CN116504946A - Layered oxide positive electrode material, preparation method thereof and sodium ion battery - Google Patents
Layered oxide positive electrode material, preparation method thereof and sodium ion battery Download PDFInfo
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- CN116504946A CN116504946A CN202310582008.2A CN202310582008A CN116504946A CN 116504946 A CN116504946 A CN 116504946A CN 202310582008 A CN202310582008 A CN 202310582008A CN 116504946 A CN116504946 A CN 116504946A
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 23
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 23
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000011734 sodium Substances 0.000 claims abstract description 36
- 239000010406 cathode material Substances 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 31
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 18
- 230000002776 aggregation Effects 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 238000004220 aggregation Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 67
- 239000004094 surface-active agent Substances 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 30
- 238000000713 high-energy ball milling Methods 0.000 claims description 29
- 239000011572 manganese Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 20
- 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 description 18
- 230000008569 process Effects 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 14
- 239000011324 bead Substances 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- -1 alkyl glucosides Chemical class 0.000 claims description 7
- 229930182478 glucoside Natural products 0.000 claims description 7
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- 239000003093 cationic surfactant Substances 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- 239000002888 zwitterionic surfactant Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 229920000136 polysorbate Polymers 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 3
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 150000001413 amino acids Chemical class 0.000 claims description 3
- 229960003237 betaine Drugs 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 239000000787 lecithin Substances 0.000 claims description 3
- 229940067606 lecithin Drugs 0.000 claims description 3
- 235000010445 lecithin Nutrition 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 229950008882 polysorbate Drugs 0.000 claims description 3
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000000498 ball milling Methods 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 28
- 239000000463 material Substances 0.000 description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 14
- 159000000000 sodium salts Chemical class 0.000 description 13
- 229910002551 Fe-Mn Inorganic materials 0.000 description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 11
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 10
- 239000012046 mixed solvent Substances 0.000 description 10
- 238000004321 preservation Methods 0.000 description 10
- 239000002243 precursor Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 239000011787 zinc oxide Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 230000000630 rising effect Effects 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229910000480 nickel oxide Inorganic materials 0.000 description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 6
- 239000011163 secondary particle Substances 0.000 description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910018970 NaNi0.5Mn0.5O2 Inorganic materials 0.000 description 1
- 102000000591 Tight Junction Proteins Human genes 0.000 description 1
- 108010002321 Tight Junction Proteins Proteins 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003513 alkali Substances 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 210000001578 tight junction Anatomy 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
-
- 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
-
- 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 layered oxide positive electrode material, a preparation method thereof and a sodium ion battery, and belongs to the technical field of batteries. The chemical formula of the layered oxide positive electrode material is Na x Zn y Ni z Fe α Mn β C 1‑y‑z‑α‑β O 2 X is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, alpha is more than or equal to 0 and less than or equal to 1, beta is more than or equal to 0 and less than or equal to 1-y-z-alpha-beta is more than or equal to 1, and C is any element except Na, zn, ni, fe, mn and O; the layered oxide cathode material has at least one of the following characteristics: has a single crystal grain structure; single crystalThe particles are complete and uniform, and no aggregation exists; the grain diameter is 1-20 μm. The preparation method of the positive electrode material is simple, the cost is low, and the sodium ion battery prepared by the positive electrode material has higher voltage, first-week coulomb efficiency and cyclicity and good safety.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a layered oxide positive electrode material, a preparation method thereof and a sodium ion battery.
Background
The positive electrode materials of the sodium ion battery at present mainly comprise polyanions, prussian and layered oxides. Generally, polyanion materials have a low specific capacity due to their large molecular weight, prussian materials have a poor cycle life due to the influence of conductivity and crystal water, and layered oxide materials have a high specific capacity and energy density, thereby attracting a great deal of attention from researchers.
The general formula of the lamellar oxide is Na x MO 2 Wherein M is mainly a transition metal element and also contains a part of main group metal elements including Li + 、Ni 2+ 、Mg 2+ 、Zn 2+ 、Co 2+ 、Ca 2+ 、Ba 2+ 、Sr 2+ 、Al 3+ 、B 3+ 、Cr 3+ 、Co 3+ 、V 3+ 、Zr 4+ 、Ti 4+ 、Sn 4+ 、V 4+ 、Mo 5+ 、Mo 6+ 、Ru 4+ 、Nb 5+ 、Si 4+ 、Sb 5+ 、Nb 5+ 、Mo 6+ And Te (Te) 6+ One or more of (a) and (b). Wherein Na is x Ni y Mn z Fe 1-y-z O 2 The lithium ion ternary nickel cobalt manganese-based positive electrode material has similar structural characteristics as a lithium ion ternary nickel cobalt manganese-based positive electrode material and has the advantage of low cost, however, the actual discharge capacity is far lower than the theoretical capacity, and the energy density of a sodium ion battery is severely restricted.
Modification of structures by doping with multiple ions is currently the main technical means, and reported methods for doping Zn ions are mainly focused on one element (e.g. Na x MnO 2 ) Or binary (e.g. Na x Ni y Mn 1-y O 2 ) The method comprises ball milling with ethanol or diethyl ether as adjuvant to uniformly mix the precursors or to mix the precursors in volatile stateStirring uniformly in organic solvent (such as ethanol or diethyl ether), volatilizing completely to obtain precursor powder, or spray drying the precursor and ethanol or water slurry to obtain precursor powder, placing the precursor powder in muffle furnace, and heat treating in air at 800-1000deg.C for 10-24 hr to obtain Na x A (1-y) Zn y O 2 Or Na (or) x A y B z Zn 1-y-z O 2 Wherein A or B is a transition metal element or a part of a main group metal element.
