CN111017958A - Preparation method of nano spherical Prussian blue compound - Google Patents
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- C01C3/08—Simple or complex cyanides of metals
- C01C3/12—Simple or complex iron cyanides
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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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- C01P2004/32—Spheres
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention discloses a preparation method of a nano spherical Prussian blue compound, which adopts sodium ferrocyanide and polyvinylpyrrolidone as raw materials, controls the self-assembly growth speed of the Prussian blue compound by reasonably regulating and controlling the pH value and the hydrothermal temperature in a solution, has low defect in the material structure, and effectively relieves the structural collapse of an electrode in the circulating charge-discharge process. The nano spherical Prussian blue compound prepared by the invention is nano-sized, has obviously increased specific surface area, can effectively increase the contact area between the electrolyte and the compound, fully utilizes the active substances, and can reduce the diffusion distance of sodium ions, thereby showing higher specific capacity and rate capability.
Description
Technical Field
The invention belongs to the technical field of nano materials and electrochemistry, and particularly relates to a preparation method of a nano spherical Prussian blue compound.
Background
With the rise of modern new energy automobiles and smart power grids, the development of efficient and convenient energy storage technology becomes a research hotspot in the world. Currently, the widely studied energy storage technology is a lithium ion battery, which has the advantages of large energy density, long cycle life, high working voltage, small self-discharge, no memory effect, wide working temperature range, and the like, and is considered as the most promising energy storage technology. However, the high cost and shortage of lithium resources of lithium ion batteries have largely limited their widespread use. In addition, the global lithium resource reserves are limited, the distribution is regional, and the resource and supply problems become hidden troubles for large-scale application in the future. Therefore, in order to alleviate the problems of the reserves and supplies of the raw materials of the lithium ion battery, the development of the next generation of energy storage technology with excellent comprehensive properties is urgently needed. The sodium reserves are quite abundant compared to the scarce lithium resources, which are about 2.64% in the crust, and the price of the sodium raw material is 30-40 times lower than that of lithium. Sodium and lithium are the same main group elements and have similar chemical properties, and although the radius of sodium ions is larger than that of lithium ions, the development of sodium ion batteries by replacing lithium with sodium is completely feasible as long as a proper compound is found.
Compared with other positive electrode materials for sodium ion batteries, the Prussian blue compound as the disintercalable positive electrode material for the sodium ion battery has the following advantages: 1) the device has larger channels and sites for accommodating sodium ions, and the framework is hard, so that the volume change is smaller in the process of sodium ion deintercalation; 2) the potential barrier for the migration of sodium ions in the framework is low, so that the rapid migration of the sodium ions is facilitated, and the power density of the battery is improved; 3) environment-friendly, easy synthesis, low cost and suitability for large-scale application. And may contain two different redox active sites (M) in its latticen/n+1、Fe+2/+3) Theoretically, about 170mAh g can be realized-1The capacity of (c). The excellent characteristics enable Prussian blue to show extremely attractive application prospect in the aspect of scale energy storage. However, prussian blue compound particles formed by a general preparation method are easy to agglomerate, so that the crystallinity is low, the structure of the material is easy to damage in the cyclic charge and discharge process, and the stability is poor; in addition, in the conventional studies, the particle size of the prussian blue compound is on the order of micrometers, so that the specific surface area is small, and the specific capacity is low. Therefore, in order to solve the technical problem, a controllable and highly dispersed nano-sized morphology structure becomes an important ring for improving the electrochemical performance of the prussian blue compound.
