CN116130617A - Carbon-coated sodium ion layered oxide positive electrode material and preparation method thereof - Google Patents

Carbon-coated sodium ion layered oxide positive electrode material and preparation method thereof Download PDF

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CN116130617A
CN116130617A CN202211442604.2A CN202211442604A CN116130617A CN 116130617 A CN116130617 A CN 116130617A CN 202211442604 A CN202211442604 A CN 202211442604A CN 116130617 A CN116130617 A CN 116130617A
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carbon
sodium
positive electrode
sodium ion
electrode material
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盛鹏
李圣驿
徐丽
薛晴
王博
李慧
张翀
闵红
陈哲
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Beijing Smart Energy Research Institute
North China Electric Power University
State Grid Shanghai Electric Power Co Ltd
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Beijing Smart Energy Research Institute
North China Electric Power University
State Grid Shanghai Electric Power Co Ltd
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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
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H—ELECTRICITY
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    • 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
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
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    • 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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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H01M4/52—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
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    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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Abstract

The invention discloses a carbon material coated sodium ion layered oxide anode material, the chemical expression is Na x TMO 2 Carbon material. The carbon material is uniformly coated on the layered metal oxide Na x TMO 2 Wherein the carbon material is at least one of graphene, carbon nanotubes and porous conductive carbon; TM is at least one of Ni, mn and Ti. The invention obtains the layered oxide material through one-time high-temperature sintering, and then the obtained layerThe shaped oxide material and the coating material are fully and integrally coated by a fusion coating machine, so that the carbon material coated anode material with excellent electrochemical performance is obtained. The preparation method is simple, the material cost is low, and the cycle stability and the multiplying power performance of the layered anode material are effectively improved.

Description

Carbon-coated sodium ion layered oxide positive electrode material and preparation method thereof
Technical Field
The invention belongs to the field of chemical power supplies, and relates to a sodium ion battery anode material, in particular to a carbon material coated sodium ion battery layered anode material and a preparation method thereof.
Background
With the rapid development of the large-scale energy storage field in the last decade, the application of lithium ion batteries is more and more extensive, and the development of lithium resources is severely restricted due to the fact that the lithium resources are extracted in large quantities and the problem of uneven distribution of the lithium resources in the global scope is caused. In contrast, sodium resources similar to lithium in physicochemical properties are abundant and widely distributed, so sodium ion batteries are expected to gradually replace lithium ion batteries in the field of large-scale energy storage.
The positive electrode material of the sodium ion battery is used as a key component for forming the sodium ion battery, so that the practical application of the sodium ion battery is limited to a great extent in terms of performance, a great deal of research work is carried out on the positive electrode material of the sodium ion battery by researchers, and the positive electrode material mainly researched at present comprises layered transition metal oxide, polyanion compound, prussian blue analogue, organic material and the like.
Among the positive electrode materials of many sodium ion batteries, the layered oxide has the advantages of simple preparation, high capacity, environmental friendliness and wide raw materials. However, most of the sodium ion layered oxides have various problems such as capacity decrease, structural stability deterioration, dissolution of transition metal, corrosion of electrolyte, etc. during charge and discharge, which limit further commercialization applications. The protective layer is coated on the surface of the layered oxide, which is a technology frequently adopted at the present stage, and the coating layer can relieve the corrosion of electrolyte to the surface of the material in the material circulation process, reduce the dissolution of transition metal ions, and further improve the circulation stability and the rate capability of the anode material.
CN107026267a discloses a preparation method of a carbon-coated ternary material, which comprises the steps of preparing a three-dimensional flower-shaped porous carbon material, and filling the ternary material into carbon gaps to obtain the carbon-coated positive electrode material. However, the preparation process of the method is complicated and difficult to operate, and is not suitable for large-scale preparation. CN104900869a discloses a preparation method of a carbon-coated nickel-cobalt-aluminum ternary cathode material, which comprises the steps of uniformly mixing a cathode material, an organic carbon source and a catalyst, and calcining under the protection of inert gas, so as to obtain the required carbon-coated cathode material. The method needs to be subjected to heat treatment under inert gas, is easy to generate other side reactions in the presence of reducing organic matters, and is not beneficial to large-scale preparation in the industrialization process.
