CN109052492B - Method for preparing ternary cathode material from laterite nickel ore nitric acid leaching solution - Google Patents
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Abstract
A method for preparing a ternary cathode material from a laterite-nickel ore nitric acid leaching solution. The preparation process comprises the steps of regulating the pH of a nitric acid leaching solution of the laterite-nickel ore to obtain iron-aluminum slag and a filtrate, adding villiaumite to deeply decalcify and magnesium to obtain calcium-magnesium slag and a nickel-cobalt-manganese-rich solution, regulating and controlling the pH to precipitate nickel, cobalt and manganese, filtering and washing after reaction to obtain primary nickel, cobalt and manganese slag and a nickel-cobalt-manganese-poor solution, deeply precipitating nickel, cobalt and manganese in the nickel-cobalt-manganese-poor solution, and using the obtained primary nickel, cobalt and manganese slag of the secondary nickel, cobalt and manganese slag to prepare a ternary cathode material precursor; adding the precursor, a lithium source and an additive into a pressure kettle according to the measurement, directly drying/grinding after hydrothermal reaction, and roasting at high temperature to obtain the ternary cathode material. The secondary nickel cobalt manganese slag is used for regulating and controlling the pH value. The method improves the comprehensive utilization of associated resources in the laterite-nickel ore, and has the characteristics of wide raw material source, simple process flow, low cost and the like. The ternary cathode material prepared by the method provided by the invention has the advantages of uniform particle size distribution, good stability, high specific capacity and high activity.
Description
Technical Field
The invention relates to a preparation method of a lithium ion battery anode material, in particular to a method for preparing a nickel-cobalt-manganese ternary anode material from a nitric acid leaching solution of laterite-nickel ore.
Background
In recent years, lithium ion batteries are widely used as secondary energy sources in electric vehicles, unmanned aerial vehicles, mobile intelligent terminals such as mobile phones, tablet computers and notebook computers. With the rapid development of the application market in the global scope, the output of the lithium ion battery is also increased sharply. At present, many lithium ion battery anode materials are being researched and developed, wherein a nickel-cobalt-manganese ternary anode material is considered to be one of the lithium ion battery anode materials with development prospects due to the advantages of high capacity, stable cycle performance, good safety performance, low price and the like, and the domestic annual demand of the nickel-cobalt-manganese ternary anode material is gradually replacing lithium cobaltate at the annual growth rate of 20%.
However, the raw materials for producing the nickel-cobalt-manganese ternary cathode material directly influence the production cost and performance of the lithium ion cathode material. At present, the preparation of ternary materials mostly takes refined sulfate, nitrate, chloride and the like as raw materials. Most of the salts are prepared from ores, and a series of impurity removal and extraction processes are needed from the ores to products, so that the process is long, the emission is large, and the energy consumption is high. In addition, nickel and cobalt belong to important strategic non-ferrous metals, and the nickel and cobalt resource shortage in China depends on foreign import in a large quantity and is expensive.
In fact, China has mastered billions of tons of overseas laterite-nickel ore resources. The resource is a typical complex multi-metal resource accompanied by various valuable metals such as nickel, cobalt, chromium, manganese and the like. At present, the research is mostly focused on the recovery of nickel, but other elements such as cobalt, manganese, copper, iron, aluminum and the like are not efficiently utilized, so that resources are wasted, and environmental pollution is caused. In fact, the laterite-nickel ore simultaneously contains nickel, cobalt and manganese elements required for preparing the ternary cathode material, and if the ternary cathode material can be directly prepared from the laterite-nickel ore, the laterite-nickel ore is beneficial to comprehensive utilization of resources and environment-friendly development, and the production cost of the ternary cathode material can be reduced.
At present, the treatment of laterite-nickel ore mainly comprises a pyrogenic process for producing ferronickel and a wet process for producing nickel salt, and the methods have the problems of low resource utilization rate, high energy consumption, serious environmental pollution and the like. The novel efficient comprehensive utilization and clean production process of the original limonitic laterite-nickel ore developed by the inventor in the research team can realize the efficient extraction and comprehensive utilization of nickel, cobalt, chromium, aluminum and iron in the laterite-nickel ore, reduce the emission of wastes from the source and lead the main technical indexes to the world. According to the process, laterite-nickel ore is decomposed by nitric acid, nickel, cobalt, manganese and the like in nitric acid leachate are all produced and sold as nickel-cobalt compounds, and a method for directly preparing a new energy material from the nitric acid leachate is not reported.
