CN117239076A - Negative electrode material of sodium ion battery, preparation method and application thereof, and sodium ion battery - Google Patents
Negative electrode material of sodium ion battery, preparation method and application thereof, and sodium ion battery Download PDFInfo
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- CN117239076A CN117239076A CN202311138224.4A CN202311138224A CN117239076A CN 117239076 A CN117239076 A CN 117239076A CN 202311138224 A CN202311138224 A CN 202311138224A CN 117239076 A CN117239076 A CN 117239076A
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- selenide
- cobalt
- sodium ion
- ion battery
- iron
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 56
- MHWZQNGIEIYAQJ-UHFFFAOYSA-N molybdenum diselenide Chemical compound [Se]=[Mo]=[Se] MHWZQNGIEIYAQJ-UHFFFAOYSA-N 0.000 claims abstract description 41
- WALCGGIJOOWJIN-UHFFFAOYSA-N iron(ii) selenide Chemical compound [Se]=[Fe] WALCGGIJOOWJIN-UHFFFAOYSA-N 0.000 claims abstract description 35
- QVYIMIJFGKEJDW-UHFFFAOYSA-N cobalt(ii) selenide Chemical compound [Se]=[Co] QVYIMIJFGKEJDW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910020598 Co Fe Inorganic materials 0.000 claims description 43
- 229910002519 Co-Fe Inorganic materials 0.000 claims description 43
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 38
- 229960003351 prussian blue Drugs 0.000 claims description 38
- 239000013225 prussian blue Substances 0.000 claims description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 31
- 229910021641 deionized water Inorganic materials 0.000 claims description 31
- 239000010405 anode material Substances 0.000 claims description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 26
- 239000011889 copper foil Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000011669 selenium Substances 0.000 claims description 17
- 229960003638 dopamine Drugs 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 15
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 229910052711 selenium Inorganic materials 0.000 claims description 13
- 239000002135 nanosheet Substances 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000012692 Fe precursor Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 7
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 7
- 239000011267 electrode slurry Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000006258 conductive agent Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002064 nanoplatelet Substances 0.000 claims description 5
- -1 potassium ferricyanide Chemical compound 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 150000003346 selenoethers Chemical class 0.000 claims 2
- MHIHMSLBLJXMFH-UHFFFAOYSA-N [C].[Fe].[Co] Chemical compound [C].[Fe].[Co] MHIHMSLBLJXMFH-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 4
- 239000007784 solid electrolyte Substances 0.000 abstract description 4
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 229910016001 MoSe Inorganic materials 0.000 description 43
- 239000000243 solution Substances 0.000 description 41
- 150000004771 selenides Chemical class 0.000 description 26
- 239000007795 chemical reaction product Substances 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 14
- 239000002002 slurry Substances 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000005119 centrifugation Methods 0.000 description 9
- 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 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- 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 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000007709 nanocrystallization Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 239000002078 nanoshell Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 238000000197 pyrolysis Methods 0.000 description 1
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- 230000006798 recombination Effects 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The application belongs to the technical field of sodium ion batteries, and relates to a sodium ion battery negative electrode material, a preparation method and application thereof, and a sodium ion battery, wherein a three-phase heterojunction material formed based on cobalt selenide/iron selenide/molybdenum selenide has complex interface contact, and the sodium ion battery negative electrode material based on the heterostructure is beneficial to inhibiting the formation of a solid electrolyte interface film, slowing down the volume change and structural rupture of the material, and reducing the capacity attenuation rate of the battery, thereby prolonging the cycle life and improving the stability of the battery.
Description
Technical Field
The application belongs to the technical field of sodium ion batteries, and particularly relates to a three-phase heterojunction sodium ion battery negative electrode material formed based on cobalt selenide, iron selenide and molybdenum selenide, a preparation method and application thereof, and a sodium ion battery.
Background
Sodium Ion Batteries (SIBs) have a similar energy storage mechanism as Lithium Ion Batteries (LIBs), and the abundant sodium resources and lower redox potential make SIBs a suitable alternative to LIBs. However, the volume change and slow reaction kinetics due to the large na+ radius still prevent practical application. Therefore, it is important to design and build a suitable SIB electrode material to improve its electrochemical performance.
Among the transition metal compound electrode materials, metal chalcogenides have been widely studied due to their narrow band gap and high theoretical density. Among them, metal selenides have been recently explored as effective electrode materials for sodium ion batteries due to their large surface area and good electrochemical activity. In addition, for metal selenides, the metal-selenium bond is relatively easier to break than the metal-oxygen bond in metal oxides and the metal-sulfur bond in metal sulfides due to the large atomic radius of seleniumSplitting, which results in a relatively high conversion reaction efficiency of the selenide. However, metal selenide electrode materials still suffer from inherent poor conductivity, volume expansion, and other problems. For example, molybdenum selenide (MoSe 2 ) As a typical layered structure, this material, while having a larger interlayer spacing and a smaller band gap, is considered as a potential SIB anode material, significant volume expansion occurs during the electrochemical reaction, which is a common defect for all metal selenide materials, which seriously deteriorates the structure of the electrode, resulting in undesirable cycle stability and rate performance.
