CN107611404B - Prussian white composite material and preparation method and application thereof - Google Patents
Prussian white composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a Prussian white composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) mixing sodium ferrocyanide or a hydrate thereof with deionized water to obtain a solution A with the concentration of 0.1-0.5 mol/L; (2) will contain divalent Mn2+Mixing the soluble salt with deionized water, adding the carbon fluoride nano tube, and fully dispersing to obtain a solution B, wherein Mn is contained in the solution B2+The concentration of (A) is 0.2-1.0 mol/L; (3) and (3) dropwise adding the solution B obtained in the step (2) into the solution A obtained in the step (1), and carrying out hydrothermal reaction and post-treatment to obtain the Prussian white composite material. The Prussian white composite material prepared by the method and the application of the composite material in a sodium-ion battery. The preparation method has the advantages of simple process, low cost, short period, low energy consumption, suitability for industrial production and the like.
Description
Technical Field
The invention relates to the technical field of novel energy storage batteries, in particular to a Prussian white composite material and a preparation method and application thereof.
Background
Along with the development of society and economy, the energy consumption is increasingly aggravated, the traditional fossil energy is continuously reduced, and the environmental pollution is serious when human consumes the traditional fossil energy, under the large environment, the novel energy which is clean, renewable and low in price becomes an object developed by governments in various countries, the proportion of wind energy, solar energy and ocean energy in the energy consumption is continuously increased at present, but the renewable energy is greatly influenced by weather and time periods, has obvious unstable, discontinuous and uncontrollable characteristics, needs to develop and build a matched electric energy storage (energy storage) device, namely a battery to ensure the continuity and stability of power generation and power supply, and the large-scale battery energy storage is used for peak clipping and valley filling of electric power in the electric power industry, so that the contradiction between the supply and demand of the electric power can be greatly improved, and the utilization rate of power generation equipment can be improved. The large-scale energy storage battery has higher requirements on electrode materials such as certain energy density, service life and safety, and also has higher requirements on cost. Although the lead-acid battery is low in cost, the lead-acid battery mainly comprises lead and sulfuric acid as raw materials, so that the problems of environmental pollution, short service life command, memory effect, heavy weight of the battery, high transportation cost and the like exist; although the lithium ion battery has the advantages of large energy density, long service life, no memory effect and the like, the lithium ion battery has limited storage capacity of lithium raw materials, high cost and poor safety performance, and cannot meet the requirement of large-scale energy storage in the long run. Compared with the lithium ion battery, the sodium ion battery has the advantages of abundant resources, good safety performance, low cost, environmental friendliness and the like, and is very suitable for large-scale energy storage application.
Some Prussian blue compounds contain larger vacancy in the structure, so that the intercalation and deintercalation of larger sodium ions are facilitated, and therefore, the capacity is higher, particularly, the charge-discharge voltage of a manganese-containing material is higher, and the Prussian blue compounds are suitable for serving as the anode material of a sodium ion battery. However, the compound has poor conductivity and low tap density, so that a plurality of conductive agents are required to be added to prepare the battery, the energy density of the battery is reduced, and meanwhile, the processability of the material is poor due to the addition of the conductive agents and the low tap density of the material. In addition, the compounds are easy to decompose at high temperature, and are generally prepared at low temperature, and the synthesis temperature is lower than 200 ℃, so the prepared ferrocyanide generally has poor crystallinity and high water content, and the sodium-ion battery assembled by the ferrocyanide serving as a positive electrode material has low capacity and low charge-discharge voltage. Therefore, there is a need to optimize the preparation and compounding with conductive materials to improve their electrochemical performance.
Disclosure of Invention
The invention firstly discloses a preparation method of a Prussian white composite material, which can regulate and control the morphology and the lattice structure of a target product, and the prepared Prussian white material has good crystallinity, low water content and high sodium content, and can obviously improve the electrochemical performance, especially the capacity and the charging and discharging voltage of a sodium ion battery when being applied to a sodium ion battery electrode.
