CN113611857B - Method for preparing ternary cathode material by using manganese-containing cobalt-nickel waste residues - Google Patents
Method for preparing ternary cathode material by using manganese-containing cobalt-nickel waste residues Download PDFInfo
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Abstract
The invention discloses a method for preparing a ternary cathode material by using manganese-containing cobalt-nickel waste residues, which comprises the following steps: (1) crushing and sieving; (2) oxidizing and leaching; (3) removing calcium; (4) optimizing the proportion of manganese, cobalt, nickel and magnesium; (5) preparing a precursor of the magnesium ion doped manganese-cobalt-nickel ternary cathode material; (6) preparing a ternary cathode material; (7) surface modification: and (3) dispersing the ternary cathode material in water, taking the manganese-cobalt-nickel-magnesium-rich solution subjected to calcium removal in the step (3) and ammonium fluoride as modifiers according to a certain mass ratio, carrying out surface modification on the ternary cathode material, and carrying out post-treatment after the modification is finished to obtain a finished product. The method is simple and feasible, can realize leaching of manganese-cobalt-nickel-magnesium-containing waste residues, directly prepare the magnesium ion-doped manganese-cobalt-nickel ternary cathode material precursor after filtering and impurity removal of filtrate, and prepare the ternary cathode material, thereby realizing comprehensive utilization of the waste residues, inhibiting the increase of electrochemical impedance and improving the cycle performance.
Description
Technical Field
The invention belongs to the field of wet metallurgy and clean metallurgy, and particularly relates to a method for preparing a ternary cathode material by using manganese-cobalt-nickel-containing waste residues.
Background
Manganese, cobalt and nickel are important industrial raw materials, and the electrolytic method is a common method for producing manganese, and comprises the following basic steps: leaching manganese ores to obtain manganese-containing leachate, then neutralizing and deironing, removing heavy metals by a vulcanizing agent, finally electrolyzing to obtain electrolytic manganese, and precipitating a large amount of manganese, cobalt and nickel in the form of cobalt sulfide in the heavy metal removal by the vulcanizing agent to cause loss of valuable metals of manganese, cobalt and nickel, so that the comprehensive utilization of the manganese, cobalt and nickel has great significance.
With the rapid growth of the electric automobile industry, the power battery recycling market will develop rapidly: the scale of 50 million yuan is reached in 2018, the scale of 136 million yuan is reached in 2020, and the scale of 311 million yuan is reached in 3 years of 202. The annual output of cobalt in the world is 15 ten thousand tons, the cobalt resource in China is imported at 95%, and the cobalt used in the battery industry in China accounts for 69%. The annual output of the global nickel is about 200 ten thousand tons, and the nickel used in the battery industry is about 4 ten thousand tons and accounts for about 2 percent.
The anode material of the lithium cobalt oxide battery is lithium cobalt oxide LiCoO2, the ternary material is nickel cobalt lithium manganate Li (NiCoMn) O2, the ternary composite anode material precursor product takes nickel salt, cobalt salt and manganese salt as raw materials, the proportion of the nickel, the cobalt and the manganese in the ternary composite anode material can be adjusted according to actual needs, the battery taking the ternary material as the anode has high safety compared with the lithium cobalt oxide battery, and the lithium cobalt oxide and the ternary material are good anode materials of the lithium battery, but the chemical properties of the lithium cobalt oxide and the ternary material are different, so the application fields are different according to different chemical properties of the lithium cobalt oxide battery. The preparation method of the magnesium ion doped manganese-cobalt-nickel ternary cathode material precursor mainly uses cobalt sulfate, nickel sulfate and manganese sulfate as raw materials, and has high production cost; the existing process is to leach the manganese smelting waste residue, remove iron and calcium, extract and separate for many times to obtain manganese sulfate, cobalt sulfate and nickel sulfate. If the obtained manganese sulfate, cobalt sulfate and nickel sulfate are used for preparing the ternary cathode material, the process is complicated. We have now found patents relating to the preparation of ternary cathode materials from waste residues, such as the following:
1. application No.: 202110002935.3, title of the invention: the invention relates to a method for regenerating a ternary precursor by utilizing nickel-cobalt-manganese slag, which comprises the steps of mixing the nickel-cobalt-manganese slag, water and a reducing agent, adjusting the obtained mixed solution to be alkaline, and mixing the mixed solution with ammonium salt to obtain mixed feed liquid; and carrying out hydrothermal reaction on the mixed liquid to obtain a ternary precursor. The method mixes the nickel-cobalt-manganese slag and a reducing agent to carry out hydrothermal reaction, and under the action of the reducing agent, metal oxides in the nickel-cobalt-manganese slag are reduced into corresponding + 2-valent metal hydroxides. The method provided by the invention directly reduces the nickel-cobalt-manganese slag into the ternary precursor, can realize the recycling of the waste ternary cathode material, and has a wide application prospect. The invention has the following disadvantages: the precursor of the prepared ternary cathode material is not further optimized.
