CN113880100A - Preparation method of lithium nickel cobalt oxide battery regenerated ternary cathode material - Google Patents

Preparation method of lithium nickel cobalt oxide battery regenerated ternary cathode material Download PDF

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CN113880100A
CN113880100A CN202110966412.0A CN202110966412A CN113880100A CN 113880100 A CN113880100 A CN 113880100A CN 202110966412 A CN202110966412 A CN 202110966412A CN 113880100 A CN113880100 A CN 113880100A
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lithium
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cobalt oxide
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欧星
萧厚桂
刘赟
张宝
明磊
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Central South University
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Abstract

A method for preparing a lithium nickel cobalt oxide battery regenerated ternary cathode material. The invention comprises the following steps: (1) discharging the waste lithium ion battery by adopting a sodium chloride solution, disassembling, soaking the positive plate in an alkali liquor, and filtering to obtain black powder; (2) carrying out reduction roasting on the obtained black powder in a protective gas atmosphere; (3) dissolving black powder in an acid solution, and extracting and removing impurities to obtain a high-purity mixed solution containing nickel and cobalt. (4) After the concentrations of cobalt and nickel ions are measured, adding a corresponding manganese source and a tungsten source into the solution, adjusting the pH value, and carrying out a coprecipitation reaction to obtain a precursor; (5) and mixing and sintering the precursor, a lithium source and a boron source to obtain the cathode material. According to the method provided by the invention, the pollution generated by the waste lithium ion battery is effectively reduced, and the waste lithium nickel cobalt oxide material can be recycled and regenerated into the ternary cathode material, and the cathode material has excellent electrochemical performance.

Description

Preparation method of lithium nickel cobalt oxide battery regenerated ternary cathode material
Technical Field
The invention relates to the field of lithium ion battery recovery, in particular to a preparation method of a lithium nickel cobalt oxide battery regenerated ternary cathode material.
Background
The decommissioning wave of the first wave power battery is about to come in 2018, and the decommissioned lithium ion battery reaches over 60 gigawatts in 2020. By 2030, the population using electric cars worldwide will reach 2.28 billion. With the rapid growth of electric automobiles, the annual demand of lithium ion batteries is also rapidly growing, which means that more and more lithium ion batteries are going to be retired in the future. Because the waste lithium ion battery contains heavy metals, organic solvents and harmful electrolytes, the waste lithium ion battery has great harm to the environment if not recycled. Meanwhile, the value of impurity metals in the waste lithium ion battery reaches 101 billion yuan by 2020. From this point of view, it is a valuable secondary resource. Recycling of used lithium ion batteries should be considered. The sustainability of lithium ion batteries should be of more interest, and recycling plays an important role.
The waste lithium ion battery contains a large amount of expensive metal cobalt and metal nickel. And the resources in China are in short supply, the metal recovery rate in the production process is low, the process is complex, and the production cost is high. If the cobalt and nickel resources in the waste lithium ion battery can be recycled, the method has great significance in the prior art from the aspects of environmental protection and resource recycling, most of the cobalt and nickel in the lithium nickel cobaltate is recycled by recycling a single cobalt and nickel, and the method is complex and causes high cost. Lithium nickel cobalt oxide, molecular formula of which can be expressed as LiNixCo1-xO2Belongs to a hexagonal system and has a layered structure. At present, the process for recovering lithium nickel manganese oxide battery materials generally comprises the steps of adding a precipitator into a metal purification solution of the battery materials to precipitate nickel and cobalt metals, and then calcining at high temperature to prepare a lithium cobaltate or lithium nickelate positive electrode. However, the obtained product is too single, and the prepared positive electrode has large particlesSmall size, difficult control, more side reactions, poor electrochemical performance and the like.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method of a ternary cathode material regenerated from a waste lithium nickel cobalt oxide cathode material.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a lithium nickel cobalt oxide battery regenerated ternary cathode material is characterized by comprising the following steps:
(1) discharging the waste lithium ion battery by adopting a sodium chloride solution, then disassembling, soaking the positive plate in an alkali liquor, and filtering to obtain black powder;
(2) carrying out reduction roasting on the obtained powder in a reducing atmosphere;
(3) and dissolving the obtained black powder in an acid solution, and extracting and removing impurities to obtain a relatively pure solution containing cobalt and lithium.
