CN116314739B - Manganese-based layered oxide positive electrode material and preparation method and application thereof - Google Patents
Manganese-based layered oxide positive electrode material and preparation method and application thereof Download PDFInfo
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- CN116314739B CN116314739B CN202310384516.XA CN202310384516A CN116314739B CN 116314739 B CN116314739 B CN 116314739B CN 202310384516 A CN202310384516 A CN 202310384516A CN 116314739 B CN116314739 B CN 116314739B
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- 239000011572 manganese Substances 0.000 title claims abstract description 71
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 38
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011734 sodium Substances 0.000 claims abstract description 50
- 239000010406 cathode material Substances 0.000 claims abstract description 12
- 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 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 229910001415 sodium ion Inorganic materials 0.000 claims description 16
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 8
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 4
- -1 sodium hexafluorophosphate Chemical compound 0.000 claims description 4
- 239000002904 solvent Substances 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
- 239000000203 mixture Substances 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- GFORUURFPDRRRJ-UHFFFAOYSA-N [Na].[Mn] Chemical class [Na].[Mn] GFORUURFPDRRRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099594 manganese dioxide Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 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
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(iii) oxide Chemical compound O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 229910052749 magnesium Inorganic materials 0.000 abstract description 2
- 230000002441 reversible effect Effects 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 description 35
- 238000012360 testing method Methods 0.000 description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000011268 mixed slurry Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- XSBJUSIOTXTIPN-UHFFFAOYSA-N aluminum platinum Chemical compound [Al].[Pt] XSBJUSIOTXTIPN-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910003870 O—Li Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/006—Compounds containing, besides manganese, two or more other elements, with the exception of oxygen or hydrogen
-
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
-
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
-
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/20—Two-dimensional structures
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of new energy materials and electrochemistry, and discloses a manganese-based layered oxide positive electrode material, a preparation method and application thereof. The molecular formula of the manganese-based layered oxide positive electrode material is Na x Li y M 1‑y‑z Mn z O 2 Wherein 0.5<x≤1，0≤y≤0.2，0.5≤zLess than or equal to 1, M is at least one of Mg, zn, al, ti, fe, co, ni, cu. The preparation method of the material comprises the steps of ball milling a sodium source, a lithium source, an M source and a manganese source, uniformly mixing, and calcining at a high temperature to obtain the cathode material. The manganese-based layered oxide positive electrode material has the advantages of simple preparation method and wide sources of raw materials, and shows 210 mAh g under the voltage window of 0.05C multiplying power and 1.5-4.6V ‑1 The reversible specific capacity has excellent cycle performance and excellent air and water stability.
Description
Technical Field
The invention belongs to the technical field of new energy materials and electrochemistry, and particularly relates to a manganese-based layered oxide positive electrode material, a preparation method and application thereof.
Background
In recent years, although lithium ion batteries have occupied a global mass market for electrochemical energy storage, the scarcity and increasing cost of lithium resources make sodium ion batteries with abundant resource reserves and low cost become the most potential alternatives to the lithium ion batteriesAnd (5) substituting products. The development of new sodium-ion battery positive electrode materials is becoming particularly important for the rapid sodium-ion battery technology now developing, as positive electrode materials are critical in determining the energy density and cost of the battery. Thus, sodium ion battery technology still has an urgent need for high capacity and long life positive electrode materials to meet the large-scale application thereof. Layered sodium-based transition metal oxide (Na x TMO 2 ,0<x is less than or equal to 1) has great application prospect due to the unique intercalation mechanism, higher theoretical capacity and flexible composition.
