CN111430831A - Method for recovering waste lithium ion battery negative electrode material - Google Patents
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Abstract
The invention discloses a method for recovering a waste lithium ion battery cathode material. The method comprises the following basic steps: 1) mixing the waste lithium ion battery negative electrode powder with molten salt; 2) heat treating the mixed powder at a temperature not lower than the melting point of the molten salt; 3) and soaking the heat-treated material in water, uniformly stirring, performing solid-liquid separation, recovering the liquid phase used for extracting lithium and other valuable metals, and drying the solid phase to obtain the regenerated negative electrode material. The invention realizes the purification and structure repair of the cathode material in the cathode material of the waste lithium ion battery and the recovery of valuable metals. The method has the advantages of short treatment process, low cost, high purity and good crystallinity of the obtained regenerated cathode material, high leaching rate of valuable metals and suitability for large-scale production.
Description
Technical Field
The invention belongs to the field of waste battery recovery, and particularly relates to a high-value resource utilization method of a waste lithium ion battery negative electrode material.
Background
Lithium ion batteries are widely used in various electronic fields due to their excellent electrochemical properties. According to the data of the State statistical administration, the output of the lithium ion batteries in China in 2013 is about 18 hundred million, and the total production number of the lithium ion batteries in China is more than 250 hundred million by 2020. The service life of the lithium ion battery is generally 2-3 years, and the lithium ion battery is not suitable for being used continuously when the battery capacity is reduced to be below 80%. The increase of the using amount of the lithium ion battery brings a large amount of waste batteries, the lithium ion battery mainly comprises an anode, a cathode, an organic electrolyte and a diaphragm, the waste lithium ion battery contains a large amount of noble metals such as cobalt, lithium and the like, which account for at least one third of the cost of the battery, and the waste battery also contains the electrolyte which is harmful to the environment, so how to recycle the waste lithium ion battery is a hot problem in the current research. However, the recovery treatment of the waste batteries mainly focuses on the recovery of positive metal and negative copper materials, the research on the recovery treatment of negative active materials is few, and the existing negative material recovery scheme is complex, high in cost and single in recovery target, so that a high-value recovery scheme which is short in process, low in cost and capable of simultaneously recovering multiple valuable materials is found, and the method has great significance for the sustainable development of battery recovery industry and resources.
Disclosure of Invention
The first technical problem to be solved by the present invention is to provide a method for recovering waste lithium ion battery negative electrode powder (also referred to as negative electrode material in the present invention), which is used to recover the waste lithium ion battery negative electrode material, and can simply and efficiently recover the valuable materials therein at low cost.
The second technical problem to be solved by the present invention is to purify the recovered negative electrode material and to use it directly as a battery material.
In order to solve the technical problem, the invention provides a method for recovering a waste lithium ion battery cathode material, which comprises the following steps:
step (1): mixing the waste lithium ion battery negative electrode material with molten salt and then carrying out heat treatment; the melting point temperature of the molten salt is more than or equal to 450 ℃; the temperature of the heat treatment is higher than or equal to the melting point of the molten salt;
step (2): and (2) performing water leaching treatment and solid-liquid separation on the material subjected to heat treatment in the step (1) to obtain a water leaching solution (a leaching solution enriched with elements adsorbed by other negative electrodes such as lithium) and a regenerated negative electrode material.
The invention innovatively discovers that the negative electrode material can be purified and the microstructure can be repaired by carrying out heat treatment on the negative electrode material under the molten salt system, and the method is also beneficial to effectively extracting other valuable elements such as lithium and the like from the negative electrode microstructure. The invention realizes the purification and structure repair of graphite in the anode material of the waste lithium ion battery and the recovery of valuable metals. The method has the advantages of short treatment process, low cost, high purity and good crystallinity of the obtained cathode material, high leaching rate of valuable metals and suitability for large-scale production.
Preferably, the melting point of the molten salt is 600-900 ℃; further preferably 700 to 850 ℃.
Preferably, the method comprises the following steps: the molten salt is water-soluble metal chloride; preferably at least one of potassium chloride, sodium chloride and calcium chloride.
