CN116282219A - Method for preparing nickel-iron-manganese ternary precursor for sodium ions through process stabilization - Google Patents
Method for preparing nickel-iron-manganese ternary precursor for sodium ions through process stabilization Download PDFInfo
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- CN116282219A CN116282219A CN202310195227.5A CN202310195227A CN116282219A CN 116282219 A CN116282219 A CN 116282219A CN 202310195227 A CN202310195227 A CN 202310195227A CN 116282219 A CN116282219 A CN 116282219A
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- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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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
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- 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 a nickel-iron-manganese ternary precursor for sodium ions by stable process, belonging to the technical field of lithium battery material preparation. The invention comprises the following steps: (1) dissolving nickel sulfate and manganese sulfate in pure water according to a certain proportion to form a metal salt mixed solution A; (2) preparing a mixed solution B with a certain concentration by an iron source and a complexing agent, and adding a proper amount of dilute sulfuric acid into the solution to regulate ph; (3) mixing the mixed solution A, B and sodium hydroxide solution into a reaction kettle, and simultaneously introducing protective gas into the reaction kettle according to a certain flow; keeping the temperature in the kettle constant, adjusting ph, and performing coprecipitation reaction to obtain nickel-iron-manganese ternary precursor slurry; and (3) ageing, centrifuging, washing and drying the slurry to obtain the nickel-iron-manganese ternary precursor.
Description
Technical Field
The invention relates to the technical field of lithium ion battery preparation, in particular to a method for preparing a nickel-iron-manganese ternary precursor for sodium ions by a process stability.
Background
The energy storage plays a role in core and support for the national energy structure optimization and the national power grid safe operation in the national strategic demand layout. The large-scale energy storage technology is the basis of new energy popularization and energy revolution, is an important component part of national energy strategy demand layout, and has important roles in national energy structure optimization and safe and stable operation of a power grid.
The current electrochemical energy storage technology comprises lithium ion batteries, sodium ion batteries, lead storage batteries, sodium-sulfur batteries and the like. Na is the same main group as Li, and the physicochemical properties of the two are similar. The Na abundance is high, the reserves are very rich, and the sodium resources are distributed in various places worldwide and are not limited by regions. Development of sodium ion batteries can avoid development bottleneck problems caused by resource shortage. Therefore, the sodium ion battery is considered as a revolutionary technology in the field of large-scale energy storage, has quite optimistic industrialization prospect and has important economic value and strategic significance.
Currently, layered transition metal oxides are attracting attention because of their higher capacity and excellent cycle performance; the most representative nickel-iron-manganese ternary material is more mature one in the research.
Patent CN115188958A describes a method for preparing a ternary material of copper, iron and manganese for sodium ion batteries. The method comprises the steps of preparing a solution from chlorides of copper, iron and manganese, performing hydrothermal reaction on the solution and glycerin to obtain a carbonate precursor, pre-sintering the carbonate precursor to obtain an oxide, and finally mixing the oxide with sodium carbonate and performing high-temperature sintering to obtain the copper-iron sodium manganate anode material. The method has the problems that the chloride is adopted, the requirement on later-stage equipment is high, and the steps are complicated, so that the method is not suitable for industrial production.
Patent CN115196691a describes a method for preparing a precursor of nickel-iron-manganese for sodium ion batteries. Similar to the traditional method for preparing the nickel-cobalt-manganese ternary precursor for lithium ions, the nickel-iron-manganese ternary precursor is prepared by a high ph nucleation and low ph growth method. Because ferrous ions are extremely easy to generate oxidation reaction under the environment of high ph, the oxidation is difficult to be completely avoided by the protection of pure inert gas, and after the slurry is oxidized, the coprecipitation reaction is out of control, particles are stagnant and expand, so that the production batch is unstable.
In order to solve the problems that the nickel-iron-manganese precursor is easy to oxidize in the preparation process and three elements are difficult to co-precipitate because ammonia water does not form a complex with iron ions, the invention provides a method for preparing a nickel-iron-manganese ternary precursor for sodium ions by a stable process.
The invention mainly comprises the following steps: 1. the ferrous salt solution ph is regulated, and ferrous ions are not easy to oxidize under the condition of low ph, so that the oxidation of slurry in a reaction kettle caused by the oxidation of raw materials is effectively avoided; 2. preparing ferrous salt and complexing agent into mixed solution, complexing ferrous ion in advance, solving the problem that iron ion cannot form complex with ammonia water to cause coprecipitation; 3. ammonia is used for replacing the conventional inert gas for protection, the ammonia is recycled, the production cost is reduced, and the production process is more stable.
