CN115663155A - Composite cathode material and preparation method and application thereof - Google Patents
Composite cathode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a composite cathode material and a preparation method and application thereof, belonging to the technical field of cathode material preparation. The method comprises the following steps: placing sodium sulfate and ferrous sulfate heptahydrate in a reaction container, and sintering at a protective atmosphere to obtain an intrinsic material of sodium ferric sulfate; and introducing mixed gas of a carbon source and a carrier gas into the reaction container, coating the conductive carbon material on the sodium iron sulfate intrinsic material by using a chemical vapor deposition method, and performing secondary sintering to obtain the composite cathode material. According to the invention, the process of coating the conductive carbon material in one step after sintering the sodium iron sulfate composite material is realized through chemical vapor deposition, the preparation of the composite anode material is realized in one step, the complex steps in the step-by-step coating and synthesis method are greatly simplified, the production cost of the battery is reduced, the uniform dispersion of the carbon material in the sodium iron sulfate anode material is realized, and the electrochemical performance of the composite anode material is improved.
Description
Technical Field
The invention relates to the technical field of preparation of anode materials, in particular to a composite anode material and a preparation method and application thereof.
Background
In recent years, with the rapid growth of the population of the earth and the rapid development of the world economy, the search for low-carbon green renewable energy forms is particularly important for climate change, energy structure improvement and sustainable economy development. Among them, representative novel power generation methods such as solar energy, tidal energy, and wind energy are receiving worldwide attention. However, the forms of these energy sources are severely restricted by natural conditions, geographical locations and other factors, and the stability and continuity of the power generation thereof are not satisfied, and cannot be directly introduced into the power grid. Therefore, the search for a system for storing electric energy in a large scale becomes a key problem to be solved urgently at present.
Chemical energy sources are of great interest in various fields due to their high energy density and efficiency and good cycle stability. Among them, lithium ion batteries have been widely used in the electric vehicle industry due to their high energy density, fast charging capability, good cycle stability, and wide operating temperature range. However, the limited lithium resources in the earth will result in excessive costs for producing lithium batteries. Finding alternative secondary battery materials is therefore of great importance in chemical energy storage.
Sodium and lithium belong to the same main group in the periodic table of elements, and can be used as candidate materials for replacing lithium ions theoretically, whether the materials are physical or chemical. Meanwhile, the sodium resource reserve on the earth is very rich and is 400 times of that of the lithium resource, the distribution is wide, the refining mode is simple, and correspondingly, the production cost of the sodium ion battery is relatively low. Therefore, sodium ion batteries are widely considered as a powerful alternative to lithium ion batteries due to their cost advantages.
The operating performance of a sodium ion battery depends mainly on the electrochemical properties of the positive electrode material. At present, the positive electrode materials of the sodium-ion battery mainly comprise layered oxides, polyanions, prussian blue and the like. The polyanion compound has obvious advantages in the positive electrode material of the sodium ion battery due to the open framework structure, the ion migration path with lower energy and the adjustable voltage range, and particularly the polyanion type ferric sulfate sodium positive electrode material is widely concerned due to the lower production cost and the higher working voltage. However, the conductivity of the material is generally poor, so that the material can not exert good energy storage property, and the material is easy to absorb water and oxidized by oxygen in the air to cause material failure. In order to solve the problems of easy water absorption, poor conductivity and the like of the anode material, the material needs to be modified, and generally, the anode material can be modified by doping or coating materials with good conductivity, such as carbon nano tubes, graphene, carbon nano wires and the like. In the prior art, ferrous sulfate heptahydrate is usually dehydrated in advance, and a ball milling mode is adopted to realize mixing of a conductive carbon material and a sodium ferric sulfate composite material, so that the process is complex, the production cost is high, and the synthesized intrinsic polyanionic sodium ferric sulfate anode material has the problems of low gram volume, poor cycle stability, unsatisfactory rate capability and the like.
Disclosure of Invention
The invention solves the problems that the existing intrinsic polyanionic sodium ferric sulfate cathode material has at least one of the problems of complex production process, high production cost, low gram capacity, obvious cyclic attenuation, unsatisfactory rate performance and the like in the synthesis process.
