CN117476927A - Large single crystal layered oxide positive electrode material and preparation method and application thereof - Google Patents
Large single crystal layered oxide positive electrode material and preparation method and application thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 52
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims description 14
- 238000005245 sintering Methods 0.000 claims abstract description 36
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 27
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 18
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 17
- 239000011780 sodium chloride Substances 0.000 claims abstract description 16
- 239000011734 sodium Substances 0.000 claims abstract description 13
- 239000010405 anode material Substances 0.000 claims abstract description 10
- 238000009826 distribution Methods 0.000 claims abstract description 10
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims description 24
- 239000010406 cathode material Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
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- 239000002482 conductive additive Substances 0.000 claims description 9
- 102000020897 Formins Human genes 0.000 claims description 8
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- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052760 oxygen Inorganic materials 0.000 claims description 6
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000006245 Carbon black Super-P Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000661 sodium alginate Substances 0.000 claims description 4
- 235000010413 sodium alginate Nutrition 0.000 claims description 4
- 229940005550 sodium alginate Drugs 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
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- 239000007789 gas Substances 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 238000004537 pulping Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 claims 1
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- 238000000498 ball milling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
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- 239000000463 material Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
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- 229910004838 Na2/3Ni1/3Mn2/3O2 Inorganic materials 0.000 description 3
- 238000000227 grinding 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
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- 150000005837 radical ions Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000447 polyanionic polymer Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—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
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a large monocrystal layered oxide positive electrode material, which is Na c M1 x M2 y M3 z O 2 C is more than 0.5 and less than 1, x is more than or equal to 0 and less than or equal to 0.9, y is more than or equal to 0 and less than or equal to 0.9, z is more than or equal to 0 and less than or equal to 0.9, and x+y+z=1, wherein M1, M2 and M3 are independently selected from Ni, mn, fe, cu, co or Ti; the large single crystal layered oxide anode material is prepared by a molten salt method; in the molten salt method, the molten salt is NaCl, and the sintering aid is A a O b And/or NaA c O d A is selected from Nb, bi, W, mo, sn, sb, taAt least one of (a) and (b). According to the invention, by adding a trace amount of sintering aid into the molten salt system, the controllable synthesis of the large-size monocrystal layered anode material is realized, and the particle size distribution is narrow; the obtained monocrystal anode has excellent electrochemical performance, and is expected to promote the large-scale application and popularization of sodium ion batteries.
Description
Technical Field
The invention belongs to the field of sodium ion battery anode materials, and particularly relates to a large single crystal layered oxide anode material, a preparation method and application thereof.
Background
The lithium ion battery is a common rechargeable battery and is widely applied to the fields of mobile phones, electric vehicles, energy storage equipment and the like. Its advantages are high energy density, long service life, and quick charge, and high cost and safety. In contrast, the sodium ion battery is used as a novel battery technology and has the advantages of low cost, good safety, strong environmental protection and the like.
The positive electrode material of the sodium ion battery mainly comprises layered oxides, prussian blue compounds, polyanion compounds and the like. The laminar oxidation anode material has relatively high specific capacity and good electrochemical performance, is widely researched and focused, and has the problems of poor cycle stability and the like. The monocrystalline lamellar positive electrode oxide can reduce inter-crystal cracking in the circulation process, inhibit the generation of surface interface side reactions, and has better circulation stability compared with a polycrystalline material. Therefore, the single crystal layered anode oxide is widely researched and reported in recent years, and the synthesis method of the single crystal layered oxide of the sodium ion battery comprises coprecipitation, a molten salt method, sol-gel, solid phase sintering, element doping, a spray cracking (drying) method and the like from the aspect of the currently published synthesis technology, and the defects of complex process, multiple parameters, harsh conditions (pure oxygen environment), more required equipment and the like generally exist, and the prepared single crystal product is easy to agglomerate, contains surface residual alkali, has irregular morphology, has unobvious single crystal characteristics and the like, so that the performance of the single crystal layered anode material is severely limited.
