CN113526560B - Sodium-potassium co-embedded metal oxide cathode material and preparation method thereof - Google Patents
Sodium-potassium co-embedded metal oxide cathode material and preparation method thereof Download PDFInfo
- Publication number
- CN113526560B CN113526560B CN202110677937.2A CN202110677937A CN113526560B CN 113526560 B CN113526560 B CN 113526560B CN 202110677937 A CN202110677937 A CN 202110677937A CN 113526560 B CN113526560 B CN 113526560B
- Authority
- CN
- China
- Prior art keywords
- sodium
- potassium
- metal oxide
- cathode material
- embedded
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 52
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 48
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000010406 cathode material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011734 sodium Substances 0.000 claims abstract description 42
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 28
- 239000011591 potassium Substances 0.000 claims abstract description 28
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 28
- 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 26
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 26
- 239000007774 positive electrode material Substances 0.000 claims abstract description 18
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- -1 transition metal salt Chemical class 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 11
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000012071 phase Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000003780 insertion Methods 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 230000037431 insertion Effects 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 15
- 229910001414 potassium ion Inorganic materials 0.000 claims description 12
- 238000009830 intercalation Methods 0.000 claims description 10
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- 229910019398 NaPF6 Inorganic materials 0.000 claims description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical group [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 2
- 238000009792 diffusion process Methods 0.000 abstract description 10
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 description 27
- 239000000463 material Substances 0.000 description 25
- 239000010949 copper Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229910003251 Na K Inorganic materials 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 2
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical compound O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000000954 titration curve Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910018434 Mn0.5O2 Inorganic materials 0.000 description 1
- 229910014507 Na0.67Ni0.33Mn0.67O2 Inorganic materials 0.000 description 1
- 229910014834 Na0.7MnO2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- SYBFKRWZBUQDGU-UHFFFAOYSA-N copper manganese(2+) oxygen(2-) Chemical class [O--].[O--].[Mn++].[Cu++] SYBFKRWZBUQDGU-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/006—Compounds containing, besides manganese, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a sodium-potassium co-embedded metal oxide cathode material and a preparation method thereof, wherein the preparation method comprises the following steps: 1) taking potassium salt and transition metal salt as raw materials, and preparing a P3-phase potassium-rich layered metal oxide by a high-temperature solid phase method; 2) mixing the potassium-rich layered metal oxide powder and a sodium simple substance in an inert atmosphere according to the required sodium insertion amount, dropwise adding a sodium ion electrolyte to wet the mixture, and fully grinding to obtain uniform slurry; 3) and standing the slurry in an inert atmosphere to enable potassium-rich layered metal oxide powder to fully react with sodium simple substances, cleaning and centrifugally separating, and drying the obtained precipitate to obtain the sodium-potassium co-embedded metal oxide cathode material. The preparation method is mild and simple to operate, and the prepared sodium-potassium co-embedded metal oxide positive electrode material has the advantages of high diffusion coefficient, good rate capability, good stability and the like, and is suitable for positive electrode materials of electrochemical energy storage devices.
Description
Technical Field
The invention belongs to the technical field of energy storage material preparation, and particularly relates to a sodium-potassium co-embedded metal oxide positive electrode material and a preparation method thereof.
Background
Due to high theoretical capacity, wide material source and simple preparation method, the layered transition metal oxide has wide application in the fields of batteries, supercapacitors, electrocatalysts and the like, for example, lithium cobaltate and ternary lithium battery materials in lithium ion batteries belong to the category. Sodium-rich layered oxide positive electrode materials, e.g. Na0.7MnO2、 Na0.67Ni0.33Mn0.67O2、Na0.67Fe0.5Mn0.5O2And the like, and is also a positive electrode material with the most application prospect. But due to the radius of sodium ionsLithium ionLarger, sodium ions are inserted and removed in the electrode materialIt is difficult to embed, and therefore, it is necessary to improve the capacity and rate capability of the electrode material by promoting the diffusion of sodium ions by a modification means. There are documents in the past[2]The potassium ions with larger sizes are embedded into the sodium-rich layered oxide cathode material by a high-temperature solid phase method, and the interlayer spacing of the material is enlarged, so that the diffusion rate of the sodium ions is improved.
