CN112194122A - Preparation method of bismuth elementary substance/Prussian blue framework @ graphene composite material - Google Patents
Preparation method of bismuth elementary substance/Prussian blue framework @ graphene composite material Download PDFInfo
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Abstract
The invention provides a preparation method of a bismuth elementary substance/Prussian blue framework @ graphene composite material, which comprises the following steps: (1) dissolving potassium hexacyanoferrate in deionized water, and performing ultrasonic treatment until red particles are completely dissolved; then adding polyvinylpyrrolidone, carrying out ultrasonic dissolution, placing the solution in a forced air oven for reaction, centrifuging, washing with water, and drying to obtain blue-black precursor powder; (2) dissolving bismuth nitrate in deionized water, adding the blue-black precursor powder into the solution, stirring in a water bath, centrifuging, washing with water, and drying to obtain a blue reaction product; (3) and dispersing the blue reaction product into a graphene aqueous solution, performing ultrasonic treatment and freeze drying to obtain blue-gray powder, transferring the blue-gray powder into an argon-hydrogen mixed atmosphere to perform reduction reaction to obtain a black final reaction product, and collecting the black final reaction product to obtain the bismuth simple substance/Prussian blue framework @ graphene composite material. The invention also provides application of the material as a potassium ion battery negative electrode material.
Description
Technical Field
The invention belongs to the technical field of preparation of electrode materials of potassium ion batteries, and particularly relates to a preparation method and application of a bismuth elementary substance/Prussian blue framework @ graphene composite material.
Background
Because the potassium (K) content in the earth crust is higher (the potassium content is 1.5 percent, and the lithium content is 0.0017 percent), the natural content richness K is obviously better than that of lithium, and K/K is superior to that of lithium in Lithium Ion Batteries (LIBs)+With Li/Li+Such that Potassium Ion Batteries (PIBs) are considered a low cost energy storage system. Although K will be+The graphite-intercalated negative electrode contributes to the practical development of PIBs, but the capacity obtained by this method is generally less than 250mAh g-1. Conversion alloy/reaction based anode materials tend to have higher theoretical specific capacities. Bismuth (Bi) simple substance as alloy reaction type potassium ion battery cathode material with the mass of up to 360mAh g-1But due to K+Size ratio of (A) to (B) Li+Much larger, in practical PIBs, the problem of pulverization of Bi metal anodes based on alloying reactions is particularly severe. Therefore, a major challenge for stable Bi-based elemental cathodes in high performance PIBs is in repeated insertion/extraction K+During which inevitable volume expansion is cushioned and structural integrity is maintained. Among them, researchers have proposed that the surface of a conversion/alloy-based negative electrode is covered with a rigid coating of conductive carbon, which can reduce the interfacial resistance and improve the overall electron conductivity. However, due to the insertion of a large number of K+Causing a large volume change, cracking and structural damage of the carbon layer, which in turn leads to a decrease in electrochemical performance. The approach of two-dimensional (2D) material confinement helps to improve electron conductivity and maintain electrode integrity, but does not prevent the pulverization of the confined transformation/alloy anode material. To achieve robustness and high structural stability of the volumetrically varied electrode material, combining conductive encapsulation with 2D material confinement may be an effective strategy.
The invention provides a preparation method of a bismuth elementary substance/Prussian blue framework @ graphene composite material, which has the following main contents and innovation points: the invention utilizes Bi3+And a precursor Fe3+Ion exchange reaction of (3), adding Bi3+Packaging into a precursor, then coating with graphene, and finally reducing Bi by gas phase3+The nano composite material with controllable appearance and uniform size is prepared by reducing the Bi into a simple substance and packaging the simple substance in a Prussian blue frame, the simple substance in the nano composite material can provide considerable specific capacity, the graphene and the Prussian blue frame can provide a reliable barrier for inhibiting the volume effect for the simple substance, in addition, the graphene tightly coated on the surface of the nano particles can improve the electronic conductivity of the whole material, and the obtained material has higher capacity, superior rate capability and cycle performance, and is particularly suitable for being used as a negative electrode material of a potassium ion secondary battery.
Disclosure of Invention
The invention aims to provide a preparation method of a bismuth elementary substance/Prussian blue framework @ graphene composite material
In order to achieve the purpose, the bismuth simple substance/Prussian blue framework @ graphene composite material is prepared by a three-step method, namely (S1) a nanoparticle precursor is prepared; (S2) preparation of encapsulated Bi3+The precursor nanoparticles of (a); (S3) bismuth element/Prussian blue framework @ graphene.