Compared with small-size single crystal particles, the large-size single crystal layered cathode material has smaller specific surface area, can further reduce contact with electrolyte so as to inhibit side reaction, and has been reported in research, the large-size single crystal electrode material has higher safety, less heat generation in the circulation process and higher high pressure resistance. Therefore, the development potential of the large-sized single crystal layered oxide cathode material is very large. However, in the domestic published patent scheme, the size of sodium-based layered oxide single crystal particles is mostly below 5 μm, and chinese patent application CN115863624a discloses a single crystal layered sodium ion positive electrode material, in which the single crystal size is 10 μm at maximum, but the particle size distribution is uneven, 1 μm at minimum, and small scraps are present. Therefore, there is a need to develop a simple method for synthesizing a large single-crystal layered oxide cathode material having a uniform particle size distribution.
Disclosure of Invention
The invention provides a large monocrystal layered oxide positive electrode material, a preparation method and application thereof, and aims to solve the problem that the electrochemical stability of a positive electrode material of a sodium ion battery in the prior art can not meet the actual requirements, in particular to the problem of poor cycle stability.
The invention firstly provides a large monocrystal layered oxide positive electrode material, wherein the layered positive electrode material of the sodium ion battery is Na c M1 x M2 y M3 z O 2 C is more than 0.5 and less than 1, x is more than or equal to 0 and less than or equal to 0.9, y is more than or equal to 0 and less than or equal to 0.9, z is more than or equal to 0 and less than or equal to 0.9, and x+y+z=1, wherein M1, M2 and M3 are independently selected from Ni, mn, fe, cu, co or Ti; the large single crystal layered oxide anode material is prepared by a molten salt method; in the molten salt method, the molten salt is NaCl, and the sintering aid is A a O b And/or NaA c O d A is selected from at least one of Nb, bi, W, mo, sn, sb, ta, a, b, c, d satisfies the chemical valence balance.
Further, c is more than or equal to 2/3 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 2/3, y is more than or equal to 0 and less than or equal to 2/3, and z is more than or equal to 0 and less than or equal to 2/3; in one embodiment of the invention, c is 2/3.
The element A in the sintering aid is heavy metal and is difficult to enter the bulk phase, so that the element A does not exist in a doped form in the layered oxide positive electrode material, and therefore, the element A does not need to be represented in the chemical formula of the large single crystal layered oxide positive electrode material.
The large single crystal means that the single crystal particle size is 5 μm or more, preferably 5 to 20 μm, more preferably 7 to 15 μm, most preferably 10 to 13 μm; and the particle size distribution of the large single crystal layered oxide positive electrode material satisfies D50/D20 < 1.8, more preferably D50/D20 < 1.7, still more preferably D50/D20 < 1.6, and most preferably D50/D20 < 1.5. The D50/D20 can be used to indicate the degree of dispersion of the particle size of the particles, the closer it is to 1, the narrower the particle size distribution.
Further, the usage amount of the molten salt NaCl satisfies the mole ratio of NaCl to the sum of M1, M2 and M3 of 2-4:1, a step of; the amount of the sintering aid is 1-10% of the molar amount of the molten salt NaCl in the sintering aid, and preferably 2.5-4% of the molar amount of the molten salt NaCl is used as the metal A.
Further, the sintering aid is a mixture of a compound containing Nb and a compound containing Bi, and the amount satisfies the following conditions: according to Nb: the molar ratio of Bi is 1-3:1-3, preferably 1-2:1-2.
Further, the Nb-containing compound is selected from NbO 2 、Nb 2 O 5 、NaNbO 3 At least one of the Bi-containing compounds is selected from Bi 2 O 3 、NaBiO 3 、NaBiO 2 At least one of them. In a preferred embodiment of the present invention, the Nb-containing compound is NbO 2 The Bi-containing compound is NaBiO 2 And/or NaBiO 3 。
The invention accelerates the dissolution and mass transfer process of transition metal by combining the acid radical ion formed by the sintering aid (mineralizer) at high temperature with the transition metal ion, and the transition metal is supersaturated and separated out in molten salt, thereby accelerating the crystal growth. The inventors have unexpectedly found that, by compounding a compound containing Nb and Bi as a sintering aid in a certain ratio, the layered oxide cathode material obtained can obtain single crystal particles with good morphology, not only the single crystal particles have a large particle size (> 5 μm) but also the single crystal particles have a narrow particle size distribution, and most of the single crystal particles have a particle size mainly concentrated in a small range (D50/D20 < 1.8).
