CN109638274B - Molybdenum-ytterbium co-doped sodium iron silicate composite electrode material and preparation method thereof - Google Patents
Molybdenum-ytterbium co-doped sodium iron silicate composite electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a molybdenum-ytterbium co-doped sodium iron silicate composite electrode material, and a preparation method and application thereof, wherein the molecular formula of the composite electrode material is Na2‑x‑yFeMoxYbySiO4C, wherein 0<x≤0.2，0<y is less than or equal to 0.2. According to the invention, the molybdenum and ytterbium co-doped ferric sodium silicate is utilized to modify the ferric sodium silicate, and a high-conductivity carbon source is introduced to carry out compounding, so that the electrochemical performance of the ferric sodium silicate is effectively improved, and the molybdenum and ytterbium co-doped ferric sodium silicate composite electrode material with high conductivity, high specific capacity, high rate characteristic and long cycle life is obtained. In addition, the carbon source is introduced twice by the step-by-step ball milling method in the preparation process, so that the method is low in cost and high in controllability, and the good crystallinity and uniformity of the material are ensured by the step-by-step heat treatment process, so that the performance of the material is further improved, and the method has good economic benefits and application prospects.
Description
Technical Field
The invention relates to the technical field of sodium-ion battery positive electrode materials, in particular to a molybdenum-ytterbium co-doped ferric sodium silicate composite electrode material and a preparation method and application thereof.
Background
With the increasing fossil energy consumption of human beings, environmental problems such as haze, greenhouse effect and the like become serious. All countries change the economic mode based on fossil fuel to the economic mode based on new energy, and the development of renewable energy and clean energy is a major strategic task for the economic and social development of China. The high-speed development of the society demands high-safety and low-cost energy storage technology urgently. Currently, lithium ion batteries are the most widely used and studied energy storage batteries, but due to the limited storage capacity of metal lithium, the price is rising year by year, and the requirement of large-scale energy storage technology, the research of sodium ion batteries gradually attracts attention.
From the aspects of cost, energy consumption, resources and the like, the sodium ion battery has great market competitive advantages in the aspect of large-scale energy storage. Since the radius of sodium ions is larger than that of lithium ions, the current research is critical to develop an electrode material capable of stably and rapidly extracting and intercalating sodium ions.
Among many sodium ion battery positive electrode materials, silicate is favored because of its excellent chemical stability, abundant silicon resource, environmental friendliness, and the like, but synthesis of sodium iron silicate is difficult and the synthesis method still has certain limitations.
Shouding Li et al synthesized Na for the first time by a solid phase method and a sol-gel method2FeSiO4The material, when used as the positive electrode material of the sodium ion battery, is 10mA g-1The capacity can be kept at 106mAh g in 20 weeks of circulation under the current density-1(Li S,Guo J,Ye Z,et al.Zero-strain Na2FeSiO4as novel cathode material for sodium-ion batteries.ACS applied materials&interfaces,2016,8(27): 17233-. Wenhao Guan et al synthesized Na by sol-gel method2FeSiO4The material of the/C electrode material is in a three-dimensional cross-linked net structure, and the cycle performance of the material is obviously improved after the material is compounded with carbon. At 0.1C (1C ═ 276mA g-1) Under the current density, the capacity of the circulating 100 circles can still be kept at 181mAh g-1And pure Na2FeSiO4The capacity of the material is attenuated to 100mAh g after 40 cycles of circulation-1Left and right (Guan W, Pan B, Zhou P, et al. A high capacity, good safety a)nd low cost Na2FeSiO4-based cathode for rechargeable sodium-ion battery.ACS applied materials&interfaces,2017,9(27):22369-22377)。
In addition, in the application aspect of sodium iron silicate, CN107492630A discloses a flexible electrode material for sodium ion batteries, a preparation method thereof, and a sodium ion battery, wherein the electrode material comprises: a carbon nanofiber network skeleton composed of a plurality of carbon nanofibers, and host material particles distributed among the plurality of carbon nanofibers, wherein the host material particles can be Na2FeSiO4. CN108134089A discloses a method for preparing a high-load active material electrode, in which a pore-forming agent is added during the preparation of an electrode slurry, and the electrode slurry is blade-coated on an aluminum foil current collector by a coating device to form an electrode-current collector integrated electrode, wherein the electrode active material in the electrode slurry can be sodium ferric silicate.
