CN118198316A - Sodium-electricity positive electrode material, positive electrode plate, preparation method and application thereof - Google Patents
Sodium-electricity positive electrode material, positive electrode plate, preparation method and application thereof Download PDFInfo
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- CN118198316A CN118198316A CN202410332596.9A CN202410332596A CN118198316A CN 118198316 A CN118198316 A CN 118198316A CN 202410332596 A CN202410332596 A CN 202410332596A CN 118198316 A CN118198316 A CN 118198316A
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 68
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 43
- 238000005245 sintering Methods 0.000 claims abstract description 38
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 239000011734 sodium Substances 0.000 claims description 27
- 229910001415 sodium ion Inorganic materials 0.000 claims description 22
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 34
- 239000011247 coating layer Substances 0.000 description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 22
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 15
- 229910052708 sodium Inorganic materials 0.000 description 15
- 239000010405 anode material Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- 229910000480 nickel oxide Inorganic materials 0.000 description 10
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 10
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 9
- 239000005751 Copper oxide Substances 0.000 description 9
- 229910000431 copper oxide Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 239000001488 sodium phosphate Substances 0.000 description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 6
- 238000001338 self-assembly Methods 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(iii) oxide Chemical compound O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- -1 stirring Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
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Abstract
The application relates to the technical field of battery materials, and discloses a sodium-electricity positive electrode material, a positive electrode plate, a preparation method and application thereof. The sodium-electricity positive electrode material comprises an O3 phase layered material main body and a self-assembled heterojunction solid electrolyte coated on the surface of the O3 phase layered material main body; the mass ratio of the self-assembled heterojunction solid electrolyte to the O3 phase layered material main body is 1-10:100; a is one or more of Ni, fe and Mn, M is one or more of Cu, zn and Mg, Q is one or two of Ti and Zr, and T is one or two of P and S. The preparation method of the sodium-electricity positive electrode material comprises the step of sintering a mixture containing various elements. The sodium-electricity positive electrode material provided by the application is not easy to absorb water in air and has low residual alkali content on the surface.
Description
Technical Field
The application relates to the technical field of battery materials, in particular to a sodium-electricity positive electrode material, a positive electrode plate, a preparation method and application thereof.
Background
The O3 type sodium ion layered cathode material has the advantages of cost, excellent energy density, heat stability, low-temperature counterbalance, rapid charge and discharge and the like, and is favored by the market. However, due to the larger ionic radius of sodium ions, the O3 type sodium ion layered material has poor air stability and is accompanied by higher surface residual alkali, which is unfavorable for processing the battery cell, and excessive surface residual alkali generates a large amount of gas in the battery cycle process to swell the battery, so that the service life and the safety of the battery are reduced.
Because of the larger radius of sodium ions, sodium ions in the layered sodium ion positive electrode material are easier to dissolve out than lithium ions in the layered lithium ion positive electrode material, so that the layered sodium ion positive electrode material has high residual alkali; meanwhile, the larger interlayer spacing of the layered sodium ion positive electrode material can also cause H 2 O molecules and the like in the environment to be easier to replace Na +, and the residual alkali is further improved; therefore, lowering the sodium interlayer spacing is an effective method for lowering the residual alkali, but too low an interlayer spacing results in less tendency of sodium ion to be deintercalated, deteriorating electrical properties. Researchers found that by controlling the sodium interlayer spacing of layered sodium ion positive electrode materials to a certain range, residual alkali and electrical properties can be balanced, and the residual sodium of the materials obtained by this compromise method is controlled to a certain range, but still does not get good feedback in practical commercial applications.
The coating scheme is considered as a better effective means for improving the air stability and reducing the residual alkali, and the common scheme is to prepare materials firstly and then add additives for sintering coating. For example, CN116314704a discloses a coated modified sodium ion layered cathode material and a preparation method thereof. According to the scheme, residual alkali on the surface of the positive electrode material is effectively reduced, but the improved residual alkali is still higher at the application end, and meanwhile, the air stability of the material is not disclosed, and whether the residual sodium is continuously increased is unknown.
