CN117228691A - Prussian blue coated with graphite and analogues thereof, and preparation method and application thereof - Google Patents
Prussian blue coated with graphite and analogues thereof, and preparation method and application thereof Download PDFInfo
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- CN117228691A CN117228691A CN202311141136.XA CN202311141136A CN117228691A CN 117228691 A CN117228691 A CN 117228691A CN 202311141136 A CN202311141136 A CN 202311141136A CN 117228691 A CN117228691 A CN 117228691A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 98
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000013225 prussian blue Substances 0.000 title claims abstract description 96
- 229960003351 prussian blue Drugs 0.000 title claims abstract description 96
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 90
- 239000010439 graphite Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000008367 deionised water Substances 0.000 claims abstract description 32
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 29
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 29
- 229910021381 transition metal chloride Inorganic materials 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000000264 sodium ferrocyanide Substances 0.000 claims abstract description 15
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 230000001681 protective effect Effects 0.000 claims abstract description 8
- 238000011049 filling Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 19
- 229910001415 sodium ion Inorganic materials 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 10
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 10
- 239000007774 positive electrode material Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000000243 solution Substances 0.000 abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 abstract description 8
- 150000003624 transition metals Chemical class 0.000 abstract description 8
- 239000011229 interlayer Substances 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 239000007770 graphite material Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 230000006872 improvement Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000011165 3D composite Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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 application discloses a graphite coated Prussian blue and analogues thereof, and a preparation method and application thereof, belonging to the technical field of preparation of graphite materials, and comprising the following steps: mixing one or more of ferric chloride or transition metal chloride with graphite according to the mass ratio of 10-0.5, placing the mixture in a reaction device, and filling protective gas in the reaction device; heating the reaction device to obtain solid powder; mixing sodium ferrocyanide and solid powder according to the molar mass ratio of 4-1, adding the mixture into deionized water, wherein the mass ratio of solid matters to deionized water is 1:50-500, and then stirring and reacting for 12-48 hours; the solution after the completion of the reaction was filtered. According to the application, ferric chloride or transition metal chloride is gasified at high temperature in a protective gas atmosphere, so that the ferric chloride or transition metal is perfectly doped into interlayer gaps of graphite, and then sodium ferrocyanide aqueous solution fully reacts with the ferric chloride or transition metal chloride in the graphite, so that a Prussian blue completely coated structure of the graphite is obtained.
Description
Technical Field
The application belongs to the technical field of preparation of graphite materials, and particularly relates to graphite coated Prussian blue and analogues thereof, a preparation method and application.
Background
Sodium ion batteries have been increasingly studied and focused as substitutes for lithium ion batteries in large-scale electrical energy storage applications due to their advantages of abundant sodium resources, low cost, and the like. At present, the complete machine material of the sodium ion battery mainly comprises transition metal oxide, polyanion material, prussian blue and derivatives thereof, and the like. Prussian blue and derivatives thereof have the advantages of high specific capacity, easiness in synthesis, low cost and the like, and become a research hot spot of sodium ion battery anode materials.
The iron-based Prussian blue synthesis method is mainly divided into a single iron raw solution method and a double iron raw coprecipitation method. The single iron source solution method is easy to release toxic ions due to the need of adding acid in the preparation process, has low yield, and is not suitable for large-scale preparation of iron-based Prussian blue. The double iron source coprecipitation method is considered to be a simple method capable of being popularized and prepared into iron-based Prussian blue on a large scale. The classical synthesis process of the double iron source coprecipitation method is to add transition metal salt solution drop by drop into sodium ferrocyanide solution according to stoichiometric ratio, to make precipitation reaction, and the obtained precipitate is washed by deionized water and ethanol, and centrifugally collected.