Disclosure of Invention
The invention aims to provide a method for directly preparing a nickel-cobalt-manganese ternary cathode material from a laterite-nickel ore nitric acid leaching solution, which has the advantages of simple process flow and stable product quality. The method for preparing the nickel-cobalt-manganese ternary cathode material precursor combines materials and metallurgical technology, takes the nitric acid leaching solution of the laterite-nickel ore as a raw material, and has the advantages of short process flow and low cost. In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows:
A. deep removal of impurities
Taking a nitric acid leaching solution of laterite-nickel ore as a raw material, adjusting the pH value of the solution to deeply precipitate iron and aluminum, and performing solid-liquid separation to obtain iron-aluminum slag and filtrate; adding villiaumite into the filtrate to deeply decalcify and magnesium to obtain calcium magnesium slag and a nickel-cobalt-manganese-rich solution;
B. controllable precipitation of nickel, cobalt and manganese
B, adjusting the pH value of the nickel-cobalt-manganese-rich liquid obtained in the step A to selectively precipitate nickel, cobalt and manganese, and filtering and washing to obtain primary nickel-cobalt-manganese slag and a nickel-cobalt-manganese-poor liquid;
C. deep precipitation of nickel, cobalt and manganese
Adjusting the pH value of the nickel-cobalt-manganese poor solution obtained in the step B to precipitate and separate residual nickel, cobalt and manganese, and returning secondary nickel, cobalt and manganese residues obtained after filtering to the step A for adjusting the pH value of the nitric acid leaching solution of the laterite-nickel ore;
D. preparation of ternary cathode material precursor
(1) Dissolving the obtained primary nickel cobalt manganese slag in an acid solution to obtain a pure nickel cobalt manganese solution,
(2) supplementing one or more of soluble nickel salt, cobalt salt and manganese salt into the pure nickel-cobalt-manganese solution obtained in the step (1) according to the proportion of nickel-cobalt-manganese components in the target product, so that the concentration of total metal ions of nickel-cobalt-manganese is 0.5-3.0 mol/L
(3) Slowly adding the mixed solution obtained in the step (2), a sodium hydroxide solution and ammonia water into a reaction kettle under the protection of nitrogen or argon, and filtering, washing and drying after the reaction is finished to obtain a precursor NixCoyMn1-x-y(OH)2；
E. Preparation of ternary cathode material
Adding the prepared ternary cathode material precursor, a lithium source, an additive and water into a high-pressure reaction kettle according to a certain proportion for hydrothermal reaction, directly drying after the reaction is finished, then grinding and mixing the materials, and then roasting at a high temperature to obtain the nickel-cobalt-manganese-lithium ternary cathode material.
Further, in the step A, one or more of secondary nickel-cobalt-manganese slag, magnesium oxide, magnesium carbonate, calcium oxide and calcium carbonate are added, the pH value is adjusted to be 4.2-4.5, the reaction temperature is controlled to be 30-80 ℃, and the reaction time is 0.5-2 hours.
And further, in the step B, one or more of magnesium oxide, calcium oxide and sodium hydroxide are added to adjust the pH value to 7.0-7.6, the reaction temperature is controlled to be 30-80 ℃, and the reaction time is 0.5-2 hours.
And further, in the step C, one or more of magnesium oxide, calcium oxide and sodium hydroxide are added to adjust the pH value to 7.6-8.3, the reaction temperature is controlled to be 30-80 ℃, and the reaction time is 0.5-2 hours.
Further, the acid solution adopted in the step D is one or more of sulfuric acid, nitric acid and hydrochloric acid solution;
the nickel salt is one or more of nickel sulfate, nickel nitrate, nickel chloride or nickel hydroxide;
the cobalt salt is one or more of cobalt sulfate, cobalt nitrate, cobalt chloride or cobalt hydroxide;
the manganese salt is one or more of manganese sulfate, manganese nitrate or manganese hydroxide;
the concentration of the sodium hydroxide is 0.5-2.5 mol/L, the concentration of the ammonia water is 0.2-1.0 mol/L, the reaction temperature is 40-70 ℃, and the reaction time is 5-20 h.