CN108493423A discloses a method for preparing nanocubes, which comprises dissolving anionic surfactant, nonionic surfactant, reducing agent and sodium ferrocyanide in a mixed solution of water and organic solvent to obtain a salt solution, and reacting the salt solution under certain conditions to obtain the product. Although the particle size distribution is generally uniform, the initial specific capacity of the material is lower due to the existence of larger micron-sized particles and local agglomeration phenomenon, the voltage range of charge and discharge is 2-4V, and the current density is 25mA g-1Under the condition of (1), the first specific capacity of the battery is less than 100mAh g-1。
CN107082438A discloses a method for preparing a Prussian blue compound with a nanometer flower structure, which comprises the step of preparing a Prussian blue compound table under the action of strong alkaliThe surface is dissolved and recrystallized to finally form the nanometer flower shape. As a positive active material of the sodium-ion battery, the structure effectively increases the reaction sites of the electrolyte and the compound and reduces the ion diffusion distance. However, the charge-discharge capacity of the morphology material is low, and the initial discharge capacity is only 80-90mAh g-1。
In addition, in the reports of the prior art documents, Huang et al prepared a hollow-core shell heterostructure Prussian blue compound, and obtained 123mAh g-1The initial capacity of (1), the cycle retention of which after 600 cycles is 82% (Huang Y, Xie M, Wang Z, et a1.A Chemical Precipitation Method prepared Hollow-Core-Shell 11 heterogeneous Blue Based on the applied Blue analytes for sodium-Ion Batteries [ J]Small, 2018, 14: 1801246.). However, the preparation process is cumbersome and the initial capacity needs to be further increased. Feng et al describe a Prussian Blue compound in the form of a Hollow rod, and studies have shown that the rod increases the contact area between the compound and the electrolyte to some extent (Feng F, Chen S, Liao X Z, eta1. High grade 1 Hollow Prussian Blue strips Synthesized via glass-SacrificeTemplate as Cathode for High performance sodium Ion Battery [ J]Small Methods, 2018, 1: 1800259.). However, the rod-shaped diameter is too large, so that the specific surface area of the material is increased, and the specific capacity is lower (the first capacity is 117.3mAh g)-1)。
In conclusion, the design of different shapes of the prussian blue compound is a way to effectively improve the electrochemical performance of the prussian blue compound, and the application space of the prussian blue is inevitably expanded. However, although the current research reduces the defects of the material to some extent and improves the cycling stability of the material as a compound, the current research still has some defects: firstly, the process is complex, the preparation cost is high, and the prussian blue compound with a special morphology is often synthesized by combining a plurality of medicines; secondly, the capacity utilization rate is low, the particle size of the Prussian blue compound is generally about micron level, so that the specific surface area is small, and the specific capacity is low; thirdly, the rate performance is poor, and prussian blue compound particles formed by a general preparation method are easy to agglomerate and have low crystallinity, so that the structure of the material is easy to damage in the charging and discharging process, and the stability is poor.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a nano spherical Prussian blue compound.
The technical scheme of the invention is as follows:
a preparation method of a nano spherical Prussian blue compound comprises the following steps:
(1) adding sodium ferrocyanide and polyvinylpyrrolidone with a K value of 27.4-32.0 into a first solvent at the same time, and fully stirring and dissolving to obtain a first mixed solution;
(2) adding a pH regulator into the first mixed solution to stabilize the pH value to be 0.6-0.9, and then continuously stirring for 0.4-0.6h to obtain a second mixed solution;
(3) and transferring the second mixed solution to a hydrothermal reaction kettle, aging at 60-90 ℃ for 1-6h, naturally cooling to room temperature, centrifugally separating, cleaning for a plurality of times, and performing vacuum drying to obtain the nano spherical Prussian blue compound with the particle size of 200-500 nm.
In a preferred embodiment of the present invention, the mass ratio of the sodium ferrocyanide to the polyvinylpyrrolidone is 2-4: 3-5.
In a preferred embodiment of the present invention, the first solvent is deionized water or an aqueous ethanol solution.
In a preferred embodiment of the present invention, the pH adjusting agent is hydrochloric acid, nitric acid or sulfuric acid.
In a preferred embodiment of the present invention, the rotation speed of the centrifugation in the step (3) is 9000-11000rpm for 8-15 min.
In a preferred embodiment of the present invention, the washing in the step (3) is washing with deionized water or absolute ethyl alcohol 5 to 7 times.
In a preferred embodiment of the present invention, the temperature of the vacuum drying in the step (3) is 75 to 82 ℃ for 10 to 15 hours.