In view of the above, development of a preparation method of a carbon-coated sodium ion positive electrode material which is simple in process and suitable for industrial production has important significance for development of sodium ion batteries.
Disclosure of Invention
In order to solve the defects in the aspects of the performance and the preparation method of the prior sodium ion battery anode material, the invention provides the carbon-coated sodium ion layered oxide anode material and the preparation method thereof, wherein the preparation method is simple, the material cost is low, and the cycle stability and the multiplying power performance of the layered anode material are effectively improved.
In order to achieve the above object, the present invention provides the following technical solutions:
in one aspect, the invention provides a carbon-coated sodium ion layered oxide positive electrode material, the chemical expression of which is Na x TMO 2 Carbon material.
The carbon material is at least one of graphene, carbon nano tube and porous conductive carbon, and is uniformly coated on the layered oxide Na x TMO 2 Is a surface of the substrate.
TM is at least one of transition metals Ni, mn and Ti, and x is 2/3 to 1.
Further, x is 2/3 or 1; when x is 2/3, the layered positive electrode material is shown to be in a P2 phase structure; when x is 1, it indicates that the layered cathode material has an O3 phase structure.
Further, TM is Ni 0.5 Mn 0.5-n Ti n The method comprises the steps of carrying out a first treatment on the surface of the Wherein n is more than or equal to 0 and less than or equal to 0.5;
further, TM is Ni 0.5 Mn 0.3 Ti 0.2 ；
Further, the sodium ion layered oxide positive electrode material is O3-NaNi 0.5 Mn 0.3 Ti 0.2 O 2 。
The sodium ion layered oxide anode material has less phase change, good structural reversibility, higher capacity and excellent cycling stability.
Further, the carbon coating layer has a thickness of 5 to 30nm, preferably 10 to 15nm.
The thickness of the coating layer needs to be proper, and when the coating layer is too thick, the specific capacity is attenuated, and when the coating layer is too thin, the circulation is not greatly improved.
The surface of the conventional sodium ion battery layered oxide positive electrode material is not provided with a protective layer, so that the surface of the material is corroded by electrolyte in the circulating process, the surface of the material is damaged, transition metal ions are dissolved out, and the electrochemical performance is reduced. According to the invention, the carbon material is coated on the surface of the layered oxide, so that the protection effect can be achieved, the conductivity of the material can be improved, and the performance can be improved.
In another aspect, the invention provides a method for preparing the carbon-coated sodium ion layered oxide cathode material, comprising the following steps:
s1: source material mixing: the sodium source and the transition metal TM source are fed according to the stoichiometric ratio, wherein the sodium source is fed according to 102-120% of the stoichiometric ratio, and the sodium source and the transition metal TM source are ground and mixed uniformly to form a mixture;
further, the sodium source is at least one selected from sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium oxide and sodium peroxide; sodium carbonate is preferred;
further, the TM source is selected from at least one of an oxide, sulfate, nitrate, carbonate, acetate, oxalate, and a hydrated compound thereof of TM;
and feeding the sodium source and the transition metal TM source according to the stoichiometric ratio determined by the structural general formula, wherein the feeding ratio of the sodium source material is 102-120% of the stoichiometric ratio, and ball milling and mixing uniformly to form a mixture.
S2: sintering of the positive electrode material: calcining the mixture obtained in the step S1 in a muffle furnace, heating to 600-1000 ℃, preserving heat for 12-48h, and cooling to room temperature to obtain layered metal oxide Na x TMO 2 ；
Further, the calcining atmosphere is at least one of oxygen and air, the heating rate is 1-10 ℃/min, and the cooling rate during cooling is 1-10 ℃/min.
S3: coating of positive electrode material: and (3) fully and integrally coating the layered metal oxide and the carbon material obtained in the step (S2) in a fusion coating machine.
Further, the carbon material is at least one of graphene, carbon nanotubes and porous conductive carbon.