Further, the lithium source in the step E is one or more of lithium hydroxide, lithium sulfate, lithium nitrate, lithium acetate and lithium oxalate;
the additive is one or more of hydrogen peroxide, oxygen and ozone;
the lithium source is added in a molar ratio of Li/(Ni + Co + Mn) of 1.0-1.07 times;
the dosage of the additive is 0.1-10 times of the molar ratio of O/(Ni + Co + Mn);
the liquid-solid ratio L/S in the hydrothermal reaction process is 1: 1-5: 1, the hydrothermal temperature is 140-250 ℃, and the heat preservation time is 1-6 h;
the drying temperature is 80-120 ℃, and the drying time is 2-10 h;
the roasting temperature is 750-900 ℃, and the roasting time is 2-10 h.
According to the method for preparing the nickel-cobalt-manganese ternary cathode material, the nitric acid leaching solution of the laterite-nickel ore is directly used as the raw material for preparation, so that the non-ferrous smelting and the material preparation are deeply combined, the comprehensive utilization of associated resources in the laterite-nickel ore is improved, and the method has the characteristics of wide raw material source, simple process flow, low cost and the like. The adopted hydrothermal synthesis anode material has low lithium consumption and no solid-liquid separation, can realize the embedding of lithium in a precursor in the hydrothermal process, preliminarily forms a ternary material, and can obtain the anode material with no agglomeration, good crystal form and excellent electrochemical performance by the subsequent roasting.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a process flow diagram for preparing a ternary cathode material from a lateritic nickel ore nitric acid leach solution provided by the invention;
FIG. 2 is a graph of charge-discharge cycle performance at 1C for the ternary cathode material prepared in EXAMPLE 1; fig. 3 is an electron microscope image of the ternary cathode material prepared in example 2.
Detailed Description
The following examples are intended to further illustrate the invention without limiting it
Example 1:
the embodiment provides a method for preparing a nickel-cobalt-manganese ternary cathode material from a laterite-nickel ore nitric acid leaching solution, which comprises the following specific steps:
A. deeply removing impurities: taking 300mL of laterite-nickel ore nitric acid leaching solution, wherein the content of each element is shown in the following table
By adding magnesium carbonate slurry, adjusting pH to 4.2, controlling temperature to 50 deg.C, and separating solid and liquid after reaction, the precipitation rates of iron and aluminum are 99.9% and 99.5%, respectively. Then adding sodium fluoride into the filtrate, wherein the precipitation rate of calcium and magnesium is more than 99.9%.
B. Controllable precipitation of nickel, cobalt and manganese
Then adding magnesium oxide into the filtrate, adjusting the pH to 7.2, controlling the temperature to be 60 ℃, and carrying out solid-liquid separation after the reaction is finished for 2 hours to obtain primary nickel-cobalt-manganese slag. The precipitation rates of nickel, cobalt and manganese are 85.2 percent, 83.5 percent and 70.4 percent respectively,
C. deep precipitation of nickel, cobalt and manganese
Adding magnesium hydroxide into the filtrate, adjusting pH to 8.0, controlling temperature to 55 deg.C, separating solid and liquid after reaction, precipitating residual nickel, cobalt and manganese respectively at 99.6%, 99.7% and 96.5%,
D. preparation of ternary cathode material precursor
(1) The content of the nickel-cobalt-manganese-rich solution obtained by dissolving the primary nickel-cobalt-manganese slag with sulfuric acid is shown in the following table
(2) According to the proportion of nickel, cobalt and manganese components in the target product, cobalt sulfate and manganese sulfate are supplemented in the solution to ensure that the concentrations of nickel, cobalt and manganese in the solution are respectively 90g/L, 11.25g/L and 11.25g/L,
(3) dropwise adding the mixed solution, 0.5mol/L sodium hydroxide solution and 1.0mol/L ammonia water into a nitrogen-protected stirring reactor in parallel, controlling the pH to be 11.0 and the temperature to be 60 ℃, carrying out heat preservation reaction for 15 hours, and filtering to obtain a precursor Ni0.8Co0.1Mn0.1(OH)2。
E. Preparation of ternary cathode material
Adding 60g of dried precursor into a high-pressure kettle, adding water according to the liquid-solid ratio L/S of 2:1, and adding lithium hydroxide according to the molar ratio of Li/(Ni + Co + Mn) of 1.04; sealing the autoclave, heating to 200 ℃, stirring, introducing oxygen until the pressure is 3MPa, and keeping the temperature for 6 hours; and (3) cooling, pouring out the slurry, directly drying for 2h at 120 ℃, grinding, uniformly mixing, and roasting in a box-type muffle furnace at 850 ℃ for 4h to obtain a ternary cathode material finished product.