The other technical scheme of the invention is as follows:
the nanometer spherical Prussian blue compound prepared by the preparation method is applied as an active material of a positive electrode of a sodium-ion battery.
The invention has the beneficial effects that:
1. the invention can controllably synthesize highly dispersed nanometer spherical Prussian blue compounds, and improve the capacity and rate capability of the sodium ion battery.
2. The nano spherical Prussian blue compound prepared by the invention is nano-sized, has obviously increased specific surface area, can effectively increase the contact area between the electrolyte and the compound, fully utilizes the active substances, and can reduce the diffusion distance of sodium ions, thereby showing higher specific capacity and rate capability.
3. According to the invention, sodium ferrocyanide and polyvinylpyrrolidone are used as raw materials, and the self-assembly growth speed of the Prussian blue compound is controlled by reasonably regulating the pH value and the hydrothermal temperature in the solution, so that the defects in the material structure are low, and the structural collapse of the electrode in the circulating charge-discharge process is effectively relieved.
4. The invention has the advantages of low cost of raw materials, simple preparation process, mild reaction conditions, environmental protection, excellent electrochemical performance of the materials and the like, meets the conditions of mass production, has strong feasibility because the materials are dried in vacuum at low temperature, and is beneficial to market popularization.
Drawings
Fig. 1 is an SEM image of the nano-spherical prussian blue compound prepared in example 1 of the present invention.
Fig. 2 is a charge-discharge curve diagram of the nano spherical prussian blue compound prepared in example 1 of the present invention under different current densities.
Fig. 3 is a graph of rate capability of the nano spherical prussian blue compound prepared in example 1 of the present invention.
Fig. 4 is a charge-discharge cycle graph of the nano spherical prussian blue compound prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Example 1
(1) 1200mg of sodium ferrocyanide (Na) was first taken4Fe(CN)6) Adding 1600mg of polyvinylpyrrolidone (PVP, the K value is 30) into 200mL of deionized water at the same time, and magnetically stirring until the polyvinylpyrrolidone is completely dissolved to obtain a first mixed solution;
(2) dropwise adding hydrochloric acid into the first mixed solution in the magnetic stirring process to stabilize the pH of the solution at about 0.6, and continuously stirring for 0.6h to form a second mixed solution;
(3) transferring the second mixed solution to a hydrothermal kettle, placing the hydrothermal kettle in an electric furnace with the temperature of 80 ℃, aging for 4 hours, and cooling to room temperature along with the furnace;
(4) centrifuging the material obtained in the step (3) for 10min under the condition that the centrifugal rotating speed is 10000rpm, collecting precipitates, and washing for 6 times by using deionized water;
(5) and (4) drying the precipitate centrifuged in the step (4) at 80 ℃ in vacuum for 12h to obtain the prussian blue nanosphere compound with the particle size of 200-500 nm.
Taking the nano spherical prussian blue compound prepared in this example as an example, the morphology of the compound is determined by SU-70 thermal field emission scanning electron microscope. As shown in the attached figure 1, the prepared Prussian blue compound nanospheres are uniform in morphology and highly dispersed. The particle size of the nano spherical Prussian blue electrode material prepared by the invention is 200-500nm, the specific surface area is obviously increased due to the shape of the nanospheres, so that the contact area between the electrolyte and the electrode material is increased, the ion diffusion distance is effectively reduced, the deintercalation of sodium ions between a positive electrode and a negative electrode is promoted, and the nano spherical Prussian blue electrode material has high capacity and excellent rate capability.
