CN114956132B - Method for selectively extracting lithium and recycling waste lithium ion batteries - Google Patents
Method for selectively extracting lithium and recycling waste lithium ion batteries Download PDFInfo
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- CN114956132B CN114956132B CN202111575328.2A CN202111575328A CN114956132B CN 114956132 B CN114956132 B CN 114956132B CN 202111575328 A CN202111575328 A CN 202111575328A CN 114956132 B CN114956132 B CN 114956132B
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- C22B26/12—Obtaining lithium
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- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a method for selectively extracting lithium and recycling waste lithium ion batteries, which comprises the steps of adding a ternary positive electrode material of the waste lithium ion batteries and a ball milling agent into a plasma ball mill, performing ball milling under a protective atmosphere, placing a plasma ball milling product into ultrapure water at room temperature, performing ultrasonic water leaching, performing vacuum filtration and separation after the ultrasonic water leaching is finished, and adding saturated Na into a leaching solution 2 CO 3 Solution preparation of battery Material Li 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the Mixing leaching residues, glucose and ultrapure water for hydrothermal reaction, vacuum filtering to obtain an intermediate product of the lithium-sulfur anode material after the hydrothermal reaction is finished, and carbonizing the intermediate product at low temperature to prepare the lithium-sulfur anode material; the method is simple and feasible, has short reaction time and low reaction temperature, can systematically recycle valuable metals in the battery, is environment-friendly, and can be applied on a large scale.
Description
Technical Field
The invention relates to a method for recycling waste lithium ion batteries by selectively extracting lithium, belonging to the field of waste battery recycling.
Background
The lithium ion battery is widely applied to mobile electronic products such as mobile phones, notebook computers, digital cameras and the like by virtue of the advantages of high energy density, high charge and discharge efficiency, no memory effect, low self-discharge rate and the like. Meanwhile, the performance of the power battery is a key of the development of the new energy automobile industry, and the ternary power lithium ion battery is selected as the power battery of the new energy automobile by virtue of the excellent performance of the ternary power lithium ion battery. In addition, the energy storage battery is continuously applied to wind power generation, solar power generation, new power grid technology and the like, and the lithium ion battery is also paid attention to in the energy storage field due to the excellent characteristics of the lithium ion battery. The service life of the lithium ion battery is relatively limited, and the problem of capacity fading of the lithium ion battery inevitably occurs after the lithium ion battery is recycled for a long time, so that the lithium ion battery is retired into a waste lithium ion battery. In 2019, lithium ion batteries are retired in a large scale, and the number of waste lithium ion batteries produced and popularized by green electric vehicles is greatly increased. By 2025, the waste lithium ion batteries in China can reach 134.5GWh, and the NCM battery accounts for over 70%. The battery material is rich in Li, ni, co, mn and other high-valence metal resources, and can be recycled, so that the utilization efficiency of the resources is improved, and the pressure of the supply of lithium, nickel, cobalt and other resources in China can be relieved. Meanwhile, harmful substances in the battery pollute water sources, soil and the like, so that the health and ecological environment of human beings are endangered. Therefore, the research on the recycling technology of the waste ternary lithium ion battery has important significance and practical value.
Despite the heavy weight of most recovery processes currently availableThe point is to recover high-value metals such as Ni, co, mn, etc., but shortage of lithium resources and continuous increase of lithium price make recovery of lithium an inevitable choice. Researchers have adopted a method of combining reduction roasting and water leaching to carry out LiNi x Co y Mn z O 2 Decomposition is carried out and lithium is selectively recovered, but due to the decomposition product Li 2 CO 3 The solubility of the obtained percolate is limited, and the concentration of lithium in the obtained percolate is low, so that the preparation of subsequent lithium compounds is not facilitated. The other heat-acid combined process of reducing roasting waste NCM material and combining with phosphoric acid leaching is adopted, so that the manganese is leached simultaneously with the lithium leaching, and the selective extraction of lithium is not really realized.
Disclosure of Invention
The invention provides a method for selectively extracting lithium and recycling waste lithium ion batteries, which combines plasma ball milling and ultrasonic water leaching, and systematically recycles lithium and valuable metals in the waste batteries.
