CN115188958A - Spherical porous sodium-ion battery material and preparation method thereof - Google Patents
Spherical porous sodium-ion battery material and preparation method thereof Download PDFInfo
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- CN115188958A CN115188958A CN202210805753.4A CN202210805753A CN115188958A CN 115188958 A CN115188958 A CN 115188958A CN 202210805753 A CN202210805753 A CN 202210805753A CN 115188958 A CN115188958 A CN 115188958A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- 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
- H01M4/50—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A spherical porous sodium ion battery material and its preparation method, the chemical formula of the battery material is Na 0.67 Fe 0.23‑ x Cu x Mn 0.77 O 2 Wherein 0 is<x is less than or equal to 0.2; the battery material is spherical porous particles, and the preparation method comprises the following steps: s1, mixing a salt solution of a ferric salt, a cupric salt and a manganous salt with glycerol to perform a hydrothermal reaction, and washing and drying to obtain a carbonate precursor containing iron, copper and manganese; s2, pre-burning the carbonate precursor of the iron, copper and manganese to obtain a ternary iron, copper and manganese oxide; and S3, mixing and calcining the ternary iron-copper-manganese oxide and sodium carbonate to obtain the sodium ion battery material. The purity of the positive electrode material of the sodium-ion battery prepared by the inventionHigh specific capacity, simple preparation process, high production efficiency and suitability for large-scale production and popularization.
Description
Technical Field
The invention relates to the technical field of energy materials, in particular to a spherical porous sodium-ion battery material and a preparation method thereof.
Background
Lithium ion batteries, as a representative of high energy density energy storage battery systems, are widely used in the fields of portable electronic devices, electric automobiles and the like, however, due to low lithium storage capacity, uneven resource distribution and year-by-year increase in material price, large-scale application of lithium ion batteries is restricted to a certain extent.
In the periodic table, sodium and lithium are in the same main group, and their physical and chemical properties are very similar. The sodium ion battery has a similar working principle as the lithium ion battery, and is different in that sodium ions are deintercalated in the charging and discharging processes. Compared with lithium resources, sodium is more abundant in earth crust, is widely distributed globally, is simple to refine and has lower cost, so that the sodium-ion battery has a greater cost advantage after being used in large-scale commercial use. In addition, sodium ions have lower solvation energy and better interfacial ion diffusion capacity than lithium ions; the stokes diameter is smaller and the ionic conductivity is higher than that of lithium ions in the electrolyte with the same concentration. Meanwhile, the high-low temperature performance of the sodium ion battery is more excellent, and because the internal resistance is slightly high, the heating value under the short circuit condition is lower, and the safety is higher, so that the sodium ion battery becomes one of the most promising substitutes of the lithium ion battery. In view of the above, the development of sodium ion batteries and the realization of high specific energy sodium ion batteries are the focus of research.
The positive electrode materials of the sodium-ion battery which are researched at present are mainly concentrated on crystalline materials, including transition metal layered and tunnel-shaped oxides Na x MO 2 (M = Mn, co, fe, ni, etc.), polyanionic compound Na 3 V 2 (PO 4 ) 3 Iso, prussian blue compounds Na 2 Fe (CN) 6 Etc. partially amorphous material concentrated in glassy Fe-PO 4 ，V 2 O 5 -P 2 O 5 The system is glass. Among them, the layered material has been widely studied because of its stable structure and suitability for deintercalation.
Patent CN105161703A introduces a five-membered layered oxide positive electrode material for sodium ion battery and its preparation method. The single-phase quinary layered oxide is prepared by mixing and tabletting sodium carbonate, nickel oxide, cobalt oxide, iron oxide, titanium oxide and manganese oxide which are weighed in proportion, and calcining the mixture in oxygen and air atmosphere. The problems with this approach are: the controllability is poor, and the large-scale production is not facilitated.
