Preparation method of nickel-iron-based oxide / sulfide based on laterite-nickel ore and application of nickel-iron-based oxide / sulfide in field of supercapacitor
Through the nickel-iron-based oxide/sulfide preparation method based on laterite nickel ore, the application restriction of supercapacitors in fast charging and discharging and high-power energy storage systems is solved, and high specific capacitance, excellent energy storage and low-cost material preparation are achieved.
Patent Information
- Application Number
- CN202411837699.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-13
- Publication Date
- 2025-03-21
AI Technical Summary
The application of existing supercapacitors in fast charging and discharging and high-power energy storage systems is limited by their low energy density, low power density and high cost problems.
Using the preparation method of nickel-iron-based oxide/sulfide based on laterite nickel ore, pseudocapacitor-type materials with high specific capacitance are prepared through acid leaching, chemical deposition and calcining processes.
High specific capacitance, excellent energy storage properties and low-cost pseudocapacitor type materials are realized, reducing production costs and avoiding the problem of difficult separation and high cost of separation of polymetals.
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Figure CN119660821A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of pseudocapacitor electrode material preparation and supercapacitors, and specifically relates to a preparation method of nickel-iron-based oxide / sulfide based on laterite nickel ore and application thereof in the field of supercapacitors. Background Art
[0002] In recent years, the development of energy storage technologies such as supercapacitors and lithium-ion batteries has attracted widespread attention because they can solve the intermittent and instability problems of clean renewable energy such as solar energy and wind energy. Although conventional ion batteries show excellent energy storage properties, high energy density and cycle life. However, their relatively low safety, long charging time, low power density and other problems have greatly limited their application in fast charging and discharging and high-power energy storage systems. In contrast, supercapacitors, also known as electrochemical capacitors, have many advantages such as much higher energy density than traditional capacitors, higher power density than lithium-ion batteries, long cycle life, fast charging and discharging capacity, low cost, and high safety, and they occupy an important position in the requirements of specific energy and power density. Therefore, they have been further applied in smart grid variable frequency speed regulation, intermittent energy configuration of renewable energy, portable consumer electronics, computer memory systems, hybrid vehicles and electric vehicles. However, their inherent disadvantages such as low energy density also hinder their large-scale commercial application in future energy storage conversion equipment. Therefore, it is of great practical significance to use energy storage materials with ultra-high specific capacitance and excellent cycle stability with simple and fast processes and low cost.
[0003] At present, common electrode materials include three categories: carbon-based materials, organic electrode materials, and transition metal compounds. Carbon-based materials are one of the earliest developed and utilized supercapacitor electrode materials, including activated carbon, graphene, carbon nanotubes, carbon microtubes, etc.; they have the characteristics of wide source of raw materials, low price, stable chemical properties, no pollution to the environment, good conductivity, and large specific surface area. There are many types of organic conductive materials, and they come from a wide range of sources, including metal organic frameworks, conductive polymers, covalent organic frameworks, etc. However, most organic electrode materials have problems such as volume expansion or collapse, poor structural stability, and poor conductivity during energy storage. Transition metal compounds and their derivative materials have the advantages of high theoretical specific capacitance, wide sources, and simple production. They are a class of electrode materials with great research value. At present, researchers on transition metal electrode materials have found that a single transition metal compound is difficult to meet current needs, and most transition metal compounds are semiconductors, and their conductivity needs to be improved.
[0004] On the other hand, the current world economy is developing rapidly, and the consumption of nickel is expanding extremely. Due to the sharp decline in the consumption of high-grade nickel resources, the efficient and comprehensive utilization of laterite nickel ore has attracted widespread attention from researchers in the fields of metallurgy, chemical industry, and materials. New processes for its efficient treatment are constantly being proposed. Based on its own characteristics, such as clay, porosity, polymetallic, or high iron or high magnesium or high silicon, the application scenarios of laterite nickel ore are becoming more and more extensive, including catalytic hydrogenation, battery materials, sewage treatment, magnetized materials and many other fields. To this end, in order to obtain transition metal electrode materials with good conductivity, high specific capacitance, good stability and low price, seeking a simple method to develop nickel-iron-based compounds, such as oxides, sulfides, etc. as excellent pseudocapacitor materials, will have important research significance and bring huge social benefits. Summary of the invention
[0005] The main purpose of the present invention is to provide a method for preparing nickel-iron-based oxides / sulfides using limonite-type laterite nickel ore as a metal source and its application as a highly efficient and inexpensive pseudocapacitive energy storage material.