2. Application No.: 201611180242.9, title of the invention: a method for preparing a nickel-cobalt-manganese ternary material precursor by utilizing nickel-cobalt slag comprises the following steps: step (1): acid leaching the nickel-cobalt slag material with the nickel/cobalt molar ratio of 3/1-8/1 at the pH of 1-5 and at the temperature of 30-80 ℃, and then carrying out solid-liquid separation to obtain an acid leaching slag material with the nickel-cobalt molar ratio of 1: 0.9-1.1; step (2): reducing and leaching the acid leaching slag material by hydrogen peroxide, chemically removing impurities, extracting and purifying to obtain a nickel-cobalt solution; and (3): manganese sulfate is added into the nickel-cobalt solution, and the nickel-cobalt-manganese ternary material precursor is prepared through coprecipitation. In the invention, under the synergistic leaching of the nickel-cobalt slag material under the pH and temperature, the method is beneficial to preparing acid leaching slag material with the molar ratio close to 1:1, and then the reduction leaching, impurity removal, purification and coprecipitation are carried out, so as to further prepare the nickel-cobalt-manganese ternary material precursor meeting the requirements. The invention has the following disadvantages: the leaching solution adopts a complex multi-stage extraction impurity removal process, and components which are beneficial to modification of the anode material are not utilized.
3. Application No.: 201810928293.8, title of the invention: a method for preparing a ternary material by recycling cobalt-manganese waste residues comprises the following steps: s1, extracting cobalt manganese salt; s2, removing iron ions; s3, preparing a cobalt and manganese mixed solution; s4, detecting cobalt sulfate and manganese sulfate solutions; s5, preparing a ternary precursor solution; and S6, synthesizing a ternary cathode material. The method can recover all cobalt and manganese, adopts an iron removal process at the same time, ensures the purity of the recovered cobalt and manganese to the maximum extent, adds a supplementary material into the recovered cobalt and manganese to meet the proportioning requirement of the ternary cathode material, avoids the waste of cobalt and manganese ions, and finally synthesizes the ternary cathode material with better electrochemical performance. The invention has the following disadvantages: the performance of the prepared ternary cathode material is not optimized.
4. Application No.: 201210135193.2, title of the invention: a method for preparing an electronic ternary material precursor by utilizing nickel cobalt slag adopts one or more methods of physics and chemistry to be used together, waste slag or waste containing nickel cobalt is pretreated, and nickel cobalt elements are primarily separated from other substances; for various waste slag or waste containing nickel and cobalt, the proportion of nickel and cobalt elements is adjusted to be 1 to (1-0.2) in mol ratio. The method is characterized in that other elements except nickel and cobalt are deeply purified by adopting an extraction method, the nickel and cobalt are treated as a group of clusters, other impurities are separated and purified, the nickel and cobalt are not separated any more, and a nickel and cobalt oxide precursor suitable for the ternary electronic material is directly generated through a metallurgical process technology. Adding sodium carbonate or sodium hydroxide into the sulfuric acid solution of nickel and cobalt to directly produce carbonate or hydroxide of nickel and cobalt. The invention has the important characteristic or innovation point that the combination of nickel and cobalt occurs on the ion level. Improves the environmental impact, obtains a new product of nickel and cobalt, and is beneficial to the resource recycling and the environment-friendly development. The invention has the following disadvantages: only a cobalt-nickel oxide precursor is obtained, a manganese oxide precursor is additionally introduced for preparing the ternary cathode material, and the sintering effect of the cobalt-nickel oxide precursor and the manganese oxide precursor is good without directly generating a precursor of the magnesium ion-doped manganese-cobalt-nickel ternary cathode material.