Patent CN112456567a introduces a preparation method of a sodium ion battery anode material with a coating structure. Dissolving metal salt in a volatile solvent to prepare a suspension, adding a precursor of the positive electrode material, uniformly mixing, drying and calcining to obtain the sodium-ion battery material with the coating structure. The material prepared by the method has better stability, but has the following problems: the volatile solvent (acetone, N-methyl pyrrolidone) is dangerous, has certain harm to the environment and is not beneficial to sustainable development.
Therefore, the development of the preparation method of the positive electrode material of the sodium-ion battery, which has the advantages of stable and simple process and mild material, has important significance in the field.
Disclosure of Invention
The invention aims to provide a spherical porous sodium-ion battery material and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention on the material level is as follows:
a spherical porous sodium ion battery material with chemical formula of Na 0.67 Fe 0.23-x Cu x Mn 0.77 O 2 Wherein 0 is<x is less than or equal to 0.2; the sodium ion battery material is spherical porous particles and has a layered structure.
In order to achieve the purpose, the technical scheme adopted by the invention in the aspect of the method is as follows:
a preparation method of a spherical porous sodium-ion battery material comprises the following steps:
S1preparing a precursor: weighing MnCl in proportion 2 、FeCl 3 、CuCl 2 Preparing a mixed salt solution, carrying out hydrothermal reaction on the mixed salt solution and glycerol, and washing and drying a product after the reaction to obtain a carbonate precursor containing iron, copper and manganese;
s2, pre-burning: pre-burning the carbonate precursor obtained in the step S1 to obtain a ternary iron-copper-manganese oxide;
s3, calcining: dispersing the ternary iron-copper-manganese oxide obtained in the step S2 and sodium carbonate into water, mixing, freezing, drying and calcining, wherein the mixing mass ratio of the ternary iron-copper-manganese oxide to the sodium carbonate is 2.5-3.5: 1, obtaining the sodium-ion battery material.
The relevant content in the above technical solution is explained as follows:
1. in the above scheme, in S1, the doping amount of each element in the mixed salt solution is Cu mol /(Fe+Mn+Cu) mol =0.05~0.3。
2. In the scheme, in S1, the temperature of the hydrothermal reaction is controlled to be 160-200 ℃, and the reaction time is 10-20h.
3. In the scheme, in S2, the temperature of the pre-sintering is 350 to 500 ℃, and the time is 3 to 8h.
4. In the scheme, in S1, the washing is deionized water or ethanol ultrasonic cleaning; the drying temperature is 60 to 80 ℃.
5. In the scheme, in S3, the calcining temperature is 800 to 1000 ℃.
6. In the scheme, the chemical formula of the sodium-ion battery material obtained through S3 is Na 0.67 Fe 0.23- x Cu x Mn 0.77 O 2 Wherein 0 is<x≤0.2。
The working principle and the advantages of the invention are as follows:
1. the positive electrode material of the sodium-ion battery prepared by the invention is spherical porous particles, has a layered structure, high purity and uniform phase, and by the design, the multiplying power performance and the cycling stability of the material are further improved, and the working voltage range is also improved to a certain extent;
2. the sodium ion battery material adopts copper salt to replace cobalt salt and nickel salt, and can effectively reduce the production cost of the material on the premise of meeting high energy density and being environment-friendly;
3. the preparation method provided by the invention has the advantages of mild reaction conditions, simplicity, high efficiency, easily obtained raw materials, greenness, environmental protection and suitability for industrial large-scale production.
Drawings
FIG. 1 is an XRD pattern of a battery material obtained in example 1 of the present invention;
FIG. 2 is an SEM photograph of a battery material obtained in example 1 of the present invention;
FIG. 3 is an SEM photograph of a battery material obtained in example 2 of the present invention;
FIG. 4 is an SEM photograph of a battery material obtained in example 3 of the present invention;
fig. 5 is an SEM image of the battery material obtained in example 4 of the present invention.
Detailed Description
The invention is further described with reference to the following figures and examples:
the present disclosure will be described in detail and with reference to the drawings, and it is to be understood that various changes and modifications can be made by those skilled in the art without departing from the spirit and scope of the present disclosure.
