CN115714175A - Sodium ion battery positive electrode material and preparation method thereof - Google Patents
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Abstract
The invention belongs to the technical field of electrochemistry, and discloses a sodium-ion battery anode material and a preparation method thereof, wherein the molecular general formula of the anode material is NaNi0.3Fe0.4-m-nM0.3XmYnO2. The positive electrode material is a Ni, fe and Mn ternary sodium ion battery positive electrode material doped with a trace element X and coated with an element Y. The precursor particles are flaky, and after primary sintering, the particles are spherical-like particles formed by crossed or overlapped flaky shapes. The anode after secondary sintering is uniform spheroidal particles, and has less micro powder and excellent processing performance. In addition, the X, Y element is doped and coated, so that the stability of the crystal structure is improved, and the cycle performance is obviously improved.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and relates to a sodium-ion battery positive electrode material and a preparation method thereof.
Background
The cost and pressure of lithium ion batteries are increased due to the consumption of lithium sources and insufficient abundance of earth crust. Although the energy density of the sodium ion battery is lower than that of the lithium ion battery, the sodium ion battery can be used as a beneficial supplement of the lithium battery due to the rich storage capacity of the Na source and the processing mode similar to the lithium battery.
The sodium-electricity positive electrode plays a decisive role in the electrochemical performance of the battery, and the current layered transition metal oxide NaxMeO2 (Me represents Ni, co, fe, mn and the like) has the highest theoretical specific capacity which can reach 200 mAh.g -1 . However, the structural stability of the material is inferior to that of polyanionic compounds and prussian blue materials, which mainly means that Mn < 3+ > in the system can bring Jahn-Teller effect, so that more phase change occurs in the charging and discharging process, and Na < + > is continuously embedded and removed, so that the crystal structure is gradually damaged, and the cycle performance is greatly reduced. In order to take capacity and stability into consideration, people develop researches on how to improve the electrical property of the layered sodium. For example, in chinese patent CN112467119a, in order to exert synergistic effects of different elements, fe2O3, niO, co3O4, snO2, ti2O are used as main metals, and then Li2Co3 is doped, and finally Na2Co3 is mixed for sintering to obtain the layered high-entropy sodium-electricity positive electrode material. But compared with the lithium battery, the preparation cost advantage is not obvious, and the improvement of the electrochemical performance is limited. Also, as in chinese patent CN112234200, O3 type namn0.5ni0.5o2 is doped with a specific trivalent metal cation (Y3 +, la3+, ac3+, ca3+, or Sc3 +) by combustion methodAt least one) to suppress structural distortion during charge and discharge. However, the shape and physical and chemical characteristics of the precursor prepared by the method are uncontrollable, and the particle uniformity and the processing performance are unstable. Patent CN112374551A prepares M1-x-yFexMny (OH) 2 type precursor (M is Ni2+, ca2+, mg2+, zn2+, co3+, ag +, etc.) by liquid phase synthesis, and then obtains more uniform layered oxide by calcining.
In a plurality of patent researches, sodium-electricity doping and coating are rarely carried out by using a coprecipitation method to improve the material performance, doping elements are often used as main elements to be synthesized or calcined, the cost of some elements is not low, and the performance when a small amount of doping is carried out is not related.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a positive electrode material of a sodium-ion battery and a preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a sodium ion battery anode material with a molecular general formula of NaNi 0.3 Fe 0.4-m-n Mn 0.3 XmYnO 2 Wherein m + n is more than or equal to 0.02 and less than or equal to 0.08, X is one or more of Mg, zr, zn, cr, V and Nb, and Y is one or more of Cu, al, ti, sn and Li.
