Preparation method of hydrated ferronickel fluoride functional nano material

Abstract

The invention relates to a preparation method of a hydrated ferronickel fluoride functional nano material, in particular to a low-temperature preparation method of a ferronickel compound functional nano material, which comprises the following steps: 1, generating a precipitate of a hydrated ferronickel fluoride (NiFeF5. 7H2O) material through liquid-phase synthesis, and then centrifuging and washing; and 2, solvent heat treatment: putting the hydrated ferronickel fluoride (NiFeF5. 7H2O) material prepared in the step 1 and an alcohol solvent into a reaction kettle for solvent heat treatment. In solvent heat treatment, processes such as crystal water removal and the like are carried out, and morphology and phase conversion is carried out in the processes, so that the hydrated ferronickel fluoride nano material (NiFeF5. 2H2O) is finally obtained. The hydrated ferronickel fluoride (NiFeF5. 2H2O) functional nano material contains fluorine anions with high electronegativity, and nickel and iron bimetals have rich redox valence states and a unique crystal structure, so that the hydrated ferronickel fluoride (NiFeF5. 2H2O) functional nano material is suitable for the related fields and many fields of electrochemistry, electrocatalysis and the like. Therefore, the method has a plurality of application prospects and application values.

Description

Technical Field

[0001] The invention relates to a low-temperature preparation method of a nickel-iron compound functional nano material, in particular to a preparation method of a hydrated nickel-iron fluoride functional nano material. Background Art

[0002] Hydrated nickel iron fluoride (NiFeF 5 ·2H 2 O) functional nanomaterials contain Ni, Fe metal active ions and highly electronegative fluoride anions. The high electronegativity of fluoride ions and the rich redox states of iron and nickel ions make hydrated nickel iron fluoride (NiFeF 5 ·2H 2 O) has some excellent physical and chemical properties. In addition, nano-sizing will further bring it various surface and quantum size effects, thereby increasing its basic research and application value. Hydrated nickel iron fluoride (NiFeF 5 ·2H 2 O) Functional nanomaterials are expected to be used in batteries, electrocatalysis or other energy fields and many other fields. Summary of the invention

[0003] The purpose of the present invention is to provide a method for preparing a hydrated nickel-iron fluoride functional nanomaterial. The hydrated nickel-iron fluoride functional nanomaterial (NiFeF5·2H2O) prepared by the present invention contains Ni, Fe metal active ions, and fluoride ions. This material has excellent physical and chemical properties. Nano-sizing will further bring it various surface and quantum size effects. This material has opened up the basic research and application value in this field.

[0004] The objective of the present invention is achieved through the following technical solutions: A method for preparing hydrated nickel-iron fluoride functional nanomaterial, the method comprising the following preparation process: The first step is liquid phase synthesis: a solution containing a fluoride salt precursor is mixed with a solution containing an iron salt and a nickel salt precursor, and a chemical reaction occurs between the fluoride salt and the iron salt and the nickel salt to generate a hydrated nickel iron fluoride material (NiFeF 5 7H 2 O) precipitation, followed by centrifugation and washing; the second step is solvent thermal treatment: the hydrated nickel iron fluoride material (NiFeF 5 7H 2 O) and an alcohol solvent are placed in a reactor for solvent thermal treatment; during the solvent thermal treatment, the crystal water is removed, and the morphology and phase transformation are accompanied during the process, and finally hydrated nickel iron fluoride (NiFeF 5 ·2H 2 O) Functional nanomaterials.

[0005] The method for preparing a hydrated nickel iron fluoride functional nanomaterial, wherein the hydrated nickel iron fluoride (NiFeF 5 ·2H 2 O) The particle size of functional nanomaterials is 0.01 nm - 500 nm; each particle is composed of several nanoregions (0.1-20 nm).

[0006] The method for preparing a hydrated nickel-iron fluoride functional nanomaterial, wherein the fluoride salt precursor in the liquid phase synthesis is NH 4 F. NH 4 HF 2 One or two of the following, the iron salt precursor is Fe(NO 3 ) 3 9H 2 O, FeCl 3 6H 2 O, Fe(OH)(CH 3 COO 2 , Fe 2 (SO 4 ) 3 and one or more of trivalent iron salts, the nickel salt precursor is NiCl 2 6H 2 O、NiSO 4 And one or more of divalent nickel salts.

[0007] In the method for preparing a hydrated nickel-iron fluoride functional nanomaterial, the ratio of the iron salt precursor to the nickel salt precursor in the liquid phase synthesis satisfies that the molar ratio of Fe:Ni is between 0.001:1-999:1.

[0008] The method for preparing a hydrated nickel-iron fluoride functional nanomaterial is as follows: the solvent in the fluorine-containing salt precursor solution in the liquid phase synthesis is one or more of water, ethanol, various alcohols and organic solvents; the solvent in the iron salt and nickel salt precursor solution is one or more of water, ethanol, alcohols and organic solvents.

[0009] In the method for preparing hydrated nickel-iron fluoride functional nanomaterial, the alcohol in the solvent thermal treatment is one or more of alcohols with hydroxyl groups (such as ethanol, ethylene glycol, and glycerol).

[0010] In the method for preparing the hydrated nickel-iron fluoride functional nanomaterial, the reaction temperature in the solvent thermal treatment is 80-150°C.

[0011] In the method for preparing hydrated nickel-iron fluoride functional nanomaterial, the heat preservation time of the reaction in the solvent thermal treatment is 0.1-24 hours.

[0012] The advantages and effects of the present invention are: 1. The hydrated nickel iron fluoride (NiFeF 5 ·2H 2 O) The particle size of functional nanomaterials is nanometer-scale, and each nanoparticle is composed of several nanoregions.

[0013] 2. The present invention is the first to obtain hydrated nickel iron fluoride (NiFeF) at a relatively low temperature (between 80-150°C). 5 ·2H 2 O) Functional nanomaterials and their nanoparticles.

[0014] 3. The hydrated nickel-iron fluoride functional nanomaterial (NiFeF 5 ·2H 2 O) contains Ni, Fe metal active ions, and fluoride ions. The high electronegativity of fluoride ions, the rich redox states of iron and nickel ions, and the unique crystal structure give this material excellent physical and chemical properties. Nano-sizing will further bring it various surface and quantum size effects, thereby increasing its basic research and application value, and it can be used in batteries, electrocatalysis or other energy fields and many other fields. DETAILED DESCRIPTION

[0015] The present invention is described in detail below with reference to the embodiments.

[0016] The present invention is a hydrated nickel iron fluoride functional nanomaterial (NiFeF 5 ·2H 2 O) Preparation method. Hydrated nickel iron fluoride functional nanomaterial (NiFeF5·2H2O) contains Ni, Fe metal active ions, and fluoride ions. The high electronegativity of fluoride ions, the rich redox valence of iron ions and nickel ions, and the unique crystal structure make this material have excellent physical and chemical properties. In addition, nano-sizing will further bring it surface and quantum size effects, thereby increasing its basic research and application value. It can be applied to batteries, electrocatalysis or other energy fields and many other fields. The present invention proposes a two-step method for low-temperature preparation. The first step of liquid phase synthesis involves mixing a solution of a fluoride salt precursor with a solution containing an iron salt and a nickel salt precursor, and a chemical reaction occurs between the fluoride salt and the iron salt and the nickel salt to generate a hydrated nickel iron fluoride material. The second step of solvent thermal treatment involves using the hydrated nickel iron fluoride material prepared in the first step as a precursor, mixing it with alcohols and water to form a solid-liquid mixture; the solid-liquid mixture is subjected to a hydrothermal / solvent thermal reaction (80-150°C) in a reactor to obtain a hydrated nickel iron fluoride functional nanomaterial. Example

[0017] Preparation of hydrated nickel iron fluoride (NiFeF5·2H2O) functional nanomaterials: Prepare 20 mL of aqueous solution containing 0.25 g of PEG4000, add 2.12 g of NH 4 HF 2 The powder was placed in the above clear solution and stirred with a magnetic stirrer until the mixture was uniform. 60 mL of anhydrous ethanol containing 1 g of PEG4000 was prepared, and 4.4 g of NiCl 2 6H 2 O powder, 4.0 g FeCl 3 6H 2 O powder was placed in the above clear solution and stirred with a magnetic stirrer until the mixture was uniform. 4 HF 2 The solution containing NiCl was dripped into the 2 6H 2 O and FeCl 3 6H 2 O solution. Stirring was continued for 2 hours. Centrifugation, washing and drying were performed to obtain hydrated nickel iron fluoride material (NiFeF 5 7H 2 O) powder.