(4) After the concentration of cobalt and nickel ions is measured, adding a corresponding manganese source and a tungsten source into the solution, adding a precipitator and a coordination agent, adjusting the pH value, and carrying out a coprecipitation reaction to obtain a precursor;
(5) and mixing and sintering the precursor, a lithium source and a boron source to obtain the cathode material.
The chemical formula of the cathode material is LiNixCoyMnzWpBqO2@ aB2O3, wherein x, y, z, p, q and a are mole numbers, x is more than or equal to 0.6 and less than or equal to 1, y is more than 0 and less than or equal to 0.2, z is more than 0 and less than or equal to 0.2, p is more than 0 and less than or equal to 0.08, q is more than 0 and less than or equal to 0.05, a is more than 0 and less than or equal to 0.05, and x + y + z is 1.
Preferably, in the step (1), the discharging process includes soaking the waste lithium ion battery in a 0.2-6% sodium chloride solution for 18-48 hours, wherein alkali in the adopted alkali solution is selected from one or more of sodium hydroxide, ammonia water and calcium hydroxide, the pH value is 12-14, the soaking time is 1-2 hours, and partial metal impurities (magnesium, calcium, aluminum and the like) are removed.
Preferably, the mass ratio of the reducing agent to the black powder is 1: 1-3, and the roasting temperature is 500-800 ℃; the roasting time is 8-12 h, electrolyte in the lithium nickel cobalt oxide is removed, and Fe3+ is reduced to Fe2 +.
Preferably, an acid solution only containing two metal elements of nickel and cobalt is obtained by extraction purification; the specific operation is as follows: filtering the inorganic acid solution dissolving the anode powder to remove insoluble substances, controlling the pH of the filtrate to be 2, adding an extractant with the volume 2-3 times that of the inorganic acid solution, balancing for 15min, and back-extracting with inorganic acid with the volume of the extractant 1/2 for 15min to obtain mixed acid containing nickel and cobalt;
preferably, the components of the extracting agent are one or more of P204 or P507 with a volume fraction of 30% and sulfonated kerosene with a volume fraction of 70%, wherein the adopted inorganic acid is one or more of hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid.
Preferably, the method for measuring the concentration of cobalt and lithium ions adopted in the step (4) is an inductively coupled plasma spectrometer method, the manganese source is selected from one or more of manganese sulfate or manganese nitrate, and the tungsten source is tungsten oxide.
Preferably, the precipitator added in the step (4) is one or more of sodium hydroxide, potassium hydroxide and sodium carbonate, and the concentration is 6-7 mol/L; the complexing agent is one or more of ammonia water, ammonium sulfate, oxalic acid and ammonium bicarbonate, the concentration is 4-5 mol/L, the pH value is 10-11, and the solution temperature is 45-60 ℃.
Preferably, in the step (5), the lithium source is selected from one or more of lithium nitrate and lithium hydroxide; the boron source is selected from one or more of boron nitrate and boron oxide. The sintering temperature is 750-850 ℃, and the time is 12-16 h.
The invention has the beneficial effects that:
(1) the problems of complex recovery process and low recovery product benefit in the recovery of the nickel cobalt lithium battery material are solved.
(2) The method adopts a simple method to recycle the waste lithium nickel cobalt oxide anode material and regenerate the ternary anode material, and the anode material has excellent electrochemical performance.
(3) The preparation method is simple and easy to operate, has little environmental pollution and is suitable for large-scale industrial production
Drawings
FIG. 1 is an SEM image of a precursor prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a positive electrode material according to example 1 of the present invention;
fig. 3 is a graph of cycle performance of the positive electrode material of example 1 of the present invention and comparative example 1.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
Example 1
The embodiment comprises the following steps:
(1) soaking the waste lithium nickel cobalt oxide battery in a 2% sodium chloride solution for 20h, then drying and disassembling, soaking in a 6mol/L sodium hydroxide solution for 1h, filtering and washing to obtain black powder;
(2) taking 10g of black powder (lithium nickel cobaltate active substance), and roasting the obtained black powder and iron powder in a muffle furnace at 800 ℃ for 8 hours according to the mass ratio of 1: 1;
(3) taking 10g of lithium nickel cobaltate active substance, then dissolving the lithium nickel cobaltate active substance in 4mol/L sulfuric acid, controlling the pH of the filtrate to be 2, adding 10L of extracting agent, wherein the components of the extracting agent are 30% by volume of P204 and 70% by volume of sulfonated kerosene, the balance time is 15min, then back-extracting with 5L of 2mol/L sulfuric acid, and the balance time is 15min, so that the obtained solution is a mixed solution of nickel nitrate and cobalt nitrate.