Preferably, the method comprises the following steps: molten salt: the mass ratio of the negative electrode material is 0.1: 1-1: 1; preferably 0.5-1: 1.
Preferably, the method comprises the following steps: the negative electrode material is stripped from the waste lithium ion battery with residual voltage more than 0V.
The research of the invention unexpectedly discovers that the waste lithium ion battery cathode powder obtained by crushing and separating the waste lithium ion battery which is not discharged or is not completely discharged is matched with the molten salt heat treatment process of the invention, which is beneficial to further improving the lithium extraction effect, the purity and the microstructure of the recycled regenerated cathode material and further improving the electrical performance of the regenerated cathode material. The method provided by the invention is used for recycling the cathode material of the waste lithium ion battery which is not completely discharged or discharged, so that the process is saved, and the comprehensive improvement on the recycling effect is facilitated.
In the invention, the cathode material can be obtained by adopting the existing method and equipment for separation.
Preferably, the method comprises the following steps: and disassembling the charged waste battery with the residual voltage larger than 0 to obtain a negative plate, and separating a current collector in the negative plate to obtain the negative material.
Preferably, the method comprises the following steps: and crushing the negative plate, placing the crushed negative plate into water, stirring, sieving and separating to obtain a current collector and the negative material.
The negative electrode material of the present invention contains a negative electrode active material (e.g., graphite), and allows a conductive agent and a binder to be contained.
The heat treatment process is performed in a protective atmosphere, or a reducing gas-protective atmosphere. The protective atmosphere is, for example, nitrogen or an inert gas. The reducing atmosphere is, for example, hydrogen.
The mixture of the negative electrode powder and the metal chloride is subjected to heat treatment in the atmosphere, impurities such as an organic binder are removed at high temperature, and simultaneously the crystallinity of the waste negative electrode material is recovered to a certain extent. Under a high-temperature molten salt system, lithium salt in the negative electrode material and metal impurities in the material are transformed, deionized water is used for achieving the effects of recovering lithium and removing the metal impurities, and lithium ions which are not separated yet between the negative electrode material layers and in the pore structure are transferred to the molten salt system in the heat treatment process, so that the content of recoverable lithium is higher.
Preferably, the atmosphere of the heat treatment process is, for example, N2Atmosphere or Ar atmosphere or H2Mixed with Ar gas.
In the invention, the control of the heat treatment temperature is beneficial to further improving the separation effect of valuable elements such as lithium and the like, improving the purity of the recycled negative electrode material, regenerating the microstructure of the recycled negative electrode material and further improving the electrical property of the regenerated negative electrode material.
Preferably, the temperature of the heat treatment process is 1 to 1.5 times of the melting point of the molten salt.
The heat treatment temperature is preferably 600 to 900 ℃, and more preferably 700 to 900 ℃.
Preferably, the method comprises the following steps: the time of the heat treatment process is 1-2 h.
Stirring the heat-treated negative electrode powder in deionized water, using the deionized water as a leaching agent and an impurity removing agent, washing off metal impurities and redundant metal chloride existing in the material while recovering lithium in the material, and simply separating and filtering to obtain a lithium-containing leaching solution and a purified and repaired negative electrode material.
The lithium ion leaching agent is deionized water, the mass ratio of the material to water in water leaching is 1:10-1:25, the temperature is 20-80 ℃, and the time is 0.5-2 h.
The invention discloses a preferable recovery method of waste lithium ion battery negative electrode powder, which comprises the following steps:
the first step is as follows: mixing the waste lithium ion battery negative electrode powder with metal chloride;
the second step is that: placing the uniformly mixed materials in an inert atmosphere for heat treatment to obtain a heat-treated material;
the third step: and (3) placing the heat-treated material in deionized water, stirring, performing solid-liquid separation, leaching lithium and redundant metal chloride in the material, recovering valuable metals from the liquid phase for lithium extraction, and filtering and drying the solid phase to obtain the purified negative electrode material.
Compared with the prior art, the invention has the following advantages:
① adopts molten salt heat treatment, which can remove organic impurities and transform lithium and metal impurities in the negative electrode, and the lithium which is not removed between the negative electrode layers and in the pore structure is transferred to the molten salt system, so that the recovery rate is higher.