The technology adopted by the invention is as follows: a preparation method of a Prussian white composite material comprises the following steps:
(1) mixing sodium ferrocyanide or a hydrate thereof with deionized water to obtain a solution A with the concentration of 0.1-0.5 mol/L;
(2) will contain divalent Mn2+Mixing the soluble salt with deionized water, adding the carbon fluoride nano tube, and fully dispersing to obtain a solution B, wherein Mn is contained in the solution B2+The concentration of (A) is 0.2-1.0 mol/L;
(3) and (3) dropwise adding the solution B obtained in the step (2) into the solution A obtained in the step (1), and carrying out hydrothermal reaction and post-treatment to obtain the Prussian white composite material.
The invention introduces the carbon fluoride nanotube in the synthesis, can reduce the speed of coprecipitation reaction and improve the crystallinity of Prussian white due to the adsorption effect of fluorine ions on manganese ions, and can reduce the crystal water content of the product and improve the conductivity due to the hydrophobic effect and the conductive effect of the graphite fluoride, thereby improving the capacity and the charge-discharge voltage of the product. In addition, fluorine ions and manganese ions or ferrous ions are easy to form coordinate bonds, and the bonding effect of the fluorine ions and the manganese ions or the ferrous ions enables the composite material to have good uniformity.
Preferably, the fluorine content of the fluorinated carbon nanotube is 10-20%, and the fluorine content is too low, so that the effects of improving the crystallinity of a product and reducing the content of crystal water are not facilitated, and the uniformity of the composite material is improved; the over-high fluorine content can reduce the conductivity of the graphite fluoride, thereby reducing the overall conductivity of the composite material;
preferably, the adding amount of the carbon fluoride nanotubes is 4-8% of the theoretical weight of the Prussian white material, and excessive carbon fluoride nanotubes can reduce the specific capacity of the product; the addition of the over-low carbon fluoride nanotubes has no obvious effect on improving the crystallinity of the product, reducing the content of crystal water, improving the uniformity of the composite material and improving the conductivity;
preferably, the soluble salt is one or more of manganese chloride, manganese sulfate and manganese nitrate which are optionally mixed, or one or more of hydrates corresponding to the manganese chloride, manganese sulfate and manganese nitrate which are optionally mixed;
preferably, the solution B contains Mn in soluble salt2+The molar ratio of the compound to the ferrous cyanide ions is 1.5: 2.5, too little Mn2+The molar amount is not favorable for the crystalline integrity of the product, too much Mn2+The molar amount will result in an increase in the production cost and a waste of raw materials.
Preferably, the temperature of the hydrothermal reaction is 70-90 ℃; the hydrothermal reaction temperature is too low, the Prussian white material is not completely crystallized, and the Prussian white material and the carbon fluoride nano tube are not uniformly compounded; the reaction temperature is too high, water used as a reaction medium is evaporated too fast, the formation of a product is influenced, and the content of crystal water is high. Further preferably, the time of the hydrothermal reaction is 6-10 h; the reaction time is too short, the Prussian white material is incomplete in crystallization, low in sodium content and high in water content of crystallization; the reaction time is too long, the influence on product crystallization is not great, the synthesis efficiency is reduced, and the preparation cost is increased.
The product after hydrothermal reaction needs post-treatment including cooling, washing and vacuum drying treatment, wherein the vacuum drying temperature is not lower than 120 deg.C, and the drying time is not less than 12 hours, under the drying condition, adsorbed water and zeolite water can be effectively removed, in addition, in the vacuum drying process, the bonding action of fluorine ion and manganese or ferrous ion can remove part of crystal water, therefore, the product has lower water content, thereby having higher capacity.
The invention also discloses a Prussian white composite material prepared by the method, and the chemical formula of the Prussian white composite material is NaxMnFe(CN)6·yH2O, wherein x is 1.6 to 2, 0<y<1, the product has high sodium content and low water of crystallization content, and the high sodium content and the low water of crystallization content can improve the crystallinity, the capacity and the charge-discharge voltage of the product; the lattice structure is rhombohedral and is believed to contribute to the product's capacity relative to cubic.