Although the sodium iron silicate material is synthesized and applied to the electrode material, the sodium iron silicate has the problems of poor electronic conductivity, slow ion diffusion rate and the like, so that the further application of the sodium iron silicate material is influenced, the electrochemical properties such as the cycle stability, the rate capability and the like of the sodium iron silicate material still need to be further improved, and the synthesis process also needs to be further optimized.
Disclosure of Invention
In order to solve the technical problems, the invention provides a molybdenum-ytterbium co-doped sodium iron silicate composite electrode material, and a preparation method and application thereof.
In a first aspect, the invention provides a molybdenum-ytterbium co-doped sodium iron silicate composite electrode material, and the molecular formula of the composite electrode material is Na2-x-yFeMoxYbySiO4C, wherein 0<x≤0.2，0<y≤0.2。
The invention adopts a mode of codoping and introducing a second phase to modify the sodium ferric silicate. The co-doping of molybdenum ions and ytterbium ions can improve the conductivity of the material body, improve the crystal structure of the material body and convert the diffusion mechanism of sodium ions, and the doping of high-valence ions can enable Na sites to generate a small amount of vacant sites, thereby being beneficial to the migration of the sodium ions and improving the multiplying power performance of the material; the introduction of the high-conductivity carbon source can further improve the electronic conductivity of the material and improve the cycling stability of the material.
According to the invention, x in the formula is in the range 0< x.ltoreq.0.2, and may be, for example, 0.01, 0.03, 0.05, 0.08, 0.1, 0.13, 0.15, 0.18 or 0.2, and the values between these values are not exhaustive for reasons of brevity and brevity.
According to the invention, y in the formula is in the range 0< y.ltoreq.0.2, and may be, for example, 0.01, 0.03, 0.05, 0.08, 0.1, 0.13, 0.15, 0.18 or 0.2, and the values between these values are not exhaustive for reasons of brevity and brevity.
According to the invention, the carbon content of the composite electrode material is 1-30% by mass, for example 1%, 5%, 10%, 15%, 20%, 25% or 30%, and the specific values between the above values are not exhaustive for reasons of space and simplicity.
In a second aspect, the present invention provides a method for preparing a molybdenum-ytterbium co-doped sodium iron silicate composite electrode material, wherein the method comprises the following steps:
(1) preparing materials according to the proportion of each element in the molecular formula, mixing a sodium source, an iron source, a molybdenum source, an ytterbium source and a silicon source, performing primary ball milling, adding a carbon source after the ball milling is finished, and performing secondary ball milling to obtain a precursor;
(2) and (2) carrying out heat treatment on the precursor obtained in the step (1) to obtain the composite electrode material.
According to the present invention, the sodium source in step (1) is at least one of anhydrous sodium acetate, sodium hydroxide, sodium carbonate, sodium oxalate, sodium nitrite, disodium hydrogen phosphate, sodium bicarbonate, sodium citrate, anhydrous sodium sulfate, sodium stearate, sodium oleate, sodium tartrate, sodium alginate, sodium carboxymethylcellulose, sodium lactate or sodium humate, preferably at least one of anhydrous sodium acetate, sodium hydroxide, sodium carbonate or sodium oxalate, for example, any one of anhydrous sodium acetate, sodium hydroxide, sodium carbonate, sodium oxalate, sodium nitrite, disodium hydrogen phosphate, sodium bicarbonate, sodium citrate, anhydrous sodium sulfate, sodium stearate, sodium oleate, sodium tartrate, sodium alginate, sodium carboxymethylcellulose, sodium lactate or sodium humate, and a typical but non-limiting combination is: anhydrous sodium acetate and hydroxide, sodium carbonate and oxalate, sodium nitrite and disodium hydrogen phosphate, sodium bicarbonate and citrate, anhydrous sodium sulfate and stearate, sodium oleate and tartrate, sodium alginate and sodium carboxymethylcellulose, sodium lactate and sodium humate, and the like.
According to the invention, the iron source in the step (1) is ferrous oxalate and/or ferrous acetate.
According to the invention, the molybdenum source in step (1) is molybdenum dioxide.
According to the invention, the ytterbium source of step (1) is ytterbium oxide.
According to the invention, the silicon source in the step (1) is silicon dioxide and/or ethyl orthosilicate.
