CN114864927B - High-performance zinc ion battery anode material copper-doped bismuth selenide and preparation method thereof - Google Patents
High-performance zinc ion battery anode material copper-doped bismuth selenide and preparation method thereof Download PDFInfo
- Publication number
- CN114864927B CN114864927B CN202210548806.9A CN202210548806A CN114864927B CN 114864927 B CN114864927 B CN 114864927B CN 202210548806 A CN202210548806 A CN 202210548806A CN 114864927 B CN114864927 B CN 114864927B
- Authority
- CN
- China
- Prior art keywords
- copper
- bismuth selenide
- doped
- ion battery
- zinc ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- FBGGJHZVZAAUKJ-UHFFFAOYSA-N bismuth selenide Chemical compound [Se-2].[Se-2].[Se-2].[Bi+3].[Bi+3] FBGGJHZVZAAUKJ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000010405 anode material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000010949 copper Substances 0.000 claims abstract description 17
- BOQDCUQEMSEYOO-UHFFFAOYSA-N [Se].[Bi].[Cu] Chemical compound [Se].[Bi].[Cu] BOQDCUQEMSEYOO-UHFFFAOYSA-N 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims abstract description 11
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims abstract description 11
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010406 cathode material Substances 0.000 claims abstract description 6
- 239000002135 nanosheet Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 13
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 8
- 229960001471 sodium selenite Drugs 0.000 claims description 8
- 235000015921 sodium selenite Nutrition 0.000 claims description 8
- 239000011781 sodium selenite Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 238000011049 filling Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 235000010288 sodium nitrite Nutrition 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [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 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
The invention relates to a high-performance zinc ion battery anode material doped with copper bismuth selenide and a preparation method thereof, which is prepared by taking bismuth nitrate pentahydrate and sodium nitrite as raw materials, adding cuprous iodide, and adopting hydrothermal synthesis to obtain a copper-doped bismuth selenide nano-sheet with the thickness of only 4 nm. The method has the advantages of simple process, convenient operation, environmental protection, simple equipment, low production cost, high specific capacity of the copper-doped bismuth selenide cathode material prepared by the method, good cycle stability and suitability for large-scale industrial production. The prepared bismuth selenide doped with copper is used as a positive electrode and a negative electrode to be assembled into a battery, and the battery has higher capacity and good cycling stability.
Description
Technical Field
The invention relates to a high-performance zinc ion battery anode material copper-doped bismuth selenide and a preparation method thereof, belonging to the technical field of zinc ion batteries.
Background
With the further development of science and technology, energy and environmental problems are increasingly conflicting, and new secondary batteries are attracting great attention from researchers. Compared with a lithium ion battery, the water-based Zinc Ion Battery (ZIB) has higher theoretical capacity (Zn cathode 820mAh g) -1 /5855mAh cm -3 ) Low Zn/Zn 2+ Oxidation-reduction potential (-0.76V vs standard hydrogen electrode), and the price of Zn cathode is one eighth of lithium, and the electrolyte is water-based electrolyte with pH near neutral, compared with the electrolyteThe inflammable ester-based electrolyte in the lithium ion battery has the unique advantages of excellent stability and no toxicity in water, rich resources, low cost, safety and the like, and has great application potential in novel batteries. In addition, the zinc ion battery can be directly assembled in the air, so that not only is the waste of energy reduced, but also the preparation steps of the device are simplified, and the preparation cost of the battery is effectively reduced.
Common cathode materials for zinc ion batteries include various transition metal compounds such as manganese, vanadium or molybdenum based oxides/sulfides, prussian blue analogues, conductive polymers and the like. However, factors such as dendrite and hydrogen evolution of the zinc ion battery inhibit the development of the zinc ion battery as a novel battery, and various methods are also proposed to solve the problems, such as high-concentration electrolyte, membrane improvement and the like, and play a role in promoting the development of the zinc ion battery, but for the battery, the improvement of the positive electrode and the negative electrode is an optimal scheme for improving the performance and the stability of the zinc ion battery.