Disclosure of Invention
For MoSe existing in related technology 2 The application provides a sodium ion battery cathode material, a preparation method and application thereof, and a sodium ion battery, wherein the sodium ion battery cathode material is based on three-phase heterojunction materials formed by cobalt selenide, iron selenide and molybdenum selenide, and the cobalt selenide/iron selenide/molybdenum selenide heterojunction is beneficial to inhibiting the formation of a solid electrolyte interface film, slowing down the volume change and structural rupture of the material, reducing the capacity attenuation rate of the battery, thereby improving the cycle life and stability of the battery.
The technical scheme adopted by the application is as follows:
the first aspect of the application provides a sodium ion battery anode material, which comprises a cobalt selenide/iron selenide/molybdenum selenide heterojunction material with a three-phase heterojunction, wherein the three-phase heterojunction material formed by the cobalt selenide, the iron selenide and the molybdenum selenide has complex interface contact.
As described above, in some embodiments, the cobalt selenide/iron selenide/molybdenum selenide heterojunction material is formed by growing vertically oriented molybdenum selenide nanoplatelets on a bi-metallic selenide nanoplatelet formed of cobalt selenide/iron selenide.
As described above, the heterojunction material is supported by a nitrogen-doped carbon nano-backbone in some embodiments.
The second aspect of the present application provides a method for preparing a negative electrode material of a sodium ion battery, the negative electrode material of a sodium ion battery comprising a cobalt selenide/iron selenide/molybdenum selenide heterojunction material supported by a nitrogen-doped carbon nano-skeleton, the method comprising the steps of:
constructing a dopamine hydrochloride (PDA) coating on a cobalt iron Prussian blue (Co-Fe PBA) nanocube to obtain dopamine-coated cobalt iron Prussian blue (Co-Fe-PBA@PDA), and obtaining nitrogen-doped carbon-supported cobalt iron Prussian blue (Co-Fe PBA@NC) by using the dopamine-coated cobalt iron Prussian blue (Co-Fe-PBA@PDA); the method comprises the steps of,
growing vertically oriented molybdenum selenide nano-sheets on a nitrogen-doped carbon-supported cobalt-iron bimetallic selenide nano-cube through hydrothermal selenization of nitrogen-doped carbon-supported cobalt-iron Prussian blue (Co-Fe PBA@NC) to obtain a cobalt selenide/iron selenide/molybdenum selenide heterojunction material supported by a nitrogen-doped carbon nano-skeleton (Co-Fe-MoSe) 2 @NC）。
In some embodiments, the cobalt iron Prussian blue (Co-Fe PBA) nanocubes are prepared as follows: dissolving potassium ferricyanide in deionized water, and stirring to form a yellow solution; dissolving cobalt nitrate hexahydrate and sodium citrate in deionized water, and stirring to form a red solution; and (3) dropwise adding the red solution into the yellow solution, stirring, ageing at room temperature, washing with deionized water and ethanol, centrifuging and drying in vacuum to obtain the cobalt iron Prussian blue (Co-Fe PBA) nanocubes.
In some embodiments, the hydrothermal selenization step comprises: dissolving selenium powder in N 2 H 4 Obtaining a selenium precursor solution from the solution; na is mixed with 2 MoO 4 ·2H 2 O and nitrogen-doped carbon supported cobalt iron Prussian blue (Co-Fe-PBA@NC) were dissolved in N, N-dimethylformamide to obtain a Mo-Co-Fe precursor solution; the selenium precursor solution is dripped into the Mo-Co-Fe precursor solution, and is transferred into the lining of a high-pressure reaction kettle for reaction after being stirred, and the reaction is finished by using the ethyl acetateWashing with alcohol and deionized water, centrifuging and drying to obtain the cobalt selenide/iron selenide/molybdenum selenide heterojunction material supported by the nitrogen-doped carbon nano skeleton.
In some embodiments, the step of obtaining nitrogen doped carbon supported cobalt iron Prussian blue (Co-Fe PBA@NC) using dopamine coated cobalt iron Prussian blue (Co-Fe-PBA@PDA) comprises: dopamine-coated cobalt iron Prussian blue (Co-Fe-PBA@PDA) was calcined in an argon stream.
In a third aspect, the present application provides an application of a negative electrode material of a sodium ion battery, including: mixing the sodium ion battery anode material or the sodium ion battery anode material prepared according to the preparation method with the conductive agent acetylene black, the binder CMC and the solvent deionized water to prepare electrode slurry; and coating the electrode slurry on a copper foil, and processing the copper foil to form the electrode plate after vacuum drying.
A fourth aspect of the present application provides a sodium ion battery comprising a sodium ion battery anode material as described above, or comprising a sodium ion battery anode material prepared according to a preparation method as described above.
Compared with the prior art, the scheme provided by the application has the following beneficial effects:
the sodium ion battery cathode material provided by the application comprises a cobalt selenide/iron selenide/molybdenum selenide heterojunction material with a three-phase hetero interface, wherein three phases in the ternary heterojunction material are mutually supported, complex interface contact is provided, additional active sites are provided by the interface contact, and the capacity is improved by the increased active sites; in addition, the built-in electric field formed at the contact interface can lower the diffusion barrier, thereby enhancing ion diffusion and charge transfer. Therefore, when the ternary heterojunction material is used as a negative electrode material of a sodium ion battery, the ternary heterojunction material can inhibit the formation of a solid electrolyte interface film, slow down the volume change and structural rupture of the material, and reduce the capacity attenuation rate of the battery, so that the cycle life and the stability of the battery are improved.
