CN113415811B - Preparation method of ferrocyanide and application of ferrocyanide in flow battery - Google Patents

Preparation method of ferrocyanide and application of ferrocyanide in flow battery Download PDF

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CN113415811B
CN113415811B CN202110551822.9A CN202110551822A CN113415811B CN 113415811 B CN113415811 B CN 113415811B CN 202110551822 A CN202110551822 A CN 202110551822A CN 113415811 B CN113415811 B CN 113415811B
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ferrocyanide
solution
deionized water
dilute
cation exchange
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CN113415811A (en
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吴晓宏
李晓彤
姚远
秦伟
刘杨
卢松涛
李杨
康红军
洪杨
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Harbin Institute of Technology
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a preparation method of ferrocyanide and application of ferrocyanide in a flow battery, and belongs to the technical field of flow batteries. The preparation method provided by the invention has mild reaction conditions, and the obtained ferrocyanide has high purity and high yield. The invention firstly elutes the water solution containing the target product cation to the cation exchange resin to prepare the cation exchange column, and then washes the cation exchange column with the water solution of potassium ferrocyanide or sodium ferrocyanide to obtain the solution containing the ferrous cyanide ions. After removal of water, the prepared ferrocyanide is obtained quantitatively. The ferrocyanide prepared by the method is used for preparing the catholyte for the flow battery. The method for preparing the ferrocyanide has mild reaction conditions and high reaction yield, and the obtained ferrocyanide has high purity, the production yield of the preparation method provided by the invention is 100%, and the purity of the prepared ferrocyanide salt is 100%.

Description

Preparation method of ferrocyanide and application of ferrocyanide in flow battery
Technical Field
The invention belongs to the technical field of flow batteries; relates to the technical field of inorganic compound synthesis, in particular to a preparation method of ferrocyanide and application thereof in a flow battery, and particularly relates to preparation of a cathode electrolyte material for the flow battery.
Background
With the wide development of intermittent renewable energy sources such as wind energy, solar energy and the likeThe development of reliable large-scale electrical energy storage technologies has also received increased attention. The flow battery is an ideal large-scale energy storage technology, and compared with other energy storage technologies, the flow battery has the advantages of high energy efficiency, large energy storage scale, long cycle life, deep charging and discharging, simple structure, flexible system design, safety, environmental protection, low maintenance cost and the like, and can be widely applied to the aspects of power generation and energy storage of renewable energy sources such as wind energy, solar energy and the like, an emergency power supply system, a standby power station, an electric power system and the like, and peak clipping and valley filling can be realized. Aqueous phase flow batteries based on inorganic energy storage materials have been extensively studied and developed over the past several decades, with all vanadium flow batteries (VRFB) and Zn-Br2Flow batteries have been commercialized. However, problems such as installation cost and battery performance limit the spread of these aqueous-phase inorganic flow batteries. For example, the cost of redox-active species alone in all-vanadium flow batteries is up to about $ 200/kWh; therefore, researchers have turned to other inorganic compounds with redox activity to find suitable energy storage materials for use in flow batteries.
The electrolyte solution is an energy storage medium of the flow battery and is one of key materials of the flow battery. The energy storage capacity of the flow battery system is determined by the concentration and the capacity (volume) of the energy storage active substance of the electrolyte solution, and the concentration of the total active substance of the electrolyte, the conductivity of the electrolyte and the like directly influence the charge-discharge capacity and the battery performance of the battery. Therefore, the electrolyte is required to have higher active material concentration and conductivity, and also to have better chemical stability and lower cost.
Cyanide is an important gold leaching solvent in the gold industry, most gold production enterprises adopt a cyanidation method, and various cyanides related to the gold industry belong to inorganic cyanides. Ferrocyanide salt in inorganic cyanide is an important raw material such as electrode material, coating, catalyst and the like, and can be mainly used as a carburizing agent in the steel industry to improve the surface hardness of steel parts: the oxidation assistant is used for gradually dyeing the cotton cloth of the fine element and keeping the dyeing quality. The medicine industry can use the flocculant as a coagulant, can achieve an ideal impurity removal process, and improves the quality of medicines. The pigment industry is used as a main raw material for producing pigment iron blue, and the chemical industry is used as an iron remover and the like, so that the ferrocyanide has great application prospect.
