CN111224098A - Nitrogen-doped carbon modified FeSe negative electrode material for high-performance sodium battery and preparation method thereof - Google Patents
Nitrogen-doped carbon modified FeSe negative electrode material for high-performance sodium battery and preparation method thereof Download PDFInfo
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- CN111224098A CN111224098A CN202010046127.2A CN202010046127A CN111224098A CN 111224098 A CN111224098 A CN 111224098A CN 202010046127 A CN202010046127 A CN 202010046127A CN 111224098 A CN111224098 A CN 111224098A
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a nitrogen-doped carbon modified FeSe cathode material for a high-performance sodium battery and a preparation method thereof, wherein the preparation method comprises the following steps: mixing Prussian blue and selenium powder, and grinding to fully and uniformly mix the powder; transferring the powder into a porcelain boat, calcining under the inert gas atmosphere, and cooling to room temperature; and washing, centrifuging and drying the obtained product to obtain the nitrogen-doped carbon modified FeSe material. According to the invention, the limited conductivity and stability of FeSe are effectively solved by carrying out nitrogen-doped carbon modification on FeSe. FeSe is fixed in the N-C grid, so that the FeSe is not easy to agglomerate and peel off in a circulation process, and the unique structure of the FeSe electrode effectively improves the conductivity and the structural durability of the FeSe electrode. In addition, the nitrogen-doped carbon modified FeSe material prepared by the invention also has excellent specific capacity and cycling stability.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a nitrogen-doped carbon modified FeSe cathode material for a high-performance sodium battery and a preparation method thereof.
Background
In recent years, most of electronic products on the market have widely used lithium ion batteries, and rechargeable lithium ion batteries have to be said to have penetrated the aspects of our daily lives due to the advantages of high energy density, but the resources of lithium are limited, and the lithium content on the earth cannot meet the industrial requirements, so people have shifted the direction to sodium ion batteries. However, the storage capacity of the graphite negative electrode which is already commercialized in the lithium ion battery is low in the sodium ion battery, so that the practical application is limited, and therefore, a negative electrode material with higher capacity and energy density needs to be searched.
A large number of research facts prove that the selenide has higher conductivity and lower energy consumption of conversion reaction. Taking FeSe as an example, as a typical two-dimensional layered structure, alkali metal ions are theoretically efficiently intercalated and deintercalated between layers, which also provides a structural basis for secondary alkali metal ion batteries. However, due to limited conductivity and volume change and poor stability, the sodium ion battery performance of FeSe cannot be effectively improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a nitrogen-doped carbon modified FeSe cathode material for a high-performance sodium battery and a preparation method thereof.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of a nitrogen-doped carbon modified FeSe negative electrode material for a high-performance sodium battery comprises the following steps:
mixing Prussian blue and selenium powder, and grinding to fully and uniformly mix the powder;
transferring the powder into a porcelain boat, calcining the powder in an inert gas atmosphere, and naturally cooling the calcined powder to room temperature;
and step three, washing the obtained product with water and ethanol, centrifuging and drying to obtain the nitrogen-doped carbon modified FeSe material.
Further, in the first step, the mass ratio of the Prussian blue to the selenium powder is 1:0.9, and the molar mass ratio of Fe to Se is 1: 1.4.
Further, the milling time was 30 min.
Further, in the second step, the inert gas is argon, the calcining temperature is 650 ℃, the calcining time is 5 hours, and the calcining temperature rise rate is 1 ℃/min.
Further, the drying temperature in the third step is 60 ℃.
The nitrogen-doped carbon modified FeSe cathode material prepared by any one of the preparation methods.
Further, the nitrogen-doped carbon modified FeSe cathode material is used as a cathode material of a sodium battery.
Has the advantages that: the high performance and the mass production of the sodium battery cathode material can be realized.
According to the invention, the problem of limited conductivity and poor stability of FeSe is effectively solved by carrying out nitrogen-doped carbon modification on FeSe. FeSe is fixed in the N-doped C grid, so that the FeSe is not easy to agglomerate and peel off in the circulating process, and the unique structure of the FeSe electrode effectively improves the conductivity and the structural durability of the FeSe electrode. In addition, the preparation method has cheap raw materials and is easy for large-scale production.
The nitrogen-doped carbon modified FeSe material prepared by the invention has the reversible capacity of 468.5mAh/g after 100 times of circulation under the test current of 0.5C, still has the high specific capacity of 333.9mAh/g after 800 times of circulation under the test multiplying power of 2C, and has excellent specific capacity and circulation stability.