However, this part of the research results are not ideal because potassium ions are larger than sodium ions in size and are more difficult to be embedded into the layered oxide, and even under the condition of high-temperature sintering, the number of potassium ions embedded into the material is less than 5%, so that the performance of the material is difficult to be remarkably improved.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a sodium-potassium co-embedded metal oxide positive electrode material and a preparation method thereof. The sodium-potassium co-intercalation metal oxide anode material is prepared by taking a potassium-rich layered oxide material as a base material and taking a sodium simple substance as a sodium intercalation agent and promoting the reaction by grinding at normal temperature. The sodium-potassium co-embedded metal oxide cathode material prepared by the invention has the advantages of high potassium ion embedding amount, large diffusion coefficient, high capacity and rate capability, and is a cathode material with good potential.
The invention adopts the following specific technical scheme:
in a first aspect, the invention provides a preparation method of a sodium-potassium co-embedded metal oxide positive electrode material, which comprises the following specific steps:
1) the P3 phase potassium-rich layered metal oxide (P3-K) is prepared by high-temperature solid phase method by using potassium salt and transition metal salt as raw materialsxTMO2Preferably, TM is one or more of Ni, Mn, Cu, Fe); the method can adopt a high-temperature solid phase method commonly used in the prior art to prepare P3-KxTMO2。
2) Weighing certain mass of potassium-rich layered metal oxide powder and sodium simple substance in an inert atmosphere according to the required sodium-insertion amount, mixing the weighed potassium-rich layered metal oxide powder and sodium simple substance, and dropwise adding a small amount of sodium ion electrolyte to wet the mixture (potassium-rich layered metal oxide powder and sodium simple substance)Layered metal oxide powder and sodium simple substance), and obtaining uniform slurry after fully grinding; preferably, the sodium simple substance and P3-K can be adjusted according to the expected sodium insertion amountxTMO2The mass ratio of the powder is generally 1:5 to 1: 2;
3) standing the slurry in an inert atmosphere to enable potassium-rich layered metal oxide powder to fully react with sodium simple substance, cleaning and centrifugally separating, drying the obtained precipitate in a vacuum environment or a protective atmosphere to obtain the sodium-potassium co-embedded metal oxide cathode material (marked as Na)yKzTMO2)。
Preferably, the mixing molar ratio of the potassium salt to the transition metal salt is 1:1 to 1: 2.
Preferably, the sintering temperature in the high-temperature solid-phase method is 700 ℃ or higher.
Preferably, the potassium salt is one or more of carbonate, carbonate hydrate, acetate hydrate, oxalate or oxalate hydrate containing potassium ions; the transition metal salt is one or more of carbonate, carbonate hydrate, acetate hydrate, oxalate or oxalate hydrate containing transition metal ions.
Further, the transition metal is one or more of Ni, Mn, Cu and Fe.
Preferably, the sodium ion electrolyte is any commercial ester or ether solution containing sodium ions.
Further, the solute of the sodium ion electrolyte is sodium perchlorate NaClO4Or sodium hexafluorophosphate NaPF6The solvent is one of a mixed solution of ethylene carbonate and propylene carbonate in a volume ratio of 1: 2-2: 1, a mixed solution of ethylene carbonate and diethyl carbonate in a volume ratio of 1: 2-2: 1, and ethylene glycol dimethyl ether.
Preferably, the solute of the sodium ion electrolyte is sodium perchlorate NaClO4Or sodium hexafluorophosphate NaPF6The solvent is a mixed solution of ethylene carbonate and propylene carbonate with the volume ratio of 1: 2-2: 1, a mixed solution of ethylene carbonate and diethyl carbonate with the volume ratio of 1: 2-2: 1, or ethylene glycol dimethyl etherOne kind of (1).
Preferably, in the step 2), the grinding time is more than 15 min; in the step 3), the standing time is more than 1 h.
Preferably, in the step 3), the slurry after sufficient reaction is washed by ethanol to remove excessive sodium.
