CN110921681A - Prussian blue material and preparation method and application thereof - Google Patents
Prussian blue material and preparation method and application thereof Download PDFInfo
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- CN110921681A CN110921681A CN201911188166.XA CN201911188166A CN110921681A CN 110921681 A CN110921681 A CN 110921681A CN 201911188166 A CN201911188166 A CN 201911188166A CN 110921681 A CN110921681 A CN 110921681A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/08—Simple or complex cyanides of metals
- C01C3/12—Simple or complex iron cyanides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a Prussian blue material and a preparation method and application thereof. The preparation method comprises the following steps: mixing sodium ferrocyanide or a hydrate of sodium ferrocyanide with deionized water to obtain a solution I; mixing soluble ferrous salt, ascorbic acid, sodium citrate and deionized water to obtain a solution II; dripping the solutions I and II into deionized water at the same time, and obtaining a suspension of the Prussian blue material through coprecipitation reaction; and aging and post-treating the suspension to obtain the micron-sized Prussian blue material with the cubic stepped structure. The Prussian blue material prepared by the method is applied to the positive electrode of the sodium-ion battery, and can obviously improve the capacity and the cycling stability of the sodium-ion battery.
Description
Technical Field
The invention relates to the field of low-cost energy storage battery materials, in particular to a Prussian blue material and a preparation method and application thereof.
Background
With the increasing global energy and environmental problems, the development of sustainable clean energy sources, such as solar energy, tidal energy, wind energy, is gaining increasing attention, and the effective utilization of these clean energy sources depends on high-performance, sustainable, cheap and environmentally friendly energy storage batteries. On the other hand, with the development of smart grids, energy storage batteries also play a key role in effectively using the power grids.
At present, common energy storage batteries include lithium ion batteries, lead-acid batteries, flow batteries and the like. Lithium ion batteries have high energy density and long service life, but have high cost and are limited by lithium resources and also face potential safety hazards. The lead-acid battery has the advantages of mature technology, low cost, good safety performance and the like, but the lead-acid battery has low energy density and short service life and is easy to face the problem of environmental protection. The cost of the liquid flow current is high, and the energy density is low. In contrast, the sodium ion battery has the advantages of good safety, low cost, abundant resources, environmental friendliness and the like, and is very suitable for large-scale energy storage. In view of the large radius of sodium ions, the development of suitable electrode materials is extremely critical. Some Prussian blue-based material structures have open framework structures, so that the insertion and extraction of sodium ions are facilitated, and therefore, the capacity is high and the rate capability is good. However, the Prussian blue material is generally synthesized in water and contains more defects and crystal water, so that the actual capacity is lower; in addition, the released crystal water is easy to react with sodium salt to form hydrogen fluoride to corrode the material, and the cycle life is influenced. Therefore, optimizing the synthesis process and controlling the product structure are very important.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art and provide a Prussian blue material and a preparation method and application thereof.
Therefore, the invention adopts the following technical scheme: a preparation method of a Prussian blue material comprises the following steps:
1) mixing sodium ferrocyanide or a hydrate of sodium ferrocyanide with deionized water to obtain a solution I;
2) mixing soluble ferrous salt, ascorbic acid, sodium citrate and deionized water to obtain a solution II;
3) dripping the solutions I and II into deionized water at the same time, and obtaining a suspension of the Prussian blue material through coprecipitation reaction;
4) and aging and post-treating the suspension to obtain the micron-sized Prussian blue material with the cubic stepped structure.
Aiming at the defects of low Prussian blue capacity, unstable material structure, easiness in corrosion of electrolyte and the like, the capacity, the cycling stability and the rate capability of the Prussian blue are improved by optimizing the preparation process and improving the product appearance.
As a preferable mode of the above production method, in the step 1), the concentration of sodium ferrocyanide or a hydrate of sodium ferrocyanide in the solution I is 0.01 to 0.1 mol/L. The raw material can be selected from sodium ferrocyanide and hydrate of sodium ferrocyanide, under the condition, the product has high sodium content and complete crystal structure.
As the preferable preparation method, in the step 2), the concentration of the ferrous salt in the solution II is 0.01-0.1 mol/L. Under these conditions, the product can have a high sodium content and a complete crystal structure.
Preferably, in the step 2), the soluble ferrous salt is selected from ferrous chloride, ferrous sulfate, ferrous nitrate, ferrous acetate, or a hydrate thereof.