Drawings
Fig. 1 is an X-ray diffraction pattern of a nitrogen-doped carbon-modified FeSe material prepared in example 2 of the present invention;
fig. 2 is an electron microscope photograph of a nitrogen-doped carbon-modified FeSe material prepared in example 2 of the present invention;
fig. 3 is a performance curve of a sodium battery with a negative electrode made of nitrogen-doped carbon-modified FeSe material prepared in example 2 of the invention after 100 cycles at a test rate of 0.5C;
fig. 4 is a cycle performance curve obtained by assembling the unmodified FeSe material prepared in example 1 and the nitrogen-doped carbon-modified FeSe material prepared in experimental example 2 into a sodium battery at a test rate of 2.0C.
Detailed Description
The following detailed description of the present invention is provided in connection with the accompanying drawings and examples, but not intended to limit the scope of the invention. Unless otherwise specified, the reagents and materials used in the present invention are commercially available products or products obtained by a known method.
Example 1: preparation of unmodified FeSe material
Mixing Fe powder and Se powder, and grinding for 30min by using a mortar to fully and uniformly mix the Fe powder and the Se powder;
placing the ground sample into a tubular furnace, calcining in an argon atmosphere at the temperature of 650 ℃ for 5h at the temperature rise rate of 1 ℃/min, and naturally cooling to room temperature after calcining;
and step three, washing the obtained product with water and ethanol in sequence, centrifuging, and drying at 60 ℃ to obtain the unmodified FeSe material.
Wherein the molar ratio of the Fe powder to the Se powder is 1: 1.4.
Example 2: preparation of nitrogen-doped carbon modified FeSe material
Step one, mixing commercially available Prussian blue with Se powder, and grinding for 30min by using a mortar to uniformly mix;
placing the ground sample into a tubular furnace, calcining in an argon atmosphere at the temperature of 650 ℃ for 5h at the temperature rise rate of 1 ℃/min, and naturally cooling to room temperature after calcining;
and step three, washing the obtained product with water and ethanol in sequence, centrifuging, and drying at 60 ℃ to obtain the nitrogen-doped carbon modified FeSe material.
Wherein the mass ratio of the Prussian blue to the Se powder is 1:0.9, and the molar ratio of Fe to Se is 1: 1.4.
The nitrogen-doped carbon modified FeSe material obtained in the example 2 is subjected to characterization test: and performing X-ray diffraction analysis and electron microscope analysis on the prepared nitrogen-doped carbon modified FeSe material to obtain the characterization results shown in the figure 1 and the figure 2.
Example 3: performance testing
The unmodified FeSe material obtained in example 1 and the nitrogen-doped carbon modified FeSe material obtained in experimental example 2 are used as electrode materials, and are mixed with super p and sodium carboxymethyl cellulose (CMC) binder according to the mass ratio of 7:2:1Mixing uniformly according to the proportion, adding a proper mixed solution of ethanol and water (the volume ratio of the ethanol to the water is 2:3), ball-milling for 3h in a ball mill, collecting slurry, uniformly coating the slurry on the carbon-coated copper foil with the thickness of 200 mu m, and drying for 10h in vacuum at the temperature of 110 ℃. Cutting the dried electrode plate into round pieces with uniform diameter of 12mm, using lithium disk as counter electrode, and Ethylene Carbonate (EC)/diethyl carbonate (DEC) (1:1, v/v) as 1M NaClO4Vinyl fluoride carbonate (FEC, 5%) as electrolyte, coin cell (2025) was performed in a glove box with low humidity and low oxygen values, and the cycle life of the cells was determined on a new weil cell measurement system at room temperature.
The reversible capacity of the nitrogen-doped carbon modified FeSe material after 100 cycles is detected to be 468.5mAh/g under the test current of 0.5C (the detection result is shown in figure 3). Under the 2C test multiplying power, the nitrogen-doped carbon modified FeSe material still has high specific capacity of 333.9mAh/g after being cycled for 800 times, and the unmodified FeSe material has reversible capacity of only 100.6mAh/g after being cycled for 250 times (the detection result is shown in figure 4).
According to the invention, the limited conductivity and stability of FeSe are effectively solved by carrying out nitrogen-doped carbon modification on FeSe. FeSe is fixed in the N-C grid, so that the FeSe is not easy to agglomerate and peel off in a circulation process, and the unique structure of the FeSe electrode effectively improves the conductivity and the structural durability of the FeSe electrode. In addition, the preparation method has cheap raw materials and is easy for large-scale production.
The nitrogen-doped carbon modified FeSe material prepared by the invention has the reversible capacity of 468.5mAh/g after 100 times of circulation under the test current of 0.5C, still has the high specific capacity of 333.9mAh/g after 800 times of circulation under the test multiplying power of 2C, and has excellent capacitance and circulation stability.