CN114725357a discloses a method for reducing the residual sodium content of a sodium ion positive electrode material, and residual sodium on the surface of the material can be reduced by an acid washing method, but the effect of the scheme is limited because the washing does not fundamentally improve the dissolution state of sodium in the bulk phase of the material, and sodium in the material can still be dissolved out at a higher speed after the residual sodium is washed off in a drying treatment and a subsequent storage process, so that the material is deteriorated.
In view of this, the present application has been made.
Disclosure of Invention
The application aims to provide a sodium-electricity positive electrode material, a positive electrode plate, a preparation method and application thereof, and aims to reduce the residual alkali content on the surface of a layered sodium-electricity positive electrode material and improve the cycle performance of the layered sodium-electricity positive electrode material.
The application is realized in the following way:
In a first aspect, an embodiment of the present application provides an illustrative sodium-electricity positive electrode material, including an O3-phase layered material body and a self-assembled heterojunction solid-state electrolyte coated on a surface of the O3-phase layered material body;
the chemical formula of the O3 phase layered material main body is Na x1Aa1My1Qz1Tb1O2, and the chemical formula of the self-assembled heterojunction solid electrolyte is Na x2Aa2My1Qz1T b2O4;
Wherein x=x1+x2, a=a1+a2, y=y1+y2, z=z1+z2, b=b1+b2, 0.9.ltoreq.x.ltoreq.1.11, b+y/a.ltoreq.0.28, y/a.ltoreq.0.20, a+y+z=1, 0 < z.ltoreq.0.05, 0 < b.ltoreq.0.08.
The mass ratio of the self-assembled heterojunction solid electrolyte to the O3 phase layered material main body is 1-10:100;
A is one or more of Ni, fe and Mn, M is one or more of Cu, zn and Mg, Q is one or two of Ti and Zr, and T is one or two of P and S.
In an alternative embodiment, the mass ratio of self-assembled heterojunction solid-state electrolyte to the bulk of the O3 phase layered material is 1.8-6.1:100.
In a second aspect, an embodiment of the present application provides a method for preparing a sodium-electricity positive electrode material, including:
And sintering the mixed material containing Na element, A element, M element, Q element and T element to form an O3 phase layered material main body, and self-assembling on the surface of the O3 phase layered material main body to form the heterojunction solid electrolyte.
In an alternative embodiment, the sintering conditions are: preserving heat for 4-6 h at 650-750 ℃, and preserving heat for 12-20 h at 900-1000 ℃.
In an alternative embodiment, the mixture includes at least one of an oxide, hydroxide, phosphate, sulfate, and carbonate.
In a third aspect, an embodiment of the present application provides a positive electrode sheet, where an active component includes the sodium-electricity positive electrode material provided by the embodiment of the present application.
In a fourth aspect, an embodiment of the present application provides a method for preparing a positive electrode sheet, where the preparation raw materials include the sodium-electricity positive electrode material provided by the embodiment of the present application.
In a fifth aspect, an embodiment of the present application provides a sodium ion battery, which includes the positive electrode sheet provided by the embodiment of the present application.
In a sixth aspect, an embodiment of the present application provides an electrical apparatus, including a sodium ion battery provided by the embodiment of the present application.
The application has the following beneficial effects:
According to the sodium-electricity positive electrode material provided by the embodiment of the application, the surface of the O3-phase layered material main body is coated with a layer of self-assembled heterojunction solid electrolyte, and the heterojunction solid electrolyte is coated on the surface of the O3-phase layered material main body, so that the material can be well protected from being stored in air, the material main body is prevented from absorbing water in the air, and the residual alkali amount on the surface of the positive electrode material is reduced; the heterojunction solid electrolyte has excellent ion conductivity, can store certain sodium, and improves the cycle performance of the material while affecting the capacity as little as possible; because the heterojunction solid electrolyte is formed by self-assembly, the cladding combination stability is good, and the ionic conductivity is improved, so that the multiplying power cycle performance is improved; the sodium-electricity positive electrode material has the advantages that the preparation method is simple, the sodium-electricity material with the self-assembled heterojunction solid electrolyte coating layer can be prepared by only one sintering, the bonding strength of the coating phase and the material main body is high, the repeated sintering is avoided, and the manufacturing cost is reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is an XRD pattern of a sodium ion positive electrode material prepared in example 2 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The sodium-electricity positive electrode material, the positive electrode plate, the preparation method and the application thereof provided by the embodiment of the application are specifically described below.