The use of ferrocyanide salts is quite widespread, but its use has further developed due to lower solubility in water. For example, conventional potassium ferrocyanide (K)4[Fe(CN)6]) And sodium ferrocyanide (Na)4[Fe(CN)6]) Has been widely used in the research of zinc-iron flow batteries as a standard cathode electrolyte material in aqueous flow batteries. However, the lower solubility of the two in water limits the unit volume capacity and energy density of the battery, the solubility in water is only 0.76M and 0.56M, and the application of the two in the aspect of battery energy storage is far from being met, so that the industrialization prospect of the system flow battery is limited. Esswein, A.J et al reported that Na was substituted4[Fe(CN)6]And K4[Fe(CN)6]Mixing at a ratio of 1:1 to obtain H2In O [ Fe (CN)6]4-The total concentration of (2) is up to 1.5M, and in the mixed solution of NaOH and KOH, it can be up to 1.0M [ Fe (CN)6]4-. However, mixed salts are not suitable for practical application of flow batteries (RFB), because Na+And K+Has different migration rates in the whole cation exchange process, and simultaneously Na+And K+Changes in the ratio alter [ Fe (CN)6]4-The solubility of (a). In addition, mixed cations may also adversely affect the anolyte used in RFB, indirectly increasing the cost of the electrolyte in the flow battery. Therefore, it is important to develop a catholyte having high concentration, high conductivity, and at the same time, excellent stability. Ammonium ferrocyanide and lithium ferrocyanide, both of which are ferrocyanide salts, are composed of [ Fe (CN)6]4-Ions and NH4 +Or Li+The complex is prepared by complexing, and has very good solubility, so that the complex is more widely applied. Besides being applied to ink, safety paper, fuel, animal feed, anti-caking agent and the like, the electrolyte can also be applied to the research of various liquid batteries, and has very large market application prospect.
Although ammonium ferrocyanide and lithium ferrocyanide have good solubility and can be applied to various aspects, especially the research of various liquid batteries, the synthesis process is complex, the product purity is difficult to improve, a detailed systematic research system is lacked, and industrialization is difficult to realize, so that the price of the product is high in the market. For example, the introduction of ferrocyanide ion in the iron system of volume ninth book of inorganic chemistry book by Xigaoyang et al is simplified, and it is summarized in terms of the synthesis of ferrocyanide ion: the potassium salt reacts with hydrogen chloride in ether, or the potassium salt water solution reacts with concentrated hydrochloric acid: however, the yield and purity of ammonium ferrocyanide obtained by the two methods are not high, and the reaction is difficult to complete because potassium ferrocyanide is insoluble in diethyl ether, the diethyl ether and concentrated hydrochloric acid have strong volatility, and the concentrated hydrochloric acid has strong corrosivity, so the method has certain dangerousness and toxicity when in use, and is difficult to produce on a large scale. With respect to the synthesis of ammonium ferrocyanide and lithium ferrocyanide, there are relatively rare literature reports, such as the summary of the synthesis of ammonium ferrocyanide in Journal of Physics and Chemistry of Solids 64(2003)685-693 by J.Balmaseda et al, entitled document of practical blue-based materials in presentation of ammonia: the ferrocyanide ions are solid acid and are neutralized with ammonia water to obtain ammonium ferrocyanide: the reaction conditions are not mentioned, so the method is difficult to popularize.
Therefore, it is a problem to be solved to provide a method for producing ferrocyanide such as ammonium ferrocyanide and lithium ferrocyanide, which can be applied to industrial production.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of ferrocyanide and application thereof in a flow battery. The invention provides a preparation method of ferrocyanide and application thereof in a flow battery, which comprises the steps of eluting cation exchange resin from dilute alkaline aqueous solution containing cations in the prepared ferrocyanide to prepare a cation exchange column, and flushing the cation exchange column with aqueous solution of potassium ferrocyanide or sodium ferrocyanide to obtain solution containing ferrocyanide ions. After removal of water, the prepared ferrocyanide is obtained quantitatively.
The method for preparing the ferrocyanide has the advantages of mild reaction conditions, high reaction yield and high purity of the obtained ferrocyanide, and experimental results show that the production yield of the preparation method provided by the invention is 100%, and the purity of the prepared ferrocyanide salt is 100%.
The invention adopts a cation exchange strategy to carry out ferrocyanide ([ Fe (CN) 6)]4-) And ferricyanide ([ Fe (CN) 6)]3-) As a feasible molecular engineering research of redox active molecules, the ferrocyanide prepared by the method comprises ammonium ferrocyanide, lithium ferrocyanide and the like.
The preparation method of the ferrocyanide is carried out according to the following steps:
step one, pretreating cation exchange resin, and then filling a column;
step two, washing with a dilute acid solution and washing with deionized water until the pH value is 7;
washing with a dilute solution of alkali, and washing with deionized water until the pH value is 7;
step four, washing with a dilute acid solution and washing with deionized water until the pH value is 7;
step five, eluting with an aqueous solution containing target product cations, and washing with deionized water until the pH value is 7;
sixthly, washing with an aqueous solution of potassium ferrocyanide or sodium ferrocyanide, and washing with deionized water after the exchange is finished;
and seventhly, drying the solution obtained after the exchange is finished in vacuum to remove moisture, and obtaining a product.