The technical scheme of the invention is as follows:
a method for selectively extracting lithium and recycling waste lithium ion batteries comprises the following specific steps:
(1) Adding the ternary cathode material of the waste lithium ion battery and a ball milling agent into a plasma ball mill, and performing ball milling in a protective atmosphere;
(2) At room temperature, placing a plasma ball-milling product into ultrapure water, carrying out ultrasonic water leaching, separating filtrate and filter residue by vacuum suction filtration after the ultrasonic water leaching is completed, selectively leaching lithium from a ternary positive electrode material of a waste lithium ion battery, dissolving the lithium-leached ternary positive electrode material into leaching liquid, and adding saturated Na 2 CO 3 Solution and ph=14 adjustment can be used to prepare battery material Li 2 CO 3 Nickel, cobalt and manganese in the ternary positive electrode material of the waste lithium ion battery are remained in leaching residues;
(3) Co in leaching slag is Co 9 S 8 Adding leaching residue and glucose into a hydrothermal reaction kettle, adding ultrapure water for hydrothermal reaction to uniformly coat the glucose on the surface of the leaching residue, performing vacuum suction filtration to obtain an intermediate product of the lithium sulfur anode material after hydrothermal reaction, and then placing the intermediate product into a tube furnace for carrying outCarbonizing at low temperature to obtain carbon-coated Co 9 S 8 The lithium-sulfur cathode material is mainly used, and has good electrochemical performance.
The ternary positive electrode material of the waste lithium ion battery in the step (1) comprises LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622)、LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM523)、LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM111)。
The ball grinding agent in the step (1) is Na 2 S 2 O 3 、Na 2 SO 3 、K 2 S 2 O 3 、K 2 SO 3 Etc.
The mass ratio of the ternary positive electrode material of the waste lithium ion battery to the ball grinding agent in the step (1) is 1:3-10.
The protective atmosphere in the step (1) is nitrogen or argon.
Ball milling parameters in the step (1): the mass ratio of the ball materials is 30-50: 1, ball milling speed 980-1500 r/min, ball milling time 0.5-1.5 h, excitation voltage 10-20 Kv, working current 1-3A, pressure value 0.01-0.1 Mpa, temperature 300-400 ℃.
The parameters of the ultrasonic water immersion in the step (2) are as follows: the ultrasonic power is 90-100W, the time is 0.5-1 h, and the solid-liquid ratio is 4-8 g/L.
The mass ratio of the leaching slag to the glucose in the step (3) is 1:1-1.2, and the mass volume ratio g of the leaching slag to the ultrapure water in the step (3) is 1:40-60.
The hydrothermal reaction temperature of the step (3) is 150-200 ℃ and the time is 4-6 h.
The low-temperature carbonization temperature in the step (3) is 400-550 ℃, the time is 1-2 h, and the atmosphere is argon.
Compared with the prior art, the invention has the following advantages and beneficial effects;
(1) According to the invention, the plasma ball milling is applied to the recovery of the waste lithium ion battery, and the mechanical force and the plasma are cooperatively acted on the reaction of the ternary positive electrode material of the waste lithium ion battery and the ball milling agent, so that the contact area of the reaction is enlarged, more reaction sites are provided, and 94.06% of Li can be quickly leached and extracted by the ultrasonic water leaching at normal temperature of the ball milling product, so that the reaction temperature is reduced, and the reaction time is shortened.
(2) The leaching residue of the invention contains Co 9 S 8 The Co coated with carbon can be prepared by hydrothermal and carbonization treatment 9 S 8 The lithium-sulfur positive electrode material is mainly used, valuable metals in the battery can be recycled systematically, the resource utilization rate is high, and the lithium-sulfur positive electrode material is environment-friendly and can be applied on a large scale.
