GB2627835A - Coated Prussian white, method for preparing same, and use thereof - Google Patents

Coated Prussian white, method for preparing same, and use thereof Download PDF

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GB2627835A
GB2627835A GB2311864.9A GB202311864A GB2627835A GB 2627835 A GB2627835 A GB 2627835A GB 202311864 A GB202311864 A GB 202311864A GB 2627835 A GB2627835 A GB 2627835A
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coated
solution
potassium
sodium
centrifuge
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Li Yongguang
Li Changdong
XU Xueliu
Liu Genghao
Ruan Dingshan
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Priority claimed from CN202210914516.1A external-priority patent/CN115196653B/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

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Abstract

Provided are a coated Prussian white, a method for preparing same, and use thereof. The coated Prussian white has the chemical formula of K xNa 2 - xAFe(CN) 6 and consists of a kernel having the chemical formula of Na 2AFe(CN) 6 and a coating layer having the chemical formula of K 2AFe(CN) 6, wherein x = 0.06-0.6, and A is at least one of Ni 2+, Co 2+, Mn 2+, or Fe 2+. The preparation method comprises: under the action of centrifugal force, washing Prussian white with a potassium salt solution, so that at least some sodium ions on the surface of the Prussian white are replaced with potassium ions, thus obtaining the coated Prussian white. The coated Prussian white can reduce the water absorption performance of Prussian white and can also greatly improve the rate capability of a sodium ion battery prepared using the coated Prussian white.

Description

COATED PRUSSIAN WHITE (PW) AND PREPARATION METHOD AND USE
THEREOF
TECHNICAL FIELD
[0001] The present disclosure belongs to the technical field of new energy storage batteries, and specifically relates to coated Prussian white (PW) and a preparation method and use thereof.
BACKGROUND
[0002] With the price of lithium carbonate going up, the profit of lithium-ion batteries (LI:13s) has been greatly reduced. Compared with lithium-ion cathode materials, sodium-ion cathode materials have a lower manufacturing cost. In sodium-ion cathode materials, sodium is a commonly available element, which significantly reduces a manufacturing cost of the materials and is increasingly favored in the energy storage industry. As a sodium-ion cathode material, PW has strong water absorption property, which has a great adverse influence on the cycling and rate performance of a cell. Thus, it is of great significance to reduce the moisture content and water absorption property of PW.
[0003] Coating is a common material modification method, and there are currently many methods for coating PW. A conventional coating process is generally as follows: a material to he coated is first prepared through liquid-phase synthesis, filtration, washing, drying, and the like, then the material to he coated is placed in a reactor, water is added for slurrying, a coating agent is added to the reactor to allow a coating reaction, and a resulting material is filtered out, washed, and dried to obtain a coated product. The above process is complicated and involves repeated steps, a large time consumption, and a high loss rate. In some coating processes, in order to simplify the procedures and improve the yield, a slurry including a material to he coated prepared through liquid-phase synthesis is left in a reactor and stirred at a specified temperature, then a coating agent is added to allow a coating reaction, and a resulting material is filtered out, washed, and dried to obtain a target coated material. However, these processes also have many drawbacks. For example, a slurry prepared through liquid-phase synthesis includes a large number of salt impurities, which will interfere with a coating reaction, thereby affecting the performance of a product. Thus, when these processes are used to coat PW, a purity of PW will he inevitably compromised, which will affect the performance of sodium-ion batteries (SIGs).
[0004] Therefore, it is urgent to provide coated PW with a simple preparation method thereof, where the preparation method can greatly shorten the preparation time and the prepared PW material can improve the performance of SIBs.
SUMMARY
[0005] The present disclosure is intended to solve at least one of the technical problems existing in the prior art. In view of this, the present disclosure provides coated PW and a preparation method and use thereof. The coated PW provided by the present disclosure can reduce the water absorption of PW and improve the performance of an SIB. Moreover, the preparation method is simple and can greatly shorten the preparation time.
[0006] In a first aspect of the present disclosure, coated PW is provided.
[0007] Specifically, coated PW with a chemical formula of K,Na2_,AFe(CN)6 is provided, where the coated PW includes a core of Na2AFe(CN)6 and a coating layer of K2AFe(CN)6; and x is 0.06 to 0.6 and A is at least one selected from the group consisting of Nit*, Coe*, M n2*, and Fe2*.
[0008] Preferably, in the chemical formula, x is 0.06 to 0.3.
[0009] Preferably, the coated PW is prepared as follows: under an action of a centrifugal force, washing PW with a potassium salt solution such that at least a part of sodium ions on a surface of the PW are replaced by potassium ions.
[0010] In a second aspect of the present disclosure, a preparation method of the coated PW is provided.
[0011] Specifically, the preparation method of the coated PW includes the following steps: [0012] under an action of a centrifugal force, washing PW with a potassium salt solution such that at least a part of sodium ions on a surface of the PW are replaced by potassium ions; and water-washing and drying resulting PW to obtain the coated PW, where the centrifugal force is generated with a rotational frequency of 10 Hz to 60 Hz.
[0013] The centrifugal force is generated with a rotational frequency of preferably 15 Hz to 50 Hz and more preferably 20 Hz to 40 Hz. Test results show that, when the PW is washed with the potassium salt solution, the control of the centrifugal force is one of the important factors affecting a coating effect. When the rotational frequency is too low during the washing, the potassium salt solution undergoes an insufficient centrifugal force and thus is difficult to infiltrate the PW; and when the rotational frequency is too high (that is, the number of revolutions per minute is too large) during washing, a centrifugal effect is too strong and thus the potassium salt solution is easy to he quickly thrown off a centrifugal apparatus, such that a contact time between the potassium salt solution and the PW is too short to result in a prominent coating effect.