In order to solve the above problems, the present invention provides a method for preparing a composite positive electrode material, comprising:
placing sodium sulfate and ferrous sulfate heptahydrate in a reaction container, and performing primary sintering under a protective atmosphere to obtain an intrinsic material of sodium ferric sulfate;
and introducing mixed gas of a carbon source and a carrier gas into the reaction container, coating the conductive carbon material on the sodium iron sulfate intrinsic material by using a chemical vapor deposition method, and performing secondary sintering to obtain the composite anode material.
Preferably, the flow rate of the mixed gas is controlled to be 0.1-0.5L/min, the deposition temperature of the chemical vapor deposition is controlled to be 300-500 ℃, and the deposition time is controlled to be 0.1-10h.
Preferably, the volume fraction of the carbon source in the mixed gas is controlled to be 5-8%.
Preferably, the carbon source comprises one of acetylene, methane and acetone.
Preferably, the flow rate of the protective atmosphere is controlled to be 1-10L/min.
Preferably, the temperature of the primary sintering is controlled to be 300-500 ℃, and the time is controlled to be 6-24h.
Preferably, the amount of the substance of sodium sulfate is x, the amount of the substance of ferrous sulfate heptahydrate is y, and the ratio of x to y satisfies the following relation:
0.1≤x/y≤4，2≤x+2y≤100。
preferably, the temperature of the secondary sintering is controlled to be 300-500 ℃, and the time is controlled to be 6-24h.
Compared with the prior art, the preparation method of the composite cathode material has the advantages that:
according to the invention, the sintering of the sodium ferric sulfate intrinsic material and the coating process of the conductive carbon are simultaneously carried out in the reaction container, so that the preparation of the composite anode material is realized in one step, the complicated steps in the step-by-step coating and synthesis method are greatly simplified, the consumed time is short, the synthesis process is optimized, and the production cost of the battery is reduced. And the process of coating the conductive carbon material by one step after sintering the sodium iron sulfate composite material is realized through chemical vapor deposition, so that the carbon material is uniformly dispersed in the sodium iron sulfate anode material, and the electrochemical performance of the composite anode material is improved.
The invention also provides a composite cathode material prepared by the preparation method of the composite cathode material.
The invention also provides an application of the composite anode material as an anode material of a sodium-ion battery.
Compared with the prior art, the composite anode material and the application thereof as the anode material of the sodium-ion battery have the same advantages as the composite anode material, and are not repeated herein.
Drawings
FIG. 1 is a flow chart of a method for preparing a composite cathode material according to an embodiment of the present invention;
FIG. 2 is another flow chart of a method for preparing the composite cathode material according to the embodiment of the invention;
fig. 3 is an XRD pattern of the composite cathode material synthesized in example 1 of the present invention;
fig. 4 is a graph of the first two cycles of charge and discharge when the voltage interval is 2.0V-4.5V and the current density is 0.1C for the composite cathode material synthesized in example 1 of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
As shown in fig. 1, an embodiment of the present invention provides a method for preparing a composite positive electrode material, including:
placing sodium sulfate and ferrous sulfate heptahydrate in a reaction container, and sintering at a protective atmosphere to obtain an intrinsic material of sodium ferric sulfate;
and introducing mixed gas of a carbon source and a carrier gas into the reaction container, coating a conductive carbon material on the sodium iron sulfate intrinsic material by using a chemical vapor deposition method, and performing secondary sintering to obtain the composite anode material.
In the embodiment, the sodium sulfate and the ferrous sulfate heptahydrate are directly mixed and placed in the reaction container for primary sintering, the crystal water of the ferrous sulfate heptahydrate is not required to be removed in advance, the crystal water of the ferrous sulfate heptahydrate is converted into a water vapor form by using high temperature in the primary sintering process, and is taken out of the reaction container through a protective atmosphere, so that the process of material pretreatment dewatering in the prior art is omitted, the process flow is shortened, and the cost is reduced. After sintering, introducing mixed gas into the reaction container, depositing a conductive carbon material on the surface of the sodium iron sulfate intrinsic material obtained by primary sintering by using a chemical vapor deposition method to obtain a sodium iron sulfate composite material with good size uniformity of the coated carbon, improving the compactness of a coating layer by secondary sintering, improving the material performance, and finally obtaining the sodium iron sulfate composite anode material with uniform coated conductive carbon.
