CN117154047A - ZrO (ZrO-like grain) 2 Surface coating, zr 4+ Process for the preparation of doped layered oxides and use thereof - Google Patents
ZrO (ZrO-like grain) 2 Surface coating, zr 4+ Process for the preparation of doped layered oxides and use thereof Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract description 70
- 238000000576 coating method Methods 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000008569 process Effects 0.000 title claims abstract description 11
- 239000011734 sodium Substances 0.000 claims abstract description 116
- 239000011247 coating layer Substances 0.000 claims abstract description 19
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 14
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010410 layer Substances 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 238000005253 cladding Methods 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 91
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 86
- 239000011572 manganese Substances 0.000 claims description 72
- 238000010438 heat treatment Methods 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 43
- 239000000843 powder Substances 0.000 claims description 36
- 238000000498 ball milling Methods 0.000 claims description 32
- 238000005245 sintering Methods 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 19
- 239000007790 solid phase Substances 0.000 claims description 19
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 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 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 53
- 229920000642 polymer Polymers 0.000 abstract description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 98
- 229910001928 zirconium oxide Inorganic materials 0.000 description 98
- 238000001816 cooling Methods 0.000 description 30
- 238000000227 grinding Methods 0.000 description 15
- 238000003760 magnetic stirring Methods 0.000 description 15
- 239000011812 mixed powder Substances 0.000 description 15
- 238000007873 sieving Methods 0.000 description 15
- 239000007774 positive electrode material Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- -1 Sodium transition metal Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
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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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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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 belongs to the technical field of sodium ion battery materials, and particularly relates to a ZrO (ZrO-based polymer) 2 Surface coating, zr 4+ Doped layered oxide Na x TMO 2 And a preparation method and application thereof. The ZrO of the invention 2 Surface coating, zr 4+ A doped layered oxide is provided which is a layer of a metal,comprises Zr (zirconium) 4+ Doped layered oxide Na x TMO 2 Located in the layered oxide Na x TMO 2 ZrO of surface 2 A cladding layer, wherein: x is more than 0.8 and less than or equal to 1, and TM is selected from one or more of Mn, fe and Ni. The ZrO of the invention 2 Surface coating, zr 4+ Doped layered oxide, layered oxide Na x TMO 2 ZrO of surface 2 Dense coating layer and Zr 4+ The air stability of the layered oxide can be improved by doping, and the structural stability of the material in the circulation process is enhanced, so that the multiplying power performance and the circulation stability of the material are improved.
Description
Technical Field
The invention belongs to the technical field of sodium ion battery materials, and particularly relates to a ZrO (ZrO-based polymer) 2 Surface coating, zr 4+ A method for preparing doped layered oxide and application thereof.
Background
The global new energy automobile and energy storage industry are growing rapidly and continuously, and lithium resources as core raw materials are becoming important factors influencing industry development due to supply and demand mismatch and economic problems. The sodium resource reserves are rich, the distribution is uniform, the working principle of the sodium battery produced by taking the sodium resource reserves as a raw material is basically consistent with the production process, and compared with a lithium battery, the lithium battery has the advantages of better low-temperature performance, rate capability and economy, and the disadvantage of cycle life and energy density, so that the sodium battery becomes an effective supplement of the lithium battery in the fields of energy storage, commercial vehicles and partial passenger vehicles in the future.
Sodium transition metal layered oxide (Na x MO 2 X is more than 0 and less than or equal to 1, M is a transition metal element Mn, fe, ni, cu and the like), has the characteristics of higher average voltage, high specific capacity, easiness in synthesis and the like due to a periodic layered structure and a two-dimensional ion transmission channel, and is expected to realize industrialization, so that the layered oxide is considered as a sodium ion battery anode material with the most application prospect.
Although the specific capacity of the layered oxide sodium ion battery is higher, the layered oxide sodium ion battery is prepared by the process of sodium ion deintercalationThe middle-layer oxide is easy to generate structural change or phase transformation, and the structural damage of the positive electrode material is easy to be caused, so that the specific capacity, the service life and the safety performance of the sodium ion battery are all greatly influenced. In addition, the transition metal layered oxide has high residual alkali content on the surface, is easy to absorb water in air and is compatible with CO 2 The reaction, air stability is poor.
The layered oxide material has the defects of poor stability and the like, so that the application of the layered oxide material in sodium ion batteries is greatly limited. Therefore, improving the structural stability of the layered oxide, and further improving the cycle life and rate capability of the battery becomes a key problem in the related technology of sodium ion batteries.
Disclosure of Invention
In order to solve the problem of poor structural stability of layered oxides in the prior art, the invention provides a ZrO 2 Surface coating, zr 4+ Doped layered oxide, preparation method and application thereof, and ZrO (zirconium oxide) of the invention 2 Surface coating, zr 4+ The doped layered oxide can improve the air stability of the layered oxide and improve the multiplying power performance and the cycle life of the layered oxide material.
In order to achieve the above purpose, the invention adopts the following technical scheme:
it is an object of the present invention to provide a ZrO 2 Surface coating, zr 4+ Doped layered oxide comprising Zr 4+ Doped layered oxide Na x TMO 2 Located at the Zr 4+ Doped layered oxide Na x TMO 2 ZrO of surface 2 A cladding layer, wherein: x is more than 0.8 and less than or equal to 1, and TM is selected from one or more of Mn, fe and Ni.
