CN109638241B - Superfine iron-based Prussian blue and analogue thereof, preparation method and sodium ion battery - Google Patents
Superfine iron-based Prussian blue and analogue thereof, preparation method and sodium ion battery Download PDFInfo
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- H—ELECTRICITY
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- H01M4/00—Electrodes
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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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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- 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 preparation method of superfine iron-based Prussian blue and analogues thereof, which comprises the following steps: s1: adding sodium ferrocyanide and metal salt into a ball milling device; s2: adding a proper amount of solvent into the ball milling device; s3: placing the mixed raw materials into the ball milling device for ball milling; s4: washing the mixture obtained in the step S3 with absolute ethyl alcohol and deionized water; s5: and drying the cleaned product to prepare the iron-based Prussian blue and the analogues thereof. The invention also discloses iron-based Prussian blue corresponding to the iron-based Prussian blue, an analogue of the iron-based Prussian blue and a sodium ion battery. The preparation method of the superfine iron-based Prussian blue and the analogues thereof adopts the solid-liquid ratio of more than 50 percent and promotes the reaction by a ball milling mode, so that the method has high yield and is suitable for large-scale production, and the grain diameter of the superfine iron-based Prussian blue and the analogues thereof is less than 100nm, so that the superfine iron-based Prussian blue and the analogues thereof are applied to the anode material of a sodium-ion battery, and have the characteristics of long cycle life, good rate capability and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of Prussian blue and analogues thereof, and particularly relates to a preparation method of ultrafine iron-based Prussian blue and analogues thereof and application of the ultrafine iron-based Prussian blue and analogues thereof in the aspect of positive electrode materials of sodium-ion batteries.
Background
The sodium ion battery has the characteristics of low raw material cost, abundant resources, large potential of electrochemical performance and the like, so the sodium ion battery is expected to be applied to the field of large-scale energy storage and is one of important research directions of next-generation battery technology. At present, the positive electrode material of the sodium ion battery mainly comprises transition metal oxide, phosphate, prussian blue material and the like. Wherein, the Prussian blue material has higher voltage platform (>3V), large ion channel and large specific capacity (170 mAh g)-1) The material has the advantages of low cost, no toxicity, easy preparation and the like, and becomes a research hotspot of the anode material of the sodium-ion battery.
Iron-based Prussian blue andanalogs thereof (PBAs, Na)2M[Fe(CN)6]M ═ one or a combination of Fe, Co, Mn, Ni, and the like) generally has a face-centered cubic structure. In its cubic lattice, M2+And N-six-fold coordination in CN ligands, Fe2+And C in CN ligand to form a 3D rigid frame, which enables the Prussian blue and the like to have spacious lattice gaps for accommodating sodium ions, and open transmission channels for reversible transmission of the sodium ions.
At present, a water-phase coprecipitation method and a hydrothermal method are generally adopted for synthesizing PBAs, and patent document CN103474659B discloses a preparation method and application of a sodium-ion battery positive electrode material, and specifically discloses that the preparation method of the prussian blue complex composite material provided by the method at least comprises the following steps: uniformly dispersing transition metal salt, acid and a reducing agent in water to obtain a reaction solution, and heating the solution for a period of time under a protective atmosphere to obtain the Prussian blue complex material. In order to ensure the crystallization quality of the product, the method has low reactant concentration, low yield and unsuitability for large-scale production. In addition, the particle size of the PBAs synthesized using mild liquid phase reactions tends to be larger than 200nm, while the intrinsic electronic conductivity of PBAs is very low (4.08X 10)-9S cm-1) Leading to poor dynamic performance when the material is used as the anode material of the sodium-ion battery. Therefore, the search for a synthetic process for producing PBAs in a large scale and the improvement of the sodium storage kinetic performance of PBAs is very important for the practical application of PBAs.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a preparation method of superfine iron-based Prussian blue and analogues thereof, which adopts sodium ferrocyanide and metal salt as raw materials, and superfine PBAs with the particle size of less than 100nm are prepared by a ball milling method.
In order to accomplish the above objects, according to one aspect of the present invention, there is provided a method for preparing ultra-fine iron-based prussian blue and the like, comprising the steps of:
s1: adding sodium ferrocyanide and metal salt into a ball milling device;
s2: adding a proper amount of solvent into the ball milling device;
s3: placing the mixed raw materials into the ball milling device for ball milling;
s4: washing the mixture obtained in the step S3 with absolute ethyl alcohol and deionized water;
s5: and drying the cleaned product to prepare the iron-based Prussian blue and the analogues thereof.