Further, preferably, in terms of mole ratio, ni: fe: mn: x: y =3:3.4:3:0.4:0.2.
based on a general inventive concept, the present application also provides a preparation method of the positive electrode material of the sodium-ion battery, comprising the following steps:
preparing a salt solution, wherein the salt solution comprises a Ni salt solution, a Fe salt solution, a Mn salt solution, an X salt solution and a Y salt solution;
step two, preparing a precipitator, wherein the precipitator is a sodium hydroxide solution or an ammonium phosphate solution;
preparing a complexing agent solution, wherein the complexing agent solution comprises an ammonia water solution, a sodium citrate solution and an EDTA-2Na solution;
injecting pure water into the reaction kettle, starting stirring, heating to 45-65 ℃, and introducing nitrogen to form an inert atmosphere;
adding a precipitator and at least one complexing agent solution into the reaction kettle to enable the pH value of a solution system in the reaction kettle to reach 10.5-11.5 and the total concentration of the complexing agent to be 0.05-0.5mol/L;
step six, respectively and uniformly introducing a salt solution, a precipitator and a complexing agent into the reaction kettle according to the requirements of the coprecipitation reaction, wherein the flow rates are set according to the proportion;
seventhly, stopping feeding when the reaction is carried out for 30-50h, reducing the stirring speed, and keeping the constant temperature for 2h; then stirring and recovering the original rotating speed, and then introducing the Y salt solution, the complexing agent solution and the precipitating agent into the reaction kettle at a certain flow rate; stopping feeding when the coating amount of the Y salt solution meets the design requirement, and then reducing the stirring rotating speed for aging;
step eight, performing solid-liquid separation on the aged slurry, and treating solid precipitates to obtain precursor particles;
step nine, mixing the precursor and Na by using a high-efficiency mixer 2 CO 3 Uniformly mixing in a ratio of 1:1-1;
placing the mixed materials in an atmosphere sintering furnace for primary sintering, wherein the heating rate in the primary sintering is 2-4 ℃/min, the air flow is 300-1000L/h, and the temperature is kept at 700-850 ℃ for 10-15h; cooling to room temperature, taking out, grinding, air breaking and screening;
step eleven, performing secondary sintering on the sieve-blanking material obtained in the step eleven, placing the sieve-blanking material in an atmosphere sintering furnace, setting the heating rate to be 2-4 ℃/min and the air flow to be 300-1000L/h, and sequentially preserving heat for 10-15h at the temperature of 750-900 ℃; cooling to room temperature, taking out, grinding, air breaking and screening; and obtaining a finished product.
Further, preferably, the ternary salt solution is 1.8-2mol/L sulfate, and the X salt and the Y salt are 0.1-1mol/L sulfate or chloride respectively.
Further, preferably, in the second step, the concentration of the sodium hydroxide solution is 4-10mol/L, and the concentration of the ammonium phosphate solution is 1.5-2.5mol/L.
Further, preferably, in the third step, the concentration of the ammonia water solution is 4-10mol/L, the concentration of the sodium citrate solution is 1-3mol/L, and the concentration of the EDTA-2Na solution is 0.1-0.3mol/L.
Further, preferably, in the fourth step, the stirring speed is 600-900rpm; in the seventh step, the reduced stirring speed is 300-600rpm.
Further, preferably, in the eighth step, the solid precipitate obtained by the solid-liquid separation is washed, dried and sieved.
Based on a general inventive concept, the present application also provides a sodium ion battery having a positive electrode made of the above positive electrode material, or made of the positive electrode material prepared by the above preparation method.
Compared with the prior art, the invention has the advantages and positive effects that:
1. no cobalt and less nickel, a small amount of doping and coating elements, all raw materials are soluble salts, nano-scale oxides are not needed, and the raw material cost is low;
2. the precursor and the anode material are uniform spheroidal particles, the micro powder is less and easy to process, the raw material yield is improved, and the processing cost is reduced;
3. the doping and cladding are completed in the synthesis stage of the precursor, the doping is more uniform, the cladding degree is more complete, the electrochemical performance of the material is effectively improved, and at least one section of sintering process can be reduced;
4. the invention is based on low cost, and aims at capacity and cycle performance, and the method of coprecipitation and two-stage sintering is used to prepare the anode material with low raw material and processing cost and good cycle performance.