The embodiment provides a preparation method for synthesizing a sodium ferric sulfate cathode material in a reaction container by a one-step method, and a conductive carbon material is deposited on the surface of the sodium ferric sulfate cathode material in one step by introducing a carbon source gas into the reaction container through a chemical vapor deposition technology. The one-step process is that after reaction raw materials of sodium sulfate and ferrous sulfate heptahydrate are placed in a reaction container, the sintering temperature and time are adjusted, and relevant parameters of mixed gas are introduced, so that the process of synthesizing the ferric sulfate sodium cathode material in the reaction container and depositing the conductive carbon material on the surface of the cathode material is realized. Compared with the solid-phase two-step method in the prior art that ferrous sulfate heptahydrate needs to be dehydrated, sintered and mixed with a conductive carbon material after sintering, the embodiment improves the sintering process of sodium sulfate and ferrous sulfate heptahydrate and the coating process of the conductive carbon material on the basis of synthesizing the iron sulfate sodium composite anode material by the solid-phase method, and realizes the preparation of the composite anode material by sintering the iron sulfate sodium intrinsic material and coating the conductive carbon in a reaction container at the same time, thereby greatly simplifying the complicated steps in the step-by-step coating and synthesizing method and reducing the production cost of the battery. In addition, in the embodiment, by a chemical vapor deposition method, uniform carbon deposition can be performed inside the material, so that the carbon material is more uniformly dispersed in the sodium iron sulfate cathode material, the instability of the cathode material in the synthesis process is inhibited, the material cycle performance is further improved, and the problem of uniform dispersion of the conventional carbon material in the sodium iron sulfate composite material is solved. In addition, the conductive carbon material is directly deposited in a reaction container filled with carbon source atmosphere by a one-step method through a mixture of sodium sulfate and ferrous sulfate heptahydrate to form the carbon-coated iron sodium sulfate composite material, and a conductive carbon coating layer with uniform and compact thickness can be formed by adjusting the flow rate of the carbon source gas, the coating time and the thickness of the coating layer in the process, so that the problems of easy water absorption, poor conductivity and rate capability and the like of the composite anode material are solved, the overall comprehensive performance of the material is greatly improved, and the gram volume performance of the material is improved. In addition, the chemical vapor deposition method in the process is simple, is easy for industrial application, reduces the production cost, and has important significance for the commercial application of the cathode material.
In some embodiments, the reaction vessel is a rotary vacuum tube furnace for chemical vapor deposition. The sodium sulfate and the ferrous sulfate heptahydrate are directly mixed and placed into the rotary tube furnace, and the sintering of the intrinsic material of the sodium iron sulfate and the coating process of the conductive carbon are simultaneously carried out in the tube furnace, so that the cost is saved, the sodium iron sulfate composite anode material with more uniform coating effect can be obtained, the composite anode material has a very important effect on improving the conductivity of the sodium iron sulfate anode material, and the electrochemical performance of the anode material is effectively exerted.
In some of the embodiments, sodium sulfate and ferrous sulfate heptahydrate are put into a vacuum rotary tube furnace for chemical vapor deposition according to a specific molar ratio, a protective atmosphere such as argon is introduced, and evaporated water vapor is blown out by controlling the flow rate of the protective atmosphere. Wherein the amount of the sodium sulfate substance is x, the amount of the ferrous sulfate heptahydrate substance is y, and the ratio of x to y satisfies the following relational expression:
0.1≤x/y≤4，2≤x+2y≤100。
the flow rate of the protective atmosphere is controlled to be 1-10L/min, the temperature of the primary sintering is controlled to be 300-500 ℃, and the time is 6-24h.
In this embodiment, dehydration of ferrous sulfate heptahydrate and reaction of sodium sulfate and ferrous sulfate heptahydrate are performed simultaneously, crystal water in the ferrous sulfate heptahydrate is evaporated by using the temperature in the primary sintering reaction to obtain water vapor, and then the water vapor is carried away by using a protective gas by controlling the flow rate of a protective atmosphere to discharge water in the material. It can be understood that the flow rate of the protective gas has a great influence on the effect of the primary sintering reaction, and if the flow rate of the protective gas is too low, the generated water vapor cannot be discharged, so that the normal operation of the reaction is influenced; if the flow rate of the protective gas is too high, on one hand, the gas is wasted, and on the other hand, the temperature in the furnace is uneven, so that the temperature in the furnace is too low. Therefore, in the embodiment, the flow rate of the protective atmosphere is controlled to be 1-10L/min, and in the flow rate range, the water vapor can be blown out to realize the dehydration of the ferrous sulfate heptahydrate, and the reaction temperature of the sodium sulfate and the ferrous sulfate heptahydrate is not influenced.
