CN108878836B - Method for directly preparing lithium zincate modified ternary cathode material by using waste lithium battery cathode material - Google Patents
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Abstract
The invention belongs to the technical field of ternary material precursor preparation, and particularly relates to a method for directly preparing a lithium zincate modified ternary positive electrode material by using a waste lithium battery positive electrode material, which comprises the following steps: separating the anode material from the waste lithium ion battery; leaching with caustic solution, and filtering; adding carbonate into the filtrate to obtain lithium carbonate; leaching the filter cake with sulfuric acid to obtain a leaching solution; adjusting the mole ratio of nickel, cobalt and manganese in the leaching solution; enabling the leachate, an ammonia water solution and a caustic alkali solution to flow into a reaction kettle in parallel, and preparing a ternary material precursor through coprecipitation; mixing the lithium carbonate with the mixture and roasting the mixture to obtain a ternary cathode material; mixing zinc acetate, glycol ether, amine and lithium methoxide, adding the ternary cathode material to obtain gel, and roasting to obtain the lithium zincate modified ternary cathode material. The lithium zincate modified ternary cathode material has the advantages of strong structural stability, good electrochemical performance, reduced production cost, high product quality and realization of directional circulation of nickel, cobalt, manganese and lithium resources.
Description
Technical Field
The invention belongs to the technical field of ternary material precursor preparation, and particularly relates to a method for directly preparing a lithium zincate modified ternary positive electrode material by using a waste lithium battery positive electrode material.
Background
Global energy consumption and carbon dioxide emission show an exponential growth trend, and the demand for new renewable energy sources is increasing. Since 2014, the related policies of new energy automobiles are concentrated, along with the continuous progress of the power battery technology, the whole industrial chain enters a high-speed development period, the shipment volume of the power battery presents a high-speed growth situation, and the first decommissioning tide of the power battery is about to come in 2018. Ternary lithium ion batteries are of higher recycling value in consumer batteries. The decommissioning scale of the ternary lithium ion battery is rapidly increased in the last three years, and the decommissioned ternary lithium ion battery reaches more than 60Gwh by 2020. Along with the large-scale application of ternary lithium ion batteries in the fields of passenger vehicles and logistics vehicles, the demand of cobalt is greatly improved, and the price of the cobalt in China is continuously increased. In addition, the cost of recycling each ton of nickel through the waste power batteries is below ten thousand yuan, and the cost of producing each ton of nickel through direct nickel ore is below 6 ten thousand yuan, so the cost of recycling the metal raw materials is lower than the cost of directly developing from mineral products. Therefore, the ternary material battery resource recycling has the significance of reducing the cost. However, the ternary and lithium composite materials produced during the recycling process often have a large impact on the electrochemical performance.
Chinese patent CN102751549A discloses a method for recycling all components of a waste lithium ion battery anode material, which comprises the following steps: (1) separating active substances and aluminum foils in the anode materials of the waste lithium ion batteries by adopting a fluorine-containing organic acid aqueous solution, and performing liquid-solid separation to obtain a leaching solution, a lithium-containing active substance and the aluminum foils; (2) respectively carrying out high-temperature roasting and alkali liquor impurity removal treatment on the lithium-containing active substances; (3) respectively carrying out acid distillation on the leachate to recover fluorine-containing organic acid, alkali precipitation of impurity ions and ammonium carbonate coprecipitation to prepare a nickel-cobalt-manganese carbonate ternary precursor; (4) regulating and controlling the components of the treated active substance and the nickel-cobalt-manganese carbonate ternary precursor mixture, adding a certain proportion of lithium carbonate, and then carrying out high-temperature solid phase sintering to prepare the nickel-cobalt-manganese lithium manganate ternary composite positive electrode material. Firstly, leaching materials by adopting a fluorine-containing organic acid aqueous solution, completely leaching nickel, cobalt, manganese, lithium and aluminum in a waste lithium ion battery positive electrode material, precipitating to obtain a nickel cobalt lithium manganate ternary composite positive electrode material, adding a certain proportion of lithium carbonate, and preparing the nickel cobalt lithium manganate ternary composite positive electrode material by high-temperature solid phase sinteringAnd mixing the positive electrode material. The nickel cobalt lithium manganate ternary composite positive electrode material is not modified, and the nickel cobalt lithium manganate prepared by the method is characterized by XRD (X-ray diffraction), has complete crystal structure, low impurity content, average particle size of 5.0-8.5 mu m and specific surface area of 0.39-0.61m2·g-1(ii) a The first discharge capacity is 143-155 mAh.g through electrochemical detection-1And the product can be maintained at 130mAh g after 30 cycles-1As described above, the electrochemical performance is good.