Drawings
FIG. 1 shows the leaching rates of the respective elements in the step (2) of example 1;
FIG. 2 is a scanning electron microscope image of the leaching residue of the step (2) of example 1;
FIG. 3 is Li obtained by the preparation of step (2) of example 1 2 CO 3 An XRD pattern of (b);
FIG. 4 is Li obtained by the preparation of step (2) of example 1 2 CO 3 Scanning electron microscope images of (2);
FIG. 5 is an XRD pattern of the leach residue of step (2) of example 1;
FIG. 6 is a graph showing cycle performance and coulombic efficiency of the lithium sulfur cathode material prepared in step (3) of example 1;
FIG. 7 shows the leaching rates of the respective elements in the step (2) of example 2;
FIG. 8 is a scanning electron microscope image of the leaching residue of the step (2) of the embodiment 2;
FIG. 9 shows the leaching rates of the respective elements in the step (2) of example 3;
FIG. 10 is a scanning electron microscope image of the leaching residue of the step (2) of example 3;
FIG. 11 shows the leaching rates of the respective elements in the step (2) of example 4;
FIG. 12 is a scanning electron microscope image of the leaching residue of the step (2) of example 4.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1
A method for selectively extracting lithium and recycling waste lithium ion batteries comprises the following specific steps:
(1) Ternary cathode material LiNi of waste lithium ion battery 0.6 Co 0.2 Mn 0.2 O 2 (NCM 622) and ball milling agentNa 2 SO 3 Adding the mixture into a plasma ball mill according to the mass ratio of 1:3, and performing ball milling under nitrogen in a protective atmosphere, wherein the ball milling parameters are as follows: ball material mass ratio is 30:1, ball milling rotating speed is 980r/min, ball milling time is 1.5h, excitation voltage is 10Kv, working current is 1A, pressure value is 0.1Mpa, temperature is 300 ℃, and grinding balls are tungsten carbide balls;
(2) At room temperature, placing the plasma ball-milling product into ultrapure water for ultrasonic water immersion, wherein the parameters of the ultrasonic water immersion are as follows: ultrasonic power 90W, time 1h, solid-to-liquid ratio 4g/L, separating filtrate from filter residue by vacuum filtration after ultrasonic leaching, selectively leaching lithium in NCM622, dissolving in leaching solution, adding saturated Na 2 CO 3 The solution is added with sodium hydroxide to adjust the pH value to 14 to prepare the battery material Li 2 CO 3 Nickel, cobalt and manganese in the NCM622 remain in the leaching residue;
(3) Adding leaching slag and glucose into a hydrothermal reaction kettle according to the mass ratio of 1:1, adding ultrapure water, carrying out hydrothermal reaction at the temperature of 150 ℃ for 6 hours, uniformly coating the glucose on the surface of the leaching slag, carrying out vacuum suction filtration to obtain an intermediate product of the lithium sulfur anode material, and then placing the intermediate product into a tubular furnace for low-temperature carbonization, wherein the low-temperature carbonization temperature is 400 ℃, the time is 2 hours, and the atmosphere is argon atmosphere, so as to prepare the lithium sulfur anode material.
FIG. 1 shows the leaching rates of the respective elements in the step (2) of example 1; as can be seen from the figure, na is used 2 SO 3 Is ball-milling agent, is ball-milled by plasma and immersed by ultrasonic water, and is LiNi 0.6 Co 0.2 Mn 0.2 O 2 The leaching rate of Li in the (NCM 622) battery anode material can reach 94.06%, while Ni, co and Mn are hardly leached out and remain in slag, so that the selective extraction of Li is realized.
Fig. 2 is a scanning electron microscope image of leaching residue obtained in step (2) of example 1, and it can be seen from the image that the leaching residue is composed of primary and secondary particles with irregular morphology, and can be used as lithium sulfur anode material after subsequent hydrothermal and carbonization treatment.
FIG. 3 is a preparation of example 1, step (2)Li obtained 2 CO 3 From the XRD pattern of (C), it can be seen that Li is prepared from the leachate as a raw material 2 CO 3 The phase corresponds to the standard phase, has no impurity phase and has higher purity.
FIG. 4 is Li obtained by the preparation of step (2) of example 1 2 CO 3 From the scanning electron microscope image of (2), it can be seen that Li was prepared 2 CO 3 Primary and secondary particles in the form of rods, morphology and commercial Li 2 CO 3 Similarly.
FIG. 5 is an XRD pattern of the leaching residue of step (2) of example 1, from which it can be seen that the residue contains lithium sulfur cathode material Co 9 S 8 The leached slag can be prepared into Co with carbon coating layer through subsequent hydrothermal and carbonization treatment 9 S 8 Lithium sulfur positive electrode material.
FIG. 6 is a graph showing the cycle performance and coulombic efficiency of the lithium-sulfur cathode material prepared in example 1, and the prepared lithium-sulfur cathode material and lithium-sulfur anode material were tested to prepare a lithium-sulfur battery, which was shown to be 0.2Ag -1 The current density of the lithium sulfur anode material is subjected to charge and discharge tests, the battery is stable and good in circulation, and the capacity retention rate is high, so that the prepared lithium sulfur anode material has good electrochemical performance.