Further, the rotation speed of the ball milling in the step S3 is 100r/min to 5000r/min, and the ball milling time is 1min to 48 hours.
Further, the temperature of the ball milling in the step S3 is 0 to 80 ℃.
Further, the particle size of the mixture in step S4 is less than or equal to 100 nm.
Further, the sodium ferrocyanide and the metal salt are crystal water or crystal water-free, and the molar ratio of the sodium ferrocyanide to the metal salt is 1: 0.5-1: 1.5.
further, the solvent may be water or acetonitrile, ethanol, glycerol or other organic solvents.
Further, the weight ratio of the total weight of the sodium ferrocyanide and the metal salt to the solvent is 100: 0-100: 100.
Further, the metal salt comprises a metal chloride salt, a metal sulfate salt or a perchlorate salt, wherein the metal chloride salt comprises FeCl2、CoCl2、MnCl2One or more of the metal sulfates comprise FeSO4、CoSO4、MnSO4One or more of the perchlorate salts comprise Fe (ClO)4)2、Mn(ClO4)2、Co(ClO4)2One or more of them.
According to another aspect of the present invention, there is provided an ultra-fine iron-based prussian blue and analogues thereof, wherein the ultra-fine iron-based prussian blue and analogues thereof are prepared by a preparation method, and the particle size of the ultra-fine iron-based prussian blue and analogues thereof is less than 100 nm.
According to another aspect of the present invention, there is provided a sodium ion battery comprising a positive electrode, a negative electrode, an electrolyte and a separator, wherein the positive electrode material is the ultra-fine iron-based prussian blue according to claim 9 and the like.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) the preparation method of the superfine iron-based Prussian blue and the analogues thereof adopts the solid-liquid ratio of more than 50 percent and promotes the reaction by a ball milling mode, so that the method has high yield and is suitable for large-scale production.
(2) The preparation method of the superfine iron-based Prussian blue and the analogue thereof has the advantages that the particle size of the superfine PBAs is less than 100nm, the superfine PBAs are applied to the anode material of the sodium-ion battery, and the preparation method has the characteristics of long cycle life, good rate capability and the like.
(3) According to the preparation method of the superfine iron-based Prussian blue and the analogues thereof, the rotation speed of ball milling is 100 r/min-5000 r/min, and the ball milling time is 1 min-48 hours, so that the sodium ferrocyanide and the metal salt mixture are fully ground, the powder particles are uniform in size and are superfine round particles, and the particle size of the superfine round particles is ensured to be less than or equal to 100 nm.
(4) According to the preparation method of the superfine iron-based Prussian blue and the analogues thereof, the ball milling temperature is controlled to be 0-80 ℃ according to the volatility of the solvent, the reaction rate of the sodium ferrocyanide and the metal salt mixture in the grinding process can be further accelerated by increasing the temperature, and the preparation efficiency of the iron-based Prussian blue and the analogues thereof is greatly improved.
(5) The particle size of the superfine iron-based Prussian blue and the analogue thereof is less than 100nm, and the size of the superfine iron-based Prussian blue and the analogue thereof is smaller than that of the Prussian blue and the analogue thereof prepared in aqueous solution.
(6) The sodium ion battery has the advantages of high charge capacity up to 130mAh/g, discharge capacity up to 116mAh/g, excellent cycle stability and rate capability.
Drawings
FIG. 1 is a XRD plot of the product after ball milling in example 1 of the present invention before washing;
FIG. 2 is a XRD plot of the product after ball milling in example 1 of the present invention after washing;
FIG. 3 shows NaxFe [ Fe (CN) ] synthesized in example 1 of the present invention6]Scanning electron microscope images of;
FIG. 4 shows NaxFe [ Fe (CN) ] synthesized in example 1 of the present invention6]Transmission electron microscopy images of;
FIG. 5 shows NaxFe [ Fe (CN) ] synthesized in example 1 of the present invention6]The curve is used as the charge-discharge curve of the positive electrode of the sodium ion battery;
FIG. 6 shows NaxFe [ Fe (CN) ] synthesized in example 1 of the present invention6]As a cycle performance diagram of the positive electrode of the sodium-ion battery;
FIG. 7 shows NaxFe [ Fe (CN) ] synthesized in example 1 of the present invention6]The rate performance graph of the positive electrode of the sodium-ion battery is shown.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a preparation method of superfine iron-based Prussian blue and analogues thereof, which comprises the following steps:
(1) adding sodium ferrocyanide and metal salt into a ball milling device;
(2) adding a proper amount of solvent into the ball milling device;
(3) placing the mixed raw materials into the ball milling device for ball milling;
(4) the obtained PBAs were washed with absolute ethanol and deionized water.
