CN112234201A - A kind of O3 type layered sodium ion battery positive electrode material and preparation method thereof - Google Patents
A kind of O3 type layered sodium ion battery positive electrode material and preparation method thereof Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 28
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000011734 sodium Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims description 20
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000011812 mixed powder Substances 0.000 claims description 10
- 239000010405 anode material Substances 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims 1
- 239000001632 sodium acetate Substances 0.000 claims 1
- 235000017281 sodium acetate Nutrition 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- 235000011121 sodium hydroxide Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- JOUIQRNQJGXQDC-AXTSPUMRSA-N namn Chemical compound O1[C@@H](COP(O)([O-])=O)[C@H](O)[C@@H](O)[C@@H]1[N+]1=CC=CC(C(O)=O)=C1 JOUIQRNQJGXQDC-AXTSPUMRSA-N 0.000 abstract description 11
- 150000002500 ions Chemical class 0.000 abstract description 7
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 abstract description 5
- 150000003624 transition metals Chemical class 0.000 abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 239000000843 powder Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-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
- 230000000694 effects Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
本发明公开了一种O3型层状钠离子电池正极材料，分子式为Na(Mn0.5Ni0.5)1‑x(M10.5M20.5)xO2，其中0＜x≤0.4，M1为Ti4+、Hf4+、Zr4+、Sn4+、Ge4+和Pb4+中的至少一种；M2为Mg2+和Zn2+中的至少一种。本发明通过对O3型NaMn0.5Ni0.5O2层状钠离子电池正极同时采用等量+2价M2和+4价M1离子进行共掺，不会引起NaMn0.5Ni0.5O2材料中过渡金属价态的变化，且能够提高其高电压循环稳定性。The invention discloses an O3 type layered sodium ion battery positive electrode material, the molecular formula is Na(Mn 0.5 Ni 0.5 ) 1-x (M1 0.5 M2 0.5 ) x O 2 , wherein 0<x≤0.4, and M1 is Ti 4+ , at least one of Hf 4+ , Zr 4+ , Sn 4+ , Ge 4+ and Pb 4+ ; M2 is at least one of Mg 2+ and Zn 2+ . In the invention, the positive electrode of the O3 type NaMn 0.5 Ni 0.5 O 2 layered sodium ion battery is co-doped with the same amount of +2 valence M2 and +4 valence M1 ions at the same time, so that the transition metal valence in the NaMn 0.5 Ni 0.5 O 2 material will not be caused. state changes, and can improve its high-voltage cycling stability.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, relates to a sodium secondary battery material and a preparation method thereof, and particularly relates to an O3-type layered sodium ion battery positive electrode material and a preparation method thereof.
Background
Because sodium resources are abundant and widely distributed on the earth, high-performance sodium ion batteries are considered as powerful competitors in the field of large-scale energy storage. Positive electrode material as an important component of sodium ion battery, which stores Na+Is Na in the battery+The provider's important sources, which largely determine its energy density and production cost, also have a significant impact on the power density, cycle life, and safety performance of the battery. The layered transition metal oxide positive electrode material of the sodium-ion battery is considered to be the most suitable sodium-electricity positive electrode material for commercial application due to the advantages of high specific capacity, abundant resources, environmental friendliness, capability of referring to the production process of the layered lithium-ion battery positive electrode material and the like. The layered transition metal oxide sodium positive electrode material is formed by alternately arranged transition metal layers (TMO)2) And a sodium layer (NaO)2) Is formed according to TMO2Layer arrangement rule and Na+Can be divided into two types of P2 and O3. In comparison with P2 type layered cathode material, Na in O3 type layered cathode material+Higher content, no need of additional Na supplement in the charging and discharging process+Also can exert higher specific capacity, thereby having better commercial application prospect. Manganese-nickel binary anode material, in particular O3 type NaMn, without expensive and toxic Co element in layered sodium-electricity anode material0.5Ni0.5O2The layered positive electrode material has the advantage of high capacity in a full battery due to high Na content, and has good large-scale application prospect, so that the layered positive electrode material is widely concerned. However, NaMn of O3 type0.5Ni0.5O2The layered positive electrode also has a complex phase change process in the charge-discharge process, especially when charged to a high voltage of more than 4.1VThe irreversible P3 "phase change that occurs can lead to rapid decay of the specific capacity of the positive electrode material, reducing cycle life. It is an effective method to reduce the charge cut-off voltage in order to suppress irreversible phase transition at high voltage, however, the reduction of the cut-off voltage inevitably leads to a reduction in the specific capacity of the positive electrode material, and the advantage of high specific capacity cannot be fully exerted.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide an O3 type layered sodium-ion battery positive electrode material and a preparation method thereof, and O3 type NaMn is subjected to0.5Ni0.5O2The positive electrode of the layered sodium-ion battery adopts the same amount of + 2-valent M2 and + 4-valent M1 ions for co-doping, and NaMn can not be caused0.5Ni0.5O2The valence state of transition metal in the material is changed, and the high-voltage cycling stability of the material can be improved.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
an O3-type layered positive electrode material of sodium-ion battery with Na (Mn) molecular formula0.5Ni0.5)1-x(M10.5M20.5)xO2Wherein x is more than 0 and less than or equal to 0.4, and M1 is Ti4+、Hf4+、Zr4+、Sn4+、Ge4+And Pb4+At least one of; m2 is Mg2+And Zn2+At least one of (1).