The average charging voltage of the obtained product exceeds 3.8V, the average discharging voltage exceeds 3.6V and is higher than the value reported in the open, and the product can be applied to a high-voltage sodium-ion battery by matching with a negative electrode.
The Prussian white material prepared by the method is irregular particles with submicron size. Preferably, the size of the Prussian white material is 300-500 nm. Particles that are too large to facilitate sodium ion diffusion reduce capacity, particles that are too small to facilitate electrode coating, and reduce the volumetric specific energy density of the battery.
Preferably, fluorinated carbon nanotubes are introduced, and fluorine ions on the surface of the fluorinated carbon nanotubes can attract Mn2+The coprecipitation reaction rate is reduced, so that the crystallinity and the capacity of the product are improved; the introduction of the carbon fluoride nano tube can improve the conductivity of the product, thereby reducing the polarization of the electrode and improving the working voltage of the battery; in addition, the hydrophobicity of the fluorinated carbon nanotube can also reduce the content of crystal water of the product, so that the crystallinity of the product is further improved, and the capacity of the product is improved; moreover, due to the bonding effect of the fluorine ions and the manganese ions or the ferrous ions, the obtained composite material has good uniformity.
Compared with the prior art, the invention has the following advantages:
1. the carbon fluoride nanotubes are introduced to optimize the preparation of the Prussian white cathode material, the prepared Prussian white cathode material has high sodium content, low crystal water content and good crystallinity and conductivity, and a sodium ion battery assembled by using the carbon fluoride nanotubes as the cathode material has high capacity and high charge-discharge voltage, so that the energy density is high.
2. The preparation method has the advantages of simple process, low cost, short period, low energy consumption, suitability for industrial production and the like.
Drawings
FIG. 1 is an X-ray diffraction pattern of the Prussian white composite prepared in example 1;
FIG. 2 is a scanning electron micrograph of a Prussian white composite prepared in example 1;
fig. 3 is a charge-discharge curve diagram of a sodium ion battery assembled from the prussian white composite prepared in example 1.
Detailed Description
The invention is further illustrated by way of example in the accompanying drawings of the specification:
example 1
Dissolving sodium ferrocyanide in deionized water, and uniformly stirring to obtain a solution A with the concentration of 0.1mol/L in terms of ferrous cyanide ions; dissolving manganous chloride in deionized water to obtain Mn2+The solution with the concentration of 0.2mol/L is calculated, wherein the molar weight of manganous chloride is 1.5 times of that of sodium ferrocyanide, and then the carbon fluoride nano tube is added, the fluorine content of the carbon fluoride nano tube is 15 percent, the addition amount is 6 percent of the theoretical weight of Prussian white, and the solution B is obtained through full ultrasonic dispersion; and then, dropwise adding the solution B into the solution A under the condition of continuous stirring, carrying out hydrothermal reaction at 80 ℃ for 10 hours, cooling, washing, and carrying out vacuum drying at the temperature of not less than 120 ℃ for not less than 12 hours to obtain the Prussian white composite material.
Fig. 1 is an X-ray diffraction spectrum of the prussian white cathode material prepared by the present embodiment, which can be attributed to rhombohedral sodium ferrimanganite, and the carbon nanotubes are not shown in the figure due to low content. Fig. 2 is a scanning electron micrograph of the prussian white cathode material prepared in this embodiment, which shows that the prussian white particles have a size of 300 to 500nm, and the fluorinated carbon nanotubes are uniformly dispersed in the prussian white particles. By analysis, NaxMnFe(CN)6·yH2In O, x is 1.75 and y is 0.97.
The Prussian white composite material prepared in the embodiment is used as a positive electrode, metal sodium is used as a negative electrode, glass fiber (trademark Whatman GF/D) is used as a diaphragm, and NaPF6The battery was assembled in a glove box filled with argon gas, and a charge and discharge test was performed, with a charge and discharge curve as shown in fig. 3, using the Ethylene Carbonate (EC)/diethyl carbonate (DEC) solution as an electrolyte. Constant current charge and discharge test (current density 15mA/g, voltage range 2-4V). As can be seen from the figure, the capacity can reach 146mAh/g, the average discharge voltage exceeds 3.6V, and the average charge voltage exceeds 3.8V.