② negative electrode powder obtained by disassembling battery without discharge or incomplete discharge has higher lithium content and lower recovery difficulty.
③ deionized water is used as lithium leaching agent and impurity removing agent, which is safe, environment-friendly, low in cost, high in leaching rate, easy to treat the leachate and simple in process.
Researches show that the recovery rate of lithium in the negative electrode powder of the waste lithium ion battery is higher than 85%.
According to the method for recovering the cathode powder of the waste lithium ion battery, the purity of high-purity carbon powder prepared from the recovered carbon powder reaches over 99.9 percent; the lithium ion battery cathode material prepared based on the recycled carbon powder can meet the requirements of the cathode for the conventional battery, namely, the capacity is higher than 350mAh/g, and the first efficiency is higher than 90%.
The material provided by the invention is simple in preparation process and easy for large-scale production, and realizes resource and high-value utilization of the waste lithium ion battery cathode powder.
Drawings
FIG. 1 is an SEM image of the anode material powder of the waste lithium ion battery used in the invention.
Fig. 2 is an SEM image of the regenerated anode material obtained in example 1 of the present invention.
FIG. 3 is an EDS diagram of a regenerated anode material obtained in example 1 of the present invention.
FIG. 4 is a schematic flow chart.
As shown in the attached figure 1, the untreated waste lithium ion battery negative electrode material has uneven appearance and a layer of viscous impurities covers the surface of particles;
as can be seen from the attached figure 2, the material after purification treatment has uniform appearance, small granularity and smooth surface, and impurities are removed;
it can be seen from fig. 3 that all impurities except carbon in the treated material are removed, and the purity of the obtained regenerated anode material is very high.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the following examples.
The electrochemical test method used in the following examples and comparative examples comprises the steps of uniformly mixing the recycled negative electrode material, the conductive agent acetylene black, the binder L A-133 and the dispersant CMC in a ratio of 90:5:3:2, using deionized water as a solvent, uniformly grinding, coating the mixture on a copper foil, placing the copper foil in a vacuum drying oven at 100 ℃ for 12 hours for drying, and tabletting to obtain a working electrode, using metal lithium as a counter electrode, using a porous polypropylene film as a diaphragm, using 1M L iPF6-EC/DEC/DMC as an electrolyte to prepare a CR2025 type button cell in a glove box under the protection of Ar atmosphere, and performing constant current charge and discharge test by using a blue cell test system under the condition that the current density is 37.2mA/g, wherein the voltage test range is 0.01-2V.
In the case of the invention, the cathode material (graphite cathode material) can be obtained by the existing method and equipment, or the cathode material recovered by a battery manufacturer can be directly recovered.
Example 1:
taking a waste lithium ion battery, soaking the waste lithium ion battery in a sodium chloride solution for complete discharge (short-circuit discharge is carried out until the residual voltage is 0V), then disassembling the waste lithium ion battery to obtain a negative plate, crushing the negative plate, stirring the negative plate in water, separating and drying to obtain waste lithium ion battery negative electrode powder;
taking 10g of waste lithium ion battery negative electrode powder, and uniformly mixing with sodium chloride, wherein the mass ratio of the sodium chloride to the negative electrode powder is 0.5: 1;
and (3) heating the uniformly mixed material to the melting point temperature of sodium chloride at the heating rate of 5 ℃/min under the argon atmosphere, keeping the temperature for 1h, and naturally cooling after the heat treatment is finished.
And (3) placing the heat-treated material into deionized water at a solid-to-liquid ratio of 1:20, stirring for 1h at normal temperature, and filtering and separating to obtain a lithium-containing filtrate and a purified negative electrode material.
Through detection, the leaching rate of lithium ions in the process of extracting lithium by water reaches 87%, and about 18g of lithium can be recovered after 1kg of waste negative electrode powder is treated by the process. The impurity content in the purified negative electrode material is lower than 0.1%, the first coulombic efficiency reaches 89.5% (0.1C), the reversible capacity after 150 cycles of 0.1C circulation is 352mAh/g, and the capacity retention rate is 98%.