In a second aspect, the invention provides a sodium-potassium co-intercalation metal oxide cathode material obtained by the preparation method in any one of the first aspect, wherein the crystal form of the sodium-potassium co-intercalation metal oxide cathode material is one or more (mostly P2 type) of P2, P3 and O3 type layered oxides, sodium ions and potassium ions are mixed and embedded in a layered structure, the mole number of the potassium ions is not less than 10% of that of the sodium ions, and the sodium ion diffusion coefficient of the material is obviously improved compared with that of a layered oxide material containing only sodium.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts a potassium-rich layered oxide positive electrode material (namely, a potassium-rich layered metal oxide) as a base material, and sodium ions are embedded into the potassium-rich material (namely, the potassium-rich layered metal oxide) to prepare the sodium-potassium co-embedded positive electrode material (the sodium-potassium co-embedded metal oxide positive electrode material). Because the potassium ion size is large, the potassium-rich layered oxide has larger interlayer spacing, so the sodium ions are easy to be embedded into the potassium-rich material, the potassium content in the final product is greatly improved compared with the potassium content in the prior art, the K/Na molar ratio reaches more than 0.1, and the sodium-potassium co-embedding reaction can be completed at normal temperature without a high-temperature solid phase method. The sodium-potassium co-embedded metal oxide positive electrode material prepared by the method has good sodium ion diffusion dynamics, the diffusion coefficient is greatly increased, and the capacity and rate capability of the material are also remarkably improved.
Drawings
FIG. 1 shows Na-K co-inserted Na prepared in example 1xKyFe0.2Mn0.8O2Scanning electron microscope pictures of the positive electrode material;
FIG. 2 shows Na-K co-inserted Na prepared in example 1xKyFe0.2Mn0.8O2An XRD spectrum of the anode material;
FIG. 3 shows Na-K co-insertion of Na prepared in example 2xKyCu0.2Mn0.8O2Potentiostatic intermittent titration curve of the positive electrode material.
Detailed Description
The invention will be further elucidated and described with reference to the drawings and the detailed description. The technical features of the embodiments of the present invention can be combined correspondingly without mutual conflict.
Example 1
1) Taking ferrous oxalate (FeC)2O4) And manganese acetate ((CH)3COO)2Mn) as a transition metal salt, potassium acetate (CH)3COOK) as potassium salt.
2) Preparing P3-phase potassium-rich layered metal oxide P3-K by using a high-temperature solid-phase methodxFe0.2Mn0.8O2The method comprises the following steps: weighing 5mmol FeC2O4、20mmol(CH3COO)2Mn and 15mmol CH3COOK, grinding uniformly, placing in a crucible, heating to 700 deg.C with a muffle furnace at a rate of 2.5 deg.C/min, holding for 2 hr, taking out, and quenching in air to obtain P3-KxFe0.2Mn0.8O2(since K will evaporate a little, x here is about 0.5).
3) Sodium ions are intercalated by a grinding method, which comprises the following steps: 200mg of sodium blocks (simple sodium) and 800mg of P3-K prepared in step 2) were weighed in a glove box (i.e. under an inert atmosphere)xFe0.2Mn0.8O2Grinding and mixing the mixture in a mortar, and dripping 1ml of NaClO4the/EC/DEC electrolyte (sodium ion electrolyte) was used to wet the mixture and milling was continued for 15 minutes until a uniform, viscous slurry was formed.
4) The slurry was allowed to stand in a glove box (i.e., under an inert atmosphere) for 1 hour, washed with absolute ethanol three times or more, and centrifuged to obtain a precipitate.