S1, dissolving potassium hexacyanoferrate in deionized water, and performing ultrasonic treatment until red particles are completely dissolved; adding polyvinylpyrrolidone, ultrasonically dissolving, placing the solution in a blast oven at 60-90 ℃ for reacting for 1-24 hours, centrifugally washing with water (3-4 times), and placing in an oven at 60 ℃ for drying for 12 hours to obtain blue-black precursor powder;
s2, dissolving bismuth nitrate in deionized water to prepare a bismuth nitrate solution, adding the blue-black precursor powder into the solution, stirring in a water bath at 40-80 ℃ for 1-24 hours, centrifugally washing (3-4 times), and drying in an oven at 60 ℃ for 12 hours to obtain a blue reaction product;
s3, dispersing the blue reaction product in a graphene aqueous solution with the mass percent of 20%, performing ultrasonic dispersion for two hours, performing freeze drying for 24 hours to obtain blue-gray powder, then transferring the blue-gray powder into a tubular furnace in an argon-hydrogen mixed atmosphere to perform a reduction reaction at the temperature of 400-800 ℃ for 1-12 hours at the temperature rising speed of 2-5 ℃/min, and cooling and collecting to obtain a black final reaction product, namely the bismuth simple substance/Prussian blue framework @ graphene composite material. The invention also provides application of the material as a potassium ion battery negative electrode material.
Preferably, the average molecular weight of the polyvinylpyrrolidone in the step S1 is 8000-1300000.
Preferably, the mass ratio of the potassium hexacyanoferrate to the polyvinylpyrrolidone in step S1 is 1: 1-1: 20.
Preferably, the mass ratio of the bismuth nitrate to the black precursor powder in step S2 is 1: 0.1-1: 2.
Preferably, the mass ratio of the graphene solution to the blue reaction product in step S3 is 1: 0.1-1: 2.
Drawings
Fig. 1 is an XRD spectrum of the elemental bismuth/prussian blue framework @ graphene composite prepared in example 1;
fig. 2 is an SEM image of the elemental bismuth/prussian blue framework @ graphene composite electrode material prepared in example 1;
fig. 3 is an SEM image of the elemental bismuth/prussian blue framework @ graphene composite prepared in example 1;
fig. 4 shows that the current density of the elemental bismuth/prussian blue framework @ graphene composite material prepared in example 1 is 0.5A g-1A graph of cyclic performance of time;
FIG. 5 shows that the current density of the bismuth simple substance/Prussian blue framework @ graphene composite material prepared in the embodiment example 2 is 0.05-2A g-1Graph of rate performance.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
Dissolving 1mmol potassium hexacyanoferrate in 100mL deionized water, and performing ultrasonic treatment for 1 hour until the solution turns redThe particles are completely dissolved; then adding 1g of polyvinylpyrrolidone with molecular weight of 8000, carrying out ultrasonic treatment for 1 hour until the polyvinylpyrrolidone is completely dissolved, placing the solution in a forced air oven at 80 ℃ for reaction for 16 hours, carrying out centrifugal water washing (3-4 times), and placing in an oven at 60 ℃ for drying for 12 hours to obtain blue-black precursor powder; dissolving 2mmol of bismuth nitrate in 100ml of deionized water to prepare a bismuth nitrate solution, then adding 0.1g of the blue-black precursor powder into the solution, stirring in a water bath at 60 ℃ for 12 hours, centrifugally washing (3-4 times), and then drying in an oven at 60 ℃ for 12 hours to obtain a blue reaction product; and (2) dispersing 0.1g of the blue reaction product in 100mL of graphene aqueous solution with the mass percentage of 20%, performing ultrasonic dispersion for 2 hours, performing freeze drying for 24 hours to obtain blue-gray powder, then transferring 0.1g of the powder to a tubular furnace in an argon-hydrogen mixed atmosphere to perform reduction reaction at 500 ℃ for 8 hours at the heating rate of 5 ℃/min, and cooling and collecting to obtain a black final reaction product, namely the bismuth simple substance/Prussian blue frame @ graphene composite material. The XRD pattern is shown in figure 1, and the comparison with a standard PDF card can show that the material synthesized by the method can be well matched with a Prussian blue framework. Scanning electron micrographs of the precursor and the final material are shown in fig. 2 and fig. 3, which show the regular nano-sphere morphology, and the final product graphene is tightly coated. FIG. 4 shows that the current density was 0.5A g-1The rate performance graph shows that the current density specific capacity of the composite material is 0.5A g-1The time capacity is as high as 170mAh g-1After 100 cycles, the product can still maintain 155mAh g-1The method provided by the invention is proved to be capable of obviously improving the cycle performance of the elementary substance Bi.
