CN117416995A - Preparation method and application of sodium ion positive electrode material - Google Patents
Preparation method and application of sodium ion positive electrode material Download PDFInfo
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- CN117416995A CN117416995A CN202311348442.0A CN202311348442A CN117416995A CN 117416995 A CN117416995 A CN 117416995A CN 202311348442 A CN202311348442 A CN 202311348442A CN 117416995 A CN117416995 A CN 117416995A
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 82
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 45
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 31
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000005751 Copper oxide Substances 0.000 claims abstract description 27
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000005245 sintering Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 238000007873 sieving Methods 0.000 claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 238000000975 co-precipitation Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 239000010406 cathode material Substances 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 8
- 239000010405 anode material Substances 0.000 abstract description 5
- 238000005056 compaction Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 29
- 239000011572 manganese Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- 239000013078 crystal Substances 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 239000012535 impurity Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000010438 heat treatment 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
- 238000002441 X-ray diffraction Methods 0.000 description 2
- IREHHCMIJCTSKK-UHFFFAOYSA-H [OH-].[Fe+2].[Mn+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [OH-].[Fe+2].[Mn+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-] IREHHCMIJCTSKK-UHFFFAOYSA-H 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method of a sodium ion positive electrode material, which comprises the following steps: according to a certain proportion, the precursor Ni of the positive electrode material 1/ 3 Fe 1/3 Mn 1/3 (OH) 2 Uniformly mixing the sodium source compound, the copper oxide and the ferric oxide to obtain a mixture; and sintering, crushing and sieving the mixture under a certain condition to obtain the sodium ion anode material. The sodium ion positive electrode material monocrystal prepared by the preparation method has obvious appearance, high crystallinity and higher compaction density and cycle performance. The preparation method has simple process flow and is suitable for large-scale industrial production. The invention also provides a sodium ion positive electrode material prepared by the preparation method, and the sodium ion positive electrode material comprisesThe sodium ion battery of the sodium ion positive electrode material.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a preparation method of a sodium ion positive electrode material, the sodium ion positive electrode material and a sodium ion battery.
Background
As a representative secondary battery with the highest comprehensive performance, commercialization of a lithium ion battery can be traced back to the 90 th century, and research on the lithium ion battery has been conducted for many years to have a mature battery technology route. However, lithium ion batteries are difficult to support in the current growing energy storage market, limited by the abundance of lithium element crust. The working principle of the sodium ion battery is similar to that of a lithium ion battery, the sodium salt reserves are rich, the exploitation is simple, and the method has more advantages in the large-scale application direction in the subsequent energy storage field.
Sodium-electricity positive electrode material is the energy density source of sodium ion battery, and research scholars find in the preparation process that the sodium positive electrode material that uses the precursor sintering to obtain is in the process, and sintering temperature only needs to be less than 1000 ℃ in order to fully react, obtains sodium positive electrode material on the one hand, and secondly because sintering temperature is too high, finally sinters into the sodium positive electrode material that single crystal appearance is mostly sheet structure. On one hand, the energy is wasted due to high temperature, and the production cost is increased; on the other hand, the obtained sheet-like structure of the sodium positive electrode material causes deterioration of the battery cycle performance by structural change or phase transition.
In the prior art, researchers also add CuO as a sintering aid to a precursor of the sodium-electricity positive electrode material to perform sintering, and generally the molar quantity of copper oxide is 2% of that of the precursor of the sodium-electricity positive electrode material, so that the sintering aid effect can be achieved, and the sintering temperature can be successfully reduced to not higher than 1000 ℃. However, such excessive addition of copper oxide can enhance the firing assisting effect, but also results in generation of a hetero-phase, thereby causing a decrease in the electrical properties of the obtained sodium-electric positive electrode material.
Disclosure of Invention
In view of the above, the present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a preparation method and application of a sodium ion positive electrode material. The preparation method provided by the invention can be used for preparing the sodium ion positive electrode material with low sulfur and low impurities, and further can be used for preparing the ferric hydrogen phosphate and the sodium ion positive electrode material with low impurities, and can be used for improving the utilization rate of the battery material. Meanwhile, the preparation method has simple process flow and is suitable for large-scale industrial production.