In the embodiment, when the ferric sodium sulfate cathode material is synthesized, the sodium sulfate and the ferrous sulfate are directly coated by one-step carbon deposition by using the vacuum rotary furnace, crystal water of ferrous sulfate heptahydrate is not required to be removed in advance, water vapor is blown out in the gradual temperature rise process of the furnace by controlling the flow rate of inert gas in the sintering process of the vacuum rotary furnace, and compared with the prior art in which the ferrous sulfate heptahydrate is required to be dehydrated in advance, the method simplifies the production process, reduces the production cost and is beneficial to large-scale production.
In some embodiments, the sintering and deposition processes are performed by controlling the sintering temperature, time and type of inlet gas of the rotary tube furnace, wherein during the sintering process, argon or the like is used as a protective gas, during the carbon deposition, acetylene, methane or acetone is used as a carbon source, argon or the like is used as a carrier gas, a mixed gas of the carbon source and argon is gradually introduced, and the conductive carbon material is chemically vapor-deposited within a specific temperature range by controlling the flow rate and deposition time of the mixed gas. Wherein the flow rate of the mixed gas is controlled to be 0.1-0.5L/min, the deposition temperature of the chemical vapor deposition is controlled to be 300-500 ℃, and the deposition time is controlled to be 0.1-10h, so that carbon coating layers with different thicknesses are obtained.
In a preferred embodiment, the volume fraction of the carbon source in the mixed gas is controlled to be 5-8%, and the carbon coating layers with different deposition thicknesses are obtained by controlling the volume proportion of the carbon source in the mixed gas and the flow rate of the mixed gas. The rest of the mixed gas is carrier gas, the carrier gas is used for transporting carbon source gas, and meanwhile, inert gases such as argon and the like are used as the carrier gas to ensure an oxygen-free environment in the carbon deposition process.
In order to improve the conductivity of the intrinsic material of sodium ferric sulfate and improve the electrochemical performance thereof, in this embodiment, a carbon-coated manner is selected for the positive electrode material, so as to obtain a carbon-coated sodium ferric sulfate positive electrode material. In the process of carbon coating, the embodiment selects and applies the advantage of uniformity of the chemical vapor deposition technology in the coating process, carbon source gas is introduced in the sintering process of the sodium ferric sulfate cathode material, and the thickness of the coating layer is controlled by adjusting the flow rate and the coating time of the carbon source gas, so that the conductive carbon coating layer with uniform thickness and compactness is formed. Compared with the mixing of the conductive carbon material and the sodium ferric sulfate composite material by ball milling in the prior art, the embodiment realizes the uniform dispersion of the carbon material in the sodium ferric sulfate anode material, and simultaneously, the chemical vapor deposition and the sintering can be carried out in the same reaction vessel, and only carbon source gas needs to be introduced into the reaction vessel during the chemical deposition, so the process flow is simple and convenient, and the production cost is reduced.
In some embodiments, after the deposition is finished, secondary sintering is performed, wherein the temperature of the secondary sintering is controlled to be 300-500 ℃, the time is controlled to be 6-24h, and the sodium ferric sulfate cathode material uniformly coated with the conductive carbon is obtained after the secondary sintering.
As shown in fig. 2, in this embodiment, sodium sulfate and ferrous sulfate heptahydrate are placed into a vacuum rotary tube furnace for chemical vapor deposition according to a specific molar ratio, argon is introduced for protection, then the sintering temperature and the sintering time are controlled, a carbon source and a carrier gas are introduced after sintering is completed, and the chemical vapor deposition of the conductive carbon material is performed within a specific temperature range and with the control of the gas flow rate and the deposition time. And after the deposition is finished, performing secondary sintering to obtain the conductive carbon uniformly-coated ferric sodium sulfate composite cathode material with a specific thickness.
In the embodiment, the crystal water of the ferrous sulfate heptahydrate is not removed in advance, but the flow rate of the inert gas in the sintering process of the vacuum rotary furnace is increased, and the water vapor is blown out in the process of gradually increasing the temperature of the furnace. The method simplifies the commercial synthesis process and is beneficial to commercial mass production. In addition, the process of coating the conductive carbon material in one step after the sintering of the sodium iron sulfate composite material is finished is realized through chemical vapor deposition, and compared with the process of ball-milling and mixing the conductive carbon material and the sodium iron sulfate composite material, the process solves the problem of uniformity of the conductive carbon material in coating the sodium iron sulfate composite material, and improves the electrochemical performance of the composite material. Meanwhile, after the sintering and deposition processes are combined, the synthesis operation of the cathode material is simple, the consumed time is short, the synthesis process is optimized, and the industrial production cost is reduced.
