CN114597370B - Air-stable high-voltage long-cycle-life sodium ion battery positive electrode material and preparation method thereof - Google Patents
Air-stable high-voltage long-cycle-life sodium ion battery positive electrode material and preparation method thereof Download PDFInfo
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- sodium ion
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 56
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011572 manganese Substances 0.000 claims abstract description 50
- 239000011701 zinc Substances 0.000 claims abstract description 44
- 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 claims abstract description 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000010405 anode material Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000003980 solgel method Methods 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 238000010583 slow cooling Methods 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 48
- -1 sodium hexafluorophosphate Chemical compound 0.000 claims description 14
- 239000003570 air Substances 0.000 claims description 13
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 13
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 9
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 9
- 229940071125 manganese acetate Drugs 0.000 claims description 9
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 9
- 229940078494 nickel acetate Drugs 0.000 claims description 9
- 239000001632 sodium acetate Substances 0.000 claims description 9
- 235000017281 sodium acetate Nutrition 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical group CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 4
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000007772 electrode material Substances 0.000 abstract 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 abstract 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000011149 active material Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 230000002441 reversible effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011268 mixed slurry Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 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
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920000447 polyanionic polymer Chemical class 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229960000314 zinc acetate Drugs 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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 discloses an air-stable high-voltage long-cycle-life sodium ion battery positive electrode material and a preparation method and application thereof, and belongs to the technical field of battery material synthesis. The method mixes the reaction precursors containing sodium, nickel, manganese, zinc and zirconium sources according to a proportion, calcines the precursors at high temperature and keeps the temperature for a period of time after a sol-gel method, and obtains the lamellar O3-NaNi through a slow cooling process 0.5‑ x Zn x Mn 0.5‑y Zr y O 2 And a positive electrode material. The sodium ion battery anode material provided by the invention has excellent air stability, and after the sodium ion battery anode material is exposed in the air for a week, the crystal structure still maintains the O3 phase crystal structure, so that the sodium ion battery anode material is suitable for commercial sodium ion battery anodes. Used as electrode materials, exhibit high voltages and long cycle life. The preparation method of the positive electrode material disclosed by the invention is simple and easy to control, low in cost and good in application prospect.
Description
Technical Field
The invention belongs to the technical field of battery material synthesis, and particularly relates to a preparation method of a double-ion doped O3 phase positive electrode material and application of a sodium ion battery.
Background
Sodium ion batteries have received attention in recent years, and have advantages over lithium ion batteries in that: (1) The sodium salt raw material is rich in reserve (accounting for about 2.64 percent of the reserve of the crust), wide in distribution and low in price; (2) The solvation energy of sodium ions is lower than that of lithium ions, namely, the sodium ions have better interfacial ion diffusion capability; (3) The stokes diameter of sodium ions is smaller than that of lithium ions, and the electrolyte with the same concentration has higher ionic conductivity than that of lithium salt electrolyte. Therefore, the sodium ion battery has some unique advantages of low cost, high-low temperature performance and safety performance, and is expected to be an important supplementary technology in the field of large-scale energy storage.
In the positive electrode material, layered transition metal oxides, prussian blue analogues, polyanion compounds, part of organic molecules and the like have all been demonstrated to have reversible sodium removal/intercalation active sites. Among them, the O3 phase Ni/Mn-based layered transition metal oxide is widely focused by researchers at home and abroad due to its high reversible capacity, abundant resources, environmental friendliness, high volumetric energy density and unique two-dimensional diffusion channel. However, problems such as complex phase transformation process, surface chemical substance inactivation, interfacial electrode/electrolyte side reaction and the like in the O3 phase circulation process lead to material circulation performance degradation and voltage attenuation, and seriously obstruct the commercialization process. Therefore, the development of high voltage, long cycle life and air stable sodium ion battery positive electrode materials is critical to the development of large scale energy storage systems.
Disclosure of Invention
The invention aims to solve the problems of complex phase transition process, surface chemical substance inactivation, interface electrode/electrolyte side reaction and the like in the circulating process of the O3 phase layered positive electrode material of the sodium ion battery, and provides a double-ion doped O3 phase positive electrode material, a preparation method and application thereof in the sodium ion battery. The layered positive electrode material of the sodium ion battery provided by the invention has the advantages of stable air, long cycle life and high average discharge voltage, and can be applied to commercial sodium ion batteries.