Disclosure of Invention
The invention aims to solve the technical problems and provides a method for preparing a ternary cathode material by using manganese-containing cobalt-nickel waste residues, which is simple and feasible, can realize leaching of the manganese-containing cobalt-nickel-magnesium waste residues, filtering and impurity removal of filtrate, directly prepare a magnesium ion-doped manganese-cobalt-nickel ternary cathode material precursor, and prepare the ternary cathode material, thereby realizing comprehensive utilization of the waste residues, realizing ionic conductivity of the product, inhibiting increase of electrochemical impedance and improving cycle performance.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for preparing a ternary cathode material by using manganese-cobalt-nickel-containing waste residues comprises the following steps:
(1) crushing and sieving: crushing and sieving the manganese-cobalt-nickel-containing waste residue;
(2) oxidizing and leaching: adding dilute sulfuric acid into the sieved waste residue containing manganese, cobalt and nickel, stirring and heating, introducing oxygen, leaching for a certain time, and filtering to obtain filter residue and filtrate;
(3) calcium removal: adding an organic extracting agent formed by mixing saponified P204 and sulfonated kerosene into the filtrate for extraction to obtain a calcium-loaded organic phase and a manganese-rich cobalt-nickel-magnesium solution;
(4) optimizing the proportion of manganese, cobalt, nickel and magnesium: taking the manganese-rich cobalt-nickel-magnesium solution, adding cobalt salt and nickel salt solution to adjust the molar ratio of manganese, cobalt, nickel and magnesium;
(5) preparing a precursor of the magnesium ion doped manganese-cobalt-nickel ternary cathode material: taking the manganese-cobalt-nickel-magnesium-rich solution with the optimized proportion, taking sodium hydroxide as a precipitator and ammonia water as a complexing agent to carry out coprecipitation reaction, and then filtering, drying and grinding to obtain a precursor of the magnesium ion-doped manganese-cobalt-nickel ternary positive electrode material;
(6) preparing a ternary cathode material: uniformly mixing a magnesium ion doped manganese cobalt nickel ternary positive electrode material precursor and lithium hydroxide according to a certain mass ratio, and sintering at high temperature to obtain Li (N)i0.6Co0.2Mn0.2)0.99Mg0.01O2A ternary positive electrode material;
(7) surface modification: and (3) dispersing the ternary cathode material in water, taking the manganese-cobalt-nickel-magnesium-rich solution subjected to calcium removal in the step (3) and ammonium fluoride as modifiers according to a certain mass ratio, carrying out surface modification on the ternary cathode material, and carrying out post-treatment after the modification is finished to obtain a finished product.
As a further technical scheme, the crushing and sieving are carried out, and the number of sampling meshes is 200-400 meshes.
As a further technical scheme, in the step (2), the mass concentration of the dilute sulfuric acid is 50-200 g/L, the liquid-solid ratio of the reaction is 5: 1-10: 1, the leaching temperature is 50-90 ℃, the oxygen pressure is 0.1-1 MPa, the leaching time is 60-180 min, and the end-point pH of the leaching is 3.0-4.0.
As a further technical scheme, in the step (3), before the extracting agent is added for extraction, the pH of the filtrate is adjusted to 0.5-2.0; the organic extractant is prepared by mixing P204 and sulfonated kerosene according to the volume fraction of P204 being 10-30%, then adding sodium hydroxide for saponification, wherein the saponification rate is 10-50%, and the O/A ratio of an organic phase to a water phase is 1: 1-3: 1.
As a further technical scheme, in the step (4), the cobalt salt is one or a mixture of cobalt sulfate, cobalt chloride and cobalt nitrate; the nickel salt is one or a mixture of nickel sulfate, nickel chloride and nickel nitrate.
As a further technical scheme, in the step (4), the molar ratio of manganese, cobalt, nickel and magnesium is adjusted to (0.5-0.8): (0.1-0.3): (0.1-0.3): (0.01-0.03).
As a further technical scheme, in the coprecipitation reaction, the molar concentration of sodium hydroxide is 1-3 mol/L, the volume percentage of ammonia water is 10-20%, the reaction pH is 10.0-12.0, the reaction temperature is 50-80 ℃, the stirring rate is 600-1200r/min, the time for dropwise adding the sodium hydroxide and the ammonia water is controlled to be 10-30 min, and the aging time after the coprecipitation reaction is 8-12 h.
As a further technical scheme, in the step (6), the sintering temperature is 650-900 ℃, the sintering time is 10 hours, and the lithium hydroxide dosage is 1-10% of the theoretical excess lithium hydroxide mass.
As a further technical scheme, in the step (7), the addition amount of the modifier is 1-5% of the mass of the ternary cathode material; the molar ratio of the manganese-rich cobalt-nickel-magnesium solution after calcium removal to ammonium fluoride is 1: 1.
as a further technical scheme, the post-treatment is to obtain a finished product after washing, filtering, drying and grinding the modified product.