The above-described embodiments are intended to be illustrative of the nature of the invention, but those skilled in the art will recognize that the scope of the invention is not limited to the specific embodiments.
Claims (7)
1. A preparation method of a nitrogen-doped carbon modified FeSe cathode material for a high-performance sodium battery is characterized by comprising the following steps:
mixing Prussian blue and selenium powder, and grinding to fully and uniformly mix the powder;
transferring the powder into a porcelain boat, calcining the powder in an inert gas atmosphere, and naturally cooling the calcined powder to room temperature;
and step three, washing the obtained product with water and ethanol, centrifuging and drying to obtain the nitrogen-doped carbon modified FeSe material.
2. The method of claim 1, wherein: in the first step, the mass ratio of the Prussian blue to the selenium powder is 1:0.9, and the molar mass ratio of Fe to Se is 1: 1.4.
3. The method of claim 2, wherein: the grinding time was 30 min.
4. The method of claim 1, wherein: in the second step, the inert gas is argon, the calcining temperature is 650 ℃, the calcining time is 5h, and the calcining speed is 1 ℃/min.
5. The method of claim 1, wherein: the drying temperature in the third step is 60 ℃.
6. The nitrogen-doped carbon-modified FeSe anode material prepared by the preparation method of any one of claims 1 to 5.
7. Use of the nitrogen-doped carbon-modified FeSe anode material of claim 6 as a sodium battery anode material.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111785970A (en) * | 2020-07-16 | 2020-10-16 | 长沙理工大学 | Double-layer carbon-coated-metal selenide composite electrode material and preparation method thereof |
| CN113178571A (en) * | 2021-03-17 | 2021-07-27 | 湖南理工学院 | Hierarchical porous Fe3Se4@ NC @ CNTs composite material and preparation method and application thereof |
| CN114180537A (en) * | 2021-11-18 | 2022-03-15 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nitrogen-doped carbon-coated lithium ion battery cathode material |
| CN116332137A (en) * | 2023-01-05 | 2023-06-27 | 南京信息工程大学 | Multi-metal selenide wave-absorbing material and preparation method thereof |
| CN117543010A (en) * | 2023-11-02 | 2024-02-09 | 北京化工大学 | FeSe electrode material with high tap density and homologous heterostructure and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106848274A (en) * | 2017-03-09 | 2017-06-13 | 华中科技大学 | The preparation method and sodium-ion battery of a kind of Nanoscale Iron selenium compound |
| CN107195876A (en) * | 2017-04-27 | 2017-09-22 | 华中科技大学 | The preparation method and sodium-ion battery of a kind of Nanoscale Iron selenium sulfide |
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- 2020-01-16 CN CN202010046127.2A patent/CN111224098A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106848274A (en) * | 2017-03-09 | 2017-06-13 | 华中科技大学 | The preparation method and sodium-ion battery of a kind of Nanoscale Iron selenium compound |
| CN107195876A (en) * | 2017-04-27 | 2017-09-22 | 华中科技大学 | The preparation method and sodium-ion battery of a kind of Nanoscale Iron selenium sulfide |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111785970A (en) * | 2020-07-16 | 2020-10-16 | 长沙理工大学 | Double-layer carbon-coated-metal selenide composite electrode material and preparation method thereof |
| CN111785970B (en) * | 2020-07-16 | 2021-11-02 | 长沙理工大学 | Double-layer carbon-coated-metal selenide composite electrode material and preparation method thereof |
| CN113178571A (en) * | 2021-03-17 | 2021-07-27 | 湖南理工学院 | Hierarchical porous Fe3Se4@ NC @ CNTs composite material and preparation method and application thereof |
| CN113178571B (en) * | 2021-03-17 | 2022-06-24 | 湖南理工学院 | Hierarchical porous Fe3Se4@ NC @ CNTs composite material and preparation method and application thereof |
| CN114180537A (en) * | 2021-11-18 | 2022-03-15 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nitrogen-doped carbon-coated lithium ion battery cathode material |
| CN114180537B (en) * | 2021-11-18 | 2023-05-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nitrogen-doped carbon-coated negative electrode material for lithium ion battery |
| CN116332137A (en) * | 2023-01-05 | 2023-06-27 | 南京信息工程大学 | Multi-metal selenide wave-absorbing material and preparation method thereof |
| CN116332137B (en) * | 2023-01-05 | 2024-05-24 | 南京信息工程大学 | Multi-metal selenide wave-absorbing material and preparation method thereof |
| CN117543010A (en) * | 2023-11-02 | 2024-02-09 | 北京化工大学 | FeSe electrode material with high tap density and homologous heterostructure and preparation method thereof |
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Application publication date: 20200602 |