CN117800411A - A sodium positive electrode material precursor uniformly doped with stable valence elements and a preparation method thereof, and a sodium positive electrode material - Google Patents
A sodium positive electrode material precursor uniformly doped with stable valence elements and a preparation method thereof, and a sodium positive electrode material Download PDFInfo
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Abstract
The invention provides a stable valence element uniformly doped sodium-electricity positive electrode material precursor, a preparation method thereof and a sodium-electricity positive electrode material, wherein the chemical formula of the positive electrode material precursor is Ni x Fe y Mn z M (1‑x‑y‑z) (OH) 2 ，0.10≤x≤0.40，0.20≤y≤0.50，0.20≤z≤0.50，x+y+z<1.00, wherein M is a steady-state metallic element, and M comprises one or more of Ca, mg, zn, cu, zr, ti, sr, ba, sn, the precursor of the invention stabilizes metallic oxygen bonds and expands by doping elementsThe sodium-electricity positive electrode material prepared from the precursor has a large unit cell volume, more stable structure and better capacity and cycle performance.
Description
Technical Field
The invention relates to the technical field of fuels, in particular to a sodium-electricity positive electrode material precursor uniformly doped with stable valence elements, a preparation method thereof and a sodium-electricity positive electrode material.
Background
In recent years, with the vigorous development of national environmental protection and dual carbon targets and electric automobile industry, secondary batteries, especially lithium ion batteries, are beginning to be applied on a large scale, and due to the lack and uneven distribution of lithium resources, the cost of the lithium ion batteries is high, so that the lithium ion batteries are urgently required to find suitable substitutes. Sodium ion batteries are the first choice for replacing lithium batteries by virtue of abundant raw material resources, better electrical performance and similar working principles as lithium batteries. The sodium-electricity performance mainly depends on the cathode material, but the stability of the current sodium-electricity cathode material is still poor, and the precursor of the cathode material needs to be optimized.
The precursor is a key factor of the performance of the sodium-electricity positive electrode material, and the patent document of publication No. CN115196691A discloses a nickel-iron-manganese ternary precursor for sodium ion batteries and a preparation method thereof. However, in the process of preparing the precursor, the valence state of metal is unstable, ferrous iron is easily oxidized into ferric iron, meanwhile, the solubility product is larger due to different precipitation pH values of metal ions, uneven precipitation of metal is easy to generate, uneven distribution of metal elements in the precursor material is further caused, the structure of the positive electrode material prepared by the precursor is unstable, the gram capacity is low, the first effect is low, the cycle performance is poor, and the internal resistance is large.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a precursor of the sodium-electricity positive electrode material uniformly doped with stable valence state elements, a preparation method thereof and the sodium-electricity positive electrode material. The positive electrode material sintered by the precursor material has the advantages of high gram capacity, high coulomb efficiency, high cycle retention rate and the like.
According to an embodiment of the invention, a stable valence element uniformly doped sodium-electricity positive electrode material precursor is characterized in that the chemical formula of the positive electrode material precursor is Ni x Fe y Mn z M (1-x-y-z) (OH) 2 ，0.10≤x≤0.40，0.20≤y≤0.50，0.20≤z≤0.50，x+y+z<1.00, wherein M is a steady-state metallic element, and M comprises one or more of Ca, mg, zn, cu, zr, ti, sr, ba, sn.
Preferably, the particle morphology of the positive electrode material precursor is spherical or spheroid, the particle diameter D50 of the positive electrode material precursor is 2.80-8.50 mu m, and the tap density of the positive electrode material precursor is 1.20-2.00g/cm 3 The specific surface area of the positive electrode material precursor is 6.00-16.00m 2 /g。
Further preferably, the particle diameter D50 of the positive electrode material precursor is 3.50-5.50 μm, and the tap density of the positive electrode material precursor is 1.40-1.70g/cm 3 The positive electrodeThe specific surface area of the material precursor is 8.00-12.00m 2 /g。
According to an embodiment of the present invention, there is also provided a method for preparing a precursor of a sodium electric positive electrode material, for preparing the precursor of a sodium electric positive electrode material uniformly doped with the stable valence element, including the steps of:
firstly, mixing a nickel source, an iron source, a manganese source, soluble salts of doping elements and a reducing agent, and dissolving the mixture in deionized water to obtain a mixed metal salt solution;
step two, deionized water, a precipitator and a complexing agent are mixed according to a fixed proportion and added into a reaction kettle to obtain a reaction base solution;
step three, adding the mixed metal salt solution, the precipitator, the complexing agent and the chelating agent into the reaction base solution simultaneously according to a proportion for coprecipitation reaction;
and step four, finally, sequentially aging, washing, solid-liquid separation and drying the slurry obtained by the coprecipitation reaction to obtain a precursor of the sodium electric anode material.