However, the material formed by the method has serious morphology agglomeration, only secondary particles can be formed, and when the material is used for a sodium ion battery, the voltage, the first-week coulomb efficiency and the circularity are poor.
In view of this, the present invention has been made.
Disclosure of Invention
It is an object of the present invention to provide a layered oxide cathode material having a complete and uniform single crystal grain structure with no aggregation between single crystal grains.
The second object of the present invention is to provide a method for preparing the layered oxide cathode material.
The third object of the invention is to provide a sodium ion battery containing the layered oxide positive electrode material, which has higher voltage, first week coulombic efficiency and cycle property and good safety.
The application can be realized as follows:
in a first aspect, the present application provides a layered oxide cathode material having the formula Na x Zn y Ni z Fe α Mn β C 1-y-z-α-β O 2 X is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, alpha is more than or equal to 0 and less than or equal to 1, beta is more than or equal to 0 and less than or equal to 1-y-z-alpha-beta is more than or equal to 1, and C is any element except Na, zn, ni, fe, mn and O;
the layered oxide cathode material has at least one of the following characteristics:
characteristic one: the layered oxide positive electrode material has a single crystal grain structure;
and the second characteristic is: the single crystal particles of the layered oxide cathode material are complete and uniform and have no aggregation;
and (3) the following characteristics: the particle size of the layered oxide cathode material is 1-20 μm.
In a second aspect, the present application provides a method for preparing a layered oxide cathode material according to the foregoing embodiment, including the steps of: and (3) mixing the mixture of the sodium source, the zinc source, the nickel source, the iron source and the manganese source according to a preset proportion and carrying out high-energy ball milling on the mixture and the solution containing the surfactant.
In an alternative embodiment, the sodium source comprises at least one of sodium carbonate, sodium hydroxide, and sodium citrate;
and/or the zinc source comprises ZnO;
and/or, the nickel source comprises NiO;
and/or the iron source comprises Fe 2 O 3 And FeO;
and/or the manganese source comprises MnO 2 And Mn of 2 O 3 At least one of them.
In an alternative embodiment, the surfactant-containing solution includes a surfactant and a solvent; the surfactant includes at least one of a cationic surfactant, an anionic surfactant, a zwitterionic surfactant and a nonionic surfactant; the solvent includes ethanol and water.
In an alternative embodiment, the anionic surfactant comprises at least one of stearic acid and sodium dodecylbenzenesulfonate;
and/or, the cationic surfactant comprises a quaternary ammonium compound;
and/or, the zwitterionic surfactant comprises at least one of lecithin, an amino acid type, and a betaine type;
and/or the nonionic surfactant comprises at least one of alkyl glucosides, fatty acid glycerides, fatty acid sorbitan, polysorbate, and polyvinylpyrrolidone.
In some preferred embodiments, the surfactant comprises at least one of polyvinylpyrrolidone and sodium dodecylbenzenesulfonate.
In an alternative embodiment, the surfactant is used in an amount of 0.1 to 15wt% of the mixture.
In alternative embodiments, the high energy ball milling includes at least one of the following features:
characteristic one: the rotating speed of high-energy ball milling is more than or equal to 1200r/min; preferably 1200-2000r/min;
and the second characteristic is: the high-energy ball milling time is 3-7 hours;
and (3) the following characteristics: the grading ratio of the zirconium beads is more than or equal to grade 3;
and four characteristics: in the upper and lower gradations, the diameter of the small-diameter zirconium beads is 0.5-0.8 times of the diameter of the large-diameter zirconium beads.
In an alternative embodiment, the method further comprises: and drying and tabletting the ball-milled sample after high-energy ball milling, and then carrying out heat treatment.
In an alternative embodiment, the drying is carried out at 60-120 ℃ for 1-5 hours;
and/or tabletting under 10-20MPa for 1-5min.
In an alternative embodiment, the heat treatment comprises at least one of the following features:
characteristic one: the heat treatment includes: firstly, carrying out the process for 12-24 hours under the condition of 750-1200 ℃, and then carrying out the process for 12-20 hours under the condition of 950-1200 ℃;
and the second characteristic is: the heating rate in the heat treatment process is 3-10 ℃/min; preferably, the temperature is firstly increased to 750-1200 ℃ at a heating rate of 3-5 ℃/min, and then is increased to 950-1200 ℃ at a heating rate of 5-10 ℃/min;
and (3) the following characteristics: a grinding process is also arranged between the two heat treatment stages;
and four characteristics: the heat treatment is carried out in air or oxygen atmosphere;
and fifth feature: after the heat treatment, furnace cooling is carried out, and the dew point temperature of the environment is not higher than-25 ℃ when the furnace cooling is carried out.
In a third aspect, the present application provides a sodium ion battery having the layered oxide cathode material of the foregoing embodiments.
The beneficial effects of this application include:
the layered oxide positive electrode material provided by the application has a complete and uniform monocrystalline particle structure, and the monocrystalline particles are free from aggregation.
The zinc source, the nickel source, the iron source, the manganese source, the sodium source and the solution containing the surfactant are subjected to high-energy ball milling, so that the distribution state of the sodium source and the oxide can be changed, and the added oxide can form ZnNiFeMnO connected in a chemical bonding mode under the action of high-energy ball milling 2 The sodium source after ball milling is uniformly distributed in ZnNiFeMnO 2 The surface of the particles. And the carbon chain of the surfactant can be pyrolyzed and volatilized to form an interconnected microporous structure to prevent aggregation among particles, so that secondary particles are prevented from being formed, and finally the obtained material has good single crystallinity and uniform particles.