[0018] The hydrated nickel iron fluoride material (NiFeF 5 7H 2 O) 2g was added to a mixture of "45 mL ethanol and 1 mL deionized water", ultrasonically dispersed, and then placed in a 50 mL hydrothermal kettle at 120°C / 10h. After cooling, the hydrothermal kettle was opened, the supernatant was poured out, and the remainder was poured into a test tube and centrifuged. Finally, it was placed in an electric constant temperature drying oven at 60°C and dried for 2 hours to obtain hydrated nickel iron fluoride (NiFeF 5 ·2H 2 O) Powders of functional nanomaterials.

Claims

1. A method for preparing hydrated nickel-iron fluoride functional nanomaterials, characterized in that: The method comprises the following preparation process: The first step is liquid phase synthesis: a solution containing a fluorine salt precursor is mixed with a solution containing an iron salt and a nickel salt precursor, and a chemical reaction occurs between the fluorine salt and the iron salt and the nickel salt to generate a precipitate of hydrated nickel iron fluoride material (NiFeF5·7H2O), which is then centrifuged and washed; the second step is solvent thermal treatment: the hydrated nickel iron fluoride material (NiFeF5·7H2O) prepared in the first step is placed in a reactor with an alcohol solvent for solvent thermal treatment; during the solvent thermal treatment, the material undergoes a process of de-crystallization water, accompanied by morphology and phase transformation, and finally a functional nanomaterial of hydrated nickel iron fluoride (NiFeF5·2H2O) is obtained.

2. The method for preparing a hydrated nickel-iron fluoride functional nanomaterial according to claim 1, characterized in that: The particle size of the hydrated nickel iron fluoride (NiFeF5·2H2O) functional nanomaterial is 0.01 nm - 500 nm; each particle is composed of several nano regions (0.1-20 nm).

3. The method for preparing a hydrated nickel-iron fluoride functional nanomaterial according to claim 1, characterized in that: The fluoride salt precursor in the liquid phase synthesis is one or two of NH4F and NH4HF2, the iron salt precursor is one or more of Fe(NO3)3·9H2O, FeCl3·6H2O, Fe(OH)(CH3COO)2, Fe2(SO4)3 and trivalent iron salts, and the nickel salt precursor is one or more of NiCl2·6H2O, NiSO4 and divalent nickel salts.

4. The method for preparing a hydrated nickel-iron fluoride functional nanomaterial according to claim 1, characterized in that: The ratio of the iron salt precursor and the nickel salt precursor in the liquid phase synthesis satisfies that the molar ratio of Fe:Ni is between 0.001:1 and 999:

1.

5. The method for preparing a hydrated nickel-iron fluoride functional nanomaterial according to claim 1, characterized in that: The solvent in the fluorine-containing salt precursor solution in the liquid phase synthesis is one or more of water, ethanol, and alcohol organic solvents; the solvent in the iron salt and nickel salt precursor solution is one or more of water, ethanol, and alcohol organic solvents.

6. The method for preparing a hydrated nickel-iron fluoride functional nanomaterial according to claim 5, characterized in that: The alcohol in the solvent thermal treatment is one or more of alcohols with hydroxyl groups (such as ethanol, ethylene glycol, glycerol).

7. The method for preparing a hydrated nickel-iron fluoride functional nanomaterial according to claim 1, characterized in that: The reaction temperature in the solvothermal treatment is 80 - 150°C.

8. The method for preparing a hydrated nickel-iron fluoride functional nanomaterial according to claim 1, characterized in that: The reaction temperature holding time in the solvent thermal treatment is 0.1-24 hours.