CN113044892A - Preparation method of nickel manganese oxide - Google Patents
Preparation method of nickel manganese oxide Download PDFInfo
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- CN113044892A CN113044892A CN202110262156.7A CN202110262156A CN113044892A CN 113044892 A CN113044892 A CN 113044892A CN 202110262156 A CN202110262156 A CN 202110262156A CN 113044892 A CN113044892 A CN 113044892A
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Abstract
The invention belongs to the field of energy storage materials and electrochemistry, and particularly relates to a preparation method of nickel-manganese oxide. Aiming at the problems of more complex reaction process, longer flow and the like in the prior art. The invention provides a method which is simple, has less control conditions and can quickly prepare a high-quality precursor. The method takes manganous-manganic oxide as a template, only nickel hydroxide is deposited on the surface of the manganous-manganic oxide, the water consumption is low, the ammonia water consumption is low, and the ammonia nitrogen removal cost is low. The product of the nickel oxide manganese material obtained after high-temperature sintering has controllable particle size and high tap density.
Description
Technical Field
The invention belongs to the field of energy storage materials and electrochemistry, and particularly relates to a preparation method of nickel manganese oxide as a precursor of lithium nickel manganese oxide and a lithium-rich manganese-based positive electrode material.
Background
Commercial lithium nickel manganese oxide and lithium-rich manganese-based cathode materials are generally prepared by mixing a precursor and a lithium salt in a high-temperature environment through a solid-phase reaction. The performance of the precursor determines a plurality of key indexes of the anode material. Such as: the compact density, the particle size distribution, the specific surface area and the like, and the precursor structure also determines the synthesis process of the material. Has important significance for the production of anode materials.
The industrialized precursor preparation technology is mainly a chemical coprecipitation method. The metal salt solution, the complexing agent and the precipitant solution are prepared by chemical reaction under certain conditions under the condition of parallel flow. For lithium nickel manganese oxide and lithium-rich manganese-based positive electrode materials, there are two general types, one is hydroxide precipitation, and the other is carbonate precipitation. The reaction principle is simple, namely general displacement reaction, but the reaction process is relatively complex and the flow is relatively long.
The coprecipitation method has longer flow, more influence factors and more key points which need to be controlled to obtain qualified products. The industrial production has certain difficulty, a large amount of water needs to be wasted in the chemical coprecipitation, a large amount of ammonia water needs to be used as a complexing agent, and the cost for removing ammonia nitrogen in the wastewater in the later period is high.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of nickel manganese oxide, which is a precursor of a nickel lithium manganate and lithium-rich manganese-based positive electrode material, and the method is simple, has less control conditions and is beneficial to quickly preparing a high-quality precursor.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of nickel manganese oxide, which comprises the following steps:
step 2, fully dissolving sodium hydroxide in pure water to prepare an alkali solution with the concentration of 4 mol/L;
step 3, adding manganous-manganic oxide into the reaction kettle to prepare suspension with 50% of solid content;
step 4, adding the salt solution prepared in the step 1, the alkali solution prepared in the step 2 and a complexing agent into the reaction kettle containing the manganous-manganic oxide suspension in the step 3 in a parallel flow manner, fully stirring the slurry in the reaction kettle for reaction, standing the slurry after the reaction is finished to form a converted slurry, filtering the slurry obtained after standing the converted slurry, washing the slurry with water, and drying the slurry to obtain a semi-finished product;
and 5, putting the dried semi-finished product into a pot for sintering, and performing subsequent treatment procedures of crushing, batch mixing, demagnetizing, packaging and the like on the sintered material to obtain the nickel-manganese oxide.
Further, the molecular formula of the nickel manganese oxide is Mn1.5Ni0.5O2The crystal structure is a spinel structure.
Further, the volume ratio of the salt solution, the alkali solution and the complexing agent added into the reaction kettle in the step 4 is 1: 1: 1.
further, the stirring speed in the step 4 is 200-800 r/min, the reaction temperature is 40-60 ℃, and the reaction time is 2-8 h.
Further, the standing and forming time of the step 4 is 2-8 hours.
Further, the sintering temperature in the step 5 is 700-1200 ℃, and the sintering time is 1-5 h.
Further, the nickel salt in the step 1 comprises nickel nitrate, nickel sulfate and nickel chloride.
Further, the trimanganese tetroxide in the step 3 is battery grade trimanganese tetroxide with a purity of 99% or more.
Further, the complexing agent in the step 4 is ammonia water, and the concentration of the ammonia water is 1 mol/L.
Compared with the prior art, the invention has the following advantages:
the method has the advantages that the manganous-manganic oxide is taken as the template, only nickel hydroxide is deposited on the surface of the manganous-manganic oxide, the water consumption is low, the ammonia water consumption is low, and the ammonia nitrogen removal cost is low. The product of the nickel oxide manganese material obtained after high-temperature sintering has controllable particle size and high tap density.
Drawings
Fig. 1 is a photograph of a scan of nickel manganese oxide.
Figure 2 is a nickel manganese oxide XRD pattern.