The cathode material is a Ni, fe and Mn ternary sodium-ion battery cathode material doped with trace elements X (one or more of Mg, zr, zn, cr, V and Nb) and coated with Y (one or more of Cu, al, ti, sn and Li). The primary particles of the precursor are flaky, and the secondary particles are spherical-like particles formed by crossed or overlapped flaky shapes. The secondary sintering finished product is uniform spheroidal particles, less micro powder and excellent processing performance. The stability of the crystal structure is improved by doping and cladding, and the cycle performance is obviously improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an electron microscope image of a precursor in example 1 of the present invention;
FIG. 2 is an electron microscope image of the material after one sintering in example 1 of the present invention;
FIG. 3 is an electron microscope image of the material after the second sintering in example 1 of the present invention;
FIG. 4 is a cycle chart of the rate test in example 1 of the present invention;
FIG. 5 is an electron microscope image of the material after the second sintering in example 2 of the present invention;
FIG. 6 is a cycle chart of the magnification test in example 2 of the present invention;
FIG. 7 is an electron microscope image of the material after the secondary sintering of comparative example 1 of the present invention;
FIG. 8 is a graph showing the cycle of the magnification test of comparative example 1 according to the present invention;
FIG. 9 is an electron microscope image of the material after the secondary sintering of comparative example 2 of the present invention;
FIG. 10 is a graph showing the cycle of the rate test of comparative example 2 according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention; the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance, and furthermore, unless otherwise explicitly stated or limited, the terms "mounted," "connected," and "connected" are to be construed broadly and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Example 1
A preparation method of a sodium ion battery anode material, the molecular general formula of the anode material is NaNi0.3Fe0.4-m-nM0.3XmYnO2, wherein m + n is more than or equal to 0.02 and less than or equal to 0.08, and the preparation method comprises the following steps:
step one, preparing a composite material according to a molar ratio of Ni: fe: mn: x: y =3:3.4:3:0.4: weighing salt raw materials in a proportion of 0.2;
respectively preparing Ni, fe and Mn ternary salt solutions of nickel sulfate, manganese sulfate and ferrous sulfate with the total concentration of 2mol/L by using pure water, wherein a mixed salt solution of zirconium oxychloride and magnesium sulfate with the total concentration of 0.5mol/L is an X salt, and a mixed salt solution of titanium tetrachloride and lithium sulfate with the total concentration of 0.5mol/L is a Y salt;
step two, preparing a precipitator, wherein the precipitator is 8mol/L sodium hydroxide solution and 2mol/L ammonium phosphate solution;
and step three, preparing a complexing agent solution, wherein the complexing agent solution comprises 4mol/L ammonia water solution and 2mol/L sodium citrate solution.
Step four, injecting 40% pure water into the reaction kettle, starting stirring at 850rpm, heating to 55 ℃, and then blowing N with the purity of 99.99% into the kettle 2 Gas;
step five, after the nitrogen is blown in for 2 hours, adding a sodium hydroxide precipitator, an ammonia water solution and a sodium citrate solution into the reaction kettle, so that the pH value of a solution system in the reaction kettle reaches 11.0 +/-0.1, the concentration of the ammonia water solution reaches 0.1mol/L, and the concentration of the sodium citrate solution reaches 0.05mol/L;
setting the ternary salt solution to be 4L/h and the X salt solution to be 1.02L/h according to the proportion requirement; setting the flow of the complexing agent ammonia water solution according to growth requirements, and keeping the ammonia concentration of the reaction kettle at 2-3g/L; setting the flow of the complexing agent sodium citrate solution to maintain the concentration of the reaction kettle at 0.05-0.1mol/L; setting the flow rate of the precipitant to maintain the pH value of the reaction kettle at 10.8-11.0; uniformly pumping the solution into a reaction kettle by using a metering pump to perform coprecipitation synthesis reaction, and discharging a mother solution by using a thickener in the reaction process;
step seven, stopping feeding when the reaction is carried out for 40 hours, reducing the stirring rotating speed to 600rpm, and keeping the constant temperature for 2 hours; then stirring and recovering the original rotating speed to 850rpm, introducing Y salt solution at the flow rate of 2L/h, stopping introducing the complexing agent solution, and changing the precipitator into ammonium phosphate solution, so that the ammonia value in the reaction kettle is maintained at 6-8g/L; stopping feeding when the coating amount of the Y salt solution meets the design requirement, and then reducing the stirring rotating speed to 600rpm for aging;
step eight, performing solid-liquid separation on the aged slurry, and washing, drying and screening solid precipitates to obtain a precursor; the electron microscope image of the precursor is shown in FIG. 1;
step nine, precursor particles and Na 2 CO 3 Uniformly mixing the materials in a mixer according to the proportion of 1.05;
placing the mixed materials in a sagger, placing the sagger in an atmosphere sintering furnace for primary sintering, wherein the heating rate in the primary sintering is 3 ℃/min, the air flow is 1000L/h, and the temperature is kept at 750 ℃ for 12h; cooling to room temperature, taking out, grinding, air breaking and screening; the electron microscope image of the material after primary sintering is shown in FIG. 2;
step eleven, performing secondary sintering on the sieve-blanking material obtained in the step eleven, placing the sieve-blanking material in an atmosphere sintering furnace, setting the heating rate to be 2-4 ℃/min and the air flow to be 1000L/h, and preserving heat for 12h at 800 ℃; cooling to room temperature, taking out, grinding, gas breaking and sieving; and obtaining a finished product. The electron microscope image of the material after the second sintering is shown in FIG. 3.