The application of the nano spherical Prussian blue compound obtained in the embodiment as the positive electrode active material of the sodium-ion battery is as follows:
the preparation process of the positive plate adopts a nano spherical Prussian blue compound as an active material, conductive carbon black and Keqin black as a conductive agent, and polytetrafluoroethylene as a binder. The mass ratio of the active material, the conductive agent and the binding agent is 60: 30: 10; mixing them in proportionThen, adding a proper amount of N-methyl pyrrolidone (NMP), uniformly stirring, and pressing an electrode plate with the thickness of about 0.3mm on a roller press; and (5) drying the pressed electrode slice in a vacuum oven at 60 ℃ for 48h for later use. With 1M sodium perchlorate (NaClO)(4)Dissolved in Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) as electrolytes, and 5% fluoroethylene carbonate (FEC) additive was added. The sodium sheet is a cathode, the glass fiber (GF/D) is a diaphragm, and CR2025 type stainless steel is a battery shell to assemble the button type sodium ion battery. The remaining steps of the sodium ion battery manufacturing method are the same as the general manufacturing method.
FIG. 2 shows the charging and discharging curves of the nano-spherical Prussian blue compound prepared in this example as the active material at different current densities, which are clearly shown to be at 50, 100, 200, 400, and 800mA g-1The first discharge capacity of the active material can reach 148, 137, 134, 129 and 121mAh g respectively at the current density of (2)-1. The rate capability of the nano-spherical prussian blue compound as an active material is shown in fig. 3, and it can be seen that the rate capability of the active material is excellent and is 50-800mA g-1After charging and discharging under different current densities, the material is 50mA g-1The capacity at the current density of (2) can be recovered to 138mAh g-1The capacity retention rate reaches 93 percent, which proves that the active material has good structural stability. Furthermore, as shown in FIG. 4, at 400mA g-1The first discharge capacity can reach about 126mAh g under the current density-174% of the theoretical capacity, and the capacity retention remains at 80% after 250 cycles. The test result proves that the nano spherical Prussian blue compound prepared by the embodiment has excellent electrochemical performance as an active material of a positive plate, and is a potential application material of a high-capacity and high-rate sodium-ion battery.
Example 2
(1) 1200mg of sodium ferrocyanide (Na) was first taken4Fe(CN)6) Adding 1600mg of polyvinylpyrrolidone (PVP, the K value is 30) into 200mL of mixed solution of deionized water and absolute ethyl alcohol at the same time, and magnetically stirring until the PVP and the absolute ethyl alcohol are completely dissolved to obtain a first mixed solution;
(2) dropwise adding nitric acid into the first mixed solution in the magnetic stirring process to stabilize the pH of the solution at about 0.7, and continuously stirring for 0.5h to form a second mixed solution;
(3) transferring the second mixed solution to a hydrothermal kettle, placing the hydrothermal kettle in an electric furnace at the temperature of 70 ℃, aging the hydrothermal kettle for 6 hours, and cooling the hydrothermal kettle to room temperature along with the furnace;
(4) centrifuging the material obtained in the step (3) for 10min under the condition that the centrifugal rotating speed is 10000rpm, collecting precipitates, and washing for 6 times by using deionized water;
(5) and (4) drying the precipitate centrifuged in the step (4) at 80 ℃ in vacuum for 12h to obtain the nano spherical Prussian blue compound with the particle size of 200-500 nm.
Taking the nano spherical Prussian blue compound obtained in the example as an example, the concentration is 50mA g-1The initial discharge capacity of the material can reach 128mAh g under the current density of the material-1As the current density increased to 800mA g-1The specific discharge capacity of the material is 102mAhg-1。
Example 3
(1) 1200mg of sodium ferrocyanide (Na) was first taken4Fe(CN)6) Adding 1600mg of polyvinylpyrrolidone (PVP, K value of 28) into 200mL of deionized water at the same time, and magnetically stirring until the polyvinylpyrrolidone is completely dissolved to obtain a first mixed solution;
(2) dropwise adding sulfuric acid into the first mixed solution in the process of magnetic stirring to stabilize the pH of the solution at about 0.7, and continuously stirring for 0.5h to form a second mixed solution;
(3) transferring the second mixed solution to a hydrothermal kettle, placing the hydrothermal kettle in an electric furnace at the temperature of 70 ℃, aging for 5 hours, and cooling to room temperature along with the furnace;
(4) centrifuging the material obtained in the step (3) for 10min under the condition that the centrifugal rotating speed is 10000rpm, collecting precipitates, and washing for 6 times by using absolute ethyl alcohol;
(5) and (4) drying the precipitate centrifuged in the step (4) at 80 ℃ in vacuum for 12h to obtain the nano spherical Prussian blue compound with the particle size of 200-500 nm.