Disclosure of Invention
The invention hopefully provides a method for preparing a nickel-iron-manganese ternary precursor for sodium ions by a process stability. The preparation method has stable process control, spherical porous structure and great cost advantage; has the general formula (Ni) x Fe y Mn z ）OH 2 Wherein 0 < x.ltoreq.5, y > 0, z > 0, x+y+z=1. The specific scheme is as follows:
the method for preparing the ternary precursor of nickel, iron and manganese for sodium ions by stable process comprises the following steps:
(1) Dissolving nickel sulfate and manganese sulfate in pure water to form a metal salt mixed solution A;
(2) Preparing a mixed solution B from an iron source and a complexing agent, and adding a proper amount of dilute sulfuric acid into the solution to regulate ph;
(3) Preparing a base solution in a reaction kettle, and mixing the mixed solution A, B with sodium hydroxide solutionAnd flow into the reaction kettle, and meanwhile, protective gas is introduced into the reaction kettle; keeping the temperature in the kettle constant, and adjusting ph and ammonia concentration in the kettle, wherein the ammonia concentration in the kettle is 2-10g/L; performing coprecipitation reaction to obtain nickel-iron-manganese ternary precursor slurry; ageing, centrifuging, washing and drying the slurry to obtain a nickel-iron-manganese ternary precursor; the general formula of the nickel-iron-manganese ternary precursor is (Ni x Fe y Mn z ）OH 2 Wherein 0 < x.ltoreq.5, y > 0, z > 0, x+y+z=1.
The iron source in the step (2) is one or more of ferrous sulfate, ferrous chloride, ferrous nitrate and ferrous oxalate. Further preferred iron sources are ferrous sulfate.
The complexing agent in the step (2) is one or more of EDTA, EDTA-2Na, citric acid and sodium citrate. Further preferred complexing agents are EDTA-2Na.
The concentration of the iron ions in the step (2) is 0.5-1.5mol/L, and the concentration of the complexing agent is 1-10g/L.
And (3) adjusting ph in the step (2) to be 1-5.
The protective gas in the step (3) is ammonia.
The concentration of ammonia in the kettle in the step (3) is 5-10g/L.
The mass ratio of nickel to manganese in the step (1) is 20:40.
The temperature in the kettle in the step (3) is 40-70 ℃, and the PH is 11.3-11.8.
The preparation method provided by the invention can effectively solve the problems of particle stagnation and poor morphology caused by oxidation of the nickel-iron-manganese precursor in the slurry in the preparation process; meanwhile, nitrogen is replaced by ammonia, part of the ammonia is dissolved in water to form ammonia water after entering the reaction kettle, so that the ammonia is easier to disperse, the ammonia concentration is easier to control, the nitrogen cost is saved, and overflowed ammonia can be recycled.
Drawings
FIG. 1 is a scanning electron microscope image of a nickel-manganese ternary precursor prepared in example 1;
FIG. 2 is a graph showing the particle size distribution of the ternary nickel-iron-manganese precursor prepared in example 1.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments.
Example 1
Respectively weighing nickel sulfate and manganese sulfate according to the nickel-manganese metal ratio (mass) of 20:40, and dissolving the nickel sulfate and the manganese sulfate in pure water to prepare a mixed metal salt solution A with the concentration of 1.5 mol/L. Preparing a ferrous sulfate solution B with the concentration of 1mol/L, adding EDTA-2Na according to the concentration of 2g/L, and simultaneously dripping dilute sulfuric acid to adjust the ph of the solution to 3; adding 35L of pure water and sodium hydroxide solution into a 50L reaction kettle until ph is 11.5, and continuously introducing ammonia gas into the reaction kettle until the concentration of the bottom liquid ammonia is 5g/L; mixing the mixed solution A, B and sodium hydroxide solution according to a set flow, flowing into a reaction kettle, measuring the ammonia concentration in the kettle, and maintaining the ammonia concentration in the kettle to be 5g/L by adjusting the flow of ammonia; and (3) keeping the temperature in the reaction kettle constant at 50 ℃, automatically controlling the flow of sodium hydroxide to adjust ph to 11.3 by an online system, enabling particles to uniformly grow, aging, centrifuging, washing and drying the slurry when the particles grow to the target granularity of 6.0 mu m, and obtaining the nickel-iron-manganese ternary precursor.