Example 2:
taking a waste lithium ion battery, disassembling the waste lithium ion battery under a water spraying condition (incomplete discharge and residual voltage >0V) to obtain a negative pole piece, crushing the negative pole piece, stirring in water, separating and drying to obtain negative pole powder (namely incomplete discharge negative pole powder) of the waste lithium ion battery;
taking 10g of waste lithium ion battery negative electrode powder, and uniformly mixing with potassium chloride, wherein the mass ratio of the potassium chloride to the negative electrode powder is 0.5: 1;
and (3) heating the uniformly mixed material to 800 ℃ at the heating rate of 5 ℃/min in the argon atmosphere, keeping the temperature for 1h, and naturally cooling after the heat treatment is finished.
And (3) placing the heat-treated material into deionized water according to the solid-to-liquid ratio of 1:20, stirring for 1h at 40 ℃, and filtering and separating to obtain lithium-containing filtrate and a purified negative electrode material.
The detection shows that the leaching rate of lithium ions in the process of extracting lithium by water reaches 89%, and about 24g of lithium can be recovered after 1kg of waste negative electrode powder is treated by the process. The impurity content in the purified negative electrode material is lower than 0.1%, the first coulombic efficiency reaches 90.2% (0.1C), the reversible capacity after 150 cycles of 0.1C circulation is 362mAh/g, and the capacity retention rate is 98%.
Example 3:
the negative electrode powder was the same as in example 2;
taking 10g of waste lithium ion battery negative electrode powder, and uniformly mixing the waste lithium ion battery negative electrode powder with metal chloride, wherein the mass ratio of the metal chloride to the negative electrode powder is 0.5:1, the metal chloride is a mixture of sodium chloride and calcium chloride, and the ratio of the metal chloride to the calcium chloride is 1: 1;
and (3) heating the uniformly mixed material to 800 ℃ at the heating rate of 5 ℃/min in the argon atmosphere, keeping the temperature for 1h, and naturally cooling after the heat treatment is finished.
And (3) placing the heat-treated material into deionized water according to the solid-to-liquid ratio of 1:20, stirring for 1h at 60 ℃, and filtering and separating to obtain lithium-containing filtrate and a purified negative electrode material.
Through detection, the leaching rate of lithium ions in the process of extracting lithium by water reaches 90%, and about 25g of lithium can be recovered after 1kg of waste negative electrode powder is treated by the process. The impurity content in the purified negative electrode material is lower than 0.1%, the first coulombic efficiency reaches 89.7% (0.1C), the reversible capacity after 150 cycles of 0.1C circulation is 360mAh/g, and the capacity retention rate is 98%.
Example 4:
the negative electrode powder was the same as in example 2;
taking 10g of waste lithium ion battery negative electrode powder, and uniformly mixing the waste lithium ion battery negative electrode powder with metal chloride, wherein the mass ratio of the metal chloride to the negative electrode powder is 1:1, and the metal chloride is a mixture of sodium chloride and calcium chloride, and the ratio of the metal chloride to the calcium chloride is 1: 1;
and (3) heating the uniformly mixed material to 900 ℃ at the heating rate of 5 ℃/min in the argon atmosphere, keeping the temperature for 1h, and naturally cooling after the heat treatment is finished.
And (3) placing the heat-treated material into deionized water according to the solid-to-liquid ratio of 1:20, stirring for 1h at 60 ℃, and filtering and separating to obtain lithium-containing filtrate and a purified negative electrode material.
Through detection, the leaching rate of lithium ions in the process of extracting lithium by water reaches 90%, and about 24g of lithium can be recovered after 1kg of waste negative electrode powder is treated by the process. The impurity content in the purified negative electrode material is lower than 0.1%, the first coulombic efficiency reaches 90.1% (0.1C), the reversible capacity after 150 cycles of 0.1C circulation is 357mAh/g, and the capacity retention rate is 98%.
Comparative example 1: without purification and recovery treatment
Compared with the embodiment 1, the difference is that the separated cathode material is directly adopted for electrical property measurement; the method specifically comprises the following steps:
the waste lithium ion battery negative electrode powder is directly ground and sieved by a 400-mesh sieve, and the smear test is carried out according to the proportion of 90:5:3:2 (waste negative electrode material: conductive carbon: CMC: L A-133).