Comparative example 1
The preparation process of the prussian white cathode material is similar to that of example 1, except that carbon nanotubes are not introduced into the solution B, and other reaction conditions are the same. The results show that the method has the advantages of high yield,because the reaction rate is faster, the product crystallization is worse than the material containing carbon tubes, and because no carbon nanotubes are introduced, the product conductivity is worse and the crystal water content is high. By analysis, NaxMnFe(CN)6·yH2In O, x<1.6，y>2。
Prussian white material prepared by the comparative example is used as a positive electrode, metal sodium is used as a negative electrode, glass fiber (brand Whatman GF/D) is used as a diaphragm, and NaPF6The EC/DEC solution of (1) was used as an electrolyte, and a battery was mounted in a glove box filled with argon gas to perform a charge/discharge test. Constant current charge and discharge tests (the current density is 15mA/g, the voltage range is 2-4V shows that the capacity is lower than 130mAh/g, and the charge and discharge voltage is lower.
Comparative example 2
The preparation process of the prussian white cathode material is similar to that of example 1, except that a common carbon nanotube is introduced into the solution B, and other reaction conditions are the same. The results show that the product crystallization is worse than the material containing fluorinated carbon nanotubes due to the faster reaction rate, the water content of crystallization is high due to the absence of fluorine in the carbon nanotubes, and the carbon nanotubes are unevenly distributed in the prussian white particles. By analysis, NaxMnFe(CN)6·yH2In O, x<1.6，y>2。
Prussian white material prepared by the comparative example is used as a positive electrode, metal sodium is used as a negative electrode, glass fiber (brand Whatman GF/D) is used as a diaphragm, and NaPF6The EC/DEC solution of (1) was used as an electrolyte, and a battery was mounted in a glove box filled with argon gas to perform a charge/discharge test. Constant current charge and discharge tests (the current density is 15mA/g, the voltage range is 2-4V shows that the capacity is lower than 130mAh/g, and the charge and discharge voltage is lower.
Comparative example 3
The preparation process of the prussian white cathode material is similar to that of example 1, except that the fluorine content of the carbon fluoride nanotubes introduced into the solution B exceeds 40%, and other reaction conditions are the same. The result shows that the fluorine content in the carbon fluoride nanotube is too high, the conductivity of the composite material is poor, and the bonding between fluorine ions and manganese or ferrous ions is strong, so that the electrochemical activity of the composite material is low.
Prussian white material prepared by the comparative example is used as a positive electrode, metal sodium is used as a negative electrode, glass fiber (brand Whatman GF/D) is used as a diaphragm, and NaPF6The EC/DEC solution of (1) was used as an electrolyte, and a battery was mounted in a glove box filled with argon gas to perform a charge/discharge test. Constant current charge and discharge tests (the current density is 15mA/g, the voltage range is 2-4V shows that the capacity is lower than 120mAh/g, and the low charge and discharge voltage is shown.
Example 2
Dissolving sodium ferrocyanide in deionized water, and uniformly stirring to obtain a solution A with the concentration of 0.15mol/L in terms of ferrous cyanide ions; dissolving manganous sulfate in deionized water to obtain Mn2+Calculating a solution with the concentration of 0.3mol/L, wherein the molar weight of manganous sulfate is 2 times of that of sodium ferrocyanide, adding a carbon fluoride nanotube, the adding amount of which is 7 percent of the theoretical weight of Prussian white, and fully stirring to obtain a solution B; and then, dropwise adding the solution B into the solution A under the condition of continuous stirring, carrying out hydrothermal reaction at 90 ℃ for 8 hours, cooling, washing, and carrying out vacuum drying at the temperature of not less than 120 ℃ for not less than 12 hours to obtain the Prussian white composite material. XRD shows that the product is rhombohedral phase sodium iron manganese cyanide, a scanning electron microscope shows that the particle size of Prussian white is 300-500 nm, the carbon fluoride nanotubes are uniformly dispersed in Prussian white particles, and analysis shows that NaxMnFe(CN)6·yH2In O, x is 1.72 and y is 0.87.