The corresponding sodium ion battery has higher voltage, first-week coulomb efficiency and cyclicity and good safety.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows NaZn as provided in example 1 of the present application 0.05 Ni 0.317 Mn 0.317 Fe 0.317 O 2 An XRD pattern of (a);
FIG. 2 shows NaZn as provided in example 2 of the present application 0.05 Ni 0.317 Mn 0.317 Fe 0.317 O 2 SEM images of (a);
fig. 3 is a charge-discharge curve of the sodium half cell provided in example 3 in the test example of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The layered oxide cathode material, the preparation method thereof and the sodium ion battery provided by the application are specifically described below.
The application provides a layered oxide positive electrode material, the chemical formula of which is Na x Zn y Ni z Fe α Mn β C 1-y-z-α-β O 2 X is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, alpha is more than or equal to 0 and less than or equal to 1, beta is more than or equal to 0 and less than or equal to 1-y-z-alpha-beta is more than or equal to 1, and C is any element except Na, zn, ni, fe, mn and O.
The layered oxide anode material is monocrystalline Zn-Ni-Fe-Mn sodium salt layered oxide.
The layered oxide positive electrode material has a complete and uniform monocrystalline particle structure, and no aggregation exists among monocrystalline particles.
For reference, the particle diameter of the above layered oxide cathode material is 1 to 20 μm, such as 1 μm, 2 μm, 5 μm, 10 μm, 12 μm, 15 μm, 18 μm, or 20 μm, etc., and may be any other value in the range of 1 to 20 μm.
The layered oxide positive electrode material has higher voltage, high first-week coulomb efficiency and high circularity, and is good in safety.
Correspondingly, the application also provides a preparation method of the layered oxide cathode material, which comprises the following steps: and (3) mixing the mixture of the sodium source, the zinc source, the nickel source, the iron source and the manganese source according to a preset proportion and carrying out high-energy ball milling on the mixture and the solution containing the surfactant.
For reference, the sodium source may include at least one of sodium carbonate (anhydrous sodium carbonate and/or aqueous sodium carbonate), sodium hydroxide, and sodium citrate, for example. The zinc source may include ZnO. The iron source may include Fe 2 O 3 And at least one of FeO. The nickel source may comprise NiO. The manganese source may include MnO 2 And Mn of 2 O 3 At least one of them.
In this application, the surfactant-containing solution includes a surfactant and a solvent. Wherein the surfactant may include at least one of a cationic surfactant, an anionic surfactant, a zwitterionic surfactant, and a nonionic surfactant.
Illustratively, the anionic surfactant may include at least one of stearic acid and sodium dodecylbenzenesulfonate, for example; cationic surfactants may include, for example, quaternary ammonium compounds; the zwitterionic surfactant may include, for example, at least one of lecithin, an amino acid type, and a betaine type; the nonionic surfactant may include, for example, at least one of alkyl glucosides (APG), fatty acid glycerides, fatty acid sorbitan (span), polysorbate (tween), and polyvinylpyrrolidone (PVP).
The solvent includes ethanol and water. The volume ratio of ethanol to water may be 1:1 to 25:1, such as 1:1, 5:1, 10:1, 15:1, 20:1, or 25:1, etc. The ratio of surfactant to solvent may be from 1g:10mL to 1g:50mL, such as 1g:10mL, 1g:15mL, 1g:20mL, 1g:25mL, 1g:30mL, 1g:35mL, 1g:40mL, 1g:45mL, or 1g:50mL, etc.
In some preferred embodiments, the surfactant comprises at least one of polyvinylpyrrolidone and sodium dodecylbenzenesulfonate. The polyvinylpyrrolidone is suitable for a solvent in which ethanol and water are mixed in any ratio, and the addition amount does not need to be adjusted due to the change of the solvent composition. Sodium dodecyl benzene sulfonate contains Na element, when pyrolysis occurs at high temperature, residual Na can react with transition metal oxide without Na, and finally the obtained material phase composition is more uniform.
The amount of the above surfactant may be 0.1 to 15wt%, such as 0.1wt%, 0.2wt%, 0.5wt%, 1wt%, 2wt%, 5wt%, 8wt%, 10wt%, 12wt% or 15wt%, etc. of the mixture, and may be any other value within the range of 0.1 to 15wt%.
The surfactant with the dosage can form uniform and stable solution in the solvent, and in the high-energy ball milling process, the surfactant combines various oxide particles with sodium ions to play a role of connecting bridges, so that the problem of uneven distribution of sodium sources and oxides in the traditional ball milling process is solved. And in the high-energy ball milling process, various oxides can form ZnNiFeMnO 2 The precursors, which are synthesized in the conventional scheme, are ZnO/NiO/Fe in a non-physically tight junction 2 O 3 /MnO 2 . The method utilizes mechanical energy to induce chemical reaction and change of material organization, structure and performance under the coordination of high-energy ball milling and surfactant to form the sodium source tightly packed ZnNiFeMnO x A complex.
If the amount of the surfactant is too small, the above-mentioned effects cannot be obtained; if the amount of surfactant is too large, the structural formation of the material during the post heat treatment is affected.