1. Preferably, the layered oxide Na x TMO 2 Is Na (Na) x Ni i Fe j Mn k O 2 Wherein: x is more than 0.8 and less than or equal to 1, x+i+j+k=2, i is more than or equal to 0 and less than or equal to 1, j is more than or equal to 0 and less than or equal to 1, and k is more than or equal to 0 and less than or equal to 1.
Preferably, the ZrO 2 Surface coating, zr 4+ Doped layered oxide Na x TMO 2 The particle diameter D50 of the particles is 1-6 mu m; the Z isrO 2 The thickness of the coating layer is 1-20 nm.
It is another object of the present invention to provide a ZrO 2 Surface coating, zr 4+ A method for preparing a doped layered oxide comprising the steps of:
(1) Solid phase method for preparing layered oxide Na x TMO 2 A powder;
(2) The layered oxide Na obtained in the step (1) is reacted with x TMO 2 The powder was added to zirconyl nitrate { ZrO (NO) 3 ） 2 Tetrabutyl zirconate { C } or 16 H 36 O 4 Heating by magnetic stirring in ethanol solution of Zr till the solution is dried to obtain a mixture;
(3) Sintering the mixture obtained in the step (2) to obtain ZrO 2 Surface coating, zr 4+ Doped layered oxides.
Preferably, in step (1), the layered oxide Na x TMO 2 The preparation method of (2) comprises the following steps:
s1, ball-milling and mixing one or more of nickel oxide, iron oxide and manganese oxide with sodium carbonate to obtain a mixture;
s2, performing solid-phase sintering on the mixture obtained in the step S1 to obtain the layered oxide Na x TMO 2 。
Preferably, in step S1, the nickel oxide includes NiO, ni 2 O 3 One or more of the following;
the manganese oxide comprises MnO 2 One or more of MnO;
the iron oxide includes Fe 2 O 3 、Fe 3 O 4 One or more of the following;
the sodium source is preferably sodium carbonate.
Preferably, in step S2, the temperature of the solid phase sintering is 800 to 1000 ℃, and the time of the solid phase sintering is 12 to 24 h.
Preferably, in the step (2), the ZrO 2 The addition amount is the layered oxide Na x TMO 2 Quality of1 to 4 weight percent; the heating temperature is 40-120 ℃, and the heating time is 1-12 h.
Preferably, in the step (3), the temperature of the calcination treatment is 600 to 1000 ℃, and the time of the calcination treatment is 12 to 24 h.
It is a further object of the present invention to provide a ZrO 2 Surface coating, zr 4+ Use of doped layered oxides, said ZrO 2 Surface coating, zr 4+ The doped layered oxide can be applied as a positive electrode material of a sodium ion battery.
Advantageous effects
The invention discloses a ZrO 2 Surface coating, zr 4+ Compared with the prior art, the doped layered oxide and the preparation method and application thereof have the beneficial effects that:
(1) ZrO according to the invention 2 Surface coating, zr 4+ In the doped layered oxide, layered oxide Na x TMO 2 Has ZrO on the surface of 2 A dense coating layer which on the one hand hinders the material from being mixed with H in the air 2 O、CO 2 The reaction occurs, so that the air stability of the material is greatly improved; on the other hand, the structural change of the layered oxide material caused by sodium ion deintercalation in the circulation process is inhibited, and the structural stability of the material in the circulation process is improved.
(2) ZrO according to the invention 2 Surface coating, zr 4+ In doped layered oxides, zrO 2 The existence of the compact coating layer prevents the material from being in direct contact with the electrolyte to a certain extent, ensures the stability of the material interface and improves the cycle performance of the layered oxide material.
(3) ZrO according to the invention 2 Surface coating, zr 4+ Doped layered oxide, zr during sintering 4+ The sodium ions can diffuse into the bulk phase of the material at high temperature to form bulk phase doping, so that the interlayer spacing of the material is enlarged, the diffusion capacity of the sodium ions in the material is improved, and the rate capability of the material is improved; and Zr (Zr) 4+ Is an ion with high valence and can be doped with the ion with high valenceSo as to improve the electronic conductivity of the material and further improve the multiplying power performance of the material; in addition, zr 4+ The doping into the material can also play a role in stabilizing the structure, so that the cycling stability of the material can also be improved.
(4) ZrO according to the invention 2 Surface coating, zr 4+ The preparation method of the doped layered oxide can finish the surface coating and doping process by one step in the sintering process, and is simple and convenient for large-scale application.
Drawings
FIG. 1 shows the result of example 1, which shows 2 wt% ZrO 2 Coated layered oxide Na 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 X-ray diffraction pattern (XRD);
FIG. 2 shows the result of example 1, which shows 2 wt% ZrO 2 Coated layered oxide material Na 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 Scanning Electron Microscope (SEM);
FIG. 3 shows the result of example 1, which shows 2 wt% ZrO 2 Coated layered oxide Na 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 Charge-discharge curves at different rates of (3)
FIG. 4 shows a different ZrO 2 Content of coated layered oxide Na 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 Is a ratio performance comparison of the (c).
