CN115522244A - 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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- CN115522244A CN115522244A CN202211219479.9A CN202211219479A CN115522244A CN 115522244 A CN115522244 A CN 115522244A CN 202211219479 A CN202211219479 A CN 202211219479A CN 115522244 A CN115522244 A CN 115522244A
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- 239000011734 sodium Substances 0.000 title claims abstract description 19
- 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 18
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- PEEDYJQEMCKDDX-UHFFFAOYSA-N antimony bismuth Chemical compound [Sb].[Bi] PEEDYJQEMCKDDX-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 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 29
- 239000010949 copper Substances 0.000 claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 4
- 238000000151 deposition Methods 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 18
- 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
- 229910052787 antimony Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 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
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 6
- 229940000207 selenious acid Drugs 0.000 claims description 6
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical group O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 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
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical group Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 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 5
- 238000000137 annealing Methods 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
- 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
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000000376 reactant Substances 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
- 102000020897 Formins Human genes 0.000 claims 1
- 108091022623 Formins Proteins 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000004070 electrodeposition Methods 0.000 abstract description 3
- 150000003346 selenoethers Chemical class 0.000 abstract description 3
- 240000007594 Oryza sativa Species 0.000 abstract description 2
- 235000007164 Oryza sativa Nutrition 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- 235000009566 rice Nutrition 0.000 abstract description 2
- 229910018289 SbBi Inorganic materials 0.000 abstract 1
- 239000010405 anode material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 4
- 229910002056 binary alloy Inorganic materials 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000007773 negative electrode material Substances 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- CUNAJIREFWUWGY-UHFFFAOYSA-N [Sb].[C] Chemical compound [Sb].[C] CUNAJIREFWUWGY-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- -1 antimony bismuth-bismuth selenide-selenide Chemical compound 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000001514 detection method Methods 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
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- OMEPJWROJCQMMU-UHFFFAOYSA-N selanylidenebismuth;selenium Chemical compound [Se].[Bi]=[Se].[Bi]=[Se] OMEPJWROJCQMMU-UHFFFAOYSA-N 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 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
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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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- 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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Abstract
The invention provides a preparation method of a high-safety sodium storage material based on an antimony-bismuth nano array, belonging to the field of novel chemical power sources. The method aims to solve the practical problem that the existing anode material cannot give consideration to both high capacity and long cycle stability. The main scheme includes growing rice spike-shaped nanometer wall array structure with homogeneous heterogeneous interface distribution on copper base board, and in the electrodeposition process, bi, sb and Se are combined into nanometer wall simultaneously to form SbBi alloy and metal selenide Bi with homogeneous dispersed phase 2 Se 3 And Sb 2 Se 3 Of the array structure of (1), thisSo that the heterogeneous interface between different phases is also uniformly distributed in the whole structure, and contributes to Na + Diffusion and promotion of electron conduction, and improvement of rate capability of the material. The self-supporting three-dimensional structure brings extra buffer space, can reduce side effects caused 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 a sodium-ion battery cathode material and a novel chemical power supply applied to a battery, 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 aim of coping with climate change in China, the search for renewable green clean energy becomes more and more important. Lithium ion batteries are considered to be one of the most successful energy storage devices at present, and due to the fact that the demand is continuously increased in recent years, the problem of lithium resource exhaustion is caused, so that the search for alternative energy storage battery systems which are richer in reserve and low in price and have similar working principles with the lithium ion batteries becomes a problem to be solved urgently, and sodium ions become a potential choice. Despite its cost and resource advantages, sodium ion presents many challenges in its practical application due to its large ionic radius and high potential, one of the key being the lack of high capacity, high stability negative electrode materials.
Among the numerous negative electrode materials, the material of the alloying sodium storage mechanism, such as antimony-based (Sb: 660mAh g) -1 ， Sb 2 Se 3 ：670mAh g -1 ) Has attracted much attention due to its higher theoretical capacity and suitable sodium storage potential (-0.4V). However, due to the alloying/dealloying reaction mechanism of multi-electron transfer, the volume change of the antimony material is severe (390%) in the charging and discharging processes, and large structural stress is easily generated to cause pulverization and shedding of the active material and loss of electric contact with a current collector, so that the electrode material is inactivated. In addition, the pulverization exposes more active interfaces and causes the SEI film to be continuously formed, thereby consuming sodium ions and reducing cycle performance.