The Prussian white composite material prepared in the embodiment is used as a positive electrode, metal sodium is used as a negative electrode, glass fiber (trademark Whatman GF/D) is used as a diaphragm, and NaPF6And (3) taking an EC/DEC solution as an electrolyte, assembling a battery in a glove box filled with argon, and performing charge and discharge tests. Constant current charge and discharge tests (the current density is 15mA/g, the voltage range is 2-4V) show that the capacity can reach 144mAh/g, the average discharge voltage exceeds 3.6V, and the average charge voltage exceeds 3.8V.
Example 3
Dissolving sodium ferrocyanide in deionized water, and uniformly stirring to obtain a solution A with the concentration of 0.2mol/L in terms of ferrous cyanide ions; dissolving manganous nitrate in deionized water to obtain Mn2+The concentration is 0.4molThe method comprises the following steps of (1) adding a fluorinated carbon nanotube into a solution per liter, wherein the molar weight of manganous nitrate is 2.5 times that of sodium ferrocyanide, wherein the fluorine content of the fluorinated carbon nanotube is 10%, the addition amount of the fluorinated carbon nanotube is 5% of the theoretical weight of Prussian white, and fully stirring to obtain a solution B; and then, dropwise adding the solution B into the solution A under the condition of continuous stirring, carrying out hydrothermal reaction for 6h at 60 ℃, cooling, washing and carrying out vacuum drying for 12 h at 120 ℃ to obtain the Prussian white composite material. XRD shows that the product is rhombohedral phase sodium iron manganese cyanide, a scanning electron microscope shows that the particle size of Prussian white is 300-500 nm, the carbon fluoride nanotubes are uniformly dispersed in Prussian white particles, and analysis shows that NaxMnFe(CN)6·yH2In O, x is 1.81 and y is 0.92.
The Prussian white composite material prepared in the embodiment is used as a positive electrode, metal sodium is used as a negative electrode, glass fiber (trademark Whatman GF/D) is used as a diaphragm, and NaPF6The EC/DEC solution of (1) was used as an electrolyte, and a battery was mounted in a glove box filled with argon gas to perform a charge/discharge test. Constant current charge and discharge tests (current density 15mA/g, voltage range 2V-4V) show that the capacity can reach 149mAh/g, the average discharge voltage exceeds 3.6V, and the average charge voltage exceeds 3.8V.
Example 4
Dissolving sodium ferrocyanide in deionized water, and uniformly stirring to obtain a solution A with the concentration of 0.5mol/L in terms of ferrous cyanide ions; dissolving manganous sulfate in deionized water to obtain Mn2+The solution with the calculated concentration of 1.0mol/L, wherein the molar weight of manganous sulfate is 2.2 times of that of sodium ferrocyanide, adding a fluorinated carbon nanotube, wherein the fluorine content of the fluorinated carbon nanotube is 20 percent, the adding amount of the fluorinated carbon nanotube is 8 percent of the theoretical weight of Prussian white, and fully stirring to obtain a solution B; and then, dropwise adding the solution B into the solution A under the condition of continuous stirring, carrying out hydrothermal reaction at 90 ℃ for 10 hours, cooling, washing, and carrying out vacuum drying at the temperature of not less than 120 ℃ for not less than 12 hours to obtain the Prussian white composite material. XRD shows that the product is rhombohedral phase sodium iron manganese cyanide, a scanning electron microscope shows that the particle size of Prussian white is 300-500 nm, the carbon fluoride nanotubes are uniformly dispersed in Prussian white particles, and analysis shows that NaxMnFe(CN)6·yH2In O, x is 1.77 and y is 0.93.
