CN109252181B - Method for preparing sodium hexafluoroferrite by electrolysis - Google Patents
Method for preparing sodium hexafluoroferrite by electrolysis Download PDFInfo
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- CN109252181B CN109252181B CN201811067896.XA CN201811067896A CN109252181B CN 109252181 B CN109252181 B CN 109252181B CN 201811067896 A CN201811067896 A CN 201811067896A CN 109252181 B CN109252181 B CN 109252181B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/245—Fluorine; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for preparing sodium hexafluoroferrite by electrolysis. The invention takes a mixed solution of hydrofluoric acid and soluble sodium salt or a mixed solution of sodium fluoride and inorganic acid as an electrolyte, takes pure iron or iron alloy as an anode, takes graphite, nickel, stainless steel, iron or iron alloy as a cathode, and adopts 0.01-1A/cm2Controlling the electrolysis temperature to be 25-95 ℃, carrying out direct current or alternating current electrolysis, adding an oxidant to oxidize a product, filtering, washing and drying a precipitate to obtain the sodium hexafluoroferrite. The method has mild reaction conditions, easy operation and low cost; the obtained product has small granularity and can be directly used as an electrode material of a lithium/sodium ion battery; is easy for industrialized production and has good social and economic benefits.
Description
Technical Field
The invention relates to preparation of an electrode material, in particular to a method for preparing sodium hexafluoroferrite by electrolysis.
Background
Sodium ion batteries have the same working principle as lithium ion batteries, and the research begins around the eighties of the last century. However, the development of sodium ion batteries is very slow because the electrode materials developed in the early stage show very poor electrochemical performance. With the rapid development of electric vehicles and smart grids, great challenges are brought to the development of lithium ion batteries. Therefore, the sodium ion battery with abundant raw material reserves and low price is paid attention again, and the search for a proper sodium ion electrode material becomes the first research task of the current sodium ion battery.
Cryolite type fluoride sodium hexafluoroferrite (Na)3FeF6) Is beige, has the capability of storing sodium ions and lithium ions, and can be used as the anode material of lithium ion batteries and sodium ion batteries. In 2012, K.kang and J.W.Choi, etc. of Korea Seoul national university adopt a high-energy ball milling method to prepare carbon-coated sodium hexafluoroferrite, and find that Na in sodium-ion battery3FeF6The discharge specific capacity of the lithium ion battery is 111 mAh/g (0.5-4.25V), and Na in the lithium ion battery3FeF6The specific discharge capacity of the anode material is 241mAh/g (0.5-4.25V), and the cycle performance of the anode material and the cathode material is poor (R.A. Shakoor, S.Y. Lim, H.Kim, K.W.Nam, J.K. Kang, K.Kang, J.W. Choi, mechanical synthesis and electrochemical catalyst of Na)3FeF6in sodium and lithium batteries. SolidState Ionics, 2012, 218: 35-40）。Y, Shi, etc. increase Na content by coating with carbon nanotubes3FeF6Electrochemical performance in lithium ion batteries (S. Sun, Y. Shi, S. Bian, Q. Zhuang, M. Liu, Y.Cui, Solid State Ionics, 2017, 312: 61-66). In the previous studies, we have prepared sodium hexafluoroferrite and its coating material having excellent electrochemical properties by using a low-temperature liquid phase method (title of the invention: a method for preparing sodium hexafluoroferrite and its coating material, which are positive electrode materials suitable for sodium or lithium ion batteries, application No. 201710440651.6, application date: 2017.06.12).
Disclosure of Invention
In order to further meet the requirement of industrial production, the invention provides a method for preparing sodium hexafluoroferrite by electrolysis.
The purpose of the invention is realized by the following technical scheme:
an electrolytic preparation method of sodium hexafluoroferrite, comprising the following steps:
(1) in an electrolytic cell, a mixed solution of hydrofluoric acid and soluble sodium salt or a mixed solution of sodium fluoride and inorganic acid is used as an electrolyte, pure iron or iron alloy is used as an anode, graphite, nickel, stainless steel, iron or iron alloy is used as a cathode, and 0.01-1A/cm is adopted2Controlling the electrolysis temperature to be 25-95 ℃ and carrying out direct current or alternating current electrolysis for 1-20 h;
(2) after the electrolysis is finished, adding an oxidant according to the content of ferrous ions, and oxidizing for 0.5-10 h;
(3) and (3) filtering the precipitate obtained in the step (2), washing and drying to obtain sodium hexafluoroferrite.