Example 2:
the embodiment provides a method for preparing a nickel-cobalt-manganese ternary cathode material from a laterite-nickel ore nitric acid leaching solution, which comprises the following specific steps:
A. deeply removing impurities: taking 300mL of laterite-nickel ore nitric acid leaching solution, wherein the content of each element is shown in the following table
By adding magnesium carbonate slurry, adjusting pH to 4.3, controlling temperature to 55 deg.C, time to 1.5h, solid-liquid separation after reaction, the precipitation rates of iron and aluminum are 99.9% and 99.4% respectively. Then adding sodium fluoride into the filtrate, wherein the precipitation rate of calcium and magnesium is more than 99.9%.
B. Controllable precipitation of nickel, cobalt and manganese
Then adding magnesium oxide into the filtrate, adjusting the pH to 7.1, controlling the temperature to 65 ℃ and the time to 1.5h, and carrying out solid-liquid separation after the reaction is finished to obtain primary nickel-cobalt-manganese slag. The precipitation rates of nickel, cobalt and manganese are respectively 84.2 percent, 83.1 percent and 70.1 percent,
C. deep precipitation of nickel, cobalt and manganese
Adding magnesium hydroxide into the filtrate, adjusting pH to 8.1, controlling temperature at 60 deg.C for 2 hr, performing solid-liquid separation after reaction to obtain nickel, cobalt and manganese with precipitation rates of 99.2%, 99.3% and 99.4% respectively,
D. preparation of ternary cathode material precursor
(1) The nickel, cobalt and manganese slag is dissolved by nitric acid, and the content of the obtained nickel, cobalt and manganese-rich solution is shown in the table
(2) According to the proportion of nickel, cobalt and manganese components in the target product, supplementing cobalt nitrate and manganese nitrate into the solution to ensure that the concentrations of nickel, cobalt and manganese in the solution are respectively 120g/L, 48g/L and 72g/L,
(3) mixing the aboveDropwise adding the mixed solution, 1.0mol/L sodium hydroxide solution and 1.5mol/L ammonia water into an argon-protected reaction kettle in parallel, controlling the pH to be 11.2 and the temperature to be 65 ℃, carrying out heat preservation reaction for 16 hours, and filtering to obtain a precursor Ni0.5Co0.2Mn0.3(OH)2。
E. Preparation of ternary cathode material
Adding 80g of dried precursor into a high-pressure kettle, adding water according to the liquid-solid ratio L/S being 3:1, and adding lithium hydroxide according to the molar ratio of Li/(Ni + Co + Mn) being 1.03; sealing the autoclave, heating to 210 ℃, stirring, introducing oxygen until the pressure is 2MPa, and keeping the temperature for 6 hours; and (3) cooling, pouring out the slurry, directly drying for 2h at 120 ℃, grinding, uniformly mixing, and roasting in a box-type muffle furnace for 5h at 800 ℃ to obtain a ternary cathode material finished product.
Example 3:
the embodiment provides a method for preparing a nickel-cobalt-manganese ternary cathode material from a laterite-nickel ore nitric acid leaching solution, which comprises the following specific steps:
A. deeply removing impurities: taking 300mL of laterite-nickel ore nitric acid leaching solution, wherein the content of each element is shown in the following table
By adding magnesium carbonate slurry, adjusting pH to 4.5, controlling temperature to 50 deg.C, time to 2.0h, solid-liquid separation after reaction, the precipitation rates of iron and aluminum are 99.9% and 99.9% respectively. Then adding ammonium fluoride into the filtrate, wherein the precipitation rate of calcium and magnesium is over 99.9 percent.