As used herein, the terms "comprising," "including," "having," and the like are open-ended terms that mean including, but not limited to.
As used herein, the term (terms), unless otherwise indicated, shall generally have the ordinary meaning as commonly understood by one of ordinary skill in the art, in this written description and in the claims. Certain words used to describe the disclosure are discussed below or elsewhere in this specification to provide additional guidance to those skilled in the art in describing the disclosure.
Example 1:
s1 precursor preparation: respectively weighing MnCl in proportion 2 ·4H 2 O、FeCl 3 ·6H 2 O、CuCl 2 ·2H 2 O (Mn, fe and Cu molar ratio is 1):0.24:0.06 Dissolved in deionized water to prepare a salt-forming solution, the salt solution is mixed with glycerol (the volume ratio of glycerol to deionized water is 1: 2) Carrying out hydrothermal reaction for 12h at 180 ℃, and washing and drying to obtain a carbonate precursor containing iron, copper and manganese;
s2, pre-burning: pre-burning the carbonate precursor obtained in the step S1 for 5 hours at 450 ℃ in an air atmosphere to obtain a ternary iron-copper-manganese oxide;
s3, calcining: and (2) fully mixing the oxide obtained in the S2 and sodium carbonate according to the mass ratio of (n (Mn + Fe + Cu) = n (Na) = 0.66), heating to 350 ℃ at the heating rate of 5 ℃/min, calcining for 2h, then heating to 850 ℃ at the same heating rate of 5 ℃/min, and calcining for 11 h, thus obtaining the sodium-ion battery material.
From FIG. 1, it can be seen that the chemical formula of the sodium-ion battery material prepared in this example is Na 0.67 Fe 0.18 Cu 0.05 Mn 0.77 O 2 Fig. 2 is a scanning electron microscope image of the battery material prepared in this embodiment, and it can be seen from the image that the microstructure of the prepared battery material is spherical.
Example 2:
s1 precursor preparation: respectively weighing MnCl in proportion 2 ·4H 2 O、FeCl 3 ·6H 2 O、CuCl 2 ·2H 2 Dissolving O (the molar ratio of Mn to Fe to Cu is 1;
s2, pre-burning: pre-sintering the carbonate precursor obtained in the step S1 at 450 ℃ for 5 hours to obtain a ternary iron-copper-manganese oxide;
s3, calcining: and (2) fully mixing the oxide obtained in the S2 with sodium carbonate according to the mass ratio of (n (Mn + Fe + Cu) = n (Na) = 1) to 0.66, heating to 350 ℃ at the heating rate of 5 ℃/min, calcining for 2h, then heating to 850 ℃ at the same heating rate of 5 ℃/min, and calcining for 11 h, thus obtaining the sodium-ion battery material.
The chemical formula of the sodium-ion battery material prepared in the embodiment is Na 0.67 Fe 0.08 Cu 0.15 Mn 0.77 O 2 Fig. 3 is a scanning electron microscope image of the battery material prepared in this embodiment, and it can be seen from the image that the microstructure of the prepared battery material is spherical.
Example 3:
s1 precursor preparation: respectively weighing MnCl in proportion 2 ·4H 2 O、FeCl 3 ·6H 2 O、CuCl 2 ·2H 2 Dissolving O (the molar ratio of Mn to Fe to Cu is 1;
s2, pre-burning: pre-burning the carbonate precursor obtained in the step S1 at 400 ℃ for 6h to obtain a ternary iron-copper-manganese oxide;
s3, calcining: and (2) fully mixing the oxide obtained in the S2 and sodium carbonate according to the mass ratio of (n (Mn + Fe + Cu) = n (Na) = 0.66), heating to 350 ℃ at the heating rate of 5 ℃/min, calcining for 2h, then heating to 850 ℃ at the same heating rate of 5 ℃/min, and calcining for 11 h, thus obtaining the sodium-ion battery material.