[0014] It should be understood that an apparatus for generating the centrifugal force is not limited, and a centrifuge is commonly used in such a process. A centrifuge can be used not only for the procedure of washing the PW with the potassium salt solution, but also for the subsequent water-washing procedure, which reduces the number of material transfers and simplifies the preparation procedures.
[0015] Preferably, a potassium salt in the potassium salt solution is at least one selected from the group consisting of potassium sulfate, potassium nitrate, potassium chloride, and potassium citrate.
[0016] The potassium salt solution has a concentration of preferably 0.3 mol/L to 3 mol/L and more preferably 0.5 mol/L to 2 mol/L.
[0017] Preferably, an molar mass of the potassium salt solution is 20% to 100% of an molar mass of the PW, such as 20%, 25%, 30%, 35%, 40%, 50%, 60%, 70%, 80%, and 90%.
[0018] The washing is conducted for preferably 2 min to 15 min and more preferably 5 min to 10 min When the PW is washed with the potassium salt solution, the control of washing time can effectively prevent the deterioration of a coating layer. After the PW is added to the potassium salt solution, a reaction can he completed almost within a few minutes, and after the reaction is completed, brief aging is conducted (that is, the washing includes reacting and aging), such that a prominent coating effect can be achieved. If the washing time is too long, potassium ions originally in the coating layer on the surface of the material will migrate and diffuse to an inside of the material in the aqueous solution, such that the coating layer deteriorates, many pores appear on the surface of the material, and in a battery prepared from the material, a contact area between the material and an electrolyte increases, resulting in decreased stability.
[0019] Preferably, the drying is conducted at 150°C to 180°C.
[0020] It should be understood that the PW can be purchased directly or prepared by a conventional method.
[0021] Preferably, the PW is prepared through the following process: [0022] in a protective gas atmosphere, mixing a fen-ocyanide solution, a metal salt solution, and a complexing agent solution to allow a reaction at 40°C to 95°C, aging a slung obtained after the reaction for 6 h to 48 h, centrifuging, and removing a resulting washing water to obtain the PW.
[0023] Preferably, the sodium ferrocyanidc solution has a concentration of 0.3 mol/L to 0.6 mol/L.
[0024] Preferably, a metal salt in the metal salt solution is one or more selected from the group consisting of a sulfate, a nitrate, an acetate, and a chloride of nickel, cobalt, manganese, and ferrous iron.
[0025] Preferably, the metal salt solution has a concentration of 0.5 mon to 2 mol/L.
[0026] Preferably, when the reaction is conducted, a pH is controlled at 6.5 to 9.5.
[0027] Preferably, the complexing agent is at least one selected from the group consisting of citric acid, maleic acid, 2-043-D-glucopyranosyl-L-ascorbic acid, ethylenediaminetetraacetic acid (EDTA), sodium citrate, and ammonia water.
[0028] Preferably, the complexing agent solution has a concentration of 0.5 mon to 5 mol/L.
[0029] More specifically, the preparation method of the coated PW includes the following steps: [0030] ( I) preparing a ferrocyanide solution, a metal salt solution, and a complexing agent solution, introducing a protective gas into a reactor to prevent oxidation, raising a temperature to 40°C to 95°C, and adding the fenocyanide solution, the metal salt solution, and the complexing agent solution to the reactor to allow a reaction, during which an addition amount of the ferrocyanide solution is controlled to maintain a pH at 6.5 to 9.5 during the reaction; and aging a slurry obtained after the reaction for 6 h to 48 h, centrifuging, and removing a resulting supernatant to obtain the PW; and [0031] (2) placing the PW in a centrifuge with a rotational frequency controlled at 10 Hz to 60 Hz, and washing the PW with a potassium salt solution such that a part of sodium ions on a surface of the PW are replaced by potassium ions to form a coating layer; and washing resulting PW with water to remove impurities, and drying the PW at 150°C to 180°C to obtain the coated PW.
[0032] In a third aspect of the present disclosure, a use of the coated PW is provided.
[0033] Specifically, the use refers to a use of the coated PW in the preparation of a battery cathode material.
[0034] A positive electrode sheet including the coated PW is provided. [0035] In a fourth aspect of the present disclosure, an SIB is provided.
[0036] Specifically, an SIB including the positive electrode sheet is provided.
[0037] Preferably, the battery cathode material is a cathode material for an SIB.
[0038] Tn the technical solution provided by the present disclosure, under an action of a centrifugal force, PW is washed with a potassium salt solution. When the potassium salt solution flows through the PW, due to low Ksp of potassium-containing PW, a part of sodium ions on a surface of the PW can be replaced by potassium ions in the solution (an actual utilization rate of the potassium salt is 10% to 30% and finally 3% to 30% of sodium in the PW is replaced by potassium) to form a coating layer on the surface of the PW. A core of the PW has a structure of Na2AFe(CN)6 and the coating layer has a structure of K2AFe(CN)6, where A is one or more selected from the group consisting of nickel, cobalt, manganese, and ferrous iron. In addition, there will be a small amount of adhesion on the surface of the material, which is formed due to the dissolution and recrystallization of the material and has a consistent structure with the coating layer. During the washing to prepare the coated PW, because K has a slightly larger ionic radius than Na, when Na is replaced by K, the lattices of the material arc distorted to reduce the spacing and channel. After being dried and taken out, uncoated PW is easy to absorb moisture in the air, resulting in a slightly high moisture content in a product. Because the water molecule channel is reduced due to the surface lattice distortion, after being dried and taken out, the coated PW prepared by the washing shows significantly-reduced water absorption, resulting in a significantly-decreased moisture content in a product. In addition, the presence of the coating layer can effectively improve the structural stability of the coated PW during a charge-discharge process, reduce side reactions between the coated PW and an electrolyte, improve the interface stability and cycling performance, and greatly improve the rate performance of the coated PW. A specific capacity of the coated PW at a high rate is almost twice that of the uncoated PW.