The technical scheme of the invention is as follows:
a double-ion doped O3 phase layered positive electrode material, which is an air-stable, high discharge voltage and long cycle life sodium ion battery positive electrode material, has a chemical formula of O3-NaNi 0.5-x Zn x Mn 0.5-y Zr y O 2 (x is more than 0 and less than or equal to 0.1, y is more than 0 and less than or equal to 0.05), belongs to a hexagonal system, wherein the space group is R-3m, the arrangement mode of the transition metal layer is ABCABC, and the transition metal layers at the same position of Zn and Zr elements are arranged in disorder.
The preparation method of the O3 phase sodium ion battery anode material with stable air, high voltage and long cycle life comprises the following steps:
(1) According to the sol-gel method, a sodium source, a nickel source, a manganese source, a zinc source and a zirconium source are mixed according to stoichiometric ratio, different dispersing agents and complexing agents are added, and a gel sample is obtained after stirring and drying, and is subjected to forced air drying.
(2) High-temperature presintering, namely presintering the precursor obtained by the sol-gel method in the step (1) at high temperature:
(3) And (3) calcining at high temperature, calcining at high temperature after presintering, and slowly cooling to obtain the O3 phase positive electrode active material.
Preferably, in step (1), the sodium source is sodium acetate or sodium nitrate; the nickel source is nickel acetate or nickel nitrate; the manganese source is manganese acetate or manganese nitrate; the zinc source is zinc acetate or zinc nitrate; the zirconium source is zirconium acetate or zirconium nitrate.
Preferably, in the step (2), the presintering temperature is 400-600 ℃, the calcining atmosphere is air, nitrogen or oxygen, and the calcining time is 4-6h; in the step (3), the high-temperature calcination temperature is 800-1200 ℃, the calcination atmosphere is air, nitrogen or oxygen, the heat treatment time is 10-15h, and the slow cooling rate is 5-10 ℃/min.
The invention also provides application of the air-stable, high-voltage and long-cycle-life sodium ion battery anode material in sodium ion batteries.
Preferably, the positive electrode material electrode plate comprises the following components in percentage by mass: 60% -90% of active material O3-NaNi 0.5-x Zn x Mn 0.5-y Zr y O 2 (x is more than 0 and less than or equal to 0.1, y is more than 0 and less than or equal to 0.05), conductive carbon black accounting for 5 to 20 percent, polyvinylidene fluoride accounting for 5 to 20 percent.
Preferably, the negative electrode material is a metal sodium sheet, and the current collector is aluminum foil.
Preferably, the organic solvent in the sodium ion battery electrolyte is any one or any combination of propylene carbonate or diethylene glycol dimethyl ether.
Preferably, the sodium salt in the electrolyte of the sodium ion battery is any one or any combination of sodium hexafluorophosphate and sodium perchlorate.
Preferably, the concentration of sodium salt in the electrolyte is 0.1mol/L to 1mol/L.
The invention has the advantages and beneficial effects that:
the layered positive electrode material of the sodium ion battery provided by the invention is stable in air, easy to store and transport and is paintPrepared O3-NaNi 0.5-x Zn x Mn 0.5-y Zr y O 2 The positive electrode has excellent cycle performance and high average discharge operating voltage. The sodium ion battery assembled by the positive electrode material provided by the invention has high output voltage and long cycle life.