The invention also provides a preparation method of the large single crystal layered oxide positive electrode material, which comprises the following steps: mixing sodium carbonate, oxides of metals M1, M2 and M3, molten salt NaCl and sintering aid, calcining, and cooling to obtain the large single crystal layered oxide anode material.
Further, the steps of washing, filtering and drying are carried out after calcination and cooling; the washing is to soak and clean the calcined product by using deionized water and ethanol; drying is not particularly limited, and may be, for example, oven drying, vacuum drying, or the like.
Further, the calcination temperature is 500-1000 ℃ and the calcination time is 10-25h.
Further, in the preparation method of the large single crystal layered oxide cathode material, the purity of the used raw materials is more than 99%.
Further, the mixing mode is not limited, and includes manual grinding or mechanical mixing, and specifically at least one of mechanical ball milling, manual grinding and mechanical grinding is selected.
Further, the calcination is divided into two sections, wherein the primary calcination temperature is 500-700 ℃, preferably 600-650 ℃; the primary calcination time is 6-12h, preferably 8-10h; the secondary calcination temperature is 800-1000 ℃, preferably 850-950 ℃; the secondary calcination time is 10 to 20 hours, preferably 12 to 15 hours. The temperature rising rate is 3-15 ℃ for min -1 Preferably at 5-10deg.C for min -1 。
In the preparation method, the calcined gas atmosphere is air or oxygen or any atmosphere containing oxygen, and the oxygen volume content is more than or equal to 10 percent.
In the preparation method, the cooling mode is furnace-mounted cooling or cooling at 2-10deg.C for min -1 Cooling, preferably at 3-5deg.C for min -1 And (5) cooling.
The invention also provides a sodium ion battery, and the positive electrode of the sodium ion battery comprises the large single crystal layered oxide positive electrode material.
Further, the positive electrode comprises the large single crystal layered oxide positive electrode material, a conductive additive, a binder and a solvent, and is prepared by pulping, coating and drying the large single crystal layered oxide positive electrode material, the conductive additive, the binder and the solvent together.
Further, the conductive additive is one or more of carbon black, super-P and ketjen black, preferably Super-P; the binder and the corresponding solvent are one or more of polyvinylidene fluoride (PVDF) (N-methyl pyrrolidone (NMP) is used as solvent) or polyacrylic acid (PAA), sodium carboxymethyl cellulose (CMC), styrene butadiene rubber/sodium carboxymethyl cellulose, sodium Alginate (SA) and gelatin (both of which are used as solvent).
Further, the mass ratio of the large single crystal layered oxide positive electrode material, the conductive additive and the binder PVDF is 6-8:1-2:1-2.
Compared with the prior art, the invention has the advantages that:
(1) The monocrystalline lamellar positive electrode material synthesized by the invention has the problems of small particles, high agglomeration degree, residual alkali on the surface and the like, but the monocrystalline lamellar positive electrode material synthesized by the invention has larger particle size, no agglomeration and smooth surface, can reduce contact with electrolyte so as to inhibit side reaction, has higher safety, less heat generation in the circulation process and higher pressure resistance, and has been reported in research
(2) The invention uses the fused salt to assist the sintering process, through selecting proper sintering auxiliary agent and controlling the usage amount, the invention can synthesize the monocrystalline particles with controllable particle size, larger particle size and narrow particle size distribution.
(3) The synthesized large monocrystal lamellar positive electrode material has higher tap density, better mechanical property and cycling stability, and fewer surface interface side reactions.
Drawings
FIG. 1 is an XRD spectrum of the positive electrode material prepared in example 1;
FIG. 2 is an SEM spectrum of the positive electrode material prepared in example 1;
FIG. 3 is a graph of cycling capacity of an example sodium ion battery;
fig. 4 is an SEM image of the positive electrode prepared in comparative example 1;
FIG. 5 is a graph showing the cycle capacity of the positive electrode prepared in comparative example 1;
fig. 6 is a particle size distribution diagram of example 1 and comparative example 1.