Detailed Description
The technical solution in the embodiments of the present invention will be specifically and specifically described below with reference to the embodiments of the present invention and the accompanying drawings.
Example 1
Preparation of nickel manganese oxide:
(1) fully dissolving battery-grade nickel nitrate in pure water to prepare a salt solution with the concentration of 2 mol/L;
(2) fully dissolving sodium hydroxide in pure water to prepare an alkali solution with the concentration of 4 mol/L;
(3) adding battery grade manganous-manganic oxide with the purity of more than 99 percent into a reaction kettle to prepare suspension with the solid content of 50 percent;
(4) according to the volume ratio of 1: 1: 1 adding the salt solution, the alkali solution and the complexing agent ammonia water with the concentration of 1mol/L into a reaction kettle containing manganous-manganic oxide turbid liquid in a cocurrent flow mode, fully stirring the slurry in the reaction kettle for 8 hours at 40 ℃ at 200 r/min to react, standing for 8 hours after the reaction is finished to form slurry, filtering the slurry which is kept standing for forming, washing with water, and drying to obtain a semi-finished product.
(5) And (3) putting the dried semi-finished product into a pot, sintering for 5 hours at 700 ℃, and performing subsequent treatment procedures of crushing, batch mixing, demagnetizing, packaging and the like on the sintered material to obtain the nickel-manganese oxide.
Example 2
Preparation of nickel manganese oxide:
(1) fully dissolving a mixture of battery-grade nickel nitrate and nickel sulfate in any proportion in pure water to prepare a salt solution with the concentration of 2 mol/L;
(2) fully dissolving sodium hydroxide in pure water to prepare an alkali solution with the concentration of 4 mol/L;
(3) adding battery grade manganous-manganic oxide with the purity of more than 99 percent into a reaction kettle to prepare suspension with the solid content of 50 percent;
(4) according to the volume ratio of 1: 1: 1, adding the salt solution, the alkali solution and complexing agent ammonia water with the concentration of 1mol/L into a reaction kettle containing manganous-manganic oxide suspension in a cocurrent flow manner, fully stirring slurry in the reaction kettle at 60 ℃ at 800 r/min for 2 hours to react, standing for forming slurry for 2 hours after the reaction is finished, filtering the standing formed slurry, washing with water, and drying to obtain a semi-finished product;
(5) and (3) putting the dried semi-finished product into a pot, sintering for 1h at 1200 ℃, and performing subsequent treatment procedures of crushing, batch mixing, demagnetizing, packaging and the like on the sintered material to obtain the nickel-manganese oxide.
Example 3
Preparation of nickel manganese oxide:
(1) fully dissolving a mixture of battery-grade nickel nitrate, nickel sulfate and nickel chloride in any proportion in pure water to prepare a salt solution with the concentration of 2 mol/L;
(2) fully dissolving sodium hydroxide in pure water to prepare an alkali solution with the concentration of 4 mol/L;
(3) adding battery grade manganous-manganic oxide with the purity of more than 99 percent into a reaction kettle to prepare suspension with the solid content of 50 percent;
(4) according to the volume ratio of 1: 1: 1, adding the salt solution, the alkali solution and complexing agent ammonia water with the concentration of 1mol/L into a reaction kettle containing manganous-manganic oxide suspension in a cocurrent flow manner, fully stirring slurry in the reaction kettle for 4 hours at 50 ℃ at 500 r/min to react, standing for 5 hours after the reaction is finished to form slurry, filtering the slurry subjected to standing for forming, washing with water, and drying to obtain a semi-finished product;
(5) and (3) putting the dried semi-finished product into a pot, sintering for 2h at 1100 ℃, and performing subsequent treatment procedures of crushing, batch mixing, demagnetizing, packaging and the like on the sintered material to obtain the nickel-manganese oxide.
Example 4
Preparation of nickel manganese oxide:
(1) fully dissolving battery-grade nickel chloride in pure water to prepare a salt solution with the concentration of 2 mol/L;
(2) fully dissolving sodium hydroxide in pure water to prepare an alkali solution with the concentration of 4 mol/L;
(3) adding battery grade manganous-manganic oxide with the purity of more than 99 percent into a reaction kettle to prepare suspension with the solid content of 50 percent;
(4) according to the volume ratio of 1: 1: 1, adding the salt solution, the alkali solution and the complexing agent ammonia water into a reaction kettle containing manganous-manganic oxide turbid liquid in a cocurrent flow manner, fully stirring slurry in the reaction kettle at 55 ℃ at 750 revolutions per minute for 3 hours to react, standing for 3 hours after the reaction is finished to form slurry, filtering the slurry which is kept standing for forming, washing with water, and drying to obtain a semi-finished product;
(5) and (3) putting the dried semi-finished product into a pot, sintering for 4 hours at 800 ℃, and performing subsequent treatment procedures of crushing, batch mixing, demagnetizing, packaging and the like on the sintered material to obtain the nickel-manganese oxide.
The molecular formula of the nickel manganese oxide prepared in the above embodiment is Mn1.5Ni0.5O2The crystal structure is a spinel structure.