Example 2
Dissolving 2mmol of potassium hexacyanoferrate in 100mL of deionized water, and carrying out ultrasonic treatment for 1 hour until red particles are completely dissolved; then adding 1g of polyvinylpyrrolidone with the molecular weight of 45000, performing ultrasonic treatment for 1 hour until the polyvinylpyrrolidone is completely dissolved, placing the solution in a blast oven with the temperature of 60 ℃ for reaction for 24 hours, centrifugally washing (3-4 times), and placing in an oven with the temperature of 60 ℃ for drying for 12 hours to obtain a blue-black precursor powder; dissolving 1mmol of bismuth nitrate in 100mL of deionized water to obtain a bismuth nitrate solution, adding 0.1g of the blue-black precursor powder into the solution, stirring in a water bath at 80 ℃ for 24 hours,centrifugally washing with water (3-4 times), drying in an oven at 60 ℃ for 12 hours to obtain a blue reaction product; and (2) dispersing 0.1g of the blue reaction product in 80mL of graphene aqueous solution with the mass percentage of 20%, performing ultrasonic dispersion for 2 hours, performing freeze drying for 24 hours to obtain blue-gray powder, then transferring 0.1g of the powder to a tubular furnace in argon-hydrogen mixed atmosphere to perform reduction reaction at 800 ℃ for 6 hours at the temperature rise speed of 2 ℃/min, and cooling and collecting to obtain a black final reaction product, namely the bismuth simple substance/Prussian blue framework @ graphene composite material. FIG. 5 shows that the current density is 0.05-2A g-1The rate performance graph shows that the current density specific capacity of the composite material is 2A g-1The time capacity is as high as 95mAh g-1The rate capability is good.
Example 3
Dissolving 1mmol of potassium hexacyanoferrate in 100mL of deionized water, and performing ultrasonic treatment for 1 hour until red particles are completely dissolved; then adding 1g of polyvinylpyrrolidone with molecular weight of 8000, carrying out ultrasonic treatment for 1 hour until the polyvinylpyrrolidone is completely dissolved, placing the solution in a blast oven with the temperature of 70 ℃ for reaction for 12 hours, carrying out centrifugal water washing (3-4 times), and then placing in an oven with the temperature of 60 ℃ for drying for 12 hours to obtain blue-black precursor powder; dissolving 2mmol of bismuth nitrate in 100ml of deionized water to prepare a bismuth nitrate solution, then adding 0.1g of the blue-black precursor powder into the solution, stirring in a water bath at 50 ℃ for 12 hours, centrifugally washing (3-4 times), and drying in an oven at 60 ℃ for 12 hours to obtain a blue reaction product; and (2) dispersing the blue reaction product in a graphene aqueous solution with the mass percentage of 20%, performing ultrasonic dispersion for 2 hours, performing freeze drying for 24 hours to obtain blue-gray powder, then transferring 0.1g of the powder to a tubular furnace in an argon-hydrogen mixed atmosphere to perform a reduction reaction at 600 ℃ for 4 hours at the temperature rise speed of 4 ℃/min, and collecting a black final reaction product, namely the bismuth simple substance/Prussian blue frame @ graphene composite material after cooling. It is at 0.5A g-1The time capacity is up to 320mAh g-1The capacity retention after 300 cycles was 90.7%, at 2A g-1The specific capacity of the material under large-multiplying power charge and discharge reaches 105mAh g-1。
Claims (7)
1. A preparation method of a bismuth elementary substance/Prussian blue framework @ graphene composite material comprises the following steps:
s1, dissolving potassium hexacyanoferrate in deionized water, and performing ultrasonic treatment until red particles are completely dissolved; adding polyvinylpyrrolidone, ultrasonically dissolving, placing the solution in a blast oven at 60-90 ℃ for reacting for 1-24 hours, centrifugally washing with water (3-4 times), and placing in an oven at 60 ℃ for drying for 12 hours to obtain blue-black precursor powder;
s2, dissolving bismuth nitrate in deionized water to prepare a bismuth nitrate solution, adding the blue-black precursor powder into the solution, stirring in a water bath at 40-80 ℃ for 1-24 hours, centrifugally washing (3-4 times), and drying in an oven at 60 ℃ for 12 hours to obtain a blue reaction product;
s3, dispersing the blue reaction product in a graphene aqueous solution with the mass percentage of 20%, performing ultrasonic dispersion for two hours, performing freeze drying for 24 hours to obtain blue-gray powder, then transferring the blue-gray powder into a tubular furnace in an argon-hydrogen mixed atmosphere to perform a reduction reaction at the temperature of 400-800 ℃ for 1-12 hours at the temperature rising speed of 2-5 ℃/min, and cooling and collecting to obtain a black final reaction product, namely the bismuth simple substance/Prussian blue framework @ graphene composite material. The invention also provides application of the material as a potassium ion battery negative electrode material.