Regarding the energy density, the Li or Mg ions replace transition metal ions, so that the anion redox reaction can be induced in the charging and discharging process of the material to realize high voltage and high capacity, and the energy density of the positive electrode material is further improved. However, for P2-phase manganese-based layered oxides, the anionic redox reaction is usually accompanied by a high voltage region [ ]>4 Vvs. Na + Na) and low voltage region<2 Vvs. Na + Phase changes of/Na) (P2-O2/OP 4 and P2-P' 2) and long-term and local structure changes of lattice oxygen precipitation, so that anisotropic strain and huge unit cell volume changes of the material occur, further leading to rapid decay of battery performance. Therefore, how to achieve a balance between specific capacity and structural stability, and even to break this balance, i.e. to achieve both high capacity and low strain, is a great challenge in the technology of positive electrode materials for sodium-ion batteries.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a manganese-based layered oxide positive electrode material, a preparation method and application thereof, and specifically adopts the following technical scheme:
the invention provides a manganese-based layered oxide positive electrode material, the molecular formula of which is Na x Li y M 1-y-z Mn z O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is at least one of Mg, zn, al, ti, fe, co, ni, cu; 0.5<x≤ 1，0 ≤y≤ 0.2，0.5 ≤z≤ 1。
Na in the invention x Li y M 1-y-z Mn z O 2 The positive electrode material is P2-phase lithium double-site substituted sodium-manganese-based layered oxide, is of a single crystal structure, has a hexagonal sheet shape, and has a particle size range of 2-4 mu m. The prepared manganese-based layered oxide positive electrode material is pure phase, belongs to a hexagonal system and has a space group ofP6 3 /mmc. The doping site of Li of the positive electrode material passes through solid nuclear magnetism 7 Li MAS NMR), it is known that Li is simultaneously substituted at the transition metal site and the alkali metal site, the Li of the transition metal site forms a localized Na-O-Li electron configuration, more anionic redox reactions are excited, and the specific capacity of the material is improved; meanwhile, li at the alkali metal site plays a role of a pillar to inhibit phase transition of P2-OP4 and P2-P'2 in the charge and discharge process of the material. The material has high energy density and high electrochemical stability, and simultaneously has excellent stability to air and water, thus being suitable for large-scale industrialized production.
More preferably, the manganese-based layered oxide cathode material is Na 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 . Na produced in the present invention 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 The material has higher specific capacity and lower unit cell volume change when sodium is removed.
The invention also provides a preparation method of the manganese-based layered oxide cathode material, which comprises the following steps: ball milling is carried out on a sodium source, a lithium source, an M source and a manganese source, and the mixture is uniformly mixed; and reacting at 600-1200 ℃ and 6-h-24-h, and cooling to obtain the manganese-based layered oxide cathode material. Preferably, the conditions of ball milling: the rotating speed is 100 r/min-500r/min, and the time is 4 h-8 h. Under the conditions of the ball milling rotating speed and time, the source materials can be fully and uniformly mixed, and the generation of impurity phases in the subsequent synthesis process is avoided. More preferably, the heating temperature is 800 ℃ to 1000 ℃ and the heating time is 12 h to 24 h, under the heating temperature and heating time conditions, the material is more likely to form a pure P2 phase structure. The sodium source is at least one of sodium carbonate, sodium acetate, sodium nitrate, sodium fluoride and sodium chloride. The lithium source is at least one of lithium carbonate, lithium acetate, lithium nitrate, lithium fluoride, lithium chloride and lithium hydroxide.
Preferably, the M source is a Mg source. When Mg is introduced, not only can the anionic oxidation-reduction reaction be excited, but also the superlattice structure of the material can be stabilized, so that the electrochemical performance of the material is improved.
Preferably, the manganese source is at least one of manganese monoxide, manganese sesquioxide, manganese dioxide, manganese carbonate, manganese acetate, manganese chloride, manganese sulfate, and manganese nitrate.
The invention also provides a manganese-based layered oxide positive electrode material prepared by the method.
The invention also provides application of the manganese-based layered oxide as a positive electrode material of a sodium ion battery, and the sodium ion battery prepared by taking the manganese-based layered oxide as the positive electrode material, taking a carbon material or metal sodium as a negative electrode material, taking at least one of sodium hexafluorophosphate, sodium perchlorate and sodium trifluoromethylsulfonate as electrolyte sodium salt, and taking at least one of Propylene Carbonate (PC), ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and fluoroethylene carbonate (FEC) as electrolyte solvent. Li double-site substituted Na prepared in the invention x Li y M 1-y-z Mn z O 2 The positive electrode material is assembled into a sodium ion battery, and the sodium ion battery shows 210 mAh g under the conditions of 0.05C multiplying power and 1.5V-4.6V voltage window -1 The reversible specific capacity and the better cycle performance.