Further, the carbon material accounts for 0.1% -10% of the total mass, preferably 0.5% -2%.
Further, the working conditions of the fusion coating machine are as follows: and (3) putting the layered metal oxide obtained in the step (S2) and the carbon material into a fusion coating machine, wherein the rotating speed is 800-2000rpm.
The inventor surprisingly found that the carbon material is used as a coating layer, and the fusion coating machine is used for coating, so that the carbon material can be better uniformly coated on the surface of the positive electrode particles, thereby being beneficial to constructing a three-dimensional conductive network, improving conductivity and inhibiting interface reaction.
In still another aspect, the invention provides a sodium ion battery positive electrode material, which is prepared from the carbon-coated sodium ion layered oxide positive electrode material.
Further, the preparation raw materials of the sodium ion battery anode material also comprise a conductive agent and a binder; the mass ratio of the carbon-coated sodium ion layered oxide positive electrode material to the conductive agent to the binder is 6-9:0.5-2:0.5-2, preferably 8-9:0.5-1:0.5-1.
Further, the conductive agent includes, but is not limited to, at least one of acetylene black, VGCF, SP, CNT, graphite.
Further, the binder includes, but is not limited to, at least one of polyvinylidene fluoride, polyvinyl alcohol, polytetrafluoroethylene, and sodium carboxymethyl cellulose.
The sodium ion battery anode material can be prepared by adopting a conventional method in the art, for example, the carbon-coated sodium ion layered oxide anode material, the conductive agent and the binder are mixed and dissolved in a solvent according to the mass ratio, uniform slurry is obtained through stirring, and then the slurry is uniformly coated on the surface of an aluminum foil, dried and sliced to obtain the required sodium ion battery anode material.
In yet another aspect, the present invention provides a sodium ion battery comprising the carbon-coated sodium ion layered oxide cathode material described above or the sodium ion battery cathode material described above.
The invention has the beneficial effects that:
1. the sodium ion layered oxide anode material of the invention is O3-NaNi 0.5 Mn 0.5-n Ti n O 2 The preparation method is simple, no harmful gas is generated in the preparation process, the environment is friendly, the positive electrode material has less phase change, good structure reversibility, higher capacity and excellent cycle stability.
2. The preparation method of the carbon-coated positive electrode material is solid-phase coating, so that the coating process is simplified, the synthesis method is simple, and the production efficiency is high. Meanwhile, the raw materials used in the invention are easy to obtain, nontoxic and low in cost, and the production process is protected by a disordered special process, so that the method is suitable for large-scale production.
3. The surface of the anode material prepared by the method is provided with the carbon material coating layer, and the coating layer can effectively inhibit the problems of corrosion of electrolyte on the surface of the material, dissolution of transition metal and the like.
4. The layered oxide surface coating strategy can effectively improve the cycle stability and the multiplying power performance of the battery, does not influence the capacity of the battery, and provides a new research idea for the industrialization of sodium ion batteries.
Drawings
FIG. 1 is a schematic illustration of a sodium ion layered oxide coating according to the present invention;
FIG. 2 is a schematic diagram of O3-NaNi prepared in example 1 0.5 Mn 0.3 Ti 0.2 O 2 XRD spectrum of @ graphene.
Detailed Description
The carbon-coated sodium ion layered oxide cathode material according to the present invention will be further described with reference to specific examples, but it should be understood that the scope of the present invention is not limited to the following examples.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
In addition, the raw materials related to the invention are common commercial products unless otherwise specified.
Example 1 preparation of O3-NaNi 0.5 Mn 0.3 Ti 0.2 O 2 Graphene @
S1: weigh 0.525mmol Na 2 CO 3 、0.5mmol NiO、0.3mmol MnO 2 、0.2mmol TiO 2 Grinding uniformly in a mortar.