According to the present invention, the carbon source in step (1) is at least one of glucose, sucrose, fructose, polyethylene glycol, graphene, polyvinyl alcohol, carbon fiber, soluble starch, coal pitch, carbon black, dextrin, coke, cellulose, phenolic resin or carbon nanotube, for example, any one of glucose, sucrose, fructose, polyethylene glycol, graphene, polyvinyl alcohol, carbon fiber, soluble starch, coal pitch, carbon black, dextrin, coke, cellulose, phenolic resin or carbon nanotube, and a typical but non-limiting combination is: glucose and sucrose, fructose and polyethylene glycol, graphene and polyvinyl alcohol, carbon fiber and soluble starch, coal pitch and carbon black, dextrin and coke, cellulose, phenolic resin, carbon nanotubes and the like.
In the blending process in the step (1), the sodium source can be added according to the proportion in the molecular formula, but in order to compensate for sodium loss in the preparation process, the sodium source can be added in an excessive amount, the addition amount is within 10 wt% (relative to the sodium source), the specific addition amount is based on the material required for synthesis, and the sodium content in the product can meet the proportion in the molecular formula.
According to the present invention, the ball milling medium added in the primary ball milling and secondary ball milling processes in step (1) is at least one of water, ethanol, ethylene glycol or acetone, and may be any one of water, ethanol, ethylene glycol or acetone, for example, and a typical but non-limiting combination is: water and ethanol, ethylene glycol and acetone, water, ethanol and ethylene glycol, and the like.
According to the invention, the mass ratio of the grinding balls to the materials in the primary ball milling and the secondary ball milling in the step (1) is (4-20):1, and for example, the mass ratio can be 4:1, 5:1, 8:1, 10:1, 13:1, 15:1, 18:1 or 20:1, and the specific values between the above values are limited by space and for the sake of brevity, and the invention is not exhaustive.
According to the invention, the time of the primary ball milling in the step (1) is 2-10h, for example, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h, and the specific values between the above values are limited by space and for the sake of brevity, and the invention is not exhaustive.
According to the invention, the time of the secondary ball milling in the step (1) is 1-5h, for example, 1h, 2h, 3h, 4h or 5h, and the specific values between the above values are limited by space and for the sake of brevity, and the invention is not exhaustive.
According to the invention, the heat treatment of step (2) is carried out under a protective atmosphere, which is at least one of nitrogen, argon or helium.
According to the invention, the specific operation of the heat treatment in step (2) is as follows: the obtained precursor is firstly insulated for 1-10h at the temperature of 500 ℃ for 300-.
The step-by-step heat treatment mode can enable the electrode material to react more fully, has good crystallinity and uniformity, and further improves the electrochemical performance of the composite electrode material.
According to the present invention, the temperature of the first heat treatment in the step heat treatment process is 300-,
and the specific values therebetween, are not exhaustive for the invention, but are limited to the space and for the sake of brevity.
According to the present invention, the time of the first heat treatment in the step heat treatment process is 1-10h, for example, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h, and the specific values between the above values are limited by space and for the sake of brevity, and the present invention is not exhaustive.
According to the present invention, the temperature of the second heat treatment in the step heat treatment process is 500-.
According to the present invention, the time of the second heat treatment in the step heat treatment process is 6-18h, for example, 6h, 8h, 10h, 12h, 14h, 16h or 18h, and the specific values between the above values are limited by space and for brevity, the present invention is not exhaustive.
As a preferred technical scheme, the preparation method of the molybdenum-ytterbium co-doped sodium iron silicate composite electrode material comprises the following steps:
(1) preparing materials according to the proportion of each element in the molecular formula, mixing a sodium source, an iron source, a molybdenum source, an ytterbium source and a silicon source, placing the mixture into a ball milling tank, controlling the mass ratio of milling balls to materials to be (4-20):1, adding a ball milling medium, carrying out primary ball milling for 2-10h, adding a carbon source after the ball milling is finished, and carrying out secondary ball milling for 1-5h to obtain a precursor;
(2) and (3) under a protective atmosphere, firstly, preserving the heat of the precursor obtained in the step (1) at the temperature of 300-500 ℃ for 1-10h, then, heating to the temperature of 500-900 ℃ and preserving the heat for 6-18h to obtain the composite electrode material.