In addition, the heterojunction material formed by growing vertically oriented molybdenum selenide nanosheets on the bimetallic selenide nano cubes formed by cobalt selenide/iron selenide is adopted in the application, and has the following characteristics: the vertically oriented growing molybdenum selenide nano-sheet is beneficial to increasing the specific surface area and active sites, so that the surface reactivity and the adsorption characteristic performance are enhanced; the heterostructure is formed in a vertical orientation, and energy band bending or energy band mutation can be formed at an interface, so that the electron transmission characteristic of the material is optimized, and the conductivity of the device is improved. In addition, the nano-sheet frame vertically grown relative to the surface of the cube can remarkably release mechanical stress, improve structural stability, promote electron/ion transfer and accelerate electrochemical reaction kinetics.
And, a heterojunction material of cobalt selenide/iron selenide/molybdenum selenide supported by an N-doped carbon nano-skeleton (Co-Fe-MoSe 2 At NC), the nitrogen-doped carbon form and the nanocrystallization structure enhance the conductivity and sodium storage activity of the material, so that the electrode material has good sodium storage performance, and the nanocrystallization structure also helps to relieve the volume expansion in the circulation process, thereby ensuring the structural integrity in the circulation process.
According to the application, the ternary metal selenide heterostructure material is prepared by taking cobalt iron Prussian blue as a template for the first time, and a brand new thought is provided for the selenide serving as a sodium ion battery cathode material.
Drawings
FIG. 1 is an XRD spectrum of a negative electrode material for a sodium ion battery obtained in example 1;
FIG. 2 is a scanning electron micrograph of the negative electrode material of the sodium ion battery obtained in example 1 at different magnifications;
FIG. 3 shows that the negative electrode material of the sodium-ion battery obtained in example 1 was prepared at 0.2mV s -1 Cyclic voltammogram at sweep rate;
FIG. 4 shows that the negative electrode material of sodium-ion battery obtained in example 1 was prepared at 0.2Ag -1 A cycle curve at current density of (2);
FIG. 5 is a graph showing the rate performance of the negative electrode material for sodium ion battery obtained in example 1;
FIG. 6 shows a sodium-ion battery anode material obtained in example 1 at 5A g -1 Long cycle performance at current density;
fig. 7 is a microstructure of the negative electrode material of the sodium ion battery obtained in example 1, which is characterized under a high resolution transmission electron microscope.
Detailed Description
For the purpose of making the objects, technical solutions and advantageous effects of the present application more apparent, embodiments of the present application will be described in detail below with reference to the accompanying drawings. However, the embodiments described below are exemplary only for explaining the present disclosure, and are not to be construed as limiting the present disclosure. Those of ordinary skill in the art will understand that in various embodiments of the present application, numerous technical details have been set forth in order to provide a better understanding of the present application. However, the claimed technical solution of the present application can be realized without these technical details and various changes and modifications based on the following embodiments. The following embodiments are divided for convenience of description, and should not be construed as limiting the specific implementation of the present application, and the embodiments can be mutually combined and referred to without contradiction.
The application provides a sodium ion battery anode material, a preparation method and application thereof, and a sodium ion battery. The negative electrode material of the sodium ion battery provided by the application comprises a cobalt selenide/iron selenide/molybdenum selenide heterojunction material with a three-phase heterojunction, and the material is based on the three-phase heterojunction material formed by cobalt selenide, iron selenide and molybdenum selenide to obtain complex interface contact. In some embodiments, the cobalt selenide/iron selenide/molybdenum selenide heterojunction material is formed by growing vertically oriented molybdenum selenide nanoplatelets on a cobalt selenide/iron selenide formed nanoplatelet. In a specific implementation, the heterojunction material is supported by a nitrogen-doped carbon nano-backbone.
The application provides a preparation method of a sodium ion battery anode material, which comprises a cobalt selenide/iron selenide/molybdenum selenide heterojunction material supported by a nitrogen-doped carbon nano skeleton, wherein dopamine hydrochloride (PDA) coating is constructed on cobalt iron Prussian blue (Co-Fe PBA) nanocubes to obtain dopamine-coated cobalt iron Prussian blue (Co-Fe-PBA@PDA), and the dopamine-coated cobalt iron Prussian blue (Co-Fe-PBA@PDA) is utilizedPDA) obtaining nitrogen-doped carbon-supported cobalt iron Prussian blue (Co-Fe PBA@NC); and growing vertically oriented molybdenum selenide nano-sheets on the nitrogen-doped carbon-supported cobalt-iron bimetallic selenide nano-cubes through a one-step hydrothermal selenizing process step to obtain cobalt selenide/iron selenide/molybdenum selenide heterojunction materials (Co-Fe-MoSe) supported by the nitrogen-doped carbon nano-frameworks 2 @ NC). In particular, the preparation method can be carried out according to the procedure described in example 1, example 2 and example 3 below. In the descriptions of example 1, example 2 and example 3, a nitrogen-doped carbon-supported cobalt-iron Prussian-blue (Co-Fe PBA@NC) heterojunction material (Co-Fe-MoSe) was prepared for a nitrogen-doped carbon-nanoshell-supported cobalt/iron selenide/molybdenum selenide heterojunction material (Co-Fe-MoSe) 2 @ NC) are described in detail respectively.