To this end, in a first aspect, an embodiment of the present invention provides a method for preparing a sodium ion positive electrode material, where the method includes:
s10, according to a certain proportion, the precursor Ni of the positive electrode material 1/3 Fe 1/3 Mn 1/3 (OH) 2 Uniformly mixing the sodium source compound, the copper oxide and the ferric oxide to obtain a mixture;
and S20, sintering, crushing and sieving the mixture under a certain condition to obtain the sodium ion positive electrode material.
Preferably, the sodium source compound comprises at least one of sodium carbonate, sodium hydroxide, sodium phosphate, sodium chloride.
Preferably, the molar ratio of the copper oxide to the addition of the positive electrode material precursor in the mixture is less than 0.02:1.
Preferably, the molar ratio of the copper oxide to the addition of the positive electrode material precursor in the mixture is less than 0.008:1; and/or the molar ratio of the ferric oxide to the addition of the positive electrode material precursor in the mixture is less than 0.008:1; and/or the molar ratio of the sodium source compound to the addition amount of the positive electrode material precursor is (0.87-1.04): 1.
Preferably, the particle size D50 of the positive electrode material precursor is 3 μm to 7 μm; and/or the number of the groups of groups,
the mixing time of the mixture in a high-speed mixer is 30-60 min, and the mixing rotating speed is 600-900 rpm.
Preferably, the preparation method further comprises:
s5, mixing the mixed salt solution of Ni, fe and Mn, the sodium hydroxide solution and the ammonia water solution in parallel flow according to a certain proportion, and performing coprecipitation reaction to obtain a precipitation intermediate; washing, drying and screening the precipitated intermediate to obtain the precursor Ni of the sodium ion positive electrode material x Fe y Mn z (OH) 2 。
Preferably, the molar ratio of Ni, fe and Mn in the mixed salt solution is 1:1:1; the total molar concentration of Ni, fe and Mn in the mixed salt solution is 1.8 mol/L-2.5 mol/L; and/or the number of the groups of groups,
the mass fraction of the sodium hydroxide solution is 20% -40%; and/or the number of the groups of groups,
the molar concentration of the ammonia water solution is 1.5mol/L-8mol/L; and/or the number of the groups of groups,
the coprecipitation reaction is carried out under an inert atmosphere; and/or the number of the groups of groups,
the pH value of the coprecipitation reaction mixed solution is 9-11, and the reaction temperature is 40-60 ℃; and/or the number of the groups of groups,
the stirring speed of the coprecipitation reaction is 200r/min-800r/min.
Preferably, the washing, drying and screening steps specifically include:
washing the precipitation intermediate with sodium hydroxide of 0mol/L-1mol/L for three times, and washing with pure water until the conductivity is less than or equal to 30us/cm; drying to obtain Ni x Fe y Mn z (OH) 2 Sieving the dried material with a 200-350 mesh sieve, and obtaining the precursor of the anode material compound after sieving.
In a second aspect, the present invention also provides a sodium ion positive electrode material, which is prepared according to the preparation method described in the first aspect.
In a third aspect, an embodiment of the present invention further provides a sodium ion battery, where the sodium ion battery includes the sodium ion positive electrode material provided in the second aspect.
According to the preparation method of the sodium ion positive electrode material, copper oxide and ferric oxide are added in one-time sintering, the synergistic fluxing effect of the copper oxide and the ferric oxide can promote the formation of single crystals, the molar quantity of CuO added can be obviously reduced, the sintering temperature is greatly reduced due to the synergistic effect of copper and ferric, the sintering temperature is reduced, and the addition of ferric iron can replace Ni, so that the formation of impurity phases caused by trivalent nickel formed by charge balance is reduced, the single-dispersed single-crystal sodium ion positive electrode material is obtained, the single crystal morphology of crystal grains is obvious, the crystallinity is high, and meanwhile, the compaction density and the cycle performance are higher. In addition, the preparation method has the advantages of simple process flow, high efficiency, no need of high-end equipment, no need of adding expensive reagents, low-cost and easily-obtained raw materials, no involvement of toxic and harmful raw materials, and suitability for large-scale industrialized production.