Bi 2 Se 3 As a topological insulator two-dimensional layered nano material, the graphene-like layered structure has excellent light, heat, electricity and magnetic properties, and has great application prospects in the aspects of metal-ion batteries, thermoelectric devices, sensors and the like. Bi reported so far 2 Se 3 The preparation method mainly comprises a chemical vapor deposition method (CVD), a hydrothermal method, a high-pressure synthesis method, a magnetron sputtering method and the like, the CVD technology has low rate, tail gas participating in deposition is inflammable, explosive and toxic, certain corrosion effect is also provided for equipment, the high-pressure synthesis and magnetron sputtering modes also need more accurate control on the reaction, the operation process is more complex, and compared with the methods, the hydrothermal method has simple operation and safe process, is an ideal Bi preparation method 2 Se 3 Method of sample. And we are doping Cu atoms in Bi by this hydrothermal mode 2 Se 3 And synthesizing the bismuth selenide anode material doped with copper.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the copper-doped bismuth selenide nano-anode material for the high-performance zinc ion battery and the preparation method thereof, wherein the preparation method is simple and environment-friendly, and the bismuth selenide nano-anode material which is used as the zinc ion battery anode material has high capacity, good high-current performance and good cycle stability, and can still exert high specific capacity after being assembled into a full battery.
The technical scheme of the invention is as follows:
the high-performance zinc ion battery anode material doped with copper bismuth selenide has a single-layer thickness of 4nm plus or minus 2nm.
Preferably, the Bi in the layered structure of the present invention 2 Se 3 Is hexagonal crystal structure (ICSD # 89-2008), zn is caused by doping copper 2+ The electrostatic repulsive force transmitted in the material is further weakened, and Zn is improved 2+ Is a diffusion rate of (a) is provided.
The preparation method of the high-performance zinc ion battery anode material doped with copper bismuth selenide comprises the following steps:
(1) Dissolving bismuth nitrate pentahydrate and sodium selenite in an organic solvent, and stirring for 30min;
(2) Dissolving cuprous iodide in an organic solvent, and stirring for 30min;
(3) Pouring a proper amount of the reaction solution prepared in the step (2) into the step (1), and stirring to mix the reaction solution;
(4) Adding ascorbic acid into the obtained solution, and stirring for 5-10min;
(5) Loading the reaction solution prepared in the step (4) into a reaction kettle, reacting for 10-20 hours at 170-220 ℃, cooling to room temperature, filtering and collecting to obtain black gray precipitate, repeatedly washing with deionized water and ethanol for 2-3 times, and drying;
(6) And collecting the dried precipitate to obtain the high-performance zinc ion battery anode material doped with copper bismuth selenide.
In the present invention, the organic solvent in the steps (1) and (2) is preferably ethylene glycol.
In the invention, preferably, the mass volume ratio of the addition amount of the bismuth nitrate pentahydrate and the sodium selenite to the organic solvent in the step (1) is (0.003-0.01): 1 and (0.002 to 0.009): 1, in g/mL.
In the step (2), preferably, the mass volume ratio of the addition amount of the cuprous iodide to the organic solvent is (0.002-0.02): 1 in g/ml.
In the preferred embodiment of the present invention, in the step (3), the addition amount of the cuprous iodide organic solvent dispersion is 1 to 10mL.
In the preferred embodiment of the present invention, in the step (5), the reaction temperature is 130-270 ℃ and the reaction time is 9-25h.
In the preferred embodiment of the present invention, in the step (5), the drying temperature is 40-120 ℃ and the drying time is 6-20 hours.
The beneficial effects of the invention are as follows:
the copper-doped bismuth selenide two-dimensional nano sheet is prepared by adopting a simple hydrothermal reaction, the thickness of the obtained copper-doped bismuth selenide is only 4nm, and the copper-doped bismuth selenide is used as a zinc ion battery anode material, so that the copper-doped bismuth selenide two-dimensional nano sheet has higher charge-discharge specific capacity and rate capability and good cycle stability. The preparation of the copper-doped bismuth selenide anode material has the advantages of simple equipment, low cost and suitability for large-scale industrial production. The ultrathin structure and abundant defects of the prepared copper-doped bismuth selenide two-dimensional nano sheet weaken electrostatic repulsive force of zinc ions and materials, improve contact between electrolyte and electrode materials, shorten diffusion distance of zinc ions and promote Zn 2+ And the positive electrode is embedded and separated, so that higher specific capacity and rate capability of the battery are obtained.