(5) And drying the cleaned product.
The preparation method of the superfine iron-based Prussian blue and the analogues thereof does not limit the size of a ball milling tank, the ball milling mode and the ball milling time. The metal salt includes metal chloride salt (FeCl)2、CoCl2、MnCl2Etc.), metal sulfates (FeSO)4、CoSO4And MnSO4Etc.) or perchlorate (Fe (ClO)4)2、Mn(ClO4)2、Co(ClO4)2) And the added sodium ferrocyanide and the metal salt can contain crystal water or not, and the molar ratio of the added sodium ferrocyanide to the metal salt is 1: 0.5-1: 1.5:. The solvent can be water or organic solvent such as acetonitrile, ethanol, glycerol, etc., and the weight ratio of the raw material to the solvent can be 100/0-100/100.
The ball milling mode comprises a planetary ball mill, a vibration ball mill, a vertical stirring ball mill, a horizontal sand mill and the like, and essentially accelerates the reaction by the impact, extrusion and grinding of ball milling beads, and has a refining effect on the particle size of a reaction product. The rotation speeds of different ball milling modes are different, for example, the rotation speed of a planetary ball mill is usually 100-300 rpm, the rotation speed of a vibration ball mill is usually 1000-2000 rpm, the rotation speed of a stirring ball mill is usually 50-150 rpm, the rotation speed of a sand mill is usually 1000-5000 rpm, and the like.
According to the preparation method of the superfine iron-based Prussian blue and the analogues thereof, the rotation speed of ball milling is 100 r/min-5000 r/min, and the ball milling time is 1 min-48 hours, so that the sodium ferrocyanide and the metal salt mixture are fully ground, the powder particles are uniform in size and are superfine round particles, and the particle size of the superfine round particles is ensured to be less than or equal to 100 nm.
Example 1
S1: 4mmol sodium ferrocyanide decahydrate and 6mmol ferrous chloride tetrahydrate are placed in a nylon ball milling tank, and the mixture is vibrated for 1min at the speed of 1200 r/min.
S2: in a glove box filled with Ar, the raw materials are placed in an agate ball milling tank, and the ball-material ratio is 1: 20.
S3: and (3) placing the agate jar in a planetary ball mill for dry milling for 12h at the rotating speed of 300 r/min.
S4: after the ball milling is finished, washing the product with absolute ethyl alcohol and deionized water, and then drying the product in a vacuum oven at 80 ℃ for 36 hours to obtain Na containing crystal waterxFe[Fe(CN)6。
FIG. 1 is an XRD diffraction of the unwashed product after ball milling for this exampleShoot at spectrum, through interaction with Na4Fe(CN)6Standard PDF card comparison (JCPDS-1-1026) shows that the unwashed product after ball milling contains no Na4Fe(CN)6This indicates that the ball milling reaction was complete. FIG. 2 is an XRD diffraction pattern of the washed product of EXAMPLE 1, by reaction with Fe4[Fe(CN)6]3Standard PDF card comparison (JCPDS-1-0239) revealed that the washing product was pure Prussian blue (Na)xFe[Fe(CN)6]). FIG. 3 shows Na prepared in example 1xFe[Fe(CN)6]The scanning electron microscope image shows that the prepared powder particles are uniform in size and are ultrafine round particles. FIG. 4 shows Na prepared in example 1xFe[Fe(CN)6]Also, it can be seen from the transmission electron microscope that the primary particle size of the powder is 50nm or less, which is smaller than that of prussian blue and the like prepared in an aqueous solution.