Compared with the prior art, the invention has the following beneficial effects:
1. the method has simple and feasible process, realizes leaching of nickel sulfide, cobalt sulfide, manganese sulfide and magnesium sulfide, and has the basic principle of oxidative leaching as follows:
4MnO2+2NiS+4O2+4H2SO4＝4MnSO4+2NiSO4+4H2O；
4MnO2+2CoS+4O2+4H2SO4＝4MnSO4+2CoSO4+4H2O；
4MnO2+2MnS+2O2+4H2SO4＝6MnSO4+4H2O；
4MnO2+2MgS+2O2+4H2SO4＝6MgSO4+4H2O；
in the step, the negative divalent sulfur is oxidized into sulfate radicals, so that the generation of hydrogen sulfide is avoided, and the safety is improved.
2. The method adopts dilute sulfuric acid as a leaching agent, oxygen is introduced to reduce the acid dosage and improve the leaching rate, the end point pH value is 3.0-4.0 by controlling the acid dosage, a small amount of leached iron is oxidized to form ferric hydroxide to be directly precipitated, and the subsequent complex iron precipitation process is avoided.
3. The method adopts the organic extractant formed by mixing the saponified P204 and the sulfonated kerosene to extract and remove calcium, avoids secondary pollution of fluoride caused by a fluoride ion precipitation method, and can recycle the extractant, thereby reducing the production cost.
4. The invention takes the original impurity magnesium ions of the filtrate as a doping source, and directly carries out coprecipitation and doping to obtain Ni0.6Co0.2Mn0.2(OH)2Precursor and Mg (OH)2Avoiding additional doping source, Mg2+The retention of (b) can increase the ionic conductivity of the product.
5. According to the invention, the calcium-removed manganese-cobalt-nickel-magnesium-rich solution and ammonium fluoride are used as surface modifiers, so that the occurrence of interface side effects can be inhibited, a self-closed loop is formed, the increase of electrochemical impedance can be inhibited by avoiding additional metal ions, and the cycle performance is improved.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a ternary cathode material by using manganese-containing cobalt-nickel waste residues.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited to the scope of the examples.
The materials involved in the examples are all available from the factory or on the market.
A method for preparing a ternary cathode material by using manganese-cobalt-nickel-containing waste residues comprises the following steps:
(1) crushing and sieving: crushing and sieving the manganese-cobalt-nickel-containing waste residue; crushing and sieving, wherein the adopted sample separation sieve mesh number is 200-400 meshes.
(2) Oxidizing and leaching: adding dilute sulfuric acid into the sieved waste residues containing manganese, cobalt and nickel, stirring and heating, introducing oxygen, leaching for a certain time, and filtering to obtain filter residues and filtrate; the mass concentration of the dilute sulfuric acid is 50-200 g/L, the liquid-solid ratio of the reaction is 5: 1-10: 1, the leaching temperature is 50-90 ℃, the oxygen pressure is 0.1-1 MPa, the leaching time is 60-180 min, and the end-point pH of the leaching is 3.0-4.0.
(3) Calcium removal: adding an organic extracting agent formed by mixing saponified P204 and sulfonated kerosene into the filtrate for extraction for 10-min to obtain a calcium-loaded organic phase and a manganese-rich cobalt-nickel-magnesium solution; before the extracting agent is added for extraction, the pH value of the filtrate is adjusted to 0.5-2.0; the organic extractant is prepared by mixing P204 and sulfonated kerosene according to the volume fraction of P204 being 10-30%, then adding sodium hydroxide for saponification, wherein the saponification rate is 10-50%, and the O/A ratio of an organic phase to a water phase is 1: 1-3: 1.
(4) Optimizing the manganese-cobalt-nickel-magnesium ratio: taking the manganese-rich cobalt-nickel-magnesium solution, adding cobalt salt and nickel salt solution to adjust the molar ratio of manganese, cobalt, nickel and magnesium; the cobalt salt is one or a mixture of cobalt sulfate, cobalt chloride and cobalt nitrate; the nickel salt is one or a mixture of nickel sulfate, nickel chloride and nickel nitrate; adjusting the molar ratio of manganese, cobalt, nickel and magnesium to (0.5-0.8): (0.1-0.3): (0.1-0.3): (0.01-0.03).
(5) Preparing a precursor of the magnesium ion doped manganese-cobalt-nickel ternary cathode material: taking the manganese-cobalt-nickel-magnesium-rich solution with the optimized proportion, taking sodium hydroxide as a precipitator and ammonia water as a complexing agent to carry out coprecipitation reaction, and then filtering, drying and grinding to obtain a precursor of the magnesium ion-doped manganese-cobalt-nickel ternary positive electrode material; in the coprecipitation reaction, the molar concentration of sodium hydroxide is 1-3 mol/L, the volume percentage of ammonia water is 10-20%, the reaction pH is 10.0-12.0, the reaction temperature is 50-80 ℃, the stirring speed is 600 plus gases for 1200r/min, the time for dropwise adding the sodium hydroxide and the ammonia water is controlled to be 10-30 min, and the aging time after the coprecipitation reaction is 8-12 h.