Further, the pretreatment of the cation exchange resin in the first step is carried out by the following operations: soaking the cation exchange resin in absolute ethyl alcohol at room temperature for 12-36 h, filtering, and soaking the cation exchange resin in deionized water at room temperature for 12-36 h to complete the pretreatment.
Further, the dilute solution of the acid in the second step is one of a dilute hydrochloric acid solution, a dilute nitric acid solution and a dilute sulfuric acid solution, and the dilute solution of the acid used in the fourth step is the same as that used in the second step.
Further, the mass percentage content of the dilute solution of the acid in the step two is 1% -15%, and the concentration of the dilute solution of the acid used in the step four is the same as that in the step two.
Further, the dilute solution of the alkali in the third step is one of dilute sodium hydroxide solution and dilute potassium hydroxide solution.
Further, the mass percentage content of the dilute solution of the alkali in the step three is 1-15%.
Further, the aqueous solution containing the target product cations in the fifth step is one or more of ammonium bicarbonate, ammonia water, ammonium chloride, lithium nitride, lithium hydroxide, potassium hydroxide and sodium hydroxide aqueous solution which are prepared according to any ratio; when a plurality of kinds are adopted, the cations are selected to be the same.
Further, in the fifth step, the mass percentage of the aqueous solution containing the target product cation is 1-20%; preferably: 1% to 15%, more preferably: 1 to 10 percent.
The ferrocyanide prepared by the method is used for preparing the catholyte for the flow battery.
Furthermore, the concentration of the ferrocyanide in the electrolyte is 1.5-2.5 mol/L.
Ferrocyanide (ammonium ferrocyanide or lithium ferrocyanide, etc.) is dissolved in deionized water and fully stirred at room temperature to prepare a uniform solution.
The electrode of the flow battery is a graphite felt, the bipolar plate is a graphite plate, the ion exchange membrane is a Nafion membrane produced by DuPont, the cathode electrolyte is a deionized water solution of ferrocyanide, and the anode electrolyte is a deionized water solution of ferricyanide.
Furthermore, the flow battery is a symmetrical flow battery which takes Fe (II)/Fe (III) as an active substance of a cathode electrolyte and Fe (III)/Fe (II) as an active substance of a cathode electrolyte, and circularly operates between a positive electrode and an ion exchange membrane (as a diaphragm) and between a negative electrode and the ion exchange membrane through positive electrolyte and negative electrolyte respectively.
Compared with the prior art, the invention provides a preparation method of ferrocyanide, and particularly newly designed neutral ammonium ferrocyanide/ammonium ferricyanide and lithium ferrocyanide/lithium ferricyanide electrolytes show unprecedented electron storage capacity and can be applied to the application of battery energy storage. The method for preparing the ferrocyanide has the advantages of mild reaction conditions, high reaction yield and high purity of the obtained ferrocyanide, and experimental results show that the yield of the preparation method provided by the invention is 100%, and the purity of the prepared ferrocyanide salt is 100%.
Ferrocyanide [ Fe (CN) ]due to the strong coordination of cyanide ions to the iron center6]4-And its oxidation state [ Fe (CN)6]3-Is very stable, non-toxic and low in cost, so that the redox active electrolyte material has remarkable advantages when being used as the redox active electrolyte material. Furthermore, since [ Fe (CN)6]4-/3-Has a modest redox potential that is safely within the electrochemical window of water and therefore has great flexibility to pair with a variety of redox species to construct an aqueous flow battery. The catholyte consists of a single active substance ammonium ferrocyanide or lithium ferrocyanide, and the concentration of the catholyte can reach 1.60mol/L and 2.30 mol/L.
The invention aims to overcome the problems of the conventional catholyte for the flow battery and provide a novel system catholyte for the flow battery. The concentration and the conductivity of active substances in the electrolyte can be greatly improved under the condition of not reducing the stability of the electrolyte, so that the catholyte for the flow battery, which has extremely low cost and excellent performance, can be obtained.
The cathode electrolyte is prepared from a ferrocyanide salt, has high active substance concentration and excellent electrolyte conductivity and stability, and greatly improves the charge-discharge capacity and the battery performance of the flow battery.
The invention expands the variety and the application range of the catholyte for the flow battery.
The preparation method of the cathode electrolyte is simple, the process is environment-friendly, the electrolyte composition is single, and the concentration of active substances is high. Compared with the traditional cathode electrolyte (potassium ferrocyanide and sodium ferrocyanide), the flow battery taking the electrolyte as the cathode has higher comprehensive performance.