5) Drying the precipitate obtained by centrifugation in a vacuum drying oven at 60 ℃ overnight to obtain the sodium-potassium co-intercalationAs positive electrode material Na of oxideyKzFe0.2Mn0.8O2。
The chemical composition of the sodium-potassium co-intercalation metal oxide cathode material prepared in the embodiment is Na0.865K0.105Fe0.171Mn0.829O2Wherein the content z of the potassium ions reaches 0.105, the molar ratio of K/Na reaches 0.121, which is obviously higher than the content level of the potassium ions reported in the literature. A scanning electron microscope picture of the material is shown in fig. 1, from which it can be seen that the material has a polygonal granular structure. The XRD pattern of the material is shown in FIG. 2, from which it can be seen that the material has a P2 phase layered oxide structure, the leftmost peak corresponds to the (002) crystal plane of the material, and the interlayer spacing of the material after intercalation of potassium isNot only the interlayer spacing of the sample without potassiumHigher and higher than the literature[1]Middle levelThe material is in the range of 2.0-3.8V (vs. Na/Na)+Hereinafter the same) potential interval reaches 1.96 multiplied by 10-12cm2S, ratio of samples containing no potassium (. about.1X 10)-12cm2/s) is significantly improved and at a higher level than in the prior art.
Example 2
1) Taking copper acetate ((CH)3COO)2Cu) and manganese acetate ((CH)3COO)2Mn) as transition metal salt, potassium carbonate (K)2CO3) As the potassium salt.
2) Preparing P3-phase potassium-rich layered metal oxide P3-K by using a high-temperature solid-phase methodxCu0.2Mn0.8O2The method comprises the following steps: weighing 10mmol (CH)3COO)2Cu、40mmol(CH3COO)2Mn and 15mmol K2CO3Uniform grindingThen placing the mixture into a crucible, heating the mixture to 900 ℃ by a muffle furnace at the speed of 3 ℃/min, preserving the heat for 1 hour, taking out the mixture, and quenching the mixture in air to obtain P3-KxCu0.2Mn0.8O2。
3) The sodium ions are intercalated by a grinding method, which comprises the following steps: 230mg of sodium blocks (simple sodium) and P3-1000mg K prepared by step 2) were weighed in a glove box (i.e. under inert atmosphere)xCu0.2Mn0.8O2Grinding and mixing the mixture in a mortar, and dropwise adding 1.5ml of NaClO4the/EC/PC electrolyte (sodium ion electrolyte) was used to wet the mixture and milling was continued for 15 minutes until a homogeneous, viscous slurry was formed.
4) The slurry was allowed to stand in a glove box (i.e., under an inert atmosphere) for 1 hour, washed with absolute ethanol three times or more, and centrifuged to obtain a precipitate.
5) Drying the precipitate obtained by centrifugation in a vacuum drying oven at 60 ℃ overnight to obtain the Na-K co-embedded metal oxide cathode material NayKzCu0.2Mn0.8O2。
The Na-K co-intercalation metal oxide cathode material prepared in this exampleyKzCu0.2Mn0.8O2Has similar properties to the material obtained in example 1, and has a specific component of Na0.7K0.1Cu0.2Mn0.8O2The molar ratio of K to Na is 1/7, and XRD characterization shows that the crystal structure of the material is P2 type oxide and the interlayer spacing isThe potentiostatic intermittent titration curve is shown in FIG. 3, from which it can be seen that the sodium ion diffusion coefficient of the material is 1.89X 10-12cm2S, and samples containing no potassium (. about.1X 10)-12cm2At a higher level than at the second level.
Example 3
1) Taking nickel acetate (Ni (CH)3COO)2·4H2O) and manganese oxalate (MnC)2O4) As the transition metal salt, potassium acetate (CH)3COOK) as potassium salt.
2) Preparing P3-phase potassium-rich layered metal oxide P3-K by using a high-temperature solid-phase methodxNi0.33Mn0.67O2The method comprises the following steps: weighing 10mmol (CH)3COO)2Ni、20mmol (CH3COO)2Mn and 15mmol K2CO3Grinding uniformly, placing into a crucible, heating to 900 deg.C with a muffle furnace at a rate of 3 deg.C/min, holding for 1 hr, taking out, and quenching in air to obtain P3-KxNi0.33Mn0.67O2。
3) Sodium ions are intercalated by a grinding method, which comprises the following steps: 100mg of sodium blocks (elemental sodium) and 500mg of P3-K prepared in step 2) were weighed in a glove box (i.e. under an inert atmosphere)xNi0.33Mn0.67O2Grinding and mixing the mixture in a ball mill tank, and dripping 0.5ml of NaPF6DME/FEC electrolyte sodium ion electrolyte) was added to wet the mixture and ball milled for 30 minutes using a mechanical ball milling method until a uniform, viscous slurry was formed.