Chinese patent CN106848470A discloses a method for recovering and preparing ternary cathode materials from waste nickel-cobalt-manganese ternary lithium ion batteries, which comprises the following steps: (1) disassembling, crushing, roasting and leaching a waste nickel-cobalt-manganese ternary lithium ion battery to obtain a leaching solution containing Li, Ni, Co and Mn, and carrying out impurity removal treatment on the leaching solution to obtain an impurity removal solution; (2) adjusting the molar ratio of Ni, Co and Mn in the impurity removal solution, then adding alkali metal hydroxide and regulating and controlling the pH value of the system to be more than or equal to 10, and performing primary precipitation to obtain turbid solution in which NCM hydroxide is precipitated; (3) adding carbonate into the turbid solution obtained in the step (2) for secondary precipitation, and then carrying out solid-liquid separation to obtain a ternary material precursor; (4) and calcining the precursor of the ternary material in the air to obtain the ternary cathode material. The ternary material obtained in the patent has the specific capacity of 169mAh/g at the maximum after 100 cycles of circulation when the ternary material is discharged at a constant current of 0.5C at room temperature.
However, the existing ternary cathode material prepared by using the waste lithium battery cathode material generally has the defect of poor stability. Therefore, research and development of a method for preparing a ternary cathode material by using a waste lithium battery cathode material are urgently needed, and the prepared ternary cathode material is strong in structural stability and good in electrochemical performance.
Disclosure of Invention
The invention aims to provide a method for directly preparing a lithium zincate modified ternary cathode material by using a waste lithium battery cathode material, and the obtained ternary cathode material has the advantages of strong structural stability, good electrochemical performance, simple process flow and low production cost.
The method for directly preparing the lithium zincate modified ternary cathode material by using the waste lithium battery cathode material comprises the following steps of:
(1) disassembling the waste lithium ion battery, separating out a positive plate, roasting, crushing and screening the positive plate, and separating out a positive material from the aluminum foil;
(2) leaching the positive electrode material with caustic alkali solution, and filtering to obtain filtrate and filter cake;
(3) adding carbonate into the filtrate for reaction, and filtering to obtain lithium carbonate solid and caustic alkali solution;
(4) leaching the filter cake with sulfuric acid to obtain a leaching solution and filter residue;
(5) adjusting the mole ratio of nickel, cobalt and manganese in the leaching solution;
(6) under the protection of inert gas, enabling leachate and an ammonia solution obtained after the molar ratio of nickel, cobalt and manganese is adjusted and the caustic alkali solution obtained in the step (3) to flow into a reaction kettle containing the ammonia solution, and carrying out coprecipitation under the protection of inert gas to prepare a ternary material precursor;
(7) drying the ternary material precursor, and mixing and roasting the dried ternary material precursor and the lithium carbonate solid obtained in the step (3) to obtain a ternary positive electrode material;
(8) zinc acetate is used as a zinc source, ethylene glycol methyl ether or a mixture of ethylene glycol methyl ether and water is used as a solvent, amines are used as a stabilizer, the mixture is mixed with lithium methoxide, the temperature is increased, a ternary cathode material is added, standing is carried out to obtain gel, and the lithium zincate modified ternary cathode material is obtained by roasting.
Wherein:
in the step (1), the molar ratio of nickel, cobalt and manganese in the anode material is one or more of 5:2:3, 3:3:3, 6:2:2, 8:1:1 or 4:2: 2; the roasting temperature is 450-700 ℃, and the roasting time is 10-60 min.
In the step (2), the caustic alkali is sodium hydroxide, calcium hydroxide, potassium hydroxide or lithium hydroxide; the concentration of the caustic alkali solution is 0.5-3 mol/L; the leaching temperature is 10-100 ℃, the leaching time is 0.5-2h, and the liquid-solid ratio of caustic alkali solution to the anode material in leaching is 4-12: 1.
In the step (3), the carbonate is potassium carbonate or sodium carbonate, the reaction temperature is 20-90 ℃, and the reaction time is 10-60 min.
In step (3), the caustic solution is recovered and returned to the process for recycling.
In the step (4), the molar concentration of the sulfuric acid is 0.5-3.5 mol/L; the leaching temperature is 50-100 ℃, the leaching time is 30-240min, and the liquid-solid ratio of the sulfuric acid to the filter cake is 4-12: 1.