Although the double iron source coprecipitation method can obtain a large amount of Prussian blue at low temperature, the Prussian blue has poor conductivity and side reaction with organic electrolyte under high voltage, so that the Prussian blue has poor cycle performance as a positive electrode material of a sodium ion battery. Prussian blue is decomposed at more than 250 ℃, whereas the conventional carbon coating method requires high-temperature heat treatment and is not suitable for Prussian blue. The current method for improving the conductivity of Prussian blue by using a carbon material mainly comprises the step of mechanically mixing carbon nanotubes, carbon nanofibers, graphene and the like with Prussian blue. The three-dimensional composite structure of Prussian blue embedded in a graphene three-dimensional current collector has high specific capacity and good cycle performance (nanoscales, 2018, 10, 14697-14704); jiahuan Luo et al coated Prussian blue in graphene by using graphene freeze-drying self-crimping, greatly improving cycle stability and rate capability of Prussian blue (ACS appl. Mate. Interfaces 2017, 9, 30, 25317-25322). Although the conductivity of Prussian blue can be improved to a certain extent by the method, complete carbon coating is not realized, and the improvement of the conductivity and the inhibition effect on side reactions are limited.
Disclosure of Invention
Aiming at one or more of the defects or improvement demands of the prior art, the application provides a preparation method of graphite coated Prussian blue and analogues thereof, which is used for solving the problem that the prior preparation method cannot realize complete carbon coating of Prussian blue.
In order to achieve the above purpose, the application provides a preparation method of graphite coated Prussian blue and analogues thereof, which comprises the following steps:
s1: mixing one or more of ferric chloride or transition metal chloride with graphite according to the mass ratio of 10-0.5, placing the mixture in a reaction device, and filling protective gas in the reaction device;
s2: heating the reaction device to obtain solid powder;
s3: mixing sodium ferrocyanide or potassium ferrocyanide with solid powder according to the molar mass ratio of 4-1, adding deionized water, and stirring for reacting for 12-48 hours;
s4: and (3) cleaning and filtering the solution obtained in the step (S3) to obtain the Prussian blue coated with graphite and analogues thereof.
As a further improvement of the present application, step S5 is further included:
the powder after washing and filtering was dried in vacuum.
As a further improvement of the application, in the step S5, the vacuum drying temperature is 80-120 ℃, the drying time is 20-24 hours, and the powder is cooled to room temperature after the vacuum drying.
As a further improvement of the present application, the transition metal chloride in step S1 includes one or more of a chloride of Fe, co, mn, ni or Cu.
As a further improvement of the application, the temperature of the heating treatment in the step S2 is 300-600 ℃, and the time of the heating treatment is 12-48 h.
As a further improvement of the present application, the step S4 is performed with deionized water for washing and filtering, and the washing and filtering is performed 3 times or more.
As a further improvement of the application, the step S4 is carried out by adopting deionized water for cleaning and filtering, and then absolute ethyl alcohol is adopted for cleaning and filtering, and the absolute ethyl alcohol is adopted for cleaning and filtering for 3 times or more.
As a further improvement of the application, in the step S3, the mass ratio of the solid powder to the deionized water is 1:50-500, and the stirring time is 12-48 h.
The application also comprises the graphite coated Prussian blue and the analogues thereof, which are prepared by adopting the preparation method of the graphite coated Prussian blue and the analogues thereof.
The application also comprises application of the graphite coated Prussian blue and the analogues thereof in the positive electrode material of the sodium ion battery.
The above-mentioned improved technical features can be combined with each other as long as they do not collide with each other.
In general, the above technical solutions conceived by the present application have the beneficial effects compared with the prior art including:
(1) According to the preparation method of the graphite coated Prussian blue and the analogues thereof, the chloride of the ferric chloride or the transition metal is gasified at high temperature in the protective gas atmosphere, so that the ferric chloride or the transition metal is perfectly doped into the interlayer gaps of the graphite, then, in the process of contacting the graphite with the aqueous solution of sodium ferrocyanide or potassium ferrocyanide, part of sodium ferrocyanide or potassium ferrocyanide is reacted with the chloride of the ferric chloride or the transition metal to generate Prussian blue, the interlayer gaps of the graphite are enlarged, and the sodium ferrocyanide or potassium ferrocyanide is continuously reacted with the chloride of the ferric chloride or the transition metal in the subsequent reaction, so that the Prussian blue is generated in the graphite, and the structure of the graphite completely coated Prussian blue is obtained.
(2) According to the preparation method of the graphite-coated Prussian blue and the analogues thereof, the ferric chloride or the transition metal chloride is gasified and expanded at high temperature, so that high temperature and high pressure are generated in a closed reaction device, the gasified ferric chloride or transition metal chloride is filled into the gaps between graphite layers, and the ferric chloride or the transition metal chloride is perfectly filled into the gaps between the graphite layers.