Drawings
FIG. 1 is a schematic representation of an ammonium ferrocyanide prepared in example 1 of the invention;
FIG. 2 is a scanning electron micrograph of ammonium ferrocyanide prepared in example 1 of the invention;
FIG. 3 is an IR spectrum of ammonium ferrocyanide prepared by the method of example 1 of the invention;
FIG. 4 is a powder diffraction pattern of ammonium ferrocyanide prepared by the method of example 1 of the invention;
FIG. 5 is a schematic diagram of a lithium ferrocyanide material prepared in example 3 of the invention;
FIG. 6 is a scanning electron micrograph of lithium ferrocyanide prepared in example 3 of the invention;
FIG. 7 is an IR spectrum of lithium ferrocyanide prepared in example 3 of the invention;
FIG. 8 is a powder diffraction pattern of lithium ferrocyanide prepared in example 3 of the invention;
FIG. 9 is a pictorial view of a comparative example of ammonium ferrocyanide;
FIG. 10 is a physical diagram of lithium ferrocyanide in comparative example 2
FIG. 11 shows the electrolyte prepared in example 5 at 10mA/cm in a symmetrical flow cell with that of comparative example 32Charging point electrical properties at current density were compared.
FIG. 12 shows the electrolyte prepared in example 6 at 10mA/cm in a symmetrical flow cell with comparative example 42Charging point electrical properties at current density were compared.
Detailed Description
Example 1
Pretreatment of cation exchange resin:
(1) 100g of cation exchange resin was weighed in a beaker and soaked with absolute ethanol at room temperature for 24 hours.
(2) Anhydrous ethanol was filtered off, and the cation exchange resin was then soaked with deionized water at room temperature for 24 hours.
(3) And (4) loading the pretreated cation exchange resin into a column.
The preparation method of the ferrocyanide comprises the following steps:
(1) 67.6ml of nitric acid is weighed by a measuring cylinder and poured into a dry beaker, diluted by deionized water and slowly added into a 250ml volumetric flask, and the volume is fixed to 250 ml.
(2) 62.5g of potassium hydroxide is weighed into a dry beaker, diluted with deionized water and slowly added into a 250ml volumetric flask to reach the volume of 250 ml.
(3) Weighing 13.2g of ammonium chloride in a dry beaker, diluting with deionized water, adding into a 250ml volumetric flask, and fixing the volume to 250ml
(4) Preparing 200ml of potassium ferrocyanide saturated solution, weighing 64.2g of potassium ferrocyanide in a dry beaker, diluting with deionized water, adding into a 200ml volumetric flask, and fixing the volume to 200 ml.
(5) The cation exchange resin was washed with 100ml of aqueous hydrochloric acid solution prepared and then with deionized water until the pH was 7.
(6) The cation exchange resin was washed with 100ml of prepared aqueous potassium hydroxide solution and washed with deionized water until the pH was 7.
(7) The cation exchange resin was washed again with 100ml of the prepared aqueous hydrochloric acid solution and washed with deionized water until the pH was 7.
(8) The cation exchange resin was eluted with 100ml of prepared aqueous ammonium chloride solution and washed with deionized water until the pH was 7.
(9) And (3) washing the cation exchange resin with 30ml of prepared saturated potassium ferrocyanide solution, and washing with deionized water after the exchange is finished.
(10) And (3) drying the solution obtained after the exchange for more than 48 hours in vacuum to remove water to obtain a light yellow green crystal, namely a product ferrocyanide-ammonium ferrocyanide, wherein the yield is 100%, and the purity is 100%.
(11) Regenerating cation exchange resin with 100ml hydrochloric acid aqueous solution until no K exists+After that, the mixture was washed with deionized water until pH 7.
The product obtained in this example is shown in FIG. 1, FIG. 1 is a physical diagram of ammonium ferrocyanide prepared in example 1 of the invention, and FIG. 2 is a scanning electron micrograph of ammonium ferrocyanide prepared in example 1 of the invention. The CHN nonmetal element analysis shows that the prepared ammonium ferrocyanide does not contain crystal water. The structure of the resulting product was analyzed and tested, and the results are shown in FIGS. 3 and 4, FIG. 3 is an infrared spectrum of ammonium ferrocyanide prepared in example 1 of the invention, and FIG. 4 is a powder diffraction pattern of ammonium ferrocyanide prepared in example 1 of the invention. As can be seen from the figure, the substance prepared by the present invention is pure ammonium ferrocyanide.
Example 2
Pretreatment of cation exchange resin:
(1) 100g of cation exchange resin was weighed in a beaker and soaked with absolute ethanol at room temperature for 24 hours.
(2) Anhydrous ethanol was filtered off, and the cation exchange resin was then soaked with deionized water at room temperature for 24 hours.
(3) And (4) loading the pretreated cation exchange resin into a column.
The preparation method of the ferrocyanide comprises the following steps:
(1) 39.1ml of sulfuric acid is weighed by a measuring cylinder and poured into a dry beaker, diluted by deionized water and slowly added into a 250ml volumetric flask, and the volume is adjusted to 250 ml.