In the step (5), the concentration of nickel in the adjusted leaching solution is 1-4mol/L, and the molar ratio of nickel, cobalt and manganese is 5:2:3, 3:3:3, 6:2:2, 8:1:1 or 4:2: 4; when the mole ratio of nickel, cobalt and manganese in the leachate is adjusted, the nickel, cobalt and manganese are added in the form of sulfate, nitrate or hydrochloride of nickel, cobalt and manganese.
In the step (6), the inert gas is nitrogen or argon; the ammonia water solution has the molar concentration of 0.5-2.5mol/L, the caustic alkali solution obtained in the step (3) has the molar concentration of 0.5-2.5mol/L, the adding speed of the leachate after the molar ratio of nickel, cobalt and manganese is adjusted is 1-8ml/min, the adding speed of the ammonia water solution is 1-8ml/min, and the adding speed of the caustic alkali solution is 2-20 ml/min; before cocurrent, the volume of the ammonia solution in the reaction kettle containing the ammonia solution accounts for 1/5-1/4 of the total volume of the reaction kettle.
In the step (7), the drying temperature is 70-120 ℃, and the drying time is 10-20 hours; the roasting is carried out for 3-6h at 30-650 ℃, and then argon is introduced for 7-15h at 700-900 ℃.
In the step (8), the mass ratio of the ethylene glycol monomethyl ether to the water in the mixture of the ethylene glycol methyl ether and the water is 1.5-2.5: 1.
In the step (8), the amine is ammonium monoacetate, the molar ratio of zinc acetate to ammonium monoacetate is 0.5-1.5:1, the molar ratio of lithium methoxide to zinc acetate is 2-2.5:1, and the molar ratio of ethylene glycol monomethyl ether to zinc acetate is 2-3: 1.
In the step (8), zinc acetate is used as a zinc source, ethylene glycol methyl ether or a mixture of ethylene glycol methyl ether and water is used as a solvent, amines are used as a stabilizer, the mixture is mixed with lithium methoxide, stirred at normal temperature for 10-40min, heated to 50-90 ℃, added with the ternary anode material, stirred for 1.5-3h, kept stand for 30-50h to obtain gel, and roasted at the temperature of 700-900 ℃ for 60-180min to obtain the lithium zincate modified ternary anode material.
The chemical reaction equation in the gelation process when the lithium zincate modified ternary cathode material is prepared is as follows:
Zn(CH3COO)2+2H2O＝Zn(OH)2+2CH3COOH；
2n Zn(OH)2＝(Zn-O-Zn)n+2n H2O+0.5nO2；
(Zn-O-Zn)n+4n LiOCH3+6.5nO2＝2n Li2ZnO2+4n CO2+6n H2O。
the invention has the following beneficial effects:
the invention provides a method for directly preparing lithium zincate modified ternary cathode material by utilizing waste lithium battery cathode material in order to overcome the current situations of insufficient nickel-cobalt-manganese-lithium resources, waste battery pollution and the like, the method comprises the steps of disassembling the waste lithium battery, separating out a cathode plate, separating out the cathode material by the cathode plate, leaching the cathode material by caustic alkali solution, and precipitating metal lithium in filtrate by carbonate to realize the recovery of lithium; leaching the filter cake with sulfuric acid, adjusting the molar concentration of nickel, cobalt and manganese, then under the protection of inert gas, enabling the leaching solution after the molar ratio of nickel, cobalt and manganese is adjusted, an ammonia water solution and a caustic alkali solution to flow into a reaction kettle in parallel, carrying out coprecipitation under the protection of inert gas to prepare a ternary material precursor, drying the ternary material precursor, and then mixing and roasting the ternary material precursor and lithium carbonate solid to obtain a ternary positive electrode material; and mixing the ternary cathode material with a mixture of zinc acetate, ethylene glycol monomethyl ether, ammonium monoacetate and lithium methoxide, and roasting to obtain the lithium zincate modified ternary cathode material. The obtained lithium zincate modified ternary cathode material has good electrochemical performance.