Example 2
A preparation method of a sodium ion battery anode material is disclosed, the molecular general formula of the anode material is NaNi0.3Fe0.4-m-nM0.3XmYnO2, wherein m + n is more than or equal to 0.02 and less than or equal to 0.08, and the method comprises the following steps:
step one, preparing a composite material according to a molar ratio of Ni: fe: mn: x: y =3:3.96:3:0.2: weighing salt raw materials in a proportion of 0.2;
preparing nickel sulfate, manganese sulfate, ni, fe and Mn ternary salt solution of ferrous sulfate, zirconium oxychloride, X salt solution of magnesium sulfate, titanium tetrachloride and Y salt solution of lithium sulfate with the total concentration of 2mol/L, respectively by using pure water;
the other steps two to eleven are the same as in example 1.
An electron microscope image of the material after the second sintering in this example is shown in FIG. 5.
Comparative example 1
A preparation method of a positive electrode material of a sodium-ion battery comprises the following steps:
step one, preparing a composite material according to a molar ratio of Ni: fe: mn =3:4:3, weighing salt raw materials in proportion;
preparing Ni, fe and Mn ternary salt solution of nickel sulfate, manganese sulfate and ferrous sulfate with the total concentration of 2mol/L by using pure water;
step two, preparing a precipitator, wherein the precipitator is 8mol/L sodium hydroxide solution;
and step three, preparing a complexing agent solution, wherein the complexing agent solution comprises 4mol/L ammonia water solution and 2mol/L sodium citrate solution.
Injecting 40% pure water by volume into the reaction kettle, starting stirring at 850rpm, heating to 55 ℃, and then blowing N2 gas with the purity of 99.99% into the kettle;
step five, after the nitrogen is blown in for 2 hours, adding a sodium hydroxide precipitator, an ammonia water solution and a sodium citrate solution into the reaction kettle, so that the pH value of a solution system in the reaction kettle reaches 10.8-11.0, the concentration of the ammonia water solution reaches 0.1mol/L, and the concentration of the sodium citrate solution reaches 0.05mol/L;
step six, setting the ternary salt solution to be 4L/h according to the proportion requirement; setting the flow of the complexing agent ammonia water solution according to growth requirements, and keeping the ammonia concentration of the reaction kettle at 2-3g/L; setting the flow of the complexing agent sodium citrate solution to maintain the concentration of the sodium citrate solution in the reaction kettle at 0.05-0.1mol/L; setting the flow rate of the precipitant to maintain the pH value of the reaction kettle at 10.8-11.0; uniformly pumping the solution into a reaction kettle by using a metering pump to perform coprecipitation synthesis reaction, and discharging mother liquor by using a thickener in the reaction process; (ii) a
Step seven, stopping feeding when the reaction is carried out for 40 hours, reducing the stirring rotating speed to 600rpm, and keeping the constant temperature for 2 hours for aging;
step eight, performing solid-liquid separation on the aged slurry, and washing, drying and screening solid precipitates to obtain a precursor;
the other steps nine to ten are the same as in example 1.
An electron micrograph of the post-secondary sintering material of this comparative example is shown in FIG. 7.