Drawings
FIG. 1 is O3-NaNi obtained in comparative example 1 0.5 Mn 0.5 O 2 An XRD pattern of (b);
FIG. 2 is O3-NaNi obtained in comparative example 2 0.5-x Zn x Mn 0.5 O 2 An XRD pattern of (b);
FIG. 3 is O3-NaNi obtained in example 3 0.4 Zn 00.1 Mn 0.48 Zr 0.02 O 2 An XRD pattern of (b);
FIG. 4 is O3-NaNi obtained in example 3 0.4 Zn 0.1 Mn 0.48 Zr 0.02 O 2 XRD pattern exposed to air for one week;
FIG. 5 is O3-NaNi obtained in example 5 0.45 Zn 0.05 Mn 0.45 Zr 0.05 O 2 An XRD pattern of (b);
FIG. 6 is O3-NaNi obtained in example 6 0.4 Zn 0.1 Mn 0.45 Zr 0.05 O 2 An XRD pattern of (b);
FIG. 7 is a charge-discharge curve of the sodium ion battery obtained in example 1 (current density: 50mA/g, electrolyte: 1.0mol/L sodium hexafluorophosphate dissolved in propylene carbonate, voltage window: 1.5-4.0V);
FIG. 8 is a charge-discharge curve of the sodium ion battery obtained in example 2 (current density: 50mA/g, electrolyte: 1.0mol/L sodium hexafluorophosphate dissolved in propylene carbonate, voltage window: 1.5-4.0V);
FIG. 9 is a charge-discharge curve of the sodium ion battery obtained in example 3 (current density: 50mA/g, electrolyte: 1.0mol/L sodium hexafluorophosphate dissolved in propylene carbonate, voltage window: 1.5-4.0V);
FIG. 10 is a graph showing the cycle performance of the sodium ion battery obtained in example 3 (current density: 100mA/g, electrolyte: 1.0mol/L sodium hexafluorophosphate dissolved in propylene carbonate, voltage window: 2.0-4.0V);
FIG. 11 is a charge-discharge curve of the sodium ion battery obtained in example 4 (current density: 50mA/g, electrolyte: 1.0mol/L sodium hexafluorophosphate dissolved in diethylene glycol dimethyl ether, voltage window: 2.0-4.0V).
Detailed Description
The present invention will now be described more fully hereinafter with reference to the accompanying drawings.
The purity of sodium acetate, nickel acetate, manganese acetate, zinc acetate, zirconium acetate, organic solvents and sodium salts used in the examples was not less than 99%.
Comparative example 1:
the embodiment synthesizes a positive electrode material and examines the performance of the sodium ion battery, and the positive electrode active material is oxide positive electrode material NaNi 1/2 Mn 1/2 O 2 The electrolyte system is an ester electrolyte.
The NaNi 1/2 Mn 1/2 O 2 The detailed synthesis method comprises the following steps:
by adopting a sol-gel method, firstly, uniformly mixing 2.2mmol of sodium acetate, 1mmol of nickel acetate and 1mmol of manganese acetate, then placing the mixture in 100mL of deionized water, heating to 100 ℃ under the stirring condition of 400r/min, heating and evaporating to dryness, drying the evaporated gel sample in a blast oven at 100 ℃ for 10 hours, and presintering at 600 ℃ for 4 hours. Grinding a dried sample, tabletting under 20MPa, sintering at 1000 ℃ for 15 hours, slowly cooling at 10 ℃/min, and rapidly transferring to an argon atmosphere glove box for storage. NaNi 1/2 Mn 1/2 O 2 The XRD pattern of (2) is shown in fig. 1. The results showed that O3-NaNi 1/2 Mn 1/2 O 2 Belongs to a hexagonal system.
Preparation of O3-NaNi 1/2 Mn 1/2 O 2 Electrode sheet of active material: composition of positive electrode of sodium ion battery (based on the mass fraction of positive electrode material being 100%): 80% NaNi 1/2 Mn 1/2 O 2 10% of conductive carbon black and 10% of polyvinylidene fluoride. The counter electrode of the sodium ion battery is a metal sodium sheet. The solvent of the electrolyte is as follows: propylene carbonate. The electrolyte salt is as follows: sodium perchlorate, the concentration of the substances in the electrolyte is 1mol/L.
The preparation method of the battery comprises the following steps: and weighing the raw materials according to the formula of the positive electrode, grinding the active material, the conductive agent and the polyvinylidene fluoride of the positive electrode, uniformly dispersing the ground active material, the conductive agent and the polyvinylidene fluoride in N-methyl-2-pyrrolidone (NMP) solution to prepare mixed slurry of the positive electrode, coating the slurry on aluminum foil of a current collector of the positive electrode, drying the aluminum foil in a blast drying box at 80 ℃ for 10 hours, and slicing the aluminum foil to obtain the positive electrode sheet.