The caustic alkali solution can not leach nickel, cobalt and manganese, and can only leach lithium, so that the low-temperature recovery of lithium is realized, the prior art does not relate to the low-temperature recovery of lithium before the recovery of nickel, cobalt and manganese, and the recovery rate of lithium is improved; because the precipitation speed of the nickel, the cobalt and the caustic alkali solution is far higher than that of the manganese and the caustic alkali solution, a part of ammonia water solution is added into the reaction kettle in advance, then the rest ammonia water solution is added into the reaction kettle together with the leachate and the caustic alkali solution after the molar ratio of the nickel, the cobalt and the manganese is adjusted, the nickel and the cobalt react with the ammonia water to form a complex, and the complex reacts with the caustic alkali solution, so that the precipitation speed of the nickel, the cobalt and the caustic alkali solution is reduced, the manganese, the nickel and the cobalt are ensured to be precipitated simultaneously, and the distribution uniformity of the nickel, the cobalt and the manganese in the ternary material is ensured.
According to the invention, under the conditions that ethylene glycol methyl ether or a mixture of ethylene glycol methyl ether and water is used as a solvent and amines are used as a stabilizer, zinc acetate is firstly hydrolyzed into zinc hydroxide, the zinc hydroxide reacts with lithium methoxide to generate lithium zincate, the lithium zincate modifies the ternary cathode material, and the lithium zincate modified ternary cathode material is obtained by roasting, so that the electrochemical performance of the ternary cathode material is improved.
When the ternary cathode material is charged to high voltage, a large amount of Co in the ternary cathode material3+And Mn2+Will oxidize into Co4+And Mn4+Thereby forming oxygen defects, and weakening the binding force between the transition metal and oxygen, thereby dissolving high-valence ions into the electrolyte. Li2ZnO2After coating modification, in the process of charging and discharging, the ternary cathode material and Li2ZnO2The contact interface can be rearranged, so that the formation of oxygen defects is reduced, and the structural stability of the ternary cathode material is improved.
The method directly utilizes the nickel-cobalt-manganese material obtained in the recovery process of the waste lithium ion battery to synthesize the lithium zincate modified nickel-cobalt-manganese ternary material, and is particularly suitable for providing high-quality nickel source, cobalt source and manganese source for the production of the lithium ion battery material. The method takes the waste lithium ion battery as the raw material, has low cost, high product quality and good economical efficiency, and realizes the directional circulation of the nickel, cobalt, manganese and lithium resources. After the integrated new formulation of lily and radix astragali decoction is subjected to scale production, huge environmental benefits, social benefits and economic benefits can be brought.
Drawings
FIG. 1 is an SEM image of a lithium zincate modified ternary cathode material of example 1;
FIG. 2 is a time-current and time-voltage plot of the lithium zincate modified ternary cathode material of example 1;
FIG. 3 is an SEM image of a lithium zincate modified ternary cathode material of example 2;
FIG. 4 is a graph of capacity versus voltage for coin cells assembled from the lithium zincate modified ternary cathode material of example 2;
FIG. 5 is an SEM image of a lithium zincate modified ternary cathode material of example 3;
FIG. 6 is a graph of the charge-discharge efficiency of a button cell assembled from the lithium zincate modified ternary cathode material in example 3;
FIG. 7 is an SEM image of a lithium zincate modified ternary cathode material of example 4;
figure 8 is a time-current and time-voltage plot of the lithium zincate modified ternary cathode material of example 4.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
Roasting the anode plate disassembled and separated from the waste lithium ion battery for 15min at 650 ℃, crushing an obtained roasted product on a crusher, screening, and separating an anode material from an aluminum foil; the molar ratio of nickel, cobalt and manganese in the anode material is 5:2:3 and 8:1: 1;
leaching the anode material with 2.5mol/L sodium hydroxide solution at 95 ℃ for 40min, wherein the liquid-solid ratio of the sodium hydroxide solution to the anode material is 10:1 during leaching, and filtering to obtain filtrate and filter cake;
adding sodium carbonate with the mole number 0.5 time that of lithium ions into the filtrate, stirring and reacting for 60min at 25 ℃ to generate a turbid solution, and filtering to obtain lithium carbonate solid and filtrate, wherein the filtrate is 2.2mol/L sodium hydroxide solution; the recovery rate of lithium is 94.6%;
leaching the filter cake for 220min at 50 ℃ by using 1.0mol/L sulfuric acid solution, wherein the liquid-solid ratio of the sulfuric acid solution to the filter cake in leaching is 11:1, so as to obtain leachate;