Preferably, the concentration of the mixed metal salt solution is 1.50-2.50mol/L; the concentration of the reducing agent is 0.10% -5.00% of the concentration of the mixed metal salt solution;
the precipitant is one of sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate, and the concentration of the precipitant is 8.50-12.50mol/L;
the complexing agent comprises at least one of ammonia water, ammonium bicarbonate, ammonium chloride, ammonium sulfate, ammonium acetate and ammonium oxalate, and the concentration of the complexing agent is 6.00-10.50mol/L;
the chelating agent comprises at least one of ethylenediamine tetraacetic acid, aminotrimethylene phosphonic acid, sodium gluconate, sodium pyrophosphate, citric acid, sodium citrate, oxalic acid, triethanolamine, sodium tripolyphosphate and hydroxyethylidene diphosphonic acid.
Preferably, in the third step:
the coprecipitation reaction includes a preceding nucleation stage and a subsequent growth stage;
the reaction time in the nucleation stage is 0-9.00h, the precipitation pH is 10.90-11.70, and the particle size D50 of the terminated material is 1.50-2.50 mu m;
the reaction time of the growth stage is 9.00-180.00h, the pH of the sediment is 10.10-10.90, and the reaction termination time depends on the set target of the material particle diameter D50 to be 2.80-8.50 mu m.
Preferably, in the fourth step, the washing process is carried out by adopting deionized water at 65.00-75.00 ℃, and the washing end point is that the Na or K content is less than 200.00ppm.
Preferably, in the fourth step, the drying temperature is 100.00-180.00 ℃, the drying time is 10.00-24.00h, and the drying is carried out until the moisture of the materials is less than 6000.00ppm.
Further preferably, in the third step:
the coprecipitation reaction is carried out under a high-speed stirring system, the rotating speed is 300.00-650.00rpm, the temperature is 40.00-75.00 ℃, the pH value is 10.10-11.70, and NH is used 3 The calculated ammonia concentration is 2.50-7.00g/L, and the reaction time is 90-180.00h;
in the coprecipitation reaction process, the slurry in the reaction kettle is filtered by a thickener, mother liquor is discharged out of the reaction kettle, the intercepted slurry with high solid content flows back to the reaction kettle to continue to participate in the reaction, and the solid content of the slurry is 15-70% when the coprecipitation reaction is finished;
the coprecipitation reaction is carried out under the protection of inert gas, wherein the inert gas comprises at least one of nitrogen, helium and argon;
in the coprecipitation reaction process, the flow of the mixed metal salt is 1.60 percent/h-8.00 percent/h of the effective volume of the reaction kettle, and the flow of the precipitant is 0.60 percent/h-3.20 percent/h of the effective volume of the reaction kettle.
According to the embodiment of the invention, the sodium-electricity positive electrode material is prepared by synthesizing the sodium-electricity positive electrode material precursor uniformly doped with any one of the stable valence elements and a sodium source through a high-temperature solid-phase method, wherein the synthesis temperature is 800.00-980.00 ℃, the calcination time is 8-20h, and the molar ratio of the metal element content in the precursor to sodium is 0.8-1.08.
Compared with the prior art, the invention has the following beneficial effects: the invention dopes stable valence metal elements in the phase of coprecipitation synthesis of the precursor, belongs to liquid phase mixing of molecular and ion levels, and has more uniform distribution and better doping effect than solid phase mixing doping elements in the traditional positive electrode material calcining phase. The doped stable valence state elements can replace Ni, fe and Mn to form metal-oxygen bonds with stronger bond energy, and meanwhile, the unit cell volume of the positive electrode material is enlarged, and the prepared positive electrode material has more stable structure and better capacity and cycle performance.