The chemical formula of the O3 phase layered material main body is Na x1Aa1My1Qz1Tb1O2, and the chemical formula of the self-assembled heterojunction solid electrolyte is Na x2Aa2My1Qz1T b2O4;
Wherein x=x1+x2, a=a1+a2, y=y1+y2, z=z1+z2, b=b1+b2, 0.9.ltoreq.x.ltoreq.1.11, b+y/a.ltoreq.0.28, y/a.ltoreq.0.20, a+y+z=1, 0 < z.ltoreq.0.05, 0 < b.ltoreq.0.08;
The mass ratio of the self-assembled heterojunction solid-state electrolyte to the O3 phase layered material host is 1-10:100 (e.g., 1:100, 2:100, 3:100, 5:100, 6:100, 8:100, or 10:100);
A is one or more of Ni, fe and Mn, M is one or more of Cu, zn and Mg, Q is one or two of Ti and Zr, and T is one or two of P and S.
According to the sodium-electricity positive electrode material provided by the embodiment of the application, the surface of the O3-phase layered material main body is coated with a layer of self-assembled heterojunction solid electrolyte, and the heterojunction solid electrolyte is coated on the surface of the O3-phase layered material main body, so that the material can be well protected from being stored in air, the material main body is prevented from absorbing water in the air, and the residual alkali amount on the material surface is reduced; the heterojunction solid electrolyte has excellent ion conductivity, can store a certain amount of sodium, and improves the cycle performance of the material while not affecting the capacity; because the heterojunction solid electrolyte is formed by self-assembly, the cladding combination stability is good, and the ionic conductivity is improved, so that the multiplying power cycle performance is improved.
It should be noted that, the amount of the coated self-assembled heterojunction solid-state electrolyte should be within the scope of the present application, and an excessive coating amount may result in a reduced capacity, an excessively small coating amount, and an inferior performance enhancing effect.
Optionally, the mass ratio of self-assembled heterojunction solid-state electrolyte to the bulk O3 phase layered material is 1.8-6.1:100 (e.g., 1.8:100, 2:100, 2.5:100, 3:100, 4:100, 5:100, 5.5:100, or 6.1:100). When the ratio of the self-assembled heterojunction solid-state electrolyte to the material body is within the above range, the comprehensive performance of the sodium-electricity positive electrode material is optimized.
The preparation method of the sodium-electricity positive electrode material provided by the embodiment of the application comprises the following steps:
And sintering the mixed material containing Na element, A element, M element, Q element and T element to form an O3 phase layered material main body, and self-assembling on the surface of the O3 phase layered material main body to form the heterojunction solid electrolyte.
According to the preparation method provided by the application, na element, A element, M element and Q element participate in forming O3 phase layered oxide in the sintering process; because the T element, the Na element, the T element and one or more elements of the Q element, the A element and the M element are added in the sintering raw material, heterojunction solid electrolyte is formed through self-assembly in the sintering process and is coated on the surface of the O3 phase layered oxide, the sodium-electricity anode material provided by the embodiment of the application can be prepared by the method provided by the application.
The addition of the T element is a key to the formation of the heterojunction solid-state electrolyte, and if the T element is not added, the coating layer of the heterojunction solid-state electrolyte cannot be formed. The addition of the T element is mainly used for forming a heterojunction solid-state electrolyte, and no or only a very small part of the T element can enter the O3 phase to be used as a constituent element of the O3 phase layered material body. In addition, Q element is also an important element for forming heterojunction solid electrolyte, and although heterojunction solid electrolyte can be formed theoretically without adding Q element, according to practical experiments, heterojunction solid electrolyte cannot be detected from the obtained product without adding Q element, and therefore, solid electrolyte cannot be formed or the content of generated solid electrolyte is extremely small and cannot be detected.
It should be further noted that, the present application realizes that the sodium-electricity anode material with the self-assembled heterojunction solid electrolyte coating layer is generated by one-time sintering due to the addition of at least one of the T elements (P and S); the inventors have not found that an oxide type heterojunction solid-state electrolyte (for example, the heterojunction solid-state electrolyte referred to in comparative example 6 below) can be produced by one-time sintering.
