CN114906881A - Preparation method of cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material - Google Patents
Preparation method of cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material Download PDFInfo
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- XLCPLIJTRIGVDU-UHFFFAOYSA-N [O-2].[Mn+2].[Ni+2].[Na+] Chemical compound [O-2].[Mn+2].[Ni+2].[Na+] XLCPLIJTRIGVDU-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000007774 positive electrode material Substances 0.000 title claims description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 239000002243 precursor Substances 0.000 claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 37
- 238000001354 calcination Methods 0.000 claims abstract description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 20
- 238000000975 co-precipitation Methods 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000010405 anode material Substances 0.000 claims abstract description 11
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 71
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 38
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 38
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 38
- 239000001099 ammonium carbonate Substances 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 239000011572 manganese Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000012266 salt solution Substances 0.000 claims description 18
- 239000010406 cathode material Substances 0.000 claims description 12
- 229940099596 manganese sulfate Drugs 0.000 claims description 10
- 239000011702 manganese sulphate Substances 0.000 claims description 10
- 235000007079 manganese sulphate Nutrition 0.000 claims description 10
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 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
- 229910014507 Na0.67Ni0.33Mn0.67O2 Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 229940071125 manganese acetate 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
- 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
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 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
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 12
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 8
- CQPZCUVAECLXTC-UHFFFAOYSA-N [Mn](=O)(=O)([O-])[O-].[Na+].[Ni+2] Chemical class [Mn](=O)(=O)([O-])[O-].[Na+].[Ni+2] CQPZCUVAECLXTC-UHFFFAOYSA-N 0.000 abstract description 7
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 abstract description 7
- 239000008139 complexing agent Substances 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000007784 solid electrolyte Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 39
- 239000000203 mixture Substances 0.000 description 32
- 239000002994 raw material Substances 0.000 description 16
- 239000011734 sodium Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 8
- 230000002572 peristaltic effect Effects 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- MJFNUPCNTOWJLO-UHFFFAOYSA-N copper manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Ni++].[Cu++] MJFNUPCNTOWJLO-UHFFFAOYSA-N 0.000 description 6
- 238000011031 large-scale manufacturing process Methods 0.000 description 6
- -1 nickel-copper-manganese carbonate Chemical compound 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000012716 precipitator Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 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
- 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
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- 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
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- 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
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- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- 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
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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
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Abstract
The invention relates to the technical field of preparation of solid electrolyte materials of sodium ion batteries, in particular to a preparation method of cation-substituted modified spherical-like sodium nickel manganese oxide. The invention discloses a preparation method of cation-substituted modified nickel sodium manganate, which comprises the steps of carrying out coprecipitation reaction on soluble nickel manganese metal salt, soluble substituted metal M salt and a carbonate precipitation complexing agent to obtain a sphere-like carbonate precursor, calcining the carbonate precursor to obtain a layered oxide precursor, uniformly mixing the layered oxide precursor with sodium salt, and calcining to obtain the cation-substituted nickel sodium manganate anode material. The substituted and modified sodium nickel manganese oxide anode material prepared by the method has excellent cycle performance, rate capability and high specific discharge capacity.
Description
Technical Field
The invention relates to the technical field of preparation of solid electrolyte materials of sodium ion batteries, in particular to cation-substituted modified spherical-like sodium nickel manganese oxide (Na) 0.67 Ni 0.33 Mn 0.67 O 2 ) The preparation method of (1).
Background
Although the lithium ion battery is the main mode of electrochemical energy storage at present, the lithium ion battery has the characteristics of high energy density, good cycle performance, energy conservation, environmental protection, no memory effect and the like, so that the lithium ion battery is favored by the market and has wide application. Although the development prospect of the lithium ion battery is far, the market demand is increasing day by day, the shortage of domestic lithium resources and the rising of price are a big problem to be faced in the future, and a novel efficient and low-price new energy storage system is required to be searched. And sodium has similar physical and chemical properties with lithium, is rich in reserve and low in cost, and is expected to replace the large-scale application of lithium ion batteries in the energy storage field with low energy density requirements. In addition, the electrode potential of the sodium ion battery is relatively high, so that the selection range of the electrolyte is wider, and the electrolyte solvent and the electrolyte salt with lower decomposition potential can be utilized; the use of sodium ion batteries has more stable electrochemical performance relative to lithium ion batteries.
However, since the radius of the sodium ions is larger than that of the lithium ions, the sodium ion battery will experience more resistance to the deintercalation of the sodium ions during the charge and discharge cycles. It is therefore important to find suitable electrode materials. Among them, as a typical representative material of the transition metal layered oxide, a P2-type layered oxide has attracted much attention because of its advantages such as high operating voltage, high specific capacity, and stable structure. But irreversible phase change can be generated during the circulation process of the oxide, and the capacity and the circulation performance are further attenuated. At present, research on improving the electrochemistry of materials mainly focuses on methods such as doping substitution, morphological structure design, coating and the like.
CN113845158A discloses a preparation method of a porous spherical nickel sodium manganate anode material, and the porous spherical nickel sodium manganate (Na) is prepared x Ni y Mn 1-y O 2 ) The anode material improves the large-rate discharge stability of the material, but the material is carried out in a low-voltage interval (2-4.15V), and the first discharge specific capacity is lower than 100mAh/g under the 1C rate. According to the invention, cation substitution modification is carried out during synthesis of the precursor by a coprecipitation method, the process is simple and controllable, the repeatability is high, large-scale production can be realized, coating modification is not required after sintering, and the prepared modified sodium nickel manganese oxide anode material has excellent cycle performance, rate capability and high specific discharge capacity. Has good reference value for large-scale production of the positive electrode material of the sodium-ion battery.
Disclosure of Invention
The invention hopes to provide a preparation method of a cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material, and the specific scheme is as follows:
a preparation method of a cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material comprises the following steps:
(1) dissolving soluble nickel salt, manganese salt and substituted metal M salt in pure water according to a certain proportion to obtain a mixed salt solution A; dissolving carbonate in pure water to obtain a solution B;
(2) adding the solution A and the solution B in the step (1) into a reaction kettle filled with a base solution for coprecipitation reaction to obtain a spheroidal carbonate precursor; during the coprecipitation reaction, the particle size is controlled to be 3-20um, the reaction temperature is controlled to be 40-70 ℃, the stirring speed is 400-1200rpm, the reaction pH is 7-9, and the reaction time is 50-120 h; before the particles are 10 mu m, controlling the pH value to be 7.5 +/-0.2 in the reaction process, controlling the reaction temperature to be 50 ℃ and controlling the stirring speed to be 550 r/min; when the particle size is between 10 and 20 mu m, controlling the pH value in the reaction process to be 8.0 +/-0.2, the reaction temperature to be 60 ℃, and the stirring speed to be 700 r/min;
(3) calcining the sphere-like carbonate precursor obtained in the step (2) to obtain a layered oxide precursor;
(4) uniformly mixing the oxide precursor obtained in the step (3) with sodium salt, and calcining to obtain the substituted and modified sodium nickel manganese oxide anode material;
the structural formula of the sodium nickel manganese oxide cathode material is Na 0.67 Ni 0.33 Mn 0.67 O 2 。
The soluble nickel salt in the step (1) is one or more of nickel sulfate, nickel chloride, nickel nitrate or nickel acetate.
The manganese salt in the step (1) is one or more of manganese sulfate, manganese nitrate, manganese chloride or manganese acetate.
The substituted metal M salt in the step (1) is one or more of copper sulfate/cobalt/yttrium/magnesium/molybdenum, copper nitrate/cobalt/yttrium/magnesium/molybdenum and copper chloride/cobalt/yttrium/magnesium/molybdenum.
The carbonate precipitant is ammonium bicarbonate.
The concentration of the metal ions in the solution A in the step (1) is 0.1-1mol/L, the molar ratio of nickel, manganese and the substituted metal cations M is (0.33-x):0.67: x, wherein x is 0.02-0.2, and the carbonate in the obtained solution B is a supersaturated solution with the concentration of about 2.7 mol/L.
The base solution in the step (2) is ammonium bicarbonate, and the concentration of the ammonium bicarbonate is 0.1-1.0 mol/L.
And (3) controlling the molar ratio of the metal salt to the carbonate to be 1:2 during the coprecipitation reaction in the step (2).
The sodium salt in the step (4) is one or more of sodium carbonate, sodium bicarbonate and sodium hydroxide.
The invention mainly provides cation (M) substituted modified sodium nickel manganese oxide (Na) 0.67 Ni 0.33 Mn 0.67 O 2 ) A preparation method of the cathode material. According to the method, soluble nickel manganese metal salt, soluble substituted metal M salt and carbonate precipitation complexing agent are subjected to coprecipitation reaction to obtain a spherical-like carbonate precursor, the carbonate precursor is calcined to obtain a layered oxide precursor, and the layered oxide precursor and sodium salt are uniformly mixed and calcined to obtain the required nickel sodium manganate anode material. The method has simple and controllable process and high repeatability, can be used for large-scale production, and the prepared sodium nickel manganese oxide cathode material has excellent cycle performance, rate capability and high energy density. Has good reference value for large-scale production of the positive electrode material of the sodium-ion battery.
Compared with the prior art, the invention has the advantages that:
firstly, the shape of the sodium nickel manganese oxide anode material in the prior art is mostly irregular block-shaped, the tap density of the material is lower, and the multiplying power performance of the material with a hollow shape is poorer. The sodium nickel manganese oxide cathode material with the spherical-like structure prepared by the invention has high tap density, is easy to produce in a large scale, has high mechanical strength, has a stable structure in the charge-discharge cycle process, and is not easy to have the phenomena of structural collapse or pulverization and the like, namely the material has good cycle performance. Specifically, the invention controls the coprecipitation regulation and the particle size between 10-20um, so that the degree of crystallinity of the sphere-like inner crystal nucleus is higher than 80%, and the degree of crystallinity of the outer layer is slightly lower than 50% under the influence of the particle size on the basis of the crystal nucleus.
Secondly, the nickel manganese acid is partially replaced by metal elementsOne or more of nickel and manganese in sodium can change charge distribution in the material and destroy Na + The ordering of the vacancy and the inhibition of the occurrence of phase change enable the material to have good cycle stability under a high voltage platform (2-4.5V), good rate capability and high specific discharge capacity. For example, the specific discharge capacity of 101.98mAh/g is still remained after 100 cycles of circulation at 0.5C (1C is 170mA/g) in the range of 2-4.5V, and the first specific discharge capacity is as high as 134.18 mAh/g.
And thirdly, the modified precursor is prepared by adopting a preparation method based on commercial coprecipitation, so that the synthesis cost is low, the process is simple, continuous production can be realized, the method is suitable for large-scale production, and the method has a commercial prospect for large-scale production of the sodium-ion battery anode material.
Drawings
FIG. 1 is an SEM image of a sodium nickel manganese oxide cathode material prepared in a comparative example;
FIG. 2 is an XRD pattern of comparative example and examples 1-5;
FIG. 3 is a graph showing short cycle curves of button cells composed of the sodium nickel manganese oxide positive electrode materials prepared in comparative example and examples 1-6 at different multiplying factors within a voltage range of 2-4.5V;
fig. 4 is a graph comparing the cycling curves of button cells composed of the sodium nickel manganese oxide positive electrode material prepared in comparative example and example 1 in the voltage interval of 2-4.5V and at 0.5C.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and all the technologies realized based on the above subject matter of the present invention are within the scope of the present invention.
Comparative example 1
Weighing raw materials of manganese sulfate and nickel sulfate according to a molar ratio of 2:1, and dissolving the raw materials in pure water to prepare 2mol/L mixed metal salt solution; preparing 2.7mol/L ammonium bicarbonate supersaturated solution as a precipitator and a complexing agent solution; preparing 0.7mol/L ammonium bicarbonate solution as a base solution. And adding the mixed metal salt solution and the ammonium bicarbonate supersaturated solution into the mixed base solution through a peristaltic pump, controlling the ratio of the mixed metal salt to the ammonium bicarbonate precipitator to be 1:2, controlling the pH value to be about 8, stirring at the speed of 900r/min and the temperature to be 50 ℃. And (3) carrying out coprecipitation reaction for 100h, and carrying out suction filtration, hot water washing and drying after the reaction is finished to obtain the spherical nickel-manganese binary carbonate precursor.
And (3) heating the precursor from room temperature to 600 ℃ at the heating rate of 5 ℃/min, and calcining for 5h to obtain the nickel-manganese binary oxide precursor. Then uniformly mixing the sieved oxide precursor and sodium carbonate according to the molar ratio of 1:1.05, putting the mixture into a muffle furnace, heating the mixture from room temperature to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 5 hours, heating the mixture to 900 ℃, and calcining the mixture for 12 hours to obtain the spherical sodium nickel manganese oxide cathode material (Na) 0.67 Ni 0.33 Mn 0.67 O 2 )。
Comparative example 2
Weighing raw materials of manganese sulfate and nickel sulfate according to a molar ratio of 1:2, and dissolving the raw materials in pure water to prepare 2mol/L mixed metal salt solution; preparing 2.7mol/L ammonium bicarbonate supersaturated solution as a precipitator and a complexing agent solution; preparing 0.7mol/L ammonium bicarbonate solution as a base solution. And adding the mixed metal salt solution and the ammonium bicarbonate supersaturated solution into the mixed base solution through a peristaltic pump, controlling the ratio of the mixed metal salt to the ammonium bicarbonate precipitator to be 1:2, controlling the pH value to be about 8, stirring at the speed of 900r/min and the temperature to be 50 ℃. And (3) carrying out coprecipitation reaction for 100h, and carrying out suction filtration, hot water washing and drying after the reaction is finished to obtain the spherical nickel-manganese binary carbonate precursor.
And (3) heating the precursor from room temperature to 600 ℃ at the heating rate of 5 ℃/min, and calcining for 5h to obtain the nickel-manganese binary oxide precursor. Then uniformly mixing the sieved oxide precursor and sodium carbonate according to the molar ratio of 1:1.05, putting the mixture into a muffle furnace, heating the mixture from room temperature to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 5h, heating the mixture to 900 ℃, and calcining the mixture for 12h to obtain the spherical-structure sodium nickel manganese oxide positive electrode material (Na) 0.67 Ni 0.33 Mn 0.67 O 2 )。
Example 1
Weighing raw materials of manganese sulfate, nickel sulfate and copper sulfate according to the molar ratio of Mn, Ni and Cu metal elements of 0.67 to 0.26 to 0.07, and dissolving the raw materials in pure water to prepare 2mol/L mixed metal salt solution; preparing 2.7mol/L ammonium bicarbonate supersaturated solution as precipitant solution; 0.7mol/L ammonium bicarbonate solution is prepared as a base solution. And adding the mixed metal salt solution and the ammonium bicarbonate precipitant solution into the mixed base solution by a peristaltic pump, controlling the ratio of the mixed metal salt to the ammonium bicarbonate precipitant solution to be 1:2, controlling the pH value to be about 8, stirring at the speed of 900r/min and the temperature to be 50 ℃. Carrying out coprecipitation reaction for 100h, controlling the particle size to be 10-20um, controlling the reaction temperature to be 50-70 ℃, controlling the stirring speed to be 400-1200rpm, controlling the reaction pH to be 7-9, controlling the reaction process pH to be 7.5 +/-0.2 when the reaction time is 4-20h before the particles are 10 mu m, controlling the reaction temperature to be 50 ℃ and controlling the stirring speed to be 550 r/min; when the particle size is between 10 and 20 mu m, controlling the pH value in the reaction process to be 8.0 +/-0.2, the reaction temperature to be 60 ℃, the stirring speed to be 700r/min, and obtaining the spherical nickel-copper-manganese carbonate precursor after the reaction is finished through suction filtration, hot water washing and drying.
And (3) heating the precursor from room temperature to 600 ℃ at the heating rate of 5 ℃/min, and calcining for 5h to obtain the nickel-copper-manganese oxide precursor. Then uniformly mixing the sieved oxide precursor and sodium carbonate according to the molar ratio of 1:1.05, putting the mixture into a muffle furnace, heating the mixture from room temperature to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 5h, heating the mixture to 900 ℃, and calcining the mixture for 12h to obtain the copper-partially-substituted and modified sodium nickel manganese oxide positive electrode material (Na) 0.67 Ni 0.26 Cu 0.07 Mn 0.67 O 2 )。
Example 2
Weighing raw materials of manganese sulfate, nickel sulfate and magnesium sulfate according to the molar ratio of Mn, Ni and Mg metal elements of 0.67 (0.21:0.12), and dissolving the raw materials in pure water to prepare 2mol/L mixed metal salt solution; preparing 2.7mol/L ammonium bicarbonate supersaturated solution as precipitant solution; preparing 0.7mol/L ammonium bicarbonate solution as a base solution. And adding the mixed metal salt solution and the ammonium bicarbonate precipitant solution into the mixed base solution by a peristaltic pump, controlling the ratio of the mixed metal salt to the ammonium bicarbonate precipitant solution to be 1:2, controlling the pH value to be about 8, stirring at the speed of 900r/min and the temperature to be 50 ℃. Carrying out coprecipitation reaction for 100h, controlling the particle size to be 10-20um, controlling the reaction temperature to be 50-70 ℃, controlling the stirring speed to be 400-1200rpm, controlling the reaction pH to be 7-9, controlling the reaction process pH to be 7.5 +/-0.2 when the reaction time is 4-20h before the particles are 10 mu m, controlling the reaction temperature to be 50 ℃ and controlling the stirring speed to be 550 r/min; when the particle size is between 10 and 20 mu m, controlling the pH value in the reaction process to be 8.0 +/-0.2, the reaction temperature to be 60 ℃, the stirring speed to be 700r/min, and obtaining the spherical nickel-copper-manganese carbonate precursor after the reaction is finished through suction filtration, hot water washing and drying.
And (3) heating the precursor from room temperature to 600 ℃ at the heating rate of 5 ℃/min, and calcining for 5h to obtain the nickel-copper-manganese oxide precursor. Then uniformly mixing the sieved oxide precursor and sodium carbonate according to the molar ratio of 1:1.05, putting the mixture into a muffle furnace, heating the mixture from room temperature to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 5h, heating the mixture to 900 ℃, and calcining the mixture for 12h to obtain the nickel sodium manganate positive electrode material (Na) with Mg partially substituted and modified 0.67 Ni 0.21 Mg 0.12 Mn 0.67 O 2 )。
Example 3
Weighing raw materials of manganese sulfate, cobalt sulfate and nickel sulfate according to the molar ratio (0.56:0.11) to 0.33 of Mn, Al and Ni metal elements, and dissolving the raw materials in pure water to prepare 2mol/L mixed metal salt solution; preparing 2.7mol/L ammonium bicarbonate supersaturated solution as precipitant solution; preparing 0.7mol/L ammonium bicarbonate solution as a base solution. And adding the mixed metal salt solution and the ammonium bicarbonate precipitant solution into the mixed base solution by a peristaltic pump, controlling the ratio of the mixed metal salt to the ammonium bicarbonate precipitant solution to be 1:2, controlling the pH value to be about 8, stirring at the speed of 900r/min and the temperature to be 50 ℃. The coprecipitation reaction is carried out for 100 hours, the particle size is controlled to be 10-20um, the reaction temperature is controlled to be 50-70 ℃, the stirring speed is 400-1200rpm, the reaction pH is 7-9, the reaction time is 4-20 hours before the particle size is 10 um, the reaction process pH is controlled to be 7.5 +/-0.2, the reaction temperature is 50 ℃, and the stirring speed is 550 r/min; when the particle size is between 10 and 20 mu m, controlling the pH value to be 8.0 +/-0.2 in the reaction process, controlling the reaction temperature to be 60 ℃, stirring at 700r/min, and after the reaction is finished, carrying out suction filtration, hot water washing and drying to obtain the spherical nickel-copper-manganese carbonate precursor.
And (3) heating the precursor from room temperature to 600 ℃ at the heating rate of 5 ℃/min, and calcining for 5h to obtain the nickel-copper-manganese oxide precursor. Then uniformly mixing the sieved oxide precursor and sodium carbonate according to the molar ratio of 1:1.05, putting the mixture into a muffle furnace, heating the mixture from room temperature to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 5h, heating the mixture to 900 ℃, and calcining the mixture for 12h to obtain the Co partially substituted and modified sodium nickel manganese oxide cathode material (Na) 0.67 Ni 0.33 Mn 0.56 Al 0.11 O 2 )。
Example 4
Weighing raw materials of manganese sulfate, aluminum sulfate and nickel sulfate according to the molar ratio of Mn, Co and Ni metal elements of 0.67 (0.165:0.165), and dissolving the raw materials in pure water to prepare 2mol/L mixed metal salt solution; preparing 2.7mol/L ammonium bicarbonate supersaturated solution as precipitant solution; preparing 0.7mol/L ammonium bicarbonate solution as a base solution. And adding the mixed metal salt solution and the ammonium bicarbonate precipitant solution into the mixed base solution by a peristaltic pump, controlling the ratio of the mixed metal salt to the ammonium bicarbonate precipitant solution to be 1:2, controlling the pH value to be about 8, stirring at the speed of 900r/min and the temperature to be 50 ℃. The coprecipitation reaction is carried out for 100 hours, the particle size is controlled to be 10-20um, the reaction temperature is controlled to be 50-70 ℃, the stirring speed is 400-1200rpm, the reaction pH is 7-9, the reaction time is 4-20 hours before the particle size is 10 um, the reaction process pH is controlled to be 7.5 +/-0.2, the reaction temperature is 50 ℃, and the stirring speed is 550 r/min; when the particle size is between 10 and 20 mu m, controlling the pH value in the reaction process to be 8.0 +/-0.2, the reaction temperature to be 60 ℃, the stirring speed to be 700r/min, and obtaining the spherical nickel-copper-manganese carbonate precursor after the reaction is finished through suction filtration, hot water washing and drying.
And (3) heating the precursor from room temperature to 600 ℃ at the heating rate of 5 ℃/min, and calcining for 5h to obtain the nickel-copper-manganese oxide precursor. Then uniformly mixing the sieved oxide precursor and sodium carbonate according to the molar ratio of 1:1.05, putting the mixture into a muffle furnace, heating the mixture from room temperature to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 5h, heating the mixture to 900 ℃, and calcining the mixture for 12h to obtain the Al partially substituted and modified sodium nickel manganese oxide cathode material (Na) 0.67 Ni 0.165 Co 0.165 Mn 0.33 O 2 )。
Example 5
Weighing raw materials of manganese sulfate, aluminum sulfate and nickel sulfate according to the molar ratio (0.56:0.11) to (0.165:0.165) of Mn, Al, Ni and Co metal elements, and dissolving the raw materials in pure water to prepare 2mol/L mixed metal salt solution; preparing 2.7mol/L ammonium bicarbonate supersaturated solution as precipitant solution; preparing 0.7mol/L ammonium bicarbonate solution as a base solution. And adding the mixed metal salt solution and the ammonium bicarbonate precipitant solution into the mixed base solution by a peristaltic pump, controlling the ratio of the mixed metal salt to the ammonium bicarbonate precipitant solution to be 1:2, controlling the pH value to be about 8, stirring at the speed of 900r/min and the temperature to be 50 ℃. Carrying out coprecipitation reaction for 100h, controlling the particle size to be 10-20um, controlling the reaction temperature to be 50-70 ℃, controlling the stirring speed to be 400-1200rpm, controlling the reaction pH to be 7-9, controlling the reaction process pH to be 7.5 +/-0.2 when the reaction time is 4-20h before the particles are 10 mu m, controlling the reaction temperature to be 50 ℃ and controlling the stirring speed to be 550 r/min; when the particle size is between 10 and 20 mu m, controlling the pH value in the reaction process to be 8.0 +/-0.2, the reaction temperature to be 60 ℃, the stirring speed to be 700r/min, and obtaining the spherical nickel-copper-manganese carbonate precursor after the reaction is finished through suction filtration, hot water washing and drying.
And (3) heating the precursor from room temperature to 600 ℃ at the heating rate of 5 ℃/min, and calcining for 5 hours to obtain the nickel-copper-manganese oxide precursor. Then uniformly mixing the sieved oxide precursor and sodium carbonate according to the molar ratio of 1:1.05, putting the mixture into a muffle furnace, heating the mixture from room temperature to 600 ℃ at the speed of 5 ℃/min, keeping the temperature for 5h, heating the mixture to 900 ℃, and calcining the mixture for 12h to obtain the Co and Al Co-substituted modified sodium nickel manganese oxide cathode material (Na) 0.67 Ni 0.165 Co 0.165 Mn 0.56 Al 0.11 O 2 )。
Example 6
Weighing raw materials of manganese sulfate, nickel sulfate and copper sulfate according to the molar ratio of Mn, Ni and Cu metal elements of 0.67 (0.20:0.13), and dissolving the raw materials in pure water to prepare 2mol/L mixed metal salt solution; preparing 2.7mol/L ammonium bicarbonate supersaturated solution as precipitant solution; preparing 0.7mol/L ammonium bicarbonate solution as a base solution. And adding the mixed metal salt solution and the ammonium bicarbonate precipitant solution into the mixed base solution by a peristaltic pump, controlling the ratio of the mixed metal salt to the ammonium bicarbonate precipitant solution to be 1:2, controlling the pH value to be about 8, stirring at the speed of 900r/min and the temperature to be 50 ℃. Carrying out coprecipitation reaction for 100h, controlling the particle size to be 10-20um, controlling the reaction temperature to be 50-70 ℃, controlling the stirring speed to be 400-1200rpm, controlling the reaction pH to be 7-9, controlling the reaction process pH to be 7.5 +/-0.2 when the reaction time is 4-20h before the particles are 10 mu m, controlling the reaction temperature to be 50 ℃ and controlling the stirring speed to be 550 r/min; when the particle size is between 10 and 20 mu m, controlling the pH value in the reaction process to be 8.0 +/-0.2, the reaction temperature to be 60 ℃, the stirring speed to be 700r/min, and obtaining the spherical nickel-copper-manganese carbonate precursor after the reaction is finished through suction filtration, hot water washing and drying.
And (3) heating the precursor from room temperature to 600 ℃ at the heating rate of 5 ℃/min, and calcining for 5h to obtain the nickel-copper-manganese oxide precursor. Then uniformly mixing the sieved oxide precursor and sodium carbonate according to the molar ratio of 1:1.02, putting the mixture into a muffle furnace, heating the mixture from room temperature to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 4h, heating the mixture to 900 ℃, and calcining the mixture for 8h to obtain the copper-partially-substituted and modified sodium nickel manganese oxide positive electrode material (Na) 0.67 Ni 0.26 Cu 0.07 Mn 0.67 O 2 )。
Assembling the button cell: mixing the sodium nickel manganese oxide cathode material prepared in the comparative example and the embodiment, a conductive agent and a binder according to the mass ratio of 8:1:1 to prepare a cathode, and assembling the cathode in a vacuum glove box, wherein a sodium sheet is a cathode, a diaphragm is a glass fiber diaphragm, and electrolyte is 1mol/LNaClO 4 (EC: DMC in a volume ratio of 1: 1). The first charge-discharge and cycle performance is tested in a voltage range of 2.0-4.5V, the rate performance of the material is tested under different rate conditions (0.1C, 0.2, 0.5C, 1C, 3C and 5C), and the results are shown in Table 1, the performance is improved after the substitution modification, and the performance of the co-substituted nickel sodium manganate anode material is the best. The results are also shown in fig. 3 and 4, and the substituted and modified sodium nickel manganese oxide positive electrode material has a reduced first discharge specific capacity, but has improved rate capability and cycle stability.
TABLE 1 electrochemical Properties of different NiMnaMnO cathode materials
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (9)
1. A preparation method of a cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material is characterized by comprising the following steps of: the preparation method comprises the following steps:
(1) dissolving soluble nickel salt, manganese salt and substituted metal M salt in pure water according to a certain proportion to obtain a mixed salt solution A; dissolving carbonate in pure water to obtain a solution B;
(2) adding the solution A and the solution B in the step (1) into a reaction kettle filled with a base solution to carry out coprecipitation reaction to obtain a quasi-spherical carbonate precursor; during the coprecipitation reaction, the particle size is controlled to be 3-20um, the reaction temperature is controlled to be 40-70 ℃, the stirring speed is 400-1200rpm, the reaction pH is 7-9, and the reaction time is 50-120 h; before the particle size is 10 mu m, controlling the pH value in the reaction process to be 7.5 +/-0.2, the reaction temperature to be 50 ℃, and the stirring speed to be 550 r/min; when the particle size is between 10 and 20 mu m, controlling the pH value in the reaction process to be 8.0 +/-0.2, the reaction temperature to be 60 ℃, and the stirring speed to be 700 r/min;
(3) calcining the sphere-like carbonate precursor obtained in the step (2) to obtain a layered oxide precursor;
(4) uniformly mixing the oxide precursor obtained in the step (3) with sodium salt, and calcining to obtain the substituted and modified sodium nickel manganese oxide anode material;
the structural formula of the sodium nickel manganese oxide cathode material is Na 0.67 Ni 0.33 Mn 0.67 O 2 。
2. The preparation method of the cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material according to claim 1, characterized in that: the nickel salt in the step (1) is one or more of nickel sulfate, nickel chloride, nickel nitrate or nickel acetate.
3. The preparation method of the cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material according to claim 1, characterized in that: the manganese salt in the step (1) is one or more of manganese sulfate, manganese nitrate, manganese chloride or manganese acetate.
4. The preparation method of the cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material according to claim 1, characterized in that: the substituted metal M salt in the step (1) is one or more of copper sulfate/cobalt/yttrium/magnesium/molybdenum, copper nitrate/cobalt/yttrium/magnesium/molybdenum and copper chloride/cobalt/yttrium/magnesium/molybdenum.
5. The preparation method of the cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material according to claim 1, characterized in that: the carbonate in the step (1) is ammonium bicarbonate.
6. The preparation method of the cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material according to claim 1, characterized in that: the concentration of the metal ions in the solution A in the step (1) is 0.1-1mol/L, the molar ratio of nickel, manganese and the substituted metal cations M is (0.33-x):0.67: x, wherein x is 0.02-0.2, and the carbonate in the obtained solution B is a supersaturated solution with the concentration of about 2.7 mol/L.
7. The preparation method of the cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material according to claim 1, characterized in that: the base solution in the step (2) is ammonium bicarbonate, and the concentration of the ammonium bicarbonate is 0.1-1.0 mol/L.
8. The preparation method of the cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material according to claim 1, characterized in that: and (3) controlling the molar ratio of the metal salt to the carbonate to be 1:2 during the coprecipitation reaction in the step (2).
9. The preparation method of the cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material according to claim 1, characterized in that: the sodium salt in the step (4) is one or more of sodium carbonate, sodium bicarbonate or sodium hydroxide.
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