In the application, the rotation speed of the high-energy ball milling is more than or equal to 1200r/min, preferably 1200-2000r/min, such as 1200 r/mm, 1300r/min, 1400r/min, 1500r/min, 1600r/min, 1700r/min, 1800r/min, 1900r/min or 2000r/min, and the like, and any other value in the range of 1200-2000r/min can be adopted.
The high-energy ball milling time can be 3-7h, such as 3h, 4h, 5h, 6h or 7h, and the like, and can be any other value within the range of 3-7 h.
If the ball milling rotating speed is too low or the ball milling time is too short, the conventional mixing effect can be achieved, and even the materials are unevenly mixed; if the ball milling rotating speed is too high or the ball milling time is too long, the structure of the material is easily damaged.
In some embodiments, in the high-energy ball milling process, the grading ratio of the zirconium beads is not less than 3 grades, namely, at least 3 zirconium beads with different diameters are adopted, so that a better high-energy ball milling effect is obtained. Preferably, in the upper and lower gradations, the diameter of the small-diameter zirconium beads is 0.5-0.8 times that of the large-diameter zirconium beads.
For example, zirconium beads having diameters of 10mm, 8mm and 4mm may be used simultaneously for the fitting.
Further, the ball-milled sample after high-energy ball milling is dried, pressed into tablets and then subjected to heat treatment.
The drying may be carried out under conditions of 60 to 120℃such as 60℃70℃80℃90℃100℃110℃120℃or the like for 1 to 5 hours such as 1 hour, 2 hours, 3 hours, 4 hours or 5 hours.
Tabletting can be carried out under 10-20MPa (such as 10MPa, 12MPa, 15MPa, 18MPa or 20 MPa) for 1-5min (such as 1min, 2min, 3min, 4min or 5 min).
The heat treatment includes: the treatment is carried out for 12-24 hours at 750-1200 ℃ and is defined as a first heat treatment stage, and the treatment is carried out for 12-20 hours at 950-1200 ℃ and is defined as a second heat treatment stage.
The temperature in the first heat treatment stage may be 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃ or the like, or any other value within the range of 750-1200 ℃. The time of the first heat treatment stage may be 12h, 14h, 16h, 18h, 20h, etc., or any other value within the range of 12-20 h.
The temperature in the second heat treatment stage may be 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, or the like, or any other value in the range of 950 to 1200 ℃. The time of the second heat treatment stage may be 12h, 14h, 16h, 18h, 20h, etc., or any other value within the range of 12-20 h.
The first heat treatment stage may further comprise furnace cooling and grinding the resulting material (e.g., the ground material particles pass through a 500 mesh screen) followed by treatment in the second heat treatment stage.
In the application, by grinding after the first heat treatment stage and performing the treatment of the second heat treatment stage, on one hand, the problem of non-uniform sintering possibly existing in the first heat treatment stage can be improved; on the other hand, the macro-pore structure formed in the material after the first heat treatment stage can be destroyed by grinding, wherein the scale of the macro-pore structure is about hundreds of micrometers to millimeters, residual gas is released, and the grinding can further promote the material to react uniformly to form a more uniform reaction product; in addition, the second heat treatment stage can promote the reaction of sodium source and transition metal, and is favorable for reducing residual alkali of materials.
The heating rate in the heat treatment process can be 3-10 ℃/min. In some preferred embodiments, the temperature increase rate corresponding to the first heat treatment stage may be 3-5℃/min, such as 3℃/min, 3.5C/min, 4℃/min, 4.5C/min or 5℃/min, etc., or any other value within the range of 3-5℃/min. The temperature rising rate corresponding to the second heat treatment stage may be 5-10deg.C/min, such as 5deg.C/min, 6deg.C/min, 7deg.C/min, 8deg.C/min, 9deg.C/min or 10deg.C/min, etc., or may be any other value within the range of 5-10deg.C/min.
If the temperature rising rate in the first heat treatment stage is lower than 3 ℃/min, the abnormal growth of the grain size is easy to be caused, the rapid transportation of sodium ions in the bulk phase is not facilitated, and if the temperature rising rate is higher than 5 ℃/min, the grown grains are easy to be subjected to two-stage crystallization, namely the coexistence of larger and smaller grains is easy to occur. If the temperature rising rate in the second heat treatment stage is lower than 5 ℃/min, single crystal particles are easy to be secondarily aggregated to form secondary particles, and if the temperature rising rate is higher than 10 ℃/min, cold and hot stress is easy to be generated on the material, so that crystal grains are easy to be broken.
In the present application, the heat treatment is performed under an air or oxygen atmosphere.
The surfactant used in the application can be pyrolyzed under the high-temperature and air environment, and an interconnected channel structure is formed in the material, so that the air concentration in the material and the external concentration are in an equilibrium state, and the chemical reaction between the solid phase material and the gas phase oxygen is more facilitated.
Further, after heat treatment, the material is furnace cooled. When cooling with furnace, the dew point temperature of the environment is not higher than-25 ℃.
By controlling the dew point temperature of the environment to be no higher than-25 ℃, less water content in the environment can be ensured, and the influence and damage to materials are avoided.