Drawings
FIG. 1 is a flow chart of a method for preparing a sodium ion positive electrode material according to an embodiment of the present invention;
FIG. 2 is an SEM image of a sodium ion positive electrode material prepared in example 1 of the present invention;
FIG. 3 is an XRD pattern of a sodium ion positive electrode material prepared in example 1 of the present invention;
FIG. 4 is an SEM image of a sodium ion positive electrode material prepared in comparative example 1 of the present invention;
FIG. 5 is an SEM image of a sodium ion positive electrode material prepared in comparative example 2 of the present invention;
fig. 6 is an XRD pattern of the sodium ion positive electrode material prepared in comparative example 3 of the present invention.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
The following disclosure provides many different embodiments, or examples, for implementing different structures of the invention. In order to simplify the present disclosure, components and arrangements of specific examples are described below. They are, of course, merely examples and are not intended to limit the invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art will recognize the applicability of other processes and/or the use of other materials.
Referring to FIG. 1, the present invention is directed to a method for preparing a sodium ion positive electrode material, specifically, a single crystal type O3-type structure positive electrode material without impurity phase, wherein the chemical formula is Na a Ni x Fe y Mn z Cu b O 2 Wherein a:0.67-1.1, x:0-0.35, y:0-0.35, z:0-0.35, b:0-0.01, x+y+z+b=1, preferably a:0.8-1.03, x:0.30-0.35, y:0.32-0.35, z:0.30-0.35, b:0-0.008.
The preparation method comprises the following steps:
s10, according to a certain proportion, the precursor Ni of the positive electrode material 1/3 Fe 1/3 Mn 1/3 (OH) 2 Uniformly mixing the sodium source compound, the copper oxide and the ferric oxide to obtain a mixture;
and S20, sintering, crushing and sieving the mixture under a certain condition to obtain the sodium ion positive electrode material.
Wherein the nickel-iron-manganese hydroxide Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 Can be prepared by wet coprecipitation or used by outsourcing.
Further, the sodium source compound comprises at least one of sodium carbonate, sodium hydroxide, sodium phosphate, and sodium chloride.
Further, the molar ratio of the copper oxide to the addition of the positive electrode material precursor in the mixture is less than 0.02:1.
Further, the molar ratio of the copper oxide to the addition of the positive electrode material precursor in the mixture is less than 0.008:1. The molar ratio of the ferric oxide to the addition of the positive electrode material precursor in the mixture is less than 0.008:1. The molar ratio of the sodium source compound to the addition amount of the positive electrode material precursor is (0.87-1.04): 1.
Further, the particle size D50 of the positive electrode material precursor is 3-7 μm. The mixing time of the mixture in a high-speed mixer is 30-60 min, and the mixing rotating speed is 600-900 rpm.
Further, the preparation method also comprises a precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 Specifically comprising the following steps:
s5, mixing the mixed salt solution of Ni, fe and Mn, the sodium hydroxide solution and the ammonia water solution in parallel flow according to a certain proportion, and performing coprecipitation reaction to obtain a precipitation intermediate; washing, drying and screening the precipitated intermediate to obtain the precursor Ni of the sodium ion positive electrode material x Fe y Mn z (OH) 2 。
Further, the molar ratio of Ni, fe and Mn in the mixed salt solution is 1:1:1; the total molar concentration of Ni, fe and Mn in the mixed salt solution is 1.8 mol/L-2.5 mol/L. The mass fraction of the sodium hydroxide solution is 20% -40%. The molar concentration of the ammonia water solution is 1.5mol/L-8mol/L. The coprecipitation reaction is carried out under an inert atmosphere. The pH value of the coprecipitation reaction mixed solution is 9-11, and the reaction temperature is 40-60 ℃. The stirring speed of the coprecipitation reaction is 200r/min-800r/min.
Further, the washing, drying and screening steps specifically comprise:
washing the precipitation intermediate with sodium hydroxide of 0mol/L-1mol/L for three times, and washing with pure water until the conductivity is less than or equal to 30us/cm; drying to obtain Ni x Fe y Mn z (OH) 2 Sieving the dried material with a 200-350 mesh sieve, and obtaining the precursor of the anode material compound after sieving.