Drawings
FIG. 1 is an X-ray diffraction pattern of a copper doped bismuth selenide sample according to example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a copper-doped bismuth selenide sample according to example 1 of the invention;
FIG. 3 is a transmission electron micrograph of a copper doped bismuth selenide sample according to example 1 of the invention;
FIG. 4 is an atomic force microscope photograph of a copper doped bismuth selenide sample according to example 1 of the present invention;
FIG. 5 is a graph showing the charge and discharge curves of a half cell made of a copper doped bismuth selenide sample according to example 1 of the present invention with respect to a zinc sheet at a voltage ranging from 0.2V to 1.6V;
FIG. 6 is a graph showing the rate curves of a copper doped bismuth selenide sample obtained in example 1 and a zinc sheet half cell made of bismuth selenide at different current densities according to the present invention;
FIG. 7 is a graph showing the cycle of a copper doped bismuth selenide sample obtained in example 1 and a half cell made of bismuth selenide versus zinc sheet according to the invention;
Detailed Description
The invention will be further illustrated with reference to specific examples. It should be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading what is set forth herein, and such equivalents are intended to fall within the scope of the claims appended hereto.
Bismuth nitrate pentahydrate, cuprous iodide, sodium selenite, ethylene glycol and ascorbic acid are commercially available products, and are purchased from national pharmaceutical group chemical reagent company.
Example 1
A high-performance zinc ion battery anode material doped with copper bismuth selenide has a layered structure with a thickness of 4nm + -2 nm.
The preparation method comprises the following steps:
(1) Uniformly dispersing 0.6mmol bismuth nitrate pentahydrate and 1mmol sodium selenite in 25mL ethylene glycol, and stirring for 30min;
(2) Uniformly dispersing 0.3mmol of cuprous iodide in 20mL of ethylene glycol, and stirring for 30min;
(3) Pouring 10mL of the reaction solution prepared in the step (2) into the step (1), and stirring to mix the reaction solution;
(4) Adding 0.1g of ascorbic acid into the solution prepared in the step (3), and stirring for 15min;
(5) Transferring the solution into a hydrothermal kettle, reacting for 10 hours at 180 ℃, cooling to room temperature, filtering, collecting black gray precipitate, washing with absolute ethyl alcohol and deionized water for several times, and drying for 20 hours at 80 ℃.
(6) And collecting the dried precipitate to obtain the high-performance zinc ion battery anode material doped with copper bismuth selenide.
The layered bismuth selenide prepared in the embodiment is used as an electrode active material, acetylene black is used as a conductive agent, polyvinylidene fluoride (PVDF) is used as an adhesive, and a proper amount of N-methylpyrrolidone (NMP) is added according to the weight ratio of 7:2:1 for mixing and grindingGrinding uniformly to form slurry, uniformly coating the slurry on carbon paper, and vacuum drying at 80 ℃ overnight to obtain the positive plate after punching. The anode metal zinc sheet and the cathode metal zinc sheet are assembled into a battery, and 1mol L of the battery is prepared by taking sulfonated polypropylene and glass fiber as a diaphragm -1 ZnSO of (2) 4 As an electrolyte, a button cell (model 2025) was assembled. The charge and discharge performance test of the battery was performed on a new power test system at room temperature, with a test voltage ranging from 0.2 to 1.6V.
FIG. 1 is an XRD pattern for copper doped bismuth selenide prepared in accordance with example 1 of the invention. As can be seen from FIG. 1, the bismuth selenide prepared has a hexagonal crystal structure (ICSD#89-2008), and the corresponding unit cell parameters are No other impurity peak appears to indicate that the prepared Cu doped Bi 2 Se 3 Is pure phase. FIG. 2 is a scanning electron micrograph of the product obtained according to example 1, and it can be seen from FIG. 2 that the material is a uniform sheet structure. FIG. 3 is a transmission electron micrograph of the product obtained in example 1 according to the invention, from which also the lamellar structure can be seen. FIG. 4 is an atomic force microscope photograph of the prepared Cu-doped bismuth selenide, from which it can be seen that the thickness of the bismuth selenide monolayer is only about 4nm, and FIG. 5 is a prepared Cu-doped Bi 2 Se 3 From the figure, it can be seen that the CV curves of the first four turns have good coincidence. Two reduction peaks (0.568V and 0.697V) appear in the reduction process, and the potential difference between the oxidation-reduction peaks is smaller, and 0.193V and 0.35V respectively show that the synthesized copper-doped bismuth selenide material has smaller potential polarization and excellent reversibility in the dezincification process. FIG. 6 is a graph showing the rate performance test of the copper-doped bismuth selenide electrode prepared in example 1 and comparison with conventional bismuth selenide, which shows that the current densities are 0.1. 0.1A g, respectively -1 ，0.2Ag -1 ，0.5A g -1 ，1A g -1 ，2A g -1 ，5A g -1 ， 10A g -1 The copper-doped bismuth selenide prepared by the invention has the capacities of 326, 290.6, 237.6, 192.5, 156.1, 121.6 and 95mAh g respectively -1 . After 40 turns, the current density returns to 1A g again -1 When the capacity is still up to 303mAh g -1 The performance of the bismuth selenide is obviously better than that of bismuth selenide. FIG. 7 is a cycle stability curve (current 10A g) for the copper-doped bismuth selenide test prepared in example 1 -1 ) And compared with bismuth selenide cathode material. At 10A g -1 The copper-doped bismuth selenide prepared by the invention can still keep 85.51mA h g after 1000 circles of circulation -1 Is a specific capacity of (a). The specific capacity and the cycle stability are obviously better than those of bismuth selenide. The specific capacity and the cycling stability of the zinc ion battery assembled based on the copper-doped bismuth selenide anode in the technical invention are higher than those of the reported zinc ion battery based on the bismuth selenide anode under the same test conditions (Energy Storage material matter.2021, 42, 34-41).