In a third aspect, the invention provides an application of the molybdenum-ytterbium co-doped iron sodium silicate composite electrode material as a sodium ion battery positive electrode material.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) according to the invention, the molybdenum and ytterbium co-doped ferric sodium silicate composite electrode material with high conductivity, high specific capacity, high rate characteristic and long cycle life is obtained by modifying ferric sodium silicate by co-doping molybdenum and ytterbium and introducing a high-conductivity carbon source for compounding. The obtained material has excellent electrochemical performance, the first cyclic discharge specific capacity is more than 188mAh/g, and the capacity retention rate of 200 cycles of the cycle is more than or equal to 90 percent under the voltage window of 1.5-4.0V and the current density of 0.1C.
(2) The carbon source is introduced twice by the step-by-step ball milling method in the preparation process, the cost is low, the controllability is strong, the material has good crystallinity and uniformity by the step-by-step heat treatment process, the performance of the material is further improved, the method is beneficial to large-scale production, and the method has wide application prospect.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a molybdenum-ytterbium co-doped sodium iron silicate composite electrode material, and the molecular formula of the composite electrode material is Na1.7FeMo0.2Yb0.1SiO4The preparation was carried out according to the following method.
(1) Weighing anhydrous sodium acetate, ferrous oxalate, molybdenum dioxide, ytterbium oxide and ethyl orthosilicate according to the molar ratio of elements in the molecular formula, mixing the raw materials, placing the mixture into a ball milling tank, controlling the mass ratio of milling balls to the materials to be 10:1, carrying out ball milling in acetone for 2 hours, adding glucose after the ball milling is finished, carrying out secondary ball milling for 5 hours to obtain a precursor, and drying the precursor;
(2) and (2) under a nitrogen atmosphere, firstly, preserving the heat of the precursor obtained in the step (1) at 350 ℃ for 4h, then, heating to 900 ℃, and preserving the heat for 10h to obtain the composite electrode material, wherein the mass fraction of carbon in the composite electrode material is 10%.
The obtained electrode material is used as a positive electrode material of a sodium-ion battery to carry out electrochemical performance test, and the electrode material is prepared from the following components in percentage by weight: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking metal sodium as a reference electrode. Under the voltage window of 1.5-4.0V and the current density of 0.1C, the first cyclic discharge specific capacity is 200mAh/g, and the capacity retention rate of 200 cycles is 93%.
Example 2
The embodiment provides a molybdenum-ytterbium co-doped sodium iron silicate composite electrode material, and the molecular formula of the composite electrode material is Na1.8FeMo0.1Yb0.1SiO4The preparation was carried out according to the following method.
(1) Weighing sodium hydroxide, ferrous oxalate, molybdenum dioxide, ytterbium oxide and silicon dioxide according to the molar ratio of elements in the molecular formula, mixing the raw materials, placing the mixture into a ball milling tank, controlling the mass ratio of milling balls to the materials to be 4:1, carrying out ball milling in deionized water for 10 hours, adding cane sugar after the ball milling is finished, carrying out secondary ball milling for 1 hour to obtain a precursor, and drying the precursor;
(2) and (2) under the nitrogen atmosphere, firstly, preserving the heat of the precursor obtained in the step (1) at 400 ℃ for 2h, then, heating to 800 ℃, and preserving the heat for 12h to obtain the composite electrode material, wherein the mass fraction of carbon in the composite electrode material is 5%.
The obtained electrode material is used as a positive electrode material of a sodium-ion battery to carry out electrochemical performance test, and the electrode material is prepared from the following components in percentage by weight: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking metal sodium as a reference electrode. Under the voltage window of 1.5-4.0V and the current density of 0.1C, the first cyclic discharge specific capacity is 204mAh/g, and the capacity retention rate of 200 cycles is 92%.
Example 3
The embodiment provides a molybdenum-ytterbium co-doped sodium iron silicate composite electrode material, and the molecular formula of the composite electrode material is Na1.94FeMo0.05Yb0.01SiO4The preparation was carried out according to the following method.