Taking the nano spherical Prussian blue compound obtained in the example as an example, the concentration is 50mA g-1The initial discharge capacity of the material can reach 120mAh g under the current density-1As the current density increased to 800mA g-1The specific discharge capacity of the material is 95mAhg-1。
Example 4
(1) 1200mg of sodium ferrocyanide (Na) was first taken4Fe(CN)6) Adding 1600mg of polyvinylpyrrolidone (PVP, the K value is 28) into 200mL of mixed solution of deionized water and absolute ethyl alcohol at the same time, and magnetically stirring until the PVP and the absolute ethyl alcohol are completely dissolved to obtain a first mixed solution;
(2) dropwise adding hydrochloric acid into the first mixed solution in the magnetic stirring process to stabilize the pH of the solution at about 0.7, and continuously stirring for 0.6h to form a second mixed solution;
(3) transferring the second mixed solution to a hydrothermal kettle, placing the hydrothermal kettle in an electric furnace at the temperature of 90 ℃, aging the hydrothermal kettle for 3 hours, and cooling the hydrothermal kettle to room temperature along with the furnace;
(4) centrifuging the material obtained in the step (3) for 10min under the condition that the centrifugal rotating speed is 10000rpm, collecting precipitates, and washing for 6 times by using absolute ethyl alcohol;
(5) and (4) drying the precipitate centrifuged in the step (4) at 80 ℃ in vacuum for 12h to obtain the nano spherical Prussian blue compound with the particle size of 200-500 nm.
Taking the nano spherical Prussian blue compound obtained in the example as an example, the concentration is 50mA g-1The initial discharge capacity of the material can reach 130mAh g under the current density of the material-1As the current density increased to 800mA g-1The specific discharge capacity of the material is 105mAhg-1。
Example 5
(1) 1200mg of sodium ferrocyanide (Na) was first taken4Fe(CN)6) Adding 1600mg of polyvinylpyrrolidone (PVP, the K value is 32) into 200mL of deionized water at the same time, and magnetically stirring until the polyvinylpyrrolidone is completely dissolved to obtain a first mixed solution;
(2) dropwise adding sulfuric acid into the first mixed solution in the process of magnetic stirring to stabilize the pH of the solution at about 0.8, and continuously stirring for 0.4h to form a second mixed solution;
(3) transferring the second mixed solution to a hydrothermal kettle, placing the hydrothermal kettle in an electric furnace at the temperature of 70 ℃, aging for 2 hours, and cooling to room temperature along with the furnace;
(4) centrifuging the material obtained in the step (3) for 10min under the condition that the centrifugal rotating speed is 10000rpm, collecting precipitates, and washing for 6 times by using deionized water;
(5) and (4) drying the precipitate centrifuged in the step (4) at 80 ℃ in vacuum for 12h to obtain the nano spherical Prussian blue compound with the particle size of 200-500 nm.
Taking the nano spherical Prussian blue compound obtained in the example as an example, the concentration is 50mA g-1The initial discharge capacity of the material can reach 115mAh g under the current density of the material-1As the current density increased to 800mA g-1The specific discharge capacity of the material is 85mAhg-1。
Example 6
(1) 1200mg of sodium ferrocyanide (Na) was first taken4Fe(CN)6) Adding 1600mg of polyvinylpyrrolidone (PVP, the K value is 32) into 200mL of mixed solution of deionized water and absolute ethyl alcohol at the same time, and magnetically stirring until the PVP and the absolute ethyl alcohol are completely dissolved to obtain a first mixed solution;
(2) dropwise adding sulfuric acid into the first mixed solution in the process of magnetic stirring to stabilize the pH of the solution at about 0.8, and continuously stirring for 0.5h to form a second mixed solution;
(3) transferring the second mixed solution to a hydrothermal kettle, placing the hydrothermal kettle in an electric furnace with the temperature of 80 ℃, aging for 2 hours, and cooling to room temperature along with the furnace;
(4) centrifuging the material obtained in the step (3) for 10min under the condition that the centrifugal rotating speed is 10000rpm, collecting precipitates, and washing for 6 times by using absolute ethyl alcohol;
(5) and (4) drying the precipitate centrifuged in the step (4) at 80 ℃ in vacuum for 12h to obtain the nano spherical Prussian blue compound with the particle size of 200-500 nm.