[0039] Compared with the prior art, the present disclosure has the following beneficial effects.
[0040] (1) In the present disclosure, PW is washed with a potassium salt solution under an action of a centrifugal force, where a rotational frequency for generating the centrifugal force and a washing time are controlled to allow prominent coating on PW, such that coated PW with a core of Na2AFe(CN)6 and a coating layer of K2AFe(CN)6 is obtained. The coating method distorts the lattices of the material to reduce the spacing and channel, which can effectively reduce the water absorption of PW and help to improve the stability of the battery material. In addition, the rate performance of an SIB prepared by the coated material can also be greatly improved, especially a specific capacity of the battery at a high rate (5 C) is almost twice that of a battery prepared by an uncoated material.
[0041] (2) The preparation method provided by the present disclosure can also effectively avoid the migration and diffusion of potassium ions in the coating layer to an inside of PW, which makes many pores appear on the surface of the material. Thus, the preparation method can reduce the deterioration risk of the coating layer and improve the s tability of the material.
[0042] (3) In the present disclosure, PW is washed with a potassium salt solution under an action of a centrifugal force, which can be completed in a centrifuge. That is, an operation of washing with a potassium salt solution is added to the normal washing process, and the operation does not need to be completed in a reactor, which reduces the number of material transfers, simplifies the preparation procedures, shortens the preparation time, and greatly reduces the manpower, material resources, and production cost.
[0043] FIG. BRIEF DESCRIPTION OF THE DRAWINGS
[0044] FIG. in Example 1, [0045] FIG. I is a process flow diagram for preparing coated PW in Example I; [0046] FIG. 2 is a scanning electron microscopy (SEM) image of the coated PW prepared 3 is an SEM image of the PW prepared in Comparative Example 1; and 4 is an SEM image of the coated PW prepared in Comparative Example 2.
DETAILED DESCRIPTION
[0047] The followina examples are provided to allow those skilled in the art to more clearly understand the technical solutions of the present disclosure. It should be noted that the following examples do not limit the protection scope of the present disclosure.
[0048] Unless otherwise specified, the raw materials, reagents, or devices used in the following examples can be obtained through conventional commercial channels or can be obtained through existing known methods.
[0049] Example 1
[0050] Coated PW with a chemical formula of Ko.,Na1.sMnFe(CN)6 was provided, including a core layer with a chemical formula of Na2MnFe(CN)6 and a coating layer with a chemical formula of K2MnFe(CN)6.
[0051] A preparation method of the coated PW was provided, including the following steps: [0052] (1) Synthesis of PW: A 0.5 mol/L sodium ferrocyanide solution, a 1.6 mol/L manganese sulfate solution, and a 2 mol/L sodium citrate solution were prepared; an appropriate amount of pure water was added to a reactor until a stirring paddle was immersed, stirring was started, nitrogen was introduced into the reactor to prevent oxidation, and a temperature was raised to 65°C; the sodium ferrocyanide solution, the manganese sulfate solution, and the sodium citrate solution were simultaneously pumped through metering pumps into the reactor to allow a precipitation reaction, where a flow rate of the sodium citrate solution was 1.2 times a flow rate of the manganese sulfate solution and a flow rate of the sodium ferrocyanide solution was controlled to maintain a pH at 8.5 during the reaction; a slurry obtained after the reaction was aged in an aging tank for 18 h and then filtered in a centrifuge; and a resulting mother liquor was removed and a resulting filter cake was left in the centrifuge.
[0053] (2) Coating of PW: The centrifuge was allowed to rotate at 20 Hz, and then a 0.5 mol/L potassium sulfate solution was introduced into the centrifuge to wash the filter cake, such that a part of sodium ions on a surface of the PW were replaced by potassium ions to form a coating layer, where a molar mass of potassium sulfate was 50% of a molar mass of the PW in the centrifuge and a flow rate of the potassium sulfate solution was determined to make the PW filter cake washed for 8 min. It was tested that a coating utilization rate of the potassium sulfate was about 20% and about 10% of sodium was replaced by potassium.
[0054] (3) Washing and drying: A filter cake in the centrifuge obtained after the washing and coating with the potassium salt solution was further washed with pure water in a volume 40% of a volume of the aged slurry to remove impurities in the filter cake, and then dried at 180°C to obtain a coated PW product with a chemical formula of Ko.2NaI.sMnFe(CN)n.
[0055] A process flow diagram of the above preparation method was shown in FIG. 1.
[0056] Example 2
[0057] Coated PW with a chemical formula of Ko.iNa1.9MnFe(CN)6 was provided, including a core layer with a chemical formula of Na2MnFe(CN)6 and a coating layer with a chemical formula of K2MnFe(CN)6.