FIG. 5 shows a different ZrO 2 Content of coated layered oxide Na 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 Is a comparison of the cycle performance of (c).
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description, it is to be understood that the terms used in this specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description set forth herein is merely a preferred example for the purpose of illustration and is not intended to limit the scope of the invention, so that it should be understood that other equivalents or modifications may be made thereto without departing from the spirit and scope of the invention.
The following examples are merely illustrative of embodiments of the present invention and are not intended to limit the invention in any way, and those skilled in the art will appreciate that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
Example 1
ZrO (ZrO-like grain) 2 Surface coating, zr 4+ Doped Na 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 A layered oxide, the method of preparation comprising the steps of:
(1) Na is mixed with 2 CO 3 、NiO、Fe 2 O 3 、MnO 2 According to Na: ni: fe: mn=1.03: placing the mixture in a ball milling tank with the rotating speed of 350 r/min in a molar ratio of 0.5:0.25:0.25, adding 100 ml ethanol, and ball milling 6 h to fully mix the mixture; placing the mixed powder into a muffle furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, performing high-temperature solid phase sintering for 24 h, naturally cooling and grinding, and sieving with a 400-mesh sieve to obtain a layered oxide material Na 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 And (3) black powder (a part volatilizes during the sintering process of sodium carbonate, and the sodium content in the product is lower than a theoretical value).
(2) The Na obtained in the step (1) is reacted with 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 Adding black powder to a mixture containing 2 wt% ZrO 2 2 In the zirconyl nitrate ethanol solution, heating to 60 ℃ under magnetic stirring until the solution is dried; then placing the mixture in a muffle furnace, and heating to 800 ℃ at 5 ℃/min to calcine the mixture for 6 h. Cooling along with the furnace to obtain the ZrO 2 Surface coating, zr 4+ Doped Na 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 A sample of layered oxide material.
The ZrO 2 Surface coating, zr 4+ Doped layered oxide Na x TMO 2 X is 0.94 and the particle diameter D50 is 1-6 mu m; the ZrO 2 The thickness of the coating layer is 5-10 nm.
The X-ray diffraction pattern (XRD) of the sample obtained in this example is shown in FIG. 1, and it can be seen from FIG. 1 that the sample is alpha-NaFeO 2 Phase with ZrO 2 The content is increased, the XRD diffraction peak of the sample shifts slightly to the left, which indicates Zr 4+ Doped to layered oxide Na x TMO 2 The interlayer spacing is increased.
The morphology of the sample obtained in the embodiment is shown in a Scanning Electron Microscope (SEM) chart 2, and as can be seen from the chart 2, the morphology of the sample is in a flat plate shape, and the particle size is 1-5 mu m.
The sample obtained in the example is taken as a positive electrode material to be assembled with a sodium sheet to form a half cell, the charge-discharge curve is shown in figure 3 within the voltage range of 2-4V, and as can be seen from figure 3, the voltage platform is about 2.7V, and the specific discharge capacity of 0.1C is 164 mAh g -1 。
The sample obtained in the example is used as a positive electrode material to assemble a half cell with a sodium sheet, the multiplying power performance is shown as figure 4 in the voltage range of 2-4V, and as can be seen from figure 4, 2 wt% ZrO 2 Surface-coated Na 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 The layered oxide material has optimal multiplying power performance. The cycle performance is shown in FIG. 5, and as can be seen from FIG. 5, the capacity retention rate for the 1C cycle 100 cycles is 77.5%.
Example 2
ZrO (ZrO-like grain) 2 Surface coating, zr 4+ Doped Na 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 A layered oxide, the method of preparation comprising the steps of:
(1) Na is mixed with 2 CO 3 、NiO、Fe 2 O 3 、MnO 2 According to Na: ni: fe: mn=1.03: placing the mixture in a ball milling tank with the rotating speed of 350 r/min in a molar ratio of 0.5:0.25:0.25, adding 100 ml ethanol, and ball milling 6 h to fully mix the mixture; placing the mixed powder into a muffle furnace at a heating rate of 5 ℃/minHeating to 900 ℃, carrying out high-temperature solid-phase sintering for 24 h, naturally cooling and grinding, and sieving with a 400-mesh sieve to obtain a layered oxide material Na 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 Is a black powder of (a).
(2) Na is mixed with 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 Adding black powder containing ZrO 1wt% 2 In the zirconyl nitrate ethanol solution, heating to 60 ℃ under magnetic stirring until the solution is dried; then placing the mixture in a muffle furnace, and heating to 800 ℃ at 5 ℃/min to calcine the mixture for 6 h. Cooling along with the furnace to obtain the ZrO 2 Surface coating, zr 4+ Doped Na 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 A sample of layered oxide material.
The ZrO 2 Surface coating, zr 4+ Doped layered oxide Na x TMO 2 X is 0.94 and the particle diameter D50 is 1-6 mu m; the ZrO 2 The thickness of the coating layer is 1-5 nm.