(4) Measuring the concentration of nickel ions and cobalt ions in the solution to be 0.60mol/L and 0.68mol/L by ICP (inductively coupled plasma), mixing manganese sulfate solutions with the same concentration after measuring the concentrations of cobalt and nickel ions, and adding tungsten oxide; adding 5mol/L sodium hydroxide and 5mol/L ammonia water into the prepared mixed solution, adjusting the pH value to 10.5, and adjusting the solution temperature to 45 ℃, wherein the ratio of nickel: cobalt: manganese: tungsten: the basic substance is added in a molar ratio of 8:1:1:0.01:20, coprecipitation reaction is carried out, the obtained product is washed and dried, and a precursor Ni is obtained0.8Co0.1Mn0.1W0.001(OH)2。
(5) The precursor Ni0.8Co0.1Mn0.1W0.001(OH)2Mixed with lithium hydroxide and boron oxide, and sintered, wherein the precursor is controlled to be: lithium hydroxide: boron oxide is 1:1.05:0.011, and sintering is carried out for 12 hours at 810 ℃ to obtain the cathode material LiNi0.8Co0.1Mn0.1W0.001B0.002O2@0.01B2O3。
Scanning the precursor prepared in the embodiment by an electron microscope, wherein the precursor has uniform particles, good sphericity, particle size of 2-4 μm and no microcrack, as shown in fig. 1(SEM picture); scanning the cathode material prepared in the embodiment with an electron microscope, and as shown in fig. 2(SEM picture), the cathode material is a single crystal particle with a particle size of 2-4 μm; as shown in FIG. 3, the cathode material has a capacity of 166mAh g-1The retention rate was 84%.
Example 2
(1) Soaking the waste lithium nickel cobalt oxide battery in a 5% sodium chloride solution for 18h, then drying and disassembling, soaking in a calcium hydroxide solution with the concentration of 8mol/L for 1.5h, filtering and washing to obtain black powder;
(2) taking 20g of black powder (lithium nickel cobaltate active substance), mixing the obtained black powder and iron powder according to the ratio of 1: 1.5, placing the mixture in a muffle furnace at 800 ℃ for roasting for 6 hours;
(3) taking 20g of lithium nickel cobaltate active substance, then dissolving the lithium nickel cobaltate active substance in 4mol/L nitric acid, controlling the pH of the filtrate to be 2, adding 20L of extracting agent, wherein the components of the extracting agent are P507 with the volume fraction of 30% and sulfonated kerosene with the volume fraction of 70%, the balance time is 15min, and then back-extracting with 10L of 2mol/L sulfuric acid, and the balance time is 15min, so that the obtained solution is a mixed solution of nickel nitrate and cobalt nitrate.
(4) Measuring the concentration of nickel ions and cobalt ions in the solution to be 0.60mol/L and 0.68mol/L by ICP (inductively coupled plasma), mixing manganese sulfate solutions with the same concentration after measuring the concentrations of cobalt and nickel ions, and adding tungsten oxide; adding 5mol/L sodium hydroxide and 5mol/L ammonia water into the prepared mixed solution, adjusting the pH value to 10.5, and adjusting the solution temperature to 45 ℃, wherein the ratio of nickel: cobalt: manganese: tungsten: basic propertyThe coprecipitation reaction is carried out on the substance (molar ratio) of 8:1:1:0.02:20, and the obtained product is washed and dried to obtain a precursor Ni0.8Co0.1Mn0.1W0.002(OH)2。
(5) The precursor Ni0.8Co0.1Mn0.1W0.002(OH)2Mixed with lithium hydroxide and boron oxide, and sintered, wherein the precursor is controlled to be: lithium hydroxide: boron oxide 1:1.04:0.022, and sintering at 820 ℃ for 13h to obtain the cathode material LiNi0.8Co0.1Mn0.1W0.001B0.004O2@0.02B2O3。
The precursor prepared by the embodiment has uniform particles, good sphericity, particle size of 2-4 μm and no microcrack; the prepared anode material is single crystal particles with the particle size of 2-4 mu m; the positive electrode material has a capacity of 160mAh g in a cycle of 100 circles at 2.75-4.4V-1The retention rate was 80%.