It should be understood that the specific parameters and the like in the following examples should not be construed as limiting the specific implementation of the present application in any way, and each example is merely to obtain cobalt iron Prussian blue (Co-Fe-PBA@NC) supported by nitrogen doped carbon by constructing a dopamine hydrochloride (PDA) coating on cobalt iron Prussian blue (Co-Fe-PBA) nanocubes to obtain dopamine-coated cobalt iron Prussian blue (Co-Fe-PBA@PDA), and obtaining cobalt iron Prussian blue (Co-Fe PBA@NC) supported by nitrogen doped carbon by using dopamine-coated cobalt iron Prussian blue (Co-Fe-PBA@PDA); and growing vertically oriented molybdenum selenide nano-sheets on the nitrogen-doped carbon-supported cobalt-iron bi-metal selenide nano-cubes through a one-step hydrothermal selenizing process step, wherein the cobalt-iron bi-metal selenide nano-cubes have a cobalt selenide and iron selenide heterogeneous interface, and the product after the growth of the molybdenum selenide nano-sheets is Co-Fe-MoSe 2 An example of an implementation of @ NC, i.e. cobalt selenide/iron selenide/molybdenum selenide heterojunction material supported by a nitrogen doped carbon nano-skeleton.
Example 1
The embodiment provides a preparation method of a negative electrode material of a sodium ion battery, which comprises the following steps ofCobalt selenide/iron selenide/molybdenum selenide heterojunction material supported by nitrogen-doped carbon nano-framework (Co-Fe-MoSe 2 @ NC), the preparation method comprising the following steps 1) to 3), wherein:
1) Preparation of Co-Fe PBA.
4 mmol of potassium ferricyanide was dissolved in 200 mL deionized water and stirred for 20min at a stirring speed of 300 r/min to form a homogeneous yellow solution A. 6 mmol of cobalt nitrate hexahydrate and 6 mmol of sodium citrate were dissolved in 200 mL deionized water and stirred for 20 minutes at a stirring rate of 300 r/min to form red solution B. The solution B was added dropwise to the solution A, stirred at a stirring speed of 500 r/min for 30min, and aged at room temperature for 24 hours. And finally, washing the reaction product with deionized water for 2 times, washing the reaction product with ethanol for 2 times, centrifuging for 15 min at a centrifugal speed of 9000 r/min, and vacuum drying at 60 centers after the centrifugation is finished to obtain cobalt iron Prussian blue (Co-Fe PBA) with a nanocube morphology.
2) Preparation of Co-Fe PBA@NC.
Adding 120 mg Co-Fe PBA into 100 mL deionized water, adding 120 mg tris buffer solution, performing ultrasonic treatment for 30min, adding 120 mg dopamine hydrochloride, stirring 10 h, washing the reaction product with deionized water for 2 times, washing the reaction product with ethanol for 2 times, centrifuging at 8000 r/min for 15 min, and vacuum drying at 60 ℃ after centrifugation to obtain the dopamine-coated cobalt iron Prussian blue (Co-Fe-PBA@PDA). Finally, placing the cobalt iron Prussian blue (Co-Fe-PBA@PDA) coated by dopamine into an argon flow with the flow rate of 80 mL/min, calcining at 450 ℃ (the heating rate can be set to be 5 ℃/min, and the ambient temperature is increased to 450 ℃), and obtaining the Co-Fe bimetallic selenide nano-cube (Co-Fe PBA@NC) supported by the nitrogen-doped carbon skeleton after 5 hours, wherein the cube morphology of the product is ensured by controlling the flow rate, the calcining temperature and the calcining time.
3）Co-Fe-MoSe 2 Preparation of @ NC.
I.e. the product of step 2) is subjected to a one-step hydrothermal selenization process, in particular 165mg selenium (Se)Powder was dissolved in N of 10 mL 2 H 4 Stirring the solution for 30min to obtain selenium precursor solution, and then adding Na 50 mg 2 MoO 4 ·2H 2 O and 100 mg Co-Fe PBA@NC are dissolved in 30 mL N, N-dimethylformamide and stirred for 30min to obtain Mo-Co-Fe precursor solution, then the selenium precursor solution is dropwise added into the Mo-Co-Fe precursor solution and stirred for 30min, then the mixture is transferred into a high-pressure reaction kettle lining of 100 mL, and the mixture is reacted at 200 ℃ in the high-pressure reaction kettle lining for 18 h. After the reaction is finished, washing the reaction product with deionized water for 2 times, washing the reaction product with ethanol for 2 times, centrifuging at 8000 r/min for 15 min, and drying in a vacuum environment at 60 ℃ after the centrifugation is finished, so that the vertically oriented MoSe can grow on the nitrogen-doped carbon Co-Fe bimetallic selenide nano-cube 2 The nanosheets obtain a cobalt selenide/iron selenide/molybdenum selenide heterojunction material supported by a nitrogen doped carbon nanoshell (Co-Fe-MoSe) 2 @NC）。
Co-Fe-MoSe obtained in this example 2 The application of the @ NC sodium ion battery anode material in an energy storage system is as follows: the button cell was assembled and tested for cycle and rate performance. Co-Fe-MoSe to be prepared 2 The three materials can be mixed according to the ratio of 7:2:1, and then the mixture is transferred to a glass bottle with a rotor of 8 mL, and then a proper amount of deionized water is added dropwise, and the mixture is stirred for 10 h to obtain slurry. Then cutting copper foil, wiping both sides of the copper foil with ethanol, coating the slurry on the copper foil after drying, uniformly coating the slurry on the copper foil with a scraper, finally placing the copper foil in a vacuum drying oven, and vacuum-drying under vacuum at 60 deg.F o Drying under the environment C. After the drying is finished, the copper foil is cut into a plurality of wafers by a slicer with the diameter of 12 mm, and the wafers are dried and stored for standby. The loading on the copper foil is controlled by the slurry concentration and doctor blade thickness. In this example, the amount of the active material was 0. mg.cm -2 ～1.2 mg·cm -2 . Negative electrode plate: the negative electrode sheet is a conventional sodium sheet, and the present example uses Shanghai Ala Biochemical technologySodium flake model S108757, available from the limited company, has a diameter of 12.4 mm.