Taking the nano spherical Prussian blue compound obtained in the example as an example, the concentration is 50mA g-1The initial discharge capacity of the material can reach 125mAh g under the current density-1As the current density increased to 800mA g-1The specific discharge capacity of the material is 93mAhg-1。
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (8)
1.A preparation method of a nano spherical Prussian blue compound is characterized by comprising the following steps: the method comprises the following steps:
(1) adding sodium ferrocyanide and polyvinylpyrrolidone with a K value of 27.4-32.0 into a first solvent at the same time, and fully stirring and dissolving to obtain a first mixed solution;
(2) adding a pH regulator into the first mixed solution to stabilize the pH value to be 0.6-0.9, and then continuously stirring for 0.4-0.6h to obtain a second mixed solution;
(3) and transferring the second mixed solution to a hydrothermal reaction kettle, aging at 60-90 ℃ for 1-6h, naturally cooling to room temperature, centrifugally separating, cleaning for a plurality of times, and performing vacuum drying to obtain the nano spherical Prussian blue compound with the particle size of 200-500 nm.
2. The method of claim 1, wherein: the mass ratio of the sodium ferrocyanide to the polyvinylpyrrolidone is (2-4): 3-5.
3. The method of claim 1, wherein: the first solvent is deionized water or ethanol water solution.
4. The method of claim 1, wherein: the pH regulator is hydrochloric acid, nitric acid or sulfuric acid.
5. The method of claim 1, wherein: the rotation speed of the centrifugation in the step (3) is 9000-11000rpm, and the time is 8-15 min.
6. The method of claim 1, wherein: and the cleaning in the step (3) is washing for 5-7 times by using deionized water or absolute ethyl alcohol.
7. The method of claim 1, wherein: the temperature of vacuum drying in the step (3) is 75-82 ℃, and the time is 10-15 h.
8. Use of the nano-spherical prussian blue compound prepared by the preparation method according to any one of claims 1 to 7 as a positive electrode active material of a sodium-ion battery.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111943226A (en) * | 2020-08-30 | 2020-11-17 | 温州大学 | Method for regulating morphology of manganese cobalt Prussian blue crystals by using surfactant |
| CN112194122A (en) * | 2020-08-12 | 2021-01-08 | 中南大学 | Preparation method of bismuth elementary substance/Prussian blue framework @ graphene composite material |
| CN114853034A (en) * | 2022-06-06 | 2022-08-05 | 华中科技大学 | Prussian blue-like electrode material pretreatment process |
| CN114853032A (en) * | 2022-04-21 | 2022-08-05 | 西北工业大学 | Preparation method of high-rate Prussian blue sodium ion battery positive electrode material |
| CN115072740A (en) * | 2022-06-23 | 2022-09-20 | 齐齐哈尔大学 | Preparation method of core-shell structure Prussian blue nanospheres |
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| CN111943226A (en) * | 2020-08-30 | 2020-11-17 | 温州大学 | Method for regulating morphology of manganese cobalt Prussian blue crystals by using surfactant |
| CN111943226B (en) * | 2020-08-30 | 2023-08-11 | 温州大学 | Method for regulating and controlling morphology of manganese-cobalt Prussian blue crystal by using surfactant |
| CN114853032A (en) * | 2022-04-21 | 2022-08-05 | 西北工业大学 | Preparation method of high-rate Prussian blue sodium ion battery positive electrode material |
| CN114853034A (en) * | 2022-06-06 | 2022-08-05 | 华中科技大学 | Prussian blue-like electrode material pretreatment process |
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