Example 3
(1) Soaking the waste lithium nickel cobalt oxide battery in a 4% sodium chloride solution for 16h, then drying and disassembling, soaking in an ammonia water solution with the concentration of 5mol/L for 1.5h, filtering and washing to obtain black powder;
(2) taking 10g of black powder (lithium nickel cobaltate active substance), mixing the obtained black powder and sulfur powder according to the ratio of 1: 1.5, placing the mixture in a tube furnace at 900 ℃ in argon atmosphere for roasting for 8 hours;
(3) taking 10g of lithium nickel cobaltate active substance, then dissolving the lithium nickel cobaltate active substance in 4mol/L nitric acid, controlling the pH of the filtrate to be 2, adding 10L of extracting agent, wherein the components of the extracting agent comprise 30% of P304 in volume fraction and 70% of sulfonated kerosene in volume fraction, carrying out back extraction for 15min, and then carrying out back extraction with 5L of 2mol/L sulfuric acid for 15min to obtain a mixed solution of nickel nitrate and cobalt nitrate.
(4) Measuring the concentration of nickel ions and cobalt ions in the solution to be 0.60mol/L and 0.68mol/L by ICP (inductively coupled plasma), mixing manganese sulfate solutions with the same concentration after measuring the concentrations of cobalt and nickel ions, and adding tungsten oxide; adding 5mol/L sodium hydroxide and 5mol/L ammonia water into the prepared mixed solution, adjusting the pH value to 10.5, and the solution temperature to45 ℃, wherein the ratio of nickel: cobalt: manganese: tungsten: the basic substance is added in a molar ratio of 8:1:1:0.03:20, coprecipitation reaction is carried out, the obtained product is washed and dried, and a precursor Ni is obtained0.8Co0.1Mn0.1W0.003(OH)2。
(5) The precursor Ni0.8Co0.1Mn0.1W0.003(OH)2Mixed with lithium hydroxide and boron oxide, and sintered, wherein the precursor is controlled to be: lithium hydroxide: boron oxide 1:1.06:0.012, and sintering at 820 ℃ for 12h to obtain the cathode material LiNi0.8Co0.1Mn0.1W0.001B0.004O2@0.01B2O3。
The precursor prepared by the embodiment has uniform particles, good sphericity, particle size of 2-4 μm and no microcrack; the prepared anode material is single crystal particles with the particle size of 2-4 mu m; the anode material is 2.75-4.4V, the capacity of 158m Ah g after 100 cycles-1The retention rate was 80.2%.
Comparative example 1
(1) Soaking the waste lithium nickel cobalt oxide battery in a 4% sodium chloride solution for 16h, then drying and disassembling, soaking in an ammonia water solution with the concentration of 5mol/L for 1.5h, filtering and washing to obtain black powder;
(2) taking 10g of black powder (lithium nickel cobaltate active substance), mixing the obtained black powder and sulfur powder according to the ratio of 1: 1.5, placing the mixture in a tube furnace at 900 ℃ in argon atmosphere for roasting for 8 hours;
(3) taking 10g of lithium nickel cobaltate active substance, then dissolving the lithium nickel cobaltate active substance in 4mol/L nitric acid, controlling the pH of the filtrate to be 2, adding 10L of extracting agent, wherein the components of the extracting agent comprise 30% of P304 in volume fraction and 70% of sulfonated kerosene in volume fraction, carrying out back extraction for 15min, and then carrying out back extraction with 5L of 2mol/L sulfuric acid for 15min to obtain a mixed solution of nickel nitrate and cobalt nitrate.
(4) Measuring the concentration of nickel ions in the solution to be 0.60mol/L and the concentration of cobalt ions to be 0.68mol/L by ICP (inductively coupled plasma), and mixing manganese sulfate solutions with the same concentrations after measuring the concentrations of cobalt and nickel ions; adding 5mol/L sodium hydroxide and 5mol/L ammonia water into the prepared mixed solution, and adjusting the pH value10.5, solution temperature 45 ℃, where nickel: cobalt: manganese: carrying out coprecipitation reaction on alkaline substances in a molar ratio of 8:1:1: 20, washing and drying the obtained product to obtain a precursor Ni0.8Co0.1Mn0.1(OH)2。
(5) The precursor Ni0.8Co0.1Mn0.1(OH)2Mixed sintering with lithium hydroxide, wherein the precursor: lithium hydroxide is 1:1.06, and sintering is carried out for 12h at 820 ℃ to obtain the cathode material LiNi0.8Co0.1Mn0.1O2。
The precursor prepared by the embodiment has uniform particles, good sphericity, particle size of 2-4 μm and no microcrack; the prepared anode material is single crystal particles with the particle size of 2-4 mu m; as shown in figure 3, the capacity of the cathode material is only 116mAh g in the circulation of 100 circles under the condition of 2.75-4.4V-1The retention ratio was 58%.