The sample obtained in the embodiment is used as a positive electrode material to assemble a half cell with a sodium sheet, the multiplying power performance is shown as figure 4 in the voltage range of 2-4V, and the multiplying power performance is improved compared with that of an uncoated sample as seen in figure 4. The cycle performance is shown in FIG. 5, and it can be seen from FIG. 5 that the capacity retention rate for 100 cycles of 1C cycle is 73.6%.
Example 3
ZrO (ZrO-like grain) 2 Surface coating, zr 4+ Doped Na 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 A layered oxide, the method of preparation comprising the steps of:
(1) Na is mixed with 2 CO 3 、NiO、Fe 2 O 3 、MnO 2 According to Na: ni: fe: mn=1.03: placing the mixture in a ball milling tank with the rotating speed of 350 r/min in a molar ratio of 0.5:0.25:0.25, adding 100 ml ethanol, and ball milling 6 h to fully mix the mixture; placing the mixed powder into a muffle furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, performing high-temperature solid phase sintering for 24 h, naturally cooling and grinding, and sieving with a 400-mesh sieve to obtain a layered oxide material Na 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 Is a black powder of (a).
(2) Na is mixed with 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 Adding black powder to a mixture containing 4. 4wt% ZrO 2 2 In the zirconyl nitrate ethanol solution, heating to 60 ℃ under magnetic stirring until the solution is dried; then placing the mixture in a muffle furnace, and heating to 800 ℃ at 5 ℃/min to calcine the mixture for 6 h. Cooling along with the furnace to obtain the ZrO 2 Surface coating, zr 4+ Doped Na 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 A sample of layered oxide material.
The ZrO 2 Surface coating, zr 4+ Doped layered oxide Na x TMO 2 X is 0.94 and the particle diameter D50 is 1-6 mu m; the ZrO 2 The thickness of the coating layer is 10-20 nm.
The sample obtained in the embodiment is used as a positive electrode material to assemble a half cell with a sodium sheet, the multiplying power performance is shown as figure 4 in the voltage range of 2-4V, and the multiplying power performance is improved compared with that of an uncoated sample as seen in figure 4. The cycle performance is shown in fig. 5, and it can be seen from fig. 5 that the capacity retention rate for 100 cycles of 1C cycle is 74%.
Example 4
ZrO (ZrO-like grain) 2 Surface coating, zr 4+ Doped Na 0.85 Ni 0.55 Fe 0.3 Mn 0.3 O 2 A layered oxide, the method of preparation comprising the steps of:
(1) Na is mixed with 2 CO 3 、NiO、Fe 2 O 3 、MnO 2 According to Na: ni, fe: mn=1: placing the mixture in a ball milling tank with the rotating speed of 350 r/min in a molar ratio of 0.5:0.25:0.25, adding 100 ml ethanol, and ball milling 6 h to fully mix the mixture; placing the mixed powder into a muffle furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, performing high-temperature solid phase sintering for 24 h, naturally cooling and grinding, and sieving with a 400-mesh sieve to obtain a layered oxide material Na 0.85 Ni 0.55 Fe 0.3 Mn 0.3 O 2 Is a black powder of (a).
(2) The Na obtained in the step (1) is reacted with 0.85 Ni 0.55 Fe 0.3 Mn 0.3 O 2 Adding black powder to a mixture containing 2 wt% ZrO 2 2 In the zirconyl nitrate ethanol solution, heating to 60 ℃ under magnetic stirring until the solution is dried; then placing the mixture in a muffle furnace, and heating to 800 ℃ at 5 ℃/min to calcine the mixture for 6 h. Cooling along with the furnace to obtain the ZrO 2 Surface coating, zr 4+ Doped Na 0.85 Ni 0.55 Fe 0.3 Mn 0.3 O 2 A sample of layered oxide material.
The ZrO 2 Surface coating, zr 4+ Doped layered oxide Na x TMO 2 X is 0.85 and the particle diameter D50 is 1-6 mu m; the ZrO 2 The thickness of the coating layer is 5-10 nm.
Example 5
ZrO (ZrO-like grain) 2 Surface coating, zr 4+ Doped Na 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 A layered oxide, the method of preparation comprising the steps of:
(1) Na is mixed with 2 CO 3 、NiO、Fe 2 O 3 、MnO 2 According to Na: ni: fe: mn=1.03: placing the mixture in a ball milling tank with the rotating speed of 350 r/min in a molar ratio of 0.5:0.25:0.25, adding 100 ml ethanol, and ball milling 6 h to fully mix the mixture; placing the mixed powder into a muffle furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, performing high-temperature solid phase sintering for 24 h, naturally cooling and grinding, and sieving with a 400-mesh sieve to obtain a layered oxide material Na 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 Is a black powder of (a).
(2) The Na obtained in the step (1) is reacted with 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 Adding black powder to a mixture containing 2 wt% ZrO 2 2 In the zirconyl nitrate ethanol solution, heating to 60 ℃ under magnetic stirring until the solution is dried; then placing the mixture in a muffle furnace, and heating to 800 ℃ at 5 ℃/min to calcine the mixture for 6 h. Cooling along with the furnace to obtain the ZrO 2 Surface coating, zr 4+ Doped NaNi 0.5 Fe 0.25 Mn 0.25 O 2 A sample of layered oxide material.