[0058] A preparation method of the coated PW was provided, including the following steps: [0059] (1) Synthesis of PW: A 0.4 rnol/L sodium ferrocyanide solution, a 2 mol/L manganese sulfate solution, and a 2 mol/L sodium citrate solution were prepared; an appropriate amount of pure water was added to a reactor until a stirring paddle was immersed, stirring was started, nitrogen was introduced into the reactor to prevent oxidation, and a temperature was raised to 75°C; the sodium ferrocyanide solution, the manganese sulfate solution, and the sodium citrate solution were simultaneously pumped through metering pumps into the reactor to allow a precipitation reaction, where a flow rate of the sodium citrate solution was 2 times a flow rate of the manganese sulfate solution and a flow rate of the sodium ferrocyanide solution was controlled to maintain a pH at 8.2 during the reaction; a slurry obtained after the reaction was aged in an aging tank for 12 h and then filtered in a centrifuge; and a resulting mother liquor was removed and a resulting filter cake was left in the centrifuge. [0060] (2) Coating of PW: The centrifuge was allowed to rotate at 20 Hz, and then a 0.5 mol/L potassium sulfate solution was introduced into the centrifuge to wash the filter cake, such that a part of sodium ions on a surface of the PW were replaced by potassium ions to form a coating layer, where a molar mass of potassium sulfate was 25% of a molar mass of the PW in the centrifuge and a flow rate of the potassium sulfate solution was determined to make the PW filter cake washed for 6 min. It was tested that a coating utilization rate of the potassium sulfate was about 20% and about 5% of sodium was replaced by potassium.
[0061] (3) Washing and drying: A filler cake in the centrifuge obtained after the washing and coating with the potassium sulfate solution was further washed with pure water in a volume 40% of a volume of the aged slurry to remove impurities in the filter cake, and then dried at 180°C to obtain a coated PW product with a chemical formula of 1(0.1Nai9MnFe(CN)6. [0062] Example 3 [0063] Coated PW with a chemical formula of Ko.osNat.92Fe[Fe(CN)6] was provided, including a core layer with a chemical formula of Na2Fe[Fe(CN)6] and a coating layer with a chemical formula of K2Feire(CN)6].
[0064] A preparation method of the coated PW was provided, including the following steps: [0065] (1) Synthesis of PW: A 0.5 rnol/L sodium fen-ocyanide solution, a 1.5 mol/L ferrous sulfate solution, and a 2 mol/L sodium citrate solution were prepared; an appropriate amount of pure water was added to a reactor until a stirring paddle was immersed, stirring was started, nitrogen was introduced into the reactor to prevent oxidation, and a temperature was raised to 75°C; the sodium ferrocyanide solution, the ferrous sulfate solution, and the sodium citrate solution were simultaneously pumped through metering pumps into the reactor to allow a precipitation reaction, where a flow rate of the sodium citrate solution was 1.5 times a flow rate of the ferrous sulfate solution and a flow rate of the sodium fen-ocyanide solution was controlled to maintain a pH at 8.1 during the reaction; a slurry obtained after the reaction was aged in an aging tank for 12 h and then filtered in a centrifuge; and a resulting mother liquor was removed and a resulting filter cake was left in the centrifuge.
[0066] (2) Coating of PW: The centrifuge was allowed to rotate at 30 Hz, and then a 2 rnol/L potassium chloride solution was introduced into the centrifuge to wash the filter cake, such that a part of sodium ions on a surface of the PW were replaced by potassium ions to form a coating layer, where a molar mass of potassium chloride was 60% of a molar mass of the PW in the centrifuge and a flow rate of the potassium chloride solution was determined to make the PW filter cake washed for 5 min. It was tested that a coating utilization rate of the potassium chloride was about 13% and about 4% of sodium was replaced by potassium.
[0067] (3) Washing and drying: A filter cake in the centrifuge obtained after the washing and coating with the potassium chloride solution was further washed with pure water in a volume 50% of a volume of the aged slurry to remove impurities in the filter cake, and then dried at 180°C to obtain a coated PW product with a chemical formula of KooriNai.92Fe [Fe(CN)6].
[0068] Example 4
[0069] Coated PW with a chemical formula of KoosNai92CoFe(CN)6 was provided, including a core layer with a chemical formula of Na2CoFe(CN)6 and a coating layer with a chemical formula of K2CoFe(CN)6.
[0070] A preparation method of the coated PW was provided, including the following steps: [0071] (1) Synthesis of PW: A 0.4 mol/L sodium ferrocyanide solution, a 2 mol/L cobalt sulfate solution, and a 2 mol/L sodium citrate solution were prepared; an appropriate amount of pure water was added to a reactor until a stirring paddle was immersed, stirring was started, nitrogen was introduced into the reactor to prevent oxidation, and a temperature was raised to 85°C; the sodium ferrocyanide solution, the cobalt sulfate solution, and the sodium citrate solution were simultaneously pumped through metering pumps into the reactor to allow a precipitation reaction, where a flow rate of the sodium citrate solution was 2 times a flow rate of the cobalt sulfate solution and a flow rate of the sodium ferrocyanide solution was controlled to maintain a pH at 8.0 during the reaction; a material obtained after the reaction was aged in an aging tank for 18 h and then filtered in a centrifuge; and a resulting mother liquor was removed and a resulting filter cake was left in the centrifuge.
[0072] (2) Coating of PW: The centrifuge was allowed to rotate at 30 Hz, and then a 2 mol/L potassium chloride solution was introduced into the centrifuge to wash the filter cake, such that a part of sodium ions on a surface of the PW were replaced by potassium ions to form a coating layer, where a molar mass of potassium chloride was 60% of a molar mass of the PW in the centrifuge and a flow rate of the potassium chloride solution was determined to make the PW filter cake washed for 5 min. It was tested that a coating utilization rate of the potassium chloride was about 13% and about 4% of sodium was replaced by potassium.
[0073] (3) Washing and drying: A filter cake in the centrifuge obtained after the washing and coating with the potassium chloride solution was further washed with pure water in a volume 50% of a volume of the aged slurry to remove impurities in the filter cake, and then dried at 180°C to obtain a coated PW product with a chemical formula of IC0.08Nat92CoFe(CN)6.