(1) Weighing sodium carbonate, ferrous acetate, molybdenum dioxide, ytterbium oxide and ethyl orthosilicate according to the molar ratio of elements in the molecular formula, mixing the raw materials, placing the mixture into a ball milling tank, controlling the mass ratio of milling balls to the materials to be 20:1, carrying out ball milling in ethanol for 4 hours, adding graphene after the ball milling is finished, carrying out secondary ball milling for 3 hours to obtain a precursor, and drying the precursor;
(2) and (2) under the argon atmosphere, firstly, preserving the heat of the precursor obtained in the step (1) for 8h at 500 ℃, then heating to 600 ℃, and preserving the heat for 18h to obtain the composite electrode material, wherein the mass fraction of carbon in the composite electrode material is 20%.
The obtained electrode material is used as a positive electrode material of a sodium-ion battery to carry out electrochemical performance test, and the electrode material is prepared from the following components in percentage by weight: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking metal sodium as a reference electrode. Under the voltage window of 1.5-4.0V and the current density of 0.1C, the first cyclic discharge specific capacity is 195mAh/g, and the capacity retention rate of 200 cycles is 91%.
Example 4
The embodiment provides a molybdenum-ytterbium co-doped sodium iron silicate composite electrode material, and the molecular formula of the composite electrode material is Na1.81FeMo0.17Yb0.02SiO4The preparation was carried out according to the following method.
(1) Weighing anhydrous sodium acetate, sodium oxalate, ferrous oxalate, molybdenum dioxide, ytterbium oxide and ethyl orthosilicate according to the molar ratio of elements in the molecular formula, mixing the raw materials, placing the mixture into a ball milling tank, controlling the mass ratio of milling balls to the materials to be 15:1, carrying out ball milling in ethylene glycol for 7 hours, adding phenolic resin after the ball milling is finished, carrying out secondary ball milling for 2 hours to obtain a precursor, and drying the obtained precursor;
(2) and (2) under the nitrogen atmosphere, firstly, preserving the heat of the precursor obtained in the step (1) at 450 ℃ for 6h, then heating to 700 ℃, and preserving the heat for 12h to obtain the composite electrode material, wherein the mass fraction of carbon in the composite electrode material is 30%.
The obtained electrode material is used as a positive electrode material of a sodium-ion battery to carry out electrochemical performance test, and the electrode material is prepared from the following components in percentage by weight: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking metal sodium as a reference electrode. Under the voltage window of 1.5-4.0V and the current density of 0.1C, the first cyclic discharge specific capacity is 189mAh/g, and the capacity retention rate of 200 cycles is 94%.
Example 5
The embodiment provides a molybdenum-ytterbium co-doped sodium iron silicate composite electrode material, and the molecular formula of the composite electrode material is Na1.79FeMo0.2Yb0.01SiO4The preparation was carried out according to the following method.
(1) Weighing disodium hydrogen phosphate, ferrous oxalate, molybdenum dioxide, ytterbium oxide and silicon dioxide according to the molar ratio of elements in the molecular formula, mixing the raw materials, placing the mixture into a ball milling tank, controlling the mass ratio of milling balls to the materials to be 20:1, carrying out ball milling in deionized water for 10 hours, adding carbon nanotubes after the ball milling is finished, carrying out secondary ball milling for 4 hours to obtain a precursor, and drying the precursor;
(2) and (2) under a helium atmosphere, firstly, preserving the heat of the precursor obtained in the step (1) at 450 ℃ for 8h, then heating to 650 ℃, and preserving the heat for 12h to obtain the composite electrode material, wherein the mass fraction of carbon in the composite electrode material is 15%.
The obtained electrode material is used as a positive electrode material of a sodium-ion battery to carry out electrochemical performance test, and the electrode material is prepared from the following components in percentage by weight: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking metal sodium as a reference electrode. Under the voltage window of 1.5-4.0V and the current density of 0.1C, the first cyclic discharge specific capacity is 198mAh/g, and the capacity retention rate is 91% after 200 cycles.
Example 6
The embodiment provides a molybdenum-ytterbium co-doped sodium iron silicate composite electrode material, and the molecular formula of the composite electrode material is Na1.78FeMo0.02Yb0.2SiO4The preparation was carried out according to the following method.