(2) Weighing 13.2g of sodium hydroxide in a dry beaker, diluting with deionized water, slowly adding into a 250ml volumetric flask, and fixing the volume to 250ml
(3) Weighing 8.9ml of ammonia water by using a measuring cylinder, pouring the ammonia water into a dry beaker, diluting the ammonia water by using deionized water, slowly adding the diluted ammonia water into a 250ml volumetric flask, and fixing the volume to 250ml
(4) Preparing 200ml of potassium ferrocyanide saturated solution, weighing 64.2g of potassium ferrocyanide in a dry beaker, diluting with deionized water, adding into a 200ml volumetric flask, and fixing the volume to 200 ml.
(5) The cation exchange resin was washed with 200ml of prepared aqueous sulfuric acid solution and washed with deionized water until the pH was 7.
(6) The cation exchange resin was washed with 200ml of the prepared aqueous sodium hydroxide solution and then with deionized water until the pH became 7.
(7) The cation exchange resin was washed again with 200ml of prepared aqueous sulfuric acid and washed with deionized water until the pH was 7.
(8) The cation exchange resin was eluted with 200ml of prepared aqueous ammonia, and washed with deionized water until the pH became 7.
(9) And (3) washing the cation exchange resin with 50ml of prepared saturated potassium ferrocyanide solution, and washing with deionized water after the exchange is finished.
(10) And (3) drying the solution obtained after the exchange for more than 48 hours in vacuum to remove water to obtain a light yellow green crystal, namely a product ferrocyanide-ammonium ferrocyanide, wherein the yield is 100%, and the purity is 100%.
(11) The prepared 200ml sulfuric acid water solution is taken to regenerate the cation exchange resin until no K exists+After that, the mixture was washed with deionized water until pH 7.
The product is analyzed and tested by infrared, powder diffraction and scanning electron microscope, and the result shows that the ammonium ferrocyanide is prepared by the method.
Example 3
Pretreatment of cation exchange resin:
(1) 100g of cation exchange resin was weighed in a beaker and soaked with absolute ethanol at room temperature for 24 hours.
(2) Anhydrous ethanol was filtered off, and the cation exchange resin was then soaked with deionized water at room temperature for 24 hours.
(3) And (4) loading the pretreated cation exchange resin into a column.
The preparation method of the ferrocyanide comprises the following steps:
(1) 3.73ml of nitric acid is weighed by a measuring cylinder and poured into a dry beaker, diluted by deionized water and slowly added into a 250ml volumetric flask, and the volume is fixed to 250 ml.
(2) Weighing 27.8g of potassium hydroxide in a dry beaker, diluting with deionized water, slowly adding into a 250ml volumetric flask, and fixing the volume to 250ml
(3) 27.8g of lithium hydroxide is weighed by a measuring cylinder and poured into a dry beaker, the dry beaker is diluted by deionized water and then slowly added into a 250ml volumetric flask, and the volume is determined to be 250ml
(4) Preparing 200ml of potassium ferrocyanide saturated solution, weighing 64.2g of potassium ferrocyanide in a dry beaker, diluting with deionized water, adding into a 200ml volumetric flask, and fixing the volume to 200 ml.
(5) The cation exchange resin was washed with 150ml of aqueous nitric acid solution and then with deionized water until the pH was 7.
(6) The cation exchange resin was washed with 150ml of prepared aqueous potassium hydroxide solution and washed with deionized water until the pH was 7.
(7) The cation exchange resin was washed again with 150ml of aqueous nitric acid solution and washed with deionized water until the pH was 7.
(8) The cation exchange resin was eluted with 150ml of prepared aqueous lithium hydroxide solution and washed with deionized water until the pH was 7.
(9) And (3) washing the cation exchange resin with 40ml of prepared potassium ferrocyanide saturated solution, and washing with deionized water after the exchange is finished.
(10) And (3) drying the solution obtained after the exchange for more than 48 hours in vacuum to remove water to obtain a light green crystal, namely a product of ferrocyanide-lithium ferrous hydride, wherein the yield is 100%, and the purity is 100%.
(11) Taking prepared 150ml nitric acid water solution to regenerate cation exchange resin until no K exists+After that, the mixture was washed with deionized water until pH 7.
The obtained product is shown in figure 5, figure 5 is a picture of a lithium ferrocyanide substance prepared in the embodiment 3 of the invention, and figure 6 is a scanning electron microscope picture of the lithium ferrocyanide prepared in the embodiment 3 of the invention. The CHN nonmetal element analysis shows that the prepared lithium ferrocyanide does not contain crystal water. The structure of the obtained product was analyzed and tested, and the results are shown in fig. 7 and fig. 8, fig. 7 is an infrared spectrum of lithium ferrocyanide prepared in example 3 of the invention, and fig. 8 is a powder diffraction pattern of lithium ferrocyanide prepared in example 3 of the invention. As can be seen from the figure, the material prepared by the present invention is pure lithium ferrocyanide.