[0074] Example 5
[0075] Coated PW with a chemical formula of KtuNat9MnFe(CN)6 was provided, including a core layer with a chemical formula of Na2MnFe(CN)6 and a coating layer with a chemical formula of K2MnFe(CN)6.
[0076] Apreparation method of the coated PW was provided, including the following steps: [0077] (1) Synthesis of PW: A 0.4 mol/L sodium ferrocyanide solution, a 2 mol/L manganese sulfate solution, and a 2 mol/L sodium citrate solution were prepared; an appropriate amount of pure water was added to a reactor until a stirring paddle was immersed, stirring was started, nitrogen was introduced into the reactor to prevent oxidation, and a temperature was raised to 75°C; the sodium ferrocyanide solution, the manganese sulfate solution, and the sodium citrate solution were simultaneously pumped through metering pumps into the reactor to allow a precipitation reaction, where a flow rate of the sodium citrate solution was 1.5 times a flow rate of the manganese sulfate solution and a flow rate of the sodium ferrocyanide solution was controlled to maintain a pH at 7.8 during the reaction; a slurry obtained after the reaction was aged in an aging tank for 12 h and then filtered in a centrifuge; and a resulting mother liquor was removed and a resulting filter cake was left in the centrifuge.
[0078] (2) Coating of PW: The centrifuge was allowed to rotate at 20 Hz, and then a 1 molt potassium nitrate solution was introduced into the centrifuge to wash the filter cake, such that a part of sodium ions on a surface of the PW were replaced by potassium ions to form a coating layer, where a molar mass of potassium nitrate was 50% of a molar mass of the PW in the centrifuge and a flow rate of the potassium nitrate solution was determined to make the PW filter cake washed for 10 min. It was tested that a coating utilization rate of the potassium nitrate was about 20% and about 5% of sodium was replaced by potassium.
[0079] (3) Washing and drying: A filter cake in the centrifuge obtained after the washing and coating with the potassium nitrate solution was further washed with pure water in a volume 40% of a volume of the aged slurry to remove impurities in the filter cake, and then dried at 170°C to obtain a coated PW product with a chemical formula of Ko.iNaL9MnFe(CN)6. [0080] Example 6 [0081] Coated PW with a chemical formula of K0.16Nm.84MnFe(CN)6 was provided, including a core layer with a chemical formula of Na2MnFe(CN)6 and a coating layer with a chemical formula of K2MnFe(CN)6.
[0082] Apreparation method of the coated PW was provided, including the following steps: [0083] (1) Synthesis of PW: A 0.5 mol/L sodium ferrocyanide solution, a 1.6 mol/L manganese sulfate solution, and a 2 molt sodium citrate solution were prepared; an appropriate amount of pure water was added to a reactor until a stirring paddle was immersed, stirring was started, nitrogen was introduced into the reactor to prevent oxidation, and a temperature was raised to 65°C; the sodium ferrocyanide solution, the manganese sulfate solution, and the sodium citrate solution were simultaneously pumped through metering pumps into the reactor to allow a precipitation reaction, where a flow rate of the sodium citrate solution was 1.2 times a flow rate of the manaanese sulfate solution and a flow rate of the sodium ferrocyanide solution was controlled to maintain a pH at 8.5 during the reaction; a slurry obtained after the reaction was aged in an aging tank for 18 h and then filtered in a centrifuge; and a resulting mother liquor was removed and a resulting filter cake was left in the centrifuge.
[0084] (2) Coating of PW: The centrifuge was allowed to rotate at 40Hz, and then a 0.5 rnol/L potassium sulfate solution was introduced into the centrifuge to wash the filter cake, such that a part of sodium ions on a surface of the PW were replaced by potassium ions to form a coating layer, where a molar mass of potassium sulfate was 50% of a molar mass of the PW in the centrifuge and a flow rate of the potassium sulfate solution was determined to make the PW filter cake washed for 5 min. It was tested that a coating utilization rate of the potassium sulfate was about 20% and about 8% of sodium was replaced by potassium.
[0085] (3) Washing and drying: A filter cake in the centrifuge obtained after the washing and coating with the potassium salt solution was further washed with pure water in a volume 40% of a volume of the aged slurry to remove impurities in the filter cake, and then dried at 180°C to obtain a coated PW product. with a chemical formula of Ko.16Nai.84MnFe(CN)6. [0086] Example 7 [0087] Coated PW with a chemical formula of Kfti7Nai.88MnFe(CN)6 was provided, including a core layer with a chemical formula of Na2MnFe(CN)o and a coating layer with a chemical formula of K2MnFe(CN)6.
[0088] A preparation method of the coated PW was provided, including the following steps: [0089] (1) Synthesis of PW: A 0.5 mol/L sodium ferrocyanide solution, a 1.6 mol/L manganese sulfate solution, and a 2 rnol/L sodium citrate solution were prepared; an appropriate amount of pure water was added to a reactor until a stirring paddle was immersed, stirring was started, nitrogen was introduced into the reactor to prevent oxidation, and a temperature was raised to 65°C; the sodium ferrocyanide solution, the manganese sulfate solution, and the sodium citrate solution were simultaneously pumped through metering pumps into the reactor to allow a precipitation reaction, where a flow rate of the sodium citrate solution was 1.2 times a flow rate of the manganese sulfate solution and a flow rate of the sodium ferrocyanide solution was controlled to maintain a pH at 8.5 during the reaction; a slurry obtained after the reaction was aged in an aging tank for 18 h and then filtered in a centrifuge; and a resulting mother liquor was removed and a resulting filter cake was left in the centrifuge.