Preferably, in the molecular formula, x is more than or equal to 0.05 and less than or equal to 0.1. In the invention, because the selected M2 doped ions have no electrochemical activity in the voltage range of 2-4.5V, the specific capacity of the material can be reduced to a certain extent by doping M2, and when the doped ions are in the preferred doped capacity range, the capacity loss of the positive electrode material is limited, and the cycling stability is obviously improved.
Preferably, in the formula, M1 is Ti4+、Hf4+、Zr4+、Sn4+、Ge4+Or Pb4+。
Preferably, in the formula, M2 is Mg2+Or Zn2+。
The invention also provides a preparation method of the O3-type layered sodium-ion battery anode material, which comprises the following steps:
(1) according to the mol ratio set in the molecular formula, the (Mn) is0.5Ni0.5)CO3Or (Mn)0.5Ni0.5)(OH)2Grinding and uniformly mixing the sodium source, the M1 source and the M2 source to obtain mixed powder;
(2) and (3) preserving the heat of the mixed powder at 400-600 ℃ for 4-8 h, and preserving the heat at 850-950 ℃ for 12-24 h to obtain the O3 type laminar sodium-ion battery anode material.
Preferably, in step (1), the sodium source is sodium carbonate or sodium nitrate or sodium hydroxide.
Preferably, in step (1), the M1 source is an oxide of M1; the source of M2 was nitrate of M2.
Preferably, in the step (2), the mixed powder is heated to 400-600 ℃ at a heating rate of 1-3 ℃/min for 4-8 h, and then heated to 850-950 ℃ at a heating rate of 5-10 ℃/min for 12-24 h.
The principle of the invention is as follows:
aiming at the prior O3 type NaMn0.5Ni0.5O2The invention adopts the introduction of M1 ion with valence of +4 to destroy the ordered arrangement of metal ions in the transition metal layer of the layered material, thereby inhibiting Na in the process of charging and discharging+And ordered conversion of vacancies, Na reduction+A diffusion energy barrier of (d); the ionic radius of the + 2M 2 ion and Ni2+Approximately 60-80 pm, and has no electrochemical activity to replace Ni with high electrochemical activity2+Since M2 does not participate in the redox reaction during charging and discharging, it can act as a stabilizer to reduce the structural distortion and slippage of the layered material during charging and discharging. Therefore, the invention adopts the same amount of + 2M 2 and + 4M 1 ions for co-doping, and does not cause NaMn0.5Ni0.5O2The valence state of transition metal in the material is changed, and the high-voltage cycling stability of the material can be improved.
Compared with the prior art, the invention has the advantages that:
the method does not need to redesign the components and the proportion of the precursor, and can inherit the original O3 type NaMn0.5Ni0.5O2The components of the layered positive electrode material are flexibly regulated and controlled on the basis of the structure and the production process of the layered positive electrode material, and the O3-type layered sodium electric positive electrode material with high voltage cycling stability is obtained.
Drawings
Fig. 1X-ray diffraction pattern of the cathode material prepared in example 1.
Fig. 2 first-turn charge and discharge curves of the positive electrode materials prepared in example 1 and comparative example 1.
