Invention
The invention aims to solve the practical problem that the existing anode material cannot achieve both high capacity and long-cycle stability.
In order to solve the technical problems, the invention adopts the following technical means:
the preparation method based on the antimony/bismuth self-supporting nano array comprises the following steps:
Step 1: sequentially placing the copper sheet into alcohol, dilute oxalic acid, deionized water, ultrasonic treating in alcohol, and drying for later use;
Step 2: 20 mL water, 30mL alcohol and 50 mL glycol were mixed. Then adding 0.025mol/L of antimony chloride (SbCl 3), 0.02 mol/L of bismuth chloride (BiCl 3), 0.005-0.015 mol/L of selenious acid (H 2SeO3) and 0.28mol/L of ethylenediamine hydrochloride (C 2H9ClN2), and fully stirring the solution on a magnetic stirring table to obtain a solution A;
Step 3: and (3) taking the dried copper sheet as a working electrode, putting the working electrode into an electrolytic cell of a three-electrode system, adding the solution A prepared in the step (2), and reacting for 20 minutes under the condition of constant current of 4-8 mA cm -2. Taking out after the deposition is finished, and further cleaning with deionized water and alcohol to obtain the self-supporting nano array with antimony-bismuth alloy and antimony selenide/bismuth;
Step 4: placing the copper sheet deposited with the reactant in the step 3 into a tube furnace for mild heat treatment, and keeping the temperature at 200 ℃ for 1h for annealing to obtain a final composite nano array product, wherein the optimal product of the composite nano array is a rice spike-shaped nano wall array structure SbBi-Bi 2Se3-Sb2Se3 (SbBi-Se) distributed in a uniform heterogeneous interface;
the invention also provides application of the self-supporting nano array of the antimony selenide/bismuth, wherein the self-supporting nano array of the composite material of the antimony-bismuth alloy and the antimony selenide/bismuth is used as a negative electrode of a sodium ion battery to be assembled into a button battery, and a temperature sensor is introduced to detect the temperature when the button battery is assembled.
The preparation method of the secondary battery comprises the following steps:
Step 1: assembling a button cell: the negative electrode cover, the elastic sheet, the gasket, the metal sodium sheet, the diaphragm, the electrolyte, the array electrode, the temperature sensor and the positive electrode cover are assembled in sequence. The sealing pressure is 40-60 kgf cm -2, and the compacting time is: 5-10 s.
In the electrodeposition process, because the Sb, bi and Se sources are simultaneously added into the electrolyte for codeposition, the obtained optimal sample consists of three phases of SbBi, bi 2Se3 and Sb 2Se3 which are uniformly distributed. Meanwhile, a large number of heterogeneous interfaces exist among the three phases, so that the advantages of the interfaces can be maximized, and the purposes of enhancing the sodium ion and electron transmission efficiency and maintaining the stability of the electrode structure are achieved. In addition, as the array electrode has a three-dimensional nano wall structure, the volume expansion in the charge and discharge process can be buffered, and meanwhile, the use of a conductive agent and a binder is not needed in the preparation of the electrode, so that the battery assembly process is simplified, the introduction of inactive substances is avoided, the energy density of the electrode is improved, and the electrode is a sodium ion battery anode material with application potential.
In summary, due to the adoption of the technical scheme, the invention has at least the following advantages:
The invention adopts the constant current electrodeposition technology to directly grow the nano array structure with the composite materials of antimony bismuth (SbBi), bismuth selenide (Bi 2Se3) and antimony selenide (Sb 2Se3) on the copper substrate. By introducing a corresponding high capacity selenide into the SbBi alloy, a higher capacity can be provided for the electrode. Meanwhile, a built-in electric field is induced to be generated by utilizing a heterogeneous interface between the selenide and the alloy, so that the transmission efficiency of charges and electrons is improved, and the structural stability of the material is enhanced. The electrode is detected in real time by using the implanted temperature sensor, so that the electrode has stable working temperature and smaller temperature fluctuation, and higher safety is reflected.
2. The array is directly grown on the metal copper sheet without additional conductive agent and binder, the electrode preparation method is simple, the operation is convenient, the required equipment is simple and easy to use and control, and the electrode can be produced in a large scale in an industrialized manner.
3. The three-dimensional ordered nano wall structure provides a channel for rapid transmission of sodium ions, provides a buffer space for volume expansion, and improves the cycling stability of the electrode.
4. The uniformly distributed heterogeneous interface improves the diffusion rate of sodium ions, enhances the electronic conductivity and ensures that the electrode shows better rate capability.