Na obtained in example 1 of the present embodimentxFe[Fe(CN)6]The method is applied to the positive electrode of the sodium-ion battery to carry out testing, and experimental data shown in fig. 5, 6 and 7 are obtained. FIG. 5 is a graph showing the charge and discharge curves of circle 1, and the charge and discharge current density in this experiment was 170 mA/g. As can be seen from the figure, the charging capacity of the material reaches 130mAh/g, and the discharging capacity reaches 116 mAh/g. FIG. 6 is Na prepared by carrying out example 1xFe[Fe(CN)6]The cycle performance graph obtained by testing after the battery is assembled by applying to the positive electrode of the sodium-ion battery can be seen from the cycle performance graph, and Na serving as the positive electrode of the sodium-ion batteryxFe[Fe(CN)6]The lithium secondary battery shows excellent cycling stability, and after 100 cycles of cycling, the discharge capacity retention rate is 84%, the capacity retention rate after 200 cycles of cycling is 78.6%, the capacity retention rate after 500 cycles of cycling is 70.3%, and the capacity retention rate after 1000 cycles of cycling is 62.6%. FIG. 7 is Na prepared by carrying out example 1xFe[Fe(CN)6]The method is applied to a multiplying power performance diagram obtained by testing the assembled battery of the positive electrode of the sodium-ion battery. As can be seen from the figure, Na was prepared as the positive electrode of the sodium ion batteryxFe[Fe(CN)6]Showing excellent rate capability. At 0.2C, i.e. 35mA/g current, NaxFe[Fe(CN)6]A discharge capacity of111mAh/g, and under the large current of 30C, namely 5000mA/g, the discharge capacity is still kept about 97mAh/g, and the retention rate is 87.3%.
Example 2
S1: 4mmol of anhydrous sodium ferrocyanide and 4mmol of anhydrous manganous chloride are placed in a nylon ball milling tank, and the materials are mixed for 1min by vibration at the speed of 800 r/min.
S2: 20ml of acetonitrile was added to the ball mill pot.
S3: and continuously carrying out vibration ball milling on the vibration ball mill for 30min at the vibration speed of 1200 r/min.
S4: after the ball milling is finished, filtering the product, washing the product with absolute ethyl alcohol, and drying the product in a vacuum oven at 80 ℃ for 36 hours to obtain Na without crystal waterxMn[Fe(CN)6。
Example 3
S1: 2L of deionized water is added into a circulating tank (with a stirrer) of the horizontal sand mill;
s2: adding 4mol of sodium ferrocyanide decahydrate into a circulating tank, and stirring until the sodium ferrocyanide decahydrate is dissolved;
s3: starting a horizontal sand mill, rotating at 3000rpm, and then adding 6mol of cobaltous chloride hexahydrate into a circulating tank for ball milling for 2 hours.
S4: after the ball milling is finished, filtering the product, washing the product with deionized water and absolute ethyl alcohol respectively, and then drying the product in a vacuum oven at 80 ℃ for 36 hours to obtain Na containing crystal waterxCo[Fe(CN)6。
The preparation method can adopt the solid-liquid ratio of more than 50 percent and promote the reaction by a ball milling mode, so the method has high yield and is suitable for large-scale production. As shown in example 1, the product was obtained even in the absence of a solvent. In addition, the particle size of the superfine PBAs synthesized by the method is less than 100nm, and the superfine PBAs are applied to the anode material of the sodium-ion battery and have the characteristics of long cycle life, good rate capability and the like.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The preparation method of the superfine iron-based Prussian blue and the analogues thereof is characterized by comprising the following steps:
s1: adding sodium ferrocyanide and metal salt into a ball milling device;
s2: adding a proper amount of solvent or not adding the solvent into the ball milling device;
s3: placing the mixed raw materials into the ball milling device for ball milling;
s4: washing the mixture obtained in the step S3 with absolute ethyl alcohol and deionized water;
s5: drying the cleaned product to prepare the superfine iron-based Prussian blue and the analogues thereof;
the superfine iron-based Prussian blue and the analogue thereof are iron-based Prussian blue with the particle size of less than 100nm and the analogue thereof, and the superfine iron-based Prussian blue and the analogue thereof are Na2M[Fe(CN)6]Wherein M = one or a combination of Fe, Co, Mn, Ni.
2. The method for preparing ultra-fine iron-based prussian blue and the like as claimed in claim 1, wherein the rotation speed of the ball milling in step S3 is 100r/min to 5000r/min, and the ball milling time is 1min to 48 hours.