Fig. 3 is a cycle test curve of the positive electrode materials prepared in example 1 and comparative example 1.
Fig. 4 rate performance curves of the positive electrode materials prepared in example 1 and comparative example 1.
Fig. 5X-ray diffraction pattern of the cathode material prepared in example 2.
Detailed Description
The following is a detailed description of the preferred embodiments of the invention and is not intended to limit the invention in any way, i.e., the invention is not intended to be limited to the embodiments described above, and modifications and alternative compounds that are conventional in the art are intended to be included within the scope of the invention as defined in the claims.
Example 1
1.0514g (Mn) were weighed0.5Ni0.5)CO3Powder, 0.5459gNa2CO3Powder, 0.04gTiO2Powder and 0.1282gMg (NO)3)2·6H2Placing the O in a mortar for fully grinding and crushing, uniformly stirring at the stirring speed of 500r/min, transferring the uniformly mixed powder in a muffle furnace, heating to 450 ℃ at the heating rate of 1 ℃/min, preserving heat for 6h, heating to 850 ℃ at the heating rate of 5 ℃/min, preserving heat for 20h, cooling to room temperature along with the furnace to obtain Mg2+And Ti4+Co-doped O3 type layered oxide sodium anode material (NaMn)0.45Ni0.45Mg0.05Ti0.05O2)。
As shown in fig. 1, it can be seen that the XRD diffraction pattern of the material conforms to the PDF card of O3 phase structure, and there is no impurity peak, indicating that the material purity is high; (003) and (104) the peak is shifted to the left, both with a slight increase in the lattice constant c.
Using NMP as medium, adding the NaMn0.45Ni0.45Mg0.05Ti0.05O2Uniformly mixing acetylene black and PVDF in a mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on an aluminum foil, drying, cutting the aluminum foil into a positive plate with the diameter of 12mm, taking a sodium metal sheet as a negative electrode, taking glass fiber GF/D as a diaphragm, and 1M NaClO4The solution of PC/FEC (95: 5 by volume) as an electrolyte was charged into an argon-filled glove box to prepare a CR2016 type coin cell.
Comparative example 1
The only difference from example 1 is that the material obtained is NaMn O30.5Ni0.5O2A layered positive electrode material.
The batteries assembled in the example 1 and the comparative example 1 are subjected to charge-discharge cycle test in a blue CT2001A battery test system, the test conditions are the same, the voltage range is 2-4.2V, and the test temperature is 28 ℃.
As shown in fig. 2, which is the first-turn charge-discharge curve of the cycle of example 1 and comparative example 1, it can be seen that the charge-discharge curve of example 1 is significantly smoother, the number of plateaus is relatively less, and the phase change during the charge-discharge process of the material of example 1 is less.
As shown in fig. 3, as a result of the cycle performance test of example 1 and comparative example 1, the initial capacity of the battery of comparative example 1 is slightly higher, but the capacity retention rate at 200 cycles of 0.2C cycle is only 50.7%, whereas the capacity retention rate of the battery of example 1 is improved to 72.6% after 200 cycles of 0.2C cycle, and the cycle performance is obviously improved.
As shown in fig. 4, the results show that the capacity of example 1 is also significantly better than that of comparative example 1 under different rate test conditions.
In conclusion, the electrochemical performance test results show that the cycle performance and the rate performance of the battery in example 1 are both obviously improved compared with those in comparative example 1.