The conventional method for relieving volume expansion and improving cycle stability in the sodium storage process of antimony-based materials is to compound antimony and conductive carbon, but the method is complex in process and poor in capacity performance. For example, chinese patent (application number: 201911110217.7) prepares a0.5A mg of nitrogen-doped antimony-carbon composite material -1 After 100 cycles under the current, only 325mAh g -1 The discharge capacity of (2). In addition to compounding with carbon materials, binary alloys in combination with other elements are also one of the methods to improve the stability of antimony-based materials. The introduction of the second metal can act as a buffer layer to mitigate volume changes during electrode cycling. For example, chinese patent (CN 201611002285.8) introduces inactive Cu and antimony to form binary alloy, and generates unbonded antimonized copper in situ on the surface of a copper foil. Although the material did not decay significantly after 100 cycles, its reversible capacity was low. Chinese patent (CN 201680005500.1) discloses a bismuth-antimony negative electrode for a rechargeable sodium ion battery, the first sodium removal capacity of which is 428mAh g -1 After 50 cycles, the capacity is attenuated to 113mAh g -1 The stability performance is not good.
Disclosure of Invention
The invention aims to solve the practical problem that the conventional cathode material cannot give consideration to 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 putting the copper sheet into alcohol, diluted oxalic acid and deionized water, then performing ultrasonic treatment in the alcohol, and drying for later use;
and 2, step: 20mL of water, 30mL of alcohol and 50mL of ethylene glycol were mixed. Followed by the addition of antimony chloride (SbCl) 3 ) 0.025mol/L, bismuth chloride (BiCl) 3 ) 0.02mol/L, selenious acid (H) 2 SeO 3 ) 0.005-0.015mol/L and ethylenediamine hydrochloride (C) 2 H 9 ClN 2 ) 0.28mol/L, and fully stirring the solution on a magnetic stirring table to obtain solution A;
and step 3: putting the dried copper sheet as a working electrode into an electrolytic cell of a three-electrode system, adding the solution A prepared in the step 2, and performing constant current of 4-8mA em -2 The reaction was carried out for 20 minutes under the conditions. Taking out after deposition is finished, further cleaning with deionized water and alcohol to obtain the product containing antimony-bismuth alloy and antimony selenide/bismuthA self-supporting nano-array;
and 4, step 4: putting the copper sheet deposited with the reactant in the step 3 into a tubular 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 composite nano array product is a rice spike-shaped nano wall array structure SbBi-Bi distributed on a uniform heterogeneous interface 2 Se 3 -Sb 2 Se 3 (SbBi- Se)；
The invention also provides the application of the antimony selenide/bismuth self-supporting nano array, the antimony-bismuth alloy and antimony selenide/bismuth composite material self-supporting nano array is used as the cathode of the sodium ion battery to assemble the button battery, and a temperature sensor is introduced to carry out temperature detection when the button battery is assembled.
The preparation method of the secondary battery comprises the following steps:
step 1: assembling a button cell: and sequentially assembling 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. The sealing pressure is 40-60kgf cm -2 The compacting time is as follows: 5-10s.
In the process of electrodeposition, as the Sb, bi and Se sources are simultaneously added into the electrolyte for codeposition, the optimal sample is prepared from evenly distributed SbBi and Bi 2 Se 3 And Sb 2 Se 3 Three phases. 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 transmission efficiency of sodium ions and electrons and maintaining the structural stability of the electrode are achieved. In addition, the array electrode has a three-dimensional nano wall structure, so that the volume expansion in the charging and discharging process can be buffered, and meanwhile, a conductive agent and a binder are not required to be used in the preparation of the electrode, so that the battery assembly process is simplified, the introduction of an inactive substance is avoided, the energy density of the electrode is improved, and the array electrode is a sodium ion battery cathode material with application potential.
In summary, due to the adoption of the technical scheme, the invention at least has the following advantages:
the invention adopts the constant-current electrodeposition technology to directly grow on the copper substrateLong length of antimony-bismuth (SbBi) alloy, bismuth selenide (Bi) 2 Se 3 ) And antimony selenide (Sb) 2 Se 3 ) A nano-array structure of a composite material. 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 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, and the electrode is found to have stable working temperature and smaller temperature fluctuation, so that higher safety is embodied.
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 large-scale industrial production can be realized.
3. The three-dimensional ordered nano-wall structure provides a channel for the rapid transmission of sodium ions, provides a buffer space for volume expansion, and improves the cycling stability of the electrode.
4. The uniformly distributed multiphase heterogeneous interface improves the diffusion rate of sodium ions, enhances the electronic conductivity and enables the electrode to show better rate performance.
5. The result of an in-situ test of the built-in temperature sensor shows that the Sb Bi-Se array does not show obvious temperature fluctuation in the circulating process and has higher safety.