2. The method of claim 1, wherein in step S1, the polyvinylpyrrolidone has an average molecular weight of 8000-1300000.
3. The preparation method according to claim 1, wherein in step S1, the mass ratio of the potassium hexacyanoferrate to the polyvinylpyrrolidone is 1: [ 1-20 ].
4. The method according to claim 1, wherein the mass ratio of the bismuth nitrate to the black precursor powder in step S2 is 1: [ 0.1-2 ].
5. The preparation method of claim 1, wherein in step S3, the mass ratio of the graphene solution to the blue reaction product is 1: [ 0.1-2 ].
6. The composite material prepared by the preparation method of any one of claims 1 to 5 is characterized by comprising bismuth, a Prussian blue framework and a graphene composite material.
7. The bismuth simple substance/Prussian blue framework @ graphene composite material prepared in the claims 1-5 is applied as a potassium ion battery negative electrode material.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130260222A1 (en) * | 2012-03-28 | 2013-10-03 | Yuhao Lu | Electrode Forming Process for Metal-Ion Battery with Hexacyanometallate Electrode |
| CN103768619A (en) * | 2012-10-25 | 2014-05-07 | 常州柯艾医药科技有限公司 | Bismuth-based prussian blue compound nano CT contrast agent and preparation method therefor |
| CN108840351A (en) * | 2018-05-23 | 2018-11-20 | 上海市第六人民医院 | Hollow mesoporous prussian blue nano grain of one kind and preparation method thereof |
| CN110426433A (en) * | 2019-08-23 | 2019-11-08 | 衡阳师范学院 | A kind of the nitrogen-doped graphene composite material and preparation method and application of silver-Prussian blue load |
| CN111017958A (en) * | 2019-11-13 | 2020-04-17 | 厦门大学 | Preparation method of nano spherical Prussian blue compound |
| CN111048762A (en) * | 2019-12-19 | 2020-04-21 | 哈尔滨理工大学 | Preparation method and application of graphene/sulfur/Prussian blue analogue composite material |
-
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- 2020-08-12 CN CN202010804240.2A patent/CN112194122B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130260222A1 (en) * | 2012-03-28 | 2013-10-03 | Yuhao Lu | Electrode Forming Process for Metal-Ion Battery with Hexacyanometallate Electrode |
| CN103768619A (en) * | 2012-10-25 | 2014-05-07 | 常州柯艾医药科技有限公司 | Bismuth-based prussian blue compound nano CT contrast agent and preparation method therefor |
| CN108840351A (en) * | 2018-05-23 | 2018-11-20 | 上海市第六人民医院 | Hollow mesoporous prussian blue nano grain of one kind and preparation method thereof |
| CN110426433A (en) * | 2019-08-23 | 2019-11-08 | 衡阳师范学院 | A kind of the nitrogen-doped graphene composite material and preparation method and application of silver-Prussian blue load |
| CN111017958A (en) * | 2019-11-13 | 2020-04-17 | 厦门大学 | Preparation method of nano spherical Prussian blue compound |
| CN111048762A (en) * | 2019-12-19 | 2020-04-21 | 哈尔滨理工大学 | Preparation method and application of graphene/sulfur/Prussian blue analogue composite material |
Non-Patent Citations (3)
| Title |
|---|
| BARMAN, BARUN KUMAR等: "Prussian blue as a single precursor for synthesis of Fe/Fe3C encapsulated N-doped graphitic nanostructures as bi-functional catalysts", 《GREEN CHEMISTRY》 * |
| WENYUE LI等: "Prussian blue based vertical graphene 3D structures for high frequency electrochemical capacitors", 《ENERGY STORAGE MATERIALS》 * |
| XU YANG等: "High-capacity graphene-confined antimony nanoparticles as a promising anode material for potassium-ion batteries", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
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