Example 4
Pretreatment of cation exchange resin:
(1) 100g of cation exchange resin was weighed in a beaker and soaked with absolute ethanol at room temperature for 24 hours.
(2) Anhydrous ethanol was filtered off, and the cation exchange resin was then soaked with deionized water at room temperature for 24 hours.
(3) And (4) loading the pretreated cation exchange resin into a column.
The preparation method of the ferrocyanide comprises the following steps:
(1) 135ml of hydrochloric acid is weighed by a measuring cylinder and poured into a dry beaker, and the dry beaker is diluted by deionized water and then slowly added into a 250ml volumetric flask to be constant volume to 250 ml.
(2) Weighing 2.53g of sodium hydroxide in a dry beaker, diluting with deionized water, slowly adding into a 250ml volumetric flask, and fixing the volume to 250ml
(3) Weighing 62.5g of lithium chloride by using a measuring cylinder, pouring the lithium chloride into a dry beaker, diluting the lithium chloride by using deionized water, slowly adding the diluted lithium chloride into a 250ml volumetric flask, and fixing the volume to 250ml
(4) Preparing 200ml of potassium ferrocyanide saturated solution, weighing 64.2g of potassium ferrocyanide in a dry beaker, diluting with deionized water, adding into a 200ml volumetric flask, and fixing the volume to 200 ml.
(5) The cation exchange resin was washed with 250ml of aqueous hydrochloric acid solution prepared and washed with deionized water until the pH was 7.
(6) The cation exchange resin was washed with 250ml of the prepared aqueous sodium hydroxide solution and then with deionized water until the pH was 7.
(7) The cation exchange resin was washed again with 250ml of the prepared aqueous hydrochloric acid solution and washed with deionized water until the pH was 7.
(8) The cation exchange resin was eluted with 250ml of prepared aqueous lithium chloride solution and washed with deionized water until the pH was 7.
(9) And (3) washing the cation exchange resin with 40ml of prepared potassium ferrocyanide saturated solution, and washing with deionized water after the exchange is finished.
(10) And (3) drying the solution obtained after the exchange for more than 48 hours in vacuum to remove water to obtain a light green crystal, namely a product of ferrocyanide-lithium ferrous hydride, wherein the yield is 100%, and the purity is 100%.
(11) Regenerating cation exchange resin with prepared 250ml hydrochloric acid aqueous solution until no K exists+After that, the mixture was washed with deionized water until pH 7.
The product is analyzed and tested by infrared, powder diffraction and scanning electron microscope, and the result shows that the lithium ferrocyanide is prepared by the method.
From the above examples, the present invention was prepared with 100% yield and purity of ferrocyanide-ammonium ferrocyanide, lithium ferrocyanide.
Comparative example 1
Pretreatment of cation exchange resin:
(1) 100g of cation exchange resin was weighed in a beaker and soaked with absolute ethanol at room temperature for 24 hours.
(2) Anhydrous ethanol was filtered off, and the cation exchange resin was then soaked with deionized water at room temperature for 24 hours.
(3) And (4) loading the pretreated cation exchange resin into a column.
The preparation method of the ferrocyanide comprises the following steps:
(1) 39.1ml of sulfuric acid is weighed by a measuring cylinder and poured into a dry beaker, diluted by deionized water and slowly added into a 250ml volumetric flask, and the volume is adjusted to 250 ml.
(2) 13.2g of sodium hydroxide is weighed into a dry beaker, diluted with deionized water and slowly added into a 250ml volumetric flask to reach the volume of 250 ml.
(3) Weighing 8.9ml of ammonia water by using a measuring cylinder, pouring the ammonia water into a dry beaker, diluting the ammonia water by using deionized water, slowly adding the diluted ammonia water into a 250ml volumetric flask, and fixing the volume to 250ml
(4) Preparing 200ml of potassium ferrocyanide saturated solution, weighing 64.2g of potassium ferrocyanide in a dry beaker, diluting with deionized water, adding into a 200ml volumetric flask, and fixing the volume to 200 ml.
(5) The cation exchange resin was washed with 100ml of prepared aqueous sulfuric acid solution and washed with deionized water until the pH was 7. ()
(6) The cation exchange resin was washed with 100ml of the prepared aqueous sodium hydroxide solution and then with deionized water until the pH was 7.
(7) The cation exchange resin was washed again with 100ml of the prepared aqueous sulfuric acid solution and washed with deionized water until the pH was 7.