(3) According to the preparation method of the graphite-coated Prussian blue and the analogues thereof, ferric chloride or transition metal chloride is removed by adopting deionized water for cleaning, and then the drying rate of powder is accelerated by adopting absolute ethyl alcohol for cleaning, so that the output efficiency of the graphite-coated Prussian blue and the analogues thereof is improved.
(4) The preparation method adopts a solution method, is simple, nontoxic and harmless, has high yield and is suitable for large-scale production. Meanwhile, the prepared graphite coated Prussian blue and analogues thereof have fine particles, are applied to the positive electrode of a sodium ion battery, and have the advantages of good circulation and high multiplying power. According to the material for coating the Prussian blue with the graphite, the conductivity of the Prussian blue is greatly improved, the capacity of the Prussian blue is facilitated to be exerted, the cycle rate performance is improved, the contact between the Prussian blue and electrolyte can be reduced by the graphite coating layer, and the occurrence of side reactions is inhibited.
Drawings
FIG. 1 is an XRD pattern of graphite-coated Prussian blue and its analogues in example 1 of the present application;
fig. 2 is a raman spectrum of graphite-coated prussian blue and analogues thereof in example 1 of the present application;
FIG. 3 is a scanning electron microscope image of Prussian blue and analogues thereof coated with graphite in example 1 of the present application;
FIG. 4 is a transmission electron microscope image of Prussian blue and the like coated with graphite in example 1 of the present application;
fig. 5 is a graph of the first charge and discharge of the graphite-coated prussian blue and the like applied to a sodium ion battery in example 1 of the present application;
FIG. 6 is a cycle curve of the graphite coated Prussian blue and its analogues applied to sodium ion batteries in example 1 of the present application;
fig. 7 is a graph showing the magnification of the graphite-coated prussian blue and the like applied to the sodium ion battery in example 1 of the present application.
Detailed Description
The present application will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application. In addition, the technical features of the embodiments of the present application described below may be combined with each other as long as they do not collide with each other.
Examples:
referring to fig. 1 to 7, the preparation method of the graphite coated prussian blue and the analogues thereof in the preferred embodiment of the application comprises the following steps:
s1: mixing one or more of ferric chloride or transition metal chloride with graphite according to the mass ratio of 10-0.5, placing the mixture in a reaction device, and filling protective gas in the reaction device;
s2: heating the reaction device to obtain solid powder;
s3: mixing sodium ferrocyanide or potassium ferrocyanide with solid powder according to the molar mass ratio of 4-1, adding deionized water, and stirring for reacting for 12-48 hours;
s4: and (3) cleaning and filtering the solution obtained in the step (S3) to obtain the Prussian blue coated with graphite and analogues thereof.
According to the preparation method of the graphite-coated Prussian blue and the analogues thereof, ferric chloride or chloride of transition metal is gasified at high temperature in a protective gas atmosphere, so that the ferric chloride or the transition metal is perfectly doped into interlayer gaps of the graphite, then sodium ferrocyanide or potassium ferrocyanide aqueous solution invades the graphite, and fully reacts with the ferric chloride or the transition metal chloride to obtain the structure of the graphite-completely-coated Prussian blue. The composite material prepared by the method has good structure conductivity, high tap density and long cycle life when being used as a positive electrode material of a sodium ion battery, and has good practical value.
Specifically, the transition metal chloride in the present application refers to one or more of chlorides such as Fe, co, mn, ni or Cu. Prussian blue and analogues thereof are metal organic frameworks with simple cubic structures, and the chemical general formula of the Prussian blue is A 2 M [M'(CN) 6 ]Wherein A is an alkali metal ion or zeolite water; M/M' is Fe, co, mn, ni or Cu, etc. In Prussian blue and analogues thereof, a large space is formed between metal ions and-CN-groups, and alkali metal ions such as Li+, na+ and K+ can be effectively contained, so that Prussian blue and analogues thereof show excellent electrochemical performance in sodium ion batteries.