The beneficial effects of the invention are as follows: the manganese-based layered oxide anode material prepared by the method adopts a lithium double-site substitution mode, provides high energy density and high electrochemical stability, and simultaneously shows excellent stability to air and water; the preparation method is simple and easy to implement, has low price of the used raw materials, and is suitable for large-scale industrialized production.
Drawings
FIG. 1 shows Na synthesized in example 1 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 An XRD pattern of (b);
FIG. 2 shows the Na synthesized in example 2 0.7 Mg 0.15 Mn 0.85 O 2 Is of the XRD pattern of (C)；
FIG. 3 shows the Na synthesized in example 1 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 NPD map of (a);
FIG. 4 shows the Na synthesized in example 2 0.7 Mg 0.15 Mn 0.85 O 2 NPD map of (a);
FIG. 5 shows the Na synthesized in example 1 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 SEM images of (a);
FIG. 6 shows the Na synthesized in example 2 0.7 Mg 0.15 Mn 0.85 O 2 SEM images of (a);
FIG. 7 shows the Na synthesized in example 1 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 A kind of electronic device 7 Li MAS NMR map;
FIG. 8 shows the Na synthesized in example 1 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 The first week charge and discharge curve of (rate: 0.05C, voltage window: 1.5V-4.6V);
FIG. 9 shows the Na synthesized in example 2 0.7 Mg 0.15 Mn 0.85 O 2 The first week charge and discharge curve of (rate: 0.05C, voltage window: 1.5V-4.6V);
FIG. 10 shows the Na synthesized in example 1 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 And Na synthesized in example 2 0.7 Mg 0.15 Mn 0.85 O 2 Cycle performance graph (magnification: 0.5C, voltage window: 1.5-4.6V);
FIG. 11 shows the Na synthesized in example 1 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 A cell volume change map during charge and discharge;
FIG. 12 shows the Na synthesized in example 1 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 XRD pattern after air exposure and water treatment.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described below with reference to the embodiments and the drawings to fully understand the objects, aspects and effects of the present invention. It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other.
Example 1
A manganese-based layered oxide positive electrode material has a molecular formula of Na 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 The synthesis method comprises the following steps:
weighing 2.16 g sodium carbonate (2% excess), 0.22 g lithium carbonate (2% excess), 0.34 g magnesium oxide and 3.73 g manganese dioxide according to the stoichiometric ratio in the molecular formula, uniformly mixing the raw materials, putting into a ball mill, ball-milling at a rotating speed of 400r/min for 8 h, and further uniformly mixing to obtain a precursor. Taking a proper amount of precursor, tabletting under the pressure of 10 MPa, calcining the precursor at 1000 ℃ for 12 h, and naturally cooling the material to obtain the lithium double-site substituted sodium ion battery anode material Na 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 。
Example 2
A manganese-based layered oxide positive electrode material has a molecular formula of Na 0.7 Mg 0.15 Mn 0.85 O 2 The synthesis method comprises the following steps:
weighing 2.16 g sodium carbonate (2% excess), 0.34 g magnesium oxide and 4.26 g manganese dioxide according to the stoichiometric ratio in the molecular formula, uniformly mixing the raw materials, putting the raw materials into a ball mill, ball-milling the raw materials at a rotational speed of 400r/min for 4 h, and further uniformly mixing the raw materials to obtain the precursor. Taking a proper amount of precursor, tabletting under the pressure of 10 MPa, calcining the precursor at 900 ℃ to 15 h, and naturally cooling the material to obtain the Na-ion battery anode material 0.7 Mg 0.15 Mn 0.85 O 2 。
Example 3
This example characterizes the manganese-based layered oxide cathode materials prepared in examples 1 and 2.