The above description is only a basic description of the present invention, and any equivalent changes made according to the technical solution of the present invention should fall within the protection scope of the present invention.

Claims (7)

1. A preparation method of a lithium nickel cobalt oxide battery regenerated ternary cathode material is characterized by comprising the following steps:
(1) discharging the waste lithium ion battery by adopting a sodium chloride solution, then disassembling, soaking the positive plate in an alkali liquor, and filtering to obtain black powder;
(2) carrying out reduction roasting on the obtained powder in a reducing atmosphere;
(3) and dissolving the obtained black powder in an acid solution, and extracting and removing impurities to obtain a relatively pure solution containing cobalt and lithium.
(4) After the concentration of cobalt and nickel ions is measured, adding a corresponding manganese source and a tungsten source into the solution, adding a precipitator and a coordination agent, adjusting the pH value, and carrying out a coprecipitation reaction to obtain a precursor;
(5) and mixing and sintering the precursor, a lithium source and a boron source to obtain the cathode material.
Wherein the chemical formula of the cathode material is LiNixCoyMnzWpBqO2@aB2O3Wherein x, y, z, p, q and a are mole numbers, x is more than or equal to 0.6<1，0<y≤0.2，0<z≤0.2，0<p≤0.08，0<q≤0.05，0<a≤0.05，x+y+z＝1。
2. The method for preparing the lithium nickel cobalt oxide battery regenerated ternary cathode material according to claim 1, wherein in the step (1), the discharge process is to immerse the waste lithium ion battery in a 0.2-6% sodium chloride solution for 18-48 h, the alkali in the adopted alkali solution is one or more of sodium hydroxide, ammonia water and calcium hydroxide, the pH value is 12-14, the immersion time is 1-2 h, and part of metal impurities (magnesium, calcium, aluminum and the like) are removed.
3. The preparation method of the lithium nickel cobalt oxide battery regenerated ternary cathode material according to claim 1, characterized in that the mass ratio of the reducing agent carbon powder used in the step (2) to the obtained black powder is 1: 1-3, and the roasting temperature is 500-800 ℃; the roasting time is 8-12 h, the electrolyte in the lithium nickel cobalt oxide is removed, and Fe is added3+Reduction to Fe2+。
4. According to the method, an acid solution only containing two metal elements of nickel and cobalt is obtained by extraction purification; the specific operation is as follows: filtering the inorganic acid solution dissolving the anode powder to remove insoluble substances, controlling the pH of the filtrate to be 2, adding an extractant with the volume 2-3 times that of the inorganic acid solution, balancing for 15min, and back-extracting with inorganic acid with the volume of the extractant 1/2 for 15min to obtain mixed acid containing nickel and cobalt; the components of the extractant are one or more of P204 or P507 with the volume fraction of 30 percent and sulfonated kerosene with the volume fraction of 70 percent, wherein the adopted inorganic acid is one or more of hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid.
5. The method for preparing the lithium nickel cobalt oxide battery regenerated ternary cathode material according to claim 1, wherein the method for measuring the concentration of cobalt and lithium ions adopted in the step (4) is an inductively coupled plasma spectrometer method, the manganese source is selected from one or more of manganese sulfate or manganese nitrate, and the tungsten source is tungsten oxide.
6. The method for preparing the lithium nickel cobalt oxide battery regenerated ternary cathode material according to claim 1, wherein the precipitator added in the step (4) is one or more of sodium hydroxide, potassium hydroxide and sodium carbonate, and the concentration is 6-7 mol/L; the complexing agent is one or more of ammonia water, ammonium sulfate, oxalic acid and ammonium bicarbonate, the concentration is 4-5 mol/L, the pH value is 10-11, and the solution temperature is 45-60 ℃.
7. The method for preparing the lithium nickel cobalt oxide battery regenerated ternary cathode material according to claim 1, wherein in the step (5), the lithium source is one or more selected from lithium nitrate and lithium hydroxide; the boron source is selected from one or more of boron nitrate and boron oxide. The sintering temperature is 750-850 ℃, and the time is 12-16 h.
CN202110966412.0A 2021-08-23 2021-08-23 Preparation method of lithium nickel cobalt oxide battery regenerated ternary cathode material Pending CN113880100A (en)

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