Further, as a preferred embodiment of the present application, the present application further includes step S5: the powder after washing and filtering was dried in vacuum. In order to use the graphite coated Prussian blue and the like powder, not only is excessive ferric chloride or transition metal chloride removed, but also the product is required to be dried, so that the later use is convenient.
Further, the temperature of the vacuum drying is 80-120 ℃, and the drying time is 20-24 hours. The residual cleaning liquid in the cleaning and filtering stage can be sufficiently removed at the drying temperature and the drying time. The vacuum drying is completed and the obtained powder is cooled to room temperature.
Further preferably, in the step S2, the heating treatment temperature is 300-600 ℃, and the heating treatment time is 12-48 h. According to the application, excessive ferric chloride or transition metal chloride is selected, and is gasified in a high-temperature environment, so that the internal air pressure of the reaction device is increased, and a high-temperature and high-pressure environment is formed, so that the ferric chloride or transition metal chloride is doped into interlayer gaps of graphite.
Preferably, the reaction device in the application is a stainless steel reaction kettle, and the protective gas is inert gas, preferably argon.
Further, as a preferred embodiment of the present application, step S4 of the present application is to use deionized water for washing and filtering, wherein the above ferric chloride or transition metal chloride can be dissolved in the deionized water, and the excessive ferric chloride or transition metal chloride can be removed by the deionized water. Preferably, the deionized water is washed 3 times or more, and usually, ferric chloride or transition metal chloride can be removed by 3-4 times of washing and filtering.
Further preferably, the powder is cleaned by using absolute ethyl alcohol after the deionized water is cleaned, and the absolute ethyl alcohol has higher volatility than the deionized water, so that the subsequent drying process can be quickened, and the preparation efficiency of the graphite coated Prussian blue and the analogues thereof can be quickened. The washing times of the absolute ethyl alcohol are the same as or equivalent to the washing and filtering times of the deionized water, and the washing times are 3 times or more.
Further preferably, in the step S3, the mass ratio of the solid powder to the deionized water is 1:50-500, and the stirring reaction time is 12-48 h. The aqueous solution of sodium or potassium ferrocyanide is then reacted with the iron chloride or transition metal chloride within the graphite sufficiently to produce Prussian blue and its analogues within the inter-layer interstices of the graphite.
Furthermore, the preparation method can be used for preparing the graphite-coated Prussian blue and analogues thereof, and the graphite-coated Prussian blue and analogues thereof are applied to the positive electrode material of the sodium ion battery, and the graphite-coated Prussian blue and analogues thereof have the characteristics of good cycle performance and high multiplying power.
In some embodiments, the preparation method of the graphite-coated Prussian blue comprises the following steps:
s1: mixing ferric chloride or one or more of (Fe, co, mn, ni, cu) chlorides with graphite according to a mass ratio of 10-0.5, placing the mixture in a stainless steel reaction kettle, and filling argon for protection;
s2: placing the stainless steel reaction kettle in the step S1 in a muffle furnace, and treating for 12-48 h at 300-600 ℃;
s3: mixing sodium ferrocyanide or potassium ferrocyanide with solid powder according to the mass ratio of 4-1, adding the mixture into deionized water, wherein the mass ratio of solid matters to deionized water is 1:50-500, and stirring and reacting for 12-48 hours;
s4: filtering the solution in the step S3, washing with deionized water for 3 times, and then washing with absolute ethyl alcohol for 3 times to obtain the Prussian blue coated with graphite and analogues thereof.
S5: and (3) carrying out vacuum drying on the product cleaned in the step (S4), wherein the drying temperature is 80-120 ℃, the drying time is 20-24 h, and cooling to room temperature to obtain the powder of the Prussian blue coated with the graphite.
In order to better illustrate the preparation method, product and application of the present application, the following specific examples and comparative examples are provided:
example 1:
s1: 5g of ferric chloride and 0.5g of graphite are uniformly mixed, and the mixture is placed in a stainless steel reaction kettle and is protected by argon.
S2: and (3) placing the reaction kettle in the step S1 in a muffle furnace, and performing heat treatment at 600 ℃ for 12h.
S3: 0.968g of sodium ferrocyanide and 0.1g of the solid powder obtained in step S2 were added to 53.4g of deionized water, followed by stirring for reaction for 12 hours.