Example 2
0.7265g (Mn) were weighed0.5Ni0.5)(OH)2Powder, 0.8755gNaNO3Powder, 0.08gTiO2Placing the powder and 0.0403g MgO in a mortar for full grinding and crushing, uniformly stirring at a stirring speed of 600r/min, transferring the uniformly mixed powder into a muffle furnace, heating to 500 ℃ at a heating rate of 2 ℃/min, preserving heat for 4h, heating to 900 ℃ at a heating rate of 8 ℃/min, preserving heat for 15h, and cooling with the furnace to obtain Mg2+And Ti4+Co-doped O3 type layered sodium anode material (NaMn)0.4Ni0.4Mg0.1Ti0.1O2)。
Example 3
Weighing 0.993g (Mn)0.5Ni0.5)CO3Powder, 0.5459gNa2CO3Powder, 0.113g SnO2Powders and 0.2231gZn (NO)3)2·6H2Placing O in a mortar for fully grinding and crushing, uniformly stirring at the stirring speed of 400r/min, transferring the uniformly mixed powder in a muffle furnace, heating to 400 ℃ at the heating rate of 1 ℃/min, preserving heat for 8h, heating to 950 ℃ at the heating rate of 5 ℃/min, preserving heat for 12h, and cooling with the furnace to obtain Zn2+And Sn4+Co-doped O3 type layered sodium anode material (NaMn)0.425Ni0.425Zn0.075Sn0.075O2)。
Example 4
0.8177g (Mn) were weighed0.5Ni0.5)CO3Powder, 0.8755gNaNO3Powder, 0.3846gMg (NO)3)2·6H2O powder and 0.1848gZrO2Grinding in mortar, stirring at 800r/min, transferring the uniformly mixed powder into muffle furnace, heating to 600 deg.C at a heating rate of 3 deg.C/min, maintaining for 6 hr, heating to 900 deg.C at a heating rate of 10 deg.C/min, maintaining for 20 hr, and cooling to obtain Mg2+And Zr4+Co-doped O3 type layered sodium anode material (NaMn)0.35Ni0.35Mg0.15Zr0.15O2)。
Claims (9)
1. O3-type layered sodium ionsA battery positive electrode material, characterized in that: molecular formula of Na (Mn)0.5Ni0.5)1-x(M10.5M20.5)xO2Wherein x is more than 0 and less than or equal to 0.4, and M1 is Ti4+、Hf4+、Zr4+、Sn4+、Ge4+And Pb4+At least one of; m2 is Mg2 +And Zn2+At least one of (1).
2. The O3 type layered sodium-ion battery positive electrode material of claim 1, wherein: in the molecular formula, x is more than or equal to 0.05 and less than or equal to 0.1.
3. The O3 type layered sodium-ion battery positive electrode material of claim 1, wherein: in the molecular formula, M1 is Ti4+、Hf4+、Zr4+、Sn4+、Ge4+Or Pb4+。
4. The O3 type layered sodium-ion battery positive electrode material of claim 1, wherein: in the molecular formula, M2 is Mg2+Or Zn2+。
5. The preparation method of the O3 type layered sodium-ion battery positive electrode material as claimed in any one of claims 1-4, characterized by comprising the following steps:
(1) according to the mol ratio set in the molecular formula, the (Mn) is0.5Ni0.5)CO3Or (Mn)0.5Ni0.5)(OH)2Grinding and uniformly mixing the sodium source, the M1 source and the M2 source to obtain mixed powder;
(2) and (3) preserving the heat of the mixed powder at 400-600 ℃ for 4-8 h, and preserving the heat at 850-950 ℃ for 12-24 h to obtain the O3 type laminar sodium-ion battery anode material.
6. The method of claim 5, wherein: in the step (1), the sodium source is sodium carbonate or sodium nitrate or sodium hydroxide or sodium acetate.
7. The method of claim 5, wherein: in the step (1), the M1 source is an oxide of M1.
8. The method of claim 5, wherein: in the step (1), the M2 source is nitrate of M2.
9. The method of claim 5, wherein: in the step (2), the mixed powder is heated to 400-600 ℃ at a heating rate of 1-3 ℃/min for 4-8 h, and then heated to 850-950 ℃ at a heating rate of 5-10 ℃/min for 12-24 h.
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| CN114394632A (en) * | 2022-02-23 | 2022-04-26 | 浙江格派钴业新材料有限公司 | Preparation method of nanoscale LLZO coated high-nickel positive electrode material |
| CN114744180A (en) * | 2022-05-17 | 2022-07-12 | 无锡钠科能源科技有限公司 | Composite coated positive electrode material of sodium-ion battery |
| ES2948257R1 (en) * | 2021-09-15 | 2024-08-23 | Guangdong Brunp Recycling Technology Co Ltd | LAYERED SODIUM ION BATTERY POSITIVE ELECTRODE MATERIAL AND METHOD OF PREPARATION THEREOF |
| WO2024243794A1 (en) * | 2023-05-30 | 2024-12-05 | 广东邦普循环科技有限公司 | Sodium-ion positive electrode material, preparation method therefor, and use thereof |
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