Complexing agent ammonia used in traditional precursor synthesis method, which is matched with Fe 2+ The complex effect of Ni, fe and Mn metals is poor, the precipitation pH and solubility product are large, the uneven precipitation is easy to generate, and the chelating agent is added to Fe in the coprecipitation process 2+ Chelating it with Ni 2+ 、Mn 2+ And the problem of uneven distribution of metal elements is solved by coprecipitation.
The invention adds the reducing agent in the preparation of the mixed metal salt solution, uses the chelating agent with reducibility in the precipitation reaction process, and can inhibit Fe 2+ The oxidation of ferric iron is prevented, so that the coprecipitation reaction is more stable, the impurity of the precursor material phase is avoided, and the electrochemical performance of the positive electrode material is further provided.
Drawings
FIG. 1 is a scanning electron microscope image of a precursor of a sodium-electric positive electrode material prepared in example 1 of the present invention.
Fig. 2 is a scanning electron microscope image of a precursor of a sodium-electric positive electrode material prepared in example 2 of the present invention.
Fig. 3 is a scanning electron microscope image of a precursor of a sodium electric positive electrode material prepared in example 3 of the present invention.
Fig. 4 is a scanning electron microscope image of a precursor of the sodium electric positive electrode material prepared in comparative example 1 of the present invention.
Fig. 5 is an XRD pattern of the sodium-electric positive electrode material prepared in example 1 of the present invention.
Fig. 6 is an XRD pattern of the sodium-electric positive electrode material prepared in example 2 of the present invention.
Fig. 7 is an XRD pattern of the sodium-electric positive electrode material prepared in example 3 of the present invention.
Fig. 8 is an XRD pattern of the sodium-electric positive electrode material prepared in comparative example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings and examples.
The invention provides a stable valence element uniformly doped sodium-electricity positive electrode material precursor, wherein the chemical formula of the positive electrode material precursor is Ni x Fe y Mn z M (1-x-y-z) (OH) 2 ，0.10≤x≤0.40，0.20≤y≤0.50，0.20≤z≤0.50，x+y+z<1.00, wherein M is a steady-state metallic element, and M comprises one or more of Ca, mg, zn, cu, zr, ti, sr, ba, sn;
the precursor of the positive electrode material is a ternary structure doped with M element, the content of Ni, fe and Mn serving as main elements is high, the framework of the transition metal layer is composed of three main elements of Ni, fe and Mn, and the type and the content of the Ni, fe and Mn as well as the type and the content of the M influence the interlayer spacing and the unit cell volume of the precursor of the positive electrode material.
The particle morphology of the positive electrode material precursor is spherical or spheroid, the particle diameter D50 of the positive electrode material precursor is 2.80-8.50 mu m, and the tap density of the positive electrode material precursor is 1.20-2.00g/cm 3 The specific surface area of the positive electrode material precursor is 6.00-16.00m 2 /g。
As a more preferable scheme, the particle size D50 of the positive electrode material precursor is 3.50-5.50 mu m, and the tap density of the positive electrode material precursor is 1.40-1.70g/cm 3 The specific surface area of the positive electrode material precursor is 8.00-12.00m 2 /g
Example 1:
the invention provides a preparation method of a stable valence element doped sodium-electricity positive electrode material precursor, which specifically comprises the following steps:
adding nickel sulfate, ferrous sulfate and manganese sulfate crystals into deionized water according to the molar ratio of Ni to Fe to Mn of 1:1:1 to prepare a mixed metal salt solution with the concentration of 2.00mol/L, adding a reducer ethylenediamine tetraacetic acid with the concentration of 0.20mol/L, adding soluble salt magnesium sulfate crystals of doping elements according to 1% of the total molar amount of Ni, fe and Mn metals, heating to 40.00 ℃, stirring at the temperature of 40.00 ℃, and completely dissolving to obtain a final mixed metal salt solution; introducing excessive inert gas to remove dissolved oxygen in the base solution and protect the atmosphere of the reaction kettle so as to prevent metal elements from being oxidized; when a nickel source, an iron source, a manganese source and a soluble salt of a doping element are used, the fact that cations and anions are not combined to form solid precipitates is ensured;
step two, 200.00L of deionized water and 4.00L of 8.00mol/L ammonia water are added into a 500.00L reaction kettle, 10.80mol/L sodium hydroxide solution is slowly added to adjust the pH of the base solution to 11.60, the base solution is heated to 55.00 ℃ and nitrogen is introduced, so that dissolved oxygen in the base solution is removed, and the preparation of the base solution is completed;