Example 2
Respectively weighing nickel sulfate and manganese sulfate according to a nickel-manganese metal ratio of 20:40, and dissolving the nickel sulfate and the manganese sulfate in pure water to prepare a mixed metal salt solution A with a mol/L of 1.8. Preparing a ferrous sulfate solution B with the concentration of 1mol/L, adding EDTA-2Na according to the concentration of 3g/L, and simultaneously dripping dilute sulfuric acid to adjust the ph of the solution to 3; adding 35L of pure water and sodium hydroxide solution into a 50L reaction kettle until ph is 11.5, and continuously introducing ammonia gas into the reaction kettle until the concentration of the bottom liquid ammonia is 5g/L; mixing the mixed solution A, B and sodium hydroxide solution according to a set flow, flowing into a reaction kettle, measuring the ammonia concentration in the kettle, and maintaining the ammonia concentration in the kettle to be 5g/L by adjusting the flow of ammonia; and (3) keeping the temperature in the reaction kettle constant at 50 ℃, automatically controlling the flow of sodium hydroxide to adjust ph to 11.5 by an online system, enabling particles to uniformly grow, aging, centrifuging, washing and drying the slurry when the particles grow to the target granularity of 6.0 mu m, and obtaining the nickel-iron-manganese ternary precursor.
Example 3
Respectively weighing nickel sulfate and manganese sulfate according to a nickel-manganese metal ratio of 20:40, and dissolving the nickel sulfate and the manganese sulfate in pure water to prepare a mixed metal salt solution A with the concentration of 2.0 mol/L. Preparing a ferrous sulfate solution B with the concentration of 1mol/L, adding EDTA-2Na according to the concentration of 5g/L, and simultaneously dripping dilute sulfuric acid to adjust the ph of the solution to 3; adding 35L of pure water and sodium hydroxide solution into a 50L reaction kettle until ph is 11.5, and continuously introducing ammonia gas into the reaction kettle until the concentration of the bottom liquid ammonia is 10g/L; mixing the mixed solution A, B and sodium hydroxide solution according to a set flow, flowing into a reaction kettle, measuring the ammonia concentration in the kettle, and maintaining the ammonia concentration in the kettle to be 10g/L by adjusting the flow of ammonia; and (3) keeping the temperature in the reaction kettle constant at 50 ℃, automatically controlling the flow of sodium hydroxide to adjust ph to 11.8 by an online system, enabling particles to uniformly grow, aging, centrifuging, washing and drying the slurry when the particles grow to the target granularity of 6.0 mu m, and obtaining the nickel-iron-manganese ternary precursor.
Example 4
Respectively weighing nickel sulfate and manganese sulfate according to a nickel-manganese metal ratio of 33:33, and dissolving the nickel sulfate and the manganese sulfate in pure water to prepare a mixed metal salt solution A with the concentration of 2.0 mol/L. Preparing a ferrous sulfate solution B with the concentration of 1mol/L, adding EDTA-2Na according to the concentration of 5g/L, and simultaneously dripping dilute sulfuric acid to adjust the ph of the solution to 3; adding 35L of pure water and sodium hydroxide solution into a 50L reaction kettle until ph is 11.7, and continuously introducing ammonia gas into the reaction kettle until the concentration of the bottom liquid ammonia is 10g/L; mixing the mixed solution A, B and sodium hydroxide solution according to a set flow, flowing into a reaction kettle, measuring the ammonia concentration in the kettle, and maintaining the ammonia concentration in the kettle to be 10g/L by adjusting the flow of ammonia; and (3) keeping the temperature in the reaction kettle constant at 55 ℃, automatically controlling the flow of sodium hydroxide to adjust ph to 11.3 by an online system, enabling particles to uniformly grow, aging, centrifuging, washing and drying the slurry when the particles grow to the target granularity of 6.0 mu m, and obtaining the nickel-iron-manganese ternary precursor.
Example 5
Respectively weighing nickel sulfate and manganese sulfate according to a nickel-manganese metal ratio of 40:40, and dissolving the nickel sulfate and the manganese sulfate in pure water to prepare a mixed metal salt solution A with the concentration of 2.0 mol/L. Preparing a ferrous sulfate solution B with the concentration of 1mol/L, adding EDTA-2Na according to the concentration of 5g/L, and simultaneously dripping dilute sulfuric acid to adjust the ph of the solution to 3; adding 35L of pure water and sodium hydroxide solution into a 50L reaction kettle until ph is 11.8, and continuously introducing ammonia gas into the reaction kettle until the concentration of the bottom liquid ammonia is 10g/L; mixing the mixed solution A, B and sodium hydroxide solution according to a set flow, flowing into a reaction kettle, measuring the ammonia concentration in the kettle, and maintaining the ammonia concentration in the kettle to be 10g/L by adjusting the flow of ammonia; and (3) keeping the temperature in the reaction kettle constant at 55 ℃, automatically controlling the flow of sodium hydroxide to adjust ph to 11.5 by an online system, enabling particles to uniformly grow, aging, centrifuging, washing and drying the slurry when the particles grow to the target granularity of 6.0 mu m, and obtaining the nickel-iron-manganese ternary precursor.