The material obtained in example 1 is shown in XRD and NPD of FIGS. 1 and 3Prepared Na 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 Is P2 phase pure phase, belongs to hexagonal crystal system, and has space group ofP6 3 /mmc. As shown in the SEM image of fig. 5, the sample is of a single crystal structure, the particle morphology is of a hexagonal sheet shape, and the particle size range is 2 mu m-4 mu m. As shown in figure 7 of the drawings, 7 the Li MAS NMR results showed that Li in the sample was substituted at both the transition metal site and the alkali metal site.
The material obtained in example 2 is shown in XRD and NPD of FIGS. 2 and 4, and Na is prepared 0.7 Mg 0.15 Mn 0.85 O 2 Is P2 phase pure phase, belongs to hexagonal crystal system, and has space group ofP6 3 /mmc. As shown in the SEM image of fig. 6, the sample is of a single crystal structure, the particle morphology is of a hexagonal sheet shape, and the particle size range is 2 mu m-4 mu m.
Example 4
This example the manganese-based layered oxide cathode materials prepared in examples 1 and 2 were assembled into sodium-ion batteries and subjected to battery performance tests according to the following methods.
1. Na obtained in example 1 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 Testing of cathode materials
(1) Preparation of positive electrode material pole piece
Na is mixed with 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 The positive electrode material, conductive carbon black (Super P) and a binder polyvinylidene fluoride (PVDF) are ground according to the mass ratio of 8:1:1 and uniformly dispersed in an N-methyl pyrrolidone (NMP) solvent, so as to obtain mixed slurry of the positive electrode material. The mixed slurry is uniformly coated on aluminum platinum of a positive electrode current collector, and after being dried overnight in vacuum, the positive electrode plate is cut into a round positive electrode plate with the diameter of 10 mm.
(2) Assembly of sodium ion batteries
The positive electrode sheet was used as a positive electrode, and the sodium sheet was used as a negative electrode, and 1M sodium hexafluorophosphate (NaPF) 6 ) Propylene Carbonate (PC) +2 wt% fluoroethylene carbonate (DEC) is used as electrolyte, and other necessary battery components (diaphragm, housing, etc.) are arranged in a hand filled with high-purity argon gasAnd assembling the button cell in the sleeve box.
(3) Performance test of a battery
The battery assembled by the method is subjected to charge and discharge performance test in a battery test system, wherein the test temperature is 25 ℃, and the voltage window is sequentially 1.5-V-4.6-V. The test results show that the implementation provides Na 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 The first charge capacity of the positive electrode material is 197 mAh g under the multiplying power of 0.05C -1 The first discharge capacity is 266 mAh g -1 And the charge curve exhibited a single voltage plateau around 4.2V, a characteristic plateau of the oxyanion reaction, indicating that charge capacity was contributed substantially by oxygen oxidation, as shown in fig. 8. As shown in fig. 10, na at 0.5C magnification 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 The positive electrode material has good cycle performance, and the capacity retention rate after 50 weeks of cycle is 80.9%.
(4) In situ XRD testing of positive electrode materials
The positive electrode plate tested by in-situ XRD is manufactured by the method, the current collector is changed into ultrathin aluminum platinum, and the test battery adopts a die battery with a beryllium plate window. In-situ charge and discharge processes of the die battery are carried out in-situ XRD test, the test temperature is 25 ℃ in the two-week charge and first-week discharge process, the multiplying power is 0.05 and C, and the voltage window is 1.5V-4.6 and V. The in situ XRD results were refined to give unit cell volume parameters, the results are shown in FIG. 11. The test results show Na 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 The change rate of the unit cell volume of the positive electrode material in the whole charge and discharge process is only 1.2%, and the low lattice strain characteristic of the positive electrode material is proved.
(5) Testing of air and Water stability of Positive electrode Material
For Na after 180 days of air exposure 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 Na after water treatment 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 XRD testing was performed and the results are shown in fig. 11. The test results show that the P2 phase can be well maintained, and the good air and water resistance of the catalyst is provedIs stable.
