CN115995533B - Layered composite oxide of sodium ion battery - Google Patents
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- CN115995533B CN115995533B CN202211498513.0A CN202211498513A CN115995533B CN 115995533 B CN115995533 B CN 115995533B CN 202211498513 A CN202211498513 A CN 202211498513A CN 115995533 B CN115995533 B CN 115995533B
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- ion battery
- sodium ion
- composite oxide
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- isopropyl alcohol
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 92
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000000498 ball milling Methods 0.000 claims abstract description 40
- 238000001354 calcination Methods 0.000 claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims abstract description 23
- 229940039790 sodium oxalate Drugs 0.000 claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 71
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 40
- 238000001816 cooling Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 19
- XJIPZQRDWCIXPA-UHFFFAOYSA-N [Mo+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] Chemical group [Mo+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] XJIPZQRDWCIXPA-UHFFFAOYSA-N 0.000 claims description 18
- QKWWDTYDYOFRJL-UHFFFAOYSA-N 2,2-dimethoxyethanamine Chemical compound COC(CN)OC QKWWDTYDYOFRJL-UHFFFAOYSA-N 0.000 claims description 17
- VJFCXDHFYISGTE-UHFFFAOYSA-N O=[Co](=O)=O Chemical compound O=[Co](=O)=O VJFCXDHFYISGTE-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- HFLAMWCKUFHSAZ-UHFFFAOYSA-N niobium dioxide Chemical compound O=[Nb]=O HFLAMWCKUFHSAZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 12
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 claims description 11
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 10
- 229910052758 niobium Inorganic materials 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- DQTJHJVUOOYAMD-UHFFFAOYSA-N oxotitanium(2+) dinitrate Chemical compound [O-][N+](=O)O[Ti](=O)O[N+]([O-])=O DQTJHJVUOOYAMD-UHFFFAOYSA-N 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 8
- 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 abstract description 6
- 229910052708 sodium Inorganic materials 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000007774 positive electrode material Substances 0.000 description 20
- 239000003792 electrolyte Substances 0.000 description 19
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 14
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 229910000314 transition metal oxide Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 238000007086 side reaction Methods 0.000 description 8
- 229910052723 transition metal Inorganic materials 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 150000003624 transition metals Chemical class 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- UYLYBEXRJGPQSH-UHFFFAOYSA-N sodium;oxido(dioxo)niobium Chemical compound [Na+].[O-][Nb](=O)=O UYLYBEXRJGPQSH-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 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 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000447 polyanionic polymer Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a layered composite oxide of a sodium ion battery, which is prepared by the following steps: mixing sodium oxalate, a cobalt source, an M source and an iron source, performing ball milling, tabletting, calcining, and grinding to obtain calcined powder; stirring an isopropyl alcohol salt solution and powder to obtain a reaction precursor; calcining the reaction precursor to obtain the catalyst. The layered composite oxide of the sodium ion battery prepared by the invention is assembled into the positive electrode battery, has good cycle performance and multiplying power performance, has large capacity, and meanwhile, the preparation method is simple, can effectively solve the defects of poor stability and easy attenuation of the sodium battery, and is suitable for large-scale popularization.
Description
Technical Field
The invention relates to the technical field of ion batteries, in particular to a layered composite oxide of a sodium ion battery.
Background
Sodium ion batteries, which are secondary batteries (rechargeable batteries), operate mainly by means of sodium ions moving between a positive electrode and a negative electrode, similar to the principle of operation of lithium ion batteries, but research into sodium ion batteries has been put aside for a long time. This is mainly due to the fact that the atomic weight of sodium is larger than that of lithium and the operating voltage is lower, and the mass and volumetric specific energy density of a sodium ion battery is significantly lower than that of a lithium ion battery at the same specific capacity. Therefore, the development of sodium ion batteries with high specific capacity, long cycle life and low cost is a key to commercialization of sodium ion batteries in the future. In general, the battery performance and cost of sodium ion batteries and lithium ion batteries are largely dependent on the cathode material, so that it is important to develop low-cost, high-performance cathode materials. At present, common positive electrode materials of sodium ion batteries mainly comprise layered transition metal oxides, prussian blue analogues, polyanion compounds, tunnel oxides and the like. Compared with materials such as Prussian blue analogues, polyanion compounds, tunnel oxides and the like, the layered transition metal oxide has higher specific capacity and meets the requirement of high energy density.