Example 2
A method for selectively extracting lithium and recycling waste lithium ion batteries comprises the following specific steps:
(1) Ternary cathode material LiNi of waste lithium ion battery 0.6 Co 0.2 Mn 0.2 O 2 (NCM 622) ball milling agent Na 2 S 2 O 3 Adding the mixture into a plasma ball mill according to the mass ratio of 1:10, and performing ball milling under nitrogen in a protective atmosphere, wherein the ball milling parameters are as follows: ball material mass ratio is 50:1, ball milling rotating speed is 1500r/min, ball milling time is 0.5h, excitation voltage is 20Kv, working current is 3A, pressure value is 0.01Mpa, temperature is 400 ℃, and grinding balls are tungsten carbide balls;
(2) At room temperature, placing the plasma ball-milling product into ultrapure water for ultrasonic water immersion, wherein the parameters of the ultrasonic water immersion are as follows: ultrasonic power 100W for 0.5h, solid-to-liquid ratio 8g/L, and vacuum filtrationSeparating the filtrate from the residue, selectively leaching lithium in NCM622, dissolving in the leaching solution, adding saturated Na 2 CO 3 The solution is added with sodium hydroxide to adjust the pH value to 14 to prepare the battery material Li 2 CO 3 Nickel, cobalt and manganese in the NCM622 remain in the leaching residue;
(3) Adding leaching slag and glucose into a hydrothermal reaction kettle according to the mass ratio of 1:1.2, adding ultrapure water, carrying out hydrothermal reaction at the temperature of 200 ℃ for 4 hours, uniformly coating the glucose on the surface of the leaching slag, carrying out vacuum suction filtration after the hydrothermal reaction is finished to obtain an intermediate product of the lithium sulfur anode material, and then placing the intermediate product into a tube furnace for low-temperature carbonization, wherein the temperature of the low-temperature carbonization is 550 ℃, the time is 1 hour, and the atmosphere is argon atmosphere, so as to prepare the lithium sulfur anode material.
FIG. 7 shows the leaching rates of the respective elements in the step (2) of example 2; as can be seen from the figure, na is used 2 S 2 O 3 The method combines the ball milling agent, the plasma ball milling and the ultrasonic water leaching, can leach Li in the positive electrode material of the NCM622 battery, the leaching rate is 93.45 percent, and Ni, co and Mn are hardly leached out and remain in slag, thereby realizing the selective extraction of Li.
FIG. 8 is a scanning electron microscope image of the leaching residue of the step (2) of the embodiment 2; the graph shows that the leaching slag is composed of primary and secondary particles with irregular morphology, the particle size is between 2 and 10 mu m, and the leaching slag can be used as a lithium sulfur anode material after subsequent hydrothermal and carbonization treatment.
Example 3
A method for selectively extracting lithium and recycling waste lithium ion batteries comprises the following specific steps:
(1) Ternary cathode material LiNi of waste lithium ion battery 0.6 Co 0.2 Mn 0.2 O 2 (NCM 622) ball milling agent K 2 S 2 O 3 Adding the mixture into a plasma ball mill according to the mass ratio of 1:5, and performing ball milling under nitrogen in a protective atmosphere, wherein the ball milling parameters are as follows: ball material mass ratio is 40:1, ball milling rotating speed is 1100r/min, ball milling time is 1h, excitation voltage is 15Kv, working current is 2A, pressure value is 0.05Mpa, temperature is 350 ℃, and grinding ball isTungsten carbide pellets;
(2) At room temperature, placing the plasma ball-milling product into ultrapure water for ultrasonic water immersion, wherein the parameters of the ultrasonic water immersion are as follows: ultrasonic power 95W for 0.6h, solid-to-liquid ratio 5g/L, separating filtrate from residue by vacuum filtration after ultrasonic leaching, selectively leaching lithium in NCM622, dissolving in leaching solution, adding saturated Na 2 CO 3 The solution is added with sodium hydroxide to adjust the pH value to 14 to prepare the battery material Li 2 CO 3 Nickel, cobalt and manganese in the NCM622 remain in the leaching residue;
(3) Adding leaching slag and glucose into a hydrothermal reaction kettle according to the mass ratio of 1:1.1, adding ultrapure water, carrying out hydrothermal reaction at the temperature of 180 ℃ for 5 hours, uniformly coating the glucose on the surface of the leaching slag, carrying out vacuum suction filtration after the hydrothermal reaction is finished to obtain an intermediate product of the lithium sulfur anode material, and then placing the intermediate product into a tube furnace for low-temperature carbonization, wherein the temperature of the low-temperature carbonization is 450 ℃, the time is 1.8 hours, and the atmosphere is argon atmosphere, so as to prepare the lithium sulfur anode material.