The chemical formula of the sodium-ion battery material prepared in the embodiment is Na 0.67 Fe 0.08 Cu 0.15 Mn 0.77 O 2 Fig. 4 is a scanning electron microscope image of the battery material prepared in this embodiment, and it can be seen from the image that the microstructure of the prepared battery material is spherical.
Example 4:
s1 precursor preparation: respectively weighing MnCl in proportion 2 ·4H 2 O、FeCl 3 ·6H 2 O、CuCl 2 ·2H 2 Dissolving O (molar ratio of Mn, fe and Cu is 1;
s2, pre-burning: pre-sintering the carbonate precursor obtained in the step S1 at 400 ℃ for 6 hours to obtain a ternary iron-copper-manganese oxide;
s3, calcining: and (2) fully mixing the oxide obtained in the S2 with sodium carbonate according to the mass ratio of (n (Mn + Fe + Cu) = n (Na) = 1) to 0.66, heating to 350 ℃ at the heating rate of 5 ℃/min, calcining for 2h, then heating to 850 ℃ at the same heating rate of 5 ℃/min, and calcining for 11 h, thus obtaining the sodium-ion battery material.
The chemical formula of the sodium-ion battery material prepared in the embodiment is Na 0.67 Fe 0.08 Cu 0.15 Mn 0.77 O 2 Fig. 5 is a scanning electron microscope image of the battery material prepared in this embodiment, and it can be seen from the image that the microstructure of the prepared battery material is spherical.
The above embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention by this means. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. A spherical porous sodium ion battery material is characterized in that:
has a chemical formula of Na 0.67 Fe 0.23-x Cu x Mn 0.77 O 2 Wherein 0 is<x≤0.2；
The sodium ion battery material is spherical porous particles and has a layered structure.
2. A preparation method of a spherical porous sodium-ion battery material is characterized by comprising the following steps: the method comprises the following steps:
s1 precursor preparation: weighing MnCl in proportion 2 、FeCl 3 、CuCl 2 Preparing a mixed salt solution, carrying out hydrothermal reaction on the mixed salt solution and glycerol, and washing and drying a product after the reaction to obtain a carbonate precursor containing iron, copper and manganese;
s2, pre-burning: pre-sintering the carbonate precursor obtained in the step S1 to obtain a ternary iron-copper-manganese oxide;
s3, calcining: dispersing the ternary iron-copper-manganese oxide obtained in the step S2 and sodium carbonate into water, mixing, freezing, drying and calcining, wherein the mixing mass ratio of the ternary iron-copper-manganese oxide to the sodium carbonate is 2.5-3.5: 1, obtaining the sodium-ion battery material.
3. The method of claim 2, wherein: in S1, the doping amount of each element in the mixed salt solution is Cu mol /(Fe+Mn+Cu) mol =0.05~0.3。
4. The method of claim 2, wherein: in S1, the temperature of the hydrothermal reaction is controlled to be 160-200 ℃, and the reaction time is 10-20h.
5. The method of claim 2, wherein: and in S2, the temperature of the pre-sintering is 350 to 500 ℃, and the time is 3 to 8h.
6. The method of claim 2, wherein: in S1, the washing is deionized water or ethanol ultrasonic cleaning; the drying temperature is 60 to 80 ℃.
7. The method of claim 2, wherein: in S3, the calcining temperature is 800 to 1000 ℃.
8. The method of claim 2, wherein: the chemical formula of the sodium-ion battery material obtained through S3 is Na 0.67 Fe 0.23-x Cu x Mn 0.77 O 2 Wherein 0 is<x≤0.2。
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| CN117509740A (en) * | 2023-11-03 | 2024-02-06 | 江门市科恒实业股份有限公司 | Copper-iron-manganese precursor for sodium ion battery and positive electrode material |
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| CN117509740A (en) * | 2023-11-03 | 2024-02-06 | 江门市科恒实业股份有限公司 | Copper-iron-manganese precursor for sodium ion battery and positive electrode material |
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