[0006] The first aspect of the present invention provides a method for preparing nickel-iron-based oxide / sulfide based on laterite nickel ore, the method comprising:
[0007] 1) crushing the ore to obtain laterite nickel ore powder;
[0008] 2) immersing the laterite nickel ore powder obtained in step 1) in an acidic solution, stirring and leaching, then performing solid-liquid separation, and collecting the supernatant;
[0009] 3) using the supernatant obtained in step 2) as a metal salt solution, adding an alkaline solution dropwise to adjust the pH value to between 8 and 9 under mechanical stirring and ultrasound assistance, performing a chemical deposition reaction, and selectively depositing the transition metal therein to obtain a precursor;
[0010] 4) The precursor material obtained in step 3) is washed with deionized water and then calcined in a tubular furnace to obtain nickel-iron-based oxides / sulfides based on limonite-type laterite nickel ore.
[0011] The above-mentioned method for preparing nickel-iron-based oxide / sulfide based on laterite nickel ore, wherein:
[0012] The laterite nickel ore is a limonite-type laterite nickel ore, the particle size of the powder after crushing is 100-350 meshes, and the ore is characterized by high iron content, with an iron oxide content of about 25%-50%.
[0013] The acidic solution in step 2) is a nitric acid solution, a hydrochloric acid solution or a sulfuric acid solution, preferably a sulfuric acid solution. Further, the concentration of the sulfuric acid solution is 0.1 mol / L to 8.9 mol / L.
[0014] The leaching temperature in step 2) is 60° C. to 120° C., the reaction time is 60 min to 200 min, and the stirring speed is 150 r / min to 600 r / min.
[0015] The alkaline solution is one or two of sodium oxalate solution, sodium carbonate solution, sodium hydroxide solution and sodium sulfide solution with a concentration of 0.005 mol / L to 3 mol / L, and the dropping rate is 0.3 mL / min to 3 mL / min.
[0016] The chemical deposition reaction is carried out in a normal pressure reactor, the stirring system is mechanical stirring plus ultrasonic composite action, the reaction temperature is 20°C to 89°C, and the reaction time is 20min to 200min.
[0017] The transition metal elements in step 3) include iron, nickel and cobalt.
[0018] The precursor may contain metals such as cobalt and manganese in the limonite-type laterite nickel ore, so it also contains corresponding metal elements.
[0019] The calcination process is completed in a tubular furnace, the calcination temperature is 180°C to 690°C, the calcination insulation time is 60min to 160min, the heating system of the calcination process is 1°C / min to 10°C / min, and the cooling system is natural cooling.
[0020] The second aspect of the present invention provides a pseudocapacitive material nickel-iron-based oxide / sulfide based on limonite-type laterite nickel ore, which is prepared according to the method described in the first aspect.
[0021] The third aspect of the present invention provides a method according to the first aspect to prepare a pseudocapacitive material nickel-iron-based oxide / sulfide based on laterite nickel ore and use it in the field of supercapacitor energy storage.
[0022] The pseudocapacitive material based on limonite-type laterite nickel ore has excellent energy storage properties in a 2 mol / L to 6 mol / L KOH system.
[0023] When the current density is 1 A / g, the specific capacitance of the pseudocapacitive material nickel-iron-based oxide / sulfide is not less than 1866 F / g.
[0024] Compared with the prior art, the present invention has the following beneficial effects:
[0025] 1. The present invention adopts a simple acid leaching-chemical deposition-calcination process, and uses the complex and difficult-to-process limonite-type nickel oxide ore as the metal source to prepare a high specific capacitance pseudocapacitive material. This method can not only provide a new idea for solving the resource utilization of limonite-type laterite nickel ore, but also obtain cheap pseudocapacitive materials, reduce costs, and have high economic value.
[0026] 2. The present invention prepares a multi-metal salt solution through a simple sulfuric acid leaching process, and then uses an ultrasonic-assisted chemical deposition method to deposit transition metal ions in the leaching solution to obtain a precursor of a nickel-iron-based oxide / sulfide material. The cleaned precursor is then calcined in a tubular furnace to obtain a pseudocapacitive material. This not only realizes the production from minerals to pseudocapacitive materials, but also effectively avoids the problem of difficult separation and high cost of separation of multi-metals in the treatment process of limonite-type laterite nickel ore.
[0027] 3. The method of the present invention has a short preparation process from ore to high specific capacity capacitor material, a simple process, a low process cost, low equipment requirements, and is easy to achieve large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS
[0028] Figure 1 Scanning electron microscope image of laterite nickel ore.
[0029] Figure 2 Chemical composition analysis results of laterite nickel ore.
[0030] Figure 3 Schematic diagram of the preparation process of nickel-iron-based oxide / sulfide materials based on limonite-type laterite nickel ore.
[0031] Figure 4 Cyclic voltammetry curves of the nickel-iron-based oxide prepared in Example 1 at different scan rates.