Detailed Description
The invention will be further illustrated with reference to specific examples, which are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Example 1
(1) Preparation of cathode Material Na 2/3 Ni 1/3 Mn 2/3 O 2
Accurately weigh 0.01mol Na according to stoichiometric ratio 2 CO 3 、0.01mol Mn 2 O 3 0.01mol of NiO, 0.12mol of NaCl as molten salt and 0.0015mol of NbO as sintering aid 2 、0.0015mol NaBiO 3 Ball-milling the materials for 0.5h to obtain a precursor.
The precursor is held in a crucible, placed in a muffle furnace for calcination, heated to 650 ℃ at a heating rate of 5 ℃/min, then kept for 10 hours, heated to 950 ℃ at a heating rate of 5 ℃/min and kept for 15 hours, cooled to room temperature at 3 ℃/min after the calcination is finished, rinsed 3 times with deionized water, finally washed with ethanol and dried in a vacuum oven at 80 ℃ for 8 hours to obtain Na 2/3 Ni 1/3 Mn 2/ 3 O 2 A layered positive electrode material.
(2) Preparation of positive electrode sheet
The obtained Na 2/3 Ni 1/3 Mn 2/3 O 2 Mixing a layered positive electrode material, a conductive additive SP and a binder PVDF according to the weight ratio of 8:1:1, dissolving in a solvent NMP, stirring to obtain uniform slurry, uniformly coating the slurry on a carbon-coated aluminum foil by using a 200 mu m scraper, drying, and slicing to obtain the positive electrode plate.
(3) Assembled sodium ion battery
Assembling the positive electrode and the metal sodium negative electrode of the prepared composite into a sodium ion battery, and selecting carbonate electrolyte (1M NaClO as electrolyte 4 PC solution of (r)), membrane selected glass fiber membrane (Whatman,GF/D)。
example 2
Compared with example 1, the only difference is that: the sintering aid in the step (1) is changed into 0.003mol NbO 2 。
Example 3
Compared with example 1, the only difference is that: the sintering aid in the step (1) is changed into NaBiO with the concentration of 0.003mol 3 。
Example 4
Compared with example 1, the only difference is that: in the sintering auxiliary agent in the step (1), 0.0015mol NbO 2 0.00075mol Nb 2 O 5 ，NaBiO 3 0.00075mol Bi is changed 2 O 3 。
Example 5
Compared with example 1, the only difference is that: in the sintering auxiliary agent in the step (1), 0.0015mol NbO 2 Changing to 0.0015mol NaNbO 3 ，0.0015mol NaBiO 3 Changing to 0.0015mol NaBiO 2 。
Example 6
Compared with example 1, the only difference is that: the sintering aid in the step (1) is changed to 0.0024mol NbO 2 、0.0024mol NaBiO 3 。
Example 7
Compared with example 1, the only difference is that: the sintering aid in the step (1) is changed into 0.001mol NbO 2 、0.001mol NaBiO 3 。
Example 8
Compared with example 1, the only difference is that: the sintering aid in the step (1) is changed into 0.003mol NbO 2 、0.0015mol NaBiO 3 。
Example 9
Compared with example 1, the only difference is that: the sintering aid in the step (1) is changed into 0.001mol NbO 2 、0.003mol NaBiO 3 。
Example 10
Compared with example 1, the only difference is that: in the sintering auxiliary agent in the step (1), 0.0015mol NbO 2 0.0015mol SnO 2 。
Example 11
And example 1In comparison, the only differences are: in the sintering auxiliary agent in the step (1), 0.0015mol NbO 2 Change to 0.0015mol WO 3 。
Example 12
Compared with example 1, the only difference is that: in the sintering auxiliary agent in the step (1), 0.0015mol NaBiO 3 Modified to 0.0015mol NaWO 4 。
Example 13
Compared with example 1, the only difference is that: in the sintering auxiliary agent in the step (1), 0.0015mol NaBiO 3 Changed to 0.0015mol Na 2 MoO 4 。
Example 14
Compared with example 1, the only difference is that:
(1) Preparation of cathode Material Na 2/3 Ni 1/3 Mn 1/3 Ti 1/3 O 2
Accurately weigh 0.01mol Na according to stoichiometric ratio 2 CO 3 、0.005mol Mn 2 O 3 、0.01mol NiO、0.01mol TiO 2 0.12mol NaCl in molten salt and 0.0015mol NbO in sintering aid 2 And 0.0015mol NaBiO 3 Ball-milling the materials for 0.5h to obtain a precursor.