Assembling a sodium ion battery: the batteries were assembled in the glove box sequentially. Wherein, secondary electrolyte is required to be dripped into the two ends of the diaphragm respectively. After the battery is assembled, standing for a period of time, and then performing electrochemical test, wherein the test results are shown in the accompanying drawings, and the following steps are shown in the specification:
FIG. 1 is a schematic diagram of a sodium ion battery anode material Co-Fe-MoSe obtained in example 1 2 XRD spectrum of @ NC, confirmed by X-ray diffraction spectrum (XRD) that Co-Fe-MoSe was prepared 2 The crystal structure of the @ NC material is shown in fig. 1. Co-Fe-MoSe 2 XRD spectra of @ NC clearly showed CoSe 2 (PDS#53-0449)、FeSe 2 (PDS # 79-1892) and MoSe 2 (PDS # 29-0914). No characteristic carbon peaks were observed in the heterojunction material formed by the recombination of the three selenides, indicating that only a small amount of carbon was derived from the pyrolysis of PBA. In addition, no other impurity peaks were detected, indicating that the composite material was very pure.
FIG. 2 is a schematic diagram of a sodium ion battery anode material Co-Fe-MoSe obtained in example 1 2 Scanning electron microscope pictures of @ NC at different magnifications; co-Fe-MoSe 2 The particle size of @ NC is slightly less than 100 nm, and from the enlarged SEM image, ultra-thin MoSe is seen 2 The nano-sheets are uniformly dispersed in Co-FeSe 2 The surface forms an open distorted layered porous structure that facilitates electrolyte penetration.
FIG. 3 is a schematic diagram of a sodium ion battery anode material Co-Fe-MoSe obtained in example 1 2 NC at 0.2mV s -1 Cyclic voltammogram at sweep rate; the first three cyclic voltammograms in the range of 0.01 to 3.0V are shown in fig. 3. In the initial cathodic scan, a peak of 0.81. 0.81V could be detected, indicating that sodium reaction occurred, at Co-Fe-MoSe 2 The @ NC surface forms a solid electrolyte interface layer (SEI). Subsequent anodic scans showed a broad peak range of about 1.7 to 2.1V, which corresponds to the sodium removal reaction. The CV curves of the second and third cycles remained the same shape, indicating that the electrode was characterized by high reversibility.
FIG. 4 is a schematic diagram showing a negative electrode material Co-Fe-MoSe of a sodium ion battery obtained in example 1 2 NC at 0.2A g -1 A cycle curve at current density of (2); co-Fe-MoSe 2 Initial discharge capacity of @ NC for first cycle was 524.3 mAh g -1 The coulombic efficiency was 80.17%. After 100 cycles, the reversible capacity is kept at 415.5 mAh g -1 The coulomb efficiency is close to 100%. The composition shows higher reversible capacity after 100 cycles, and highlights the superior structural stability.
FIG. 5 is a schematic diagram of a sodium ion battery anode material Co-Fe-MoSe obtained in example 1 2 A multiplying power performance diagram of @ NC; when the current density is increased from 0.1 to 5 ag -1 Co-Fe-MoSe 2 The capacities corresponding to @ NC are 436.4 mAh g respectively -1 、426.8 mAh g -1 、413.9 mAh g -1 、399.1 mAh g -1 、380.6 mAh g -1 And 339.8 mAh g -1 . After that, when the current density was restored to 0.1A g -1 Co-Fe-MoSe 2 The specific capacity of @ NC is restored to 463.1 mAh g -1 Exhibits excellent rate performance.
FIG. 6 is a schematic diagram of a sodium ion battery anode material Co-Fe-MoSe obtained in example 1 2 @ NC at 5A g -1 Long cycle performance at current density. As shown in FIG. 6, at 5A g -1 After 600 cycles at current density of Co-Fe-MoSe 2 The capacity retention of @ NC was 94.9%, exhibiting ultra-high capacity retention and cycling stability.
In addition, the inventors characterized the microstructure of the negative electrode material of sodium ion battery obtained in example 1 under a high resolution transmission electron microscope, as shown in FIG. 7, in which lattice spacing of 0.373nm and 0.369nm correspond to CoSe, respectively 2 (110) And FeSe 2 (110) Crystal plane, lattice spacing 0.646nm corresponds to MoSe 2 (002) The crystal planes, the microstructure of which is characterized, verifies that the material obtained in example 1 is present in CoSe 2 、FeSe 2 And MoSe 2 And forming a heterostructure.