[0032] Figure 5 Constant current charging curves of the nickel-iron-based oxide prepared in Example 1 at different scan rates. DETAILED DESCRIPTION
[0033] The present invention discloses a method for preparing nickel-iron-based oxide / sulfide based on limonite-type laterite nickel ore, such as Figure 3 As shown, the specific steps are as follows:
[0034] 1) treating limonite-type laterite nickel ore to obtain laterite nickel ore powder, the particle size of which is 100-350 meshes; the limonite-type laterite nickel ore has an iron oxide content of 25%-50%; the scanning electron microscope of the laterite nickel ore is as follows: Figure 1 As shown in Figure 2, the chemical composition analysis results of laterite nickel ore are as follows: Figure 2 As shown;
[0035] 2) soaking the laterite nickel ore powder obtained in step 1) in a 0.1 mol / L to 8.9 mol / L acidic solution and stirring for leaching at a leaching temperature of 60° C. to 120° C., a reaction time of 60 min to 200 min, and a stirring speed of 150 r / min to 600 r / min, then performing solid-liquid separation and collecting the supernatant;
[0036] 3) using the supernatant obtained in step 2) as a metal salt solution, adjusting the pH of the system with an alkaline solution having a concentration of 0.005 mol / L to 3 mol / L under stirring and ultrasound assistance to perform a chemical deposition reaction, the reaction temperature being 20° C. to 89° C., the reaction time being 20 min to 200 min, and the drop rate being 0.3 mL / min to 3 mL / min, to obtain a precursor;
[0037] 4) washing the precursor with deionized water and then calcining it. The calcination process is completed in a tubular furnace. The calcination temperature is 180° C. to 690° C., the calcination time is 60 min to 160 min, the heating system of the calcination process is 1° C. / min to 10° C. / min, and the cooling system is natural cooling to obtain the nickel-iron-based oxide / sulfide based on laterite nickel ore.
[0038] Example 1
[0039] Take 20g of 120 mesh limonite-type laterite nickel ore powder and mix it with 60mL of 6mol / L sulfuric acid solution, then stir it in an oil bath at 390r / min for 59min, and the oil bath temperature is 110℃. After the leaching is completed, solid-liquid separation is performed and the supernatant is collected. Then the beaker containing the leaching solution is placed in an ultrasonic cleaning machine, and under the action of mechanical stirring, the pH of the system is adjusted to 8 with 1.0mol / L sodium oxalate solution, and chemical deposition is performed. The reaction temperature is 89℃, the reaction time is 20min, and the drop rate is 0.3mL / min. After the obtained metal oxalate precursor is cleaned with deionized water, the precursor is placed in a porcelain boat and calcined at 350℃ in a tube furnace for 120min. The heating system during the calcination process is 5℃ / min. After the calcination is completed, the nickel-iron-based oxide material is obtained. Figure 4 The cyclic voltammetry curves of the nickel-iron-based oxide prepared in Example 1 at different scan rates. Figure 5 The constant current charging curves of the nickel-iron-based oxide prepared in Example 1 at different scan rates. The pseudocapacitive material based on limonite-type laterite nickel ore has excellent energy storage properties in a 2mol / L to 6mol / L KOH system. When the current density is 1A / g, the specific capacitance of the pseudocapacitive material nickel-iron-based oxide is 1866F / g.
[0040] Example 2
[0041] Take 20g of 120 mesh limonite-type laterite nickel ore powder and mix it with 60mL of 6mol / L sulfuric acid solution, then stir it in an oil bath at 390r / min for 59min, and the oil bath temperature is 110℃. After the leaching is completed, solid-liquid separation is performed and the supernatant is collected. Then the beaker containing the leaching solution is placed in an ultrasonic cleaning machine, and under the action of mechanical stirring, the pH of the system is adjusted to 8.9 with 2.0mol / L sodium carbonate solution for chemical deposition. The reaction temperature is 80℃, the reaction time is 30min, and the drop rate is 1.0mL / min. After the obtained metal carbonate precursor is cleaned with deionized water, the precursor is placed in a porcelain boat and calcined at 600℃ in a tube furnace for 150min. The heating system during the calcination process is 5℃ / min. After the calcination is completed, the nickel-iron-based oxide material is obtained.
[0042] Example 3
[0043] Take 16g of 120 mesh limonite-type laterite nickel ore powder and mix it with 60mL of 5mol / L sulfuric acid solution, then stir it in an oil bath at 390r / min for 90min, and the oil bath temperature is 110℃. After the leaching is completed, solid-liquid separation is performed and the supernatant is collected. Then the beaker containing the leaching solution is placed in an ultrasonic cleaning machine, and under the action of mechanical stirring, the pH of the system is adjusted to 8.9 with 3mol / L sodium sulfide solution for chemical deposition. The reaction temperature is 60℃, the reaction time is 169min, and the drop rate is 2.5mL / min. After the obtained metal sulfide salt precursor is cleaned with deionized water, the precursor is placed in a porcelain boat and calcined at 200℃ in a tube furnace for 120min. The heating system of the calcination process is 6℃ / min. After the calcination is completed, the nickel-iron-based sulfide material is obtained.