One embodiment of the present invention can be implemented by the following steps.
Preparing Ni salt, fe salt and Mn salt solution according to the molar ratio of Ni to Fe to Mn of 1:1:1, wherein the total molar concentration of Ni, fe and Mn is 1.8-2.5 mol/L;
preparing a sodium hydroxide solution with the mass fraction of 20-40% and an ammonia water solution with the concentration of 1.5-8 mol/L;
adding salt solution, sodium hydroxide solution and ammonia water solution into a reaction device in parallel flow, and introducing inert gas, wherein the pH value is 1:9-11, temperature 40-60 ℃, rotating speed: performing a first coprecipitation reaction at 200-800 r/min; d50 reached 3-7um stop.
Alkali washing with 0-1mol/L sodium hydroxide for three times, and then washing with pure water until the conductivity is less than or equal to 30us/cm; drying to obtain Ni 1/ 3 Fe 1/3 Mn 1/3 (OH) 2 Sieving the dried material with a 200-350 mesh sieve, wherein the sieved material is a nickel-iron-manganese hydroxide precursor, and the obtained precursor is a spherical or spheroidic precursor.
The precursor, the sodium source, the copper oxide and the ferric oxide are weighed according to a certain proportion, then are added into a high-speed mixer to be mixed according to a certain rotating speed and time, and after the materials are uniformly mixed, the materials are taken out.
Sintering: sintering the obtained uniformly mixed materials in a box furnace under a certain temperature condition, and controlling the temperature and atmosphere uniformity in the sintering process.
Crushing: and crushing the material obtained by sintering by a roller machine to obtain powder.
Sieving: sieving the crushed material to obtain the single-crystal sodium ion layered anode material.
In a second aspect, the present invention also provides a sodium ion positive electrode material, which is prepared according to the preparation method described in the first aspect.
In a third aspect, an embodiment of the present invention further provides a sodium ion battery, where the sodium ion battery includes the sodium ion positive electrode material provided in the second aspect.
According to the scheme, copper oxide and ferric oxide are added in one-time sintering, the formation of single crystals can be promoted at the temperature of not higher than 1000 ℃ through the synergistic fluxing effect of the copper oxide and the ferric oxide, and the pure-phase O3 type sodium ion positive electrode material is obtained; the addition amount of copper is greatly reduced, and meanwhile, the addition of ferric iron can replace Ni, so that the trivalent nickel formed by charge balance is reduced.
The copper oxide in the scheme can be used as a fluxing agent and also can be used as a doping agent, so that the air stability and the electrochemical performance of the sodium-electricity anode material are improved; meanwhile, the ferric oxide is used as a fluxing agent and a doping agent and is used as an element with electrochemical activity, so that the electrochemical performance is improved.
The following describes in further detail the specific procedures and effects of the preparation method of the sodium ion positive electrode material according to the present invention with reference to some specific examples, but is not limited to the scope of the present invention. Preparation of a cathode Material precursor or a commercially available precursor Ni by the foregoing method 1/3 Fe 1/3 Mn 1/3 (OH) 2 Further applies to the different embodiments.
Example 1
The preparation method of the sodium ion positive electrode material comprises the following steps:
1. mixing and sintering ferric oxide, copper oxide, a precursor and a sodium source, adding the mixture according to the ratio of the sodium source to the precursor of 1:1, wherein the addition amount of the ferric oxide is 0.05% of the molar amount of the precursor, the addition amount of the copper oxide is 0.05% of the molar amount of the precursor, and then mixing the mixture in a high-speed mixer for 60 minutes according to the rotating speed of 750 rpm.
2. And (2) filling the mixture obtained in the step (1) into a cordierite-mullite sagger, placing the sagger into a box furnace, heating to 500 ℃ at 3 ℃/min, preserving heat for 2 hours, heating to 800 ℃ at 3 ℃/min, preserving heat for 4 hours, heating to 970 ℃ at 3 ℃/min, preserving heat for 12 hours, cooling the sintering atmosphere to air, and crushing the cooled mixture by a pair of rollers to obtain powder materials.