Example 2
The embodiment provides a preparation method of a negative electrode material of a sodium ion battery, which comprises the following steps ofCarbon nano-framework supported doped cobalt selenide/iron selenide/molybdenum selenide heterojunction material (Co-Fe-MoSe) 2 @ NC), the preparation method comprising the following steps 1) to 3), wherein:
1) Preparation of Co-Fe PBA.
4 mmol of potassium ferricyanide was dissolved in 200 mL deionized water and stirred for 20min at a stirring speed of 300 r/min to form a homogeneous yellow solution A. 6 mmol of cobalt nitrate hexahydrate and 6 mmol of sodium citrate were dissolved in 200 mL deionized water and stirred for 20 minutes at a stirring rate of 300 r/min to form red solution B. The solution B was added dropwise to the solution A, vigorously stirred at 500 r/min for 30 minutes, and aged at room temperature for 24 hours. And finally, washing the reaction product with deionized water for 2 times, washing the reaction product with ethanol for 2 times, centrifuging at 9000 r/min for 15 min, and vacuum drying at 60 ℃ after centrifuging to obtain the Co-Fe PBA.
2) Preparation of Co-Fe PBA@NC.
120 mg of Co-Fe PBA is added into 100 mL deionized water, tris buffer solution is added for 120 mg, ultrasound is carried out for 30min, then 120 mg dopamine hydrochloride is added, stirring is carried out for 10 h, then deionized water is used for cleaning the reaction product for 2 times, absolute ethyl alcohol is used for cleaning the reaction product for 2 times, centrifugation is carried out for 15 min at 8000 r/min, and vacuum drying is carried out at 60 ℃ after centrifugation is finished. Finally, calcining at a high temperature of 450 ℃ in an argon gas flow with a flow rate of 80 mL/min for 5 hours to obtain the Co-Fe bimetallic selenide nanometer cube (Co-Fe PBA@NC) supported by the nitrogen-doped carbon nanometer skeleton.
3）Co-Fe-MoSe 2 Preparation of @ NC.
I.e. the product of step 2) is subjected to a one-step hydrothermal selenization process, in particular, 165mg selenium (Se) powder is dissolved in 10 mL N 2 H 4 Stirring the solution for 30min to obtain selenium precursor solution, and then adding Na 100 mg 2 MoO 4 ·2H 2 O and 100 mg Co-Fe PBA@NC are dissolved in 30 mL N, N-dimethylformamide and stirred for 30min to obtain Mo-Co-Fe precursor solution, then the selenium precursor solution is dropwise added into the Mo-Co-Fe precursor solution and stirred for 30min, and then transferred into a high-pressure reactor lining of 100 mL, and reacted under high pressureThe reaction is carried out in the lining of the kettle at 200 ℃ for 18 h. After the reaction is finished, washing the reaction product with ionized water for 2 times, washing the reaction product with ethanol for 2 times, centrifuging at 8000 r/min for 15 min, and drying in a vacuum environment at 60 ℃ after the centrifugation is finished, so that the vertically oriented MoSe can grow on the nitrogen-doped carbon Co-Fe bimetallic selenide nano-cube 2 The nano-sheet obtains the cobalt selenide/iron selenide/molybdenum selenide heterojunction material supported by the N-doped carbon nano-framework.
Co-Fe-MoSe obtained in this example 2 The application of the @ NC sodium ion battery anode material in an energy storage system is as follows: the button cell was assembled and tested for cycle and rate performance. Co-Fe-MoSe to be prepared 2 The method comprises the steps of (1) taking NC as an active substance, taking conductive carbon black (SP) as a conductive agent, taking carboxymethyl cellulose (CMC) as a binder, mixing the three materials in proportion, grinding for 20min, transferring the mixture into a glass bottle with a rotor of 8 mL, then dropwise adding a proper amount of deionized water, and stirring for 10 h to obtain slurry. Then cutting copper foil, wiping both sides of the copper foil with ethanol, coating the slurry on the copper foil after drying, uniformly coating the slurry on the copper foil with a scraper, finally placing the copper foil in a vacuum drying oven, and vacuum-drying under vacuum at 60 deg.F o And C, drying in the environment. After the drying is finished, the copper foil is cut into a plurality of wafers by a slicer with the diameter of 12 mm, and the wafers are dried and stored for standby. The loading on the copper foil is controlled by the slurry concentration and doctor blade thickness. In this example, the amount of the active material was 0. mg.cm -2 ～1.2 mg cm -2 . Negative electrode plate: the negative electrode sheet was a conventional sodium sheet having a diameter of 12.4. 12.4 mm.
Assembling a sodium ion battery: the batteries were assembled in the glove box sequentially. Wherein, secondary electrolyte is required to be dripped into the two ends of the diaphragm respectively. After the battery is assembled, the battery is stood for a period of time for formation, and then an electrochemical test is carried out.
Example 3
The embodiment provides a preparation method of a sodium ion battery anode material, which comprises cobalt selenide/iron selenide/molybdenum selenide heterojunction material (Co-Fe-MoSe) supported by a nitrogen-doped carbon nano skeleton 2 @ NC), the preparation method comprising the following steps 1) to 3), wherein:
1) Preparation of Co-Fe PBA.