Example 6
Respectively weighing nickel sulfate and manganese sulfate according to a nickel-manganese metal ratio of 20:30, and dissolving the nickel sulfate and the manganese sulfate in pure water to prepare a mixed metal salt solution A with the concentration of 2.0 mol/L. Preparing a ferrous sulfate solution B with the concentration of 1.5mol/L, adding EDTA-2Na according to the concentration of 5g/L, and simultaneously dripping dilute sulfuric acid to adjust the ph of the solution to 3; adding 35L of pure water and sodium hydroxide solution into a 50L reaction kettle until ph is 11.2, and continuously introducing ammonia gas into the reaction kettle until the concentration of the bottom liquid ammonia is 10g/L; mixing the mixed solution A, B and sodium hydroxide solution according to a set flow, flowing into a reaction kettle, measuring the ammonia concentration in the kettle, and maintaining the ammonia concentration in the kettle to be 10g/L by adjusting the flow of ammonia; and (3) keeping the temperature in the reaction kettle constant at 55 ℃, automatically controlling the flow of sodium hydroxide to adjust ph to 11.8 by an online system, enabling particles to uniformly grow, aging, centrifuging, washing and drying the slurry when the particles grow to the target granularity of 6.0 mu m, and obtaining the nickel-iron-manganese ternary precursor.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (9)
1. A method for preparing a nickel-iron-manganese ternary precursor for sodium ions through process stabilization is characterized by comprising the following steps of:
(1) Dissolving nickel sulfate and manganese sulfate in pure water to form a metal salt mixed solution A;
(2) Preparing a mixed solution B from an iron source and a complexing agent, and adding dilute sulfuric acid into the solution to regulate ph;
(3) Preparing a base solution in a reaction kettle, allowing a mixed solution A, B and a sodium hydroxide solution to flow into the reaction kettle, and simultaneously introducing protective gas into the reaction kettle; keeping the temperature in the kettle constant, and adjusting ph and ammonia concentration in the kettle, wherein the ammonia concentration in the kettle is 2-10g/L; performing coprecipitation reaction to obtain nickel-iron-manganese ternary precursor slurry; ageing, centrifuging, washing and drying the slurry to obtain a nickel-iron-manganese ternary precursor;
the general formula of the nickel-iron-manganese ternary precursor is (Ni x Fe y Mn z ）OH 2 Wherein 0 < x.ltoreq.5, y > 0, z > 0, x+y+z=1.
2. The method for preparing the ternary nickel-iron-manganese precursor for sodium ions through process stabilization according to claim 1, wherein the method comprises the following steps of: the iron source in the step (2) is one or more of ferrous sulfate, ferrous chloride, ferrous nitrate and ferrous oxalate.
3. The method for preparing the ternary nickel-iron-manganese precursor for sodium ions through process stabilization according to claim 1, wherein the method comprises the following steps of: the complexing agent in the step (2) is one or more of EDTA, EDTA-2Na, citric acid and sodium citrate.
4. The method for preparing the ternary nickel-iron-manganese precursor for sodium ions through process stabilization according to claim 1, wherein the method comprises the following steps of: the concentration of the iron ions in the step (2) is 0.5-1.5mol/L, and the concentration of the complexing agent is 1-10g/L.
5. The method for preparing the ternary nickel-iron-manganese precursor for sodium ions through process stabilization according to claim 1, wherein the method comprises the following steps of: and (3) adjusting ph in the step (2) to be 1-5.
6. The method for preparing the ternary nickel-iron-manganese precursor for sodium ions through process stabilization according to claim 1, wherein the method comprises the following steps of: the protective gas in the step (3) is ammonia.
7. The method for preparing the ternary nickel-iron-manganese precursor for sodium ions through process stabilization according to claim 1, wherein the method comprises the following steps of: the concentration of ammonia in the kettle in the step (3) is 5-10g/L.
8. The method for preparing the ternary nickel-iron-manganese precursor for sodium ions through process stabilization according to claim 1, wherein the method comprises the following steps of: the mass ratio of nickel to manganese in the step (1) is 20:40.
9. The method for preparing the ternary nickel-iron-manganese precursor for sodium ions through process stabilization according to claim 1, wherein the method comprises the following steps of: the temperature in the kettle in the step (3) is 40-70 ℃, and the PH is 11.3-11.8.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116621234A (en) * | 2023-07-20 | 2023-08-22 | 宜宾光原锂电材料有限公司 | Sodium ion positive electrode material precursor, preparation method and positive electrode material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116621234A (en) * | 2023-07-20 | 2023-08-22 | 宜宾光原锂电材料有限公司 | Sodium ion positive electrode material precursor, preparation method and positive electrode material |
| CN116621234B (en) * | 2023-07-20 | 2023-11-07 | 宜宾光原锂电材料有限公司 | Sodium ion positive electrode material precursor, preparation method and positive electrode material |
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