As a preference of the preparation method, in the step 2), the molar ratio of the ferrous salt in the solution II to the sodium ferrocyanide in the solution I is 1.05-1.15: 1, under the condition, the sodium content of the product is higher, and the crystal structure is more complete, so that high capacity and cycle life are realized; the molar ratio of ascorbic acid in the solution II to sodium ferrocyanide in the solution I is 0.5-1: under the condition, the oxidation of ferrous ions can be effectively inhibited, so that the high sodium content and the complete crystal structure of a product are realized, and the high capacity and the long cycle life are realized; the molar ratio of the sodium citrate in the solution II to the sodium ferrocyanide in the solution I is 10-50: 1, under the condition, the speed of coprecipitation reaction can be effectively controlled, thereby realizing the control of the morphology of the product. The conditions are correlated, and high sodium content, proper particle morphology and size of the product are realized under the combined action, so that good capacity and long cycle life of the product are realized.
As the preferable preparation method, in the step 3), the temperature of the coprecipitation reaction is 15-30 ℃. Under the condition, the product crystal has less defects and less water content, and under the coordination of other conditions, the product has a micron-sized cubic stepped structure, so that the product has high electrochemical activity and chemical/electrochemical stability, thereby improving the capacity and the cycle life.
As the optimization of the preparation method, in the step 4), the aging temperature is 15-30 ℃, and the aging time is 2-4 hours.
As the optimization of the preparation method, in the step 4), the aged product is subjected to post-treatment, including cooling, washing, separation and vacuum drying treatment, wherein the vacuum degree of vacuum drying is lower than 1 Pa. Through the optimization treatment, the crystallinity of the product is further improved and the content of crystal water is reduced.
The invention also provides a Prussian blue material prepared by the method, and the product contains NaxFeFe(CN)6The general formula is that x is more than 1.5 and less than 2, the particle has a monoclinic phase structure, the particle has a stepped cubic hierarchical structure, and the particle size is 3-5 micrometers.
The invention also provides an application of the Prussian blue material in a sodium ion battery, wherein in the organic sodium ion battery, Prussian blue is used as a positive electrode, hard carbon, soft carbon or a hard carbon/soft carbon composite material is used as a negative electrode, and an organic solution containing an organic solvent, sodium salt and an additive is used as an electrolyte.
Preferably, the organic solvent is selected from, but not limited to, at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and propyl methyl carbonate. Further preferably, the organic solvent is selected from a mixed solvent of ethyl methyl carbonate/propylene carbonate, a mixed solvent of dimethyl carbonate/propylene carbonate and a mixed solvent of ethylene carbonate/propylene carbonate in a volume ratio of 1:1, and the organic solvent is used for forming an effective SEI protective film on the surfaces of the positive electrode and the negative electrode.
Preferably, the sodium salt is selected from, but not limited to, at least one of sodium perchlorate, sodium hexafluorophosphate, sodium trifluoromethanesulfonate, sodium bistrifluoromethanesulfonylimide, sodium bifluorosulfonylimide, sodium tetrafluoroborate, and sodium bisoxalato. Further preferably, the sodium salt is selected from sodium hexafluorophosphate.
Preferably, the additive is selected from at least one of fluoroethylene carbonate, vinylene carbonate, 1, 3-propane sultone, 1, 3-propylene sultone, vinylene sulfate and vinyl sulfite. Further preferably, the weight ratio of the additive to the organic solvent is 1-10%: 100 percent.
Compared with the prior art, the invention has the following advantages:
1. the Prussian blue material has complete crystal lattices and low crystal water by optimizing the preparation process, so that the product has high capacity, long cycle life and excellent rate performance, and can be used in a high-performance organic sodium-ion battery by combining the optimization of the components of the organic electrolyte.
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 (XRD) spectrum of a Prussian blue material prepared in example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) spectrum of the Prussian blue material prepared in example 1 of the invention;
fig. 3 is a charge-discharge curve diagram of a sodium ion battery assembled by the prussian blue material prepared in example 1;
fig. 4 is a graph showing the cycle performance of a sodium ion battery assembled with the prussian blue material prepared in example 1.