Optionally, the sintering conditions are: 650-750deg.C (e.g., 650deg.C, 750deg.C, 700deg.C, 720deg.C, or 750deg.C) for 4-6 hours (e.g., 4 hours, 5 hours, or 6 hours), and then 900-1000deg.C (e.g., 900deg.C, 920 deg.C, 950 deg.C, 980 deg.C, or 1000 ℃) for 12-20 hours (e.g., 12 hours, 15 hours, 18 hours, or 20 hours).
Alternatively, the raw material involved in sintering may be at least one of an oxide, a hydroxide, a phosphate, a sulfate, and a carbonate.
The active component of the positive electrode plate provided by the embodiment of the application comprises the sodium-electricity positive electrode material provided by the application.
The preparation method of the positive electrode plate provided by the embodiment of the application comprises the steps of preparing the sodium-electricity positive electrode material provided by the embodiment of the application.
The sodium ion battery provided by the embodiment of the application comprises the positive electrode plate provided by the embodiment of the application. The sodium ion battery can be a battery cell or a battery pack.
The power utilization device provided by the embodiment of the application comprises the sodium ion battery provided by the embodiment of the application.
The features and capabilities of the present application are described in further detail below in connection with the examples.
Example 1
The preparation method of the sodium-electricity positive electrode material provided by the embodiment is as follows:
Mixing nickel oxide, manganese oxide, ferric oxide, copper oxide, titanium oxide, sodium phosphate and sodium carbonate according to the mol ratio of Ni, fe, mn, cu, ti, P, na elements of 0.32:0.20:0.37:0.08:0.03:0.05:0.85, sintering at 700 ℃ for 5 hours, sintering at 900 ℃ for 15 hours, and crushing to obtain the sodium-electricity anode material.
The phase composition is calculated by detecting: b+y/a=0.14, y/a=0.09, the mass ratio of the coating layer to the bulk of the O3 phase layered material is about 4.7:100.
Example 2
The preparation method of the sodium-electricity positive electrode material provided by the embodiment is as follows:
Mixing nickel oxide, manganese oxide, ferric oxide, copper oxide, titanium oxide, sodium phosphate and sodium carbonate according to the molar ratio of Ni, fe, mn, cu, ti, P, na elements of 0.32:0.20:0.33:0.12:0.03:0.05:0.85, sintering at 700 ℃ for 5 hours, sintering at 900 ℃ for 15 hours, and crushing to obtain the sodium-electricity anode material.
The XRD pattern of the prepared sodium-electricity positive electrode material is shown in figure 1, and the existence of phosphate can be seen from figure 1, which shows that heterojunction solid-state electrolyte is generated.
The phase composition is calculated by detecting: b+y/a=0.17, y/a=0.14, the mass ratio of the coating layer to the bulk of the O3 phase layered material is about 5.0:100.
Example 3
The sodium-electricity positive electrode material provided in this example is substantially the same as that in example 1, except that: nickel oxide, manganese oxide, ferric oxide, copper oxide, titanium oxide, sodium phosphate and sodium carbonate are mixed and sintered according to the mol ratio of Ni, fe, mn, cu, ti, P, na elements of 0.31:0.20:0.30:0.16:0.03:0.08:0.82.
The phase composition is calculated by detecting: b+y/a=0.28, y/a=0.20, the mass ratio of the coating layer to the bulk of the O3 phase layered material is about 10.1:100.
Example 4
The sodium-electricity positive electrode material provided in this example is substantially the same as that in example 1, except that: mixing and sintering nickel oxide, manganese trioxide, ferric oxide, zinc oxide, zirconium oxide, sodium sulfate and sodium carbonate according to the mol ratio of Ni, fe, mn, zn, zr, S, na elements of 0.32:0.20:0.37:0.08:0.03:0.05:0.85.
The phase composition is calculated by the following steps: b+y/a=0.14, y/a=0.09, the mass ratio of the coating layer to the bulk of the O3 phase layered material is about 5.5:100.