4) The slurry was allowed to stand overnight in a glove box (i.e., under an inert atmosphere), washed with absolute ethanol three or more times, and filtered to obtain a precipitate.
5) Placing the precipitate obtained by centrifugation in a tubular furnace, introducing nitrogen to protect and heat to 160 ℃, heating for 2 hours to fully dry to obtain the Na-K co-embedded metal oxide anode material NayKzNi0.33Mn0.67O2。
In this example, the obtained sodium-potassium co-intercalation metal oxide cathode material nickel phosphate/gold nanoparticle composite aerogel Na is preparedyKzNi0.33Mn0.67O2Having similar properties to the material obtained in example 1, the component of which is in particular Na0.67K0.11Ni0.33Mn0.67O2The molar ratio of K to Na is 1/6, and the XRD characterization shows that the crystal structure is mixed oxide of P2/O3 type and the interlayer spacing isThe diffusion coefficient of sodium ion is 1.71X 10-12cm2S, and do not containSamples of potassium (. about.1X 10)- 12cm2At a higher level than at s).
The preparation method is suitable for various material systems such as nickel-manganese, iron-manganese, copper-manganese oxides and the like, and has certain universal applicability. The preparation method is mild, the operation is simple and convenient, and the prepared sodium-potassium co-embedded metal oxide anode material has the advantages of high diffusion coefficient, good rate capability, good stability and the like, and is suitable for anode materials of electrochemical energy storage devices.
The above-described embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, the technical scheme obtained by adopting the mode of equivalent replacement or equivalent transformation is within the protection scope of the invention.
The references cited in the present invention are as follows:
[1]Kai Wang et al.Electrochimica Acta 216(2016)51–57.
[2]Divya Sehrawat et al.CrystEngComm,2019,21,172。
Claims (8)
1. a preparation method of a sodium-potassium co-embedded metal oxide positive electrode material is characterized by comprising the following steps:
1) taking potassium salt and transition metal salt as raw materials, and preparing a P3-phase potassium-rich layered metal oxide by using a high-temperature solid phase method;
2) mixing the potassium-rich layered metal oxide powder and a sodium simple substance in an inert atmosphere according to the required sodium insertion amount, dropwise adding a sodium ion electrolyte to wet the mixture, and fully grinding to obtain uniform slurry;
3) standing the slurry under an inert atmosphere to enable potassium-rich layered metal oxide powder to fully react with sodium simple substances, cleaning and centrifugally separating, and drying the obtained precipitate to obtain a sodium-potassium co-embedded metal oxide positive electrode material;
the solute of the sodium ion electrolyte is sodium perchlorate NaClO4Or sodium hexafluorophosphate NaPF6Solvent(s)The ethylene carbonate/propylene carbonate mixed solution is one of a mixed solution of ethylene carbonate and propylene carbonate with a volume ratio of 1: 2-2: 1, a mixed solution of ethylene carbonate and diethyl carbonate with a volume ratio of 1: 2-2: 1, and ethylene glycol dimethyl ether.
2. The method for preparing a sodium-potassium co-embedded metal oxide cathode material as claimed in claim 1, wherein the mixing molar ratio of the potassium salt to the transition metal salt is 1: 1-1: 2.
3. The method for preparing a sodium-potassium co-embedded metal oxide positive electrode material as claimed in claim 1, wherein the sintering temperature of the high-temperature solid-phase method is 700 ℃ or higher.
4. The method for preparing the sodium-potassium co-intercalation metal oxide cathode material as claimed in claim 1, wherein the potassium salt is one or more of carbonate, acetate or oxalate containing potassium ions; the transition metal salt is one or more of carbonate, acetate or oxalate containing transition metal ions.
5. The method for preparing a sodium-potassium co-intercalation metal oxide cathode material as claimed in claim 1 or 4, wherein the transition metal is one or more of Ni, Mn, Cu, Fe.