Fig. 2 is an SEM image of the sodium ion cathode material prepared in example 1, from which it can be seen that the sodium ion cathode material particles are single crystal particles, and the crystallinity is high.
As shown in the figure 3, the obtained sodium ion positive electrode material has single phase, high purity and no impurity peak.
Example 2
The amount of iron oxide added was 0.08% of the molar amount of the precursor, and the amount of copper oxide added was 0.05% of the molar amount of the precursor, except that the conditions were the same as in example 1.
Example 3
The amount of iron oxide added was 0.08% of the molar amount of the precursor, and the amount of copper oxide added was 0.08% of the molar amount of the precursor, except that the conditions were the same as in example 1.
Comparative example 1
The other conditions were the same as in example 1 except that iron oxide and copper oxide were not added.
Fig. 4 is an SEM image of the sodium ion cathode material prepared in comparative example 1, and it can be seen from the SEM image that the sodium ion cathode material particles are polycrystalline particles, and the morphology of the material is poor.
Comparative example 2
The addition amount of copper oxide was 0.05% of the molar amount of the precursor without adding iron oxide, and the other conditions were the same as in example 1.
Fig. 5 is an SEM image of the sodium ion cathode material prepared in comparative example 2, from which it can be seen that the sodium ion cathode material particles are a large number of agglomerated single crystal particles, and the morphology of the material is poor.
Comparative example 3
The addition amount of copper oxide was 5.6% of the molar amount of the precursor without adding iron oxide, and the other conditions were the same as in example 1.
The prepared sodium ion positive electrode material is analyzed by XRD, and the result is shown in figure 6, and the prepared sodium ion positive electrode material is obtained by comparing with a standard card, wherein the prepared sodium ion positive electrode material is in a single crystal morphology, but the XRD result shows that the prepared sodium ion positive electrode material has NiO hetero-phase.
Correlation test analysis was performed for examples and comparative examples. The sodium ion layered cathode materials prepared in example 1, comparative example 1 and comparative example 2 were subjected to SEM, and the test results are shown in fig. 2, 4 and 5, wherein the cathode materials in comparative examples 1-2 are polycrystalline particles or a large number of agglomerated single crystal particles. In example 1, the particles of the sodium ion layered cathode material are monocrystalline particles, and the primary particles are dispersed, have high crystallinity and are pure phases, which indicates that the addition of ferric oxide can promote the formation of monocrystalline. Comparative example 3 is a single crystal morphology, but the XRD results show a NiO impurity phase, indicating that excessive CuO can cause the formation of the NiO impurity phase, and the addition of ferric oxide does inhibit the formation of the impurity phase.
Further, the samples are taken as a negative electrode, a CR2025 type button cell is prepared, the discharge capacity of 0.1C is tested in the voltage range of 2.0-4.0V, specific data are shown in Table 1, and it can be seen that the sodium ion positive electrode materials prepared by adopting the schemes of examples 1-3 have better capacities than those of comparative examples under the voltage of 4.0V and have more excellent cycle performance.
TABLE 1 residual alkali and electrochemical results
| Sequence number | First discharge capacity (mAh/g) | 1C 50 cycle capacity retention (%) |
| Example 1 | 142.77 | 94.1 |
| Example 2 | 141.61 | 94.7 |
| Example 3 | 141.35 | 93.9 |
| Comparative example 1 | 139.30 | 83.3 |
| Comparative example2 | 139.66 | 85.6 |
| Comparative example 3 | 135.25 | 89.2 |
According to the preparation method of the sodium ion positive electrode material, copper oxide and ferric oxide are added in one-time sintering, the synergistic fluxing effect of the copper oxide and the ferric oxide can promote the formation of single crystals, the molar quantity of CuO added can be obviously reduced, the sintering temperature is greatly reduced due to the synergistic effect of copper and ferric, the sintering temperature is reduced, and the addition of ferric iron can replace Ni, so that the formation of impurity phases caused by trivalent nickel formed by charge balance is reduced, the single-dispersed single-crystal sodium ion positive electrode material is obtained, the single crystal morphology of crystal grains is obvious, the crystallinity is high, and meanwhile, the compaction density and the cycle performance are higher. In addition, the preparation method has the advantages of simple process flow, high efficiency, no need of high-end equipment, no need of adding expensive reagents, low-cost and easily-obtained raw materials, no involvement of toxic and harmful raw materials, and suitability for large-scale industrialized production.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: many changes, modifications, substitutions and variations may be made to the embodiments without departing from the spirit and principles of the invention, the scope of which is defined by the claims and their equivalents.