The ZrO 2 Surface coating, zr 4+ Doped layered oxide Na x TMO 2 X is 0.94 and the particle diameter D50 is 1-6 mu m; the ZrO 2 The thickness of the coating layer is 5-10 nm.
Example 6
ZrO (ZrO-like grain) 2 Surface coating, zr 4+ Doped NaNi 0.5 Fe 0.25 Mn 0.25 O 2 A layered oxide, the method of preparation comprising the steps of:
(1) Na is mixed with 2 CO 3 、NiO、Fe 2 O 3 、MnO 2 According to Na: ni: fe: mn=1.05: placing the mixture in a ball milling tank with the rotating speed of 350 r/min in a molar ratio of 0.5:0.25:0.25, adding 100 ml ethanol, and ball milling 6 h to fully mix the mixture; placing the mixed powder into a muffle furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, performing high-temperature solid phase sintering for 24 h, naturally cooling and grinding, and sieving with a 400-mesh sieve to obtain a layered oxide material NaNi 0.5 Fe 0.25 Mn 0.25 O 2 Is a black powder of (a).
(2) The NaNi obtained in the step (1) is treated 0.5 Fe 0.25 Mn 0.25 O 2 Adding black powder to a mixture containing 2 wt% ZrO 2 2 In the zirconyl nitrate ethanol solution, heating to 60 ℃ under magnetic stirring until the solution is dried; then placing the mixture in a muffle furnace, and heating to 800 ℃ at 5 ℃/min to calcine the mixture for 6 h. Cooling along with the furnace to obtain the ZrO 2 Surface coating, zr 4+ Doped NaNi 0.5 Fe 0.25 Mn 0.25 O 2 A sample of layered oxide material.
The ZrO 2 Surface coating, zr 4+ Doped layered oxide Na x TMO 2 X is 1 and the particle diameter D50 is 1-6 mu m; the ZrO 2 The thickness of the coating layer is 5-10 nm.
Example 7
ZrO (ZrO-like grain) 2 Surface coating, zr 4+ Doped NaNi 0.5 Fe 0.25 Mn 0.25 O 2 A layered oxide, the method of preparation comprising the steps of:
(1) Na is mixed with 2 CO 3 、Ni 2 O 3 、Fe 2 O 3 、MnO 2 According to Na: ni: fe: mn=1.05: placing the mixture in a ball milling tank with the rotating speed of 350 r/min in a molar ratio of 0.25:0.25:0.25, adding 100 ml ethanol, and ball milling 6 h to fully mix the mixture; placing the mixed powder into a muffle furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, performing high-temperature solid phase sintering for 24 h, naturally cooling and grinding, and sieving with a 400-mesh sieve to obtain a layered oxide material NaNi 0.5 Fe 0.25 Mn 0.25 O 2 Is a black powder of (a).
(2) The NaNi obtained in the step (1) is treated 0.5 Fe 0.25 Mn 0.25 O 2 Adding black powder to a mixture containing 2 wt% ZrO 2 2 In the zirconyl nitrate ethanol solution, heating to 60 ℃ under magnetic stirring until the solution is dried; then placing the mixture in a muffle furnace, and heating to 800 ℃ at 5 ℃/min to calcine the mixture for 6 h. Cooling along with the furnace to obtain the ZrO 2 Surface coating, zr 4+ Doped NaNi 0.5 Fe 0.25 Mn 0.25 O 2 A sample of layered oxide material.
The ZrO 2 Surface coating, zr 4+ Doped layered oxide Na x TMO 2 X is 1 and the particle diameter D50 is 1-6 mu m; the ZrO 2 The thickness of the coating layer is 5-10 nm.
Example 8
ZrO (ZrO-like grain) 2 Surface coating, zr 4+ Doped NaNi 0.5 Fe 0.25 Mn 0.25 O 2 A layered oxide, the method of preparation comprising the steps of:
(1) Na is mixed with 2 CO 3 、Ni 2 O 3 、Fe 3 O 4 、MnO 2 According to Na: ni: fe: mn=1.05: placing the mixture in a ball milling tank with the rotating speed of 350 r/min in a molar ratio of 0.25:0.25:0.25, adding 100 ml ethanol, and ball milling 6 h to fully mix the mixture; placing the mixed powder into a muffle furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, performing high-temperature solid phase sintering for 24 h, naturally cooling and grinding, and sieving with a 400-mesh sieve to obtain a layered oxide material NaNi 0.5 Fe 0.25 Mn 0.25 O 2 Is a black powder of (a).
(2) The NaNi obtained in the step (1) is treated 0.5 Fe 0.25 Mn 0.25 O 2 Adding black powder to a mixture containing 2 wt% ZrO 2 2 In the zirconyl nitrate ethanol solution, heating to 60 ℃ under magnetic stirring until the solution is dried; then placing the mixture in a muffle furnace, and heating to 800 ℃ at 5 ℃/min to calcine the mixture for 6 h. Cooling along with the furnace to obtain the ZrO 2 Surface coating, zr 4+ Doped NaNi 0.5 Fe 0.25 Mn 0.25 O 2 A sample of layered oxide material.