(1) Weighing anhydrous sodium sulfate, ferrous oxalate, ferrous acetate, molybdenum dioxide, ytterbium oxide and ethyl orthosilicate according to the molar ratio of elements in the molecular formula, mixing the raw materials, placing the mixture into a ball milling tank, controlling the mass ratio of milling balls to the materials to be 6:1, carrying out ball milling in ethylene glycol for 5 hours, adding glucose after the ball milling is finished, carrying out secondary ball milling for 1 hour to obtain a precursor, and drying the obtained precursor;
(2) and (2) under a nitrogen atmosphere, firstly, preserving the heat of the precursor obtained in the step (1) at 400 ℃ for 2h, then heating to 680 ℃, and preserving the heat for 14h to obtain the composite electrode material, wherein the mass fraction of carbon in the composite electrode material is 8%.
The obtained electrode material is used as a positive electrode material of a sodium-ion battery to carry out electrochemical performance test, and the electrode material is prepared from the following components in percentage by weight: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking metal sodium as a reference electrode. Under the voltage window of 1.5-4.0V and the current density of 0.1C, the first cyclic discharge specific capacity is 201mAh/g, and the capacity retention rate of 200 cycles is 90%.
Comparative example 1
The molecular formula of the composite electrode material provided by the comparative example is Na1.9FeYb0.1SiO4The preparation process is completely the same as the example 1 except that anhydrous sodium acetate, ferrous oxalate, ytterbium oxide and ethyl orthosilicate are weighed according to the molar ratio of each element in the molecular formula in the step (1) for proportioning.
The obtained electrode material is used as a positive electrode material of a sodium-ion battery to carry out electrochemical performance test, and the electrode material is prepared from the following components in percentage by weight: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking metal sodium as a reference electrode. Under the voltage window of 1.5-4.0V and the current density of 0.1C, the first cyclic discharge specific capacity is 180mAh/g, and the capacity retention rate of 200 cycles is 86%.
Comparative example 2
The molecular formula of the composite electrode material provided by the comparative example is Na1.8FeMo0.2SiO4and/C, except that anhydrous sodium acetate, ferrous oxalate, molybdenum dioxide and ethyl orthosilicate are weighed according to the molar ratio of each element in the molecular formula in the step (1) to prepare the ingredients in the preparation process, other steps and conditions are completely the same as those in the example 1.
The obtained electrode material is used as a positive electrode material of a sodium-ion battery to carry out electrochemical performance test, and the electrode material is prepared from the following components in percentage by weight: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking metal sodium as a reference electrode. Under the voltage window of 1.5-4.0V and the current density of 0.1C, the first cyclic discharge specific capacity is 181mAh/g, and the capacity retention rate of 200 cycles is 84%.
Comparative example 3
The molecular formula of the electrode material provided by the comparative example is Na1.7FeMo0.2Yb0.1SiO4The preparation process is completely the same as that of example 1 except that the precursor obtained in step (1) is directly subjected to heat treatment (without adding a carbon source) after the first ball milling.
The obtained electrode material is used as a positive electrode material of a sodium-ion battery to carry out electrochemical performance test, and the electrode material is prepared from the following components in percentage by weight: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking metal sodium as a reference electrode. Under the voltage window of 1.5-4.0V and the current density of 0.1C, the first cyclic discharge specific capacity is 186mAh/g, and the capacity retention rate of 200 cycles is 65%.
Comparative example 4
The molecular formula of the electrode material provided by the comparative example is Na2FeSiO4Except that anhydrous sodium acetate, ferrous oxalate and tetraethoxysilane are weighed according to the molar ratio of each element in the molecular formula in the step (1) for mixing, and the obtained precursor is directly subjected to heat treatment (without adding a carbon source) after the first ball milling, other steps and conditions are completely the same as those in the example 1.
The obtained electrode material is used as a positive electrode material of a sodium-ion battery to carry out electrochemical performance test, and the electrode material is prepared from the following components in percentage by weight: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking metal sodium as a reference electrode. Under the voltage window of 1.5-4.0V and the current density of 0.1C, the first cyclic discharge specific capacity is 154mAh/g, and the capacity retention rate of 200 cycles is 52%.
Comparative example 5
The molecular formula of the composite electrode material provided by the comparative example is Na1.55FeMo0.35Yb0.1SiO4The preparation process comprises the following steps, conditions and practices except that anhydrous sodium acetate, ferrous oxalate, molybdenum dioxide, ytterbium oxide and ethyl orthosilicate are weighed according to the molar ratio of each element in the molecular formula in the step (1) for proportioningExample 1 is identical.