adjusting the concentration of nickel ions in the leachate to be 1.5mol/L, and simultaneously adding cobalt chloride and manganese chloride to ensure that the molar ratio of nickel, cobalt and manganese in the solution is 6:2: 2;
adding 200ml of 0.6mol/L ammonia water solution into a reaction kettle, stirring at the speed of 800r/min, adding the 0.6mol/L ammonia water solution, leachate obtained after adjusting the molar ratio of nickel, cobalt and manganese and the sodium hydroxide solution with the concentration of 2.2mol/L into the reaction kettle in a concurrent flow manner, using nitrogen as atmosphere protection, carrying out coprecipitation, carrying out solid-liquid separation, and drying to obtain a ternary material precursor; wherein the adding speed of ammonia water is 3ml/min, the dropping speed of the leaching solution after adjusting the mole ratio of nickel, cobalt and manganese is 5ml/min, and the adding speed of sodium hydroxide solution is 10 ml/min;
drying the ternary material precursor at 80 ℃ for 20 hours, mixing the dried ternary material precursor with the obtained lithium carbonate solid, roasting the mixture at 100 ℃ for 6 hours, and then introducing argon gas at 700 ℃ for 14 hours to obtain a ternary cathode material;
zinc acetate is used as a zinc source, ethylene glycol monomethyl ether is used as a solvent, ammonium monoacetate is used as a stabilizer, the mixture is stirred for 15min at normal temperature after being mixed with lithium methoxide, the temperature is raised to 60 ℃, the ternary cathode material is added, the mixture is stirred for 2.5h and is kept stand for 50h to obtain gel, the gel is roasted for 150min at 750 ℃, and the ternary cathode material modified by lithium zincate is obtained, wherein the molar ratio of zinc acetate to ammonium monoacetate is 0.5:1, the molar ratio of lithium methoxide to zinc acetate is 2:1, and the molar ratio of ethylene glycol monomethyl ether to zinc acetate is 2: 1. SEM, time-current and time-voltage graphs of the lithium zincate modified ternary cathode material are shown in fig. 1 and fig. 2. The upper part of fig. 2 is a voltage diagram, and the lower part is a current diagram.
Example 2
Roasting the anode plate disassembled and separated from the waste lithium ion battery for 30min at 580 ℃, crushing an obtained roasted product on a crusher, screening, and separating an anode material from an aluminum foil; the molar ratio of nickel, cobalt and manganese in the anode material is 3:3:3 and 4:2: 2;
leaching the positive electrode material with 2.0mol/L potassium hydroxide solution at 75 ℃ for 60min, wherein the liquid-solid ratio of the potassium hydroxide solution to the positive electrode material is 8:1 during leaching, and filtering to obtain filtrate and filter cake;
adding potassium carbonate with the mole number 0.5 time that of the lithium ions into the filtrate, stirring and reacting for 50min at 40 ℃ to generate a turbid solution, and filtering to obtain lithium carbonate solid and a filtrate, wherein the filtrate is a 1.5mol/L potassium hydroxide solution; the recovery rate of lithium was 94.2%;
leaching the filter cake for 180min at 65 ℃ by using 1.5mol/L sulfuric acid solution, wherein the liquid-solid ratio of the sulfuric acid solution to the filter cake is 9:1 during leaching, so as to obtain leachate;
adjusting the concentration of nickel ions in the leachate to be 2.0mol/L, and simultaneously adding cobalt sulfate and manganese sulfate to ensure that the molar ratio of nickel, cobalt and manganese in the solution is 4:2: 4;
adding 200ml of 1.2mol/L ammonia water solution into a reaction kettle, stirring at the speed of 900r/min, adding 1.2mol/L ammonia water solution, leachate obtained after adjusting the molar ratio of nickel, cobalt and manganese and the potassium hydroxide solution with the concentration of 1.5mol/L into the reaction kettle in a concurrent flow manner, using argon gas as atmosphere protection, carrying out coprecipitation, carrying out solid-liquid separation, and drying to obtain a ternary material precursor; wherein the adding speed of ammonia water is 5ml/min, the dropping speed of the leaching solution after adjusting the mole ratio of nickel, cobalt and manganese is 3ml/min, and the adding speed of potassium hydroxide solution is 5 ml/min;
drying the ternary material precursor at 95 ℃ for 18 hours, mixing the dried ternary material precursor with the obtained lithium carbonate solid, roasting at 280 ℃ for 5 hours, and then introducing argon gas at 780 ℃ for 12 hours to obtain a ternary cathode material;
zinc acetate is used as a zinc source, ethylene glycol monomethyl ether is used as a solvent, ammonium monoacetate is used as a stabilizer, the mixture is stirred for 25min at normal temperature after being mixed with lithium methoxide, the temperature is raised to 70 ℃, the ternary cathode material is added, the mixture is stirred for 2.0h and kept stand for 45h to obtain gel, and the gel is roasted for 120min at 800 ℃ to obtain the lithium zincate modified ternary cathode material, wherein the molar ratio of zinc acetate to ammonium monoacetate is 0.8:1, the molar ratio of lithium methoxide to zinc acetate is 2.2:1, and the molar ratio of ethylene glycol monomethyl ether to zinc acetate is 2.2: 1. SEM images of the lithium zincate modified ternary cathode material and capacity-voltage images assembled into button cells are shown in figures 3 and 4.