The ZrO 2 Surface coating, zr 4+ Doped layered oxide Na x TMO 2 X is 1 and the particle diameter D50 is 1-6 mu m; the ZrO 2 The thickness of the coating layer is 5-10 nm.
Example 9
ZrO (ZrO-like grain) 2 Surface coating, zr 4+ Doped NaNi 0.5 Fe 0.25 Mn 0.25 O 2 A layered oxide, the method of preparation comprising the steps of:
(1) Na is mixed with 2 CO 3 、Ni 2 O 3 、Fe 2 O 3 、Mn 2 O 3 According to Na: ni: fe: mn=1.05: placing the mixture in a ball milling tank with the rotating speed of 350 r/min in a molar ratio of 0.25:0.25:0.25, adding 100 ml ethanol, and ball milling 6 h to fully mix the mixture; placing the mixed powder into a muffle furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, performing high-temperature solid phase sintering for 24 h, naturally cooling and grinding, and sieving with a 400-mesh sieve to obtain a layered oxide material NaNi 0.5 Fe 0.25 Mn 0.25 O 2 Is a black powder of (a).
(2) The NaNi obtained in the step (1) is treated 0.5 Fe 0.25 Mn 0.25 O 2 Adding black powder to a mixture containing 2 wt% ZrO 2 2 In the zirconyl nitrate ethanol solution, heating to 60 ℃ under magnetic stirring until the solution is dried; then placing the mixture in a muffle furnace, and heating to 800 ℃ at 5 ℃/min to calcine the mixture for 6 h. Cooling along with the furnace to obtain the ZrO 2 Surface coating, zr 4+ Doped NaNi 0.5 Fe 0.25 Mn 0.25 O 2 A sample of layered oxide material.
The ZrO 2 Surface coating, zr 4+ Doped layered oxide Na x TMO 2 X is 1 and the particle diameter D50 is 1-6 mu m; the ZrO 2 The thickness of the coating layer is 5-10 nm.
Example 10
ZrO (ZrO-like grain) 2 Surface coating, zr 4+ Doped NaNi 0.5 Fe 0.25 Mn 0.25 O 2 A layered oxide, the method of preparation comprising the steps of:
(1) Na is mixed with 2 CO 3 、Ni 2 O 3 、Fe 2 O 3 、MnO 2 According to Na: ni: fe: mn=1.05: placing the mixture in a ball milling tank with the rotating speed of 350 r/min in a molar ratio of 0.25:0.25:0.25, adding 100 ml ethanol, and ball milling 6 h to fully mix the mixture; placing the mixed powder into a muffle furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, performing high-temperature solid phase sintering for 24 h, naturally cooling and grinding, and sieving with a 400-mesh sieve to obtain a layered oxide material NaNi 0.5 Fe 0.25 Mn 0.25 O 2 Is a black powder of (a).
(2) The NaNi obtained in the step (1) is treated 0.5 Fe 0.25 Mn 0.25 O 2 Adding black powder to a mixture containing 2 wt% ZrO 2 2 In the zirconyl nitrate ethanol solution, heating to 60 ℃ under magnetic stirring until the solution is dried; then placing the mixture in a muffle furnace, and heating to 800 ℃ at 5 ℃/min to calcine 24 h. Cooling along with the furnace to obtain the ZrO 2 Surface coating, zr 4+ Doped NaNi 0.5 Fe 0.25 Mn 0.25 O 2 A sample of layered oxide material.
The ZrO 2 Surface coating, zr 4+ Doped layered oxide Na x TMO 2 X is 1 and the particle diameter D50 is 1-6 mu m; the ZrO 2 The thickness of the coating layer is 5-10 nm.
Example 11
ZrO (ZrO-like grain) 2 Surface coating, zr 4+ Doped NaNi 0.5 Fe 0.25 Mn 0.25 O 2 Layered oxide, process for producing the sameThe preparation method comprises the following steps:
(1) Na is mixed with 2 CO 3 、Ni 2 O 3 、Fe 2 O 3 、MnO 2 According to Na: ni: fe: mn=1.05: placing the mixture in a ball milling tank with the rotating speed of 350 r/min in a molar ratio of 0.25:0.25:0.25, adding 100 ml ethanol, and ball milling 6 h to fully mix the mixture; placing the mixed powder into a muffle furnace, heating to 800 ℃ at a heating rate of 5 ℃/min, performing high-temperature solid phase sintering for 24 h, naturally cooling and grinding, and sieving with a 400-mesh sieve to obtain a layered oxide material NaNi 0.5 Fe 0.25 Mn 0.25 O 2 Is a black powder of (a).
(2) The NaNi obtained in the step (1) is treated 0.5 Fe 0.25 Mn 0.25 O 2 Adding black powder to a mixture containing 2 wt% ZrO 2 2 In the zirconyl nitrate ethanol solution, heating to 70 ℃ under magnetic stirring until the solution is dried; then placing the mixture in a muffle furnace, and heating to 600 ℃ at 5 ℃/min to calcine 24-h. Cooling along with the furnace to obtain the ZrO 2 Surface coating, zr 4+ Doped NaNi 0.5 Fe 0.25 Mn 0.25 O 2 A sample of layered oxide material.