S4: filtering the solution in the step S3, washing with deionized water for 3 times, and then washing with absolute ethyl alcohol for 3 times;
s5: and (3) carrying out vacuum drying on the product obtained in the step (S4), wherein the drying temperature is 80-120 ℃, the drying time is 20 hours, and cooling to room temperature to obtain the Prussian blue powder coated with graphite.
Example 2:
s1: 5g of ferric chloride and 0.5g of graphite are uniformly mixed, and the mixture is placed in a stainless steel reaction kettle and is protected by argon.
S2: and (3) placing the reaction kettle in the step S1 in a muffle furnace, and performing heat treatment at 300 ℃ for 48 hours.
S3: 0.968g of potassium ferrocyanide and 0.2g of the solid powder obtained in step S2 were added to 116.8g of deionized water, followed by stirring for reaction for 24 hours.
S4: filtering the solution in the step S3, washing with deionized water for 3 times, and then washing with absolute ethyl alcohol for 3 times;
s5: and (3) carrying out vacuum drying on the product obtained in the step (S4), wherein the drying temperature is 80-120 ℃, the drying time is 22 hours, and cooling to room temperature to obtain the Prussian blue powder coated with graphite.
Example 3:
s1: 1g of ferric chloride and 2g of graphite are uniformly mixed, and the mixture is placed in a stainless steel reaction kettle and is protected by argon.
S2: and (3) placing the reaction kettle in the step S1 in a muffle furnace, and performing heat treatment at 600 ℃ for 48 hours.
S3: 0.968g of sodium ferrocyanide and 0.4g of the solid powder obtained in step S2 were added to 684g of deionized water, followed by stirring for 48 hours.
S4: filtering the solution in the step S3, washing with deionized water for 3 times, and then washing with absolute ethyl alcohol for 3 times;
s5: and (3) carrying out vacuum drying on the product obtained in the step (S4), wherein the drying temperature is 80-120 ℃, the drying time is 24 hours, and cooling to room temperature to obtain the Prussian blue powder coated with graphite.
Comparative examples:
s1: 0.968g sodium ferrocyanide, 0.2g ferric chloride and 2g graphite were added to 116.8g deionized water, and then stirred for reaction for 24 hours.
S2: filtering the solution obtained in the step S1, washing with deionized water for 3 times, and then washing with absolute ethyl alcohol for 3 times;
s3: and (3) carrying out vacuum drying on the product obtained in the step (S2), wherein the drying temperature is 80-120 ℃, the drying time is 24 hours, and cooling to room temperature to obtain the Prussian blue powder coated with graphite.
FIG. 1 shows the XRD diffraction pattern of Prussian blue powder coated with graphite obtained in example 1 of the present application, as can be seen by comparing with the XRD standard pattern of Prussian blue, the product is pure Prussian blue (NaxFe [ Fe (CN)) 6 ]). FIG. 2 is a Raman spectrum of the Prussian blue powder coated with graphite obtained in example 1 of the present application, wherein two peaks 1348cm-1 and 1580cm-1 respectively represent a D peak and a G peak of graphite, and 2094.5cm-1 and 2132.3cm-1 are two peaks of Prussian blue. FIG. 3 is a scanning electron microscope image of Prussian blue coated with graphite obtained in example 1 of the present application, from which it can be seen that the Prussian blue coated with graphite is a micron-sized particle, and the outside of the particle is not seenAnd the fine Prussian blue particles are embedded in the graphite inner layer and are completely coated by the graphite. Fig. 4 is a transmission electron microscope image of the Prussian blue coated with graphite obtained in example 1 of the present application, and it can be seen from the image that the Prussian blue particles are smaller than 50nm and are completely coated with graphite.