step three, in the nucleation stage of coprecipitation reaction, starting a reaction kettle for stirring, starting a temperature control system of the reaction kettle for keeping the temperature in the kettle at 55.00 ℃ unchanged, adding mixed metal salt solution at a flow rate of 10.00L/h, precipitant sodium hydroxide solution at a flow rate of 3.70L/h and complexing agent ammonia water at a flow rate of 1.50L/h into a base solution at the same time, keeping the pH value at 11.60 unchanged, and finely adjusting the flow rate of the sodium hydroxide solution according to pH value fluctuation; after 6 hours, slightly reducing the flow rate of the sodium hydroxide solution to enable the pH value in the reaction kettle to slowly decrease to 11.00, and then starting to enter the coprecipitation reaction growth stage; after the pH value reaches a set value, the flow speed of the mixed metal salt solution is adjusted to 25.00L/h, the flow speed of the precipitant sodium hydroxide solution is adjusted to 9.30L/h, and the flow speed of the complexing agent ammonia water is adjusted to 3.80L/h; meanwhile, when the liquid level in the reaction kettle reaches the position of a feeding hole of the thickener, starting the thickener to concentrate, maintaining the temperature and the pH value of a reaction system unchanged, enabling the particle size D50 of the materials in the reaction kettle to continuously grow, and stopping the reaction when the D50 reaches 5.30 mu m;
step four, adding a proper amount of sodium hydroxide solution after stopping the reaction to adjust the pH value to 12.00, continuously stirring and aging for 3.00 hours, transferring the slurry in the reaction kettle to a filter press for washing, and washing by adopting deionized water at 75.00 ℃ until the Na+ content is reduced to be within 300.00 ppm; carrying out pressure filtration on the slurry by using high-pressure nitrogen to ensure that the water content of a filter cake is less than 15%; transferring the dehydrated filter cake into a blast drying oven, and drying at 120.00 ℃ for 24.00 hours; obtain a precursor Ni of the sodium-electricity positive electrode material 0.33 Fe 0.33 Mn 0.33 Mg 0.01 (OH) 2 The particle size D50 was 5.50. Mu.m.
Fig. 1 is a scanning electron microscope image of a precursor of a sodium-electric positive electrode material according to example 1 of the present invention.
Example 2
The preparation method of the embodiment is basically the same as that of the embodiment 1, the only difference is that the doping element soluble salt is zinc sulfate crystal, and the precursor Ni of the sodium electric positive electrode material is obtained 0.33 Fe 0.33 Mn 0.33 Zn 0.01 (OH) 2 The particle size D50 was 5.40. Mu.m.
Fig. 2 is a scanning electron microscope image of a precursor of a sodium-electric positive electrode material according to example 2 of the present invention.
Example 3
The preparation method of the embodiment is basically the same as that of the embodiment 1, the only difference is that the doping element soluble salt is copper sulfate crystal, and the precursor Ni of the sodium electric positive electrode material is obtained 0.33 Fe 0.33 Mn 0.33 Cu 0.01 (OH) 2 The particle size D50 was 5.30. Mu.m.
Fig. 3 is a scanning electron microscope image of a precursor of a sodium-electric positive electrode material according to example 3 of the present invention.
Comparative example 1
The preparation method of the comparative example is basically the same as that of example 1, except that no doping element is added to obtain the precursor Ni of the sodium-electricity positive electrode material 0.33 Fe 0.33 Mn 0.34 (OH) 2 The particle size D50 was 5.50. Mu.m.
Fig. 4 is a scanning electron microscope image of a sodium-electron positive electrode material precursor of comparative example 1.
The sodium electric positive electrode material precursor prepared by the method of the example and the comparative example and the sodium source are synthesized by a high-temperature solid phase method, wherein the molar ratio of the metal content in the precursor to the sodium source is 0.80-1.08, and the sodium electric positive electrode material is obtained by calcining at 800-980 ℃ for 8-20 hours;
the electrochemical cycle performance of the sodium-electricity positive electrode material was tested by the following method: mixing the sodium-electricity anode material, conductive carbon black and a binder PVDF according to the mass ratio of 80:10:10, adding NMP to prepare uniform slurry, coating the slurry on an aluminum foil, drying, rolling and pressing, and cutting into round pole pieces with the diameter of 14.00 mm. A CR2032 button cell is assembled into a sodium ion cell, a diaphragm is made of glass fiber, electrolyte is NaPF6 solution with solvent of 1.00mol/L of EC/PC/DEC, and a negative plate is made of sodium plate; the sodium ion battery test conditions were: the temperature is 25.00+/-1.00 ℃, the voltage range of charge-discharge cycle is 3.00V-4.00V, the current is 0.10C (140 mAh/g), and the cycle test is carried out according to the charge of 0.50C and the discharge of 1.00C for 100 weeks.