Chinese patent application No. 202210298760.X discloses a layered transition metal oxide positive electrode material and a preparation method thereof, and the invention mainly adopts MOF template method to synthesize layered porous transition metal oxide nano particles. Mainly comprises the following steps: firstly, synthesizing a graphene composite transition metal MOF frame material by combining a graphene material through a hydrothermal method; and then carrying out solid phase mixing on the MOF material, sodium oxide and other metal oxides, and further calcining at high temperature to obtain the reduced graphene oxide composite porous transition metal oxide nano particles with the layered structure. Although the layered porous transition metal oxide nano particles prepared by the method have controllable material structure, uniform element distribution and consistent particle size, the feasibility and effectiveness of the method are proved, and stable structural guarantee is provided for improving the sodium-electricity performance. However, the layered transition metal oxide positive electrode material of the present invention has low rate performance and sodium ion diffusion and has low gram capacity, and further improvement is required.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a layered composite oxide of a sodium ion battery.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the layered composite oxide of the sodium ion battery comprises the following steps:
(1) Mixing sodium oxalate, a cobalt source, an M source and an iron source, adding the mixture into a ball milling tank, and adding n-propanol for ball milling to obtain a mixed material;
(2) Pressing the mixed material into a sheet, placing the sheet into a muffle furnace for calcination, cooling to room temperature, and grinding to obtain calcined powder;
(3) Adding isopropyl alcohol into isopropyl alcohol for ultrasonic treatment to obtain isopropyl alcohol solution; stirring the isopropyl alcohol salt solution and the powder in the step (2) to obtain a reaction precursor;
(4) And (3) placing the reaction precursor in a muffle furnace for calcination, and cooling to room temperature to obtain the sodium ion battery layered composite oxide.
Preferably, the preparation method of the layered composite oxide of the sodium ion battery comprises the following steps:
(1) Mixing sodium oxalate, a cobalt source, an M source and an iron source, adding the mixture into a ball milling tank, and adding n-propanol and aminoacetaldehyde dimethyl acetal for ball milling to obtain a mixed material;
(2) Pressing the mixed material into a sheet, placing the sheet into a muffle furnace for calcination, cooling to room temperature, and grinding to obtain calcined powder;
(3) Adding isopropyl alcohol into isopropyl alcohol for ultrasonic treatment to obtain isopropyl alcohol solution; stirring an isopropyl alcohol salt solution and the calcined powder obtained in the step (2) to obtain a reaction precursor;
(4) And (3) placing the reaction precursor in a muffle furnace for calcination, and cooling to room temperature to obtain the sodium ion battery layered composite oxide.
The layered composite oxide of sodium ion battery has poor stability in air and serious capacity fading in long-cycle and high-current charge and discharge. There are two main methods for solving this problem: firstly, adding transition metal elements for doping, such as titanium, niobium, aluminum, zirconium and the like, and changing the intrinsic stability of the material through doping; and secondly, a coating isolation layer is added to prevent the electrolyte from directly contacting with the material, so that the defects of serious interface side reaction and the like easily occurring in the electrolyte are avoided, for example, metal oxide and carbon coating are adopted.
Firstly, based on the layered transition metal oxide with reversible ion deintercalation capability and stable layered structure, other ions or molecules are inserted between layers, so that the inventor adds transition metal for doping in the preparation process, and after the positive electrode material of the sodium ion battery replaces the conventional manganese element with titanium element, the titanium-oxygen bond is stronger than the manganese-oxygen bond, thereby not only improving the stability of the positive electrode material of the sodium ion battery, but also expanding the sodium interlayer spacing of the positive electrode material due to the introduction of the titanium element, and being more beneficial to deintercalation of sodium ions. The niobium is doped into the material, and the atomic radius of the niobium is larger, so that the lattice spacing is enlarged, the function of supporting a metal layer of the material is achieved, the lattice structure is stabilized, and meanwhile, the sodium ion transmission is facilitated. Meanwhile, sodium niobate has higher ion conductivity, provides a three-dimensional rapid transmission channel for sodium ions, and can increase the sodium ion transmission rate and the material circulation stability.
The material has good multiplying power performance and excellent cycle stability, and the preparation method is simple and controllable. Although the doping method can effectively improve the stability of the anode material, the layered composite oxide of the sodium ion battery still has serious interface side reaction with the result of electrolyte in the use process, and the improvement of the cycle performance and the multiplying power performance is still limited.
The inventor finds that although the stability performance problem of the material is solved, the multiplying power performance and the cycle performance still do not reach the particularly ideal targets, so that other ions or molecules are inserted between the original layers, and the porosity in each layer is changed on the basis, so that the rapid desorption of sodium ions in the charge and discharge process is achieved, and the multiplying power performance of the battery is improved. The amino acetaldehyde dimethyl acetal can form a porous structure through the gas generated by decomposition in the high-temperature calcination process, the porous structure improves the surface area of the layered composite oxide material of the sodium ion battery, sodium ions can enter and exit the positive electrode material, carbon after the calcination can be coated on the surface of the material, the conductivity of the layered composite oxide material of the sodium ion battery is further improved, and the stability and the conductivity of the material are synergistically improved with molybdenum oxide.