Preparation of electrolyte: 1.6795g of sodium perchlorate and 10mL of propylene carbonate were weighed by an electronic balance in a glove box filled with high-purity argon, stirred uniformly and then allowed to stand for 12 hours to prepare an electrolyte. The sodium sheet, electrolyte and positive electrode sheet of the sodium ion battery prepared as described above and other necessary battery components, for example, separator and casing, etc., are assembled into a CR2032 type coin battery. The battery prepared in this example was subjected to a charge-discharge capacity test: and at normal temperature, constant-current charge and discharge tests are carried out by using a Land CT2001A battery test system, wherein the test voltage interval is 1.5-4.0V. FIG. 7 is NaNi 1/2 Mn 1/2 O 2 The current density of the front two circles of constant current charge-discharge curves of the electrode is 50mA/g, and the reversible specific capacity is 141.2mAh/g. Comparative example 2:
the embodiment synthesizes a positive electrode material and examines the performance of the sodium ion battery, and the positive electrode active material is oxide positive electrode material NaNi 0.4 Zn 0.1 Mn 0.5 O 2 The electrolyte system is an ester electrolyte.
The NaNi 0.4 Zn 0.1 Mn 0.5 O 2 The detailed synthesis method comprises the following steps:
by adopting a sol-gel method, firstly, uniformly mixing 2.2mmol of sodium acetate, 0.8mmol of nickel acetate, 0.2mmol of zinc acetate and 1mmol of manganese acetate, then placing the mixture in 100mL of deionized water, heating to 100 ℃ under the stirring condition of 400r/min, heating and evaporating, drying the evaporated gel sample in a blast oven at 100 ℃ for 10 hours, and presintering at 400 ℃ for 6 hours. Grinding a dried sample, tabletting under 20MPa, sintering at 850 ℃ for 10-15h, slowly cooling at 5-10 ℃/min, and rapidly transferring to an argon atmosphere glove box for storage. NaNi 0.4 Zn 0.1 Mn 0.5 O 2 The XRD pattern of (2) is shown in figure 2Shown. The results showed that O3-NaNi 0.4 Zn 0.1 Mn 0.5 O 2 Belongs to a hexagonal system.
Preparation of O3-NaNi 0.4 Zn 0.1 Mn 0.5 O 2 Electrode sheet of active material: composition of positive electrode of sodium ion battery (based on the mass fraction of positive electrode material being 100%): 90% NaNi 0.4 Zn 0.1 Mn 0.5 O 2 5% of conductive carbon black and 5% of polyvinylidene fluoride. The counter electrode of the sodium ion battery is a metal sodium sheet. The solvent of the electrolyte is as follows: propylene carbonate. The electrolyte salt is as follows: sodium hexafluorophosphate, the concentration of the substance in the electrolyte was 1.0mol/L.
The preparation method of the battery comprises the following steps: weighing the raw materials according to the formula of the positive electrode, mixing a positive electrode material and a conductive agent, grinding polyvinylidene fluoride, uniformly dispersing in an N-methyl-2-pyrrolidone (NMP) solution to prepare a mixed slurry of the positive electrode, coating the slurry on an aluminum foil of a current collector of the positive electrode, drying for 10 hours at 80 ℃ in a blast drying box, and slicing to obtain a positive electrode plate.
Preparation of electrolyte: 1.6795g of sodium hexafluorophosphate and 10mL of propylene carbonate were weighed by an electronic balance in a glove box filled with high-purity argon, stirred uniformly, and then allowed to stand for 12 hours to prepare an electrolyte. The sodium sheet, electrolyte and positive electrode sheet of the sodium ion battery prepared as described above and other necessary battery components, for example, separator and casing, etc., are assembled into a CR2032 type coin battery. The battery prepared in this example was subjected to a charge-discharge capacity test: and at normal temperature, constant-current charge and discharge tests are carried out by using a Land CT2001A battery test system, wherein the test voltage interval is 1.5-4.0V. FIG. 8 is NaNi 0.4 Zn 0.1 Mn 0.5 O 2 The current density is 50mA/g, and the reversible specific capacity reaches 125.8mAh/g.
Example 3:
this example synthesizes a positive electrode material of the present invention and examines the performance of sodium ion batteries, and the positive electrode active material is oxide positive electrode material NaNi 0.5-x Zn x Mn 0.5-y Zr y O 2 The electrolyte system is an ester electrolyte.