FIG. 9 shows the leaching rates of the respective elements in the step (2) of example 3; as can be seen from the figure, in K 2 S 2 O 3 Is ball-milling agent, is ball-milled by plasma and immersed by ultrasonic water, and is LiNi 0.6 Co 0.2 Mn 0.2 O 2 The leaching rate of Li in the positive electrode material of the (NCM 622) battery reaches 93.73 percent, while Ni, co and Mn are hardly leached out and remain in slag, so that Li in the NCM622 can be selectively extracted.
FIG. 10 is a scanning electron microscope image of the leaching residue of the step (2) of example 3; from the graph, the leaching slag consists of primary and secondary particles with irregular morphology, and the surface is relatively rough, so that the later carbonization is facilitated, and the leaching slag can be used for preparing lithium-sulfur anode materials.
Example 4
A method for selectively extracting lithium and recycling waste lithium ion batteries comprises the following specific steps:
(1) Ternary cathode material LiNi of waste lithium ion battery 0.6 Co 0.2 Mn 0.2 O 2 (NCM 622) andball grinding agent K 2 SO 3 Adding the mixture into a plasma ball mill according to the mass ratio of 1:7, and performing ball milling under nitrogen in a protective atmosphere, wherein the ball milling parameters are as follows: ball material mass ratio is 35:1, ball milling rotating speed is 1200r/min, ball milling time is 1.2h, excitation voltage is 15Kv, working current is 2A, pressure value is 0.05Mpa, temperature is 350 ℃, and grinding balls are tungsten carbide balls;
(2) At room temperature, placing the plasma ball-milling product into ultrapure water for ultrasonic water immersion, wherein the parameters of the ultrasonic water immersion are as follows: ultrasonic power 90W for 0.6h, solid-to-liquid ratio 6g/L, separating filtrate from residue by vacuum filtration after ultrasonic leaching, selectively leaching lithium in NCM622, dissolving in leaching solution, adding saturated Na 2 CO 3 The solution is added with sodium hydroxide to adjust the pH value to 14 to prepare the battery material Li 2 CO 3 Nickel, cobalt and manganese in the NCM622 remain in the leaching residue;
(3) Adding leaching slag and glucose into a hydrothermal reaction kettle according to the mass ratio of 1:1, adding ultrapure water, carrying out hydrothermal reaction at 160 ℃ for 5.5 hours, uniformly coating the glucose on the surface of the leaching slag, carrying out vacuum suction filtration after the hydrothermal reaction is finished to obtain an intermediate product of the lithium sulfur anode material, and then placing the intermediate product into a tubular furnace for low-temperature carbonization, wherein the low-temperature carbonization temperature is 500 ℃, the time is 1.6 hours, and the atmosphere is argon atmosphere, so as to prepare the lithium sulfur anode material.
FIG. 11 shows the leaching rates of the respective elements in the step (2) of example 4; as can be seen from the figure, in K 2 SO 3 Is ball-milling agent, is ball-milled by plasma and immersed by ultrasonic water, and is LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM 622) Ni, co and Mn in the positive electrode material of the battery remain in slag, 94.01 percent of Li is selectively leached, thus achieving the purpose of selectively extracting lithium
FIG. 12 is a scanning electron microscope image of the leaching residue obtained in the step (2) of example 4, wherein the leaching residue is composed of primary and secondary particles, is in an irregular block shape, has an average particle size of 4-10 μm, can be used as a lithium sulfur positive electrode material after subsequent hydrothermal and carbonization treatment, and valuable metals of NCM622 are systematically recovered.