Detailed Description
Example 1
Dissolving sodium ferrocyanide decahydrate in 50 ml of deionized water, and uniformly stirring to obtain a solution I with the concentration of 0.06 mol/L; dissolving ferrous sulfate, ascorbic acid and sodium citrate in 50 ml of deionized water to obtain solutions II with the concentrations of 0.066mol/L, 0.04mol/L and 1.4mol/L respectively; adding the solution I and the solution II into 100 ml of deionized water at the same time, carrying out coprecipitation reaction at the temperature of 20 ℃, washing, centrifugally separating and drying in vacuum to obtain NaxFeFe(CN)6。
Fig. 1 is an XRD of the prussian blue material prepared in this example, which was analyzed to be a monoclinic phase. Fig. 2 is an SEM photograph of the prussian blue material prepared in this example, and it can be seen from the drawing that the particles have a stepped cubic hierarchical structure and a particle size of 3 to 5 μm. Prussian blue material prepared in the embodiment is used as a positive electrode, metal sodium is used as a negative electrode, glass fiber (trademark Whatmann GF/D) is used as a diaphragm, and NaPF6The solution of Propylene Carbonate (PC)/Ethyl Methyl Carbonate (EMC) is used as an electrolyte, a battery is assembled in a glove box filled with argon, a charge-discharge test is carried out, the current density is 15mA/g, the voltage range is 2-4V, the charge-discharge curve is shown in figure 3, the initial discharge capacity of the product can reach 116mAh/g, the current density is 150mA/g, and after 500 cycles, the capacity retention rate is 93.1%, which is shown in figure 4.
Comparative example 1
The preparation of the material is the same as that of example 1, except that the concentration of ferrous sulfate in the solution II is 0.09mol/L, the other conditions are the same, the particle size of the obtained product is 2-3 micrometers, and an electrochemical test shows that the initial discharge capacity of the product is 104mAh/g when the current density is 15 mA/g.
Comparative example 2
The material was prepared as in example 1 except that sodium citrate was not placed in solution II but in 100 ml of deionized water under otherwise identical conditions, and since sodium citrate did not effectively complex the iron ions, the resulting product was a monoclinic phase with a particle size of 300-600 nm, and electrochemical tests showed that the initial discharge capacity of the product was 90mAh/g at a current density of 15 mA/g.
Comparative example 3
The preparation of the material is the same as that of example 1, except that ascorbic acid is not added into the solution II, and other conditions are the same, and electrochemical tests show that the initial discharge capacity of the product is 95mAh/g when the current density is 15 mA/g.
Comparative example 4
The material was prepared as in example 1, except that solution I and solution II were not added to 100 ml of deionized water simultaneously, but solution I was added to solution II, and the other conditions were the same, at which time cubic phase prussian blue was obtained, and electrochemical tests showed that the initial discharge capacity of the product was 88mAh/g at a current density of 15 mA/g.
Comparative example 5
The material was prepared as in example 1, except that the reaction temperature was 60 deg.CoAnd C, the other conditions are the same, although monoclinic phase Prussian blue is obtained, the reaction temperature is too high, the product is crystallized too fast, and more defects exist, and electrochemical tests show that the initial discharge capacity of the product is 70mAh/g when the current density is 15mA/g, and the platform is not obvious.
Example 2
Dissolving sodium ferrocyanide decahydrate in 50 ml of deionized water, and uniformly stirring to obtain a solution I with the concentration of 0.01 mol/L; dissolving ferrous chloride, ascorbic acid and sodium citrate in 50 ml of deionized water to obtain solutions II with the concentrations of 0.0105mol/L, 0.005mol/L and 0.1mol/L respectively; adding the solution I and the solution II into 100 ml of deionized water at the same time, carrying out coprecipitation reaction at the temperature of 20 ℃, washing, centrifugally separating and drying in vacuum to obtain NaxFeFe(CN)6. Electrochemical tests prove that the initial discharge capacity of the product can reach 115mAh/g when the current density is 15 mA/g.
Example 3
Dissolving sodium ferrocyanide decahydrate in 50 ml of deionized water, and uniformly stirring to obtain a solution I with the concentration of 0.1 mol/L; dissolving ferrous nitrate, ascorbic acid and sodium citrate in 50 ml of deionized water to obtain solutions II with the concentrations of 0.115mol/L, 0.1mol/L and 5mol/L respectively; solution I and solution II are mixed at the same timeAdding into 100 ml deionized water, coprecipitating reaction at 20 deg.C, washing, centrifuging, and vacuum drying to obtain NaxFeFe(CN)6. Electrochemical tests prove that the initial discharge capacity of the product can reach 118mAh/g when the current density is 15 mA/g.
Claims (10)
1. The preparation method of the Prussian blue material is characterized by comprising the following steps:
1) mixing sodium ferrocyanide or a hydrate of sodium ferrocyanide with deionized water to obtain a solution I;
2) mixing soluble ferrous salt, ascorbic acid, sodium citrate and deionized water to obtain a solution II;
3) dripping the solutions I and II into deionized water at the same time, and obtaining a suspension of the Prussian blue material through coprecipitation reaction;
4) and aging and post-treating the suspension to obtain the micron-sized Prussian blue material with the cubic stepped structure.
2. The method for preparing prussian blue material according to claim 1, wherein in step 1), the concentration of sodium ferrocyanide or hydrate of sodium ferrocyanide in the solution I is 0.01-0.1 mol/L.