Example 2
A high-performance zinc ion battery anode material doped with copper bismuth selenide has a layered structure with a thickness of 4nm + -2 nm.
The preparation method comprises the following steps:
(1) Uniformly dispersing 0.6mmol bismuth nitrate pentahydrate and 1mmol sodium selenite in 20mL ethylene glycol, and stirring for 30min;
(2) Uniformly dispersing 0.2mmol of cuprous iodide in 10mL of ethylene glycol, and stirring for 30min;
(3) Pouring the reaction solution prepared in the step (2) into the step (1), and stirring to mix the reaction solution;
(4) Adding 0.5g of ascorbic acid into the solution prepared in the step (3), and stirring for 15min;
(5) Transferring the solution into a hydrothermal kettle, reacting at 140 ℃ for 25 hours, cooling to room temperature, filtering, collecting black gray precipitate, washing with absolute ethyl alcohol and deionized water for several times, and drying at 45 ℃ for 20 hours.
(6) And collecting the dried precipitate to obtain the high-performance zinc ion battery anode material doped with copper bismuth selenide.
Example 3
A high-performance zinc ion battery anode material doped with copper bismuth selenide has a layered structure with a thickness of 4nm + -2 nm.
The preparation method comprises the following steps:
(1) Uniformly dispersing 1mmol of bismuth nitrate pentahydrate and 1.2mmol of sodium selenite in 30mL of ethylene glycol, and stirring for 30min;
(2) Uniformly dispersing 0.5mmol of cuprous iodide in 15mL of ethylene glycol, and stirring for 30min;
(3) Pouring 5mL of the reaction solution prepared in the step (2) into the step (1), and stirring to mix the reaction solution;
(4) Adding 1g of ascorbic acid into the solution prepared in the step (3), and stirring for 15min;
(5) Transferring the solution into a hydrothermal kettle, reacting for 20 hours at 260 ℃, cooling to room temperature, filtering, collecting black gray precipitate, washing with absolute ethyl alcohol and deionized water for several times, and drying for 15 hours at 100 ℃.
(6) And collecting the dried precipitate to obtain the high-performance zinc ion battery anode material doped with copper bismuth selenide.
Claims (6)
1. The bismuth selenide anode material doped with copper for the high-performance zinc ion battery is characterized in that the thickness of a layered structure of the bismuth selenide two-dimensional nano sheet anode material doped with copper is 4nm +/-2 nm; the preparation method of the bismuth selenide anode material doped with copper for the high-performance zinc ion battery comprises the following steps:
(1) Dissolving bismuth nitrate pentahydrate and sodium selenite in an organic solvent, and stirring for 30min;
(2) Dissolving cuprous iodide in an organic solvent, and stirring for 30min;
(3) Pouring the reaction solution prepared in the step (2) into the step (1), and stirring to mix the reaction solution;
(4) Adding ascorbic acid into the obtained solution, and stirring for 5-10min;
(5) And (3) filling the reaction liquid prepared in the step (4) into a reaction kettle, reacting at 130-270 ℃ for 9-25h, cooling to room temperature, filtering and collecting the obtained dark gray precipitate, repeatedly washing the precipitate with deionized water and ethanol for 2-3 times, and drying the precipitate.