Example 3
Roasting the anode plate disassembled and separated from the waste lithium ion battery for 45min at 500 ℃, crushing an obtained roasted product on a crusher, screening, and separating an anode material from an aluminum foil; the molar ratio of nickel, cobalt and manganese in the anode material is 8:1:1 and 4:2: 2;
leaching the positive electrode material for 100min at 50 ℃ by using 1.5mol/L potassium hydroxide solution, wherein the liquid-solid ratio of the potassium hydroxide solution to the positive electrode material is 6:1 during leaching, and filtering to obtain filtrate and filter cake;
adding potassium carbonate with the mole number 0.5 time that of the lithium ions into the filtrate, stirring and reacting for 30min at 65 ℃ to generate a turbid solution, and filtering to obtain lithium carbonate solid and a filtrate, wherein the filtrate is a 1.0mol/L potassium hydroxide solution; the recovery rate of lithium was 94.5%;
leaching the filter cake for 120min at 80 ℃ by using 2.0mol/L sulfuric acid solution, wherein the liquid-solid ratio of the sulfuric acid solution to the filter cake is 7:1 during leaching, so as to obtain leachate;
adjusting the concentration of nickel ions in the leaching solution to be 3.5mol/L, and simultaneously adding cobalt nitrate and manganese nitrate to ensure that the molar ratio of nickel, cobalt and manganese in the solution is 8:1: 1;
adding 200ml of 1.8mol/L ammonia water solution into a reaction kettle, stirring at the speed of 700r/min, adding the 1.8mol/L ammonia water solution, leachate obtained after adjusting the molar ratio of nickel, cobalt and manganese and the potassium hydroxide solution with the concentration of 1.0mol/L into the reaction kettle in a concurrent flow manner, using argon gas as atmosphere protection, carrying out coprecipitation, carrying out solid-liquid separation, and drying to obtain a ternary material precursor; wherein the adding speed of the ammonia water is 7ml/min, the dropping speed of the leaching solution after adjusting the mole ratio of the nickel, the cobalt and the manganese is 6ml/min, and the adding speed of the potassium hydroxide solution is 15 ml/min;
drying the ternary material precursor at 110 ℃ for 15 hours, mixing the dried ternary material precursor with the obtained lithium carbonate solid, roasting the mixture at 450 ℃ for 4 hours, and then introducing argon gas at 820 ℃ for roasting for 10 hours to obtain a ternary cathode material;
zinc acetate is used as a zinc source, ethylene glycol monomethyl ether and water are used as solvents, ammonium monoacetate is used as a stabilizer, the mixture is mixed with lithium methoxide and then stirred for 30min at normal temperature, the temperature is raised to 75 ℃, the ternary cathode material is added, the mixture is stirred for 1.5h and kept stand for 40h to obtain gel, the gel is roasted for 90min at 850 ℃ to obtain the lithium zincate modified ternary cathode material, wherein the mass ratio of the ethylene glycol monomethyl ether to the water in the mixture of the ethylene glycol monomethyl ether and the water is 1: 1; the molar ratio of zinc acetate to ammonium monoacetate is 1.2:1, the molar ratio of lithium methoxide to zinc acetate is 2.4:1, and the molar ratio of ethylene glycol monomethyl ether to zinc acetate is 2.6: 1. SEM images of the lithium zincate-modified ternary cathode material and charge-discharge efficiency images of the button cell assembled therefrom are shown in fig. 5 and 6.