(8) The cation exchange resin was eluted with 100ml of prepared aqueous ammonia, and washed with deionized water until the pH was 7.
(9) And (3) washing the cation exchange resin with 100ml of prepared saturated potassium ferrocyanide solution, and washing with deionized water after the exchange is finished.
(10) And (3) drying the solution obtained after the exchange for more than 48 hours in vacuum to remove water to obtain a dark green crystal, namely a failure product ferrocyanide-ammonium ferrocyanide with the purity of less than 100%.
(11) Regenerating cation exchange resin with 100ml of prepared sulfuric acid aqueous solution until no K exists+After that, the mixture was washed with deionized water until pH 7.
Comparative example 2
Pretreatment of cation exchange resin:
(1) 100g of cation exchange resin was weighed in a beaker and soaked with absolute ethanol at room temperature for 24 hours.
(2) Anhydrous ethanol was filtered off, and the cation exchange resin was then soaked with deionized water at room temperature for 24 hours.
(3) And (4) loading the pretreated cation exchange resin into a column.
The preparation method of the ferrocyanide comprises the following steps:
(1) 135ml of hydrochloric acid is weighed by a measuring cylinder and poured into a dry beaker, and the dry beaker is diluted by deionized water and then slowly added into a 250ml volumetric flask to be constant volume to 250 ml.
(2) 2.53g of sodium hydroxide is weighed into a dry beaker, diluted with deionized water and slowly added into a 250ml volumetric flask to reach a constant volume of 250 ml.
(3) 62.5g of lithium chloride is weighed by a measuring cylinder and poured into a dry beaker, and the dry beaker is diluted by deionized water and then slowly added into a 250ml volumetric flask to be constant volume of 250 ml.
(4) Preparing 200ml of potassium ferrocyanide saturated solution, weighing 64.2g of potassium ferrocyanide in a dry beaker, diluting with deionized water, adding into a 200ml volumetric flask, and fixing the volume to 200 ml.
(5) The cation exchange resin was washed with 200ml of aqueous hydrochloric acid solution prepared and washed with deionized water until the pH was 7.
(6) The cation exchange resin was washed with 200ml of the prepared aqueous sodium hydroxide solution and then with deionized water until the pH became 7.
(7) The cation exchange resin was eluted with 200ml of prepared aqueous lithium chloride solution and washed with deionized water until the pH was 7.
(8) And (3) washing the cation exchange resin with 100ml of prepared saturated potassium ferrocyanide solution, and washing with deionized water after the exchange is finished.
(9) And (3) drying the solution obtained after the exchange for more than 48 hours in vacuum to remove water to obtain a greenish crystal, namely the product ferrocyanide-lithium ferrous hydride, wherein the purity of the product ferrocyanide-lithium ferrous hydride is not 100%.
(10) Regenerating cation exchange resin with 200ml hydrochloric acid aqueous solution until no K exists+After that, the mixture was washed with deionized water until pH 7.
Example 5
(1) 42.56g of ammonium ferricyanide is weighed, dissolved in 80ml of deionized water at room temperature, and then the solution is metered to 100ml to obtain a uniform solution, wherein the concentration of the ferricyanide is 1.60 mol/L.
(2) 45.44g of ammonium ferrocyanide (prepared in example 2) were weighed out and dissolved in 80ml of deionized water at room temperature, and the volume of the solution was then adjusted to 100ml to obtain a homogeneous solution, wherein the concentration of ferrocyanide was 1.60 mol/L.
(3) The prepared electrolyte is utilized to assemble a symmetrical flow battery, wherein the electrode is a graphite felt with the area of 13.5cm2The bipolar plate is a graphite plate, the ion exchange membrane is a Nafion 117 cation exchange membrane produced by DuPont, and the current density is 10mA/cm2The catholyte is 1.60mol/L ammonium ferrocyanide, the anolyte is 1.60mol/L ammonium ferricyanide, and the ammonium ferrocyanide/ammonium ferricyanide electrolyte can realize the charge and discharge of the 1.60mol battery, the unit volume capacity of the assembled flow battery is 44.0Ah/L, and the coulombic efficiency of the battery reaches 99.9%.
Comparative example 3
(1) Compared with example 5, the catholyte was changed to a saturated solution of sodium ferrocyanide (0.56mol/L), and the anode was changed to a solution of sodium ferricyanide (0.56mol/L), and the flow battery was assembled under the same conditions. The battery had a volume capacity of 15.1 Ah/L.
(2) Compared with saturated sodium ferrocyanide, the coulombic efficiency and the charge-discharge capacity of the flow battery using the catholyte are remarkably improved. The cathode electrolyte effectively improves the concentration of active substances of the electrolyte and improves the conductivity of the electrolyte of the battery, thereby improving the efficiency and the charge-discharge capacity of the battery.