The general formula of the layered composite oxide of the sodium ion battery is Na n Co x M y Fe 1-x-y O 2 N is more than or equal to 0.7 and less than or equal to 1.0,0.1<x≤0.3，0<y≤0.4。
The M is at least one of Ti, nb, V, cu, ni, cr.
Preferably, the M is at least one of Ti and Nb; further, the M is composed of Ti and Nb mixed.
The isopropoxide is molybdenum isopropoxide and/or zirconium isopropoxide; preferably, the isopropoxide is molybdenum isopropoxide and zirconium isopropoxide according to the mass ratio (1-3): (1-3); further, the isopropoxide is molybdenum isopropoxide and zirconium isopropoxide according to the mass ratio of 1: 1.
Therefore, in order to further improve the electrical property of the battery, reduce the direct contact of the electrolyte and the material, avoid the defects of serious interface side reaction and the like easily occurring in the electrolyte, the inventor adopts metal oxide to coat the layered composite oxide of the sodium ion battery, adopts molybdenum isopropoxide to carry out high-temperature decomposition to obtain molybdenum oxide to coat the surface of the layered composite oxide material of the sodium ion battery, and because the decomposition temperature of the molybdenum isopropoxide is low and the molybdenum oxide is in a molten state after decomposition, a part of molybdenum oxide is adsorbed on the surface of the layered composite oxide material of the sodium ion battery, so that the coating layer is uniformly distributed and tightly combined on the surface of the positive electrode material; and a part of molybdenum oxide enters the sodium ion battery layered composite oxide in a doping mode, and the addition of the molybdenum oxide achieves the double purposes of cladding and doping. The surface is coated with a layer of stable molybdenum oxide, so that the surface has good stability to electrolyte, and the electrolyte can be effectively isolated from directly contacting with the positive electrode material, so that the defect generated by side reaction of a contact interface is reduced. The inertia of zirconia is utilized to effectively improve the stability of a material interface, reduce the generation of electrolyte decomposition byproducts and reduce interface impedance; meanwhile, the zirconia coating effectively prevents the electrolyte from etching the layered material so as to prevent transition metal migration and inhibit precipitation and dissolution of the transition metal; in addition, the strong combination energy between the doping cladding source and oxygen is utilized to stabilize the stability of surface oxygen during high-voltage charge and discharge, inhibit unavoidable phase change and fully improve the electrochemical performance of the material. The cycle performance and the multiplying power performance of the positive electrode material are improved and effectively improved by utilizing the synergistic effect of the two materials.
The layered composite oxide of the sodium ion battery has a P2 type structure.
The cobalt source is any one of cobalt trioxide, cobaltosic oxide, cobalt sulfate and cobalt nitrate; the iron source is any one of ferric oxide, ferrous oxide, ferric nitrate and ferric acetate.
The molar ratio of the sodium oxalate to the cobalt source to the M source to the iron source in the step (1) is (5-10): (0.5-2): (2-5): (3-6); the rotation speed of the ball milling is 600-1000rpm; the ball milling time is 1.5-3h; the mass of the n-propanol is 0.4-1 times of that of the sodium oxalate, and the mass of the aminoacetaldehyde dimethyl acetal is 1-1.5 times of that of the cobalt trioxide.
In the step (2), the pressure of the pressed membrane is 70-120MPa, and the pressure maintaining time is 3-6min; the calcination temperature is 800-1000 ℃, and the calcination time is 8-14h.
The concentration of the molybdenum isopropoxide solution in the step (3) is 0.2-0.4mol/L; the ultrasonic power is 300-500W, the ultrasonic frequency is 45-70kHz, and the ultrasonic time is 0.2-1h; the mass ratio of the molybdenum isopropoxide solution to the powder is (10-20): 1.
the calcination temperature in the step (4) is 800-950 ℃, and the calcination temperature is 10-20h.
The invention has the beneficial effects that:
1. the layered composite oxide of the sodium ion battery prepared by the invention has good multiplying power performance and cycle performance, and by adding titanium element in the preparation process, the titanium-oxygen bond is stronger than the manganese-oxygen bond, so that the stability of the positive electrode material of the sodium ion battery is improved, and the introduction of the titanium element enlarges the sodium interlayer spacing of the positive electrode material, thereby being more beneficial to the deintercalation of sodium ions. The niobium is doped into the material, and the atomic radius of the niobium is larger, so that the lattice spacing is enlarged, the function of supporting a metal layer of the material is achieved, the lattice structure is stabilized, and meanwhile, the sodium ion transmission is facilitated. Meanwhile, sodium niobate has higher ion conductivity, provides a three-dimensional rapid transmission channel for sodium ions, and can increase the sodium ion transmission rate and the material circulation stability.