The O3-NaNi 0.5-x Zn x Mn 0.5-y Zr y O 2 (x=0.1, y=0.02) the detailed synthesis method is:
2.2mmol of sodium acetate, 0.8mmol of nickel acetate, 0.96mmol of manganese acetate, 0.2mmol of zinc acetate and 0.04mmol of zirconium acetate are uniformly mixed and placed in 100mL of deionized water, the mixture is heated to 100 ℃ under the stirring condition of 400r/min and evaporated to dryness, a dried gel sample is dried for 10 hours at 100 ℃ in a blast oven, presintered for 6 hours at 400 ℃, the dried sample is taken and ground, tabletting is carried out under the pressure of 20MPa, sintering is carried out for 12 hours at 800 ℃, and the mixture is quickly transferred to an argon atmosphere glove box for storage after being slowly cooled at 5 ℃/min. NaNi under the protection of inert gas atmosphere 0.5-x Zn x Mn 0.5-y Zr y O 2 The XRD pattern of the active material is shown in FIG. 3. The crystal structure belongs to a hexagonal system. Samples sintered at 850 ℃ for 12 hours were slowly cooled at 5-10 ℃/min and then exposed to air for one week. FIG. 4XRD of O3-NaNi 0.5-x Zn x Mn 0.5-y Zr y O 2 Belongs to a hexagonal system. The crystal structure of the material can be kept stable after the material is exposed in the air for a week, and the material belongs to a hexagonal system.
Prepared O3-NaNi 0.5-x Zn x Mn 0.5-y Zr y O 2 (x=0.1, y=0.02) electrode sheet of active material: composition of positive electrode material of sodium ion battery (based on the positive electrode material mass fraction of 100%): 60% of O3-NaNi 0.5-x Zn x Mn 0.5- y Zr y O 2 20% of conductive carbon black and 20% of polyvinylidene fluoride. The counter electrode of the sodium ion battery is sodium metal. The solvent of the electrolyte is as follows: propylene carbonate. The electrolyte salt is as follows: sodium hexafluorophosphate, the concentration of the substance in the electrolyte was 0.1mol/L.
The preparation method of the battery comprises the following steps: weighing raw materials according to the formula of the positive electrode material, mixing the raw materials of the positive electrode material and the conductive agent, grinding polyvinylidene fluoride, uniformly dispersing in N-methyl-2-pyrrolidone (NMP) solution to prepare mixed slurry of the positive electrode, coating the slurry on a positive electrode current collector aluminum foil, drying for 10 hours at 80 ℃ in a vacuum drying box, and slicing to obtain the positive electrode plate.
Preparation of electrolyte: 0.1679g of sodium hexafluorophosphate and 10mL of propylene carbonate were weighed by an electronic balance in a glove box filled with high-purity argon, stirred uniformly, and then allowed to stand for 12 hours to prepare an electrolyte. The sodium sheet, electrolyte and positive electrode sheet of the sodium ion battery prepared as described above and other necessary battery components, for example, separator and casing, etc., are assembled into a CR2032 type coin battery. The battery prepared in this example was subjected to a charge-discharge capacity test: and at normal temperature, constant-current charge and discharge tests are carried out by using a Land CT2001A battery test system, wherein the test voltage interval is 1.5-4.0V and 2.0-4.0V. FIG. 9 is NaNi 0.5- x Zn x Mn 0.5-y Zr y O 2 The electrode plate charge-discharge curve graph has a current density of 50mA/g, a test voltage interval of 1.5-4.0V and a reversible specific capacity of 123.9mAh/g, and shows excellent reversible capacity. FIG. 10 is a graph showing the cycle of the sodium ion battery obtained in example 3 (current density: 100mA/g voltage interval 2.0 to 4.0V electrolyte: 1.0mol/L sodium hexafluorophosphate dissolved in propylene carbonate), and the test result shows that: the battery had a capacity retention of 83.3% after 300 cycles under the above test conditions, and had excellent cycle stability. Meanwhile, after 300 turns, the average discharge voltage was changed from 3.04V to 2.94V only, and the discharge voltage remained stable with the change of the number of the circulation turns.