Drawings
FIG. 1 is a scanning electron microscope photograph of a sample obtained in example 1;
FIG. 2 is a scanning electron microscope photograph of a sample obtained in example 2;
FIG. 3 is a scanning electron microscope photograph of a sample obtained in example 3;
FIG. 4 is a scanning electron microscope photograph of a sample obtained in example 4;
FIG. 5 is a scanning electron microscope photograph of a sample obtained in example 5;
FIG. 6 is a transmission electron microscope photograph of a sample obtained in example 1;
FIG. 7 is the X-ray diffraction pattern obtained for example 1,5;
FIG. 8 is an X-ray photoelectron spectrum of a sample obtained in example 1;
FIG. 9 is a comparison of the cycles obtained for example 1,5;
FIG. 10 is a graph of the different magnification cycles obtained for example 1,5;
FIG. 11 is temperature sensor data obtained for example 1,5;
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following embodiments and accompanying drawings.
Example 1
Sequentially putting a copper sheet of 0.5cm multiplied by 2cm into alcohol, diluted oxalic acid and deionized water, performing ultrasonic treatment in the alcohol for 15 minutes, and drying for later use; 20mL of water, 30mL of alcohol and 50mL of ethylene glycol were mixed to prepare solution A. 0.025M antimony chloride (SbCl) 3 ) 0.02M bismuth chloride (BiCl) 3 ) 0.01M selenious acid (H) 2 SeO 3 ) And 0.28M ethylenediamine hydrochloride (C) 2 H 9 ClN 2 ) Putting the solution A into the solution A and fully stirring the solution A on a magnetic stirring table; the dried copper sheet is taken as a working electrode, put into an electrolytic cell of a three-electrode system, added with the prepared electrolyte and kept at a constant current of 5.2mA cm -2 Reacting for 20 minutes under the condition, taking out after deposition is finished, and further cleaning for 15 minutes by using deionized water and alcohol; and (3) putting the deposited copper sheet into a tube furnace for mild heat treatment, and annealing for 1 hour at the temperature of 200 ℃ under argon to obtain the antimony bismuth-bismuth selenide-selenide composite material (SbBi-Se) nano array with uniform heterogeneous interface distribution.
The obtained materials are assembled into a button battery, and the button battery sequentially comprises a negative electrode cover, an elastic sheet, a gasket, a metal sodium sheet, a diaphragm, electrolyte, an array electrode, a temperature sensor and a positive electrode cover. The sealing pressure is 40-60kgf cm -2 The compacting time is as follows: 5-10s, using 1M NaPF 6 An electrolyte in dimethyl ether.
After the assembled battery is stood for 8 hours, the charge and discharge test is carried out under the voltage window of 0.01-2.5V, and the result of FIG. 5 shows thatAt 0.21A g -1 The reversible capacity of the SbBi-Se electrode reaches 525mAh g under the current density -1 . FIG. 6 at 0.7A g -1 Can have 94% capacity retention after 100 cycles at the current density of (c). In addition, the electrode also exhibits excellent rate performance at 0.35, 0.7, 1.4 and 3.5A g -1 The reversible specific capacities of the lithium ion secondary batteries under the current densities of the lithium ion secondary batteries are 516, 512, 499 and 480mAh g respectively -1 The high cycling stability is maintained at each current density.
Example 2
A copper sheet for deposition was prepared by cleaning the copper sheet in example 1, and the same electrolytic solution as in example 1 was used as a deposition solution, in contrast to example 1, which employed a current density of 4mA cm in magnitude different from that of example 1 -2 Deposition was carried out to obtain samples of different morphologies, which exhibited a granular film, without the 3D structural void space of example 1 to allow free deformation of the electrode during the sodium storage cycle, and limiting the penetration of the electrode solution, thus not contributing to the improvement of stability.
Example 3
A copper sheet for deposition was prepared by cleaning the copper sheet in example 1, and the same electrolytic solution as in example 1 was used as a deposition solution, in contrast to example 1, which employed a current density of 8mA cm in magnitude different from that of example 1 -2 The deposition is carried out to obtain samples with different morphologies, the samples show a certain sheet-shaped structure, but a large part of substances are subjected to an agglomeration phenomenon, compared with example 1, the samples under the condition are not as regular as example 1, are regularly arranged with a void space, and the agglomeration phenomenon of the samples can influence the further storage of the materials, so that the stability is not favorably improved.