S2: pressing the powder obtained in the step S1 into 10mm small powderCalcining the wafer in a muffle furnace at a heating rate of 5 ℃/min, heating to 950 ℃, preserving heat for 15 hours, and cooling to room temperature to obtain O3-NaNi 0.5 Mn 0.3 Ti 0.2 O 2 。
S3: weighing appropriate amount of above O3-NaNi 0.5 Mn 0.3 Ti 0.2 O 2 Adding 2wt% of graphene, coating by a fusion coating machine, setting a coating program to carry out coating at 1500rpm for 15min, and cooling to room temperature to obtain O3-NaNi 0.5 Mn 0.3 Ti 0.2 O 2 And transferring the @ graphene into a glove box for standby.
The coating process of the sodium ion layered oxide in this example is shown in fig. 1.
O3-NaNi obtained in this example 0.5 Mn 0.3 Ti 0.2 O 2 The XRD pattern of the @ graphene is shown in figure 2, and it can be seen that the artificially designed carbon material coating layer does not damage the layered structure of the O3 cathode material.
The O3-NaNi obtained is treated 0.5 Mn 0.3 Ti 0.2 O 2 Graphene, a conductive additive SP and a binder PVDF are mixed and dissolved in NMP according to the mass ratio of 8:1:1, uniform slurry is obtained through stirring, and then the slurry is uniformly coated on the surface of an aluminum foil by using a 200 mu m scraper, dried and sliced to obtain the required electrode slice.
Example 2
The procedure was the same as in example 1, except that the coating material was changed to 1wt% graphene.
Example 3
The procedure was the same as in example 1, except that the coating material was changed to 3wt% graphene.
Example 4
The procedure was the same as in example 1, except that the coating material was changed to 4wt% graphene.
Example 5
The procedure was the same as in example 1, except that the coating material was changed to 2wt% carbon nanotubes.
Example 6
The procedure was the same as in example 1, except that the coating material was changed to 2wt% porous conductive carbon.
Comparative example 1
Steps S1 and S2 are the same as in example 1, and S3 is:
weighing appropriate amount of above O3-NaNi 0.5 Mn 0.3 Ti 0.2 O 2 And adding 2wt% of graphene and ethanol with the mass of one time into the layered anode material, mixing, placing into a ball milling tank, controlling the ball-material ratio to be 20:1, shaping and coating in a ball mill, setting the rotation speed of the ball mill to be 500rpm, performing ball milling for 10 hours in a positive and negative rotation mode, placing into an oven, drying, and transferring into a glove box for standby.
Mixing the obtained positive electrode material, the conductive additive SP and the binder according to the mass ratio of 8:1:1, dissolving in NMP, stirring to obtain slurry, uniformly coating the slurry on the surface of an aluminum foil by using a 200 mu m scraper, drying, and slicing to obtain the required positive electrode plate.
Comparative example 2
S1: weigh 0.525mmol Na 2 CO 3 、0.4mmol NiO、0.6mmol TiO 2 Grinding uniformly in a mortar.
S2: pressing the powder obtained in the step S1 into a small wafer with the diameter of 10mm, calcining in a muffle furnace at a heating rate of 5 ℃/min, heating to 950 ℃, preserving heat for 15 hours, and cooling to room temperature to obtain NaNi 0.4 Ti 0.6 O 2 。
S3: weighing appropriate amount of NaNi 0.4 Ti 0.6 O 2 Adding 2wt% of graphene, coating by a fusion coating machine, setting a coating program to carry out coating at 1500rpm for 15min, and cooling to room temperature to obtain NaNi 0.4 Ti 0.6 O 2 And transferring the @ graphene into a glove box for standby.
The obtained NaNi 0.4 Ti 0.6 O 2 Graphene, a conductive additive SP and a binder PVDF are mixed and dissolved in NMP according to the mass ratio of 8:1:1, uniform slurry is obtained through stirring, and then the slurry is uniformly coated on the surface of an aluminum foil by using a 200 mu m scraper, dried and sliced to obtain the required electrode slice.
Comparative example 3
S1: weigh 0.525mmol Na 2 CO 3 、0.4mmol NiO、0.4mmol MnO 2 、0.2mmol TiO 2 Grinding uniformly in a mortar.