Meanwhile, the graphite-coated Prussian blue powder obtained in the embodiment 1 of the application is applied to the positive electrode of a sodium ion battery for testing, and experimental data shown in fig. 5-7 are obtained. Fig. 5 is a first charge-discharge curve obtained by testing the graphite coated Prussian blue powder prepared in example 1 of the present application applied to a sodium ion battery, and the current density in this experiment is 1c=170 mA/g. As can be seen from the graph, the specific charge capacity of the material is 106mAh/g, and the specific discharge capacity of the material is 133.6mAh/g. Fig. 6 is a cycle curve obtained by testing the application of the graphite coated Prussian blue powder prepared in the embodiment 1 of the present application with a sodium ion battery, and it can be seen from the graph that the graphite coated Prussian blue powder has excellent cycle performance as a positive electrode material of the sodium ion battery, and the capacity retention rate is 93% after 300 cycles at a current density of 1C, namely 170mA/g. FIG. 7 is a graph showing the magnification curve obtained by testing the application of the graphite-coated Prussian blue powder prepared in example 1 and a sodium ion battery, and as can be seen from the graph, the graphite-coated Prussian blue and the analogues thereof prepared in the application have excellent magnification performance as the positive electrode material of the sodium ion battery, and the discharge capacity is 114mAh/g at 0.5C, namely 85mA/g current density; the specific discharge capacity is still kept at about 91mAh/g at 100C, namely 17000mA/g, and the retention rate is 80%.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the application and is not intended to limit the application, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the application are intended to be included within the scope of the application.
Claims (10)
1. The preparation method of the graphite coated Prussian blue and the analogues thereof is characterized by comprising the following steps:
s1: mixing one or more of ferric chloride or transition metal chloride with graphite according to the mass ratio of 10-0.5, placing the mixture in a reaction device, and filling protective gas in the reaction device;
s2: heating the reaction device to obtain solid powder;
s3: mixing sodium ferrocyanide or potassium ferrocyanide with solid powder according to the molar mass ratio of 4-1, adding deionized water, and stirring for reacting for 12-48 hours;
s4: and (3) cleaning and filtering the solution obtained in the step (S3) to obtain the Prussian blue coated with graphite and analogues thereof.
2. The method for preparing the graphite-coated Prussian blue and the analogues thereof according to claim 1, further comprising step S5:
the powder after washing and filtering was dried in vacuum.
3. The method for preparing the graphite-coated Prussian blue and the analogues thereof according to claim 2, wherein in the step S5, the vacuum drying temperature is 80-120 ℃, the drying time is 20-24 hours, and the method further comprises cooling the powder to room temperature after the vacuum drying.
4. The method for preparing the graphite-coated Prussian blue and the analogues thereof according to claim 1, wherein the transition metal chloride in the step S1 comprises one or more of Fe, co, mn, ni or Cu chloride.
5. The method for preparing the graphite-coated Prussian blue and the analogues thereof according to claim 1, wherein the heating treatment temperature in the step S2 is 300-600 ℃, and the heating treatment time is 12-48 h.
6. The method for preparing the graphite-coated Prussian blue and the like according to claim 1, wherein deionized water is used for washing and filtering in the step S4, and the washing and filtering are performed for 3 times or more.
7. The method for preparing the graphite-coated Prussian blue and the like according to claim 6, wherein the step S4 is performed with deionized water and then with absolute ethyl alcohol for 3 times or more.
8. The preparation method of the graphite-coated Prussian blue and the analogues thereof according to claim 1, wherein in the step S3, the mass ratio of the solid powder to the deionized water is 1:50-500, and the stirring time is 12-48 h.
9. The graphite-coated Prussian blue and the analogues thereof, which are characterized in that the graphite-coated Prussian blue and the analogues thereof are prepared by the preparation method of any one of claims 1-8.
10. Use of the graphite-coated Prussian blue and the analogues thereof according to claim 9 in a positive electrode material of a sodium ion battery.
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|---|---|---|---|---|
| CN117534089A (en) * | 2024-01-09 | 2024-02-09 | 太原理工大学 | Preparation of high-crystallization Fe [ Fe (CN) ] without additive 6 ]Method for producing electrode material and use thereof |
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| CN117534089A (en) * | 2024-01-09 | 2024-02-09 | 太原理工大学 | Preparation of high-crystallization Fe [ Fe (CN) ] without additive 6 ]Method for producing electrode material and use thereof |
| CN117534089B (en) * | 2024-01-09 | 2024-04-05 | 太原理工大学 | Preparation of high-crystallization Fe [ Fe (CN) ] without additive 6 ]Method for producing electrode material and use thereof |
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