It should be noted that the embodiment of the present invention is not limited by the above-mentioned embodiment, and those skilled in the art can make several modifications and improvements without departing from the principle of the present invention, and all of them are included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the nickel manganese oxide is characterized by comprising the following steps of:
step 1, fully dissolving one or a mixture of at least two of battery-grade nickel salts in any proportion in pure water to prepare a salt solution with the concentration of 2 mol/L;
step 2, fully dissolving sodium hydroxide in pure water to prepare an alkali solution with the concentration of 4 mol/L;
step 3, adding manganous-manganic oxide into the reaction kettle to prepare suspension with 50% of solid content;
step 4, adding the salt solution prepared in the step 1, the alkali solution prepared in the step 2 and a complexing agent into the reaction kettle containing the manganous-manganic oxide suspension in the step 3 in a parallel flow manner, fully stirring the slurry in the reaction kettle to enable the slurry to react, standing the slurry to form a chemical slurry after the reaction is finished, filtering the slurry which is kept standing to form the chemical slurry, washing the slurry with water, and drying the slurry to obtain a semi-finished product;
and 5, putting the dried semi-finished product into a pot for sintering, and performing subsequent treatment procedures of crushing, batch mixing, demagnetizing, packaging and the like on the sintered material to obtain the nickel-manganese oxide.
2. The method of claim 1, wherein the nickel manganese oxide is prepared by: the molecular formula of the nickel manganese oxide is Mn1.5Ni0.5O2The crystal structure is a spinel structure.
3. The method of claim 1, wherein the nickel manganese oxide is prepared by: the volume ratio of the salt solution, the alkali solution and the complexing agent added into the reaction kettle in the step 4 is 1: 1: 1.
4. the method for preparing nickel manganese oxide according to claim 1, wherein the stirring speed in step 4 is 200-800 r/min, the reaction temperature is 40-60 ℃, and the reaction time is 2-8 h.
5. The method for preparing nickel manganese oxide according to claim 1, wherein the standing and formation time of step 4 is 2-8 h.
6. The method for preparing nickel manganese oxide according to claim 1, wherein the sintering temperature in step 5 is 700-1200 ℃ and the sintering time is 1-5 h.
7. The method of claim 1, wherein the nickel salt in step 1 comprises nickel nitrate, nickel sulfate, and nickel chloride.
8. The method of claim 1, wherein the manganomanganic oxide in step 3 is battery grade manganomanganic oxide with a purity of 99% or more.
9. The method for preparing nickel manganese oxide according to claim 1, wherein the complexing agent in step 4 is ammonia water, and the concentration of ammonia water is 1 mol/L.
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Citations (6)
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| US20090272939A1 (en) * | 2006-12-05 | 2009-11-05 | Yang Kook Sun | Core-shell spinel cathode active materials for lithium secondary batteries, lithium secondary batteries using the same and method for preparing thereof |
| JP2012216547A (en) * | 2011-03-31 | 2012-11-08 | Toda Kogyo Corp | Manganese-nickel composite oxide particle powder and method for producing the same, method for producing positive electrode active material particle powder for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| JP2013230969A (en) * | 2012-04-05 | 2013-11-14 | Tosoh Corp | Trimanganese tetraoxide composition, method for manufacturing the same, and use of the same |
| CN105355910A (en) * | 2015-11-13 | 2016-02-24 | 中南大学 | A preparing method of a spherical nickel cobalt lithium aluminate cathode material for lithium ion batteries |
| CN107180950A (en) * | 2017-04-17 | 2017-09-19 | 张保平 | A kind of ternary cathode material of lithium ion battery NCM, NCA spray drying process preparation method |
| CN109437333A (en) * | 2018-10-24 | 2019-03-08 | 山东齐兴能源材料有限公司 | A kind of nickel galaxite presoma and preparation method thereof and anode material for lithium-ion batteries |
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2021
- 2021-03-10 CN CN202110262156.7A patent/CN113044892A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090272939A1 (en) * | 2006-12-05 | 2009-11-05 | Yang Kook Sun | Core-shell spinel cathode active materials for lithium secondary batteries, lithium secondary batteries using the same and method for preparing thereof |
| JP2012216547A (en) * | 2011-03-31 | 2012-11-08 | Toda Kogyo Corp | Manganese-nickel composite oxide particle powder and method for producing the same, method for producing positive electrode active material particle powder for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| JP2013230969A (en) * | 2012-04-05 | 2013-11-14 | Tosoh Corp | Trimanganese tetraoxide composition, method for manufacturing the same, and use of the same |
| CN105355910A (en) * | 2015-11-13 | 2016-02-24 | 中南大学 | A preparing method of a spherical nickel cobalt lithium aluminate cathode material for lithium ion batteries |
| CN107180950A (en) * | 2017-04-17 | 2017-09-19 | 张保平 | A kind of ternary cathode material of lithium ion battery NCM, NCA spray drying process preparation method |
| CN109437333A (en) * | 2018-10-24 | 2019-03-08 | 山东齐兴能源材料有限公司 | A kind of nickel galaxite presoma and preparation method thereof and anode material for lithium-ion batteries |
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