The embodiment of the invention also provides a composite cathode material which is prepared by the preparation method of the composite cathode material. The prepared composite cathode material realizes the process of coating the conductive carbon material by one step after the sintering of the sodium ferric sulfate composite material through chemical vapor deposition in the preparation process, solves the problem of uniformity of the conductive carbon material when the conductive carbon material is coated with the sodium ferric sulfate composite material, improves the electrochemical performance of the composite material, solves the problems of easy water absorption, poor conductivity and the like of the cathode material, improves the gram capacity exertion of the cathode material, and improves the problems of poor cyclicity and rate capability and the like.
The embodiment of the invention also provides an application of the composite anode material as the anode material of the sodium-ion battery.
The invention is further illustrated by the following specific examples.
Example 1
The embodiment prepares the iron sulfate sodium composite cathode material uniformly coated with the conductive carbon material, and the specific steps comprise:
sodium sulfate and ferrous sulfate heptahydrate are placed in a 5L rotary tube furnace according to the molar ratio of 1. And (3) carrying out a deposition process of the conductive carbon material after sintering, wherein in the process, 0.1L/min of mixed gas is introduced, the mixed gas comprises a carbon source acetylene and a carrier gas argon, the carbon source content is 5%, the deposition temperature is 350 ℃, and the deposition time is 1h. After the deposition, the obtained coated carbon layer had a thickness of 20nm of sulfurPerforming secondary sintering at 350 deg.C for 12 hr to obtain composite positive electrode material denoted by Na 2 Fe 2 (S0 4 ) 3 ·C 20 。
Example 2
The difference between this example and example 1 is that the flow rates of the carbon source and the carrier gas during the CVD process were adjusted to 0.2L/min, and after the secondary sintering, the obtained sodium ferric sulfate composite cathode material with a coating carbon layer thickness of 40nm, which is recorded as Na, was used as the cathode material 2 Fe 2 (S0 4 ) 3 ·C 40 。
Example 3
The difference between this example and example 1 is that the flow rates of the carbon source and the carrier gas during the CVD process were adjusted to 0.5L/min, and after the secondary sintering, the obtained sodium ferric sulfate composite cathode material with a thickness of 100nm for the carbon coating layer was recorded as Na 2 Fe 2 (S0 4 ) 3 ·C 100 。
Example 4
The difference between this example and example 1 is that the carbon source in the chemical vapor deposition process is adjusted to methane to prepare a sodium ferric sulfate composite cathode material, and the thickness of the coated carbon layer of the composite cathode material is 10nm, which is recorded as Na 2 Fe 2 (S0 4 ) 3 ·C 010 。
Example 5
The difference between this example and example 4 is that the flow rates of the carbon source and the carrier gas during the chemical vapor deposition process were adjusted to 0.2L/min, and after the secondary sintering, the sodium ferric sulfate cathode composite material with a 20nm coated carbon layer thickness, which is recorded as Na, was obtained 2 Fe 2 (S0 4 ) 3 ·C 020 。
Example 6
The difference between this example and example 5 is that the flow rates of the carbon source and the carrier gas during the CVD process were adjusted to 0.5L/min, and after the secondary sintering, the sodium ferric sulfate cathode composite material with a 50nm thickness of the obtained coated carbon layer, which is denoted as Na, was obtained 2 Fe 2 (S0 4 ) 3 ·C 050 。
Example 7
This example differs from example 1 in that acetone was used as the carbon source to prepare a sodium iron sulfate composite positive electrode material having a carbon coating layer of 30nm in thickness and denoted as Na 2 Fe 2 (S0 4 ) 3 ·C 0030 。
Example 8
The difference between this example and example 6 is that the flow rates of the carbon source and the carrier gas during the chemical vapor deposition process were adjusted to 0.2L/min, and after the secondary sintering, the sodium ferric sulfate cathode composite material with a thickness of 60nm of the obtained coated carbon layer, which is recorded as Na, was obtained 2 Fe 2 (S0 4 ) 3 ·C 0060 。
Example 9
The difference between this example and example 6 is that the flow rates of the carbon source and the carrier gas during the CVD process were adjusted to 0.5L/min, and after the secondary sintering, the obtained sodium ferric sulfate cathode composite material with 150nm of the coated carbon layer thickness, which is recorded as Na 2 Fe 2 (S0 4 ) 3 ·C 00150 。
The application example is as follows:
the carbon-coated sodium iron sulfate composite positive electrode material obtained in each example is mixed with a conductive agent (acetylene black) and a binder (PVDF) according to the mass ratio of 8 4 The PC solution is used as electrolyte, and a button sodium ion battery is assembled in a glove box with the water oxygen content of less than 0.01 ppm. And testing the electrochemical performance of the synthesized modified material within the voltage range of 2.0V-4.5V.