Example 5
A method for selectively extracting lithium and recycling waste lithium ion batteries comprises the following specific steps:
(1) Ternary cathode material LiNi of waste lithium ion battery 0.5 Co 0.2 Mn 0.3 O 2 (NCM 523) ball milling agent K 2 SO 3 Adding the mixture into a plasma ball mill according to the mass ratio of 1:6, and performing ball milling under nitrogen in a protective atmosphere, wherein the ball milling parameters are as follows: the ball material mass ratio is 45:1, the ball milling rotating speed is 1000r/min, the ball milling time is 1h, the excitation voltage is 15Kv, the working current is 1A, the pressure value is 0.01Mpa, the temperature is 300 ℃, and the grinding balls are tungsten carbide balls;
(2) At room temperature, placing the plasma ball-milling product into ultrapure water for ultrasonic water immersion, wherein the parameters of the ultrasonic water immersion are as follows: after ultrasonic power of 90W and time of 1h and solid-to-liquid ratio of 6g/L and ultrasonic water leaching, separating filtrate from filter residue by vacuum suction filtration, selectively leaching lithium in NCM523, dissolving in leaching solution, adding saturated Na 2 CO 3 The solution is added with sodium hydroxide to adjust the pH value to 14 to prepare the battery material Li 2 CO 3 Nickel, cobalt and manganese in NCM523 remain in the leaching residue;
(3) Adding leaching slag and glucose into a hydrothermal reaction kettle according to the mass ratio of 1:1, adding ultrapure water, wherein the mass volume ratio g of the leaching slag to the ultrapure water is 1:40, carrying out hydrothermal reaction at the temperature of 150 ℃ for 5.5 hours, uniformly coating the glucose on the surface of the leaching slag, carrying out vacuum suction filtration after the hydrothermal reaction is finished to obtain an intermediate product of the lithium sulfur anode material, and then placing the intermediate product into a tubular furnace for low-temperature carbonization, wherein the low-temperature carbonization temperature is 500 ℃, the time is 1.5 hours, and the atmosphere is argon atmosphere, thus preparing the lithium sulfur anode material.
Example 6
A method for selectively extracting lithium and recycling waste lithium ion batteries comprises the following specific steps:
(1) Ternary cathode material LiNi of waste lithium ion battery 1/3 Co 1/3 Mn 1/3 O 2 (NCM 111) and ball milling agent Na 2 S 2 O 3 According to the qualityThe mass ratio is 1:8, and the materials are added into a plasma ball mill for ball milling under the protection atmosphere of argon, and the ball milling parameters are as follows: ball material mass ratio is 32:1, ball milling rotating speed is 1100r/min, ball milling time is 1.5h, excitation voltage is 20Kv, working current is 1A, pressure value is 0.05Mpa, temperature is 350 ℃, and grinding balls are tungsten carbide balls;
(2) At room temperature, placing the plasma ball-milling product into ultrapure water for ultrasonic water immersion, wherein the parameters of the ultrasonic water immersion are as follows: ultrasonic power 100W for 0.5h, solid-to-liquid ratio 7g/L, separating filtrate from residue by vacuum filtration after ultrasonic leaching, selectively leaching lithium in NCM111, dissolving in leaching solution, adding saturated Na 2 CO 3 The solution is added with sodium hydroxide to adjust the pH value to 14 to prepare the battery material Li 2 CO 3 Nickel, cobalt and manganese in NCM111 remain in leaching residues;
(3) Adding leaching slag and glucose into a hydrothermal reaction kettle according to the mass ratio of 1:1, adding ultrapure water, carrying out hydrothermal reaction at the temperature of 200 ℃ for 6 hours, uniformly coating the glucose on the surface of the leaching slag, carrying out vacuum suction filtration to obtain an intermediate product of the lithium sulfur cathode material, and then placing the intermediate product into a tubular furnace for low-temperature carbonization, wherein the low-temperature carbonization temperature is 500 ℃, the time is 1.5 hours, and the atmosphere is argon atmosphere, so as to prepare the lithium sulfur cathode material.
Claims (8)
1. A method for selectively extracting lithium and recycling waste lithium ion batteries is characterized by comprising the following specific steps:
(1) Adding the ternary cathode material of the waste lithium ion battery and a ball milling agent into a plasma ball mill, and performing ball milling in a protective atmosphere;
the ball grinding agent is Na 2 S 2 O 3 、Na 2 SO 3 、K 2 S 2 O 3 Or K 2 SO 3 ；
(2) At room temperature, placing the ball-milled product of the plasma into ultrapure water, carrying out ultrasonic water leaching, vacuum filtering and separating after the ultrasonic water leaching is completed, and adding the leaching liquidSaturated Na 2 CO 3 Solution and pH adjustment = 14 Li preparation 2 CO 3 ；
(3) Mixing leaching residues, glucose and ultrapure water for hydrothermal reaction, vacuum filtering to obtain an intermediate product of the lithium-sulfur anode material after the hydrothermal reaction is finished, and carbonizing the intermediate product at low temperature to prepare the lithium-sulfur anode material;
the mass ratio of the leaching residue to the glucose is 1:1-1.2, and the mass volume ratio g of the leaching residue to the ultrapure water is 1:40-60.
2. The method for selectively extracting lithium and recycling waste lithium ion batteries according to claim 1, wherein the ternary positive electrode material of the waste lithium ion batteries in the step (1) is NCM622, NCM111 or NCM523.
3. The method for recycling waste lithium ion batteries by selectively extracting lithium according to claim 1 is characterized in that the mass ratio of the ternary positive electrode material of the waste lithium ion batteries in the step (1) to the ball grinding agent is 1:3-10.
4. The method for recycling waste lithium ion batteries by selectively extracting lithium according to claim 1, wherein the protective atmosphere in the step (1) is nitrogen or argon.
5. The method for selectively extracting lithium and recycling waste lithium ion batteries according to claim 1, wherein the ball milling parameters in the step (1) are as follows: the mass ratio of the ball materials is 30-50: 1, ball milling speed is 980-1500 r/min, ball milling time is 0.5-1.5 h, excitation voltage is 10-20 kV, working current is 1-3A, pressure value is 0.01-0.1 mpa, and temperature is 300-400 ℃.
6. The method for recycling waste lithium ion batteries by selectively extracting lithium according to claim 1, wherein the parameters of ultrasonic water immersion in the step (2) are as follows: the ultrasonic power is 90-100W, the time is 0.5-1 h, and the solid-liquid ratio is 4-8 g/L.
7. The method for recycling waste lithium ion batteries by selectively extracting lithium according to claim 1, wherein the hydrothermal reaction temperature in the step (3) is 150-200 ℃ and the time is 4-6 hours.
8. The method for recycling waste lithium ion batteries by selectively extracting lithium according to claim 1, wherein the low-temperature carbonization temperature in the step (3) is 400-550 ℃, the time is 1-2 h, and the atmosphere is argon.
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| CN104538695A (en) * | 2015-01-08 | 2015-04-22 | 兰州理工大学 | Method for recycling metal in waste LiMn1-x-yNixCoyO2 battery and preparing LiMn1-x-yNixCoyO2 |
| CN108258224A (en) * | 2018-01-22 | 2018-07-06 | 华南理工大学 | A kind of tertiary cathode material of surface clad oxide and preparation method thereof |
| CN111180710A (en) * | 2020-01-16 | 2020-05-19 | 中南大学 | Nickel-cobalt-manganese multi-metal @ graphitized carbon @ hierarchical porous carbon material, preparation thereof and application thereof in lithium-sulfur battery |
| CN111945006A (en) * | 2020-08-21 | 2020-11-17 | 昆明理工大学 | Method for separating and recovering valuable metals in lithium ion battery roasting product |
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| CN104538695A (en) * | 2015-01-08 | 2015-04-22 | 兰州理工大学 | Method for recycling metal in waste LiMn1-x-yNixCoyO2 battery and preparing LiMn1-x-yNixCoyO2 |
| CN108258224A (en) * | 2018-01-22 | 2018-07-06 | 华南理工大学 | A kind of tertiary cathode material of surface clad oxide and preparation method thereof |
| CN111180710A (en) * | 2020-01-16 | 2020-05-19 | 中南大学 | Nickel-cobalt-manganese multi-metal @ graphitized carbon @ hierarchical porous carbon material, preparation thereof and application thereof in lithium-sulfur battery |
| CN111945006A (en) * | 2020-08-21 | 2020-11-17 | 昆明理工大学 | Method for separating and recovering valuable metals in lithium ion battery roasting product |
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