Example 4:
this example synthesizes a positive electrode material of the present invention and examines the performance of sodium ion batteries, and the positive electrode active material is oxide positive electrode material NaNi 0.5-x Zn x Mn 0.5-y Zr y O 2 The electrolyte system is an ether electrolyte.
The O3-NaNi 0.5-x Zn x Mn 0.5-y Zr y O 2 (x=0.1, y=0.02) the detailed synthesis method is:
by sol-gel method, firstly, uniformly mixing 2.2mmol of sodium acetate, 0.8mmol of nickel acetate, 0.96mmol of manganese acetate, 0.2mmol of zinc acetate and 0.04mmol of zirconium acetate, then placing into 100mL of deionized water, heating to 100 ℃ under the stirring condition of 400r/min, addingAnd (3) carrying out heat evaporation, namely drying the evaporated gel sample in a forced air oven at 100 ℃ for 10 hours, presintering at 400 ℃ for 6 hours, taking and grinding the dried sample, tabletting at 20MPa, sintering at 850 ℃ for 12 hours, slowly cooling, and rapidly transferring to an argon atmosphere glove box for storage. NaNi 0.5-x Zn x Mn 0.5-y Zr y O 2 The XRD pattern of (2) is shown in fig. 3.
Prepared O3-NaNi 0.5-x Zn x Mn 0.5-y Zr y O 2 Electrode sheet of active material: composition of positive electrode of sodium ion battery (based on 100% of positive electrode material mass percent): 80% of O3-NaNi 0.5-x Zn x Mn 0.5-y Zr y O 2 10% of conductive carbon black and 10% of polyvinylidene fluoride. The counter electrode of the sodium ion battery is sodium metal. The solvent of the electrolyte is diethylene glycol dimethyl ether, and the electrolyte salt is as follows: sodium hexafluorophosphate, the concentration of the substance in the electrolyte was 1.0mol/L.
The preparation method of the battery comprises the following steps: weighing raw materials according to the formula of the positive electrode material, mixing the raw materials of the positive electrode material and the conductive agent, grinding polyvinylidene fluoride, uniformly dispersing in N-methyl-2-pyrrolidone (NMP) solution to prepare mixed slurry of the positive electrode, coating the slurry on a positive electrode current collector aluminum foil, drying for 10 hours at 80 ℃ in a vacuum drying box, and slicing to obtain the positive electrode plate.
Preparation of electrolyte: 1.6795g of sodium hexafluorophosphate and 10mL of diethylene glycol dimethyl ether are weighed by an electronic balance in a glove box filled with high-purity argon, stirred uniformly and then left to stand for 12 hours to prepare an electrolyte. The sodium sheet, electrolyte and positive electrode sheet of the sodium ion battery prepared as described above and other necessary battery components, for example, separator and casing, etc., are assembled into a CR2032 type coin battery. The battery prepared in this example was subjected to a charge-discharge capacity test: and at normal temperature, performing constant-current charge and discharge test by using a Land CT2001A battery test system, wherein the test voltage interval is 2.0-4.0V. FIG. 11 is NaNi 0.5-x Zn x Mn 0.5-y Zr y O 2 And the current density is 50mA/g, and the reversible specific capacity is 127.5mAh/g.
Example 5:
the embodiment synthesizes a positive electrode material of the invention, wherein the positive electrode active material is oxide positive electrode material NaNi 0.5-x Zn x Mn 0.5-y Zr y O 2 。
The O3-NaNi 0.5-x Zn x Mn 0.5-y Zr y O 2 (x=0.05, y=0.05) the detailed synthesis method is:
2.2mmol of sodium acetate, 0.9mmol of nickel acetate, 0.9mmol of manganese acetate, 0.1mmol of zinc acetate and 0.1mmol of zirconium acetate are uniformly mixed and placed in 100mL of deionized water, the mixture is heated to 100 ℃ under the stirring condition of 400r/min and evaporated to dryness, a dried gel sample is dried for 10 hours at 100 ℃ in a blast oven, presintered for 6 hours at 400 ℃, the dried sample is taken and ground, tabletting is carried out under the pressure of 20MPa, sintering is carried out for 12 hours at the temperature of 850 ℃, and the mixture is slowly cooled and then is rapidly transferred to an argon atmosphere glove box for storage. NaNi 0.5-x Zn x Mn 0.5-y Zr y O 2 The XRD pattern of (2) is shown in fig. 5.