Example 6
(1) 66.01g of lithium ferricyanide is weighed and dissolved in 80ml of deionized water at room temperature, and then the solution is metered to 100ml to obtain a uniform solution, wherein the concentration of the ferricyanide is 2.30 mol/L.
(2) 71.76g of lithium ferrocyanide (prepared in example 4) was weighed, dissolved in 80ml of deionized water at room temperature, and the volume of the solution was then adjusted to 100ml to obtain a homogeneous solution, wherein the concentration of ferrocyanide was 2.30 mol/L.
(3) The prepared electrolyte is utilized to assemble a symmetrical flow battery, wherein the electrode is a graphite felt with the area of 13.5cm2The bipolar plate is a graphite plate, the ion exchange membrane is a Nafion 117 cation exchange membrane produced by DuPont, and the current density is 10mA/cm2The catholyte is 2.30mol/L lithium ferrocyanide, the anolyte is 2.30mol/L lithium ferricyanide, the lithium ferrocyanide/lithium ferricyanide electrolyte can realize the charge and discharge of a 2.30mol battery, the unit volume capacity of the assembled flow battery is 61.6Ah/L, and the coulombic efficiency of the battery reaches 99.9%.
Comparative example 4
(1) Compared with example 6, the catholyte was changed to a saturated solution of potassium ferrocyanide (0.76mol/L), and the anode was changed to a solution of potassium ferricyanide (0.76mol/L), and the flow battery was assembled under the same conditions. The battery had a volume capacity of 20.7 Ah/L.
(2) Compared with saturated potassium ferrocyanide, the coulombic efficiency and the charge-discharge capacity of the flow battery using the cathode electrolyte are remarkably improved. The cathode electrolyte effectively improves the concentration of active substances of the electrolyte and improves the conductivity of the electrolyte of the battery, thereby improving the efficiency and the charge-discharge capacity of the battery.

Claims (9)

1. A preparation method of ferrocyanide is characterized in that the preparation method is carried out according to the following steps:
step one, pretreating cation exchange resin, and then filling a column;
step two, washing with a dilute acid solution and washing with deionized water until the pH value is 7;
washing with a dilute solution of alkali, and washing with deionized water until the pH value is 7;
step four, washing with a dilute acid solution and washing with deionized water until the pH value is 7;
step five, eluting with an aqueous solution containing target product cations, and washing with deionized water until the pH value is 7;
sixthly, washing with an aqueous solution of potassium ferrocyanide or sodium ferrocyanide, and washing with deionized water after the exchange is finished;
step seven, drying the solution obtained after the exchange in vacuum to remove moisture to obtain a product;
the water solution containing the target product cations in the fifth step is one or more of ammonium bicarbonate, ammonia water, ammonium chloride, lithium nitride, lithium hydroxide, potassium hydroxide and sodium hydroxide water solution which are prepared according to any ratio; when a plurality of kinds are adopted, the cations are selected to be the same.
2. The method of claim 1, wherein the step of pretreating the cation exchange resin in the step one comprises the steps of: soaking the cation exchange resin in absolute ethyl alcohol at room temperature for 12-36 h, filtering, and soaking the cation exchange resin in deionized water at room temperature for 12-36 h to complete the pretreatment.
3. The method for preparing ferrocyanide as defined in claim 1, wherein the dilute solution of the acid in the second step is one of dilute hydrochloric acid solution, dilute nitric acid solution and dilute sulfuric acid solution; the mass percentage content of the dilute solution of the acid is 1-15%, and the dilute solution of the acid adopted in the step four is the same as that in the step two.
4. The method for preparing ferrocyanide as defined in claim 1, wherein the dilute solution of alkali in step three is one of dilute sodium hydroxide solution and dilute potassium hydroxide solution; and step three, the mass percentage of the dilute solution of the alkali is 1-15%.
5. The method as claimed in claim 1, wherein the aqueous solution containing the target product cation is used in the fifth step in an amount of 1-20 wt%.
6. The preparation method of ferrocyanide as defined in any one of claims 1-5 is used for preparing catholyte for flow batteries.
7. The use according to claim 6, wherein the concentration of ferrocyanide in the electrolyte is 1.5-2.5 mol/L.
8. The flow battery is characterized in that the electrode of the flow battery is a graphite felt, the bipolar plate is a graphite plate, the ion exchange membrane is a Nafion membrane manufactured by DuPont, the catholyte is the deionized water solution of ferrocyanide prepared by the preparation method of any one of claims 1 to 5, and the anolyte is the deionized water solution of ferricyanide.
9. The flow battery of claim 8, wherein the flow battery is a symmetric flow battery, and a positive electrolyte is circulated between the positive electrode and the ion exchange membrane and a negative electrolyte is circulated between the negative electrode and the ion exchange membrane.
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