[0090] (2) Coating of PW: The centrifuge was allowed to rotate at 10 Hz, and then a 0.5 mol/L potassium sulfate solution was introduced into the centrifuge to wash the filter cake, such that a part of sodium ions on a surface of the PW were replaced by potassium ions to form a coating layer, where a molar mass of potassium sulfate was 50% of a molar mass of the PW in the centrifuge and a flow rate of the potassium sulfate solution was determined to make the PW filter cake washed for 8 min. It was tested that a coating utilization rate of the potassium sulfate was about 20% and about 6% of sodium was replaced by potassium.
[0091] (3) Washing and drying: A filter cake in the centrifuge obtained after the washing and coating with the potassium salt solution was further washed with pure water in a volume 40% of a volume of the aged slurry to remove impurities in the filter cake, and then dried at 180°C to obtain a coated PW product with a chemical formula of K0.19NaL8sMnFe(CN)6.
[0092] Example 8
[0093] Coated PW with a chemical formula of Ko.i2NaL88MnFe(CN)6 was provided, including a core layer with a chemical formula of Na2MnFe(CN)6 and a coating layer with a chemical formula of K2MnFe(CN)6.
[0094] A preparation method of the coated PW was provided, including the following steps: [0095] (1) Synthesis of PW: A 0.5 mol/L sodium ferrocyanide solution, a 1.6 mol/L manganese sulfate solution, and a 2 mol/L sodium citrate solution were prepared; an appropriate amount of pure water was added to a reactor until a stirring paddle was immersed, stirring was started, nitrogen was introduced into the reactor to prevent oxidation, and a temperature was raised to 65°C; the sodium ferrocyanide solution, the manganese sulfate solution, and the sodium citrate solution were simultaneously pumped through metering pumps into the reactor to allow a precipitation reaction, where a flow rate of the sodium citrate solution was 1.2 times a flow rate of the manganese sulfate solution and a flow rate of the sodium ferrocyanide solution was controlled to maintain a pH at 8.5 during the reaction; a slurry obtained after the reaction was aged in an aging tank for 18 h and then filtered in a centrifuge; and a resulting mother liquor was removed and a resulting filter cake was left in the centrifuge.
[0096] (2) Coating of PW: The centrifuge was allowed to rotate at 60Hz, and then a 0.5 mol/L potassium sulfate solution was introduced into the centrifuge to wash the filter cake, such that a part of sodium ions on a surface of the PW were replaced by potassium ions to form a coating layer, where a molar mass of potassium sulfate was 50% of a molar mass of the PW in the centrifuge and a flow rate of the potassium sulfate solution was determined to make the PW filter cake washed for 8 min. It was tested that a coating utilization rate of the potassium sulfate was about 20% and about 6% of sodium was replaced by potassium. [0097] (3) Washing and drying: A filter cake in the centrifuge obtained after the washing and coating with the potassium salt solution was further washed with pure water in a volume 40% of a volume of the aged slurry to remove impurities in the filter cake, and then dried at 180°C to obtain a coated PW product with a chemical formula of Kat2Nat.ssMnFe(CN)6. [0098] Example 9 [0099] Coated PW with a chemical formula of Ko.i4Nai.s6MnFe(CN)6 was provided, including a core layer with a chemical formula of Na2MnFe(CN)6 and a coating layer with a chemical formula of K3MnFe(CN)6.
[0100] A preparation method of the coated PW was provided, including the following steps: [0101] (1) Synthesis of PW: A 0.5 mol/L sodium ferrocyanide solution, a 1.6 mol/L manganese sulfate solution, and a 2 molt sodium citrate solution were prepared; an appropriate amount of pure water was added to a reactor until a stirring paddle was immersed, stirring was started, nitrogen was introduced into the reactor to prevent oxidation, and a temperature was raised to 65°C; the sodium ferrocyanide solution, the manganese sulfate solution, and the sodium citrate solution were simultaneously pumped through metering pumps into the reactor to allow a precipitation reaction, where a flow rate of the sodium citrate solution was 1.2 times a flow rate of the manganese sulfate solution and a flow rate of the sodium ferrocyanide solution was controlled to maintain a pH at 8.5 during the reaction; a slurry obtained after the reaction was aged in an aging tank for 18 h and then filtered in a centrifuge; and a resulting mother liquor was removed and a resulting filter cake was left in the centrifuge.
[0102] (2) Coating of PW: The centrifuge was allowed to rotate at 20 Hz, and then a 0.5 mol/L potassium sulfate solution was introduced into the centrifuge to wash the filter cake, such that a part of sodium ions on a surface of the PW were replaced by potassium ions to form a coating layer, where a molar mass of potassium sulfate was 50% of a molar mass of the PW in the centrifuge and a flow rate of the potassium sulfate solution was determined to make the PW filter cake washed for 3 min. It was tested that a coating utilization rate of the potassium sulfate was about 20% and about 7% of sodium was replaced by potassium.
[0103] (3) Washing and drying: A filter cake in the centrifuge obtained after the washing and coating with the potassium salt solution was further washed with pure water in a volume 40% of a volume of the aged slurry to remove impurities in the filter cake, and then dried at 180°C to obtain a coated PW product with a chemical formula of K0.14Nat.86MnFe(CN)6. [0104] Example 10 [0105] Coated PW with a chemical formula of K0.24Na1.76MnFe(CN)6 was provided, including a core layer with a chemical formula of Na2MnFe(CN)6 and a coating layer with a chemical formula of K2MnFe(CN)6.