The ground precursor is held in a crucible, then is placed in a muffle furnace for calcination, the heating rate is 5 ℃/min, the temperature is kept for 12 hours after the temperature is raised to 600 ℃, the sintering aid B is added after the temperature is cooled to the room temperature, the mixture is ground, the temperature is raised to 900 ℃ at the heating rate of 5 ℃/min and kept for 15 hours, the mixture is cooled to the room temperature at the heating rate of 5 ℃/min, the mixture is washed by deionized water for a plurality of times, and finally the mixture is washed by ethanol and then dried in a vacuum oven for 8 hours, so that Na is obtained 2/3 Ni 1/3 Mn 1/3 Ti 1/3 O 2 A layered positive electrode material.
The other steps were the same as in example 1.
Example 15
Compared with example 1, the only difference is that:
(1) Preparation of cathode Material Na 2/3 Fe 1/2 Mn 1/2 O 2
Accurately weigh 0.01mol Na according to stoichiometric ratio 2 CO 3 、0.0075mol Fe 2 O 3 、0.0075mol Mn 2 O 3 0.12mol NaCl in molten salt and 0.0015mol NbO in sintering aid 2 And 0.0015mol NaBiO 3 Ball-milling the materials for 0.5h to obtain a precursor.
The other steps were the same as in example 1.
Example 16
Compared with the embodiment 1, the difference is that in the step (1), after the precursor is obtained, the precursor is held in a crucible, is placed in a muffle furnace for calcination, the temperature rising rate is 5 ℃/min, the temperature is kept for 25 hours after the temperature is increased to 900 ℃, after the calcination is finished, the precursor is cooled to the room temperature at 3 ℃/min, is washed 3 times by deionized water, and finally is dried in a vacuum oven at 80 ℃ for 8 hours after being washed by ethanol, so that Na is obtained 2/ 3 Ni 1/3 Mn 2/3 O 2 And a positive electrode material. Namely, the two-stage heating calcination is changed into one-stage calcination.
Comparative example 1
Compared with the example 1, the raw materials are not added with the sintering additive NbO in the preparation process 2 NaBiO 3 The remainder was the same as in example 1.
Application example
Based on half-cell testing, the positive electrode materials obtained in the examples and the comparative examples were subjected to electrochemical performance testing, the cell testing voltage range was 2.5-4.15V, and the testing magnification was 0.1C. The results are shown in Table 1 below.
Table 1 electrochemical performance test
Therefore, the invention uses a simple molten salt method, through adding a specific sintering auxiliary agent, acid radical ions formed at high temperature are combined with transition metal ions, the dissolution and mass transfer processes of the transition metal are accelerated, and the transition metal is supersaturated and separated out in the molten salt, so that the crystal growth is accelerated, large-size single crystal particles with narrow particle size distribution are obtained, the exertion of layered oxide as the electrochemical performance of a sodium ion battery is facilitated, the help and guidance significance is provided for the trend use of the sodium ion battery, and the invention has very strong industrial practicability.
Claims (10)
1. A large single crystal layered oxide positive electrode material is characterized in that the sodium ion battery layered positive electrode material is Na c M1 x M2 y M3 z O 2 C is more than 0.5 and less than 1, x is more than or equal to 0 and less than or equal to 0.9, y is more than or equal to 0 and less than or equal to 0.9, z is more than or equal to 0 and less than or equal to 0.9, and x+y+z=1, wherein M1, M2 and M3 are independently selected from Ni, mn, fe, cu, co or Ti; the large single crystal layered oxide anode material is prepared by a molten salt method; in the molten salt method, the molten salt is NaCl, and the sintering aid is A a O b And/or NaA c O d A is selected from at least one of Nb, bi, W, mo, sn, sb, ta, a, b, c, d satisfies the chemical valence balance.