Fig. 3 is an XRD spectrum of the composite cathode material synthesized in example 1, and it can be confirmed that the crystal structure of the sodium iron sulfate material is not changed by the carbon coating according to the XRD diffraction peak pattern. Meanwhile, the XRD diffraction peak is sharp, which shows that the synthesized material has good crystallinity.
FIG. 4 is a graph showing the charge and discharge curves of example 1 in a voltage range of 2.0V to 4.5V and a current density of 0.1C (12 mA/g). As can be seen from fig. 4, the specific capacity in example 1 performed well, demonstrating that the electrochemical performance can be improved by coating carbon on the surface of the sodium iron sulfate material by chemical vapor deposition.
Although the present disclosure has been described with reference to the above embodiments, the scope of the present disclosure is not limited thereto. Various changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to fall within the scope of the present disclosure.
Claims (10)
1. A preparation method of a composite cathode material is characterized by comprising the following steps:
placing sodium sulfate and ferrous sulfate heptahydrate in a reaction container, and sintering at a protective atmosphere to obtain an intrinsic material of sodium ferric sulfate;
and introducing mixed gas of a carbon source and a carrier gas into the reaction container, coating a conductive carbon material on the sodium iron sulfate intrinsic material by using a chemical vapor deposition method, and performing secondary sintering to obtain the composite anode material.
2. The preparation method of the composite cathode material according to claim 1, wherein the flow rate of the mixed gas is controlled to be 0.1-0.5L/min, the deposition temperature of the chemical vapor deposition is controlled to be 300-500 ℃, and the deposition time is controlled to be 0.1-10h.
3. The method for producing a composite positive electrode material according to claim 2, wherein the volume fraction of the carbon source in the mixed gas is controlled to 5 to 8%.
4. The method for producing a composite positive electrode material according to claim 3, wherein the carbon source includes one of acetylene, methane, and acetone.
5. The method for producing a composite positive electrode material according to claim 1, wherein a flow rate of the protective atmosphere is controlled to 1 to 10L/min.
6. The method for preparing the composite cathode material according to claim 1, wherein the temperature of the primary sintering is controlled to be 300-500 ℃ and the time is controlled to be 6-24h.
7. The method for producing a composite positive electrode material according to claim 1, wherein the amount of the substance of sodium sulfate is x, the amount of the substance of ferrous sulfate heptahydrate is y, and the ratio of x to y satisfies the following relational expression:
0.1≤x/y≤4，2≤x+2y≤100。
8. the method for preparing the composite cathode material according to claim 1, wherein the temperature of the secondary sintering is controlled to be 300-500 ℃ and the time is controlled to be 6-24h.
9. A composite positive electrode material, characterized by being produced by the method for producing a composite positive electrode material according to any one of claims 1 to 8.
10. Use of a composite positive electrode material according to claim 9 as a positive electrode material for a sodium-ion battery.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116230888A (en) * | 2023-02-17 | 2023-06-06 | 三一红象电池有限公司 | Method for preparing carbon-coated sodium iron sulfate material, carbon-coated sodium iron sulfate material and battery |
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| CN116230888A (en) * | 2023-02-17 | 2023-06-06 | 三一红象电池有限公司 | Method for preparing carbon-coated sodium iron sulfate material, carbon-coated sodium iron sulfate material and battery |
| CN116230888B (en) * | 2023-02-17 | 2024-03-08 | 三一红象电池有限公司 | Method for preparing carbon-coated sodium iron sulfate material, carbon-coated sodium iron sulfate material and battery |
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