On the premise of bearing, the high-energy ball milling is carried out on a zinc source, a nickel source, an iron source, a manganese source, a sodium source and a solution containing a surfactant, so that the distribution state of the sodium source and the oxide can be changed. Under the action of high-energy ball milling, the added oxide can form ZnNiFeMnO connected in a chemical bonding mode 2 The sodium source after ball milling is uniformly distributed in ZnNiFeMnO 2 The surface of the particles. In the prior art, aggregation of various oxides can be realized only in a physical laminating mode, and finally formed materials have serious morphology aggregation and can only form secondary particles. And the application is realized by adding a surfaceAfter the active agent, the precursor material after high-energy ball milling and drying contains a certain amount of the surfactant, and in the high-temperature heat treatment process, the carbon chain of the surfactant can be pyrolyzed and volatilized in the air or oxygen atmosphere to form an interconnected microporous structure (the microporous structure is a microscopic hole structure with a scale of about several micrometers), so that agglomeration among particles is prevented, and secondary particles are avoided. In the prior art, the precursor is directly sintered, and finally only secondary particles with serious aggregation can be formed. In the present application, the surfactant remaining in the solid mixture physically and chemically hinders the aggregation between particles, and at the same time, the interconnected pore structure can promote the contact between air and the surface of particles, reduce the concentration difference between oxygen in bulk phase and the surface of the material, and lead Na to x Zn y Ni z Fe α Mn β C 1-y-z-α-β O 2 Material and O in air 2 The reaction is more sufficient, the single crystallinity of the finally obtained material is good, and the particles are uniform.
In addition, the application also provides a sodium ion battery which is provided with the layered oxide positive electrode material. The sodium ion battery has better electrochemical performance.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
This example provides a layered oxide cathode material (Zn-Ni-Fe-Mn sodium salt layered oxide cathode material, molecular formula: naZn) 0.05 Ni 0.317 Mn 0.317 Fe 0.317 O 2 ) The preparation method comprises the following steps:
step (1): zinc oxide, nickel oxide, ferric oxide, manganese dioxide and anhydrous sodium carbonate are weighed and mixed according to the preset molar ratio of 0.05:0.317:0.317:0.156:0.56, and put into a ball milling tank (60 mL) for standby;
step (2): weighing surfactant (polyvinylpyrrolidone) accounting for 0.1% of the total mass of the step (1), adding the surfactant (polyvinylpyrrolidone) into a mixed solvent of ethanol and water (the volume ratio of the ethanol to the water is 1:1), and stirring, wherein the ratio of the mixed solvent to the surfactant is 50mL:1g;
step (3): transferring the solution obtained in the step (2) to a ball milling tank for high-energy ball milling, setting the rotating speed to 1200r/min and the ball milling time to 3h;
the grade proportion of the zirconium beads used in the high-energy ball milling process is 3 grades, and the diameters are respectively 10mm, 8mm and 4mm.
Step (4): drying the ball-milled sample in a blast drying oven at a drying temperature of 60 ℃ for 5 hours, tabletting, setting a pressure setting parameter of 10MPa, and keeping the pressure for 1min;
step (5): placing the sample subjected to tabletting in a muffle furnace, performing heat treatment under the atmosphere of air, wherein the heating rate is 3 ℃/min, the heat preservation temperature is 750 ℃, the heat preservation time is 12h, cooling along with the furnace, and taking out for grinding;
step (6): and (3) placing the powder sample in the step (5) in a muffle furnace, performing heat treatment under the air atmosphere condition, wherein the heating rate is 5 ℃/min, the heat preservation temperature is 950 ℃, the heat preservation time is 12h, cooling along with the furnace, and simultaneously controlling the dew point of the environment to be not higher than-25 ℃.
The Zn-Ni-Fe-Mn sodium salt layered oxide prepared in the embodiment is of a single crystal structure, has uniform particles and a dimension of 1-5 mu m and D 50 =3μm. The XRD pattern of the positive electrode material is shown in fig. 1, and the result shows that: diffraction peaks at 19.273 °, 39.183 °, 41.520 °, 43.117 °, 49.082 °, 53.216 °, 63.332 °, 69.205 °, 74.624 and NaNi 0.5 Mn 0.5 O 2 The (003), (006), (101), (012), (104), (015), (107), (018) and (110) crystal planes of standard cards 54-0887 coincide with partial shifts in peak position, indicating successful doping of Zn ions into the crystal structure.
Example 2
This example provides a layered oxide cathode material (Zn-Ni-Fe-Mn sodium salt layered oxide cathode material, molecular formula: naZn) 0.05 Ni 0.317 Mn 0.317 Fe 0.317 O 2 ) The preparation method comprises the following steps:
step (1): zinc oxide, nickel oxide, ferric oxide, manganese dioxide and anhydrous sodium carbonate are weighed and mixed according to a preset proportion (0.05:0.317:0.158:0.317:0.56), and are put into a ball milling tank for standby;
step (2): weighing 7.5% of the total mass of the step (1), adding the surfactant (sodium dodecyl benzene sulfonate) into a mixed solvent of ethanol and water (the volume ratio of the ethanol to the water is 25:1), and stirring, wherein the ratio of the mixed solvent to the surfactant is 50mL:1g;
step (3): transferring the solution obtained in the step (2) to a ball milling tank for high-energy ball milling, setting the rotating speed to 1500r/min and the ball milling time to 5h;
step (4): carrying out the ball milling on the sample in a blast drying oven, wherein the drying temperature is 80 ℃ and the drying time is 8 hours; tabletting, wherein the pressure setting parameter is 15MPa, and the pressure maintaining time is 2min;
step (5): placing the sample subjected to tabletting in a muffle furnace, performing heat treatment in an oxygen atmosphere, heating at a speed of 3 ℃/min, keeping the temperature at 1050 ℃ for 15 hours, cooling along with the furnace, and taking out for grinding;
step (6): and (3) placing the powder sample in the step (5) in a muffle furnace, performing heat treatment under the oxygen atmosphere condition, wherein the heating rate is 5 ℃/min, the heat preservation temperature is 950 ℃, the heat preservation time is 15h, and simultaneously controlling the dew point of the environment to be not higher than-25 ℃.