Example 5
The preparation method of the sodium-electricity positive electrode material provided by the embodiment is as follows:
Nickel oxide, manganese oxide, ferric oxide, copper oxide, titanium oxide, sodium phosphate and sodium carbonate are mixed according to the mol ratio of Ni, fe, mn, cu, ti, P, na elements of 0.32:0.20:0.32:0.12:0.04:0.06: mixing the materials according to the proportion of 0.84, sintering the mixture for 6 hours at 650 ℃, then sintering the mixture for 20 hours at 900 ℃ and then crushing the mixture to obtain the sodium-electricity positive electrode material.
The phase composition is calculated by detecting: b+y/a=0.14, y/a=0.06, the mass ratio of the coating layer to the bulk of the O3 phase layered material is about 6.1:100.
Example 6
The preparation method of the sodium-electricity positive electrode material provided by the embodiment is as follows:
Mixing nickel oxide, manganese oxide, ferric oxide, copper oxide, titanium oxide, sodium phosphate and sodium carbonate according to the mol ratio of Ni, fe, mn, cu, ti, P, na elements of 0.32:0.20:0.38:0.08:0.02:0.03:0.87, sintering at 750 ℃ for 4 hours, sintering at 1000 ℃ for 12 hours, and crushing to obtain the sodium-electricity anode material.
The phase composition is calculated by detecting: b+y/a=11.9, y/a=8.9, the mass ratio of the coating layer to the bulk of the O3 phase layered material is about 1.8:100.
Example 7
This embodiment is substantially the same as embodiment 5, except that: the proportion of each element is adjusted, so that the mass ratio of the coating layer to the O3 phase layered material main body in the prepared sodium-electricity positive electrode material is about 10:100.
Example 8
This embodiment is substantially the same as embodiment 6, except that: the proportion of each element is adjusted, so that the mass ratio of the coating layer to the O3 phase layered material main body in the prepared sodium-electricity positive electrode material is about 1.2:100.
Comparative example 1
The preparation method of the sodium-electricity positive electrode material provided by the embodiment is as follows:
mixing nickel oxide, manganese oxide, ferric oxide, copper oxide, titanium oxide and sodium carbonate according to the mol ratio of Ni, fe, mn, cu, ti, na elements of 0.32:0.20:0.40:0.08:0.03:1.00, sintering at 700 ℃ for 5 hours, sintering at 900 ℃ for 15 hours, and crushing to obtain the sodium-electricity anode material.
The sodium-electricity positive electrode material is detected to be free of a heterojunction solid electrolyte coating layer.
Comparative example 2
The comparative example provides a sodium ion positive electrode material, which is prepared by the following steps:
Mixing nickel oxide, manganese oxide, ferric oxide, copper oxide and sodium carbonate according to the molar ratio of Ni, fe, mn, cu, na elements of 0.32:0.20:0.40:0.08:1.00, sintering at 700 ℃ for 5 hours, sintering at 900 ℃ for 15 hours, and crushing to obtain the sodium-electricity anode material.
The sodium-electricity positive electrode material is detected to be free of a heterojunction solid electrolyte coating layer.
Comparative examples 1 and 2, since a raw material containing T element was not added, the prepared sodium-electricity positive electrode material contained no heterojunction solid-state electrolyte coating layer.
Comparative example 3
The comparative example provides a sodium ion positive electrode material, which is prepared by the following steps:
Mixing nickel oxide, manganese sesquioxide, ferric oxide, copper oxide, sodium phosphate and sodium carbonate according to the mol ratio of Ni, fe, mn, cu, P, na elements of 0.32:0.20:0.40:0.08:0.05:0.85, sintering at 700 ℃ for 5 hours, sintering at 900 ℃ for 15 hours, and crushing to obtain the sodium-electricity anode material.
The sodium-electricity positive electrode material is detected to be free of a heterojunction solid electrolyte coating layer.
In comparative example 3, since the Q element was not added, the prepared sodium-electricity positive electrode material contained no heterojunction solid-state electrolyte coating layer or had a very small content, which could not be detected.
Comparative example 4
The embodiment provides a sodium ion positive electrode material, and the preparation method thereof is as follows:
Mixing nickel oxide, manganese oxide, ferric oxide, copper oxide, titanium oxide and sodium carbonate according to the molar ratio of Ni, fe, mn, cu, ti, na elements of 0.32:0.20:0.40:0.08:0.03:1.00, sintering at 700 ℃ for 5 hours, sintering at 900 ℃ for 15 hours, and crushing to obtain a sodium-electricity anode material;
Adding 1.2% of NaTiO 2 solid electrolyte into the sodium-electricity anode material, uniformly mixing, and sintering at 800 ℃ for 6 hours to obtain the anode material coated with NaTiO 2.