[0106] A preparation method of the coated PW was provided, including the following steps: [0107] (1) Synthesis of PW: A 0.5 mol/L sodium ferrocyanide solution, a 1.6 rnol/L manganese sulfate solution, and a 2 mol/L sodium citrate solution were prepared; an appropriate amount of pure water was added to a reactor until a stirring paddle was immersed, stirring was started, nitrogen was introduced into the reactor to prevent oxidation, and a temperature was raised to 65°C; the sodium ferrocyanide solution, the manganese sulfate solution, and the sodium citrate solution were simultaneously pumped through metering pumps into the reactor to allow a precipitation reaction, where a flow rate of the sodium citrate solution was 1.2 times a flow rate of the manganese sulfate solution and a flow rate of the sodium ferrocyanide solution was controlled to maintain a pH at 8.5 during the reaction; a slurry obtained after the reaction was aged in an aging tank for 18 h and then filtered in a centrifuge; and a resulting mother liquor was removed and a resulting filter cake was left in the centrifuge.
[0108] (2) Coating of PW: The centrifuge was allowed to rotate at 20 Hz, and then a 0.5 mol/L potassium sulfate solution was introduced into the centrifuge to wash the filter cake, such that a part of sodium ions on a surface of the PW were replaced by potassium ions to form a coating layer, where a molar mass of potassium sulfate was 50% of a molar mass of the PW in the centrifuge and a flow rate of the potassium sulfate solution was determined to make the PW filter cake be washed for 15 min. A coating layer was formed by replacing part of the sodium ions on the PW surface with potassium ions. It was tested that a coating utilization rate of the potassium sulfate was about 20% and about 12% of sodium was replaced by potassium.
[0109] (3) Washing and drying: A filter cake in the centrifuge obtained after the washing and coating with the potassium salt solution was further washed with pure water in a volume 40% of a volume of the aged slurry to remove impurities in the filter cake, and then dried at 180°C to obtain a coated PW product. with a chemical formula of Ko.24Na1.76MnEe(CN)6.
[0110] Comparative Example 1 [0111] Comparative Example 1 was the same as Example 1, except that the filter cake was not washed with a potassium salt solution in step (2) and an uncoated PW product with a chemical formula of Na2MnFe(CN)o was prepared.
[0112] Comparative Example 2 [0113] In Comparative Example 2, coated PW was prepared by a traditional coating method in a reactor, specifically including the following steps: [0114] (1) Synthesis of PW: A 0.4 mol/L sodium ferrocyanide solution, a 2 mol/L manganese sulfate solution, and a 2 mol/L sodium citrate solution were prepared; an appropriate amount of pure water was added to a reactor until a stirring paddle was immersed, stirring was started, nitrogen was introduced into the reactor to prevent oxidation, and a temperature was raised to 75°C; the sodium ferrocyanide solution, the manganese sulfate solution, and the sodium citrate solution were simultaneously pumped through metering pumps into the reactor to allow a precipitation reaction, where a flow rate of the sodium citrate solution was 2 times a flow rate of the manganese sulfate solution and a flow rate of the sodium ferrocyanide solution was controlled to maintain a p1-1 at 8.2 during the reaction; a slurry obtained after the reaction was aged in an aging tank for 12 h and then filtered in a centrifuge; and a resulting mother liquor was removed and a resulting PW filter cake was obtained. [0115] (2) Coaling of PW: The PW filter cake was placed in a reactor, water was added for slurrying, stirring was started, and a 0.5 mol/L potassium sulfate solution was added to the reactor for coating; and a resulting slurry in the reactor was aged for 30 min and then immediately filtered and washed in a centrifuge to obtain a filler cake, and the filter cake was dried at 180°C to obtain a coated PW product with a chemical formula of 1(02N ai 8M n Fc(CN)o, where a molar mass of potassium sulfate was 10% of a molar mass of the PW in the reactor and the potassium sulfate reacted almost completely.
[0116] Product effect test [0117] The PW products prepared in Examples 1 to 10 and Comparative Examples 1 and 2 were tested.
[0118] Specific test methods and test results were as follows: [0119] (1) The coated PW products prepared in Example 1 and Comparative Example 2 and the uncoated PW product prepared in Comparative Example 1 were subjected to SEM analysis.
[0120] FIG. 2 is a scanning electron microscopy (SEM) image of the coated PW prepared in Example 1, and it can be known that a small amount of coating can be observed on a surface of the material after the coating operation in the centrifuge. FIG. 3 is an SEM image of the uncoated PW prepared in Comparative Example 1, and it can he known that the material is not coated and has a smooth surface without adhesion. FIG. 4 is an SEM image of the coated PW prepared in Comparative Example 2, and it can be known that a large number of pores appear on a surface of the material and the morphology of the material is seriously deteriorated after the coating operation in the reactor and the aging for 30 min, which is caused by the etching of potassium ions into the material; and similarly, there is a small amount of adhesion generated due to dissolution and recrystallization on a surface of the material.
[0121] (2) A particle size of each of the PW products prepared in Examples 1 to 10 and Comparative Examples 1 and 2 was tested by a dry particle size analyzer.
[0122] (3) A moisture content (wt%) in each of the PW products prepared in Examples 1 to 10 and Comparative Examples 1 and 2 was tested by an automatic moisture analyzer, where the PW products were dried at 150°C for 1 h. [0123] (4) The PW products prepared in Examples 1 to 10 and Comparative Examples 1 and 2 were each fabricated into a positive electrode sheet, and the positive electrode sheet was assembled into a button half-cell in a glove box with sodium as a negative electrode and a solution of NaPF6 in vinylene carbonate (EC)/diethyl carbonate (DEC) as an electrolyte. Then in a voltage range of 2.0 V to 4.0 V, the specific charge/discharge capacity of a battery was tested at 0.1 C and 5 C. [0124] Test results were shown in Table 1.
[0125] Table 1 Test results Sample D50 Moisture Specific discharge Specific discharge (lan) content capacity at 0.1 C capacity at 5 C (wt%) (rnAh/g) (mAh/g) Example 1 2.77 0.5 154 117 Example 2 2.45 0.6 156 122 Example 3 2.55 0.6 151 111 Example 4 2.71 0.6 153 115 Example 5 2.52 0.5 152 113 Example 6 2.68 0.5 153 116 Example 7 2.55 0.8 152 92 Example 8 2.61 0.7 150 88 Example 9 2.73 0.7 152 103 Example 10 2.66 0.8 154 105 Comparative 2.72 1.1 155 62
Example 1
Comparative 2.64 1.8 141 43
Example 2
[0126] It can be seen from Table 1 that the morphology and the specific discharge capacity at 0.1 C of the material in Example 1 are not much different from that of the material in Comparative Example 1, but the moisture content in the coated material (coated PW prepared in Example 1) is greatly reduced and the specific discharge capacity at 5 C of the coated material is significantly improved. Compared with the product in Comparative Example 1, the coated PW prepared by the conventional method in Comparative Example 2 has a large number of pores on its surface, an increased moisture content, significantly-reduced specific discharge capacities at 0.1 C and 5 C. and heavily-deteriorated performance. Compared with the product in Example 1, the coated PW products prepared in Examples 2 to 6 have a similar effect and a decreased moisture content; and the specific discharge capacity at 5 C of each of the coated PW products prepared in Examples 2 to 6 is significantly increased compared with Comparative Example 1. Compared with Comparative Example 1, the specific discharge capacity at 5 C of each of the coated PW products prepared in Examples 7 to 10 is significantly improved; and the specific discharge capacity at 0.1 C of each of the coated PW products prepared in Examples 7 to 10 is equivalent to that of Examples 1 to 6, but the moisture content and the specific discharge capacity at 5 C of each of the coated PW products prepared in Examples 7 to 10 are slightly worse than that of Examples 1 to 6. It can be seen that the coated PW prepared by washing under an action of a centrifugal force in the present disclosure can reduce the water absorption and moisture content of PW and significantly improve a specific charge/discharge capacity of an SIB prepared by the coated PW at a high rate; and a rotational frequency for generating the centrifugal force and a washing time will also affect the stability of an SIB, especially a specific discharge capacity at a high rate (5 C).

Claims (10)

  1. CLAIMS: 1. Coated Prussian white (PW) with a chemical formula of KxNa9_,AFe(CN)6, wherein the coated PW comprises a core of Na2AFe(CN)6 and a coating layer of K2AFe(CN)6; and x is 0.06 to 0.6 and A is at least one selected from the group consisting of Nit *, Co'*, Mn2*, and Fe'*.
  2. 2. The coated PW according to claim 1, wherein in the chemical formula, x is 0.06 to 0.3.
  3. 3. A preparation method of the coated PW according to claim 1 or 2, comprising the followina steps: under an action of a centrifugal force, washing a PW with a potassium salt solution such that at least a part of sodium ions on a surface of the PW are replaced by potassium ions; and water-washing and drying to obtain the coated PW, wherein the centrifugal force is generated with a rotational frequency of 10 Hz to 60 Hz.
  4. 4. The preparation method according to claim 3, wherein the centrifugal force is generated with a rotational frequency of 15 Hz to 50 Hz and preferably 20 Hz to 40 Hz.
  5. 5. The preparation method according to claim 3, wherein a potassium salt in the potassium salt solution is at least one selected from the group consisting of potassium sulfate, potassium nitrate, potassium chloride, and potassium citrate.
  6. 6. The preparation method according to claim 3, wherein the potassium salt solution has a concentration of 0.3 mol/L to 3 mol/L.
  7. 7. The preparation method according to any one of claims 3, 5, and 6, wherein a molar mass of the potassium salt solution is 20% to 100% of an molar mass of the PW.
  8. 8. The preparation method according to claim 3, wherein the washing with a potassium salt solution is conducted for 2 min to 15 min and preferably 5 min to 10 min.
  9. 9. A positive electrode sheet comprising the coated PW according to claim I or 2.
  10. 10. A sodium-ion battery (SIB) comprising the positive electrode sheet according to claim 9.
GB2311864.9A 2022-07-29 2022-09-16 Coated Prussian white, method for preparing same, and use thereof Pending GB2627835A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2366064A1 (en) * 1973-12-10 1977-09-29 Degussa Production of prussian blue - by reacting sodium ferrocyanide with ferrous chloride and potassium chloride in a single step
US20140127560A1 (en) * 2011-06-22 2014-05-08 Alveo Energy, Inc. Stabilization of battery electrodes using prussian blue analogue coatings
JP2015079685A (en) * 2013-10-18 2015-04-23 株式会社豊田中央研究所 Aqueous solution-based secondary battery
CN106549155A (en) * 2016-10-20 2017-03-29 河南师范大学 A kind of potassium sodium ferromanganese base prussian blue electrode material and its preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2366064A1 (en) * 1973-12-10 1977-09-29 Degussa Production of prussian blue - by reacting sodium ferrocyanide with ferrous chloride and potassium chloride in a single step
US20140127560A1 (en) * 2011-06-22 2014-05-08 Alveo Energy, Inc. Stabilization of battery electrodes using prussian blue analogue coatings
JP2015079685A (en) * 2013-10-18 2015-04-23 株式会社豊田中央研究所 Aqueous solution-based secondary battery
CN106549155A (en) * 2016-10-20 2017-03-29 河南师范大学 A kind of potassium sodium ferromanganese base prussian blue electrode material and its preparation method and application

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