The Zn-Ni-Fe-Mn sodium salt layered oxide prepared in the embodiment is of a single crystal structure, has uniform particles and a dimension of 2-15 mu m, D 50 =8μm. The SEM image of the positive electrode material is shown in fig. 2, and the result shows that: the surface of the monocrystalline particles is smooth and the size is uniform.
Example 3
This example provides a layered oxide cathode material (Zn-Ni-Fe-Mn sodium salt layered oxide cathode material, molecular formula: naZn) 0.1 Ni 0.317 Mn 0.317 Fe 0.317 O 2 ) The preparation method comprises the following steps:
step (1): zinc oxide, nickel oxide, ferric oxide, manganese dioxide and anhydrous sodium carbonate are weighed and mixed according to a preset proportion (0.1:0.317:0.156:0.317:0.56), and are put into a ball milling tank for standby;
step (2): weighing 15% of the total mass of the surfactant (alkyl glucoside) in the step (1), adding the surfactant (alkyl glucoside) into a mixed solvent of ethanol and water (the volume ratio of the ethanol to the water is 3:1), and stirring, wherein the ratio of the mixed solvent to the surfactant is 10mL:1g;
step (3): transferring the solution obtained in the step (2) to a ball milling tank for high-energy ball milling, setting the rotating speed to 2000r/min and the ball milling time to 7h;
step (4): carrying out the ball milling on the sample in a blast drying oven, wherein the drying temperature is 90 ℃ and the drying time is 4 hours; tabletting, wherein the pressure setting parameter is 20MPa, and the pressure maintaining time is 5min;
step (5): placing the sample subjected to tabletting in a muffle furnace, performing heat treatment in an oxygen atmosphere, heating at a rate of 3 ℃/min, maintaining the temperature at 1200 ℃ for 24 hours, cooling along with the furnace, and taking out for grinding;
step (6): and (3) placing the powder sample in the step (5) in a muffle furnace, performing heat treatment under the atmosphere condition of air, wherein the heating rate is 5 ℃/min, the heat preservation temperature is 950 ℃, the heat preservation time is 20h, and the dew point of the environment is controlled to be not higher than-25 ℃.
The Zn-Ni-Fe-Mn sodium salt layered oxide prepared in the embodiment is of a single crystal structure, has uniform particles and a dimension of about 8 mu m, and is D 50 ＝4μm。
Example 4
This example provides a layered oxide cathode material (Zn-Ni-Fe-Mn-Cu sodium salt layered oxide cathode material, molecular formula: naZn) 0.1 Ni 0.3 Mn 0.317 Fe 0.317 Cu 0.017 O 2 ) The preparation method comprises the following steps:
step (1): zinc oxide, nickel oxide, ferric oxide, manganese dioxide, copper oxide and anhydrous sodium carbonate are weighed and mixed according to a preset proportion (0.1:0.3:0.156:0.317:0.017:0.56), and are put into a ball milling tank for standby;
step (2): weighing 15% of the total mass of the surfactant (alkyl glucoside) in the step (1), adding the surfactant (alkyl glucoside) into a mixed solvent of ethanol and water (the volume ratio of the ethanol to the water is 1:1), and stirring, wherein the ratio of the mixed solvent to the surfactant is 10mL:1g;
step (3): transferring the solution obtained in the step (2) to a ball milling tank for high-energy ball milling, setting the rotating speed to 2000r/min and the ball milling time to 7h;
step (4): carrying out the ball milling on the sample in a blast drying oven, wherein the drying temperature is 60 ℃ and the drying time is 8 hours; tabletting, wherein the pressure setting parameter is 20MPa, and the pressure maintaining time is 5min;
step (5) and step (6) are the same as in example 3.
The Zn-Ni-Fe-Mn-Cu sodium salt layered oxide anode material prepared by the embodiment has a single crystal structure, uniform particles and a dimension of about 10 mu m, D 50 ＝5μm。
Example 5
This example provides a layered oxide cathode material (Zn-Ni-Fe-Mn sodium salt layered oxide cathode material, molecular formula: naZn) 0.05 Ni 0.317 Mn 0.317 Fe 0.317 O 2 ) The preparation method comprises the following steps:
step (1): zinc oxide, nickel oxide, ferrous oxide, manganese sesquioxide and anhydrous sodium carbonate are weighed and mixed according to a preset proportion (0.05:0.317:0.317:0.156:0.56), and are put into a ball milling tank for standby;
steps (2) to (6) are the same as in example 4.
The Zn-Ni-Fe-Mn sodium salt layered oxide prepared in the embodiment is of a single crystal structure, has uniform particles and a dimension of about 8 mu m, and is D 50 ＝5μm。
Example 6
This example provides a layered oxide cathode material (Zn-Ni-Fe-Mn sodium salt layered oxide cathode material, molecular formula: naZn) 0.05 Ni 0.317 Mn 0.317 Fe 0.317 O 2 ) The preparation method comprises the following steps:
step (1): zinc oxide, nickel oxide, ferric oxide, manganese dioxide and anhydrous sodium carbonate are weighed and mixed according to a preset proportion (0.05:0.317:0.158:0.317:0.56), and are put into a ball milling tank for standby;
step (2): weighing 15% of the total mass of the surfactant (sodium dodecyl benzene sulfonate) in the step (1), adding the surfactant into a mixed solvent of ethanol and water (the volume ratio of the ethanol to the water is 1:1), and stirring, wherein the ratio of the mixed solvent to the surfactant is 10mL:1g;
steps (3) to (6) are the same as in example 4.