2. The high performance zinc ion battery doped copper bismuth selenide cathode material according to claim 1, wherein the layered structure is Cu doped with Bi 2 Se 3 For hexagonal crystal structure, corresponding to crystal structure card icsd#89-2008, the cell parameters are a=4.14 a, b=4.14 a, c=28.64 a; by doping copper to make Zn 2+ The electrostatic repulsive force transmitted in the material is further weakened, and Zn is improved 2+ Is a diffusion rate of (a) is provided.
3. The high-performance zinc ion battery doped copper bismuth selenide anode material according to claim 1, wherein the mass volume ratio of the added amount of bismuth nitrate pentahydrate and sodium selenite to the organic solvent in the step (1) is (0.003-0.01): 1 and (0.002 to 0.009): 1, in g/mL.
4. The high-performance zinc ion battery doped copper bismuth selenide anode material according to claim 1, wherein the mass volume ratio of the addition amount of the cuprous iodide to the organic solvent in the step (2) is (0.002-0.02): 1, in g/mL.
5. The high performance zinc ion battery doped copper bismuth selenide cathode material according to claim 1, wherein in step (3), the addition amount of the cuprous iodide organic solvent dispersion liquid is 1-10mL.
6. The high performance zinc ion battery doped copper bismuth selenide cathode material according to claim 1, wherein in step (5), the drying temperature is 40-120 ℃ and the drying time is 6-20h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210548806.9A CN114864927B (en) | 2022-05-20 | 2022-05-20 | High-performance zinc ion battery anode material copper-doped bismuth selenide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210548806.9A CN114864927B (en) | 2022-05-20 | 2022-05-20 | High-performance zinc ion battery anode material copper-doped bismuth selenide and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114864927A CN114864927A (en) | 2022-08-05 |
| CN114864927B true CN114864927B (en) | 2023-12-29 |
Family
ID=82639635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210548806.9A Active CN114864927B (en) | 2022-05-20 | 2022-05-20 | High-performance zinc ion battery anode material copper-doped bismuth selenide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114864927B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1384047A (en) * | 2002-06-07 | 2002-12-11 | 清华大学 | Synthesis of several metal selenides and tellurides as semiconductor material |
| JP2010046625A (en) * | 2008-08-22 | 2010-03-04 | Tohoku Univ | Method of synthesizing metal/alloy nanoparticles by supercritical hydrothermal reaction |
| CN102020253A (en) * | 2010-11-09 | 2011-04-20 | 北京大学 | Topological insulator material and preparation method thereof |
| CN106876641A (en) * | 2017-03-08 | 2017-06-20 | 青岛大学 | A kind of lithium battery diaphragm and preparation method thereof and the application in lithium battery |
| CN107086322A (en) * | 2017-05-03 | 2017-08-22 | 厦门大学 | A kind of copper selenium compound can discharge and recharge aluminium ion battery for positive pole |
| CN112536016A (en) * | 2019-09-23 | 2021-03-23 | 北京大学 | Novel antimony/bismuth-based transition metal layered chalcogenide material for adsorbing harmful ions |
| WO2021212050A1 (en) * | 2020-04-17 | 2021-10-21 | Urban Electric Power Inc. | Improving zinc-manganese dioxide battery performance through interlayers |
| WO2021227594A1 (en) * | 2020-05-11 | 2021-11-18 | 中国科学院过程工程研究所 | Composite positive electrode material, preparation method therefor, and application in zinc ion battery |
-
2022
- 2022-05-20 CN CN202210548806.9A patent/CN114864927B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1384047A (en) * | 2002-06-07 | 2002-12-11 | 清华大学 | Synthesis of several metal selenides and tellurides as semiconductor material |
| JP2010046625A (en) * | 2008-08-22 | 2010-03-04 | Tohoku Univ | Method of synthesizing metal/alloy nanoparticles by supercritical hydrothermal reaction |
| CN102020253A (en) * | 2010-11-09 | 2011-04-20 | 北京大学 | Topological insulator material and preparation method thereof |
| CN106876641A (en) * | 2017-03-08 | 2017-06-20 | 青岛大学 | A kind of lithium battery diaphragm and preparation method thereof and the application in lithium battery |
| CN107086322A (en) * | 2017-05-03 | 2017-08-22 | 厦门大学 | A kind of copper selenium compound can discharge and recharge aluminium ion battery for positive pole |