The first coulombic efficiency is lower than 78% (0.1C), and the capacity is only 280mAh/g after 10 cycles of circulation
After long-time circulation, the performance attenuation of the waste lithium ion battery negative electrode material is large, the waste lithium ion battery negative electrode material cannot be directly used as a battery material after recovery, purification and impurity removal treatment are needed to recover the performance, and meanwhile, lithium is one of main recovery targets as a rare metal and needs to be recovered.
Comparative example 2: without molten salt heat treatment
Compared with example 1, the difference is only that no molten salt is added during the heat treatment process, specifically;
taking 10g of waste lithium ion battery negative electrode powder, carrying out heat treatment under the argon atmosphere, wherein the heating rate is 5 ℃/min, the heat treatment temperature is 801 ℃, and the heat preservation time is 1h, and then naturally cooling;
and (3) placing the heat-treated powder into deionized water at a solid-to-liquid ratio of 1:20, stirring for 1h at normal temperature, and filtering and separating to obtain a lithium-containing filtrate and a recovered negative electrode material.
Through detection, the leaching rate of lithium ions in the water leaching lithium extraction process is 70%, the first coulombic efficiency of the purified negative electrode material is 80% (0.1C), the reversible capacity after 150 cycles of 0.1C circulation is 140mAh/g, the capacity retention rate is 39.7%, the leaching rate in the water leaching lithium extraction step of the material is obviously reduced without carrying out heat treatment on molten salt, and meanwhile, because metal impurities in the material are not removed, the electrochemical performance is still poor, and the standard of reuse cannot be met.
The embodiment and the comparative example show that the recovery method can simultaneously recover the lithium and the negative electrode material in the negative electrode material, the recovery rate of the lithium is high, the leachate is safe, environment-friendly and easy to process, the electrochemical performance of the purified negative electrode material is greatly improved, the use requirement of the battery-grade negative electrode material is met, and the scheme is simple, efficient and suitable for large-scale production.
Claims (10)
1. A method for recovering a waste lithium ion battery cathode material is characterized by comprising the following steps: the method comprises the following steps:
step (1): mixing the waste lithium ion battery negative electrode material with molten salt and then carrying out heat treatment; the melting point temperature of the molten salt is more than or equal to 450 ℃; the temperature of the heat treatment is higher than or equal to the melting point of the molten salt;
step (2): and (3) carrying out water leaching treatment and solid-liquid separation on the material subjected to heat treatment in the step (1) to obtain a regenerated anode material and a water leaching solution.
2. The recycling method according to claim 1, characterized in that: the melting point of the molten salt is 600-900 ℃.
3. The recycling method according to claim 1, characterized in that: the molten salt is water-soluble metal chloride; preferably at least one of potassium chloride, sodium chloride and calcium chloride.
4. The recovery method according to any one of claims 1 to 3, characterized in that: molten salt: the mass ratio of the negative electrode material is 0.1: 1-1: 1.
5. The recovery method according to any one of claims 1 to 4, characterized in that: the negative electrode material is stripped from the waste lithium ion battery with residual voltage more than 0V.
6. The recycling method according to claim 5, characterized in that: and disassembling the charged waste battery with the residual voltage larger than 0 to obtain a negative plate, and separating a current collector in the negative plate to obtain the negative material.
7. The recycling method according to claim 6, characterized in that: and crushing the negative plate, placing the crushed negative plate into water, stirring, sieving and separating to obtain a current collector and the negative material.
8. The recycling method according to claim 1, characterized in that: the heat treatment process is performed in a protective atmosphere, or a reducing gas-protective atmosphere.
9. The recycling method according to claim 1, characterized in that: the time of the heat treatment process is 1-2 h.
10. The recycling method according to claim 1, characterized in that: in the water leaching process, the solid-liquid ratio is 1:10-1:25, the temperature is 20-80 ℃, and the time is 0.5-2 h.
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| WO2024130842A1 (en) * | 2022-12-22 | 2024-06-27 | 广东邦普循环科技有限公司 | Method for treating battery black mass and preparing regenerated graphite negative electrode and use thereof |
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