Example 4
A copper sheet for deposition was prepared by the method of cleaning the copper sheet of example 1, and almost the same electrolyte as that of example 1 was used as a deposition solution, except that 0.015M selenious acid (H) was used as a deposition solution 2 SeO 3 ) Samples of different morphologies were obtained, which exhibited a structure similar to that of example 1, except thatThe deposited sample under the condition has only a small amount of gaps, most of the gaps grow together, and a large amount of film phenomena can increase the transmission obstruction of charges and limit the penetration of electrolyte, so that the structure is not beneficial to sodium storage.
Example 5
A copper sheet for deposition was prepared by the method of cleaning the copper sheet of example 1, and almost the same electrolyte as that of example 1 was used as a deposition solution, except that 0.005M selenious acid (H) was used as a deposition solution 2 SeO 3 ) Finally, morphological is observed.
Example 6
A copper sheet for deposition was prepared by cleaning the copper sheet in example 1 using almost the same electrolyte as in example 1 except that 0M selenious acid (H) was used 2 SeO 3 ) As deposition solution, dried copper sheet as working electrode, and electrolytic cell with three-electrode system, adding prepared electrolyte, and constant current of 6.6mA cm -2 Reacting for 20 minutes under the condition, taking out after deposition is finished, and further cleaning for 15 minutes by using deionized water and alcohol; and (3) placing the deposited copper sheet into a tube furnace for mild heat treatment, and keeping the copper sheet for 1h for annealing at the temperature of 200 ℃ under 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 favorable for sodium storage.
In order to verify the sodium storage performance, the obtained materials were assembled into a coin cell as in example 1 and subjected to a performance test. FIG. 10 the results show that the values are at 0.35, 0.7, 1.4 and 3.5A g -1 The reversible specific capacities at the current densities of (A) were 382, 334, 299 and 263mAh g, respectively -1 。
FIG. 1 is a scanning electron microscope photograph of the uniform heterogeneous interface distribution nanowall array obtained in example 1, which exhibits a top spiked nanowall array structure, illustrating the successful preparation of SbBi-Se by transmission electron microscopy in FIG. 6, X-ray diffraction pattern in FIG. 7, and X-ray photoelectron spectroscopy in FIG. 8. FIG. 9 is a comparison of the charge and discharge cycles obtained in example 1,5, and it can be seen that example 1 exhibits better cycle stability at 0.7A g -1 Current density of (2) cycle for 100 cyclesThere was a 94% capacity retention later. In addition, the results of fig. 10 show that the electrode also exhibits excellent rate performance at 0.35, 0.7, 1.4 and 3.5A g -1 The reversible specific capacities of the lithium ion secondary batteries under the current densities of the lithium ion secondary batteries are 516, 512, 499 and 480mAh g respectively -1 The high cycling stability is maintained at each current density. Fig. 11 is data for the temperature sensors of examples 1 and 5, and the electrodes of example 1 performed very stably during long temperature testing without significant temperature fluctuations, exhibiting a high safety potential.
Claims (4)
1. A preparation method of a high-safety sodium storage material based on an antimony-bismuth nano array is characterized by comprising the following steps:
step 1: sequentially putting the copper sheet into alcohol, diluted oxalic acid and deionized water, putting the copper sheet into the alcohol again, performing ultrasonic treatment, and drying for later use;
step 2: mixing 20mL of water, 30mL of alcohol and 50mL of ethylene glycol, then adding 0.025mol/L of antimony salt, 0.02mol/L of bismuth salt, 0.005-0.015mol/L of selenium source and 0.28mol/L of ethylenediamine hydrochloride, and fully stirring the solution on a magnetic stirring table to obtain a solution A;
and step 3: putting the dried copper sheet as a working electrode into an electrolytic cell of a three-electrode system, adding the solution A prepared in the step 2, and keeping the constant current at 4-8mA cm -2 Reacting for 20 minutes under the condition, taking out after deposition is finished, and further cleaning with deionized water and alcohol to obtain a copper sheet with an antimony-bismuth alloy and an antimony selenide/bismuth self-supporting nano array;
and 4, step 4: and (3) placing the copper sheet deposited with the reactant in the step (3) into a tubular furnace for mild heat treatment, and keeping the temperature at 200 ℃ for 1h for annealing to obtain a final composite nano array product.
2. The method for preparing a high-safety sodium storage material based on an 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 selenious acid.
3. An antimony-based composition according to claim 1The preparation method of the high-safety sodium storage material of the bismuth nano array is characterized in that the gas in the step 4 is argon, the conditions are 200 ℃, and the heating rate is 2 ℃ for 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, which is disclosed by any one of claims 1 to 3, is used as a negative electrode of the sodium-ion battery.
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