Comparative example 2
Sintering according to the proportion of example 1 to prepare the nano-sized or micro-sized Na 2 CO 3 、NiO、Fe 2 O 3 、Mn 2 O 3 ，MgO、ZrO 2 Placing the mixture in a ball mill for mixing, placing the mixture in an atmosphere furnace for heat preservation for 12 hours at 750 ℃; cooling, crushing and screening; then, the second-stage sintering is carried out at 800 ℃, and the temperature is kept for 12 hours.
After crushing and screening the materials after the secondary sintering, tiO2 and Li2CO3 are added according to the proportion in the embodiment 1 and fully mixed in a mixer. Then the material is placed in an atmosphere furnace and kept at 400 ℃ for 12h. And cooling, crushing and screening.
An electron micrograph of the post-secondary sintering material of this comparative example is shown in FIG. 9.
Experimental detection of
The finished products of the cathode materials in the embodiments 1 and 2 and the comparative examples 1 and 2 are mixed with PVDF glue solution, SP powder conductive agent and a certain amount of NMP dispersing agent in a homogenizer to form active substances. And coating the prepared active substance slurry on an aluminum foil, drying and cutting into a positive pole piece with the diameter of 12 mm. And then, using glass fiber as a diaphragm, using a mixed solution of DMC, EMC, EC, naPF6 and FEC in a certain molar ratio as an electrolyte, and using a sodium sheet with the diameter of 14mm as a negative electrode to manufacture a 2032 type button cell. The manufactured buckling capacitor is placed in a blue light test system for electrochemical test, the charging and discharging voltage is selected to be 2.0-4.0V, the multiplying power is selected to be 0.1-2C, and the test temperature is 25 ℃. The 2-magnification test cycle diagrams of example 1, example 2, comparative example 1 and comparative example 2 are shown in fig. 4, 6, 8 and 10, respectively.
Table 1:
all other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments of the present invention, should be included in the protection scope of the present invention.
Claims (8)
1. A positive electrode material of a sodium-ion battery is characterized in that: the general formula of the anode material molecule is NaNi 0.3 Fe 0.4-m- n Mn 0.3 X m Y n O 2 Wherein m + n is more than or equal to 0.02 and less than or equal to 0.08, X is one or more of Mg, zr, zn, cr, V and Nb, and Y is one or more of Cu, al, ti, sn and Li.
2. The positive electrode material for sodium-ion batteries according to claim 1, characterized in that: in terms of mole ratio, ni: fe: mn: x: y =3:3.4:3:0.4:0.2.
3. a preparation method of a sodium ion battery positive electrode material is characterized by comprising the following steps: the method comprises the following steps:
preparing a salt solution, wherein the salt solution comprises a Ni salt solution, a Fe salt solution, a Mn salt solution, an X salt solution and a Y salt solution;
step two, preparing a precipitator, wherein the precipitator is a sodium hydroxide solution or an ammonium phosphate solution;
preparing a complexing agent solution, wherein the complexing agent solution comprises an ammonia water solution, a sodium citrate solution and an EDTA-2Na solution;
injecting pure water into the reaction kettle, starting stirring, heating to 45-65 ℃, and introducing nitrogen to form an inert atmosphere;
adding a precipitator and at least one complexing agent solution into the reaction kettle to enable the pH value of a solution system in the reaction kettle to reach 10.5-11.5 and the total concentration of the complexing agent to be 0.05-0.5mol/L;
step six, respectively and uniformly introducing a salt solution, a precipitator and a complexing agent into the reaction kettle according to the requirements of the coprecipitation reaction, wherein the flow rates are set according to the proportion;
seventhly, stopping feeding when the reaction is carried out for 30-50h, reducing the stirring speed, and keeping the constant temperature for 2h; then stirring and recovering the rotating speed, and then introducing the Y salt solution, the complexing agent solution and the precipitator into the reaction kettle at a certain flow rate; stopping feeding when the coating amount of the Y salt solution meets the design requirement, and then reducing the stirring rotating speed for aging;
step eight, performing solid-liquid separation on the aged slurry to form a filter cake, and treating the filter cake into precursor particles;
step nine, mixing the precursor and Na in a high-efficiency mixer 2 CO 3 Uniformly mixing in a ratio of 1:1-1;
placing the mixed materials in the step ten and the step nine into an atmosphere sintering furnace for primary sintering, wherein the heating rate in the primary sintering is 2-4 ℃/min, the air flow is 300-1000L/h, and the temperature is kept at 700-850 ℃ for 10-15h; cooling to room temperature, taking out, grinding, air breaking and screening;
step eleven, performing secondary sintering on the sieve material obtained in the step eleven, placing the sieve material in an atmosphere sintering furnace, setting the heating rate to be 2-4 ℃/min, setting the air flow to be 300-1000L/h, and keeping the temperature at 750-900 ℃ for 10-15h; cooling to room temperature, taking out, grinding, air breaking and screening; and obtaining a finished product.