The obtained electrode material is used as a positive electrode material of a sodium-ion battery to carry out electrochemical performance test, and the electrode material is prepared from the following components in percentage by weight: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking metal sodium as a reference electrode. Under the voltage window of 1.5-4.0V and the current density of 0.1C, the first cyclic discharge specific capacity is 170mAh/g, and the capacity retention rate of 200 cycles is 62%.
Comparative example 6
The molecular formula of the composite electrode material provided by the comparative example is Na1.5FeMo0.2Yb0.3SiO4and/C, except that anhydrous sodium acetate, ferrous oxalate, molybdenum dioxide, ytterbium oxide and ethyl orthosilicate are weighed according to the molar ratio of each element in the molecular formula in the step (1) to prepare the ingredients in the preparation process, other steps and conditions are completely the same as those in the example 1.
The obtained electrode material is used as a positive electrode material of a sodium-ion battery to carry out electrochemical performance test, and the electrode material is prepared from the following components in percentage by weight: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking metal sodium as a reference electrode. Under the voltage window of 1.5-4.0V and the current density of 0.1C, the first cyclic discharge specific capacity is 169mAh/g, and the capacity retention rate of 200 cycles is 60%.
Comparative example 7
The molecular formula of the composite electrode material provided by the comparative example is Na1.7FeSn0.2Yb0.1SiO4and/C, except that anhydrous sodium acetate, ferrous oxalate, tin oxide, ytterbium oxide and ethyl orthosilicate are weighed according to the molar ratio of each element in the molecular formula in the step (1) to prepare the ingredients in the preparation process, other steps and conditions are completely the same as those in the example 1.
The obtained electrode material is used as a positive electrode material of a sodium-ion battery to carry out electrochemical performance test, and the electrode material is prepared from the following components in percentage by weight: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking metal sodium as a reference electrode. Under the voltage window of 1.5-4.0V and the current density of 0.1C, the first cyclic discharge specific capacity is 176mAh/g, and the capacity retention rate of 200 cycles is 74%.
Comparative example 8
The molecular formula of the composite electrode material provided by the comparative example is Na1.7FeMo0.2Ce0.1SiO4and/C, except that anhydrous sodium acetate, ferrous oxalate, molybdenum dioxide, cerium oxide and ethyl orthosilicate are weighed according to the molar ratio of each element in the molecular formula in the step (1) to prepare the ingredients in the preparation process, other steps and conditions are completely the same as those in the example 1.
The obtained electrode material is used as a positive electrode material of a sodium-ion battery to carry out electrochemical performance test, and the electrode material is prepared from the following components in percentage by weight: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking metal sodium as a reference electrode. Under the voltage window of 1.5-4.0V and the current density of 0.1C, the first cyclic discharge specific capacity is 175mAh/g, and the capacity retention rate of 200 cycles is 71%.
Comparative example 9
The molecular formula of the composite electrode material provided by the comparative example is Na1.8FeMo0.1Yb0.1SiO4and/C, the preparation process is completely the same as the example 2 except that the precursor is directly heated to 800 ℃ in the step (2) and is kept for 12 h.
The obtained electrode material is used as a positive electrode material of a sodium-ion battery to carry out electrochemical performance test, and the electrode material is prepared from the following components in percentage by weight: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking metal sodium as a reference electrode. Under the voltage window of 1.5-4.0V and the current density of 0.1C, the first cyclic discharge specific capacity is 187mAh/g, and the capacity retention rate of 200 cycles is 88%.
From the above, the composite electrode materials prepared in embodiments 1 to 6 of the present invention have excellent electrochemical performance, and the first cyclic discharge specific capacity is greater than 188mAh/g and the capacity retention rate is greater than or equal to 90% at a current density of 0.1C and a voltage window of 1.5 to 4.0V. From comparative examples 1 to 4, it is clear that when Mo, Yb and composite carbon were not doped, the first capacity and cycle stability of the composite electrode material were significantly reduced. It is understood from comparative examples 5 to 6 that when the contents of Mo and Yb are too high, a sharp drop in the performance of the electrode material is caused. From comparative examples 7 and 8, it can be seen that when the electrode material is doped by replacing Mo with Sn or replacing Yb with Ce, the performance improvement of the electrode material is not obvious, which shows that the doped Mo and Yb can generate synergistic effect to effectively improve the electrochemical performance of the sodium iron silicate electrode material. From comparative example 9, it can be seen that when the precursor is directly prepared by one heating treatment (without step treatment), the first capacity and the cycling stability are slightly reduced, which indicates that the step heat treatment process can improve the electrochemical performance of the material to a certain extent.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (18)
1. The molybdenum-ytterbium co-doped sodium iron silicate composite electrode material is characterized in that the molecular formula of the composite electrode material is Na2-x-yFeMoxYbySiO4C, wherein 0<x≤0.2，0<y≤0.2。
2. The composite electrode material according to claim 1, wherein the carbon content in the composite electrode material is 1 to 30% by mass.
