CN116425220A - Inhibition of Mn 3+ Preparation method, product and application of sodium ion battery ternary positive electrode material with Jahn-Teller effect - Google Patents
Inhibition of Mn 3+ Preparation method, product and application of sodium ion battery ternary positive electrode material with Jahn-Teller effect Download PDFInfo
- Publication number
- CN116425220A CN116425220A CN202310445607.XA CN202310445607A CN116425220A CN 116425220 A CN116425220 A CN 116425220A CN 202310445607 A CN202310445607 A CN 202310445607A CN 116425220 A CN116425220 A CN 116425220A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- ion battery
- sodium ion
- electrode material
- preparation
- 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.)
- Pending
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 46
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 46
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000005536 Jahn Teller effect Effects 0.000 title claims abstract description 18
- 230000005764 inhibitory process Effects 0.000 title claims description 4
- 239000011572 manganese Substances 0.000 claims abstract description 77
- 239000000463 material Substances 0.000 claims abstract description 50
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 29
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000011734 sodium Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010405 anode material Substances 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 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 description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 229940071125 manganese acetate Drugs 0.000 claims description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 6
- 238000004146 energy storage Methods 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- -1 sodium tetrafluoroborate Chemical compound 0.000 description 3
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 2
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 2
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical compound CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 230000022131 cell cycle Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- 229910020892 NaBOB Inorganic materials 0.000 description 1
- 229910021201 NaFSI Inorganic materials 0.000 description 1
- 241001274216 Naso Species 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 1
- IKULXUCKGDPJMZ-UHFFFAOYSA-N sodium manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Na+] IKULXUCKGDPJMZ-UHFFFAOYSA-N 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- 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
- H01M4/362—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
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of sodium ion batteries, and in particular relates to a method for inhibiting Mn 3+ Preparation method, product and application of Jahn-Teller effect sodium ion battery ternary positive electrode material, wherein the preparation method comprises the steps of firstly mixing a Na source and a transition metal source, then sintering to obtain the sodium ion battery positive electrode material serving as a precursor, fully and uniformly mixing the precursor by adopting wet ball milling, and drying and then converting the precursorMoving the mixture into a muffle furnace, and calcining at a high temperature; and secondly, crushing the sintered sample to obtain an NFM original material, heating and stirring the NFM material and the manganese source coating agent in ethanol solution in a certain proportion until the NFM material and the manganese source coating agent are dried, and sintering the NFM original material at high temperature for a plurality of hours to obtain the NFM anode material coated with Mn in different contents. According to the invention, the anode material is coated with the manganese-rich shell layer, the residual alkali on the surface of the material is reduced, the processing performance of the material is improved, the electrochemical performance of the material is improved, and the crystal structure can be stabilized and Mn dissolution can be inhibited through a surface engineering strategy, so that the circulation stability of LMO is improved.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and in particular relates to a method for inhibiting Mn 3+ Preparation method, product and application of sodium ion battery ternary positive electrode material with Jahn-Teller effect.
Background
Sodium Ion Batteries (SIBs) are attracting attention by virtue of their low cost, high safety and the like, and can meet the worldwide demand for large-scale energy storage devices. Sodium batteries are considered to be one of the new secondary battery technologies for large-scale energy storage that can replace lithium ion batteries in the future due to the abundant and wide sources of earth sodium elements. The positive electrode material is used as an important component of the sodium ion battery, and determines the electrochemical performance of the sodium ion battery. However, due to the large radius of sodium ions, developing a cathode material that is structurally stable and has rapid sodium ion diffusion properties is one of the challenges in achieving high performance sodium ion batteries. In recent years, more and more layered positive electrode material systems are developed, and the layered positive electrode material systems show good electrochemical performance and have good application prospects for sodium ion batteries. The layered oxide has high specific capacity and is a positive electrode material of sodium ion batteries with great application potential. Transition metal oxides can be classified into tunnel oxides and layered oxides according to the structure of the material. When the sodium content in the oxide is low (x is less than 0.5), the oxide with a three-dimensional tunnel structure is formed, has unique S-shaped and pentagonal tunnels, has high stability to air and water and good rate capability, but has low first-week charge capacity and small practically usable specific capacity. When the sodium content is higher (x > 0.5), the transition metal layer is generally composed of MO octahedrons arranged on the same side mainly in a layered structure, and sodium ions are located between layers to form a layered structure which is alternately arranged. The layered oxide anode material has the advantages of simple preparation method, high specific capacity, high voltage and the like, but still has the problems of complex structural phase change, short cycle life, poor stability and the like. In the literature with article number 2095-4239 (2020) 05-1396-06, surface modification study of layered oxide cathode material of sodium ion battery is published, wherein the study comprises the steps of improving the stability in air and the cycle stability of the material and improving the application value of the material based on the existing problems of layered materials by further coating the manganese-rich shell layer. The O3 structure layered oxide material system has the advantages of high capacity, high compaction density and the like, and is regarded as the most potential anode material.
However, due to Mn 3+ The Jahn-Teller effect of the material causes the phase change of the material in the charge and discharge process, thereby reducing Na + Migration rate, and further causes particle breakage, structural defects, material amorphization, etc. during repeated charge and discharge cycles. The layered oxide has the defects of phase change, high voltage reaction with electrolyte, poor air stability and the like in charge and discharge, and restricts the large-scale commercial application of the material.
Disclosure of Invention
Compared with the prior art, the invention adopts a concentration gradient method to synthesize the ternary positive electrode material of the sodium-ion battery with the manganese-rich outer layer and the nickel-rich inner layer, so as to obtain better stability. The structure well solves the problem of poor stability of the manganese-based sodium ion battery anode material. By designing the manganese-rich shell, on one hand, the residual alkali on the surface is consumed, and sodium-deficient layered sodium-manganese oxide or manganese oxide with a tunnel structure is formed on the surface; on the other hand, mn is partially dissolved in a solid state in the sintering process, so that the surface manganese-rich layered structure material is obtained, the residual alkali of the material is comprehensively reduced, the air stability is improved, and the cycle performance of the material is improved. The material exhibits excellent electrochemical stability when used as a positive electrode material for sodium ion batteries.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
mn inhibition 3+ The preparation method of the ternary positive electrode material of the sodium ion battery with the Jahn-Teller effect comprises the following steps:
mixing a Na source with a Ti, V, cr, mn, fe, co, ni, cu, zn, li transition metal source, sintering to obtain a sodium ion battery anode material serving as a precursor, fully and uniformly mixing the precursor by adopting wet ball milling, drying, transferring into a muffle furnace, and calcining at a high temperature for NOX hours. The sintered sample is crushed to obtain NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Original material (NFM). And heating and stirring the NFM material and the manganese source coating agent in a certain proportion in ethanol solution to dryness, and sintering at a high temperature for several hours to obtain the NFM positive electrode material coated with Mn (calculated according to the mass of Mn) in different contents. And is applied to the positive electrode material of the sodium ion battery.
Preferably, the transition metal oxide is a mixture of three kinds of oxides of transition metals such as Ti, V, cr, mn, fe, co, ni, cu, zn, li.
Preferably, the Na source is one of sodium carbonate, sodium bicarbonate, sodium acetate, and sodium oxide.
Preferably, the mass ratio of the sodium source to the transition metal source is 1:1-1:3
Preferably, the calcination temperature of the precursor is 500-1000 ℃ and the sintering time is 3-8h.
Preferably, the manganese source coating agent can be one of manganese salts such as manganese acetate, manganese carbonate and manganese oxide.
Preferably, the calcination temperature is 300-600 ℃ and the sintering time is 1-3h after the NFM material and the manganese source coating agent are mixed.
Preferably, the mass ratio of the NFM material to the manganese source cladding agent is 1:1-1:5.
The invention provides a preparation method of the ternary positive electrode material of the sodium ion battery with high stability, which is prepared by any one of the methods.
The invention also provides a sodium ion battery, and the positive electrode material of the sodium ion battery is the high-stability sodium ion battery ternary positive electrode material for inhibiting the Mn < 3+ > Jahn-Teller effect.
Preferably, the electrolyte of the sodium ion battery is a mixed solution of sodium salt and any one or more of ethylene carbonate, dimethyl carbonate, ethylene carbonate, diethyl carbonate, biphenyl (BP), ethylene carbonate (VC), ethylene carbonate (VEC), fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), 1, 4-Butane Sultone (BS), 1, 3- (1-Propylene) Sultone (PST), ethylene Sulfite (ESI), ethylene Sulfate (ESA), cyclohexylbenzene (CHB), tert-butylbenzene (TBB), tert-pentylbenzene (TPB) and Ding Erqing (SN);
preferably, the sodium salt is one or a mixture of several compounds having the formula: sodium tetrafluoroborate (NaBF) 4 ) Sodium hexafluorophosphate (NaPF) 6 ) Bis-trifluoro sulfonamide (NaN (SO) 2 CF 3 ) 2 ) Sodium bis (fluorosulfonamide) (NaFSI), sodium bis (oxalato) borate (NaBOB), sodium triflate (NaSO) 3 CF 3 )；
Preferably, the operating voltage window of the sodium ion battery containing the positive electrode material is in the range of 0.9-4.0.
Compared with the prior art, the invention has the beneficial effects that,
and the anode material is coated by a manganese-rich shell layer, so that residual alkali on the surface of the material is reduced, the processing performance of the material is improved, and the electrochemical performance of the material is improved.
The average valence of Mn in the cathode material increases from 3.625 to 4 as the Mn content decreases due to Mn compensation by the Mn source coating agent. With the increase of Mn average valence state, two pairs of redox peaks in the high-voltage region gradually weaken and disappear, and the circulation stability of the layered oxide material is improved. These results are mainly due to the fact that the increase in Mn average valence effectively suppresses the Jahn-Teller effect in the local structure.
Through the strategy of surface engineering (subsequent manganese source coating agent), the crystal structure can be stabilized, mn dissolution can be inhibited, and thus the cycling stability of LMO can be improved.
The preparation method has the advantages of simple process, low cost, high production efficiency, capability of better meeting the requirements of industrial production, realization of large-scale production and great application prospect.
The preparation method is simple, high in conductivity, high in practicability and easy to popularize.
Drawings
FIG. 1 is NaNi 1/3 Fe 1/3 Mn 1/3 O 2 A positive electrode material synthesis schematic diagram;
FIG. 2 is NaNi 1/3 Fe 1/3 Mn 1/3 O 2 A schematic drawing of the planing surface of the positive electrode material;
FIG. 3 is NaNi 1/3 Fe 1/3 Mn 1/3 O 2 A scanning photograph (SEM) of the positive electrode material;
FIG. 4 is NaNi 1/3 Fe 1/3 Mn 1/3 O 2 An XRD diffraction pattern of the positive electrode material is shown schematically;
FIG. 5 is a graph of NaNi with varying manganese content 1/3 Fe 1/3 Mn 1/3 O 2 The anode material has a current density of 0.5Ag -1 The half cell cycle performance below is schematically shown.
Detailed Description
In order that the objects and advantages of the invention will become more apparent, the invention will be further described with reference to the following examples; it should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood by those skilled in the art that these embodiments are merely for explaining the technical principles of the present invention, and are not intended to limit the scope of the present invention.
It should be noted that, in the description of the present invention, terms such as "upper," "lower," "left," "right," "inner," "outer," and the like indicate directions or positional relationships based on the directions or positional relationships shown in the drawings, which are merely for convenience of description, and do not indicate or imply that the apparatus or elements must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention.
Furthermore, it should be noted that, in the description of the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention can be understood by those skilled in the art according to the specific circumstances.
Referring to FIGS. 1-5, FIG. 1 is NaNi 1/3 Fe 1/3 Mn 1/3 O 2 A positive electrode material synthesis schematic diagram; FIG. 2 is NaNi 1/ 3 Fe 1/3 Mn 1/3 O 2 A schematic drawing of the planing surface of the positive electrode material; FIG. 3 is NaNi 1/3 Fe 1/3 Mn 1/3 O 2 A scanning photograph (SEM) of the positive electrode material; FIG. 4 is NaNi 1/3 Fe 1/3 Mn 1/3 O 2 An XRD diffraction pattern of the positive electrode material is shown schematically; FIG. 5 is a graph of NaNi with varying manganese content 1/3 Fe 1/ 3 Mn 1/3 O 2 The anode material has a current density of 0.5Ag -1 The half cell cycle performance below is schematically shown.
The invention discloses a method for inhibiting Mn 3+ The preparation method of the ternary positive electrode material of the sodium ion battery with the Jahn-Teller effect comprises the following steps:
mixing a Na source and a transition metal source, sintering to obtain a sodium ion battery anode material serving as a precursor, fully and uniformly mixing the precursor by adopting wet ball milling, drying, transferring into a muffle furnace, and calcining at a high temperature;
and secondly, crushing the sintered sample to obtain an NFM original material, heating and stirring the NFM material and the manganese source coating agent in ethanol solution in a certain proportion until the NFM material and the manganese source coating agent are dried, and sintering the NFM original material at high temperature for a plurality of hours to obtain the NFM anode material coated with Mn in different contents.
Specifically, in the first step, the transition metal source is a mixture of three metal oxides in Ti, V, cr, mn, fe, co, ni, cu, zn, li.
Specifically, in the first step, the Na source is one of sodium carbonate, sodium bicarbonate, sodium acetate, and sodium oxide.
Specifically, in the first step, the mass ratio of the sodium source to the transition metal source is 1:1-1:3.
Specifically, in the first step, the calcination temperature is 500-1000 ℃ and the sintering time is 10-20h.
Specifically, in the second step, the manganese source coating agent is one of manganese salts such as manganese acetate, manganese carbonate, manganese oxide and the like.
Specifically, in the second step, the mass ratio of the NFM material to the manganese source coating agent is 1:1-1:5.
Specifically, in the second step, the calcining temperature after cladding is 600-800 degrees, and the calcining time is 1-5 hours.
The invention also discloses a ternary positive electrode material of the sodium ion battery, which can inhibit Mn according to the method 3+ The ternary positive electrode material of the sodium ion battery is prepared by a preparation method of the Jahn-Teller effect, and is characterized in that the manganese content is 10%, and the ternary positive electrode material has stable electrochemical performance.
The invention also discloses application of the ternary positive electrode material of the sodium ion battery, which is characterized by being used for preparing an energy storage battery.
Example 1:
1.5g of sodium carbonate, 0.5g of nickel oxide, 0.5g of ferric oxide and 0.1g of manganese dioxide are adopted as precursors, the precursors are fully and uniformly mixed by adopting wet ball milling, the materials are transferred into a muffle furnace after being dried, and the materials are roasted for 15 hours in an air atmosphere at 900 ℃. The sintered sample is crushed to obtain NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Raw materials.
2g of NFM material and 0.1g of manganese acetate coating agent are heated and stirred in ethanol solution until being dried, and sintered at 900 ℃ for 6 hours, so as to obtain the NFM positive electrode material with 10 percent of Mn coating content (calculated by mass of Mn).
Example 2:
1.5g of sodium carbonate, 0.5g of nickel oxide, 0.5g of ferric oxide and 0.1g of manganese dioxide are adopted as precursors, the precursors are fully and uniformly mixed by adopting wet ball milling, the materials are transferred into a muffle furnace after being dried, and the materials are roasted for 15 hours in an air atmosphere at 900 ℃. The sintered sample is crushed to obtain NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Raw materials.
2g of NFM material and 0.3g of manganese acetate coating agent are heated and stirred in ethanol solution until being dried, and sintered at 900 ℃ for 6 hours, so as to obtain the NFM positive electrode material with 20 percent of Mn coating content (calculated by mass of Mn).
Example 3:
1.5g of sodium carbonate, 0.5g of nickel oxide, 0.5g of ferric oxide and 0.1g of manganese dioxide are adopted as precursors, the precursors are fully and uniformly mixed by adopting wet ball milling, the materials are transferred into a muffle furnace after being dried, and the materials are roasted for 15 hours in an air atmosphere at 900 ℃. The sintered sample is crushed to obtain NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Raw materials.
2g of NFM material and 0.5g of manganese acetate coating agent are heated and stirred in ethanol solution until being dried, and sintered at 900 ℃ for 6 hours, so as to obtain the NFM positive electrode material with 10 percent of Mn coating content (calculated by mass of Mn).
Example 4:
1.5g of sodium carbonate, 0.5g of nickel oxide, 0.5g of ferric oxide and 0.1g of manganese dioxide are adopted as precursors, the precursors are fully and uniformly mixed by adopting wet ball milling, the materials are transferred into a muffle furnace after being dried, and the materials are roasted for 15 hours in an air atmosphere at 900 ℃. The sintered sample is crushed to obtain NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Raw materials.
2g of NFM material and 0.9g of manganese acetate coating agent are heated and stirred in ethanol solution until being dried, and sintered at 900 ℃ for 6 hours, so as to obtain the NFM positive electrode material with 50% of Mn coating content (calculated by mass of Mn).
Finally, it should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited to the above-mentioned embodiments, but may be modified or substituted for some of them by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention. While the foregoing description of the embodiments of the present invention has been presented in conjunction with the drawings, it should be understood that it is not intended to limit the scope of the invention, but rather, it is intended to cover all modifications or variations within the scope of the invention as defined by the claims of the present invention.
Claims (10)
1. Inhibition of Mn 3+ The preparation method of the ternary positive electrode material of the sodium ion battery with the Jahn-Teller effect is characterized by comprising the following steps of:
mixing a Na source and a transition metal source, sintering to obtain a sodium ion battery anode material serving as a precursor, fully and uniformly mixing the precursor by adopting wet ball milling, drying, transferring into a muffle furnace, and calcining at a high temperature;
and secondly, crushing the sintered sample to obtain an NFM original material, heating and stirring the NFM material and the manganese source coating agent in ethanol solution in a certain proportion until the NFM material and the manganese source coating agent are dried, and sintering the NFM original material at high temperature for a plurality of hours to obtain the NFM anode material coated with Mn in different contents.
2. The Mn-inhibiting composition according to claim 1 3+ The preparation method of the ternary positive electrode material of the sodium ion battery with the Jahn-Teller effect is characterized in that in the first step, the transition metal source is a mixture of three metal oxides in Ti, V, cr, mn, fe, co, ni, cu, zn, li.
3. The Mn-inhibiting composition according to claim 1 3+ JahThe preparation method of the ternary positive electrode material of the sodium ion battery with the n-Teller effect is characterized in that in the first step, the Na source is one of sodium carbonate, sodium bicarbonate, sodium acetate and sodium oxide.
4. The Mn-inhibiting composition according to claim 1 3+ The preparation method of the ternary positive electrode material of the sodium ion battery with the Jahn-Teller effect is characterized in that in the first step, the mass ratio of the sodium source to the transition metal source is 1:1-1:3.
5. The Mn-inhibiting composition according to claim 1 3+ The preparation method of the ternary positive electrode material of the sodium ion battery with the Jahn-Teller effect is characterized in that in the first step, the calcination temperature is 500-1000 ℃ and the sintering time is 10-20h.
6. The Mn-inhibiting composition according to claim 1 3+ The preparation method of the ternary positive electrode material of the sodium ion battery with the Jahn-Teller effect is characterized in that in the second step, the manganese source coating agent is one of manganese salts such as manganese acetate, manganese carbonate and manganese oxide.
7. The Mn-inhibiting composition according to claim 1 3+ The preparation method of the ternary positive electrode material of the sodium ion battery with the Jahn-Teller effect is characterized in that in the second step, the mass ratio of the NFM material to the manganese source coating agent is 1:1-1:5.
8. The Mn-inhibiting composition according to claim 1 3+ The preparation method of the ternary positive electrode material of the sodium ion battery with the Jahn-Teller effect is characterized in that in the second step, the calcining temperature after coating is 600-800 degrees, and the calcining time is 1-5 hours.
9. A ternary positive electrode material for sodium ion battery, according to any one of claims 1 to 8, wherein Mn is suppressed 3+ The sodium ion battery ternary positive electrode material with the Jahn-Teller effect is prepared by a preparation method and is characterized in thatThe manganese content is 10%, and has stable electrochemical performance.
10. Use of a ternary positive electrode material for a sodium ion battery according to claim 9 for the preparation of an energy storage battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310445607.XA CN116425220A (en) | 2023-04-24 | 2023-04-24 | Inhibition of Mn 3+ Preparation method, product and application of sodium ion battery ternary positive electrode material with Jahn-Teller effect |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310445607.XA CN116425220A (en) | 2023-04-24 | 2023-04-24 | Inhibition of Mn 3+ Preparation method, product and application of sodium ion battery ternary positive electrode material with Jahn-Teller effect |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116425220A true CN116425220A (en) | 2023-07-14 |
Family
ID=87079546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310445607.XA Pending CN116425220A (en) | 2023-04-24 | 2023-04-24 | Inhibition of Mn 3+ Preparation method, product and application of sodium ion battery ternary positive electrode material with Jahn-Teller effect |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116425220A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117466346A (en) * | 2023-12-28 | 2024-01-30 | 深圳中芯能科技有限公司 | Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
-
2023
- 2023-04-24 CN CN202310445607.XA patent/CN116425220A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117466346A (en) * | 2023-12-28 | 2024-01-30 | 深圳中芯能科技有限公司 | Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2023097982A1 (en) | Compositve anode material, manufacturing method therefor, positive plate, and sodium ion battery | |
| CN103715424B (en) | A kind of nucleocapsid structure positive electrode and preparation method thereof | |
| WO2023097984A1 (en) | Positive electrode material and preparation method therefor, positive electrode plate, and sodium ion battery | |
| CN102891309B (en) | Preparation method of spherical lithium-enriched anode material with gradient concentration | |
| CN112310376B (en) | Preparation method of composite coating layer high-nickel positive electrode material | |
| WO2015021789A1 (en) | High-magnification anode material of aqueous alkali metal electrochemical cell, and preparation method thereof | |
| CN107732193B (en) | All-solid-state lithium battery applying core-shell structure high-nickel cathode material and preparation method thereof | |
| JP2022529760A (en) | Positive electrode material, its manufacturing method and lithium secondary battery | |
| CN104425809A (en) | Lithium ion battery positive electrode material, preparation method of lithium ion battery positive electrode material, lithium ion battery comprising lithium ion battery positive electrode material | |
| WO2014169717A1 (en) | Electrochemical energy storage device of aqueous alkali metal ions | |
| CN113903884B (en) | Positive electrode active material, preparation method thereof, positive electrode and lithium ion battery | |
| CN108550791A (en) | A kind of layered cathode material and its preparation method and application of spinelle cladding | |
| CN104934592A (en) | Preparation method for anode material ZnMnO3 of lithium ion battery | |
| CN112289994B (en) | Coated high-nickel ternary material and preparation method and application thereof | |
| CN111048775A (en) | In-situ sodium doping modification method for improving lithium storage performance of ternary cathode material | |
| CN114520318A (en) | High-nickel cobalt-free nickel tungsten lithium manganate positive electrode material for power battery and preparation method thereof | |
| CN115241450A (en) | Preparation and application of doped sodium ion nickel-iron-manganese-based single crystal battery positive electrode material | |
| CN113772735A (en) | Doped manganese dioxide and preparation method thereof | |
| CN113871613B (en) | High-nickel ternary nickel cobalt lithium manganate positive electrode material and preparation method thereof | |
| CN116425220A (en) | Inhibition of Mn 3+ Preparation method, product and application of sodium ion battery ternary positive electrode material with Jahn-Teller effect | |
| CN108598463B (en) | Preparation method of nano flaky lithium-rich manganese-based positive electrode material | |
| Shumei et al. | Research progress and prospect in element doping of lithium-rich layered oxides as cathode materials for lithium-ion batteries | |
| Gupta et al. | Recent progress of layered structured P2-and O3-type transition metal oxides as cathode material for sodium-ion batteries | |
| CN111326730B (en) | Surface layer gradient doped lithium-rich layered oxide cathode material and preparation method and application thereof | |
| CN116598472A (en) | Doped positive electrode material, synthesis method and application thereof in sodium ion battery |
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 |