3. The method for preparing prussian blue material according to claim 1, wherein in step 2), the concentration of the ferrous salt in the solution II is 0.01-0.1 mol/L.
4. The method for preparing prussian blue material as claimed in claim 1, wherein in step 2), the soluble ferrous salt is selected from ferrous chloride, ferrous sulfate, ferrous nitrate, ferrous acetate, or hydrate thereof.
5. The method for preparing prussian blue material according to claim 1, wherein in step 2), the molar ratio of ferrous salt in solution II to sodium ferrocyanide in solution I is 1.05-1.15: 1; the molar ratio of the ascorbic acid in the solution II to the sodium ferrocyanide in the solution I is 0.5-1: 1; the molar ratio of the sodium citrate in the solution II to the sodium ferrocyanide in the solution I is 10-50: 1.
6. the method for preparing the prussian blue material as claimed in claim 1, wherein the temperature of the coprecipitation reaction in step 3) is 15-30 ℃.
7. The method for preparing prussian blue material as claimed in claim 1, wherein in step 4), the aging temperature is 15-30 ℃ and the aging time is 2-4 hours.
8. The method for preparing prussian blue material as claimed in claim 1, wherein in step 4), the aged product is subjected to post-treatment including cooling, washing, separating and vacuum drying under vacuum degree of less than 1 pa.
9. A Prussian blue material prepared by the method of any one of claims 1 to 8, wherein the product contains NaxFeFe(CN)6The general formula is that x is more than 1.5 and less than 2, the particle has a monoclinic phase structure, the particle has a stepped cubic hierarchical structure, and the particle size is 3-5 micrometers.
10. Use of the prussian blue material according to claim 9 in a sodium ion battery, wherein the prussian blue material is used as a positive electrode, a hard carbon, a soft carbon, or a hard carbon/soft carbon composite material is used as a negative electrode, and an organic solution containing an organic solvent, a sodium salt, and an additive is used as an electrolyte.
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Cited By (16)
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| CN111547742A (en) * | 2020-04-14 | 2020-08-18 | 浙江钠创新能源有限公司 | Sodium-ion battery positive electrode material, preparation method thereof and sodium-ion battery |
| CN111600011A (en) * | 2020-04-24 | 2020-08-28 | 国网浙江省电力有限公司电力科学研究院 | Doped prussian blue material and preparation method and application thereof |
| CN111943228A (en) * | 2020-08-24 | 2020-11-17 | 全球能源互联网研究院有限公司 | Prussian blue type sodium ion battery positive electrode material and preparation method thereof |
| CN111943225A (en) * | 2020-08-24 | 2020-11-17 | 全球能源互联网研究院有限公司 | Prussian blue type sodium ion battery positive electrode material and preparation method thereof |
| CN112174167A (en) * | 2020-08-13 | 2021-01-05 | 国网浙江省电力有限公司电力科学研究院 | Prussian blue material with core-shell structure and preparation method and application thereof |
| CN113479911A (en) * | 2021-06-21 | 2021-10-08 | 华中科技大学 | Iron-based Prussian blue, preparation method and application thereof |
| CN113540445A (en) * | 2021-06-10 | 2021-10-22 | 恒大新能源技术(深圳)有限公司 | Prussian blue and preparation method and application thereof |
| CN113839032A (en) * | 2021-09-15 | 2021-12-24 | 杭州思拓瑞吉科技有限公司 | Low-cost Prussian white material, and preparation method and application thereof |
| CN114212803A (en) * | 2021-10-28 | 2022-03-22 | 广东邦普循环科技有限公司 | Preparation method of fluorine-doped Prussian blue type sodium ion battery positive electrode material |
| CN114275798A (en) * | 2021-12-27 | 2022-04-05 | 郑州轻工业大学 | High-crystallization Prussian blue analogue material and preparation method and application thereof |
| CN114373905A (en) * | 2021-12-17 | 2022-04-19 | 合肥国轩高科动力能源有限公司 | Sodium ion positive electrode material and preparation method and application thereof |
| CN114805450A (en) * | 2022-06-15 | 2022-07-29 | 国网智能电网研究院有限公司 | Preparation method and application of high-entropy Prussian blue sodium ion battery cathode material |
| CN114873612A (en) * | 2022-06-22 | 2022-08-09 | 东北大学秦皇岛分校 | Preparation method of wool-ball-like Berlin green electrode material for aqueous ammonium ion battery |
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| CN113540445A (en) * | 2021-06-10 | 2021-10-22 | 恒大新能源技术(深圳)有限公司 | Prussian blue and preparation method and application thereof |
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