Comparative example 5
This comparative example is substantially the same as example 7, except that: the proportion of the raw materials is adjusted, so that the heterojunction solid electrolyte coating layer of the prepared sodium-electricity anode material is more, and the mass ratio of the coating layer to the O3 phase layered material main body is about 15:100.
Comparative example 6
This comparative example is substantially the same as example 1, except that:
Mixing the same O3 phase layered material main body material as in example 1 with oxide type heterojunction solid electrolyte Na 0.8Al0.2Ti0.4Nb0.2O2 according to the ratio of 4.7:100, sintering at 700 ℃ for 5h, sintering at 900 ℃ for 15h, and pulverizing to obtain the sodium-electricity anode material.
Experimental example 1
Electrochemical performance test: mixing the positive electrode materials prepared in each example and comparative example with a binder and conductive carbon black according to a ratio of 90:5:5, adding NMP solvent, stirring, coating on a current collector, drying, rolling to obtain a positive electrode plate, preparing a battery with a hard carbon negative electrode, and testing the cycle performance of the battery, wherein the initial ring voltage is 1.5-4.2V. The results of the electrical properties were recorded in table 1.
Table 1 electrochemical test results for each of the examples and comparative examples
As can be seen from Table 1, the sodium-electricity positive electrode material prepared in each example of the present application has higher capacity, charge-discharge performance and capacity retention rate. Comparing each example with comparative examples 1-3, it can be seen that each example provided by the present application has a higher capacity retention rate after the battery is fabricated, compared to the positive electrode material without the heterogenous junction solid electrolyte coating layer;
comparing example 8 with comparative example 4, comparative example 4 forms a solid electrolyte coating layer using a common solid electrolyte as a coating agent, which has significantly poorer electrochemical properties;
Comparing example 7 with comparative example 5, comparative example 5 has significantly poorer capacity due to the excessive coating amount of the coating layer, which is beyond the range required by the present application;
In comparison of example 1 and comparative example 6, comparative example 6 uses direct mixed sintering to form a coating layer, and the heterojunction solid electrolyte used to form the coating layer is of oxide type, the capacity and rate cycle performance of the obtained positive electrode material are inferior to those of example 1.
Experimental example 2
Residual sodium test: the positive electrode material was dissolved in pure water and absolute ethanol, and stirred for 30min to dissolve the residual alkali on the surface thereof in water/absolute ethanol. The carbonate content in pure water and the hydroxyl content in absolute ethyl alcohol were tested by potentiometric titration, and the pH value of the aqueous solution was tested by a pH meter.
The test objects are the newly prepared positive electrode materials of each example and comparative example and the positive electrode materials prepared in each example and comparative example and stored for a period of time in different environments.
The test result records refer to tables 2 to 4.
TABLE 2 results of residual alkali test on surface of freshly prepared cathode materials
| NaOH(％) | Na2CO3(％) | pH | |
| Example 1 | 0.0469 | 0.2735 | 12.41 |
| Example 2 | 0.0443 | 0.2539 | 12.42 |
| Example 3 | 0.0402 | 0.2564 | 12.47 |
| Example 4 | 0.0416 | 0.2461 | 12.48 |
| Example 5 | 0.0463 | 0.2657 | 12.49 |
| Example 6 | 0.0593 | 0.2671 | 12.55 |
| Example 7 | 0.0397 | 0.2536 | 12.40 |
| Example 8 | 0.0579 | 0.2894 | 12.55 |
| Comparative example 1 | 0.1536 | 1.1189 | 12.83 |
| Comparative example 2 | 0.1682 | 1.2294 | 12.85 |
| Comparative example 3 | 0.1612 | 1.3796 | 12.97 |
| Comparative example 4 | 0.1264 | 0.8715 | 12.58 |
| Comparative example 5 | 0.0482 | 0.2579 | 12.43 |
| Comparative example 6 | 0.1283 | 0.8468 | 12.79 |
Table 3 3% humidity storage for 30 days of residual alkali test results on surface of positive electrode material
TABLE 4 residual alkali test results on surface of positive electrode material after 7 days of 60% humidity storage
As can be seen from the test results in tables 2 to 4, the residual alkali amount on the surface of the positive electrode material prepared in each example of the application is significantly lower than that of the positive electrode material prepared in comparative examples 1 to 3, which indicates that coating the heterojunction solid electrolyte on the surface of the O3 phase layered oxide can significantly reduce the residual alkali amount on the surface; comparing example 1 with comparative example 4, the residual alkali amount on the surface of comparative example 4 is significantly more, which indicates that the residual alkali amount on the surface of the conventional solid electrolyte coated by the common coating method is still higher; comparing example 1 with comparative example 6, the directly coated oxide solid state electrolyte may be less effective due to the coating uniformity and binding force than the various examples provided by the present application.