B. Controllable precipitation of nickel, cobalt and manganese
Then adding magnesium oxide into the filtrate, adjusting the pH to 7.2, controlling the temperature to be 60 ℃, and the time to be 2.0h, and carrying out solid-liquid separation after the reaction is finished to obtain primary nickel-cobalt-manganese slag. The precipitation rates of nickel, cobalt and manganese are respectively 86.2 percent, 87.1 percent and 83.7 percent,
C. deep precipitation of nickel, cobalt and manganese
Adding magnesium hydroxide into the filtrate, adjusting pH to 8.3, controlling temperature to 65 deg.C, separating solid and liquid after reaction, respectively precipitating nickel, cobalt and manganese at 99.3%, 99.6% and 99.2%,
D. preparation of ternary cathode material precursor
(1) Dissolving the primary nickel-cobalt-manganese slag by adopting sulfuric acid, controlling the liquid-solid ratio to be 1:1, and obtaining the nickel-cobalt-manganese-rich solution with the content shown in the table
(2) According to the proportion of nickel, cobalt and manganese components in the target product, cobalt sulfate and manganese sulfate are supplemented in the solution to ensure that the concentrations of nickel, cobalt and manganese in the solution are respectively 150g/L, 18.75g/L and 18.75g/L,
(3) dropwise adding the mixed solution, 1.5mol/L sodium hydroxide solution and 1.0mol/L ammonia water into a nitrogen-protected stirring reactor in parallel, controlling the pH to be 11.5 and the temperature to be 50 ℃, carrying out heat preservation reaction for 20 hours, and filtering to obtain a precursor Ni0.8Co0.1Mn0.1(OH)2。
E. Preparation of ternary cathode material
Adding 100g of dried precursor into a high-pressure kettle, adding water according to the liquid-solid ratio L/S being 4:1, and adding lithium hydroxide according to the molar ratio of Li/(Ni + Co + Mn) being 1.05; sealing the autoclave, heating to 190 ℃, stirring, introducing oxygen until the pressure is 3MPa, and keeping the temperature for 5 hours; and (3) cooling, pouring out the slurry, directly drying for 2h at 120 ℃, grinding, uniformly mixing, and roasting in a box-type muffle furnace at 820 ℃ for 5h to obtain a ternary cathode material finished product.
Claims (3)
1. A method for preparing a ternary cathode material from a laterite-nickel ore nitric acid leaching solution is characterized by comprising the following steps:
A. deep removal of impurities
Adding one or more of secondary nickel-cobalt-manganese slag, magnesium oxide, magnesium carbonate, calcium oxide and calcium carbonate into a laterite-nickel ore nitric acid leaching solution serving as a raw material, adjusting the pH value to be 4.2-4.5, controlling the reaction temperature to be 30-80 ℃, reacting for 0.5-2 h, deeply removing iron and aluminum, and performing solid-liquid separation to obtain iron-aluminum slag and filtrate; adding villiaumite into the filtrate to deeply decalcify and magnesium to obtain calcium magnesium slag and a nickel-cobalt-manganese-rich solution;
B. controllable precipitation of nickel, cobalt and manganese
Adding one or more of magnesium oxide, calcium oxide and sodium hydroxide into the nickel-cobalt-manganese-rich liquid obtained in the step A, adjusting the pH value to 7.0-7.6, controlling the reaction temperature to be 30-80 ℃, and reacting for 0.5-2 h to selectively precipitate nickel, cobalt and manganese, and filtering and washing to obtain primary nickel-cobalt-manganese slag and a nickel-cobalt-manganese-poor liquid;
C. deep precipitation of nickel, cobalt and manganese
Adding one or more of magnesium oxide, calcium oxide and sodium hydroxide to adjust the pH value to 7.6-8.5, controlling the reaction temperature to 30-80 ℃, and the reaction time to 0.5-2 h, so that residual nickel, cobalt and manganese are precipitated and separated, and filtering to obtain secondary nickel, cobalt and manganese slag which is returned to the step A for adjusting the pH value of the nitric acid leaching solution of the laterite-nickel ore;
D. ternary precursor preparation
(1) Dissolving the obtained primary nickel cobalt manganese slag in an acid solution to obtain a pure nickel cobalt manganese solution,
(2) supplementing one or more of soluble nickel salt, cobalt salt and manganese salt into the pure nickel-cobalt-manganese solution obtained in the step (1) according to the proportion of nickel-cobalt-manganese components in a target product, so that the concentration of total metal ions of nickel-cobalt-manganese is 0.5-3.0 mol/L;
(3) slowly adding the mixed solution obtained in the step (2), a sodium hydroxide solution and ammonia water into a reaction kettle under the protection of nitrogen or argon, and filtering, washing and drying after the reaction is finished to obtain a precursor NixCoyMn1-x-y(OH)2；
E. Preparation of ternary cathode material
Adding the prepared ternary cathode material precursor, a lithium source, an additive and water into a high-pressure reaction kettle according to a certain proportion for hydrothermal reaction, directly drying after the reaction is finished, then grinding and mixing the materials, and then roasting at a high temperature to obtain the nickel-cobalt-manganese-lithium ternary cathode material.