Electrochemical performance test results are shown in table 1:
TABLE 1
The electrochemical performance comparison of the comprehensive examples and the comparative examples shows that the examples doped with the equivalent stable metal elements of Mg, zn and Cu have gram capacities of more than 137mAh/g, the undoped comparative example has 1 gram capacity of only 126mAh/g, and the cycle retention rate is increased by about 8% compared with the comparative examples. In conclusion, under the system of the invention, the metal element with stable valence state is doped in the process of coprecipitation reaction of the precursor, so that the gram capacity and the cycle performance of the sodium-electricity positive electrode material can be obviously improved, and the sodium-electricity positive electrode material has obvious benefits for improving the performance of the sodium-electricity positive electrode material.
The unit cell parameter data after refinement are shown in table 2:
TABLE 2
From fig. 5 to 8, as can be seen from XRD patterns of examples 1, 2, 3 and comparative example 1, the diffraction peak positions of the examples are substantially the same as those of the comparative example sodium-electric positive electrode material, and the partial peak intensity ratio and the newly added diffraction peak are slightly changed due to the difference of doping elements, and the whole has a relatively typical alpha-NaFeO 2 layered structure and a space group R-3m. In the case of the example materials doped with stable valence elements, the cell parameters c are slightly higher than those of the undoped comparative examples, and the cell volumes are also significantly higher than those of the undoped comparative examples. The unit cell volume is increased, which is more favorable for the deintercalation of sodium ions in the charge and discharge process, thereby greatly improving the diffusion rate of sodium ions and improving the capacity, first effect and cycle performance of the anode material.
The Na ratio of the positive electrode material is higher, the prepared sodium-electricity positive electrode material belongs to an O3 phase structure, and sodium ions are easier to be embedded into the material due to the fact that the interlayer spacing and the unit cell volume of the precursor material are larger, so that the positive electrode material with the O3 phase structure is easier to prepare.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (10)
1. A stable valence element uniformly doped sodium-electricity positive electrode material precursor is characterized in that the chemical formula of the positive electrode material precursor is Ni x Fe y Mn z M (1-x-y-z) (OH) 2 ，0.10≤x≤0.40，0.20≤y≤0.50，0.20≤z≤0.50，x+y+z<1.00, wherein M is a steady-state metallic element, and M comprises one or more of Ca, mg, zn, cu, zr, ti, sr, ba, sn.
2. The stable valence element uniformly doped sodium electric positive electrode material precursor according to claim 1, wherein the particle morphology of the positive electrode material precursor is spherical or spheroid, the particle diameter D50 of the positive electrode material precursor is 2.80-8.50 μm, and the tap density of the positive electrode material precursor is 1.20-2.00g/cm 3 The specific surface area of the positive electrode material precursor is 6.00-16.00m 2 /g。
3. A stable elemental homogeneous doped sodium-electrical positive electrode material precursor according to claim 1Characterized in that the particle diameter D50 of the positive electrode material precursor is 3.50-5.50 mu m, and the tap density of the positive electrode material precursor is 1.40-1.70g/cm 3 The specific surface area of the positive electrode material precursor is 8.00-12.00m 2 /g。
4. The preparation method of the sodium-electricity positive electrode material precursor is characterized by comprising the following steps of:
firstly, mixing a nickel source, an iron source, a manganese source, soluble salts of doping elements and a reducing agent, and dissolving the mixture in deionized water to obtain a mixed metal salt solution;
step two, deionized water, a precipitator and a complexing agent are mixed according to a fixed proportion and added into a reaction kettle to obtain a reaction base solution;
step three, adding the mixed metal salt solution, the precipitator, the complexing agent and the chelating agent into the reaction base solution simultaneously according to a proportion for coprecipitation reaction;
and step four, finally, sequentially aging, washing, solid-liquid separation and drying the slurry obtained by the coprecipitation reaction to obtain a precursor of the sodium electric anode material.
