CN115172695A - Surface-coated layered transition metal oxide positive electrode material and preparation method thereof - Google Patents
Surface-coated layered transition metal oxide positive electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN115172695A CN115172695A CN202210821075.0A CN202210821075A CN115172695A CN 115172695 A CN115172695 A CN 115172695A CN 202210821075 A CN202210821075 A CN 202210821075A CN 115172695 A CN115172695 A CN 115172695A
- Authority
- CN
- China
- Prior art keywords
- transition metal
- metal oxide
- sodium
- layered transition
- positive electrode
- 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.)
- Granted
Links
- 229910000314 transition metal oxide Inorganic materials 0.000 title claims abstract description 52
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000011734 sodium Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 17
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 150000003624 transition metals Chemical class 0.000 claims abstract description 5
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- 235000011008 sodium phosphates Nutrition 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 claims description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 235000019983 sodium metaphosphate Nutrition 0.000 claims description 2
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 5
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract 2
- 238000005245 sintering Methods 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 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 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—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
-
- 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
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
Abstract
The invention discloses a surface-coated layered transition metal oxide positive electrode material and a preparation method thereof. The surface of the surface-coated layered transition metal oxide positive electrode material consists of S or P doped amorphous carbon, and the near surface of the surface-coated layered transition metal oxide positive electrode material is N dopedLayered transition metal oxide of (Na) α MO 2‑z N z The material bulk phase is a layered transition metal oxide Na β MO 2 The composition, the near surface and bulk phase of the material have no transition metal offset or vacancy, and the material is prepared by adopting a solid-phase sintering method. The preparation process is simple, and the prepared surface-coated layered transition metal oxide cathode material is applied to a sodium ion battery, so that the battery has excellent rate performance and cycling stability.
Description
Technical Field
The invention belongs to the technical field of positive electrode materials of sodium-ion batteries, and relates to a surface-coated layered transition metal oxide positive electrode material and a preparation method thereof.
Background
Layered transition metal oxide Na x MO 2 The (M is a transition metal element) sodium resource has the advantages of low price, wide source, higher theoretical specific capacity and the like, so the sodium resource is considered to be one of the most promising positive electrode materials of the sodium ion battery and is widely concerned. Layered transition metal oxide Na x MO 2 Mainly comprises O3 and P2 type layered transition metal oxides, but the O3 and P2 type layered oxides Na are reported at present x MO 2 Has disadvantages in electrochemical performance. Such as O3-NaMnO 2 The positive electrode material can provide discharge capacity of up to 197mAh/g (J.electrochem. Soc.,2011,158, A1307), but the lattice structure is easy to distort due to the sliding of the oxygen layer during the charge and discharge processes, so that the capacity is rapidly attenuated. Compared with O3-NaMnO 2 ，P2-Na 0.67 MnO 2 The positive electrode material has better rate performance, but when the positive electrode material is charged to a high potential, the P2 phase also generates oxygen layer sliding, the phase transition from P2 to O2 occurs, and then a severe unit cell volume change is generated, which is very unfavorable for being used as a commercial sodium-ion battery electrode material (angew.chem.int.ed., 2016,128,12952). Therefore, modification of the layered transition metal oxide cathode material for the sodium-ion battery is very important for improving the electrochemical stability of the layered transition metal oxide cathode material.
Surface coating is a common material modification method, but the currently reported surface coating mode still has certain defects in electrochemical performance. Such as Al 2 O 3 P2 phase material N after surface coating a0.5 Mn 0.5 Co 0.5 O 2 (Hari Vignesh Ramasami, 2019,564,467) can increase its capacity from 154mAh/g to 174mAh/g at 0.5C, but only from 75% to 78% in terms of cycle. Adopting P3 phase material Na coated on the surface of phosphate 0.65 Mn 0.75 Ni 0.25 O 2 (Yu Wang,2019,372,1066) can increase the material cycle from 76.4% to 92.4% at 0.2C, but only from 130.2mAh/g to 133.6mAh/g in capacity.
Disclosure of Invention
The invention aims to provide a surface coating layer-shaped transition metal oxide positive electrode material for a sodium-ion battery and a preparation method thereof. The method adopts a composite surface coating technology, effectively inhibits the problems of transition metal migration, dissolution, surface non-crystallization and the like on the surface of the layered transition metal oxide material, and prepares the layered transition metal oxide anode material for the sodium ion battery with low cost and long cycle life.