4 mmol of potassium ferricyanide was dissolved in 200 mL deionized water and stirred for 20min at a stirring speed of 300 r/min to form a homogeneous yellow solution A. Similarly, 6 mmol of cobalt nitrate hexahydrate and 6 mmol of sodium citrate were dissolved in 200 mL deionized water and stirred for 20 minutes at a stirring rate of 300 r/min to form red solution B. The solution B was added dropwise to the solution A, stirred at a stirring speed of 500 r/min for 30 minutes, and aged at room temperature for 24 hours. And finally, washing the reaction product with deionized water for 2 times, washing the reaction product with absolute ethyl alcohol for 2 times, centrifuging at a centrifugal speed of 9000 r/min for 15 min, and vacuum drying at 60 ℃ after the centrifugation is finished to obtain the Co-Fe PBA.
2) Preparation of Co-Fe PBA@NC.
Adding 120 mg of Co-Fe PBA into 100 mL deionized water, adding tris buffer solution 120 mg, carrying out ultrasonic treatment for 30min, adding 120 mg dopamine hydrochloride, stirring for 10 h, washing the reaction product with deionized water for 2 times, washing the reaction product with absolute ethyl alcohol for 2 times, centrifuging at a centrifugal speed of 8000 r/min for 15 min, and vacuum-drying at 60 ℃ after centrifugation is finished to obtain the dopamine-coated cobalt iron Prussian blue (Co-Fe-PBA@PDA). Finally, calcining the product at a high temperature in argon flow with a flow speed of 80 mL/min and a temperature of 450 ℃ by using cobalt iron Prussian blue (Co-Fe-PBA@PDA) coated by dopamine, and obtaining the nitrogen-doped carbon Co-Fe bimetallic selenide nano cube (Co-Fe PBA@NC) after 5 hours.
3）Co-Fe-MoSe 2 Preparation of @ NC.
I.e. the product of step 2) is subjected to a one-step hydrothermal selenization process, in particular, 165mg selenium (Se) powder is dissolved in 10 mL N 2 H 4 Stirring the solution for 30min to obtain selenium precursor solution, and then adding Na 200 mg 2 MoO 4 ·2H 2 O and 200 mg of Co-Fe-PBA@NC are dissolved in N, N-dimethylformamide of 30 mL and stirred for 30min to obtain Mo-Co-Fe precursor solution, then Se precursor solution is dropwise added into the Mo-Co-Fe precursor solution and stirred for 30min and then transferredInto the autoclave liner of 100 mL and reacted at 200 ℃ 18 h. After the reaction is finished, washing the reaction product with deionized water for 2 times, washing the reaction product with ethanol for 2 times, centrifuging at 8000 r/min for 15 min, and drying in a vacuum environment at 60 ℃ after the centrifugation is finished, so that the vertically oriented MoSe can grow on the nitrogen-doped carbon Co-Fe bimetallic selenide nano-cube 2 The nano-sheet obtains the cobalt selenide/iron selenide/molybdenum selenide heterojunction material supported by the N-doped carbon nano-framework.
Co-Fe-MoSe obtained in this example 2 The application of the @ NC sodium ion battery anode material in an energy storage system is as follows: the button cell was assembled and tested for cycle and rate performance. Co-Fe-MoSe to be prepared 2 The method comprises the steps of (1) taking NC as an active substance, taking conductive carbon black (SP) as a conductive agent, taking carboxymethyl cellulose (CMC) as a binder, mixing the three materials in proportion, grinding for 20min, transferring the mixture into a glass bottle with a rotor of 8 mL, then dropwise adding a proper amount of deionized water, and stirring for 10 h to obtain slurry. Then cutting copper foil, wiping both sides of the copper foil with ethanol, coating the slurry on the copper foil after drying, uniformly coating the slurry on the copper foil with a scraper, finally placing the copper foil in a vacuum drying oven, and vacuum-drying under vacuum at 60 deg.F o And C, drying in the environment. After the drying is finished, the copper foil is cut into a plurality of wafers by a slicer with the diameter of 12 mm, and the wafers are dried and stored for standby. The loading on the copper foil is controlled by the slurry concentration and doctor blade thickness. In this example, the amount of the active material was 0. mg.cm -2 ～1.2 mg·cm -2 . The negative electrode sheet is selected from sodium sheets with the diameter of 12.4 and mm.
Assembling a sodium ion battery: the batteries were assembled in the glove box sequentially. Wherein, secondary electrolyte is required to be dripped into the two ends of the diaphragm respectively. After the battery is assembled, the battery is stood for a period of time for formation, and then an electrochemical test is carried out.
Based on the above examples 1 to 3, the present application also provides an application of the negative electrode material of the sodium ion battery, including: mixing the sodium ion battery anode material or the sodium ion battery anode material prepared by the preparation method according to any one of the embodiment 1 to the embodiment 3 with a conductive agent acetylene black, a binder CMC and solvent deionized water to prepare electrode slurry; and coating the electrode slurry on a copper foil, and processing the copper foil to form the electrode plate after vacuum drying. In addition, the application also provides a sodium ion battery, which comprises: the sodium ion battery anode material described above or the sodium ion battery anode material prepared according to the preparation method described in any one of examples 1 to 3 was used.