4. The method for preparing the positive electrode material of the sodium-ion battery according to claim 3, wherein the method comprises the following steps: the ternary salt solution is 1.8-2mol/L sulfate, and the X salt and the Y salt are 0.1-1mol/L sulfate or chloride respectively.
5. The method for preparing the positive electrode material of the sodium-ion battery according to claim 3, wherein the method comprises the following steps: in the second step, the concentration of the sodium hydroxide solution is 4-10mol/L, and the concentration of the ammonium phosphate is 1.5-2.5mol/L.
6. The method for preparing the positive electrode material of the sodium-ion battery according to claim 3, wherein the method comprises the following steps: in the third step, the concentration of the ammonia water solution is 4-10mol/L, the concentration of the sodium citrate solution is 1-3mol/L, and the concentration of the EDTA-2Na solution is 0.1-0.3mol/L.
7. The method for preparing the positive electrode material of the sodium-ion battery according to claim 3, wherein the method comprises the following steps: in the fourth step, the stirring speed is 600-900rpm; in step seven, the reduced stirring speed is 300-600rpm.
8. The preparation method of the positive electrode material of the sodium-ion battery according to claim 3, characterized by comprising the following steps: and step eight, washing, drying and sieving the solid precipitate obtained by solid-liquid separation.
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| CN116332244A (en) * | 2023-03-08 | 2023-06-27 | 江苏传艺科技股份有限公司 | Nickel-iron-manganese sodium ion battery positive electrode material and preparation method thereof |
| CN116443955A (en) * | 2023-06-14 | 2023-07-18 | 宜宾光原锂电材料有限公司 | Nickel-iron-copper-manganese precursor, preparation method thereof, positive electrode material and battery |
| CN117342630A (en) * | 2023-12-04 | 2024-01-05 | 宜宾锂宝新材料有限公司 | Sodium ion positive electrode material, preparation method thereof, positive electrode plate and sodium battery |
| WO2024178917A1 (en) * | 2023-02-27 | 2024-09-06 | 荆门市格林美新材料有限公司 | Metal-ion-doped and sodium-lithium-aluminum-titanium-phosphate-coated sodium-ion battery positive electrode material, preparation method therefor, and use thereof |
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- 2022-12-02 CN CN202211535969.XA patent/CN115714175A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024178917A1 (en) * | 2023-02-27 | 2024-09-06 | 荆门市格林美新材料有限公司 | Metal-ion-doped and sodium-lithium-aluminum-titanium-phosphate-coated sodium-ion battery positive electrode material, preparation method therefor, and use thereof |
| CN116332244A (en) * | 2023-03-08 | 2023-06-27 | 江苏传艺科技股份有限公司 | Nickel-iron-manganese sodium ion battery positive electrode material and preparation method thereof |
| CN116443955A (en) * | 2023-06-14 | 2023-07-18 | 宜宾光原锂电材料有限公司 | Nickel-iron-copper-manganese precursor, preparation method thereof, positive electrode material and battery |
| CN116443955B (en) * | 2023-06-14 | 2023-09-26 | 宜宾光原锂电材料有限公司 | Nickel-iron-copper-manganese precursor, preparation method thereof, positive electrode material and battery |
| CN117342630A (en) * | 2023-12-04 | 2024-01-05 | 宜宾锂宝新材料有限公司 | Sodium ion positive electrode material, preparation method thereof, positive electrode plate and sodium battery |
| CN117342630B (en) * | 2023-12-04 | 2024-02-23 | 宜宾锂宝新材料有限公司 | Sodium ion positive electrode material, preparation method thereof, positive electrode plate and sodium battery |
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