Example 6:
the embodiment synthesizes a positive electrode material of the invention, wherein the positive electrode active material is oxide positive electrode material NaNi 0.5-x Zn x Mn 0.5-y Zr y O 2 。
The O3-NaNi 0.5-x Zn x Mn 0.5-y Zr y O 2 (x=0.10, y=0.05) the detailed synthesis method is:
2.2mmol of sodium acetate, 0.8mmol of nickel acetate, 0.9mmol of manganese acetate, 0.2mmol of zinc acetate and 0.1mmol of zirconium acetate are uniformly mixed and placed in 100mL of deionized water, the mixture is heated to 100 ℃ under the stirring condition of 400r/min and evaporated to dryness, a dried gel sample is dried for 10 hours at 100 ℃ in a blast oven, presintered for 6 hours at 400 ℃, the dried sample is taken and ground, tabletting is carried out under the pressure of 20MPa, sintering is carried out for 12 hours at the temperature of 850 ℃, and the mixture is slowly cooled and then is rapidly transferred to an argon atmosphere glove box for storage. NaNi 0.5-x Zn x Mn 0.5-y Zr y O 2 The XRD pattern of (2) is shown in fig. 6.
Claims (8)
1. The preparation method of the sodium ion battery anode material with stable air, high voltage and long cycle life is characterized by comprising the following steps:
(1) Mixing a sodium source, a nickel source, a manganese source, a zinc source and a zirconium source according to a stoichiometric ratio by a sol-gel method, and drying to obtain a precursor;
(2) High-temperature presintering, namely presintering the precursor obtained in the step (1) at high temperature; the presintering temperature is 400-600 ℃, the calcining atmosphere is air, nitrogen or oxygen, and the calcining time is 4-6h;
(3) Calcining at high temperature, namely calcining the material obtained in the step (2) at high temperature, and slowly cooling to obtain the air-stable, high-voltage and long-cycle-life sodium ion battery anode material; the high-temperature calcination temperature is 800-1200 ℃, the calcination atmosphere is air, nitrogen or oxygen, the heat treatment time is 10-15h, and the slow cooling rate is 5-10 ℃/min.
2. The method of claim 1, wherein in step (1), the sodium source is sodium acetate or sodium nitrate; the nickel source is nickel acetate or nickel nitrate; the manganese source is manganese acetate or manganese nitrate; the zinc source is zinc acetate or zinc nitrate; the zirconium source is zirconium acetate or zirconium nitrate.
3. An air-stable, high-voltage and long-cycle life sodium ion battery positive electrode material prepared by the method of claim 1 or 2, which has a chemical formula of O3-NaNi 0.5-x Zn x Mn 0.5-y Zr y O 2 X is more than 0 and less than or equal to 0.1, y is more than 0 and less than or equal to 0.05, the space group is R-3m, the arrangement mode of the transition metal layer is ABCABC, and the transition metal layers at the same positions of Zn and Zr elements are arranged in disorder.
4. Use of the air-stable, high-voltage and long-cycle life sodium-ion battery positive electrode material of claim 3 in the preparation of a sodium-ion battery.
5. According to claim4, wherein the positive electrode of the sodium ion battery comprises the following components in percentage by mass: 60 to 90 percent of the positive electrode material O3-NaNi of claim 3 0.5-x Zn x Mn 0.5-y Zr y O 2 X is more than 0 and less than or equal to 0.1, y is more than 0 and less than or equal to 0.05,5 to 20 percent of conductive carbon black and 5 to 20 percent of polyvinylidene fluoride.
6. The use according to claim 4, wherein the organic solvent in the sodium ion battery electrolyte is any one of propylene carbonate or diethylene glycol dimethyl ether or any combination thereof.
7. The use according to claim 4, wherein the sodium salt in the electrolyte of the sodium ion battery is any one of sodium hexafluorophosphate or sodium perchlorate or any combination thereof.
8. The method according to claim 4, wherein the concentration of sodium salt in the electrolyte is 0.1mol/L to 1mol/L.
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