The Prussian white composite material prepared in the embodiment is used as a positive electrode, metal sodium is used as a negative electrode, glass fiber (trademark Whatman GF/D) is used as a diaphragm, and NaPF6The EC/DEC solution of (1) was used as an electrolyte, and a battery was mounted in a glove box filled with argon gas to perform a charge/discharge test. Constant current charge and discharge tests (current density 15mA/g, voltage range 2V-4V) show that the capacity can reach 149mAh/g, the average discharge voltage exceeds 3.6V, and the average charge voltage exceeds 3.8V.
Claims (10)
1. The preparation method of the Prussian white composite material is characterized by comprising the following steps of:
(1) mixing sodium ferrocyanide or a hydrate thereof with deionized water to obtain a solution A with the concentration of 0.1-0.5 mol/L;
(2) will contain divalent Mn2+Mixing the soluble salt with deionized water, adding the carbon fluoride nano tube, and fully dispersing to obtain a solution B, wherein Mn is contained in the solution B2+The concentration of (A) is 0.2-1.0 mol/L;
(3) and (3) dropwise adding the solution B obtained in the step (2) into the solution A obtained in the step (1), and carrying out hydrothermal reaction and post-treatment to obtain the Prussian white composite material.
2. The method for preparing the prussian white composite material as claimed in claim 1, wherein the fluorine content of the fluorinated carbon nanotubes is 10-20%.
3. The method for preparing prussian white composite material according to claim 1, wherein the amount of the fluorinated carbon nanotubes added is 4 to 8% by weight of the finally obtained prussian white composite material.
4. The preparation method of the prussian white composite material as claimed in claim 1, wherein the soluble salt is one or more of manganese chloride, manganese sulfate and manganese nitrate, or one or more of hydrates corresponding to manganese chloride, manganese sulfate and manganese nitrate.
5. The method for preparing the prussian white composite material as claimed in claim 1, wherein the solution B contains Mn2+The molar ratio of the compound to the ferrous cyanide ions is 1.5: 2.5.
6. the preparation method of the prussian white composite material according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 70-90 ℃ for 6-10 hours.
7. The method for preparing the prussian white composite material according to claim 1, wherein the product after the hydrothermal reaction is further subjected to cooling, washing and vacuum drying treatment, wherein the vacuum drying temperature is not lower than 120 ℃ and the drying time is not shorter than 12 hours.
8. A Prussian white composite material prepared by the method according to any one of claims 1 to 7, wherein the Prussian white has a chemical formula of NaxMnFe(CN)6·yH2O, wherein x is 1.6 to 2, 0<y<1; the lattice structure is rhombohedral phase.
9. The prussian white composite material according to claim 8, wherein the prussian white material is irregular in shape and 300-500 nm in size, the fluorinated carbon nanotubes are uniformly dispersed in the prussian white material, and fluorine ions and manganese ions or ferrous ions can be bonded to form the uniform composite material.
10. The use of a Prussian white composite material prepared according to the method of any one of claims 1 to 7 in a sodium ion battery, wherein the average charging voltage is more than 3.8V and the average discharging voltage is more than 3.6V.
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| CN111252784B (en) * | 2020-01-22 | 2021-06-22 | 宇恒电池有限公司 | Preparation method of manganese-based Prussian white positive electrode material and application of manganese-based Prussian white positive electrode material in sodium-ion battery electrode |
| CN112786828A (en) * | 2021-02-22 | 2021-05-11 | 宁波容百新能源科技股份有限公司 | Prussian positive plate with high compaction density and high rate performance, preparation method of prussian positive plate and sodium ion battery |
| CN114212803B (en) * | 2021-10-28 | 2023-09-12 | 广东邦普循环科技有限公司 | Preparation method of fluorine-doped Prussian blue sodium ion battery positive electrode material |
| CN115321557B (en) * | 2022-10-14 | 2023-02-10 | 江苏智纬电子科技有限公司 | Prussian white composite material for sodium ion battery and preparation method thereof |
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| CN106469828A (en) * | 2016-12-12 | 2017-03-01 | 华中科技大学 | A kind of graphite/Prussian blue composite material and preparation method thereof and its application |
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