6. The method for preparing a sodium-potassium co-embedded metal oxide positive electrode material according to claim 1, wherein in the step 2), the grinding time is more than 15 min; in the step 3), the standing time is more than 1 h.
7. The method for preparing the sodium-potassium co-embedded metal oxide cathode material as claimed in claim 1, wherein in the step 3), the slurry after sufficient reaction is washed by ethanol to remove excessive sodium.
8. The sodium-potassium co-embedded metal oxide cathode material obtained by the preparation method of any one of claims 1 to 7, wherein the crystal form of the sodium-potassium co-embedded metal oxide cathode material is one or more of P2, P3 and O3, and sodium ions and potassium ions are mixed and embedded in the layered structure.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110677937.2A CN113526560B (en) | 2021-06-18 | 2021-06-18 | Sodium-potassium co-embedded metal oxide cathode material and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110677937.2A CN113526560B (en) | 2021-06-18 | 2021-06-18 | Sodium-potassium co-embedded metal oxide cathode material and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113526560A CN113526560A (en) | 2021-10-22 |
CN113526560B true CN113526560B (en) | 2022-06-24 |
Family
ID=78125237
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110677937.2A Active CN113526560B (en) | 2021-06-18 | 2021-06-18 | Sodium-potassium co-embedded metal oxide cathode material and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113526560B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023193231A1 (en) * | 2022-04-08 | 2023-10-12 | 宁德时代新能源科技股份有限公司 | Secondary battery, preparation method for corresponding positive electrode active material, battery module, battery pack and electric device |
CN115504525B (en) * | 2022-10-27 | 2024-04-02 | 澳门大学 | P2 type layered transition metal oxide and preparation method and application thereof |
CN116081708A (en) * | 2022-12-27 | 2023-05-09 | 华南师范大学 | Layered material, preparation method thereof, positive electrode material and sodium ion battery |
CN115947377A (en) * | 2023-01-10 | 2023-04-11 | 深圳华钠新材有限责任公司 | Preparation method and application of ferro-manganese-based sodium ion layered electrode material |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104291350A (en) * | 2014-09-29 | 2015-01-21 | 中国地质大学(北京) | Process for synthesizing analcite from potassium feldspar powder by virtue of hydro-thermal alkaline method |
JP2016110991A (en) * | 2014-11-27 | 2016-06-20 | 学校法人東京理科大学 | Positive electrode for sodium secondary battery and sodium secondary battery |
CN110380024A (en) * | 2019-04-22 | 2019-10-25 | 南方科技大学 | Sodium transition metal oxide of P3 structure and preparation method thereof and sodium-ion battery |
CN110446681A (en) * | 2016-05-19 | 2019-11-12 | 纪尧姆·兰伯特 | Sulfide electrolyte for metal processing and extracting |
CN110504443A (en) * | 2018-05-16 | 2019-11-26 | 中国电力科学研究院有限公司 | Sodium magnesium manganese base layered oxide material, preparation method and the purposes appraised at the current rate with anion |
-
2021
- 2021-06-18 CN CN202110677937.2A patent/CN113526560B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104291350A (en) * | 2014-09-29 | 2015-01-21 | 中国地质大学(北京) | Process for synthesizing analcite from potassium feldspar powder by virtue of hydro-thermal alkaline method |
JP2016110991A (en) * | 2014-11-27 | 2016-06-20 | 学校法人東京理科大学 | Positive electrode for sodium secondary battery and sodium secondary battery |
CN110446681A (en) * | 2016-05-19 | 2019-11-12 | 纪尧姆·兰伯特 | Sulfide electrolyte for metal processing and extracting |
CN110504443A (en) * | 2018-05-16 | 2019-11-26 | 中国电力科学研究院有限公司 | Sodium magnesium manganese base layered oxide material, preparation method and the purposes appraised at the current rate with anion |