In summary, according to the sodium-electricity positive electrode material provided by the embodiment of the application, the surface of the O3-phase layered material main body is coated with a layer of self-assembled heterojunction solid electrolyte, and the heterojunction solid electrolyte is coated on the surface of the O3-phase layered material main body, so that the material can be well protected from being stored in air, the material main body is prevented from absorbing water in the air, and the residual alkali amount on the surface of the positive electrode material is reduced; the heterojunction solid electrolyte has excellent ion conductivity, can store a certain amount of sodium, and improves the cycle performance of the material while not affecting the capacity; because the heterojunction solid electrolyte is formed by self-assembly, the cladding combination stability is good, and the ionic conductivity is improved, so that the multiplying power cycle performance is improved.
According to the preparation method of the sodium electric positive electrode material, provided by the embodiment of the application, the sodium electric positive electrode material is prepared through one-time sintering, the operation is simple, and the coating layer on the surface of the prepared positive electrode material is formed through self-assembly and has high connection strength with the material main body.
The above is only a preferred embodiment of the present application, and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (9)
1. The sodium-electricity positive electrode material is characterized by comprising an O3 phase layered material main body and a self-assembled heterojunction solid electrolyte coated on the surface of the O3 phase layered material main body;
The chemical formula of the O3 phase layered material main body is Na x1Aa1My1Qz1Tb1O2, and the chemical formula of the self-assembled heterojunction solid electrolyte is Na x2Aa2My1Qz1Tb2O4;
Wherein x=x1+x2, a=a1+a2, y=y1+y2, z=z1+z2, b=b1+b2, 0.9.ltoreq.x.ltoreq.1.11, b+y/a.ltoreq.0.28, y/a.ltoreq.0.20, a+y+z=1, 0 < z.ltoreq.0.05, 0 < b.ltoreq.0.08;
The mass ratio of the self-assembled heterojunction solid electrolyte to the O3 phase layered material main body is (1-10) 100;
A is one or more of Ni, fe and Mn, M is one or more of Cu, zn and Mg, Q is one or two of Ti and Zr, and T is one or two of P and S.
2. The sodium-electric positive electrode material according to claim 1, wherein the mass ratio of the self-assembled heterojunction solid-state electrolyte to the O3-phase layered material body is (1.8-6.1): 100.
3. A method for producing the sodium-electricity positive electrode material according to claim 1 or 2, comprising:
and sintering the mixed material containing Na element, A element, M element, Q element and T element to form an O3 phase layered material main body, and self-assembling on the surface of the O3 phase layered material main body to form the heterojunction solid electrolyte.
4. A method according to claim 3, wherein the sintering conditions are: preserving heat for 4-6 h at 650-750 ℃, and preserving heat for 12-20 h at 900-1000 ℃.
5. A method of preparing according to claim 3, wherein the mixture comprises at least one of an oxide, hydroxide, phosphate, sulfate, and carbonate.
6. A positive electrode sheet characterized in that its active ingredient comprises the sodium-electricity positive electrode material according to claim 1 or 2.
7. A method for preparing a positive electrode sheet, characterized in that the preparation raw material comprises the sodium-electricity positive electrode material according to claim 1 or 2.
8. A sodium ion battery comprising the positive electrode sheet of claim 6.
9. An electrical device comprising a sodium ion battery as defined in claim 8.
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