2. Na produced in example 2 0.7 Mg 0.15 Mn 0.85 O 2 Testing of cathode materials
(1) Preparation of positive electrode material pole piece
Na is mixed with 0.7 Mg 0.15 Mn 0.85 O 2 The positive electrode material, the conductive carbon black (Super P) and the binder polyvinylidene fluoride (PVDF) are ground according to the mass ratio of 8:1:1 and uniformly dispersed in the following componentsN-methyl pyrrolidone (NMP) solvent to obtain a mixed slurry of positive electrode material. The mixed slurry is uniformly coated on aluminum platinum of a positive electrode current collector, and after being dried overnight in vacuum, the positive electrode plate is cut into a round positive electrode plate with the diameter of 10 mm.
(2) Assembly of sodium ion batteries
The positive electrode sheet was used as a positive electrode, and the sodium sheet was used as a negative electrode, and 1M sodium hexafluorophosphate (NaPF) 6 ) Propylene Carbonate (PC) +2 wt% fluoroethylene carbonate (DEC) is used as an electrolyte, and other necessary battery components (separator, housing, etc.) are assembled into a button cell in a glove box filled with high purity argon gas.
(3) Performance test of a battery
The battery assembled by the method is subjected to charge-discharge performance test in a blue battery test system, the test temperature is 25 ℃, and the voltage window is sequentially 1.5-V-4.6-V. The test results show that the implementation provides Na 0.7 Mg 0.15 Mn 0.85 O 2 The first charge capacity of the positive electrode material is 140 mAh g under the multiplying power of 0.05C -1 The first discharge capacity was 212 mAh g -1 The charge curve first appears ramp-like, and then around 4.35. 4.35V a charge voltage plateau appears, a characteristic plateau of the oxyanion reaction, indicating that charge capacity is partially contributed by oxygen oxidation (as shown in fig. 9). As shown in fig. 10, na at 0.5C magnification 0.7 Mg 0.15 Mn 0.85 O 2 The capacity retention of the positive electrode material after 50 weeks of cycling was 57.1%.
While the present invention has been described in considerable detail and with particularity with respect to several described embodiments, it is not intended to be limited to any such detail or embodiments or any particular embodiment, but is to be construed as providing broad interpretation of such claims by reference to the appended claims in view of the prior art so as to effectively encompass the intended scope of the invention. Furthermore, the foregoing description of the invention has been presented in its embodiments contemplated by the inventors for the purpose of providing a useful description, and for the purposes of providing a non-essential modification of the invention that may not be presently contemplated, may represent an equivalent modification of the invention.
Claims (4)
1. A manganese-based layered oxide cathode material is characterized in that the manganese-based layered oxide cathode material is Na 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The preparation method of the manganese-based layered oxide cathode material comprises the following steps:
ball milling is carried out on a sodium source, a lithium source, an Mg source and a manganese source, and the mixture is uniformly mixed; heating 12 h-24 h at 800-1000 ℃ and cooling to obtain the manganese-based layered oxide anode material; the ball milling conditions include: the rotating speed is 100 r/min-500r/min, and the time is 4 h-8 h;
the Na is 0.7 Li 0.1 Mg 0.15 Mn 0.75 O 2 The P2-phase lithium double-site-substituted sodium-manganese-based layered oxide has a single crystal structure, a hexagonal flaky shape and a particle size range of 2-4 mu m; wherein Li is substituted at both the transition metal site and the alkali metal site.
2. The manganese-based layered oxide cathode material according to claim 1, wherein the manganese source is at least one of manganese monoxide, manganese trioxide, manganese dioxide, manganese carbonate, manganese acetate, manganese chloride, manganese sulfate, and manganese nitrate.
3. Use of the manganese-based layered oxide of claim 1 as a positive electrode material for sodium ion batteries.
4. A sodium ion battery, wherein the manganese-based layered oxide according to claim 1 is used as a positive electrode material, the carbon material or the metal sodium is used as a negative electrode material, at least one of sodium hexafluorophosphate, sodium perchlorate and sodium trifluoromethane sulfonate is used as an electrolyte sodium salt, and at least one of Propylene Carbonate (PC), ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and fluoroethylene carbonate (FEC) is used as an electrolyte solvent.
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