2. According to the invention, the amino acetaldehyde dimethyl acetal is added in the preparation process, and the porous structure can be formed by decomposing the generated gas in the high-temperature calcination process, so that the porous structure improves the surface area of the sodium ion battery layered composite oxide material, facilitates sodium ions to enter and exit the positive electrode material, and carbon after the calcination can be coated on the surface of the material, so that the conductivity of the sodium ion battery layered composite oxide material is further improved, and the stability and conductivity of the material are synergistically improved with molybdenum oxide.
3. According to the invention, the metal oxide is added as a coating in the preparation process, so that the direct contact between the electrolyte and the material is reduced, the defects of serious interface side reaction and the like easily occurring in the electrolyte are avoided, the material has good rate capability and excellent cycle stability, and the preparation method is simple and controllable. The positive electrode material has the advantages of good consistency, higher ionic conductivity, high capacity and good cycle performance.
Detailed Description
The above summary of the present invention is described in further detail below in conjunction with the detailed description, but it should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples.
Example 1
The preparation method of the layered composite oxide of the sodium ion battery comprises the following steps:
(1) Sodium oxalate, cobalt trioxide and iron acetate are mixed according to a mole ratio of 7:1.5:4, adding the mixture into a ball milling tank, adding n-propanol, wherein the mass of the n-propanol is 0.5 time of that of sodium oxalate, and ball milling for 2 hours in the ball milling tank, and the rotating speed of the ball mill is 800rpm to obtain a mixed material;
(2) Pressing the mixed material into a sheet under the pressure of 80MPa, wherein the pressure maintaining time is 4min; and then placing the thin sheet in a muffle furnace at 900 ℃ for calcination for 10 hours, and cooling to room temperature to obtain the sodium ion battery layered composite oxide.
Example 2
The preparation method of the layered composite oxide of the sodium ion battery comprises the following steps:
(1) In a nitrogen environment, sodium oxalate, cobalt trioxide, titanyl nitrate and iron acetate are mixed according to the mole ratio of 7:1.5:3:4, adding the mixture into a ball milling tank, adding n-propanol, wherein the mass of the n-propanol is 0.5 time of that of sodium oxalate, and ball milling for 2 hours in the ball milling tank, and the rotating speed of the ball mill is 800rpm to obtain a mixed material;
(2) Pressing the mixed material into a sheet under the pressure of 80MPa, wherein the pressure maintaining time is 4min; and then placing the thin sheet in a muffle furnace at 900 ℃ for calcination for 10 hours, and cooling to room temperature to obtain the sodium ion battery layered composite oxide.
Example 3
The preparation method of the layered composite oxide of the sodium ion battery comprises the following steps:
(1) In a nitrogen environment, sodium oxalate, cobalt trioxide, titanyl nitrate, niobium dioxide and ferric acetate are mixed according to the mole ratio of 7:1.5:2.5:0.5:4, adding the mixture into a ball milling tank, adding n-propanol, wherein the mass of the n-propanol is 0.5 time of that of sodium oxalate, and ball milling for 2 hours in the ball milling tank, and the rotating speed of the ball mill is 800rpm to obtain a mixed material;
(2) Pressing the mixed material into a sheet under the pressure of 80MPa, wherein the pressure maintaining time is 4min; and then placing the thin sheet in a muffle furnace at 900 ℃ for calcination for 10 hours, and cooling to room temperature to obtain the sodium ion battery layered composite oxide.
Example 4
The preparation method of the layered composite oxide of the sodium ion battery comprises the following steps:
(1) In a nitrogen environment, sodium oxalate, cobalt trioxide, titanyl nitrate, niobium dioxide and ferric acetate are mixed according to the mole ratio of 7:1.5:2.5:0.5:4, adding the mixture into a ball milling tank, adding n-propanol and aminoacetaldehyde dimethyl acetal, wherein the mass of the n-propanol is 0.5 times of that of sodium oxalate, the mass of the aminoacetaldehyde dimethyl acetal is 1.2 times of that of cobalt trioxide, and ball milling the mixture in the ball milling tank for 2 hours, wherein the rotating speed of the ball milling tank is 800rpm, so as to obtain a mixed material;
(2) Pressing the mixed material into a sheet under the pressure of 80MPa, wherein the pressure maintaining time is 4min; and then placing the thin sheet in a muffle furnace at 900 ℃ for calcination for 10 hours, and cooling to room temperature to obtain the sodium ion battery layered composite oxide.
Example 5
The preparation method of the layered composite oxide of the sodium ion battery comprises the following steps:
(1) In a nitrogen environment, sodium oxalate, cobalt trioxide, titanyl nitrate, niobium dioxide and ferric acetate are mixed according to the mole ratio of 7:1.5:2.5:0.5:4, adding the mixture into a ball milling tank, adding n-propanol and aminoacetaldehyde dimethyl acetal, wherein the mass of the n-propanol is 0.5 times of that of sodium oxalate, the mass of the aminoacetaldehyde dimethyl acetal is 1.2 times of that of cobalt trioxide, and ball milling the mixture in the ball milling tank for 2 hours, wherein the rotating speed of the ball milling tank is 800rpm, so as to obtain a mixed material;
(2) Pressing the mixed material into a sheet under the pressure of 80MPa, wherein the pressure maintaining time is 4min; then placing the flake in a muffle furnace at 900 ℃ for calcination for 10 hours, cooling to room temperature, and grinding to obtain calcined powder;
(3) Adding molybdenum isopropoxide into isopropanol, and performing ultrasonic treatment for 0.5h under the conditions that the ultrasonic power is 400W and the ultrasonic frequency is 60kHz to obtain a molybdenum isopropoxide solution; mixing 20 parts by weight of molybdenum isopropoxide solution and 1.5 parts by weight of the calcined powder obtained in the step (2), and stirring at 70 ℃ and 600rpm for 1 hour to obtain a reaction precursor; the concentration of the molybdenum isopropoxide solution is 0.25mol/L;
(4) And (3) placing the reaction precursor in a muffle furnace at 850 ℃ for calcination for 14 hours, and finally cooling to room temperature at a cooling speed of 4 ℃/min to obtain the sodium ion battery layered composite oxide.
Example 6
The preparation method of the layered composite oxide of the sodium ion battery comprises the following steps:
(1) In a nitrogen environment, sodium oxalate, cobalt trioxide, titanyl nitrate, niobium dioxide and ferric acetate are mixed according to the mole ratio of 7:1.5:2.5:0.5:4, adding the mixture into a ball milling tank, adding n-propanol and aminoacetaldehyde dimethyl acetal, wherein the mass of the n-propanol is 0.5 times of that of sodium oxalate, the mass of the aminoacetaldehyde dimethyl acetal is 1.2 times of that of cobalt trioxide, and ball milling the mixture in the ball milling tank for 2 hours, wherein the rotating speed of the ball milling tank is 800rpm, so as to obtain a mixed material;
(2) Pressing the mixed material into a sheet under the pressure of 80MPa, wherein the pressure maintaining time is 4min; then placing the flake in a muffle furnace at 900 ℃ for calcination for 10 hours, cooling to room temperature, and grinding to obtain calcined powder;
(3) Adding zirconium isopropoxide into isopropanol, and performing ultrasonic treatment for 0.5h under the conditions that the ultrasonic power is 400W and the ultrasonic frequency is 60kHz to obtain zirconium isopropoxide solution; mixing 20 parts by weight of zirconium isopropoxide solution and 1.5 parts by weight of the calcined powder obtained in the step (2), and stirring at 70 ℃ and 600rpm for 1 hour to obtain a reaction precursor; the concentration of the zirconium isopropoxide solution is 0.25mol/L;
(4) And (3) placing the reaction precursor in a muffle furnace at 850 ℃ for calcination for 14 hours, and finally cooling to room temperature at a cooling speed of 4 ℃/min to obtain the sodium ion battery layered composite oxide.
Example 7
The preparation method of the layered composite oxide of the sodium ion battery comprises the following steps:
(1) In a nitrogen environment, sodium oxalate, cobalt trioxide, titanyl nitrate, niobium dioxide and ferric acetate are mixed according to the mole ratio of 7:1.5:2.5:0.5:4, adding the mixture into a ball milling tank, adding n-propanol and aminoacetaldehyde dimethyl acetal, wherein the mass of the n-propanol is 0.5 times of that of sodium oxalate, the mass of the aminoacetaldehyde dimethyl acetal is 1.2 times of that of cobalt trioxide, and ball milling the mixture in the ball milling tank for 2 hours, wherein the rotating speed of the ball milling tank is 800rpm, so as to obtain a mixed material;
(2) Pressing the mixed material into a sheet under the pressure of 80MPa, wherein the pressure maintaining time is 4min; then placing the flake in a muffle furnace at 900 ℃ for calcination for 10 hours, cooling to room temperature, and grinding to obtain calcined powder;
(3) Adding isopropyl alcohol salt into isopropyl alcohol, and performing ultrasonic treatment for 0.5h under the conditions that the ultrasonic power is 400W and the ultrasonic frequency is 60kHz to obtain an isopropyl alcohol salt solution; mixing 20 parts by weight of an isopropyl alcohol salt solution and 1.5 parts by weight of the calcined powder obtained in the step (2), and stirring at 70 ℃ and 600rpm for 1 hour to obtain a reaction precursor; the concentration of the isopropyl alcohol salt solution is 0.25mol/L; the isopropoxide is a mixture of zirconium isopropoxide and molybdenum isopropoxide according to the mass ratio of 1:1;
(4) And (3) placing the reaction precursor in a muffle furnace at 850 ℃ for calcination for 14 hours, and finally cooling to room temperature at a cooling speed of 4 ℃/min to obtain the sodium ion battery layered composite oxide.
Test example 1
Testing the charge and discharge performance of the battery: the layered composite oxides of the sodium ion batteries prepared in examples 1-7 were assembled to prepare button cells, and the preparation method was as follows: the sodium ion battery layered composite oxide and the conductive agent ketjen black and the binder polyvinylidene fluoride in the embodiment are mixed according to the proportion of 8:1:1, adding a certain amount of NMP and stirring to obtain slurry; uniformly coating the slurry on clean aluminum foil, and drying at 80 ℃ for 12 hours; and then pressing, weighing and cutting the material into round pole pieces for standby. And then a CR2032 type battery shell is selected, a self-made electrode is used as an anode, PP is used as a diaphragm, a metal sodium sheet is used as a cathode, and a dimethyl carbonate solution is used as electrolyte. And (3) assembling the battery in a glove box filled with argon, packaging the battery by using a battery sealing machine, taking out and standing for 24 hours, and performing electrochemical performance test.
The charge-discharge interval is 2.5-4.3V, the current density is 200mA/g, the charge-discharge test is sequentially carried out, the specific capacity is measured, the cycle performance test of 1C is carried out, the cycle is carried out for 100 times, the electrochemical performance of the material is evaluated, the test result is shown in Table 1, and the multiplying power performance result is shown in Table 2.
Table 1 battery performance test results
TABLE 2 results of rate performance test
Test example 2
Sodium ion kinetic performance test: the test voltage is between 2 and 4V, cyclic voltammetry under the scanning speed conditions of 0.2mV/s,0.4mV/s,0.5mV/s,0.8mV/s and 1mV/s, a linear fitting point diagram is obtained according to the peak current of the polar peak and the square root of the scanning speed, and then the sodium ion diffusion coefficient is calculated, and the result is shown in Table 3.
TABLE 3 sodium ion diffusion coefficient test results
| Sodium ion diffusion coefficient/cm 2 /s | |
| Example 3 | 2.753×10 -12 |
| Example 4 | 1.127×10 -11 |
From the above results, the layered transition metal oxide-based catalyst prepared by the invention has good cycle performance and rate capability. The reason is that the transition metal is added for doping in the preparation process, and after the conventional manganese element is replaced by the titanium element, the titanium-oxygen bond is stronger than the manganese-oxygen bond, so that the stability of the positive electrode material of the sodium ion battery is improved, the sodium interlayer spacing of the positive electrode material is enlarged due to the introduction of the titanium element, and the deintercalation of sodium ions is facilitated. The niobium is doped into the material, and the atomic radius of the niobium is larger, so that the lattice spacing is enlarged, the function of supporting a metal layer of the material is achieved, the lattice structure is stabilized, and meanwhile, the sodium ion transmission is facilitated. Meanwhile, sodium niobate has higher ion conductivity, provides a three-dimensional rapid transmission channel for sodium ions, and can increase the sodium ion transmission rate and the material circulation stability. The material has good multiplying power performance and excellent cycle stability, and the preparation method is simple and controllable. Although the doping method can effectively improve the stability of the anode material, the layered composite oxide of the sodium ion battery still has serious interface side reaction with the result of electrolyte in the use process, and the improvement of the cycle performance and the multiplying power performance is still limited.
In the embodiment 4, the aminoacetaldehyde dimethyl acetal is added in the preparation process, and the gas generated by decomposition of the aminoacetaldehyde dimethyl acetal in the high-temperature calcination process can form a porous structure, so that the porous structure improves the surface area of the layered composite oxide material of the sodium ion battery, facilitates sodium ions to enter and exit the positive electrode material, achieves rapid desorption of sodium ions in the charge and discharge process, and improves the rate capability of the battery; the carbon after being calcined conveniently can be coated on the surface of the material, so that the conductivity of the layered composite oxide material of the sodium ion battery is further improved, and the stability and the conductivity of the material are synergistically improved by the carbon and the molybdenum oxide.
In the embodiment 7, zirconium isopropoxide and molybdenum isopropoxide are added for collaborative coating, so that the direct contact between the electrolyte and the material is reduced, the defects of serious interface side reaction and the like easily occurring in the electrolyte are avoided, the inventor adopts metal oxide to coat the layered composite oxide of the sodium ion battery, and adopts molybdenum isopropoxide for high-temperature decomposition to obtain molybdenum oxide to coat the surface of the layered composite oxide material of the sodium ion battery, and as the decomposition temperature of the molybdenum isopropoxide is low and the molybdenum isopropoxide is in a molten state after decomposition, a part of molybdenum oxide is adsorbed on the surface of the layered composite oxide material of the sodium ion battery, so that the coating layer is uniformly distributed on the surface of the positive electrode material and is tightly combined; and a part of molybdenum oxide enters the sodium ion battery layered composite oxide in a doping mode, and the addition of the molybdenum oxide achieves the double purposes of cladding and doping. The surface is coated with a layer of stable molybdenum oxide, so that the surface has good stability to electrolyte, and the electrolyte can be effectively isolated from directly contacting with the positive electrode material, so that the defect generated by side reaction of a contact interface is reduced. The inertia of zirconia is utilized to effectively improve the stability of a material interface, reduce the generation of electrolyte decomposition byproducts and reduce interface impedance; meanwhile, the zirconia coating effectively prevents the electrolyte from etching the layered material so as to prevent transition metal migration and inhibit precipitation and dissolution of the transition metal; in addition, the strong combination energy between the doping cladding source and oxygen is utilized to stabilize the stability of surface oxygen during high-voltage charge and discharge, inhibit unavoidable phase change and fully improve the electrochemical performance of the material. The cycle performance and the multiplying power performance of the positive electrode material are improved and effectively improved by utilizing the synergistic effect of the two materials.
Claims (8)
1. The preparation method of the layered composite oxide of the sodium ion battery is characterized by comprising the following steps:
(1) Mixing sodium oxalate, a cobalt source, an M source and an iron source, adding the mixture into a ball milling tank, and adding n-propanol and aminoacetaldehyde dimethyl acetal for ball milling to obtain a mixed material;
(2) Pressing the mixed material into a sheet, placing the sheet into a muffle furnace for calcination, cooling to room temperature, and grinding to obtain calcined powder;
(3) Adding isopropyl alcohol salt into isopropyl alcohol for ultrasonic treatment to obtain isopropyl alcohol salt solution; taking an isopropyl alcohol salt solution and the calcined powder obtained in the step (2) to obtain a reaction precursor;
(4) Calcining the reaction precursor in a muffle furnace, and cooling to room temperature to obtain the sodium ion battery layered composite oxide;
the isopropoxide is molybdenum isopropoxide and zirconium isopropoxide according to the mass ratio (1-3): (1-3) a mixture;
the general formula of the layered composite oxide of the sodium ion battery is Na n Co x M y Fe 1-x-y O 2 ，0.7≤n≤1.0，0.1<x is less than or equal to 0.3, y is less than or equal to 0 and less than or equal to 0.4; the M consists of Ti and Nb.
2. The layered composite oxide of a sodium ion battery of claim 1, wherein the layered composite oxide of a sodium ion battery has a P2 type structure.
3. The layered composite oxide of a sodium ion battery according to claim 1, wherein the cobalt source is any one of cobalt trioxide, tricobalt tetraoxide, cobalt sulfate, and cobalt nitrate; the iron source is any one of ferric oxide, ferrous oxide, ferric nitrate and ferric acetate.
4. The layered composite oxide of a sodium ion battery according to claim 1, wherein the molar ratio of sodium oxalate, cobalt source, M source, iron source in step (1) is (8-12): (0.5-2): (2-5): (3-6); the rotation speed of the ball milling is 600-1000rpm; the ball milling time is 1.5-3h.
5. The layered composite oxide of a sodium ion battery according to claim 1, wherein in the step (2), the pressure of the pressed film is 70 to 120MPa and the dwell time is 3 to 6min; the calcination temperature is 800-1000 ℃, and the calcination time is 8-14h.
6. The layered composite oxide of a sodium ion battery according to claim 1, wherein the concentration of the isopropyl alcohol salt solution in the step (3) is 0.2 to 0.4mol/L; the ultrasonic power is 300-500W, the ultrasonic frequency is 45-70kHz, and the ultrasonic time is 0.2-1h; the mass ratio of the isopropyl alcohol salt solution to the powder is (10-20): 1.
7. the layered composite oxide of a sodium ion battery according to claim 1, wherein the calcination temperature in the step (4) is 800 to 950 ℃ and the calcination temperature is 10 to 20 hours.
8. The layered composite oxide of a sodium ion battery according to claim 1, wherein the preparation method comprises the steps of:
(1) In a nitrogen environment, sodium oxalate, cobalt trioxide, titanyl nitrate, niobium dioxide and ferric acetate are mixed according to the mole ratio of 7:1.5:2.5:0.5:4, adding the mixture into a ball milling tank, adding n-propanol and aminoacetaldehyde dimethyl acetal, wherein the mass of the n-propanol is 0.5 times of that of sodium oxalate, the mass of the aminoacetaldehyde dimethyl acetal is 1.2 times of that of cobalt trioxide, and ball milling the mixture in the ball milling tank for 2 hours, wherein the rotating speed of the ball milling tank is 800rpm, so as to obtain a mixed material;
(2) Pressing the mixed material into slices under the pressure of 80MPa, wherein the pressure maintaining time is 4min; then placing the flake in a muffle furnace at 900 ℃ for calcination for 10 hours, cooling to room temperature, and grinding to obtain calcined powder;
(3) Adding isopropyl alcohol salt into isopropyl alcohol, and performing ultrasonic treatment for 0.5h under the conditions that the ultrasonic power is 400W and the ultrasonic frequency is 60kHz to obtain an isopropyl alcohol salt solution; mixing 20 parts by weight of an isopropyl alcohol salt solution and 1.5 parts by weight of the calcined powder obtained in the step (2), and stirring at 70 ℃ and 600rpm for 1 hour to obtain a reaction precursor; the concentration of the isopropyl alcohol salt solution is 0.25mol/L; the isopropoxide is a mixture of zirconium isopropoxide and molybdenum isopropoxide according to the mass ratio of 1:1;
(4) And (3) placing the reaction precursor in a muffle furnace at 850 ℃ for calcination for 14 hours, and finally cooling to room temperature at a cooling speed of 4 ℃/min to obtain the sodium ion battery layered composite oxide.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070008115A (en) * | 2005-07-13 | 2007-01-17 | 주식회사 엘지화학 | Cathode active material for lithium secondary battery with improved cycle life and safety |
| CN103985851A (en) * | 2014-05-28 | 2014-08-13 | 武汉大学 | Sodium ion battery anode material and sodium iron battery comprising anode material |
| CN108987708A (en) * | 2018-07-19 | 2018-12-11 | 东北大学秦皇岛分校 | A kind of sodium-ion battery positive material, preparation method and sodium-ion battery |
| CN110581261A (en) * | 2018-06-07 | 2019-12-17 | 中国科学院物理研究所 | Battery oxide positive electrode material, preparation method and application thereof |
| CN111129483A (en) * | 2019-12-26 | 2020-05-08 | 上海大学 | Rare earth metal element doped P2 phase sodium ion battery positive electrode material and preparation method thereof |
| CN114982004A (en) * | 2019-11-27 | 2022-08-30 | 御国色素株式会社 | Conductive material dispersion liquid for positive electrode of lithium ion secondary battery and electrode slurry |
| CN115000388A (en) * | 2022-07-13 | 2022-09-02 | 蜂巢能源科技(无锡)有限公司 | Sodium ion positive electrode material and preparation method and application thereof |
-
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- 2022-11-28 CN CN202211498513.0A patent/CN115995533B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070008115A (en) * | 2005-07-13 | 2007-01-17 | 주식회사 엘지화학 | Cathode active material for lithium secondary battery with improved cycle life and safety |
| CN103985851A (en) * | 2014-05-28 | 2014-08-13 | 武汉大学 | Sodium ion battery anode material and sodium iron battery comprising anode material |
| CN110581261A (en) * | 2018-06-07 | 2019-12-17 | 中国科学院物理研究所 | Battery oxide positive electrode material, preparation method and application thereof |
| CN108987708A (en) * | 2018-07-19 | 2018-12-11 | 东北大学秦皇岛分校 | A kind of sodium-ion battery positive material, preparation method and sodium-ion battery |
| CN114982004A (en) * | 2019-11-27 | 2022-08-30 | 御国色素株式会社 | Conductive material dispersion liquid for positive electrode of lithium ion secondary battery and electrode slurry |
| CN111129483A (en) * | 2019-12-26 | 2020-05-08 | 上海大学 | Rare earth metal element doped P2 phase sodium ion battery positive electrode material and preparation method thereof |
| CN115000388A (en) * | 2022-07-13 | 2022-09-02 | 蜂巢能源科技(无锡)有限公司 | Sodium ion positive electrode material and preparation method and application thereof |
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