[0044] Example 4
[0045] Take 16g of 120 mesh limonite-type laterite nickel ore powder and mix it with 60mL of 7mol / L sulfuric acid solution, then stir it in an oil bath at 390r / min for 90min, and the oil bath temperature is 110℃. After the leaching is completed, solid-liquid separation is performed and the supernatant is collected. Then the beaker containing the leaching solution is placed in an ultrasonic cleaning machine, and under the action of mechanical stirring, the pH of the system is adjusted to 8 with a mixed solution of 0.5mol / L sodium carbonate and 0.5mol / L sodium hydroxide for chemical deposition. The reaction temperature is 60℃, the reaction time is 120min, and the drop rate is 1.5mL / min. After the obtained metal carbonate precursor is cleaned with deionized water, the precursor is placed in a porcelain boat and calcined at 590℃ in a tube furnace for 120min. The heating system during the calcination process is 6℃ / min. After the calcination is completed, the nickel-iron-based oxide material is obtained.
[0046] The present invention has been described through the above embodiments, but it should be understood that the above embodiments are only for the purpose of example and description, and are not intended to limit the present invention to the scope of the described embodiments. In addition, it can be understood by those skilled in the art that the present invention is not limited to the above embodiments, and more variations and modifications can be made according to the teachings of the present invention, and these variations and modifications all fall within the scope of the protection claimed by the present invention.
Claims
1. A method for preparing nickel-iron-based oxides / sulfides based on laterite nickel ore, characterized in that: The following steps are involved: 1) crushing the ore to obtain laterite nickel ore powder; 2) immersing the laterite nickel ore powder obtained in step 1) in an acidic solution, stirring and leaching, then performing solid-liquid separation, and collecting the supernatant; 3) using the supernatant obtained in step 2) as a metal salt solution, adding an alkaline solution dropwise to adjust the pH value to between 8 and 9 under mechanical stirring and ultrasound assistance, performing a chemical deposition reaction, and selectively depositing the transition metal therein to obtain a precursor; 4) The precursor material obtained in step 3) is washed with deionized water and then calcined in a tubular furnace to obtain nickel-iron-based oxides / sulfides based on limonite-type laterite nickel ore.
2. The method for preparing nickel-iron-based oxide / sulfide based on laterite nickel ore according to claim 1, characterized in that: The laterite nickel ore used is limonite-type laterite nickel ore, and the particle size of the powder after crushing is 100-350 meshes, and the characteristic is high iron content, and the iron oxide content is 25%-50%.
3. The method for preparing nickel-iron-based oxide / sulfide based on laterite nickel ore according to claim 1, characterized in that: The acidic solution is a nitric acid solution, a hydrochloric acid solution or a sulfuric acid solution, and the concentration of the acidic solution is 0.1 mol / L to 8.9 mol / L.
4. The method for preparing nickel-iron-based oxide / sulfide based on laterite nickel ore according to claim 1, characterized in that: In the step 2), the leaching temperature is 60° C. to 120° C., the reaction time is 60 min to 200 min, and the stirring speed is 150 r / min to 600 r / min.
5. The method for preparing nickel-iron-based oxide / sulfide based on laterite nickel ore according to claim 1, characterized in that: The alkaline solution is one or two of sodium oxalate solution, sodium carbonate solution, sodium hydroxide solution and sodium sulfide solution with a concentration of 0.005 mol / L to 3 mol / L, and the dropping rate is 0.3 mL / min to 3 mL / min.
6. The method for preparing nickel-iron-based oxide / sulfide based on laterite nickel ore according to claim 1, characterized in that: The chemical deposition reaction is carried out in a normal pressure reactor, the reaction temperature is 20° C. to 89° C., and the reaction time is 20 min to 200 min.
7. The method for preparing nickel-iron-based oxides / sulfides based on laterite nickel ore according to claim 1, characterized in that: The calcination process is completed in a tubular furnace, the calcination temperature is 180°C to 690°C, the calcination holding time is 60min to 160min, the heating system of the calcination process is 1°C / min to 10°C / min, and the cooling system is natural cooling.
8. A pseudocapacitive material based on limonite-type laterite nickel ore, characterized in that: The nickel-iron-based oxide / sulfide is prepared by the method for preparing nickel-iron-based oxide / sulfide based on laterite nickel ore according to any one of claims 1 to 7.
9. Application of the pseudocapacitive material based on limonite-type laterite nickel ore as claimed in claim 8 in the field of supercapacitor energy storage.
10. The use according to claim 9, characterized in that: The pseudocapacitive material has energy storage properties in a 2mol / L to 6mol / L KOH system. When the current density is 1A / g, the specific capacitance of the pseudocapacitive material is not less than 1866F / g.