S2: pressing the powder obtained in the step S1 into a small wafer with the diameter of 10mm, then placing the small wafer into a muffle furnace for calcination, heating to the temperature of 950 ℃ at the speed of 5 ℃/min, preserving heat for 15 hours, and cooling to the room temperature to obtain the O3-NaNi 0.4 Mn 0.4 Ti 0.2 O 2 。
S3: weighing appropriate amount of above O3-NaNi 0.4 Mn 0.4 Ti 0.2 O 2 Adding 2wt% of graphene, coating by a high-temperature fusion coating machine, setting a coating program to carry out coating at 1500rpm for 15min, and cooling to room temperature to obtain O3-NaNi 0.4 Mn 0.4 Ti 0.2 O 2 And transferring the @ graphene into a glove box for standby.
The O3-NaNi obtained is treated 0.4 Mn 0.4 Ti 0.2 O 2 Graphene, a conductive additive SP and a binder PVDF are mixed and dissolved in NMP according to the mass ratio of 8:1:1, uniform slurry is obtained through stirring, and then the slurry is uniformly coated on the surface of an aluminum foil by using a 200 mu m scraper, dried and sliced to obtain the required electrode slice.
Application example
Electrochemical performance test: the pole pieces obtained in examples 1 to 6 and comparative examples 1 to 3 were used as positive electrodes, glass fibers were used as separators, metallic sodium sheets were used as negative electrodes, and 1mol/L NaClO 4 (pc+5% fec) assembled coin cell for electrolyte. The battery was activated for 3 cycles at a current density of 15.5mA/g and then cycled between charge and discharge at a current density of 155 mA/g. Electrochemical properties of the corresponding button cells of the inventive examples and comparative example materials were tested and the results are shown in table 1:
TABLE 1 electrochemical Properties
Figure BDA0003948113850000071
As can be seen from the XRD pattern of fig. 2, the layered structure of the O3 cathode material is not destroyed by the artificially designed carbon material coating layer. As can be seen from the test results of the examples in table 1, after carbon coating the layered cathode material, due to the construction of the conductive three-dimensional network,the first-turn discharge capacity of the battery is slightly improved, and the capacity retention rate after 200 turns is obviously improved. For example, in example 1, the first-turn discharge capacity was 128mAh g -1 The capacity retention rate of 200 turns is 89%, and the inventor also unexpectedly found that the electrochemical performance of the positive electrode material can be obviously improved by taking graphene as a raw material of the coating layer. And when the doping proportion of the coating raw material is regulated within a proper range, the optimal electrochemical performance of the anode material can be achieved.
It will be appreciated that in various embodiments of the invention, although the invention has been described in detail in connection with specific electrolytes, separators, current collectors, active materials, binders, conductive additives, etc., the above is merely to satisfy legal requirements and illustrate the composition of the sodium-ion battery, the invention is not limited to the given embodiments. Any modification, equivalent replacement, improvement or the like made by the present specification within the spirit and principle of the present invention, or directly or indirectly applied to other related technical fields, are equally included in the scope of the patent protection of the present invention.

Claims (12)

1. Carbon-coated sodium ion layered oxide positive electrode material with chemical formula expressed as Na x TMO 2 The @ carbon material is characterized in that:
the carbon material is at least one of graphene, carbon nano tube and porous conductive carbon, and is coated on the layered metal oxide Na x TMO 2 Is a surface of (2);
the TM is at least one of transition metals Ni, mn and Ti;
x is 2/3 to 1.
2. The carbon-coated sodium ion layered oxide cathode material according to claim 1, wherein x is 2/3 or 1 and the coating layer has a thickness of 5-30nm, preferably 10-15nm.