5. The method for preparing a precursor of a sodium-electricity positive electrode material according to claim 4, wherein,
the concentration of the mixed metal salt solution is 1.50-2.50mol/L, and the concentration of the reducing agent is 0.10% -5.00% of the concentration of the mixed metal salt solution;
the precipitant is one of sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate, and the concentration of the precipitant is 8.50-12.50mol/L;
the complexing agent comprises at least one of ammonia water, ammonium bicarbonate, ammonium chloride, ammonium sulfate, ammonium acetate and ammonium oxalate, and the concentration of the complexing agent is 6.00-10.50mol/L;
the chelating agent comprises at least one of ethylenediamine tetraacetic acid, aminotrimethylene phosphonic acid, sodium gluconate, sodium pyrophosphate, citric acid, sodium citrate, oxalic acid, triethanolamine, sodium tripolyphosphate and hydroxyethylidene diphosphonic acid.
6. The method for preparing a precursor of a sodium-electricity positive electrode material according to claim 4, wherein in the third step:
the coprecipitation reaction includes a preceding nucleation stage and a subsequent growth stage;
the reaction time in the nucleation stage is 0-9.00h, the precipitation pH is 10.90-11.70, and the particle size D50 of the terminated material is 1.50-2.50 mu m;
the reaction time of the growth stage is 9.00-180.00h, the pH of the sediment is 10.10-10.90, and the reaction termination time depends on the set target of the material particle diameter D50 to be 2.80-8.50 mu m.
7. The method according to claim 4, wherein in the fourth step, deionized water at 65.00-75.00 ℃ is used for washing, and the washing end point is Na or K content less than 200.00ppm.
8. The method according to claim 4, wherein in the fourth step, the drying temperature is 100.00-180.00 ℃, the drying time is 10.00-24.00h, and the drying is performed until the water content of the material is less than 6000.00ppm.
9. The method for preparing a precursor of a sodium-electricity positive electrode material according to any one of claims 4 to 8, wherein in the third step:
the coprecipitation reaction is carried out under a high-speed stirring system, the rotating speed is 300.00-650.00rpm, the temperature is 40.00-75.00 ℃, the pH value is 10.10-11.70, and NH is used 3 The calculated ammonia concentration is 2.50-7.00g/L, and the reaction time is 90-180.00h;
in the coprecipitation reaction process, the slurry in the reaction kettle is filtered by a thickener, mother liquor is discharged out of the reaction kettle, the intercepted slurry with high solid content flows back to the reaction kettle to continue to participate in the reaction, and the solid content of the slurry is 15-70% when the coprecipitation reaction is finished;
the coprecipitation reaction is carried out under the protection of inert gas, wherein the inert gas comprises at least one of nitrogen, helium and argon;
in the coprecipitation reaction process, the flow of the mixed metal salt is 1.60 percent/h-8.00 percent/h of the effective volume of the reaction kettle, and the flow of the precipitant is 0.60 percent/h-3.20 percent/h of the effective volume of the reaction kettle.
10. A sodium-electricity positive electrode material, which is characterized in that the sodium-electricity positive electrode material precursor which is uniformly doped with stable valence elements and a sodium source are synthesized by a high-temperature solid phase method, the synthesis temperature is 800.00-980.00 ℃, and the calcination time is 8.00-20.00h;
wherein the molar ratio of the metal element content to sodium in the precursor is 0.80-1.08.
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| CN118387944A (en) * | 2024-06-26 | 2024-07-26 | 浙江帕瓦新能源股份有限公司 | Sodium ion battery positive electrode precursor material and preparation method thereof |
| CN118666318A (en) * | 2024-08-23 | 2024-09-20 | 深圳市贝特瑞新能源技术研究院有限公司 | Precursor material of P2 type five-membered positive electrode, and preparation method and application thereof |
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| CN116282228A (en) * | 2023-03-27 | 2023-06-23 | 荆门市格林美新材料有限公司 | Sodium ion precursor material and preparation method and application thereof |
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| CN116282228A (en) * | 2023-03-27 | 2023-06-23 | 荆门市格林美新材料有限公司 | Sodium ion precursor material and preparation method and application thereof |
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