Claims (10)
1. The preparation method of the sodium ion positive electrode material is characterized by comprising the following steps of:
s10, according to a certain proportion, the precursor Ni of the positive electrode material 1/3 Fe 1/3 Mn 1/3 (OH) 2 Uniformly mixing the sodium source compound, the copper oxide and the ferric oxide to obtain a mixture;
and S20, sintering, crushing and sieving the mixture under a certain condition to obtain the sodium ion positive electrode material.
2. The method for producing a sodium ion positive electrode material according to claim 1, wherein the sodium source compound comprises at least one of sodium carbonate, sodium hydroxide, sodium phosphate, and sodium chloride.
3. The method for preparing a sodium ion positive electrode material according to claim 1, wherein the molar ratio of the copper oxide in the mixture to the addition amount of the positive electrode material precursor is less than 0.02:1.
4. The method for preparing a sodium ion positive electrode material according to claim 3, wherein the molar ratio of the copper oxide to the addition amount of the positive electrode material precursor in the mixture is less than 0.008:1; and/or the molar ratio of the ferric oxide to the addition of the positive electrode material precursor in the mixture is less than 0.008:1; and/or the molar ratio of the sodium source compound to the addition amount of the positive electrode material precursor is (0.87-1.04): 1.
5. The method for producing a sodium ion positive electrode material according to claim 1, wherein the particle size D50 of the positive electrode material precursor is 3 μm to 7 μm; and/or the number of the groups of groups,
the mixing time of the mixture in a high-speed mixer is 30-60 min, and the mixing rotating speed is 600-900 rpm.
6. The method for producing a sodium ion positive electrode material according to claim 2, further comprising:
s5, mixing the mixed salt solution of Ni, fe and Mn, the sodium hydroxide solution and the ammonia water solution in parallel flow according to a certain proportion, and performing coprecipitation reaction to obtain a precipitation intermediate; washing, drying and screening the precipitated intermediate to obtain the precursor Ni of the sodium ion positive electrode material x Fe y Mn z (OH) 2 。
7. The method for preparing a sodium ion positive electrode material according to claim 6, wherein the molar ratio of Ni, fe, mn in the mixed salt solution is 1:1:1; the total molar concentration of Ni, fe and Mn in the mixed salt solution is 1.8 mol/L-2.5 mol/L; and/or the number of the groups of groups,
the mass fraction of the sodium hydroxide solution is 20% -40%; and/or the number of the groups of groups,
the molar concentration of the ammonia water solution is 1.5mol/L-8mol/L; and/or the number of the groups of groups,
the coprecipitation reaction is carried out under an inert atmosphere; and/or the number of the groups of groups,
the pH value of the coprecipitation reaction mixed solution is 9-11, and the reaction temperature is 40-60 ℃; and/or the number of the groups of groups,
the stirring speed of the coprecipitation reaction is 200r/min-800r/min.
8. The method for preparing a sodium ion cathode material according to claim 7, wherein the washing, drying and sieving steps specifically comprise:
washing the precipitation intermediate with sodium hydroxide of 0mol/L-1mol/L for three times, and washing with pure water until the conductivity is less than or equal to 30us/cm; drying to obtain Ni x Fe y Mn z (OH) 2 Sieving the dried material with a 200-350 mesh sieve, and obtaining the product after sievingA precursor of positive electrode material compound.
9. A sodium ion positive electrode material, characterized in that the sodium ion positive electrode material is produced according to the production method of any one of claims 1 to 8.
10. A sodium ion battery, wherein the sodium ion battery comprises: the sodium ion positive electrode material according to claim 9.
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