(6) Preparing a ternary cathode material: uniformly mixing a magnesium ion doped manganese cobalt nickel ternary positive electrode material precursor and lithium hydroxide according to a certain mass ratio, and sintering at high temperature to obtain Li (N)i0.6Co0.2Mn0.2)0.99Mg0.01O2A ternary positive electrode material; and (6) sintering at 650-900 ℃ for 10h, wherein the lithium hydroxide is used in an amount which is 1-10% of the theoretical excess of the lithium hydroxide.
(7) Surface modification: dispersing the ternary cathode material in water, taking the manganese-cobalt-nickel-magnesium-rich solution subjected to calcium removal in the step (3) and ammonium fluoride as modifiers according to a certain mass ratio, carrying out surface modification on the ternary cathode material, and carrying out post-treatment after the modification is finished to obtain a finished product; the addition amount of the modifier is 1-5% of the mass of the ternary cathode material; the molar ratio of the manganese-rich cobalt-nickel-magnesium solution after calcium removal to ammonium fluoride is 1: 1; and post-treatment, namely washing, filtering, drying and grinding the modified product to obtain a finished product.
The manganese-cobalt-nickel-containing waste residue is mainly from a certain smelting plant in Guangxi, and the main components are shown in Table 1
| wMn/％ | wCo/％ | wNi/％ | wCa/％ | wMg/％ | wFe/％ |
| 12.83 | 1.25 | 1.07 | 1.83 | 1.34 | 1.32 |
Example 1:
crushing and sieving 10g of manganese-containing cobalt-nickel waste residue to 200 meshes, uniformly mixing, adding 90g/L dilute sulfuric acid according to a liquid-solid ratio of 10:1, introducing 0.1Mpa of oxygen, heating to 90 ℃, leaching, mechanically stirring, leaching for 180min, measuring the end point pH to be 3.0, filtering, adjusting the pH of the filtrate to be 0.5 by using the dilute sulfuric acid, mixing the filtrate with 30% by volume fraction P204 and 70% by volume fraction sulfonated kerosene according to a ratio of O/A to 1:1, adding sodium hydroxide for saponification, wherein the saponification rate of an extracting agent is 20%, extracting for 10min, separating in a separating funnel to obtain a calcium-removed manganese-rich cobalt-nickel-magnesium solution, carrying out element analysis on the solution by using ICP, adding appropriate amounts of cobalt sulfate, nickel sulfate and manganese sulfate solution, and adjusting the molar ratio of nickel, cobalt, manganese and magnesium ions in the solution to be 0.6: 0.2: 0.2: 0.01, simultaneously adding 1mol/L sodium hydroxide solution and 10% ammonia water solution in volume fraction, maintaining the pH value of the solution at 10.5, stirring at the speed of 800r/min and the reaction temperature of 80 ℃, aging for 10 hours after the reaction is finished, filtering, washing with deionized water for multiple times, and drying to obtain Ni0.6Co0.2Mn0.2(OH)2Precursor and Mg (OH)2. Adding lithium salt with mass excess of 2%, sintering at 800 deg.C for 10h to obtain Li [ N ]i0.6Co0.2Mn0.2]0.99Mg0.01O2And (3) a positive electrode material. Mixing Li [ N ]i0.6Co0.2Mn0.2]0.99Mg0.01O2Dispersing the anode material in deionized water, adding a modifier (the molar ratio of the manganese-cobalt-nickel-magnesium-rich solution after calcium removal to ammonium fluoride is 1: 1) according to 1% of the mass of the ternary anode material, and slowly dropwise adding the modifier into the Li [ N ] (the molar ratio of the manganese-cobalt-nickel-magnesium-rich solution after calcium removal to the ammonium fluoride is 1: 1)i0.6Co0.2Mn0.2]0.99Mg0.01O2The positive electrode material solution is stirred, washed, filtered, dried and ground to obtain fluoride surface modified Li [ N ]i0.6Co0.2Mn0.2]0.99Mg0.01O2And (3) a positive electrode material.