3. The carbon-coated sodium-ion layered oxide cathode material of claim 1, wherein the TM is Ni 0.5 Mn 0.5-n Ti n Wherein n is more than or equal to 0 and less than or equal to 0.5; more preferably, the TM is Ni 0.5 Mn 0.3 Ti 0.2 。
4. A method for preparing the carbon-coated sodium ion layered oxide positive electrode material according to any one of claims 1 to 3, comprising the steps of:
s1: source material mixing: feeding a sodium source and a transition metal TM source according to a stoichiometric ratio, wherein the sodium source is fed according to 102% -120% of the stoichiometric ratio, and ball-milling and mixing uniformly to form a mixture;
s2: sintering a positive electrode material: calcining the mixture obtained in the step S1 in a muffle furnace, heating to 600-1000 ℃, preserving heat for 12-48h, and cooling to room temperature to obtain layered metal oxide Na x TMO 2 ；
S3: coating of positive electrode material: and (3) fully and integrally coating the layered metal oxide obtained in the step (S2) and the carbon material in a fusion coating machine.
5. The method according to claim 4, wherein the sodium source is at least one selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium oxide, and sodium peroxide; sodium carbonate is preferred;
the TM source is selected from at least one of the oxides, sulphates, nitrates, carbonates, acetates, oxalates and hydrated compounds of TM.
6. The preparation method according to claim 4, wherein the calcining atmosphere in S2 is at least one of oxygen and air, the heating rate is 1-10deg.C/min, and the cooling rate is 1-10deg.C/min.
7. The method according to claim 4, wherein the carbon material in S3 is 0.1% -10%, preferably 0.5% -2% of the total mass.
8. The process according to claim 4, wherein the fusion coating machine is operated at a rotational speed of 800-2000rpm, preferably 1500rpm.
9. A sodium ion battery positive electrode material, the raw materials for preparing which comprise the carbon-coated sodium ion layered oxide positive electrode material according to any one of claims 1 to 3 or the carbon-coated sodium ion layered oxide positive electrode material prepared by the method according to any one of claims 4 to 8, a conductive agent and a binder.
10. The positive electrode material of sodium ion battery according to claim 9, wherein the mass ratio of the carbon-coated sodium ion layered oxide positive electrode material, the conductive agent and the binder is 6-9:0.5-2:0.5-2, preferably 8-9:0.5-1:0.5-1.
11. The positive electrode material of sodium ion battery according to claim 9 or 10, wherein the conductive agent is at least one selected from acetylene black, VGCF, SP, CNT, graphite; the binder is at least one selected from polyvinylidene fluoride, polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethyl cellulose.
12. A sodium ion battery comprising the sodium ion battery cathode material of any one of claims 9-11.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116750802A (en) * 2023-08-21 2023-09-15 中节能万润股份有限公司 Preparation method and application of layered oxide sodium ion battery positive electrode material
CN117317200A (en) * 2023-11-29 2023-12-29 江苏正力新能电池技术有限公司 Positive electrode material, preparation method thereof and sodium ion battery
CN117497746A (en) * 2023-12-29 2024-02-02 宁波容百新能源科技股份有限公司 Sodium-electricity layered anode material and preparation method and application thereof
CN118472219A (en) * 2024-05-27 2024-08-09 湖北万润新能源科技股份有限公司 Layered oxide positive electrode material, preparation method thereof, positive electrode plate and sodium ion battery

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116750802A (en) * 2023-08-21 2023-09-15 中节能万润股份有限公司 Preparation method and application of layered oxide sodium ion battery positive electrode material
CN117317200A (en) * 2023-11-29 2023-12-29 江苏正力新能电池技术有限公司 Positive electrode material, preparation method thereof and sodium ion battery
CN117317200B (en) * 2023-11-29 2024-03-15 江苏正力新能电池技术有限公司 Positive electrode material, preparation method thereof and sodium ion battery
CN117497746A (en) * 2023-12-29 2024-02-02 宁波容百新能源科技股份有限公司 Sodium-electricity layered anode material and preparation method and application thereof
CN117497746B (en) * 2023-12-29 2024-05-14 宁波容百新能源科技股份有限公司 Sodium-electricity layered anode material and preparation method and application thereof
CN118472219A (en) * 2024-05-27 2024-08-09 湖北万润新能源科技股份有限公司 Layered oxide positive electrode material, preparation method thereof, positive electrode plate and sodium ion battery

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