The technical solution for realizing the purpose of the invention is as follows:
the surface of the material is coated with a layered transition metal oxide anode material, the surface of the material consists of S or P doped amorphous carbon, and the near surface of the material consists of N doped layered transition metal oxide Na α MO 2-z N z The material bulk phase is a layered transition metal oxide Na β MO 2 The composition of the material near surface and bulk phase has no transition metal offset or vacancy, wherein M is transition metal ion Ni 2+ 、Ni 3 + 、Fe 3+ 、Cu 2+ 、Co 3+ 、Cr 3+ 、Zn 2+ 、Ti 4+ 、V 5+ 、Nb 5+ 、Li + 、Mn 3+ 、Mn 4+ 0.05 is less than or equal to z and is less than or equal to 0.1,0.6 and is less than or equal to alpha and is less than or equal to 1,0.55 and is less than or equal to beta and is less than or equal to 0.95.
Preferably, the thickness of the surface and the near surface of the surface-coated layered transition metal oxide cathode material is 2-10 nm.
The preparation method of the surface-coated layered transition metal oxide cathode material comprises the following specific steps:
taking transition metal oxide and sodium carbonate as raw materials, ball-milling and uniformly mixing the raw materials according to a stoichiometric ratio, carrying out heat treatment for 15-18 h at 900 +/-10 ℃ in an air atmosphere, cooling to obtain precursor powder, mixing and ball-milling the precursor powder, melamine, a sulfur source and/or a phosphorus source uniformly, and carrying out heat treatment for 2-5 h at 300-600 ℃ in a nitrogen or argon atmosphere to obtain the surface-coated layered transition metal oxide.
Preferably, the transition metal oxide is NiO and Ni 2 O 3 、Fe 2 O 3 、CuO、Co 2 O 3 、Cr 2 O 3 、ZnO、TiO 2 、V 2 O 5 、Nb 2 O 5 、Li 2 O、Mn 2 O 3 Or MnO 2 。
Preferably, the phosphorus source is one or more of sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium hypophosphite and sodium metaphosphate.
Preferably, the sulfur source is one or more of thiourea, sodium sulfate, sodium bisulfate.
Preferably, the mass of melamine is 2% to 5% of the total mass of transition metal oxide and sodium carbonate.
Preferably, the mass of the sulfur source or the phosphorus source is 1 to 5% of the total mass of the transition metal oxide and the sodium carbonate.
Compared with the prior art, the invention has the following advantages:
(1) The surface of the surface-coated layered transition metal oxide is coated by amorphous carbon, so that the electronic conductivity and the rate capability of the material are improved; (2) The surface of the invention is coated with the layered transition metal oxide, thereby inhibiting the dissolution of transition metal, improving the cycle performance of the material and being used as the anode material of a sodium ion battery.
Drawings
FIG. 1 is a scanning electron micrograph of a sample prepared according to example 1.
FIG. 2 is a scanning electron micrograph of a sample prepared in example 2.
FIG. 3 is a scanning electron micrograph of a sample prepared in example 3.
Detailed Description
The invention will be further elucidated with reference to the embodiments and the drawings, without however being limited thereto.
The preparation of the surface-coated layered transition metal oxide electrode and the electrochemical performance test thereof provided by the invention comprise the following specific steps:
the surface-coated layered transition metal oxide powder prepared by the invention is mixed with superconducting carbon black (Super P) and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, dissolving the mixture in N-methyl pyrrolidone (NMP), coating the mixture on the surface of an aluminum foil, and drying the aluminum foil in a vacuum oven at the temperature of 80 ℃ for 10 hours to obtain the surface-coated layered transition metal oxide electrode.
Taking a surface-coated layered transition metal oxide electrode as a positive electrode, a sodium metal sheet as a negative electrode and 1.0mol/LNaPF 6 The method comprises the steps of taking propylene carbonate as electrolyte, assembling the electrolyte into a half cell in a glove box in an argon atmosphere, detecting the electrochemical properties of the electrode material with the surface coated with the layered transition metal oxide, wherein the electrochemical properties comprise specific capacity, rate capability, cycling stability and first coulombic efficiency, and the test voltage range is 2.5-4.5V.
In the following examples, the amount of melamine added is calculated as the mass of melamine as a percentage of the total mass of transition metal oxide and sodium carbonate.
Example 1
MnO of 2 Mixing with sodium carbonate by ball milling at a certain proportion, heating at 900 deg.C for 15 hr to obtain Na 0.67 MnO 2 . Mixing Na 0.67 MnO 2 The powder, 3wt% of melamine and 1wt% of thiourea are used as raw materials, the raw materials are ball-milled and mixed uniformly to obtain powder, and the powder is heated and treated for 5 hours at 300 ℃ in an argon atmosphere to obtain surface-coated layered transition metal oxide powder.
Example 2
MnO of 2 Mixing with sodium carbonate by ball milling at a certain proportion, heating at 900 deg.C for 15 hr to obtain Na 0.67 MnO 2 . Na is mixed with 0.67 MnO 2 The powder, 3wt% of melamine and 1wt% of disodium hydrogen phosphate are used as raw materials, the raw materials are ball-milled and mixed uniformly to obtain powder, and the powder is heated and treated for 5 hours at 300 ℃ in an argon atmosphere to obtain the powder of the surface-coated layered transition metal oxide.
Example 3
MnO of 2 After the sodium carbonate is ball milled and mixed evenly according to the proportion, the mixture is added at 900 DEG CHeat treating for 15h to obtain Na 0.67 MnO 2 . Na is mixed with 0.67 MnO 2 The powder, 3wt% of melamine, 1wt% of sodium sulfate and 1wt% of sodium phosphate are used as raw materials, the raw materials are ball-milled and mixed uniformly to obtain powder, and the powder is heated and treated for 5 hours at 300 ℃ in an argon atmosphere to obtain the surface-coated layered transition metal oxide powder.
Example 4
MnO of 2 Ball-milling and mixing sodium carbonate in proportion, heating at 900 deg.C for 18h to obtain Na 0.67 MnO 2 . Mixing Na 0.67 MnO 2 The powder, 5wt% of melamine, 5wt% of sodium sulfate and 5wt% of sodium phosphate were used as raw materials, and the raw materials were ball-milled and mixed uniformly to obtain a powder, which was heat-treated at 600 ℃ for 5 hours in an argon atmosphere to obtain a surface-coated layered transition metal oxide powder.
Example 5
MnO of 2 Mixing with sodium carbonate by ball milling at a certain proportion, heating at 900 deg.C for 18h to obtain Na 0.67 MnO 2 . Mixing Na 0.67 MnO 2 The powder, 2wt% of melamine, 1wt% of sodium sulfate and 1wt% of sodium phosphate are used as raw materials, the raw materials are ball-milled and mixed uniformly to obtain powder, and the powder is heated and treated for 2 hours at 300 ℃ in an argon atmosphere to obtain the surface-coated layered transition metal oxide powder.
Comparative example
This comparative example uses Na 0.67 MnO 2 As a positive electrode material, the capacity retention rate after 100 cycles in the voltage range of 0.02A/g and 2.5-4.5V was 43.5%.
TABLE 1
Claims (9)
1. The surface of the anode material is coated with the layered transition metal oxide, and the anode material is characterized in that the surface of the anode material consists of S or P doped amorphous carbon, and the near surface of the anode material consists of N doped layered transition metal oxide Na α MO 2-z N z Composition of materialsThe material phase is a layered transition metal oxide Na β MO 2 The composition of the material has no transition metal offset or vacancy at the near surface and bulk phase, wherein M is transition metal ion Ni 2+ 、Ni 3+ 、Fe 3+ 、Cu 2+ 、Co 3+ 、Cr 3+ 、Zn 2+ 、Ti 4+ 、V 5+ 、Nb 5+ 、Li + 、Mn 3+ 、Mn 4+ Z is more than or equal to 0.05 and less than or equal to 0.1,0.6 and less than or equal to alpha and less than or equal to 1,0.55 and less than or equal to beta and less than or equal to 0.95.
2. The surface-coated layered transition metal oxide positive electrode material according to claim 1, wherein the surface and near-surface thickness of the surface-coated layered transition metal oxide positive electrode material is 2 to 10nm.
3. The preparation method of the surface-coated layered transition metal oxide positive electrode material according to claim 1 or 2, characterized by comprising the following specific steps:
taking transition metal oxide and sodium carbonate as raw materials, ball-milling and uniformly mixing the raw materials according to a stoichiometric ratio, carrying out heat treatment for 15-18 h at 900 +/-10 ℃ in an air atmosphere, cooling to obtain precursor powder, mixing and ball-milling the precursor powder, melamine, a sulfur source and/or a phosphorus source uniformly, and carrying out heat treatment for 2-5 h at 300-600 ℃ in a nitrogen or argon atmosphere to obtain the surface-coated layered transition metal oxide.
4. The method according to claim 3, wherein the transition metal oxide is NiO or Ni 2 O 3 、Fe 2 O 3 、CuO、Co 2 O 3 、Cr 2 O 3 、ZnO、TiO 2 、V 2 O 5 、Nb 2 O 5 、Li 2 O、Mn 2 O 3 Or MnO 2 。
5. The method according to claim 3, wherein the phosphorus source is one or more of sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium hypophosphite, and sodium metaphosphate.
6. The method according to claim 3, wherein the sulfur source is one or more of thiourea, sodium sulfate, and sodium bisulfate.
7. The process according to claim 3, wherein the mass of melamine is 2 to 5% of the total mass of the transition metal oxide and the sodium carbonate.
8. The production method according to claim 3, wherein the mass of the sulfur source or the phosphorus source is 1 to 5% of the total mass of the transition metal oxide and the sodium carbonate.
9. The use of the surface-coated layered transition metal oxide positive electrode material according to claim 1 or 2 in a sodium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210821075.0A CN115172695B (en) | 2022-07-13 | 2022-07-13 | Surface-coated layered transition metal oxide positive electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210821075.0A CN115172695B (en) | 2022-07-13 | 2022-07-13 | Surface-coated layered transition metal oxide positive electrode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115172695A true CN115172695A (en) | 2022-10-11 |
| CN115172695B CN115172695B (en) | 2024-02-13 |
Family
ID=83492220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210821075.0A Active CN115172695B (en) | 2022-07-13 | 2022-07-13 | Surface-coated layered transition metal oxide positive electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115172695B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107946564A (en) * | 2017-11-16 | 2018-04-20 | 武汉理工大学 | Rich sodium manganese base Na4Mn2O5/Na0.7MnO2Composite material and its preparation method and application |
| CN112830521A (en) * | 2019-11-22 | 2021-05-25 | 南京理工大学 | F-doped P2-Na0.7MnO2Electrode material and preparation method thereof |
| KR20220008612A (en) * | 2020-07-14 | 2022-01-21 | 한국과학기술연구원 | Cathode active material for sodium ion battery and method for preparing the same |
-
2022
- 2022-07-13 CN CN202210821075.0A patent/CN115172695B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107946564A (en) * | 2017-11-16 | 2018-04-20 | 武汉理工大学 | Rich sodium manganese base Na4Mn2O5/Na0.7MnO2Composite material and its preparation method and application |
| CN112830521A (en) * | 2019-11-22 | 2021-05-25 | 南京理工大学 | F-doped P2-Na0.7MnO2Electrode material and preparation method thereof |
| KR20220008612A (en) * | 2020-07-14 | 2022-01-21 | 한국과학기술연구원 | Cathode active material for sodium ion battery and method for preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115172695B (en) | 2024-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111762768B (en) | Spinel type lithium manganate-phosphate composite cathode material and preparation method thereof | |
| CN110828783A (en) | Lithium battery positive electrode material and preparation method and application thereof | |
| CN112436123A (en) | Composite coated nickel-based ternary positive electrode material and preparation method thereof | |
| CN115000388B (en) | Sodium ion positive electrode material and preparation method and application thereof | |
| CN116605918A (en) | High-entropy doped O3 phase layered oxide, preparation method thereof, sodium ion battery positive electrode material and battery | |
| CN116435514A (en) | Ammonium fluotitanate modified lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN116741984A (en) | Positive electrode material of sodium ion battery, preparation method of positive electrode material, positive electrode and sodium ion battery | |
| CN115172695B (en) | Surface-coated layered transition metal oxide positive electrode material and preparation method thereof | |
| CN116454267A (en) | Sodium-electricity layered oxide and preparation method thereof | |
| CN116230882A (en) | High-nickel ternary positive electrode material for lithium battery, preparation method and lithium battery | |
| CN115832471A (en) | Modified positive electrode lithium supplement additive and preparation method and application thereof | |
| CN115548290A (en) | Surface modification modified lithium-rich manganese-based cathode material and preparation method thereof | |
| CN111740112B (en) | Preparation method of lithium iron phosphate/carbon nanotube composite positive electrode material | |
| CN114744184A (en) | High-performance ternary cathode material and preparation method thereof | |
| CN109616642B (en) | Composite positive electrode material, preparation method thereof and lithium ion battery | |
| CN111883749A (en) | Method for preparing transition metal oxide composite electrode for lithium battery | |
| KR20200013015A (en) | Elemental coating on oxide materials for lithium rechargeable battery | |
| CN117317200B (en) | Positive electrode material, preparation method thereof and sodium ion battery | |
| CN113707876B (en) | Multiplying power type lithium cobaltate cathode material, preparation method thereof and lithium ion battery | |
| CN114079040B (en) | Preparation method and application of scaly nitrogen-doped carbon composite molybdenum-doped titanium dioxide-sulfur electrode for potassium-sulfur battery | |
| WO2024036699A1 (en) | Positive electrode material, preparation method therefor, and use thereof | |
| CN117038854A (en) | Sodium-electricity layered transition metal oxide positive electrode material coated with cerium oxide on surface and preparation method thereof | |
| CN117276530A (en) | Abnormal O3 type sodium ion battery layered positive electrode material and preparation method thereof | |
| CN116835670A (en) | Sodium ion positive electrode material and preparation method thereof | |
| CN117673283A (en) | sp 3 Hybrid anion doped layered oxide and preparation method thereof |
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 |