Example 2:
crushing and sieving 10g of manganese-containing cobalt-nickel waste residue to 200 meshes, uniformly mixing, adding 100g/L of dilute sulfuric acid according to a liquid-solid ratio of 9:1, introducing oxygen of 0.2Mpa, heating to 80 ℃ for leaching, mechanically stirring, leaching for 180min, measuring the end point pH to be 3.0, filtering, taking the filtrate, adjusting the pH to be 0.5 by using the dilute sulfuric acid, mixing by using 30% by volume of P204+ 70% by volume of sulfonated kerosene according to a ratio of O/A to 1:1, adding sodium hydroxide for saponification, wherein the saponification rate of an extracting agent is 20%, extracting for 10min, separating in a separating funnel to obtain a calcium-removed manganese-rich cobalt-nickel-magnesium solution, carrying out element analysis on the solution by using ICP, adding a proper amount of cobalt sulfate, nickel sulfate and manganese sulfate solution, and adjusting the molar ratio of nickel, cobalt, manganese and magnesium in the solution to be 0.5: 0.3: 0.2: 0.02, simultaneously adding 2mol/L sodium hydroxide solution and ammonia water solution with volume fraction of 15%, maintaining the pH value of the solution at 11, stirring at the speed of 1200r/min and the reaction temperature of 85 ℃, aging for 10h after the reaction is finished, filtering and washing for multiple times by deionized water, and drying to obtain Ni0.5Co0.3Mn0.2(OH)2Precursor and Mg (OH)2. Adding lithium salt with 5 mass excess, sintering at 850 deg.C for 10h to obtain Li [ N ]i0.5Co0.3Mn0.2]0.98Mg0.02O2And (3) a positive electrode material. Mixing Li [ N ]i0.5Co0.3Mn0.2]0.98Mg0.02O2The cathode material is dispersed in deionized water and then added according to 5 percent of the mass of the ternary cathode materialAdding modifier (the molar ratio of the manganese-rich cobalt-nickel-magnesium solution after calcium removal to the ammonium fluoride is 1: 1), and slowly dropwise adding the modifier into the Li [ N ] (the molar ratio of the manganese-rich cobalt-nickel-magnesium solution after calcium removal to the ammonium fluoride is 1: 1)i0.5Co0.3Mn0.2]0.98Mg0.02O2The positive electrode material solution is stirred, washed, filtered, dried and ground to obtain fluoride surface modified Li [ N ]i0.5Co0.3Mn0.2]0.98Mg0.02O2And (3) a positive electrode material.
Example 3:
crushing and sieving 10g of manganese-cobalt-nickel-containing waste residue to 200 meshes, uniformly mixing, adding 110g/L of dilute sulfuric acid according to a liquid-solid ratio of 8:1, introducing oxygen of 0.15Mpa, heating to 85 ℃ for leaching, mechanically stirring, leaching for 180min, measuring the end point pH to be 3.0, filtering, adjusting the pH of the filtrate to be 0.5 by using the dilute sulfuric acid, mixing with 30% by volume of P204+ 70% of sulfonated kerosene according to a ratio of O/A to 1:1, adding sodium hydroxide for saponification, wherein the saponification rate of an extracting agent is 20%, extracting for 10min, separating in a separating funnel to obtain a calcium-removed manganese-cobalt-nickel-rich magnesium solution, performing element analysis on the solution by using ICP, adding a proper amount of cobalt sulfate, nickel sulfate and manganese sulfate solution, and adjusting the molar ratio of nickel, cobalt, manganese and magnesium in the solution to be 0.8: 0.1: 0.1: 0.03, simultaneously adding 3mol/L sodium hydroxide solution and ammonia water solution with volume fraction of 20%, maintaining the pH value of the solution at 12, stirring at the speed of 1100r/min and the reaction temperature of 85 ℃, aging for 10h after the reaction is finished, filtering and washing for multiple times by deionized water, and drying to obtain Ni0.8Co0.1Mn0.1(OH)2 precursor and Mg (OH)2. Adding lithium salt with 5 mass excess, sintering at 900 deg.C for 10h to obtain Li [ N ]i0.8Co0.1Mn0.1]0.97Mg0.03O2And (3) a positive electrode material. Mixing Li [ N ]i0.8Co0.1Mn0.1]0.97Mg0.03O2Dispersing the anode material in deionized water, adding a modifier (the molar ratio of the manganese-cobalt-nickel-magnesium-rich solution after calcium removal to ammonium fluoride is 1: 1) according to 2% of the mass of the ternary anode material, and dropwise adding the modifier into the Li [ N ] (the molar ratio of the manganese-cobalt-nickel-magnesium-rich solution after calcium removal to the ammonium fluoride is 1: 1)i0.8Co0.1Mn0.1]0.97Mg0.03O2Stirring and washing the anode material solution,filtering, drying and grinding to obtain fluoride surface modified Li [ N ]i0.8Co0.1Mn0.1]0.97Mg0.03O2And (3) a positive electrode material.