2. The large single crystal layered oxide cathode material according to claim 1, wherein c is 2/3.ltoreq.c < 1, x is 0.ltoreq.2/3, y is 0.ltoreq.2/3, z is 0.ltoreq.2/3.
3. The large single crystal layered oxide cathode material according to claim 1, wherein the large single crystal layered oxide cathode material has a size of 5 μm or more, preferably 5-20 μm, more preferably 7-15 μm, most preferably 10-13 μm; and the particle size distribution of the large single crystal layered oxide positive electrode material satisfies D50/D20 < 1.8, more preferably D50/D20 < 1.7, still more preferably D50/D20 < 1.6, and most preferably D50/D20 < 1.5.
4. The large single crystal layered oxide cathode material according to claim 1, wherein the amount of molten salt NaCl satisfies the molar ratio of NaCl to the sum of M1, M2, M3 is 2 to 4:1, a step of; the amount of the sintering aid is 1-10% of the molar amount of the molten salt NaCl in the sintering aid, and preferably 2.5-4% of the molar amount of the molten salt NaCl is used as the metal A.
5. The large single crystal layered oxide cathode material according to claim 1, wherein the sintering aid is a mixture of Nb-containing compound and Bi-containing compound in an amount satisfying the following conditions: according to Nb: the molar ratio of Bi is 1-3:1-3, preferably 1-2:1-2.
6. The large single crystal layered oxide cathode material according to claim 5, wherein the Nb-containing compound is selected from the group consisting of NbO 2 、Nb 2 O 5 、NaNbO 3 At least one of the Bi-containing compounds is selected from Bi 2 O 3 、NaBiO 3 、NaBiO 2 At least one of them.
7. The method for producing a large single crystal layered oxide positive electrode material according to any one of claims 1 to 6, comprising the steps of: mixing sodium carbonate, oxides of metals M1, M2 and M3, molten salt NaCl and sintering aid, calcining, and cooling to obtain the large single crystal layered oxide anode material.
8. The method according to claim 7, wherein the calcination temperature is 500 to 1000 ℃ and the calcination time is 10 to 25 hours;
further, the calcination is divided into two sections, wherein the primary calcination temperature is 500-700 ℃, preferably 600-650 ℃; the primary calcination time is 6-12h, preferably 8-10h; the secondary calcination temperature is 800-1000 ℃, preferably 850-950 ℃; the secondary calcination time is 10 to 20 hours, preferably 12 to 15 hours. The temperature rising rate is 3-15 ℃ for min -1 Preferably at 5-10deg.C for min -1 。
9. The preparation method according to claim 7, wherein the calcined gas atmosphere is air or oxygen or any atmosphere containing oxygen, and the oxygen volume content is not less than 10%;
the cooling mode is furnace-mounted cooling or cooling at 2-10deg.C for min -1 Cooling, preferably at 3-5deg.C for min -1 And (5) cooling.
10. A sodium ion battery whose positive electrode comprises the large single-crystal layered oxide positive electrode material according to any one of claims 1 to 6;
further, the positive electrode comprises the large single crystal layered oxide positive electrode material, a conductive additive, a binder and a solvent, and is prepared by pulping the large single crystal layered oxide positive electrode material, the conductive additive, the binder and the solvent together, coating the slurry, and drying;
further, the conductive additive is one or more of carbon black, super-P and ketjen black, preferably Super-P; the binder and the corresponding solvent are one or more of polyvinylidene fluoride (PVDF) (N-methyl pyrrolidone (NMP) is used as solvent) or polyacrylic acid (PAA), sodium carboxymethyl cellulose (CMC), styrene butadiene rubber/sodium carboxymethyl cellulose, sodium Alginate (SA) and gelatin (water is used as solvent);
further, the mass ratio of the large single crystal layered oxide positive electrode material, the conductive additive and the binder PVDF is 6-8:1-2:1-2.
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