CN110380024A (en) * | 2019-04-22 | 2019-10-25 | 南方科技大学 | Sodium transition metal oxide of P3 structure and preparation method thereof and sodium-ion battery |
Non-Patent Citations (1)
Title |
---|
"Investigation of K modified P2 Na0.7Mn0.8Mg0.2O2 as a cathode material for sodium-ion batteries";Divya Sehrawat等;《CrystEngComm》;20181119;第21卷;第172-181页 * |
Also Published As
Publication number | Publication date |
---|---|
CN113526560A (en) | 2021-10-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113526560B (en) | Sodium-potassium co-embedded metal oxide cathode material and preparation method thereof | |
Cheng et al. | Achieving stable cycling of LiCoO2 at 4.6 V by multilayer surface modification | |
Zhou et al. | Stable layered Ni-rich LiNi 0.9 Co 0.07 Al 0.03 O 2 microspheres assembled with nanoparticles as high-performance cathode materials for lithium-ion batteries | |
Park et al. | Porosity‐controlled TiNb2O7 microspheres with partial nitridation as a practical negative electrode for high‐power lithium‐ion batteries | |
Li et al. | Fabrication of hierarchical porous MnCo 2 O 4 and CoMn 2 O 4 microspheres composed of polyhedral nanoparticles as promising anodes for long-life LIBs | |
Wang et al. | Low temperature and rapid microwave sintering of Na3Zr2Si2PO12 solid electrolytes for Na-Ion batteries | |
Gong et al. | Synthesis and Characterization of Li2Mn x Fe1− x SiO4 as a Cathode Material for Lithium-Ion Batteries | |
Zheng et al. | A spinel-integrated P2-type layered composite: high-rate cathode for sodium-ion batteries | |
Sun et al. | Synthesis of high power type LiMn1. 5Ni0. 5O4 by optimizing its preparation conditions | |
Schougaard et al. | LiNi0. 5+ δMn0. 5–δO2—A High‐Rate, High‐Capacity Cathode for Lithium Rechargeable Batteries | |
EP1855334A2 (en) | Cathode material for manufacturing a rechargeable battery | |
Anh et al. | Enhanced electrochemical performance of novel K-doped Co 3 O 4 as the anode material for secondary lithium-ion batteries | |
Sun et al. | Hierarchical waxberry-like LiNi 0.5 Mn 1.5 O 4 as an advanced cathode material for lithium-ion batteries with a superior rate capability and long-term cyclability | |
Nisar et al. | Impact of surface coating on electrochemical and thermal behaviors of a Li-rich Li 1.2 Ni 0.16 Mn 0.56 Co 0.08 O 2 cathode | |
Liu et al. | A facile template method to synthesize significantly improved LiNi0. 5Mn1. 5O4 using corn stalk as a bio-template | |
Wang et al. | Effects of Na+ doping on crystalline structure and electrochemical performances of LiNi0. 5Mn1. 5O4 cathode material | |
Chudzik et al. | Surface modification and carbon coating effect on a high-performance K and S doped LiMn2O4 | |
Vaalma et al. | Beneficial effect of boron in layered sodium-ion cathode materials–the example of Na2/3B0. 11Mn0. 89O2 | |
Jiang et al. | Research on improving the electrochemical performance of LiMn2O4 via Cr-doping | |
Hu et al. | Synthesis and electrochemical performance of rod-like spinel LiMn 2 O 4 coated by Li–Al–Si–O solid electrolyte | |
Chen et al. | Role of Al-doping with different sites upon the structure and electrochemical performance of spherical LiNi 0.5 Mn 1.5 O 4 cathode materials for lithium-ion batteries | |
Shao et al. | High‐performance 3D pinecone‐like LiNi1/3Co1/3Mn1/3O2 cathode for lithium‐ion batteries | |
Mu et al. | Electrochemical performance of LiFexNi0. 5-xMn1. 5O4 cathode material for lithium-ion batteries | |
Pollen et al. | A Single‐Pot Co‐Precipitation Synthesis Route for Ni‐Rich Layered Oxide Materials with High Cycling Stability | |
Xie et al. | Synthesis and electrochemical characterization of Li1. 05RExCryMn2− x− yO4 spinel as cathode material for rechargeable Li-battery |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |