CN118039863A - P2-O3 mixed phase sodium ion positive electrode material, preparation method and application - Google Patents
P2-O3 mixed phase sodium ion positive electrode material, preparation method and application Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 101
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 101
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000011734 sodium Substances 0.000 claims abstract description 58
- 239000000126 substance Substances 0.000 claims abstract description 23
- 230000004048 modification Effects 0.000 claims abstract description 3
- 238000012986 modification Methods 0.000 claims abstract description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 28
- 229910052708 sodium Inorganic materials 0.000 claims description 28
- 239000013078 crystal Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 4
- 238000003801 milling Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 25
- 230000007547 defect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 29
- 239000011572 manganese Substances 0.000 description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 239000002994 raw material Substances 0.000 description 24
- 239000010949 copper Substances 0.000 description 19
- 230000008569 process Effects 0.000 description 15
- 239000011777 magnesium Substances 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 239000013077 target material Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910000616 Ferromanganese Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 3
- 229940112669 cuprous oxide Drugs 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910014507 Na0.67Ni0.33Mn0.67O2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 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
- 238000003837 high-temperature calcination Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910004838 Na2/3Ni1/3Mn2/3O2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- -1 copper magnesium titanium aluminum zirconium tin Chemical compound 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 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
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 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
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a P2-O3 mixed phase sodium ion positive electrode material and a preparation method and application thereof, wherein the chemical general formula of the P2-O3 mixed phase sodium ion positive electrode material is Na 0.73+αCuxNi0.24‑x+ a1Fe0.25+a2Mn0.51‑a1‑a2MβO2, wherein the chemical general formula except M satisfies chemical balancing, M is doping modification element, x is more than or equal to 0 and less than or equal to 0.1, a1 is more than or equal to 0 and less than or equal to 0.02,0, a2 is more than or equal to a2 and less than or equal to 0.03,0, alpha is more than or equal to 0.04,0 and beta is less than or equal to 0.01; the P2-O3 mixed phase sodium ion positive electrode material can improve inherent defects of P2 phase materials and O3 phase materials, simultaneously has high specific capacity, long cycle and high rate performance, and can meet various application scenes such as high voltage.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and relates to a P2-O3 mixed phase sodium ion positive electrode material, a preparation method and application thereof.
Background
Sodium ion batteries are considered as substitutes or supplements for lithium ion batteries, particularly in the energy storage of the grid scale, due to the abundance and widespread global distribution of sodium resources. Therefore, there is a need to develop sodium ion batteries that meet the requirements of high energy density and long service life, while the positive electrode material is a key component of sodium ion batteries.
In recent years, various positive electrode materials for sodium ion batteries have been widely studied, especially layered oxide materials, wherein the structural general formula of the layered oxide materials is Na xMO2, M is one or more of transition metals, generally, a metal layer is formed by forming an MO 6 octahedral structure by a transition metal element and 6 surrounding oxygen, sodium ions are positioned between the transition metal layers, and a layered structure is formed by alternately arranging an MO 6 polyhedron layer and a NaO 6 alkali metal layer. In order to distinguish various layered oxides, the layered oxides are classified into different structures of O3, O2, P3, P2, etc., according to the coordination configuration of Na in the polyhedron of MO 6 and the stacking manner of oxygen, wherein O is an abbreviation of Octahedral, i.e., octahedral position; p is an abbreviation for PRISMATIC, the triangular prism position, and the number represents the number of stacked layers of oxygen minimal repeating units.
The two most common structures are P2 and O3 phases, and the corresponding space groups are P6 3/mmc and R3m respectively, and as disclosed in CN 117199324A, a P2-phase ferromanganese-based high-entropy sodium layered positive electrode material, a preparation method and application thereof are disclosed, wherein the P2-phase ferromanganese-based high-entropy sodium layered positive electrode material is ferromanganese copper magnesium titanium aluminum zirconium tin eight-element metal oxide, and the P2-phase material has stable structure, high voltage, better cycle and rate performance, but lower sodium content and lower theoretical capacity in the original proportion of the P2-phase material; the O3 material has higher sodium proportion, high theoretical capacity and higher practical capacity, but the stability, circulation and rate performance of the material are often inferior to those of the P2 phase material.
Based on the above research, it is necessary to provide a P2-O3 mixed-phase sodium ion positive electrode material, which can improve inherent defects of the P2-phase material and the O3-phase material, so that the sodium ion positive electrode material has the characteristics of high specific capacity, long cycle and high rate performance, and satisfies more application scenes.
Disclosure of Invention
The invention aims to provide a P2-O3 mixed phase sodium ion positive electrode material, a preparation method and application thereof, wherein the P2-O3 mixed phase sodium ion positive electrode material can improve inherent defects of P2 phase materials and O3 phase materials, simultaneously has high specific capacity, long cycle and high rate performance, and can meet various application scenes such as high voltage.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
In a first aspect, the invention provides a P2-O3 mixed-phase sodium ion positive electrode material, wherein the chemical formula of the P2-O3 mixed-phase sodium ion positive electrode material is Na 0.73+αCuxNi0.24-x+a1Fe0.25+a2Mn0.51-a1-a2MβO2, wherein chemical balancing is satisfied except M in the chemical formula, M is doping modification element, x is more than or equal to 0 and less than or equal to 0.1, a1 is more than or equal to 0 and less than or equal to 0.02,0, a2 is more than or equal to 0 and less than or equal to a2 and less than or equal to 0.03,0, alpha is more than or equal to 0.04,0 and beta is less than or equal to 0.01.
According to the invention, the P2-O3 mixed phase sodium ion positive electrode material is obtained by adjusting the element proportion and the co-doping elements, and the mixed phase positive electrode material can give consideration to the good multiplying power and cycle performance of the P2 phase positive electrode material and the higher specific capacity of the O3 phase positive electrode material, so that the material obtained by the invention gives consideration to the high specific capacity, long cycle and high multiplying power performance at the same time, and can meet more high-voltage application scenes.
The 0.ltoreq.x.ltoreq.0.1 may be, for example, 0.01, 0.03, 0.05, 0.07, 0.09 or 0.1, 0.ltoreq.a1.ltoreq.0.02, for example, 0.001, 0.005, 0.01, 0.015 or 0.02,0.ltoreq.a2.ltoreq.0.03, for example, 0.001, 0.005, 0.01, 0.015, 0.02, 0.025 or 0.03,0.ltoreq.α.ltoreq.0.04, for example, 0.01, 0.015, 0.02, 0.025, 0.03, 0.035 or 0.04,0.ltoreq.β.ltoreq.0.01, for example, 0.001, 0.003, 0.005, 0.007, 0.009 or 0.01, but the values not limited to the values listed and other values not listed in the numerical ranges are equally applicable.
In the chemical formula of the present invention, except M, chemical trimming is satisfied, and thus, the parameter choices of the present invention are mutually influenced, preferably, a specific range is satisfied.
Preferably, the M comprises any one or a combination of at least two of Mg, ti, ca, sr, ba, cu, zn, zr, W, co or Al, preferably Mg, ti, ca, sr, ba, cu, zn, zr, W, co or a combination of at least two of Al.
The invention preferably dopes at least two valence metal elements, thereby ensuring the comprehensive performance of the P2-O3 mixed phase sodium ion positive electrode material.
Preferably, x, a1, a2, α and β are not simultaneously 0.
The values of x, a1, a2, alpha and beta are different and are 0, otherwise, the Na ratio is lower (0.73), the mixed phase structure of P2-O3 is still maintained, the initial Na content is low, the Na + which can be freely detached and embedded is less, meanwhile, the active element copper and other proper doping elements are absent, and the existence of Cu element can provide a certain reversible capacity based on the valence state change Cu 2+/Cu3+ of the Cu element; other proper element doping can also improve the specific capacity, the cycle performance and the multiplying power performance of the material, improve the Na + diffusion kinetics performance, change the property of the crystal lattice to a certain extent, and strengthen the crystal lattice stability, the electron conductivity, the Na + deintercalation kinetics performance and the like. Therefore, in summary, the values of x, a1, a2, a and b are not 0 at the same time, otherwise, the performance of the P2-O3 mixed phase sodium ion positive electrode material is reduced.
Preferably, in the P2-O3 mixed-phase sodium ion positive electrode material, the 2θ value range corresponding to the P2 phase (002) crystal face satisfies: the 2 theta value range corresponding to the crystal face of the P2 phase (104) is 16.00 degrees less than 2 theta (002) < 16.06 degrees, for example, 16.01 degrees, 16.02 degrees, 16.03 degrees, 16.04 degrees or 16.05 degrees, and meets the following conditions: 48.79 ° < 2θ (104) P2 < 48.98 °, for example 48.80 °, 48.85 °, 48.90 °, or 48.95 °, but are not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, in the P2-O3 mixed phase sodium ion positive electrode material, the 2θ value range corresponding to the O3 phase (003) crystal face satisfies: the 2 theta value range corresponding to the crystal face of the O3 phase (104) is satisfied, for example, 16.25 degrees, 16.30 degrees, 16.35 degrees or 16.40 degrees, and the 2 theta (003) < 16.42 degrees: 41.64 DEG < 2 theta (104) O3 < 41.88 DEG, for example 41.65 DEG, 41.70 DEG, 41.75 DEG, 41.80 DEG or 41.85 DEG, but not limited to the values recited, other non-recited values within the range of values are equally applicable.
Preferably, in the P2-O3 mixed phase sodium ion positive electrode material, the ratio of the peak intensities of the P2 phase (002) crystal face and the O3 phase (003) crystal face is as follows: 0.68 < I (002)/I(003) < 3.71, which may be, for example, 0.7, 1,2,3 or 3.5, but are not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, in the P2-O3 mixed phase sodium ion positive electrode material, the ratio of P2 phase (104) crystal plane to P2 phase (002) crystal plane peak intensities satisfies: 0.40 < I (104)P2/I(002) < 0.99, which may be, for example, 0.5, 0.6, 0.7, 0.8 or 0.9, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, in the P2-O3 mixed phase sodium ion positive electrode material, the ratio of the peak intensities of the O3 phase (104) crystal face and the O3 phase (003) crystal face is as follows: 1.18 < I (104)O3/I(003) < 1.59, which may be, for example, 1.2, 1.3, 1.4 or 1.5, but are not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the capacity retention rate of the P2-O3 mixed-phase sodium ion positive electrode material in a voltage region of 2.5-4.2V is more than or equal to 85% in 100 weeks of 1C cycle, such as 85%, 88%, 90% or 95%, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the multiplying power performance of the P2-O3 mixed phase sodium ion positive electrode material meets the following conditions: the specific discharge capacity of 0.5C/specific discharge capacity of 0.1C is not less than 0.92, for example, 0.92, 0.95, 0.98 or 0.99,1C, and the specific discharge capacity of 0.1C is not less than 0.88, for example, 0.88, 0.9, 0.925 or 0.95, but not limited to the values recited, and other values not recited in the numerical range are applicable.
The P2-O3 mixed phase sodium ion positive electrode material has excellent cycle performance and multiplying power performance.
In a second aspect, the invention provides a preparation method of the P2-O3 mixed-phase sodium ion positive electrode material according to the first aspect, which comprises the following steps:
And mixing and calcining a sodium source and a metal source according to the formula amount to obtain the P2-O3 mixed phase sodium ion positive electrode material.
The metal source is selected according to the metal in the formula.
Preferably, the metal source comprises any one or a combination of at least two of a metal oxide, a metal carbonate or a metal hydroxide.
Preferably, when the metal source is a metal oxide, the mixture obtained after the mixing and before the calcination is ball milled or sand milled until the particle diameter D50 of the mixture is 1 μm or less, for example, 1 μm, 0.8 μm, 0.5 μm, 0.3 μm or 0.1 μm, but not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
If the oxide raw materials are selected, fully mixing all the raw materials, fully grinding by adopting a ball milling or sanding process to obtain a mixture with the particle size D50 less than or equal to 1 mu m, placing the ground mixture in an atmosphere furnace with the temperature ranging from 850 ℃ to 1000 ℃ for high-temperature calcination for 12-24 hours, and crushing the obtained material to obtain a target material; if the hydroxide precursor is selected, sodium salt and the corresponding hydroxide precursor are fully mixed, the mixed raw materials are placed in an atmosphere furnace with the temperature of 850-1000 ℃ for high-temperature calcination for 12-24 hours, and the obtained material is crushed to obtain the target material.
Preferably, the sodium source comprises sodium carbonate.
Preferably, the calcination temperature is 850-1000 ℃, such as 880 ℃, 900 ℃, 925 ℃, 950 ℃, 975 ℃ or 1000 ℃, for 12-24 hours, such as 15 hours, 18 hours, 20 hours or 24 hours, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the calcination is further followed by pulverization.
In a third aspect, the invention provides a sodium ion battery comprising the P2-O3 mixed phase sodium ion positive electrode material according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
Compared with an O3 phase material, the P2-O3 mixed-phase sodium ion positive electrode material has the advantages of smaller phase change degree in the charge and discharge process, stable structure, contribution to realizing long-cycle performance, higher capacity exertion compared with a P2 phase material, higher working voltage platform similar to the P2 phase material, contribution to meeting more high-voltage use scenes, and high specific capacity, long cycle and high rate performance.
Drawings
FIG. 1 is a XRD of the P2-O3 mixed phase sodium ion positive electrode material described in example 1, a standard XRD of Na 0.67Ni0.33Mn0.67O2, and a standard XRD pattern of NaCrO 2.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a P2-O3 mixed phase sodium ion positive electrode material, wherein the chemical formula of the P2-O3 mixed phase sodium ion positive electrode material is Na 0.73Cu0.05Ni0.19Fe0.25Mn0.51Mg0.005O2;
The preparation method of the P2-O3 mixed phase sodium ion positive electrode material comprises the following steps:
Sodium carbonate is selected as a sodium source (sodium excess is 2% as uncontrollable volatilization compensation amount of sodium in the sintering process), metal oxide or hydroxide is selected as a raw material, cuprous oxide is specifically selected as a copper source, nickel hydroxide is selected as a nickel source, ferroferric oxide is selected as an iron source, manganese oxide is selected as a manganese source, magnesium hydroxide is selected as a magnesium source, all raw materials are fully ground and mixed by ball milling according to the proportion of target material elements, the final mixture particle size D50 is 0.5 mu m, sintering is carried out for 24 hours at 850 ℃ under the air atmosphere condition, and the P2-O3 mixed phase sodium ion positive electrode material is obtained after discharging from a furnace and crushing.
Example 2
The embodiment provides a P2-O3 mixed phase sodium ion positive electrode material, wherein the chemical formula of the P2-O3 mixed phase sodium ion positive electrode material is Na 0.76Cu0.05Ni0.20Fe0.26Mn0.49Ti0.01O2;
The preparation method of the P2-O3 mixed phase sodium ion positive electrode material comprises the following steps:
Sodium carbonate is selected as a sodium source (sodium excess is 2% as uncontrollable volatilization compensation amount of sodium in the sintering process), metal oxide or hydroxide is selected as a raw material, cuprous oxide is specifically selected as a copper source, nickel hydroxide is selected as a nickel source, ferric oxide is selected as an iron source, manganic oxide is selected as a manganese source and titanium dioxide is selected as a titanium source, all raw materials are fully ground and mixed by ball milling according to the proportion of target material elements, the final mixture particle size D50 is 0.8 mu m, and then the mixture is sintered for 18 hours at 900 ℃ under the air atmosphere condition, and the P2-O3 mixed phase sodium ion positive electrode material is obtained after discharging and crushing.
Example 3
The embodiment provides a P2-O3 mixed phase sodium ion positive electrode material, wherein the chemical formula of the P2-O3 mixed phase sodium ion positive electrode material is Na 0.77Cu0.01Ni0.25Fe0.25Mn0.49Ti0.01O2;
The preparation method of the P2-O3 mixed phase sodium ion positive electrode material comprises the following steps:
Sodium carbonate is selected as a sodium source (sodium excess is 2% as uncontrollable volatilization compensation amount of sodium in the sintering process), a multielement precursor Cu 0.01Ni0.25Fe0.25Mn0.49Ti0.01(HO)2 is selected as a metal source, the two raw materials are fully mixed according to the element proportion of the target material, and then sintered for 20 hours at 900 ℃ under the air atmosphere condition, and the P2-O3 mixed phase sodium ion positive electrode material is obtained after discharging and crushing.
Example 4
The embodiment provides a P2-O3 mixed phase sodium ion positive electrode material, wherein the chemical formula of the P2-O3 mixed phase sodium ion positive electrode material is Na 0.76Cu0.01Ni0.23Fe0.28Mn0.48Al0.005Ca0.005O2;
The preparation method of the P2-O3 mixed phase sodium ion positive electrode material comprises the following steps:
Sodium carbonate is selected as a sodium source (sodium excess is 2% as uncontrollable volatilization compensation amount of sodium in the sintering process), a multielement precursor Cu 0.01Ni0.23Fe0.28Mn0.48(HO)2 is selected as a metal source, aluminum hydroxide is selected as an aluminum source, calcium oxide is selected as a calcium source, raw materials are fully mixed according to the element proportion of a target material, and then sintered for 15 hours at 950 ℃ under the air atmosphere condition, and the P2-O3 mixed phase sodium ion positive electrode material is obtained after being discharged from a furnace and crushed.
Example 5
The embodiment provides a P2-O3 mixed phase sodium ion positive electrode material, wherein the chemical formula of the P2-O3 mixed phase sodium ion positive electrode material is Na 0.75Ni0.25Fe0.25Mn0.5Mg0.002Zn0.002Zr0.002W0.002O2;
The preparation method of the P2-O3 mixed phase sodium ion positive electrode material comprises the following steps:
Sodium carbonate is selected as a sodium source (sodium excess is 2% as uncontrollable volatilization compensation amount of sodium in the sintering process), a multielement precursor Ni 0.25Fe0.25Mn0.5(HO)2 is selected as a metal source, magnesium oxide is selected as a magnesium source, zinc oxide is selected as a zinc source, zirconium dioxide is selected as a zirconium source, tungsten trioxide is selected as a tungsten source, all raw materials are fully mixed according to the proportion of target material elements, and then sintered for 12 hours at 1000 ℃ under the air atmosphere condition, and the P2-O3 mixed phase sodium ion anode material is obtained after being discharged from a furnace and crushed.
Example 6
The embodiment provides a P2-O3 mixed phase sodium ion positive electrode material, wherein the chemical formula of the P2-O3 mixed phase sodium ion positive electrode material is Na 0.73Cu0.05Ni0.19Fe0.25Mn0.51O2;
The preparation method of the P2-O3 mixed phase sodium ion positive electrode material comprises the following steps:
Sodium carbonate is selected as a sodium source (sodium excess is 2% as uncontrollable volatilization compensation amount of sodium in the sintering process), metal oxide or hydroxide is selected as a raw material, cuprous oxide is specifically selected as a copper source, nickel hydroxide is selected as a nickel source, ferric oxide is selected as an iron source, manganic oxide is selected as a manganese source, all raw materials are fully ground and mixed by ball milling according to the proportion of target material elements, the grain size D50 of the final mixture is 0.5 mu m, and the P2-O3 mixed phase sodium ion positive electrode material is obtained by sintering at 900 ℃ for 18 hours under the air atmosphere condition and discharging and crushing.
Example 7
The embodiment provides a P2-O3 mixed phase sodium ion positive electrode material, wherein the chemical formula of the P2-O3 mixed phase sodium ion positive electrode material is Na 0.73Ni0.24Fe0.25Mn0.51O2;
The preparation method of the P2-O3 mixed phase sodium ion positive electrode material is the same as in example 1 except that the adopted raw material adaptability is changed.
Comparative example 1
The comparative example provides a P2-O3 mixed phase sodium ion positive electrode material, wherein the chemical formula of the P2-O3 mixed phase sodium ion positive electrode material is Na 0.7Cu0.05Ni0.18Fe0.24Mn0.53Mg0.005O2, and compared with the Ni/Mn content variation of the embodiment 1, the molecular formula Na ratio after balancing is reduced to 0.7;
the preparation method of the P2-O3 mixed phase sodium ion positive electrode material is the same as in example 1 except that the raw material adaptability is changed.
Comparative example 2
The comparative example provides a P2-O3 mixed phase sodium ion positive electrode material, wherein the chemical formula of the P2-O3 mixed phase sodium ion positive electrode material is Na 0.79Cu0.05Ni0.21Fe0.27Mn0.47Ti0.01O2, and compared with the Ni and Mn content variation of the embodiment 2, the Na ratio is increased to 0.79;
The preparation method of the P2-O3 mixed phase sodium ion positive electrode material is the same as in example 2 except that the raw material adaptability is changed.
Comparative example 3
The comparative example provides a P2-O3 mixed phase sodium ion positive electrode material, wherein the chemical formula of the P2-O3 mixed phase sodium ion positive electrode material is Na 0.79Cu0.01Ni0.26Fe0.25Mn0.49Ti0.01O2, and compared with the content change of Ni, fe and Mn in the embodiment 3, the content change of a1 is 0.03, and the Na ratio is increased to 0.79;
The preparation method of the P2-O3 mixed phase sodium ion positive electrode material is the same as in example 3 except that the raw material adaptability is changed.
Comparative example 4
The comparative example provides a P2-O3 mixed phase sodium ion positive electrode material, wherein the chemical formula of the P2-O3 mixed phase sodium ion positive electrode material is Na 0.77Cu0.01Ni0.23Fe0.29Mn0.47Al0.005Ca0.005O2, and compared with the Ni, fe and Mn content in the embodiment 4, the content of a2 is changed to be 0.04;
The preparation method of the P2-O3 mixed phase sodium ion positive electrode material is the same as in example 4 except that the raw material adaptability is changed.
Comparative example 5
The comparative example provides a P2-O3 mixed phase sodium ion positive electrode material, wherein the chemical formula of the P2-O3 mixed phase sodium ion positive electrode material is Na 0.75Ni0.25Fe0.25Mn0.5Mg0.003Zn0.003Zr0.003W0.002O2, and compared with the beta value change of the example 5;
The preparation method of the P2-O3 mixed phase sodium ion positive electrode material is the same as in example 5 except that the raw material adaptability is changed.
Cell assembly and electrochemical performance test: the P2-O3 mixed phase sodium ion positive electrode materials obtained in the above examples and comparative examples are mixed according to the mass ratio of the positive electrode materials to the SP to the PVDF of 90:5:5, NMP is added to prepare adhesive glue solution, the glue solution is coated on aluminum foil, and the glue solution is baked for 12 hours at 120 ℃ in a vacuum drying oven to obtain a positive electrode plate; a 2032 button cell was assembled in an Ar protection glove box with a metal sodium sheet as a counter electrode, glass fiber as a separator, 1mol/L NaPF 6, EC/dmc=1:1 as electrolyte, and discharge specific capacities of 0.1C, 0.5C and 1C were tested in a voltage interval of 2.5 to 4.2V, and a cycle retention of 100 weeks at 1C.
XRD test: the XRD pattern is tested by adopting a conventional X-ray diffraction instrument, the scanning speed is 5 degrees/min, the scanning range is 10-80 degrees, and meanwhile, the relevant peak position and intensity information are read, wherein the O3-phase PDF standard card is PDF#88-0720 (NaCrO 2), the P2-phase PDF standard card is PDF#54-0894 (Na 2/3Ni1/3Mn2/3O2), the XRD of the P2-O3 mixed-phase sodium-ion positive electrode material, the standard XRD of Na 0.67Ni0.33Mn0.67O2 and the standard XRD pattern of NaCrO 2 are shown in figure 1, and the obtained material contains P2 phase and O3 phase as can be seen from figure 1.
The test results are shown in tables 1 and 2:
TABLE 1
TABLE 2
| Specific capacity (mAh/g) | 0.5C/0.1C | 1C/0.1C | 100 Week cycle retention (%) | |
| Example 1 | 135.5 | 0.96 | 0.92 | 89.8 |
| Example 2 | 133.2 | 0.94 | 0.89 | 91.5 |
| Example 3 | 138.9 | 0.93 | 0.90 | 86.1 |
| Example 4 | 132.7 | 0.93 | 0.90 | 88.8 |
| Example 5 | 134.5 | 0.97 | 0.94 | 94.6 |
| Example 6 | 135.8 | 0.92 | 0.88 | 85.5 |
| Example 7 | 131.5 | 0.92 | 0.89 | 90.8 |
| Comparative example 1 | 127.4 | 0.94 | 0.91 | 86.4 |
| Comparative example 2 | 137.7 | 0.92 | 0.87 | 84.6 |
| Comparative example 3 | 142.1 | 0.87 | 0.84 | 82.8 |
| Comparative example 4 | 136.6 | 0.91 | 0.88 | 85.6 |
| Comparative example 5 | 130.5 | 0.97 | 0.94 | 93.2 |
In Table 2, 0.5C/0.1C means a ratio of a specific discharge capacity of 0.5C to a specific discharge capacity of 0.1C, and 1C/0.1C means a ratio of a specific discharge capacity of 1C to a specific discharge capacity of 0.1C.
From tables 1 and 2, it can be seen that:
In the embodiments 1-7, the anode material with the P2 and O3 mixed phase structure is prepared by adopting a ball milling and sand milling or dry mixing process and adjusting the element proportion and cooperatively doping multiple elements. In the range of 2.5-4.2V, the mixed phase positive electrode material can give consideration to the good multiplying power and cycle performance of the P2 phase positive electrode material and the higher specific capacity of the O3 phase positive electrode material, and can meet more high-voltage application scenes.
(1) Examples 1,2 and 6 were fully milled and mixed using oxide as the raw material using ball milling and sand milling processes, examples 3, 4 and 5 were directly and fully mixed using dry blending processes using hydroxide precursors as the raw material, the materials prepared between the two processes were all P2/O3 mixed phase structures, and the overall electrochemical performance of each example was at a similar level.
(2) Comparing example 1 with comparative example 1, when the selected raw materials and the process system are the same, the doping ratio of Ni/Mn element is finely adjusted in comparative example 1, so that the Na ratio is less than 0.73, the phase structure is changed from the P2/O3 mixed phase to the pure P2 phase, the (002) and (104) crystal faces move towards the low angle direction, at the moment, the specific capacity of comparative example 1 is greatly reduced by about 8mAh/g compared with example 1 due to the smaller initial Na content, and simultaneously the rate performance and the cycle performance are also reduced.
(3) Comparing example 2 with comparative example 2, comparing example 3 with comparative example 3, when the selected raw materials and the process system are the same, the fine tuning Ni/Mn ratio in comparative example 2, a1 and a2 are all within the limited range, the fine tuning Ni/Fe/Mn ratio in comparative example 3, a1 is out of the limited range, thus leading to Na ratio of comparative examples 2 and 3 > 0.77, the material structure is converted from P2/O3 mixed phase to pure O3 phase, the (003) crystal face and the (104) crystal face are shifted, and at this time, the specific capacity of comparative examples 2 and 3 is higher than that of examples 2 and 3 due to the higher initial Na content, which can remove more sodium ions; however, examples 2 and 3 contained a P2 phase structure, and the Na layer spacing was slightly larger, which could improve the sodium ion transmission rate and maintain the integrity of the layered structure, and therefore, the rate performance and cycle performance of examples 2 and 3 were superior to those of comparative examples 2 and 3.
(4) In comparison of example 4 with comparative example 4, when the selected raw materials and the process system are the same, a2 in comparative example 4 is out of range, so that the Fe content is increased and the Mn content is decreased, and the structure maintains the P2/O3 phase structure, but the rate performance and cycle performance of comparative example 4 are degraded compared with example 4.
(5) Comparing example 5 with comparative example 5, comparative example 5 only increases the total amount of doping modifying element M in the same case of the selected raw materials and process system, while maintaining the P2/O3 mixed phase structure, the rate performance and cycle performance are not greatly affected, but the specific capacity is reduced.
In summary, the invention provides a P2-O3 mixed phase sodium ion positive electrode material, a preparation method and application thereof, wherein the P2-O3 mixed phase sodium ion positive electrode material can improve inherent defects of P2 phase materials and O3 phase materials, and simultaneously has high specific capacity, long cycle and high rate capability, and can meet various application scenes such as high voltage.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.
Claims (10)
1. The P2-O3 mixed phase sodium ion positive electrode material is characterized in that the chemical formula of the P2-O3 mixed phase sodium ion positive electrode material is Na 0.73+αCuxNi0.24-x+a1Fe0.25+a2Mn0.51-a1-a2MβO2, wherein chemical balancing is satisfied except M in the chemical formula, M is doping modification element, x is more than or equal to 0 and less than or equal to 0.1, a1 is more than or equal to 0 and less than or equal to 0.02,0, a2 is more than or equal to 0 and less than or equal to a 0.03,0, alpha is more than or equal to 0.04,0 and less than or equal to 0.01.
2. The P2-O3 mixed phase sodium ion positive electrode material according to claim 1, wherein M comprises any one or a combination of at least two of Mg, ti, ca, sr, ba, cu, zn, zr, W, co or Al, preferably Mg, ti, ca, sr, ba, cu, zn, zr, W, co or a combination of at least two of Al;
preferably, x, a1, a2, α and β are not simultaneously 0.
3. The P2-O3 mixed phase sodium ion positive electrode material according to claim 1 or 2, wherein in the P2-O3 mixed phase sodium ion positive electrode material, a2θ value range corresponding to a P2 phase (002) crystal face satisfies: the value range of 2 theta corresponding to the crystal face of the P2 phase (104) is 16.00 degrees less than 2 theta (002) < 16.06 degrees, and the value range of 2 theta corresponding to the crystal face meets the following conditions: 48.79 DEG <2 theta (104) P2 < 48.98 DEG;
Preferably, in the P2-O3 mixed phase sodium ion positive electrode material, the 2θ value range corresponding to the O3 phase (003) crystal face satisfies: the value range of 2 theta corresponding to the crystal face of the O3 phase (104) is 16.20 degrees less than 2 theta (003) < 16.42 degrees, and the value range of 2 theta corresponding to the crystal face of the O3 phase meets the following conditions: 41.64 DEG < 2 theta (104) O3 < 41.88 deg.
4. A P2-O3 mixed phase sodium ion positive electrode material according to any one of claims 1 to 3, wherein, in the P2-O3 mixed phase sodium ion positive electrode material, the ratio of peak intensities of P2 phase (002) crystal face and O3 phase (003) crystal face satisfies: 0.68 < I (002)/I(003) < 3.71.
5. The P2-O3 mixed phase sodium ion positive electrode material according to any one of claims 1 to 4, wherein, in the P2-O3 mixed phase sodium ion positive electrode material, the ratio of peak intensities of P2 phase (104) crystal plane and P2 phase (002) crystal plane satisfies: i (104)P2/I(002) is more than 0.40 and less than 0.99;
Preferably, in the P2-O3 mixed phase sodium ion positive electrode material, the ratio of the peak intensities of the O3 phase (104) crystal face and the O3 phase (003) crystal face is as follows: i (104)O3/I(003) is less than 1.18 and less than 1.59.
6. The P2-O3 mixed phase sodium ion positive electrode material according to any one of claims 1 to 5, wherein the capacity retention rate of the P2-O3 mixed phase sodium ion positive electrode material in a voltage region of 2.5 to 4.2V for 100 weeks at 1C cycle is not less than 85%;
Preferably, the specific discharge capacity of 0.5C/specific discharge capacity of 0.1C of the P2-O3 mixed phase sodium ion positive electrode material is more than or equal to 0.92,1C/specific discharge capacity of 0.1C is more than or equal to 0.88.
7. A method for preparing the P2-O3 mixed phase sodium ion positive electrode material according to any one of claims 1 to 6, comprising the steps of:
And mixing and calcining a sodium source and a metal source according to the formula amount to obtain the P2-O3 mixed phase sodium ion positive electrode material.
8. The method of claim 7, wherein the metal source comprises any one or a combination of at least two of a metal oxide, a metal carbonate, or a metal hydroxide;
Preferably, when the metal source is metal oxide, ball milling or sand milling is carried out on the mixture obtained by mixing after mixing and before calcining until the particle size D50 of the mixture is less than or equal to 1 mu m;
Preferably, the sodium source comprises sodium carbonate.
9. The method according to claim 7 or 8, wherein the calcination is carried out at a temperature of 850-1000 ℃ for a period of 12-24 hours;
Preferably, the calcination is further followed by pulverization.
10. A sodium ion battery comprising the P2-O3 mixed phase sodium ion positive electrode material of any one of claims 1-6.
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