5. The in-situ test result of the built-in temperature sensor shows that the SbBi-Se array does not show obvious temperature fluctuation in the circulation process, and has higher safety.
Drawings
FIG. 1 is a scanning electron microscope picture of the sample obtained in example 1;
FIG. 2 is a scanning electron microscope picture of the sample obtained in example 2;
FIG. 3 is a scanning electron microscope picture of the sample obtained in example 3;
FIG. 4 is a scanning electron microscope image of the sample obtained in example 4;
FIG. 5 is a scanning electron microscope picture of the sample obtained in example 5;
FIG. 6 is a transmission electron microscope image of the sample obtained in example 1;
FIG. 7 shows the X-ray diffraction patterns obtained in examples 1 and 5;
FIG. 8 is an X-ray photoelectron spectrum of the sample obtained in example 1;
FIG. 9 is a comparison of the cycles obtained in examples 1, 5;
FIG. 10 shows the different rate cycles obtained in examples 1 and 5;
FIG. 11 shows the temperature sensor data obtained in examples 1 and 5;
Detailed Description
The present invention will be described in further detail with reference to the embodiments and the accompanying drawings, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent.
Example 1
Sequentially adding 0.5 cm ×2 cm copper sheet into alcohol, dilute oxalic acid, deionized water, ultrasonic treating in alcohol for 15 min, and drying; 20mL water, 30 mL alcohol and 50mL glycol were mixed as solution a. 0.025M antimony chloride (SbCl 3), 0.02M bismuth chloride (BiCl 3), 0.01M selenious acid (H 2SeO3) and 0.28M ethylenediamine hydrochloride (C 2H9ClN2) are placed in A solution and fully stirred on a magnetic stirring table; the dried copper sheet is used as a working electrode, the copper sheet is put into an electrolytic cell of a three-electrode system, the prepared electrolyte is added, the copper sheet reacts for 20 minutes under the condition of constant current of 5.2 mA cm -2, the copper sheet is taken out after deposition is finished, and the copper sheet is further washed for 15 minutes by deionized water and alcohol; and (3) placing the deposited copper sheet into a tubular furnace for mild heat treatment, and keeping the annealing for 1h under 200 ℃ argon to obtain the antimony bismuth selenide-selenide composite material (SbBi-Se) nano array with uniform heterogeneous interface distribution.
The resulting material was assembled into a button cell, which was in turn a negative electrode cap, a dome, a gasket, a metallic sodium sheet, a separator, an electrolyte, an array electrode, a temperature sensor, and a positive electrode cap. The sealing pressure is 40-60 kgf cm -2, and the compacting time is: 5-10 s, adopting electrolyte of 1M NaPF 6 in dimethyl ether.
After the assembled battery was left to stand for 8 hours, a charge and discharge test was performed in the range of 0.01 to 2.5V voltage window, and the result of fig. 5 shows that the reversible capacity of the SbBi-Se electrode reached 525 mAh g -1 at a current density of 0.21A g -1. Fig. 6 may have 94% capacity retention after 100 cycles at a current density of 0.7A g -1. In addition, the electrode also exhibits excellent rate capability, reversible specific capacities at current densities of 0.35, 0.7, 1.4 and 3.5A g -1 of 516, 512, 499 and 480 mAh g -1, respectively, with higher cycling stability maintained at each current density.
Example 2
The method of cleaning copper sheets in example 1 was used to prepare copper sheets for deposition and used the same electrolyte as in example 1 as the deposition solution, in contrast to the deposition using a current density of 4 mA cm -2 different from that of example 1, resulting in samples of different morphology that exhibited a layer of granular film, no 3D structured void space like that of example 1 to allow free deformation of the electrode during the sodium storage cycle and limited penetration of the electrode solution, thus adversely improving stability.
Example 3
The method of cleaning copper sheets in example 1 was used to prepare copper sheets for deposition and the same electrolyte as in example 1 was used as the deposition solution, in contrast to the deposition using a current density of 8 mA cm -2 different from that of example 1, resulting in samples of different morphology which exhibited a certain lamellar structure but a significant portion of the material had agglomerated, and the samples under this condition were less orderly than in example 1, were regularly and with an arrangement of void spaces, and the agglomeration of the samples had an adverse effect on the further storage of the material, thus increasing stability.
Example 4
The method of cleaning copper sheets using example 1 was used to prepare copper sheets for deposition and used almost the same electrolyte as example 1 as the deposition solution, except that 0.015M selenious acid (H 2SeO3) was used to obtain samples of different morphologies, which exhibited a structure similar to that of example 1, except that the deposited samples under this condition had a small number of voids, most grown together, and a large number of thin film phenomena would increase the transfer barrier of charges, limiting the penetration of electrolyte, and therefore the structure was unfavorable for sodium storage.
Example 5
Copper flakes for deposition were prepared using the method of example 1 to clean the copper flakes and using nearly the same electrolyte as example 1 as the deposition solution, except that 0.005M selenious acid (H 2SeO3) was used and the morphology was finally observed.
Example 6
Preparing a copper sheet for deposition by adopting the method for cleaning the copper sheet in example 1, and using the electrolyte almost the same as that in example 1, wherein the different variables are that 0M selenic acid (H 2SeO3) is adopted as a deposition solution, a dried copper sheet is adopted as a working electrode, the copper sheet is put into an electrolytic cell of a three-electrode system, the prepared electrolyte is added, the reaction is carried out for 20 minutes under the condition of constant current of 6.6mA cm -2, the copper sheet is taken out after the deposition is finished, and the copper sheet is further cleaned by deionized water and alcohol for 15 minutes; and (3) placing the deposited copper sheet into a tube furnace for mild heat treatment, and keeping the copper sheet annealed for 1h under 200 ℃ argon to obtain the binary alloy. The deposited sample exhibited the shape of a granular film, in contrast to the unique structure grown in example 1, which would be more conducive to sodium storage.
To verify the sodium storage performance, the resulting material was assembled into a button cell as in example 1 for performance testing. The results of fig. 10 show reversible specific capacities 382, 334, 299 and 263 mAh g -1 at current densities of 0.35, 0.7, 1.4 and 3.5A g -1, respectively.
FIG. 1 is a scanning electron microscope picture of a uniform heterogeneous interface distributed nanowall array obtained in example 1, which shows a nanowall array structure of a top rice spike shape, illustrating successful preparation of SbBi-Se by the transmission electron microscope of FIG. 6, the X-ray diffraction pattern of FIG. 7, and the X-ray photoelectron spectroscopy of FIG. 8. Fig. 9 is a comparison of the charge-discharge cycles obtained in examples 1,5, and it was found that example 1 exhibited better cycle stability, with 94% capacity retention after 100 cycles at a current density of 0.7A g -1. In addition, the results of fig. 10 demonstrate that the electrode also exhibits excellent rate capability, reversible specific capacities at current densities of 0.35, 0.7, 1.4 and 3.5A g -1 of 516, 512, 499 and 480 mAh g -1, respectively, with higher cycling stability maintained at each current density. Fig. 11 shows the data of the temperature sensors of examples 1 and 5, wherein the electrode of example 1 exhibited very stable, no significant temperature fluctuations and high safety potential during long-term temperature testing.
Claims (4)
1. The preparation method of the high-safety sodium storage material based on the antimony-bismuth nano array is characterized by comprising the following steps of:
Step 1: sequentially placing the copper sheet into alcohol, dilute oxalic acid and deionized water, then placing the copper sheet into alcohol for ultrasonic treatment, and drying for later use;
Step 2: mixing 20 mL water, 30mL alcohol and 50 mL glycol, then adding 0.025 mol/L of antimony salt, 0.02 mol/L of bismuth salt, 0.005-0.015 mol/L of selenium source and 0.28 mol/L of ethylenediamine hydrochloride, and fully stirring the solution on a magnetic stirring table to obtain a solution A;
Step 3: putting the dried copper sheet serving as a working electrode into an electrolytic cell of a three-electrode system, adding the solution A prepared in the step 2, reacting for 20 minutes under the condition of constant current of 4-8 mA cm -2, taking out after deposition, and further cleaning with deionized water and alcohol to obtain the copper sheet with the antimony-bismuth alloy and the antimony selenide/bismuth self-supporting nano-array;
Step 4: and (3) placing the copper sheet deposited with the reactant in the step (3) into a tube furnace for mild heat treatment, and keeping the copper sheet annealed at 200 ℃ for 1h under argon to obtain a final composite nano array product.
2. The method for preparing the high-safety sodium storage material based on the antimony-bismuth nano-array according to claim 1, wherein the antimony salt is antimony chloride, the bismuth salt is bismuth chloride, and the selenium source is selenic acid.
3. The method for preparing the high-safety sodium storage material based on the antimony-bismuth nano array, which is disclosed in claim 1, is characterized in that the condition in the step 4 is 200 ℃, and the heating rate is 2 ℃ min -1.
4. A battery is characterized in that a composite nano array product prepared by the preparation method of the high-safety sodium storage material based on the antimony-bismuth nano array according to any of claims 1-3 is used as a negative electrode of a sodium ion battery.
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