The ZrO 2 Surface coating, zr 4+ Doped layered oxide Na x TMO 2 X is 1 and the particle diameter D50 is 1-6 mu m; the ZrO 2 The thickness of the coating layer is 5-10 nm.
Example 12
ZrO (ZrO-like grain) 2 Surface coating, zr 4+ Doped NaNi 0.5 Fe 0.25 Mn 0.25 O 2 A layered oxide, the method of preparation comprising the steps of:
(1) Na is mixed with 2 CO 3 、Ni 2 O 3 、Fe 2 O 3 、MnO 2 According to Na: ni: fe: mn=1.05: placing the mixture in a ball milling tank with the rotating speed of 350 r/min in a molar ratio of 0.25:0.25:0.25, adding 100 ml ethanol, and ball milling 6 h to fully mix the mixture; placing the mixed powder into a muffle furnace, heating to 1000 ℃ at a heating rate of 5 ℃/min, performing high-temperature solid phase sintering for 12 h, naturally cooling and grinding, and sieving with a 400-mesh sieve to obtain the layered oxidationMaterial NaNi 0.5 Fe 0.25 Mn 0.25 O 2 Is a black powder of (a).
(2) The NaNi obtained in the step (1) is treated 0.5 Fe 0.25 Mn 0.25 O 2 Adding black powder to a mixture containing 2 wt% ZrO 2 2 In the zirconyl nitrate ethanol solution, heating to 120 ℃ under magnetic stirring until the solution is dried; then placing the mixture in a muffle furnace, and heating to 1000 ℃ at 5 ℃/min to calcine the mixture at 12 h. Cooling along with the furnace to obtain the ZrO 2 Surface coating, zr 4+ Doped NaNi 0.5 Fe 0.25 Mn 0.25 O 2 A sample of layered oxide material.
The ZrO 2 Surface coating, zr 4+ Doped layered oxide Na x TMO 2 X is 1 and the particle diameter D50 is 1-6 mu m; the ZrO 2 The thickness of the coating layer is 5-10 nm.
Example 13
ZrO (ZrO-like grain) 2 Surface coating, zr 4+ Doped Na 0.85 Ni 0.55 Fe 0.3 Mn 0.3 O 2 A layered oxide, the method of preparation comprising the steps of:
(1) Na is mixed with 2 CO 3 、NiO、Fe 2 O 3 、MnO 2 According to Na: ni, fe: mn=1: placing the mixture in a ball milling tank with the rotating speed of 350 r/min in a molar ratio of 0.5:0.25:0.25, adding 100 ml ethanol, and ball milling 6 h to fully mix the mixture; placing the mixed powder into a muffle furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, performing high-temperature solid phase sintering for 24 h, naturally cooling and grinding, and sieving with a 400-mesh sieve to obtain a layered oxide material Na 0.85 Ni 0.55 Fe 0.3 Mn 0.3 O 2 Is a black powder of (a).
(2) The NaNi obtained in the step (1) is treated 0.5 Fe 0.25 Mn 0.25 O 2 Adding black powder to a mixture containing 2 wt% ZrO 2 2 In tetrabutyl zirconate ethanol solution, heating to 60 ℃ under magnetic stirring until the solution is dried; then placing the mixture in a muffle furnace, and heating to 800 ℃ at 5 ℃/min to calcine the mixture for 6 h. Cooling along with the furnace to obtain the ZrO 2 Surface coating,Zr 4+ Doped Na 0.85 Ni 0.55 Fe 0.3 Mn 0.3 O 2 A sample of layered oxide material.
The ZrO 2 Surface coating, zr 4+ Doped layered oxide Na x TMO 2 X is 0.85 and the particle diameter D50 is 1-6 mu m; the ZrO 2 The thickness of the coating layer is 5-10 nm.
Example 14
ZrO (ZrO-like grain) 2 Surface coating, zr 4+ Doped NaNi 0.5 Fe 0.25 Mn 0.25 O 2 A layered oxide, the method of preparation comprising the steps of:
(1) Na is mixed with 2 CO 3 、Ni 2 O 3 、Fe 2 O 3 、MnO 2 According to Na: ni: fe: mn=1.05: placing the mixture in a ball milling tank with the rotating speed of 350 r/min in a molar ratio of 0.25:0.25:0.25, adding 100 ml ethanol, and ball milling 6 h to fully mix the mixture; placing the mixed powder into a muffle furnace, heating to 800 ℃ at a heating rate of 5 ℃/min, performing high-temperature solid phase sintering for 24 h, naturally cooling and grinding, and sieving with a 400-mesh sieve to obtain a layered oxide material NaNi 0.5 Fe 0.25 Mn 0.25 O 2 Is a black powder of (a).
(2) The NaNi obtained in the step (1) is treated 0.5 Fe 0.25 Mn 0.25 O 2 Adding black powder to a mixture containing 2 wt% ZrO 2 2 In tetrabutyl zirconate ethanol solution, heating to 70 ℃ under magnetic stirring until the solution is dried; then placing the mixture in a muffle furnace, and heating to 600 ℃ at 5 ℃/min to calcine 24-h. Cooling along with the furnace to obtain the ZrO 2 Surface coating, zr 4+ Doped NaNi 0.5 Fe 0.25 Mn 0.25 O 2 A sample of layered oxide material.