2. The method for preparing the ternary cathode material from the lateritic nickel ore nitric acid leach solution according to claim 1, wherein the acid solution used in the step D is one or more of sulfuric acid, nitric acid and hydrochloric acid solution;
the nickel salt is one or more of nickel sulfate, nickel nitrate, nickel chloride or nickel hydroxide;
the cobalt salt is one or more of cobalt sulfate, cobalt nitrate, cobalt chloride or cobalt hydroxide;
the manganese salt is one or more of manganese sulfate, manganese nitrate or manganese hydroxide;
the concentration of the sodium hydroxide is 0.5-2.5 mol/L, the concentration of the ammonia water is 0.2-2.0 mol/L, the reaction temperature is 40-70 ℃, and the reaction time is 5-20 h.
3. The method for preparing the ternary cathode material from the nitric acid leaching solution of the lateritic nickel ore according to the claim 1, wherein the lithium source in the step E is one or more of lithium hydroxide, lithium sulfate, lithium nitrate, lithium acetate and lithium oxalate;
the additive is one or more of hydrogen peroxide, oxygen and ozone;
the lithium source is added in a molar ratio of Li/(Ni + Co + Mn) of 1.0-1.07 times;
the dosage of the additive is 0.1-10 times of the molar ratio of O/(Ni + Co + Mn);
the liquid-solid ratio L/S in the hydrothermal reaction process is 1: 1-5: 1, the hydrothermal temperature is 140-250 ℃, and the heat preservation time is 1-6 h;
the drying temperature is 80-120 ℃, and the drying time is 2-10 h;
the roasting temperature is 750-900 ℃, and the roasting time is 2-10 h.
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| CN109052492B (en) * | 2018-07-24 | 2020-02-07 | 眉山顺应动力电池材料有限公司 | Method for preparing ternary cathode material from laterite nickel ore nitric acid leaching solution |
| CN110629022A (en) * | 2019-10-31 | 2019-12-31 | 眉山顺应动力电池材料有限公司 | Method for comprehensively treating laterite-nickel ore by using nitric acid medium |
| CN112095003B (en) * | 2020-08-17 | 2022-04-08 | 四川顺应动力电池材料有限公司 | Method for recycling various valuable metals and acid-base double-medium regeneration cycle from laterite-nickel ore |
| CN116325230A (en) * | 2020-10-14 | 2023-06-23 | 株式会社Lg新能源 | Method for manufacturing high nickel positive electrode active material |
| CN113061748B (en) * | 2021-03-12 | 2022-07-12 | 中国恩菲工程技术有限公司 | Laterite nickel ore leaching liquid treatment system and method |
| CN113060712B (en) * | 2021-03-15 | 2023-01-17 | 中南大学 | Method for preparing iron phosphate and nickel cobalt manganese hydroxide battery precursor material from metal nickel cobalt iron powder |
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| CN114620782B (en) * | 2022-05-16 | 2022-08-02 | 宜宾锂宝新材料有限公司 | Ternary positive electrode material and method for removing metal foreign matter thereof |
| CN115490277B (en) * | 2022-09-30 | 2024-02-13 | 山东精工电子科技股份有限公司 | Magnetic field modified ternary material for lithium ion battery and preparation method thereof |
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| CN102321812B (en) * | 2011-09-01 | 2013-04-17 | 东北大学 | Method for comprehensive utilization of laterite nickel ore |
| CN103545504B (en) * | 2013-10-17 | 2016-01-20 | 江西赣锋锂业股份有限公司 | A kind of preparation method of ternary anode material precursor |
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| CN109052492B (en) * | 2018-07-24 | 2020-02-07 | 眉山顺应动力电池材料有限公司 | Method for preparing ternary cathode material from laterite nickel ore nitric acid leaching solution |
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