In connection with the above description of the summary and embodiments of the application by applicant, applicant has emphasized that: compared with a binary heterostructure adopted by a negative electrode material of a sodium ion battery in the related art, the ternary metal selenide heterostructure provided by the application is more flexible and diversified in chemical properties, and the energy band structure, the electron density, the chemical activity and the like of the material are adjusted by introducing a third metal element, so that the electron transmission property of the material is changed, and the conductivity and the energy storage capacity of the material are improved. Compared with the binary heterostructure in the related technology, the ternary metal selenide heterostructure provided by the application has better chemical stability and structural stability, and can improve the long-term stability of the performance of the material and prolong the service life. The ternary metal selenide heterostructure provided by the application has the advantages that stronger chemical bonds and crystal defects are formed among different metal elements to improve stability, and the ternary metal selenide heterostructure is more resistant to oxidation and corrosion under the external environment condition, so that longer service life is maintained. The three metal elements in the ternary metal selenide heterostructure provided by the application can be introduced into different valence states and local energy levels, and is beneficial to optimizing the electronic structure of the material, so that the charge transmission efficiency is enhanced. In the scheme provided by the application, the method is implemented by MoSe 2 、CoSe 2 And FeSe 2 The ternary heterostructure has the advantages of good conductivity, good stability, long service life, high charge transmission speed and the like.
While the foregoing is directed to embodiments of the present application, other and further embodiments of the application may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (9)
1. The negative electrode material of the sodium ion battery is characterized by comprising a cobalt selenide/iron selenide/molybdenum selenide heterojunction material with a three-phase hetero interface.
2. The negative electrode material of sodium ion battery of claim 1, wherein the cobalt selenide/iron selenide/molybdenum selenide heterojunction material is formed by growing vertically oriented molybdenum selenide nanoplatelets on a bi-metallic selenide nano cube formed of cobalt selenide/iron selenide.
3. The sodium ion battery anode material of claim 1 or 2, wherein the heterojunction material is supported by a nitrogen-doped carbon nano-skeleton.
4. The preparation method of the sodium ion battery anode material is characterized by comprising a cobalt selenide/iron selenide/molybdenum selenide heterojunction material supported by a nitrogen-doped carbon nano skeleton, and comprises the following steps of:
constructing a dopamine hydrochloride coating on the cobalt iron Prussian blue nanocubes to obtain dopamine-coated cobalt iron Prussian blue, and obtaining nitrogen-doped carbon-supported cobalt iron Prussian blue by using the dopamine-coated cobalt iron Prussian blue; the method comprises the steps of,
and growing vertically oriented molybdenum selenide nano sheets on the nitrogen-doped carbon-supported cobalt-iron bimetallic selenide nano cubes through hydrothermal selenization of the nitrogen-doped carbon-supported cobalt-iron Prussian blue to obtain the cobalt selenide/iron selenide/molybdenum selenide heterojunction material supported by the nitrogen-doped carbon nano skeleton.
5. The preparation method according to claim 4, wherein the cobalt iron Prussian blue nanocubes are prepared according to the following steps:
dissolving potassium ferricyanide in deionized water, stirring to obtain yellow solution
Dissolving cobalt nitrate hexahydrate and sodium citrate in deionized water, and stirring to form a red solution;
and (3) dropwise adding the red solution into the yellow solution, stirring, ageing at room temperature, washing with deionized water and ethanol, centrifuging and drying in vacuum to obtain the cobalt iron Prussian blue nanocubes.
6. The method according to claim 4, wherein the step of obtaining the nitrogen-doped carbon cobalt iron Prussian blue using the dopamine-coated cobalt iron Prussian blue comprises:
the dopamine-coated cobalt iron Prussian blue was calcined in an argon gas stream.
7. The method of claim 4, wherein the step of hydrothermally selenizing comprises:
dissolving selenium powder in N 2 H 4 Obtaining a selenium precursor solution from the solution;
na is mixed with 2 MoO 4 ·2H 2 O and nitrogen-doped carbon-supported cobalt iron Prussian blue are dissolved in N, N-dimethylformamide to obtain a Mo-Co-Fe precursor solution;
and (3) dropwise adding the selenium precursor solution into the Mo-Co-Fe precursor solution, stirring, transferring to a liner of a high-pressure reaction kettle, reacting, washing with ethanol and deionized water after the reaction is finished, centrifuging, and drying to obtain the cobalt selenide/iron selenide/molybdenum selenide heterojunction material supported by the nitrogen-doped carbon nano skeleton.
8. An application of a negative electrode material of a sodium ion battery, which is characterized by comprising the following steps:
mixing the sodium ion battery anode material of any one of claims 1 to 3 or the sodium ion battery anode material prepared by the preparation method of any one of claims 4 to 7 with a conductive agent acetylene black, a binder CMC and solvent deionized water to prepare an electrode slurry; the method comprises the steps of,
and (3) coating the electrode slurry on a copper foil, and processing to form the electrode slice after vacuum drying.
9. A sodium ion battery comprising the sodium ion battery anode material according to any one of claims 1 to 3, or comprising the sodium ion battery anode material produced by the production method according to any one of claims 4 to 7.
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