3. The method for preparing the molybdenum-ytterbium co-doped sodium iron silicate composite electrode material according to claim 1 or 2, wherein the method comprises the following steps:
(1) preparing materials according to the proportion of each element in the molecular formula, mixing a sodium source, an iron source, a molybdenum source, an ytterbium source and a silicon source, performing primary ball milling, adding a carbon source after the ball milling is finished, and performing secondary ball milling to obtain a precursor;
(2) and (2) carrying out heat treatment on the precursor obtained in the step (1) to obtain the composite electrode material.
4. The method of claim 3, wherein the sodium source of step (1) is at least one of anhydrous sodium acetate, sodium hydroxide, sodium carbonate, sodium oxalate, sodium nitrite, disodium hydrogen phosphate, sodium bicarbonate, sodium citrate, anhydrous sodium sulfate, sodium stearate, sodium oleate, sodium tartrate, sodium alginate, sodium carboxymethylcellulose, sodium lactate, or sodium humate.
5. The method of claim 4, wherein the sodium source of step (1) is at least one of anhydrous sodium acetate, sodium hydroxide, sodium carbonate, or sodium oxalate.
6. The method of claim 3, wherein the iron source of step (1) is ferrous oxalate and/or ferrous acetate.
7. The method of claim 3, wherein the molybdenum source of step (1) is molybdenum dioxide.
8. The method of claim 3, wherein the ytterbium source of step (1) is ytterbium oxide.
9. The method of claim 3, wherein the silicon source of step (1) is silicon dioxide and/or ethyl orthosilicate.
10. The method of claim 3, wherein the carbon source of step (1) is at least one of glucose, sucrose, fructose, polyethylene glycol, graphene, polyvinyl alcohol, carbon fiber, soluble starch, coal pitch, carbon black, dextrin, coke, cellulose, phenolic resin, or carbon nanotubes.
11. The method of claim 3, wherein the ball milling media added during the primary and secondary ball milling in step (1) is at least one of water, ethanol, ethylene glycol, or acetone.
12. The method of claim 3, wherein the mass ratio of the grinding balls to the material in the primary ball milling and the secondary ball milling in the step (1) is (4-20): 1.
13. The method of claim 3, wherein the time of the primary ball milling in step (1) is 2 to 10 hours.
14. The method of claim 3, wherein the time of the secondary ball milling in step (1) is 1 to 5 hours.
15. The method of claim 3, wherein the heat treatment of step (2) is performed under a protective atmosphere of at least one of nitrogen, argon, or helium.
16. The method of claim 3, wherein the heat treatment in step (2) is performed by: the obtained precursor is firstly insulated for 1-10h at the temperature of 500 ℃ for 300-.
17. A method according to claim 3, characterized in that the method comprises the steps of:
(1) preparing materials according to the proportion of each element in the molecular formula, mixing a sodium source, an iron source, a molybdenum source, an ytterbium source and a silicon source, placing the mixture into a ball milling tank, controlling the mass ratio of milling balls to materials to be (4-20):1, adding a ball milling medium, carrying out primary ball milling for 2-10h, adding a carbon source after the ball milling is finished, and carrying out secondary ball milling for 1-5h to obtain a precursor;
(2) and (3) under a protective atmosphere, firstly, preserving the heat of the precursor obtained in the step (1) at the temperature of 300-500 ℃ for 1-10h, then, heating to the temperature of 500-900 ℃ and preserving the heat for 6-18h to obtain the composite electrode material.
18. The use of the molybdenum ytterbium co-doped iron sodium silicate composite electrode material as claimed in claim 1 or 2 as a positive electrode material of a sodium ion battery.
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