3. The method of claim 2, wherein the ball milling temperature in the step S3 is 0 to 80 ℃.
4. The method of claim 3, wherein the mixture of step S4 has a particle size of 100nm or less.
5. The method as claimed in claim 4, wherein the solvent is water or acetonitrile, ethanol, glycerol or other organic solvents.
6. The method of claim 5, wherein the weight ratio of the total weight of the sodium ferrocyanide and the metal salt to the solvent is (100: 0) - (100: 100).
7. The method as claimed in claim 6, wherein the metal salt includes a metal chloride salt, a metal sulfate salt or a perchlorate salt, wherein the metal chloride salt includes FeCl2、CoCl2、MnCl2One or more of the metal sulfates comprise FeSO4、CoSO4、MnSO4One or more of the perchlorate salts comprise Fe (ClO)4)2、Mn(ClO4)2、Co(ClO4)2One or more of them.
8. An ultra-fine iron-based prussian blue and analogues thereof, which is prepared by the method for preparing the ultra-fine iron-based prussian blue and analogues thereof according to any one of claims 1 to 7, and the particle size of the ultra-fine iron-based prussian blue and analogues thereof is less than 100 nm.
9. A sodium ion battery comprising a positive electrode, a negative electrode, an electrolyte and a separator, wherein the positive electrode material is the ultra-fine iron-based prussian blue according to claim 8 and the like.
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| CN111029572A (en) * | 2019-12-10 | 2020-04-17 | 中国科学院过程工程研究所 | Prussian-like blue derivative and preparation method and application thereof |
| CN113479911B (en) * | 2021-06-21 | 2023-03-17 | 华中科技大学 | Iron-based Prussian blue, preparation method and application thereof |
| CN114671468B (en) * | 2022-03-28 | 2023-11-07 | 温州大学碳中和技术创新研究院 | Preparation method and application of polyanion and Prussian blue composite positive electrode material |
| CN114709402A (en) * | 2022-04-21 | 2022-07-05 | 温州大学碳中和技术创新研究院 | Preparation and application of carbon-coated sodiumsulverine-based Prussian blue positive electrode material |
| CN115448327B (en) * | 2022-09-29 | 2024-03-12 | 广东邦普循环科技有限公司 | Preparation method and application of low-defect Prussian blue positive electrode material |
| CN117430135B (en) * | 2023-12-21 | 2024-04-05 | 山东海化集团有限公司 | Method for synthesizing ferromanganese-based Prussian blue sodium electric positive electrode material and positive electrode material prepared by method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015101523A (en) * | 2013-11-27 | 2015-06-04 | 国立研究開発法人産業技術総合研究所 | Method for synthesizing prussian blue type complex nanoparticles, and prussian blue type complex nanoparticles synthesized by the method |
| CN106654263A (en) * | 2016-12-30 | 2017-05-10 | 东莞市佳乾新材料科技有限公司 | Preparation method of Prussian blue based sodium ion battery positive electrode material |
| CN107082438A (en) * | 2017-04-28 | 2017-08-22 | 武汉理工大学 | Prussian blue nano floral structure material and its preparation and application |
| CN107634220A (en) * | 2017-08-04 | 2018-01-26 | 上海交通大学 | A kind of preparation method of prussian blue energy storage material |
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| JP5697068B2 (en) * | 2006-12-28 | 2015-04-08 | 独立行政法人産業技術総合研究所 | Method for producing Prussian blue-type metal complex nanoparticles, Prussian blue-type metal complex nanoparticles obtained thereby, dispersion thereof, color development control method thereof, electrode and transmission light control device using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015101523A (en) * | 2013-11-27 | 2015-06-04 | 国立研究開発法人産業技術総合研究所 | Method for synthesizing prussian blue type complex nanoparticles, and prussian blue type complex nanoparticles synthesized by the method |
| CN106654263A (en) * | 2016-12-30 | 2017-05-10 | 东莞市佳乾新材料科技有限公司 | Preparation method of Prussian blue based sodium ion battery positive electrode material |
| CN107082438A (en) * | 2017-04-28 | 2017-08-22 | 武汉理工大学 | Prussian blue nano floral structure material and its preparation and application |
| CN107634220A (en) * | 2017-08-04 | 2018-01-26 | 上海交通大学 | A kind of preparation method of prussian blue energy storage material |
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