Example 4
Roasting the anode plate disassembled and separated from the waste lithium ion battery for 60min at 450 ℃, crushing an obtained roasted product on a crusher, screening, and separating an anode material from an aluminum foil; the molar ratio of nickel, cobalt and manganese in the anode material is 6:2: 2;
leaching the anode material for 120min at 30 ℃ by using 0.7mol/L calcium hydroxide solution, wherein the liquid-solid ratio of the calcium hydroxide solution to the anode material is 5:1 during leaching, and filtering to obtain filtrate and filter cake;
adding potassium carbonate with the mole number 0.5 time that of the lithium ions into the filtrate, stirring and reacting for 20min at 80 ℃ to generate a turbid solution, and filtering to obtain lithium carbonate solid and filtrate, wherein the filtrate is 0.5mol/L calcium hydroxide solution; the recovery rate of lithium is 94.6%;
leaching the filter cake for 60min at 95 ℃ by using 3.5mol/L sulfuric acid solution, wherein the liquid-solid ratio of the sulfuric acid solution to the filter cake is 5:1 during leaching, so as to obtain leachate;
adjusting the concentration of nickel ions in the leaching solution to be 4.0mol/L, and simultaneously adding cobalt nitrate and manganese nitrate to ensure that the molar ratio of nickel, cobalt and manganese in the solution is 5:2: 3;
adding 200ml of 2.4mol/L ammonia water solution into a reaction kettle, stirring at the speed of 800r/min, adding 2.4mol/L ammonia water solution, leachate obtained after adjusting the molar ratio of nickel, cobalt and manganese and the calcium hydroxide solution with the concentration of 0.5mol/L into the reaction kettle in a concurrent flow manner, using nitrogen as atmosphere protection, carrying out coprecipitation, carrying out solid-liquid separation, and drying to obtain a ternary material precursor; wherein the adding speed of the ammonia water is 2ml/min, the dropping speed of the leaching solution after adjusting the mole ratio of the nickel, the cobalt and the manganese is 7ml/min, and the adding speed of the calcium hydroxide solution is 18 ml/min;
drying the ternary material precursor at 118 ℃ for 12 hours, mixing the dried ternary material precursor with the obtained lithium carbonate solid, roasting at 550 ℃ for 3 hours, and then introducing argon gas at 890 ℃ for 8 hours to obtain a ternary cathode material;
zinc acetate is used as a zinc source, a mixture of ethylene glycol monomethyl ether and water is used as a solvent, ammonium monoacetate is used as a stabilizer, the mixture is mixed with lithium methoxide and then stirred for 35min at normal temperature, the temperature is raised to 85 ℃, the ternary cathode material is added, the mixture is stirred for 3.0h and kept stand for 35h to obtain gel, the gel is roasted for 65min at 900 ℃, and the lithium zincate modified ternary cathode material is obtained, wherein the mass ratio of the ethylene glycol monomethyl ether to the water in the mixture of the ethylene glycol monomethyl ether and the water is 2: 1; the molar ratio of zinc acetate to ammonium monoacetate is 1.5:1, the molar ratio of lithium methoxide to zinc acetate is 2.3:1, and the molar ratio of ethylene glycol monomethyl ether to zinc acetate is 2.8: 1. SEM, time-current and time-voltage plots of the lithium zincate modified ternary cathode material are shown in fig. 7 and 8. In fig. 8, the upper part is a voltage diagram and the lower part is a current diagram.
Claims (10)
1. A method for directly preparing a lithium zincate modified ternary cathode material by using a waste lithium battery cathode material is characterized by comprising the following steps of:
(1) disassembling the waste lithium ion battery, separating out a positive plate, roasting, crushing and screening the positive plate, and separating out a positive material from the aluminum foil;
(2) leaching the positive electrode material with caustic alkali solution, and filtering to obtain filtrate and filter cake;
(3) adding carbonate into the filtrate for reaction, and filtering to obtain lithium carbonate solid and caustic alkali solution;
(4) leaching the filter cake with sulfuric acid to obtain a leaching solution and filter residue;
(5) adjusting the molar ratio of nickel, cobalt and manganese in the leaching solution;
(6) under the protection of inert gas, enabling leachate and an ammonia solution obtained after the molar ratio of nickel, cobalt and manganese is adjusted and the caustic alkali solution obtained in the step (3) to flow into a reaction kettle containing the ammonia solution, and carrying out coprecipitation under the protection of inert gas to prepare a ternary material precursor;
(7) drying the ternary material precursor, and mixing and roasting the dried ternary material precursor and the lithium carbonate solid obtained in the step (3) to obtain a ternary positive electrode material;
(8) zinc acetate is used as a zinc source, ethylene glycol methyl ether or a mixture of the ethylene glycol methyl ether and water is used as a solvent, amines are used as a stabilizer, the mixture is mixed with lithium methoxide, the temperature is raised, a ternary cathode material is added, standing is carried out to obtain gel, and the gel is roasted to obtain the lithium zincate modified ternary cathode material;
in the step (2), the leaching temperature is 10-100 ℃;
in the step (2), the caustic alkali is sodium hydroxide, calcium hydroxide or potassium hydroxide;
in the step (3), the carbonate is potassium carbonate or sodium carbonate;
in the step (8), the amine is ammonium monoacetate.
2. The method for directly preparing the lithium zincate modified ternary cathode material by using the waste lithium battery cathode material according to claim 1, wherein the method comprises the following steps: in the step (1), the molar ratio of nickel, cobalt and manganese in the anode material is one or more of 5:2:3, 3:3:3, 6:2:2, 8:1:1 or 4:2: 2; the roasting temperature is 450-700 ℃, and the roasting time is 10-60 min.
3. The method for directly preparing the lithium zincate modified ternary cathode material by using the waste lithium battery cathode material according to claim 1, wherein the method comprises the following steps: in the step (2), the concentration of the caustic alkali solution is 0.5-3 mol/L; the leaching time is 0.5-2h, and the liquid-solid ratio of the caustic alkali solution to the anode material during leaching is 4-12: 1.
4. The method for directly preparing the lithium zincate modified ternary cathode material by using the waste lithium battery cathode material according to claim 1, wherein the method comprises the following steps: in the step (3), the reaction temperature is 20-90 ℃ and the reaction time is 10-60 min.
5. The method for directly preparing the lithium zincate modified ternary cathode material by using the waste lithium battery cathode material according to claim 1, wherein the method comprises the following steps: in the step (4), the molar concentration of the sulfuric acid is 0.5-3.5 mol/L; the leaching temperature is 50-100 ℃, the leaching time is 30-240min, and the liquid-solid ratio of the sulfuric acid to the filter cake is 4-12: 1.
6. The method for directly preparing the lithium zincate modified ternary cathode material by using the waste lithium battery cathode material according to claim 1, wherein the method comprises the following steps: in the step (5), the concentration of nickel in the adjusted leaching solution is 1-4mol/L, and the molar ratio of nickel, cobalt and manganese is 5:2:3, 3:3:3, 6:2:2, 8:1:1 or 4:2: 4; when the molar ratio of nickel, cobalt and manganese in the leachate is adjusted, the nickel, cobalt and manganese are added in the form of sulfates, nitrates or hydrochlorides of nickel, cobalt and manganese.
7. The method for directly preparing the lithium zincate modified ternary cathode material by using the waste lithium battery cathode material according to claim 1, wherein the method comprises the following steps: in the step (6), the inert gas is nitrogen or argon; the molar concentration of the ammonia water solution is 0.5-2.5mol/L, the molar concentration of the caustic alkali solution obtained in the step (3) is 0.5-2.5mol/L, the adding speed of the leachate after the molar ratio of nickel, cobalt and manganese is adjusted is 1-8ml/min, the adding speed of the ammonia water solution is 1-8ml/min, and the adding speed of the caustic alkali solution is 2-20 ml/min; before cocurrent, the volume of the ammonia solution in the reaction kettle containing the ammonia solution accounts for 1/5-1/4 of the total volume of the reaction kettle.
8. The method for directly preparing the lithium zincate modified ternary cathode material by using the waste lithium battery cathode material according to claim 1, wherein the method comprises the following steps: in the step (7), the drying temperature is 70-120 ℃, and the drying time is 10-20 hours; the roasting is carried out for 3-6h at 30-650 ℃, and then argon is introduced for 7-15h at 700-900 ℃.
9. The method for directly preparing the lithium zincate modified ternary cathode material by using the waste lithium battery cathode material according to claim 1, wherein the method comprises the following steps: in the step (8), the molar ratio of zinc acetate to ammonium monoacetate is 0.5-1.5:1, the molar ratio of lithium methoxide to zinc acetate is 2-2.5:1, and the molar ratio of ethylene glycol monomethyl ether to zinc acetate is 2-3: 1.
10. The method for directly preparing the lithium zincate modified ternary cathode material by using the waste lithium battery cathode material according to claim 1, wherein the method comprises the following steps: in the step (8), zinc acetate is used as a zinc source, ethylene glycol methyl ether or a mixture of ethylene glycol methyl ether and water is used as a solvent, amines are used as a stabilizer, the mixture is mixed with lithium methoxide, stirred at normal temperature for 10-40min, heated to 50-90 ℃, added with the ternary anode material, stirred for 1.5-3h, kept stand for 30-50h to obtain gel, and roasted at the temperature of 700-900 ℃ for 60-180min to obtain the lithium zincate modified ternary anode material.
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