Furthermore, the electrolytic tank is a diaphragm type or non-diaphragm type electrolytic tank.
Further, in the step (1), the soluble sodium salt is one or more than two of sodium nitrate, sodium nitrite, sodium sulfate, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium fluoride, sodium chloride, sodium carbonate and sodium bicarbonate.
Further, in the step (1), the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid.
Further, in the step (1), the mass fraction of the hydrofluoric acid in the mixed solution of hydrofluoric acid and soluble sodium salt is 1-40%; the concentration of the sodium fluoride is 0.01-4 mol/L.
Further, in the step (2), the oxidant is one or more than two of oxygen, chlorine, hydrogen peroxide, hypochlorous acid, sodium hypochlorite, sodium chlorate, sodium perchlorate, sodium persulfate, potassium persulfate, ammonium persulfate, potassium permanganate and potassium dichromate.
Furthermore, in the step (2), the amount of the oxidant is 0.5-10 times of the mole number of the ferrous ions.
Further, in the step (3), washing is carried out for 3-8 times, the drying temperature is 60-100 ℃, and the drying time is 5-20 hours.
Compared with the prior art, the invention has the following beneficial effects:
the invention uses cheap iron or iron alloy as an iron source, creatively adopts an electrolytic method to prepare sodium hexafluoroferrite, has mild reaction conditions, easy operation and low cost; the obtained product has small granularity and can be directly used as an electrode material of a lithium/sodium ion battery; is easy for industrialized production and has good social and economic benefits.
Drawings
FIG. 1 shows Li/Na assembled by using sodium hexafluoroferrite material as positive electrode material and lithium sheet as negative electrode material3FeF6Button cell, at room temperature with 0.05C rate charge and discharge curve.
FIG. 2 shows Na/Na assembled by using sodium hexafluoroferrite material as positive electrode material and sodium sheet as negative electrode material3FeF6Button cell, at room temperature with 0.05C rate charge and discharge curve.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited thereto.
Example 1
Adding 10 percent by mass of hydrofluoric acid into a diaphragm-free electrolytic cell with the volume of 1.2L30mL of the solution and 800mL of the 0.2mol/L sodium fluoride solution, wherein pure iron and stainless steel with the size of 15cm × 8cm 358 cm × 1cm are respectively used as an anode and a cathode, and the current density is 0.05A/cm2The electrolysis temperature is 30 ℃, and the direct current electrolysis lasts for 3 hours. After the electrolysis is finished, the reaction solution is taken out, 40mL of 30% hydrogen peroxide is added into the reaction solution, the oxidation reaction is carried out for 1.5 h, the electrolyte is filtered, and the precipitate is washed for 4 times by deionized water. Then, the precipitate is dried in a vacuum drying oven at 90 ℃ for 10h, crushed and sieved by a 300-mesh sieve to obtain the sodium hexafluoroferrite.
Example 2
140mL of hydrofluoric acid solution with the mass fraction of 30% and 800mL of 0.5mol/L sodium sulfate solution are added into a diaphragm-free electrolytic cell with the volume of 1.2L, pure iron and graphite with the sizes of 15cm × 8cm, 8cm × 1cm and 1cm are respectively used as an anode and a cathode, and the current density is 0.1A/cm2The electrolysis temperature is 50 ℃, and the direct current electrolysis lasts for 5 hours. And after the electrolysis is finished, taking out the reaction solution, introducing pure oxygen into the reaction solution, carrying out oxidation reaction for 5 hours, filtering the electrolyte, and washing the precipitate for 5 times by using deionized water. Then, the precipitate is dried in a vacuum drying oven at 80 ℃ for 12h, crushed and sieved by a 400-mesh sieve to obtain the sodium hexafluoroferrite.
Example 3
Adding 900mL of 0.5mol/L sodium fluoride solution and 20mL of nitric acid solution with mass fraction of 69% into a diaphragm-free electrolytic cell with the volume of 1.2L, respectively using ferrosilicon and nickel with the sizes of 20cm × 10cm, 10cm × 1cm and 1cm as an anode and a cathode, and respectively using the current density of 0.3A/cm2The electrolysis temperature is 70 ℃, and the direct current electrolysis lasts 8 hours. After the electrolysis is finished, the reaction solution is taken out, 50mL of 2mol/L sodium persulfate is added into the reaction solution, the oxidation reaction is carried out for 3h, the electrolyte is filtered, and the precipitate is washed 6 times by deionized water. Then, the precipitate is dried in a vacuum drying oven at 70 ℃ for 15h, crushed and sieved by a 500-mesh sieve to obtain the sodium hexafluoroferrite.
When the sodium hexafluoroferrite material obtained by the invention is subjected to charge and discharge performance tests, the sodium hexafluoroferrite material obtained by the embodiment obtains basically consistent results, and has higher specific discharge capacity and coulombic efficiency.
Li/Na is assembled by taking the sodium hexafluoroferrite material prepared in the example 1 as a positive electrode material and a lithium sheet as a negative electrode material3FeF6The curve chart of the charge and discharge of the button cell at 0.05C rate at room temperature is shown in FIG. 1, and it can be seen that the voltage is 0.4-3.0V (vs. Li/Li)+) The charging specific capacity is 146.3mAh/g and the discharging specific capacity is 169.7mAh/g within the voltage range.
Na/Na is assembled by taking the sodium hexafluoroferrite material prepared in the embodiment 1 as a positive electrode material and a sodium sheet as a negative electrode material3FeF6The charge and discharge curve of the button cell at 0.05C rate at room temperature is shown in FIG. 2, and it is observed that the voltage is 0.4-3.0V (vs. Na/Na)+) The charging specific capacity is 134.5mAh/g and the discharging specific capacity is 123.3mAh/g within the voltage range.
Finally, it should be noted that the above-mentioned list is only a specific embodiment of the present invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. In all respects, the above-described embodiments of the invention are to be considered illustrative of the invention and not restrictive. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention.
Claims (7)
1. The method for preparing sodium hexafluoroferrite through electrolysis is characterized by comprising the following steps:
(1) in an electrolytic cell, a mixed solution of hydrofluoric acid and soluble sodium salt or a mixed solution of sodium fluoride and inorganic acid is used as an electrolyte, pure iron or iron alloy is used as an anode, graphite, nickel, stainless steel, iron or iron alloy is used as a cathode, and 0.01-1A/cm is adopted2Controlling the electrolysis temperature to be 25-95 ℃ and carrying out direct current or alternating current electrolysis for 1-20 h;
(2) after the electrolysis is finished, adding an oxidant according to the content of ferrous ions, and oxidizing for 0.5-10 h;
(3) filtering, washing and drying the precipitate obtained in the step (2) to obtain sodium hexafluoroferrite;
in the step (1), the mass fraction of hydrofluoric acid in the mixed solution of hydrofluoric acid and soluble sodium salt is 1-40%; the concentration of the sodium fluoride is 0.01-4 mol/L.
2. The electrolytic preparation of sodium hexafluoroferrite according to claim 1, wherein said electrolytic cell is a diaphragm type or a non-diaphragm type electrolytic cell.
3. The electrolytic preparation method of sodium hexafluoroferrite according to claim 1, wherein in the step (1), said soluble sodium salt is one or more of sodium nitrate, sodium nitrite, sodium sulfate, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium fluoride, sodium chloride, sodium carbonate and sodium bicarbonate.
4. The electrolytic production method of sodium hexafluoroferrite according to claim 1, wherein in the step (1), the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid.
5. The electrolytic preparation method of sodium hexafluoroferrite according to claim 1, wherein in the step (2), the oxidizing agent is one or more than two of oxygen, chlorine, hydrogen peroxide, hypochlorous acid, sodium hypochlorite, sodium chlorate, sodium perchlorate, sodium persulfate, potassium persulfate, ammonium persulfate, potassium permanganate and potassium dichromate.
6. The electrolytic preparation method of sodium hexafluoroferrite according to claim 1, wherein in the step (2), the amount of the oxidizing agent is 0.5 to 10 times the mole number of the ferrous ions.
7. The electrolytic preparation method of sodium hexafluoroferrite according to claim 1, wherein in the step (3), the washing is performed 3 to 8 times, the drying temperature is 60 to 100 ℃, and the drying time is 5 to 20 hours.
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| CN115872453B (en) * | 2022-12-05 | 2024-01-09 | 湖南工程学院 | Preparation method of battery positive electrode material sodium ferrate |
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| CN1233876C (en) * | 2003-09-05 | 2005-12-28 | 郑州大学 | Solid potassium ferrate preparing method |
| CN100427644C (en) * | 2005-07-15 | 2008-10-22 | 复旦大学 | Direct electrochemical process of preparing ferrate |
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