The Zn-Ni-Fe-Mn sodium salt layered oxide prepared in the embodiment is of a single crystal structure, has uniform particles and a dimension of about 5 mu m, and is D 50 ＝3μm。
Comparative example 1
The difference between this comparative example and example 1 is that: no surfactant was used during ball milling.
Comparative example 2
The difference between this comparative example and example 1 is that: the ball milling rotating speed is 800r/min.
Comparative example 3
The difference between this comparative example and example 1 is that: the ball milling speed is 2500r/min.
Comparative example 4
The difference between this comparative example and example 1 is that: only zirconium beads with two diameters of 10mm and 4mm are adopted for matching, and the mass ratio of the two zirconium beads is 1:1.
Comparative example 5
The difference between this comparative example and example 1 is that: the heat treatment comprises only a first heat treatment stage without a second heat treatment stage.
Comparative example 6
The difference between this comparative example and example 1 is that: there is no grinding process between the first heat treatment stage and the second heat treatment stage.
Comparative example 7
The difference between this comparative example and example 1 is that: the temperature of the first heat treatment stage was 700 ℃.
Comparative example 8
The difference between this comparative example and example 1 is that: the temperature of the first heat treatment stage was 1300 ℃.
Comparative example 9
The difference between this comparative example and example 1 is that: the temperature in the second heat treatment stage was 900 ℃.
Comparative example 10
The difference between this comparative example and example 1 is that: the temperature of the second heat treatment stage was 1300 ℃.
Comparative example 11
The difference between this comparative example and example 1 is that: the temperature rising rate of the first heat treatment stage is 8 ℃/min.
Comparative example 12
The difference between this comparative example and example 1 is that: the temperature rising rate of the first heat treatment stage is 3 ℃/min.
Comparative example 13
The difference between this comparative example and example 1 is that: in the furnace cooling process after heat treatment, the dew point of the environment is higher than-25 ℃.
Test examples
The layered oxide cathode materials obtained in examples 1 to 6 and comparative examples 1 to 13 were prepared into sodium ion batteries in the following manner, and the electrochemical properties of the obtained sodium ion batteries were tested.
Wherein, the preparation of the battery refers to the following method:
pole piece preparation:
a) Pulping: the active material, the conductive agent, the adhesive and the solvent form original slurry, wherein the ratio of the active material to the conductive agent to the adhesive is 8:1:1.
Active material: the layered oxide cathode materials obtained in examples 1 to 6 and comparative examples 1 to 13 were vacuum baked at 120℃for 4 hours before being made into a slurry; conductive agent: a CNT; and (2) a binder: PVDF with a manufacturer Sigma-Aldrich, mw-534000, CAS number 24937-79-9; solvent: NMP with purity not less than 99%.
b) Slurry preparation stage:
stirring to prepare slurry: NMP and PVDF are sequentially added into the stirring container, and the stirring is carried out by rotating a magnet (the rotating speed is less than or equal to 200 r/min), so that PVDF is prevented from being adhered to the inner wall of the container in the process; the SP and active were then added to the vessel and stirred for 4 hours.
c) Pole piece coating:
the current collector is coated on one side by adopting an aluminum foil with smooth two sides, the thickness is 16 mu m, and the width is 280mm; the height of the scraper is 200 mu m, and the dew point temperature of the low humidity room is controlled below minus 25 ℃.
Drying, rolling, pressing and weighing the pole piece:
a) Drying the pole piece:
the vacuum oven is in a mode of heat preservation at 80 ℃ for 2 hours, re-vacuumizing and heat preservation at 120 ℃ for 12 hours.
b) Tabletting and cutting:
and (3) tabletting the dried electrode slice, rolling the positive electrode slice to 18 mu m by a pair of rollers, then clamping the prepared electrode slice up and down by weighing paper, and punching the electrode slice with the thickness of 14mm by a punching machine, wherein the edge of the electrode slice is free from powder falling and obvious burrs.
c) Weighing
Five-position balance with precision of one ten thousandth (0.0001 g) is adopted for weighing, and the active material loading of the pole piece is not lower than 2mg/cm 2 。
Assembling the button cell:
the components for assembling the button cell include: the negative electrode shell, the metal sodium sheet, the diaphragm, the spring sheet, the positive electrode shell and the electrolyte are required to be pressed into pieces, a liquid transfer device and insulating tweezers.
Model: 2025;
assembly environment: in the glove box, the environmental requirement is H 2 O＜0.01ppm；O 2 < 0.01ppm; a diaphragm: model whatman.gf/D, d=19 mm;
electrolyte solution: model NP-202 (NaPF) 6 ) Taking the wet diaphragm as a judgment standard condition; sodium tablet: size 15.6mm, thickness 0.45mm, purity>99.7 percent (standard type is purchased) with smooth surface; packaging pressure: 55+ -5 kg/cm 2 。
The electrochemical performance test includes:
the button cell was placed in an incubator with a test environment temperature of 25 ℃.
0.1C test procedure (nominal specific capacity 130 mAh/g):
standing for 12h; standing for 3min;
constant current charging to 4.1V at 0.1C; standing for 3min;
constant current discharge of 0.1C to 2.5V;
repeating the steps to circulate.
The results are shown in Table 1 and FIG. 3. Fig. 3 is a charge-discharge curve of the sodium ion battery according to example 3.
Table 1 test results
As can be seen from table 1, the sodium ion battery prepared from the layered oxide cathode material provided by the application has higher voltage, first-week coulombic efficiency and cyclicity, and good safety.
In summary, the layered oxide cathode material provided by the application has a complete and uniform monocrystalline particle structure, and no aggregation exists among monocrystalline particles. The preparation method is simple, the cost is low, the raw materials are pollution-free green materials, and the sodium ion battery prepared from the sodium ion battery has higher voltage, first-week coulomb efficiency and cyclicity and good safety.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A layered oxide positive electrode material is characterized in that the chemical formula of the layered oxide positive electrode material is Na x Zn y Ni z Fe α Mn β C 1-y-z-α-β O 2 X is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, alpha is more than or equal to 0 and less than or equal to 1, beta is more than or equal to 0 and less than or equal to 1-y-z-alpha-beta is more than or equal to 1, and C is any element except Na, zn, ni, fe, mn and O;
the layered oxide positive electrode material has at least one of the following characteristics:
characteristic one: the layered oxide positive electrode material has a single crystal particle structure;
and the second characteristic is: the single crystal particles of the layered oxide cathode material are complete and uniform and have no aggregation;
and (3) the following characteristics: the particle size of the layered oxide cathode material is 1-20 mu m.
2. The method for producing a layered oxide cathode material according to claim 1, comprising the steps of: and (3) mixing the mixture of the sodium source, the zinc source, the nickel source, the iron source and the manganese source according to a preset proportion and carrying out high-energy ball milling on the mixture and the solution containing the surfactant.
3. The method of claim 2, wherein the sodium source comprises at least one of sodium carbonate, sodium hydroxide, and sodium citrate;
and/or, the zinc source comprises ZnO;
and/or, the nickel source comprises NiO;
and/or the iron source comprises Fe 2 O 3 And FeO;
and/or the manganese source comprises MnO 2 And Mn of 2 O 3 At least one of them.
4. The method of preparing according to claim 2, wherein the surfactant-containing solution comprises a surfactant and a solvent;
the surfactant includes at least one of a cationic surfactant, an anionic surfactant, a zwitterionic surfactant, and a nonionic surfactant; the solvent includes ethanol and water;
preferably, the anionic surfactant comprises at least one of stearic acid and sodium dodecyl benzene sulfonate;
and/or, the cationic surfactant comprises a quaternary ammonium compound;
and/or the zwitterionic surfactant comprises at least one of lecithin, an amino acid type, and a betaine type;
and/or the nonionic surfactant comprises at least one of alkyl glucosides, fatty acid glycerides, fatty acid sorbitan, polysorbate, and polyvinylpyrrolidone.
5. The method of any one of claims 2 to 4, wherein the surfactant is used in an amount of 0.1 to 15wt% of the mixture.
6. The method of manufacturing according to claim 2, wherein the high energy ball milling comprises at least one of the following features:
characteristic one: the rotating speed of high-energy ball milling is more than or equal to 1200r/min;
and the second characteristic is: the high-energy ball milling time is 3-7 hours;
and (3) the following characteristics: the grading ratio of the zirconium beads is more than or equal to grade 3;
and four characteristics: in the upper and lower gradations, the diameter of the small-diameter zirconium beads is 0.5-0.8 times of the diameter of the large-diameter zirconium beads.
7. The method of manufacturing according to claim 2, further comprising: and drying and tabletting the ball-milled sample after high-energy ball milling, and then carrying out heat treatment.
8. The method according to claim 7, wherein the drying is carried out at 60 to 120 ℃ for 1 to 5 hours;
and/or tabletting under 10-20MPa for 1-5min.
9. The method of manufacturing according to claim 7, wherein the heat treatment comprises at least one of the following features:
characteristic one: the heat treatment includes: firstly, carrying out the process for 12-24 hours under the condition of 750-1200 ℃, and then carrying out the process for 12-20 hours under the condition of 950-1200 ℃;
and the second characteristic is: a grinding process is also arranged between the two heat treatment stages;
and (3) the following characteristics: the heating rate in the heat treatment process is 3-10 ℃/min;
and four characteristics: the heat treatment is carried out in air or oxygen atmosphere;
and fifth feature: after the heat treatment, furnace cooling is carried out, and the dew point temperature of the environment is not higher than-25 ℃ when the furnace cooling is carried out.
10. A sodium ion battery characterized in that it has the layered oxide cathode material of claim 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116525814A (en) * | 2023-06-29 | 2023-08-01 | 宁波容百新能源科技股份有限公司 | Positive electrode material, preparation method thereof, positive electrode plate and sodium ion battery |
| CN117012948A (en) * | 2023-09-27 | 2023-11-07 | 宁波容百新能源科技股份有限公司 | Positive electrode material, preparation method thereof and sodium ion battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116525814A (en) * | 2023-06-29 | 2023-08-01 | 宁波容百新能源科技股份有限公司 | Positive electrode material, preparation method thereof, positive electrode plate and sodium ion battery |
| CN116525814B (en) * | 2023-06-29 | 2023-11-28 | 宁波容百新能源科技股份有限公司 | Positive electrode material, preparation method thereof, positive electrode plate and sodium ion battery |
| CN117012948A (en) * | 2023-09-27 | 2023-11-07 | 宁波容百新能源科技股份有限公司 | Positive electrode material, preparation method thereof and sodium ion battery |
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