The ZrO 2 Surface coating, zr 4+ Doped layered oxide Na x TMO 2 X is 1 and the particle diameter D50 is 1-6 mu m; the ZrO 2 The thickness of the coating layer is 5-10 nm.
Comparative example 1
(1) Na is mixed with 2 CO 3 、NiO、Fe 2 O 3 、MnO 2 According to 1.03: placing the mixture in a ball milling tank with the rotating speed of 350 r/min in a molar ratio of 0.5:0.25:0.25, adding 100 ml ethanol, and ball milling 6 h to fully mix the mixture; placing the mixed powder into a muffle furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, performing high-temperature solid phase sintering for 24 h, naturally cooling and grinding, and sieving with a 400-mesh sieve to obtain a layered oxide material Na 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 Is a black powder of (a).
(2) Na is mixed with 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 The black powder was placed in a muffle furnace and calcined at 5 c/min to 800 c for 6 h. Cooling along with the furnace to obtain Na 0.94 Ni 0.52 Fe 0.27 Mn 0.27 O 2 Layered oxide materials.
The sample obtained in this comparative example was used as a positive electrode material to assemble a half cell with a sodium sheet, and the rate performance was as shown in fig. 4 in the voltage range of 2 to 4V, and it can be seen from fig. 4 that the rate performance of the sample obtained in this comparative example was the lowest. The cycle performance is shown in fig. 5, and it can be seen from fig. 5 that the capacity retention rate for 100 cycles of 1C cycle is 58%.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be apparent to one skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features thereof; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (10)
1. ZrO (ZrO-like grain) 2 Surface coating, zr 4+ A doped layered oxide comprising Zr 4+ Doped layered oxide Na x TMO 2 And is located at the Zr 4+ Doped layered oxide Na x TMO 2 ZrO of surface 2 A cladding layer, wherein: x is more than 0.8 and less than or equal to 1, and TM is selected from one or more of Mn, fe and Ni.
2. A ZrO as claimed in claim 1 2 Surface coating, zr 4+ Doped layered oxide, characterized in that the layered oxide Na x TMO 2 Is Na (Na) x Ni i Fe j Mn k O 2 Wherein: x is more than 0.8 and less than or equal to 1, x+i+j+k=2, i is more than or equal to 0 and less than or equal to 1, j is more than or equal to 0 and less than or equal to 1, and k is more than or equal to 0 and less than or equal to 1.
3. A ZrO as claimed in claim 1 2 Surface coating, zr 4+ Doped layered oxide, characterized in that the ZrO 2 Surface coating, zr 4+ Doped layered oxide Na x TMO 2 The particle diameter D50 of the particles is 1-6 mu m; the ZrO 2 The thickness of the coating layer is 1-20 nm.
4. A ZrO according to any one of claims 1 to 3 2 Surface coating, zr 4+ A method for preparing a doped layered oxide, comprising the steps of:
(1) Solid phase method for preparing layered oxide Na x TMO 2 A powder;
(2) The layered oxide Na obtained in the step (1) is reacted with x TMO 2 Adding the powder into ethanol solution of zirconyl nitrate or tetrabutyl zirconate, magnetically stirring and heating until the solution is dried to obtain a mixture;
(3) Calcining the mixture obtained in the step (2) to obtain the ZrO 2 Surface coating, zr 4+ Doped layered oxides.
5. The method according to claim 4, wherein in the step (1), the layered oxide Na x TMO 2 The preparation method of the powder comprises the following steps:
s1, ball-milling and mixing one or more of nickel oxide, iron oxide and manganese oxide with sodium carbonate to obtain a mixture;
s2, mixing the obtained mixture obtained in the step S1Solid phase sintering the compound to obtain the layered oxide Na x TMO 2 And (3) powder.
6. The method according to claim 5, wherein in step S1, the nickel oxide is NiO or Ni 2 O 3 One or more of the following; the manganese oxide is MnO 2 、Mn 2 O 3 One or more of the following; the iron oxide is Fe 2 O 3 、Fe 3 O 4 One or more of the following; the sodium source is preferably sodium carbonate.
7. The method according to claim 5, wherein in step S2, the solid phase sintering is performed at a temperature of 800 to 1000 ℃ for a time of 12 to 24 h.
8. The process according to claim 4, wherein in the step (2), zrO 2 The addition amount is the layered oxide Na x TMO 2 1 to 4 weight percent of the mass; the heating temperature is 40-120 ℃, and the heating time is 1-12 h.
9. The method according to claim 4, wherein in the step (3), the temperature of the calcination treatment is 600 to 1000℃and the time of the calcination treatment is 12 to 24 h.
10. ZrO as claimed in any one of claims 1-3 2 Surface coating, zr 4+ The use of doped layered oxides, characterized in that the ZrO 2 Surface coating, zr 4+ The doped layered oxide is applied to a sodium ion battery anode material.
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