| CN112536016A (en) * | 2019-09-23 | 2021-03-23 | 北京大学 | Novel antimony/bismuth-based transition metal layered chalcogenide material for adsorbing harmful ions |
| WO2021212050A1 (en) * | 2020-04-17 | 2021-10-21 | Urban Electric Power Inc. | Improving zinc-manganese dioxide battery performance through interlayers |
| WO2021227594A1 (en) * | 2020-05-11 | 2021-11-18 | 中国科学院过程工程研究所 | Composite positive electrode material, preparation method therefor, and application in zinc ion battery |
Non-Patent Citations (4)
| Title |
|---|
| Guolong Sun等.Enhanced thermoelectric performance of n-type Bi2Se3 doped with Cu.《Journal of Alloys and Compounds》.2015,第9-14页. * |
| Lei Peng等.Reversible proton co-intercalation boosting zinc-ion adsorption and migration abilities in bismuth selenide nanoplates for advanced aqueous batteries.《Energy Storage Materials》.2021,第34-41页. * |
| Meng Wang等.A combined method for synthesis of superconducting Cu doped Bi2Se3.《Scientifi Reports》.2016,第1-5页. * |
| Zichen Wei等.Significantly enhanced thermoelectric performance of Cu-doped p-type Bi0.5Sb1.5Te3 by a hydrothermal synthesis method.《The Royal Society of Chemistry》.2017,第41111-41116页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114864927A (en) | 2022-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108539171B (en) | Preparation method of zinc sulfide and graphene oxide compound and application of compound in positive electrode material of lithium-sulfur battery | |
| CN112624199B (en) | Carbon quantum dot/manganese dioxide nanocomposite, preparation method and application thereof | |
| US11005100B2 (en) | Selenium-doped MXene material, and preparation method and use thereof | |
| WO2015054974A1 (en) | Tungsten-based material super battery and supercapacitor | |
| CN113410443B (en) | Preparation method and application of high-stability copper intercalation manganese dioxide electrode material | |
| CN113517426B (en) | Sodium vanadium fluorophosphate/reduced graphene oxide composite material and preparation method and application thereof | |
| CN113270577B (en) | Aqueous zinc ion battery and positive electrode material | |
| CN105206821A (en) | Method for synthesizing lithium ion battery positive electrode material | |
| CN110854373B (en) | Composite negative electrode material and preparation method thereof | |
| CN112010291A (en) | Preparation method and application of nickel-doped molybdenum disulfide/graphene three-dimensional composite material | |
| CN110649263A (en) | Nickel-ion battery lithium vanadium phosphate positive electrode material, sol-gel preparation method and application | |
| CN112670496A (en) | Iron-doped manganese dioxide composite reduced graphene oxide material, and preparation and application thereof | |
| WO2019104948A1 (en) | Molybdenum doping-modified lithium manganese oxide composite material, preparation method therefor and lithium ion battery | |
| CN114835091A (en) | High-performance zinc ion battery positive electrode material bismuth selenide nanosheet and preparation method thereof | |
| CN114864927B (en) | High-performance zinc ion battery anode material copper-doped bismuth selenide and preparation method thereof | |
| CN115440955A (en) | Sodium-electricity positive electrode composite material and preparation method thereof | |
| CN112670478B (en) | Carbon sphere packaged amorphous vanadium-oxygen cluster composite material, preparation method thereof and sodium storage application | |
| CN111816853B (en) | CuS-Cu7.2S4Nanocomposite, lithium battery and preparation method | |
| CN110808402A (en) | Based on Zn (OH)42-Conductive ion battery and preparation method thereof | |
| CN114300277B (en) | Aluminum manganese oxide and application thereof as positive electrode material in water-based magnesium ion capacitor | |
| CN114784243B (en) | Nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material and preparation method thereof | |
| CN114497539B (en) | Aqueous rechargeable battery based on copper ferrocyanide anode and phenazine organic matter cathode | |
| CN114094075B (en) | Iron selenide-iron oxide nanotube/graphene aerogel composite anode material and preparation method and application thereof | |
| CN115626992B (en) | Water system zinc ion battery based on sulfhydryl pyrimidine-MOF positive electrode material | |
| CN116169288B (en) | Metal quantum dot/hard carbon negative electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |