CN113839018B - Complex-phase sodium storage positive electrode material and preparation method and application thereof - Google Patents
Complex-phase sodium storage positive electrode material and preparation method and application thereof Download PDFInfo
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- 239000011734 sodium Substances 0.000 title claims abstract description 22
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 title claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title description 5
- 238000003860 storage Methods 0.000 title description 2
- 239000010405 anode material Substances 0.000 claims abstract description 9
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000012071 phase Substances 0.000 abstract description 36
- 229910052744 lithium Inorganic materials 0.000 abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000003746 solid phase reaction Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000011161 development Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000000498 ball milling Methods 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 sodium hexafluorophosphate Chemical compound 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- TWLBWHPWXLPSNU-UHFFFAOYSA-L [Na].[Cl-].[Cl-].[Ni++] Chemical compound [Na].[Cl-].[Cl-].[Ni++] TWLBWHPWXLPSNU-UHFFFAOYSA-L 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 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
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
The invention discloses a composite layered anode material Na n[Liz(Ni1‑x‑yMnxFey)1‑z]O2, which consists of a high-capacity O3 phase and a high-cycle stable P2 phase. In the solid phase reaction, the formation of the complex phase anode material is realized by regulating and controlling components and introducing lithium doping to optimize the reaction temperature. The preparation method has the advantages of simple and controllable process, low energy consumption and low cost, and is suitable for large-scale industrial production. The result shows that the prepared complex phase positive electrode material has high capacity and can be applied to the field of sodium ion batteries.
Description
Technical Field
The invention relates to the technical field of positive electrode materials for sodium ion batteries, and relates to a complex-phase positive electrode material, a preparation method and application thereof.
Background
Along with the increasing serious global problems of energy and environment, development of sustainable clean energy, such as solar energy and wind energy, is increasingly emphasized, but the clean energy changes along with weather, climate and environmental changes, and a matched energy storage battery is needed to improve the utilization efficiency of the clean energy, so that a clean energy and energy storage mode is a new energy development direction. Currently, common energy storage batteries include sodium-sulfur batteries, sodium-nickel chloride batteries, lithium ion batteries, lead-acid batteries, lead-carbon batteries, flow batteries and the like. However, such energy storage batteries face problems of resources, environment, cost and the like, and development of low-cost, sustainable and environment-friendly energy storage batteries has become a key factor for development of sustainable and clean energy. For example, a lithium ion battery has the comprehensive advantages of good safety, low cost, abundant resources, environmental friendliness and the like, and is very suitable for being applied to large-scale energy storage due to the fact that lithium resources are consumed too fast and the long-term development faces resource problems due to the rapid development of electric automobiles, and potential safety hazards exist in the lithium ion battery. For sodium ion batteries, the development of suitable cathode materials is critical, with layered oxides being one of the options. However, the layered materials with different crystal phases have advantages and disadvantages in properties, such as good P2 type circulation stability, low capacity, high O3 compatibility and unsatisfactory stability. Therefore, development of a layered positive electrode excellent in combination properties still faces a significant challenge.
Disclosure of Invention
The invention discloses a layered composite material used as a positive electrode of a sodium ion battery, which consists of a P2 type layered oxide and an O3 type layered oxide, can give consideration to the high cycle stability of the P2 phase and the high capacity of the O3 phase, and promotes the formation of composite phases by combining lithium doping, and further improves the capacity and cycle performance.
The complex phase positive electrode material disclosed by the invention is characterized in that the chemical general formula of the complex phase positive electrode material is Na n[Liz(Ni1-x-yMnxFey)1-z]O2, wherein x is more than 0 and less than or equal to 0.55, y is more than or equal to 0 and less than or equal to 0.45,0.02, z is more than or equal to 0.07,0.9, and n is more than or equal to 1.
In the above formula, the sum of Li, ni, mn, and Fe atoms is 1, the number of Na atoms is n, and the n value satisfies the charge balance condition.
Preferably, the molar ratio of the P2-type oxide to the O3-type oxide is 1:5 to 1: within this range, a balance between capacity and cycling stability of the material can be achieved.
The invention also discloses a preparation method of the complex-phase layered anode material, which comprises the following steps:
1) Uniformly mixing Na, li, ni, fe and Mn compounds in stoichiometric ratio, and then compacting the powder into a block under a certain pressure;
2) Presintering the block mixture obtained in the step 1) in an air atmosphere, and then cooling to room temperature along with a furnace;
3) Crushing the presintered material obtained in the step 2), and then pressing the powder into blocks under a certain pressure;
4) And (3) roasting the block material obtained in the step (3) in an air atmosphere to obtain the complex-phase layered anode material.
Preferably, in step 1), the Na, li, ni, fe and Mn compounds are selected from, but not limited to, oxides, hydroxides, nitrates, acetates, oxalates, carbonates or hydrates thereof; still more preferably, the compounds of Ni, fe and Mn are selected from oxides, and the compounds of Na and Li are selected from carbonates.
Preferably, when the raw materials are metered, the volatilization of Na and Li at high temperature is considered, and the molar percentage is calculated, so that the excessive amount of Na and Li compounds is 2-10%.
Preferably, the raw materials are mixed by adopting the modes of ball milling, sand milling, high-speed mixing and the like, and the raw material particles can be crushed to 100 nanometers-1 micrometer (D50) besides fully mixing the raw materials during ball milling, sand milling and high-speed mixing, so that the homogenization and refinement of the raw material particles are beneficial to the rapid and uniform reaction.
Preferably, the precursor mixture is tableted, and the reaction is sufficiently and uniformly performed by tableting, preferably, the pressure of tableting is 1 to 10MPa.
In the step 2), the heating rate is preferably 2-10 ℃/min, the presintering temperature is 300-500 ℃, the presintering time is 2-10 hours, and the presintering is favorable for promoting the subsequent reaction to be uniformly carried out.
In the step 3), preferably, the crushing can be ball milling, sand milling and air crushing; preferably, the presintered materials are tabletted, and the tableting is favorable for the full and uniform reaction; preferably, the pressure of the tablet is 1 to 10MPa. The product with uniform size and components can be obtained by the subsequent reaction through crushing and tabletting.
In the step 4), the heating rate is preferably 2-10 ℃/min, the roasting temperature is 780-880 ℃, and the roasting time is 8-24 hours; under the condition, combining lithium doping to obtain the P2 and O3 complex-phase layered anode material; it was found that lithium incorporation is beneficial for lowering the reaction temperature and obtaining a multi-phase layered material. In addition, lithium doping is beneficial to inhibiting harmful phase change in the charge-discharge process, and improves the structural stability of the material, thereby improving the cycle performance.
It should be noted that the above reaction conditions are interrelated, and the formation of the complex phase material requires cooperation of material components, lithium doping, and temperature control, and any deviation from the above parameters will not result in a complex phase positive electrode material with excellent performance.
The invention also discloses an organic sodium ion battery using the complex-phase positive electrode material, wherein the complex-phase positive electrode material is used as a positive electrode, hard carbon, soft carbon, hard carbon/soft carbon composite materials and the like are used as a negative electrode, and an organic solution containing an organic solvent, salt and an additive is used as an electrolyte.
Preferably, the organic solvent is at least one selected from propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methylpropyl carbonate and ethylmethyl carbonate, and the combination of the organic solvents is favorable for forming an effective SEI protective film on the surfaces of the positive electrode and the negative electrode.
Preferably, the sodium salt is at least one selected from sodium perchlorate, sodium hexafluorophosphate, sodium trifluoromethanesulfonate, sodium bistrifluoro-methane-sulfonyl-imide, sodium bistrifluoro-sulfonyl-imide, sodium tetrafluoroborate and sodium bisoxalato-borate.
Preferably, the additive is fluorinated carbonate, and the weight ratio of the additive to the organic electrolyte is 1-10%.
Compared with the prior art, the invention has the following advantages:
1. The preparation method adopts simple solid phase reaction to prepare the multi-phase layered anode material, has the advantages of simple and controllable process, low cost, short period, low energy consumption, suitability for industrial production and the like, and lithium doping can promote the formation of multi-phase, improve the capacity and reduce the reaction temperature.
2. The complex phase positive electrode material prepared by the invention contains a high-capacity O3 phase and a high-stability P2 phase, has capacity and cycle stability, can inhibit harmful phase change in the charge and discharge process by doping lithium, and improves the structural stability and cycle performance of the material.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of the complex phase cathode material prepared in example 1;
Fig. 2 is a charge-discharge curve of the complex phase cathode material prepared in example 1.
Detailed Description
Example 1
Weighing Na 2CO3、Li2CO3、NiO、Fe2O3、Mn2O3 according to the stoichiometric ratio of Na [ Li 0.05(Ni0.25Fe0.25Mn0.5)0.95]O2 ], ball-milling and mixing uniformly, tabletting under 1 MPa; presintering for 3 hours in an air atmosphere at 400 ℃, cooling to room temperature, and grinding and crushing; tabletting under 1MPa, roasting at 850 ℃ in air for 15 hours, and naturally cooling to room temperature. The product was analyzed by XRD to have a complex phase of P2 and O3, see figure 1. The material prepared in the embodiment is used as an anode, sodium metal is used as a cathode, glass fiber is used as a diaphragm, propylene Carbonate (PC)/methyl ethyl carbonate (EMC) solution of NaPF 6 is used as electrolyte, fluorinated Ethylene Carbonate (FEC) with the weight of 3% of the electrolyte is added, a button cell is assembled, a charge and discharge test is carried out, the current density is 15mA/g, the voltage range is 2-4V, the charge and discharge curve is shown in figure 1, and the initial discharge capacity of the product can reach 141mAh/g, which is shown in figure 2.
Comparative example 1
The material was prepared as in example 1 except that the calcination temperature in air was 900 ℃ instead of 850 ℃, the obtained product was detected as P2 phase by XRD, and the above product was subjected to electrochemical test as in example 1, and the initial discharge capacity of the product was 98mAh/g.
Comparative example 2
The material was prepared as in example 1, except that no lithium doping was performed and the resulting product was detected as O3 phase by XRD. The above product was electrochemically tested as in example 1, and the initial discharge capacity of the product was 117mAh/g.
Comparative example 3
The material was prepared as in example 1, except that the design composition was Na Li 0.05(Ni0.10Fe0.20Mn0.7)0.95]O2, and the obtained product was XRD-detected with less than 50% O3 phase. The above product was subjected to electrochemical test as in example 1, and the initial discharge capacity of the product was 121mAh/g.
Comparative example 4
The material was prepared as in example 1, except that the design component was Na [ Li 0.05(Ni0.70Fe0.20Mn0.10)0.95]O2 ], and the resulting product was XRD detected as O3 phase. The above product was electrochemically tested as in example 1, and the initial discharge capacity of the product was 125mAh/g.
Example 2
Weighing Na 2CO3、Li2CO3、NiO、Fe2O3、Mn2O3 according to the stoichiometric ratio of Na [ Li 0.03(Ni0.20Fe0.35Mn0.45)0.97]O2 ], ball-milling and mixing uniformly, tabletting under 1 MPa; presintering in air at 400 deg.C for 3 hr, cooling to room temperature, grinding, and tabletting under 1 MPa; roasting for 15 hours in an air atmosphere at 830 ℃, and naturally cooling to room temperature. The product was analyzed by XRD with P2 and O3 complex phases. The above product was subjected to electrochemical test as in example 1, and the initial discharge capacity of the product was 143mAh/g.
Example 3
Weighing Na 2CO3、Li2CO3、NiO、Fe2O3、Mn2O3 according to the stoichiometric ratio of Na [ Li 0.04(Ni0.35Fe0.25Mn0.4)0.96]O2 ], ball-milling and mixing uniformly, tabletting under 1 MPa; presintering in air at 400 deg.C for 3 hr, cooling to room temperature, grinding, and tabletting under 1 MPa; roasting for 15 hours in the air at 860 ℃ and naturally cooling to room temperature. The product was analyzed by XRD with P2 and O3 complex phases. The above product was subjected to electrochemical test as in example 1, and the initial discharge capacity of the product was up to 140mAh/g.
Claims (3)
1. The preparation method of the layered double-phase positive electrode material is characterized in that the layered double-phase positive electrode material consists of a P2 type layered oxide and an O3 type layered oxide;
the mole ratio of the P2 type oxide to the O3 type oxide is 1:5 to 1:20, a step of;
The chemical general formula of the complex phase anode material is Na n[Liz(Ni1-x-yMnxFey)1-z]O2, wherein x is more than 0 and less than or equal to 0.55, y is more than or equal to 0 and less than or equal to 0.45,0.02, z is more than or equal to 0.07,0.9, and n is more than or equal to 1;
The preparation method of the layered complex phase anode material comprises the following steps:
1) Uniformly mixing Na, li, ni, fe and Mn compounds in stoichiometric ratio, and then compacting the powder into a block under a certain pressure;
2) Presintering the block mixture obtained in the step 1) in an air atmosphere, and then cooling to room temperature along with a furnace;
3) Crushing the presintered material obtained in the step 2), and pressing the powder into blocks under a certain pressure;
4) Roasting the block material obtained in the step 3) in an air atmosphere to obtain a layered complex phase anode material;
in the step 2), the heating rate is 2-10 ℃/min, the presintering temperature is 300-500 ℃, and the presintering time is 2-10 hours;
In the step 4), the heating rate is 2-10 ℃/min, the roasting temperature is 780-880 ℃, and the roasting time is 8-24 hours.
2. The method for preparing a layered double phase cathode material according to claim 1, wherein in step 1), the Na, li, ni, fe and Mn compounds are selected from oxides, hydroxides, nitrates, acetates, oxalates, carbonates or hydrates thereof.
3. The method for preparing a layered double phase positive electrode material according to any one of claims 1 to 2, characterized in that it is applied in sodium ion batteries.
Priority Applications (1)
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| CN115448385B (en) * | 2022-11-10 | 2023-03-24 | 山东昭文新能源科技有限公司 | Four-phase mixed sodium-ion battery layered oxide positive electrode material and preparation method thereof |
| CN115911343B (en) * | 2023-02-27 | 2023-06-02 | 南开大学 | Sodium ion battery composite positive electrode material with high sodium content and high voltage |
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| CN108475782A (en) * | 2016-01-18 | 2018-08-31 | 托普索公司 | Sodium-ion battery material |
| CN109585795A (en) * | 2017-09-29 | 2019-04-05 | 中国科学院物理研究所 | Mixed phase structure layered oxide material and its preparation method and application |
| CN111244415A (en) * | 2020-01-16 | 2020-06-05 | 桂林电子科技大学 | Air-stable layered transition metal oxide positive electrode material and sodium ion battery thereof |
| CN112838206A (en) * | 2020-12-31 | 2021-05-25 | 福建师范大学 | Layered oxide cathode material with excellent air stability and method for improving air stability by adjusting sodium content |
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| CN109585795A (en) * | 2017-09-29 | 2019-04-05 | 中国科学院物理研究所 | Mixed phase structure layered oxide material and its preparation method and application |
| CN111244415A (en) * | 2020-01-16 | 2020-06-05 | 桂林电子科技大学 | Air-stable layered transition metal oxide positive electrode material and sodium ion battery thereof |
| CN112838206A (en) * | 2020-12-31 | 2021-05-25 | 福建师范大学 | Layered oxide cathode material with excellent air stability and method for improving air stability by adjusting sodium content |
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