The preparation of the ternary cathode material is achieved by recycling the manganese-cobalt-nickel-containing waste residues, the pretreatment is carried out on a large scale by using mechanical equipment to crush, so that easily-leached fine residues are obtained, the industrial production is facilitated, the leachate containing nickel, cobalt, manganese and magnesium salts is obtained, the leachate after calcium removal can be directly precipitated after the component proportion is adjusted to obtain various magnesium ion-doped manganese-cobalt-nickel ternary cathode precursor material precursors with different proportions, valuable metals manganese, cobalt and nickel are directly prepared into the ternary cathode material precursor through a wet process, the impurity magnesium ions are directly used for doping, the adoption of a magnesium ion impurity removal process is avoided, the preparation of the precursor after the manganese, cobalt and nickel are separated by adopting a complex separation process is avoided, and the low-component recycling of the waste residues is realized.
The product test indexes of examples 1 to 3 are shown in Table 2:
TABLE 2
| Element(s) | Manganese (g/g sample) | Cobalt (g/g sample) | Nickel (g/g sample) | Magnesium (g/g sample) |
| Example 1 | 0.1127 | 0.121 | 0.3598 | 0.0025 |
| Example 2 | 0.1109 | 0.1793 | 0.2981 | 0.0076 |
| Example 3 | 0.055 | 0.059 | 0.4701 | 0.0072 |
Example 1 is used as Mg2+Doping detection:
example 1: ni0.6Co0.2Mn0.2(OH)2Precursor and Mg (OH)2
Comparative example one: ni0.6Co0.2Mn0.2(OH)2Precursor body
The lithium ion diffusion coefficient of the sample was measured using a constant current batch titration technique, and the results as shown in table 3 were obtained.
TABLE 3
| Sample (I) | Example 1 | Comparative example 1 |
| Diffusion coefficient of lithium ion | 2.39×10-9cm2/s | 1.41×10-9cm2/s |
As seen from table 3, the ionic conductivity of the product doped with magnesium ions was improved.
The invention uses example 1 for the modifier comparison test:
example 1: the modifier is metal fluoride generated by rich manganese, cobalt, nickel and magnesium solution and ammonium fluoride after calcium removal.
Comparative example two: the surface modification treatment was not performed, and the procedure was otherwise the same as in example 1.
The detection is carried out by constant current-constant voltage charging (the charging cut-off current is 0.1C) and constant current discharging method, and the detection results are shown in Table 4:
TABLE 4
| Example 1 | 50 weeks | For 100 weeks | 150 weeks | 200 weeks |
| Capacity retention rate | 99.1％ | 98％ | 90.2％ | 83.2％ |
| Comparative example 2 | 50 weeks | For 100 weeks | 150 weeks | 200 weeks |
| Capacity retention rate | 98.5％ | 95.7％ | 86.4％ | 77.7％ |
As seen from table 4: the method adopts the modifier to react Li (N)i0.6Co0.2Mn0.2)0.99Mg0.01O2After the anode material is modified, the product has better cycle performance.
The above-described embodiments are only specific examples for further explaining the object, technical solution and advantageous effects of the present invention in detail, and the present invention is not limited thereto. Any modification, equivalent replacement, improvement and the like made within the scope of the present disclosure are included in the protection scope of the present invention.
Claims (10)
1. A method for preparing a ternary cathode material by using manganese-containing cobalt-nickel waste residues is characterized by comprising the following steps:
(1) crushing and sieving: crushing and sieving the manganese-cobalt-nickel-containing waste residue;
(2) oxidizing and leaching: adding dilute sulfuric acid into the sieved waste residues containing manganese, cobalt and nickel, stirring and heating, introducing oxygen, leaching for a certain time, and filtering to obtain filter residues and filtrate;
(3) calcium removal: adding an organic extracting agent formed by mixing saponified P204 and sulfonated kerosene into the filtrate for extraction to obtain a calcium-loaded organic phase and a manganese-rich cobalt-nickel-magnesium solution;
(4) optimizing the proportion of manganese, cobalt, nickel and magnesium: taking the manganese-rich cobalt-nickel-magnesium solution, adding cobalt salt and nickel salt solution to adjust the molar ratio of manganese, cobalt, nickel and magnesium;
(5) preparing a precursor of the magnesium ion doped manganese-cobalt-nickel ternary cathode material: taking the manganese-rich cobalt-nickel-magnesium solution with the optimized proportion, taking sodium hydroxide as a precipitator and ammonia water as a complexing agent to carry out coprecipitation reaction, and then filtering, drying and grinding to obtain a precursor of the magnesium ion doped manganese-cobalt-nickel ternary positive electrode material;
(6) preparing a ternary cathode material: uniformly mixing a magnesium ion doped manganese-cobalt-nickel ternary positive electrode material precursor and lithium hydroxide according to a certain mass ratio, and sintering at a high temperature to obtain a ternary positive electrode material;
(7) surface modification: and (3) dispersing the ternary cathode material in water, taking the manganese-cobalt-nickel-magnesium-rich solution subjected to calcium removal in the step (3) and ammonium fluoride as modifiers according to a certain mass ratio, carrying out surface modification on the ternary cathode material, and carrying out post-treatment after the modification is finished to obtain a finished product.
2. The method for preparing the ternary cathode material by using the manganese-cobalt-nickel-containing waste residue as claimed in claim 1, wherein the method comprises the following steps: and (4) crushing and sieving, wherein the adopted sample separation sieve mesh number is 200-400 meshes.
3. The method for preparing the ternary cathode material by using the manganese-cobalt-nickel-containing waste residue as claimed in claim 1, wherein the method comprises the following steps: in the step (2), the mass concentration of the dilute sulfuric acid is 50-200 g/L, the liquid-solid ratio of the reaction is 5: 1-10: 1, the leaching temperature is 50-90 ℃, the oxygen pressure is 0.1-1 MPa, the leaching time is 60-180 min, and the end-point pH of the leaching is 3.0-4.0.
4. The method for preparing the ternary cathode material by using the manganese-cobalt-nickel-containing waste residue as claimed in claim 1, wherein the method comprises the following steps: in the step (3), before the extracting agent is added for extraction, the pH of the filtrate is adjusted to 0.5-2.0; the organic extractant is prepared by mixing P204 and sulfonated kerosene according to the volume fraction of P204 being 10-30%, then adding sodium hydroxide for saponification, wherein the saponification rate is 10-50%, and the O/A ratio of an organic phase to a water phase is =1: 1-3: 1; the extraction time of the organic extractant is 10 min.
5. The method for preparing the ternary cathode material by using the manganese-cobalt-nickel-containing waste residue as claimed in claim 1, wherein the method comprises the following steps: in the step (4), the cobalt salt is one or a mixture of cobalt sulfate, cobalt chloride and cobalt nitrate; the nickel salt is one or a mixture of nickel sulfate, nickel chloride and nickel nitrate.
6. The method for preparing the ternary cathode material by using the manganese-cobalt-nickel-containing waste residue as claimed in claim 1, wherein the method comprises the following steps: in the step (4), the molar ratio of manganese, cobalt, nickel and magnesium is adjusted to (0.5-0.8): (0.1-0.3): (0.1-0.3): (0.01-0.03).
7. The method for preparing the ternary cathode material by using the manganese-cobalt-nickel-containing waste residue as claimed in claim 1, wherein the method comprises the following steps: in the coprecipitation reaction, the molar concentration of sodium hydroxide is 1-3 mol/L, the volume percentage of ammonia water is 10-20%, the reaction pH is 10.0-12.0, the reaction temperature is 50-80 ℃, the stirring speed is 600-1200r/min, the time for dropwise adding the sodium hydroxide and the ammonia water is controlled to be 10-30 min, and the time for aging after the coprecipitation reaction is 8-12 h.
8. The method for preparing the ternary cathode material by using the manganese-cobalt-nickel-containing waste residue as claimed in claim 1, wherein the method comprises the following steps: and (6) sintering at 650-900 ℃ for 10h, wherein the lithium hydroxide is used in an amount which is 1-10% of the theoretical excess of the lithium hydroxide.
9. The method for preparing the ternary cathode material by using the manganese-cobalt-nickel-containing waste residue as claimed in claim 1, wherein the method comprises the following steps: in the step (7), the addition amount of the modifier is 1-5% of the mass of the ternary cathode material; the molar ratio of the manganese-rich cobalt-nickel-magnesium solution after calcium removal to ammonium fluoride is 1: 1.
10. the method for preparing the ternary cathode material by using the manganese-cobalt-nickel-containing waste residue as claimed in claim 1, wherein the method comprises the following steps: and the post-treatment is to obtain a finished product after washing, filtering, drying and grinding the modified product.
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