CN110797602A - Molten salt regeneration and repair method for lithium ion battery anode material and lithium ion battery anode material obtained by same - Google Patents
Molten salt regeneration and repair method for lithium ion battery anode material and lithium ion battery anode material obtained by same Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium ion battery material recovery and repair regeneration, and particularly relates to a molten salt regeneration repair method for a lithium ion battery anode material and the lithium ion battery anode material obtained by the method. 1) Mixing powder of a lithium battery anode recycled material with at least two lithium supplement agents to obtain a mixture; 2) heating the mixture into molten salt, and supplementing lithium or supplementing lithium and removing impurities to obtain a lithium battery anode recycled material after lithium is supplemented; 3) washing and drying the lithium battery anode recycled material after lithium supplement to obtain a lithium battery anode recycled material to be sintered; 4) and sintering the lithium battery anode recycled material to be sintered to obtain the crystal-form remolded lithium battery anode regenerated material. The obtained lithium battery anode regenerated material has high purity and good performance, can be directly used as a lithium battery anode material, and has good performance.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery material recovery and repair regeneration, and particularly relates to a molten salt regeneration repair method for a lithium ion battery anode material and the lithium ion battery anode material obtained by the method.
Background
In consideration of the economic value and resource value contained in the anode material of the waste lithium ion battery and the environmental problem caused by direct abandonment, the recycling and reutilization of the anode material become hot trends. However, with the application of lithium ion batteries in the field of power, the composition of the positive electrode material in the battery is more diversified and complicated, and manufacturers often adopt the blending of multiple materials to achieve the functional complementation between different materials. For example, to make up for the safety deficiency of the high nickel material, a method of blending lithium cobaltate, lithium manganate or a low nickel material with the high nickel material is adopted.
The mixing of materials brings difficulty to impurity removal and regeneration, the research on the mixing of materials is less, and the main methods include two major methods, namely a metallurgical method and direct regeneration. The traditional metallurgical method can be used for mixing materials to realize the recovery of resources, but damages the structure of the materials, introduces the harsh conditions of high temperature/strong acid and alkali, and has complex steps and high energy consumption. The existing process of solvent soaking/high-temperature sintering stripping + high-temperature pyrogenic lithium replenishing regeneration can maintain the material structure and realize direct recovery and regeneration, but is only suitable for recovery and regeneration of a single material due to different materials with different tolerance to sintering temperature.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a molten salt regeneration repair method of a lithium ion battery anode material and the lithium ion battery anode material obtained by the method. The regeneration repairing method realizes regeneration of the lithium battery mixed anode waste material on the basis of not damaging the original structure of the material. The technical scheme can solve the problems of waste battery discarding, serious environmental pollution, immature recovery technology and high cost in the prior art; can solve the problem of impurity removal and regeneration of leftover materials/waste pole pieces of mixed positive pole materials. The method has the characteristics of good repeatability, high resource utilization rate, simple process and high efficiency.
The technical scheme provided by the invention is as follows:
a molten salt regeneration and repair method for a lithium ion battery anode material comprises the following steps:
1) mixing powder of a lithium battery anode recycled material with a lithium supplement agent to obtain a mixture, wherein the lithium supplement agent comprises or does not comprise a fluxing agent;
2) heating the mixture obtained in the step 1) into molten salt, and supplementing lithium, or supplementing lithium and removing impurities to obtain a lithium battery anode recycled material after lithium is supplemented;
3) washing and drying the lithium battery anode recycled material after lithium supplement obtained in the step 2) to obtain a lithium battery anode recycled material to be sintered;
4) sintering the lithium battery anode recycled material to be sintered obtained in the step 3) to obtain a crystal-type remolded lithium battery anode regenerated material.
In the above technical scheme:
in the step 2), a molten salt method is adopted for lithium supplement:
a) in the process of lithium supplement, the aim of removing impurities, such as residual aluminum current collectors, adhesives and the like, can be achieved by dissolving aluminum and adhesives by alkaline substances at high temperature;
b) the reaction of lithium supplement can be completed without using a solvent;
c) the molten salt method provides a high-pressure environment for crystal form restoration, and after lithium is supplemented by the molten salt method, the recycled material of the positive electrode of the lithium battery can be restored to the original layered structure or olivine structure, so that the crystal form is good;
in the step 4), after washing in the step 3), the surface can be subjected to shallow structural damage and residual lithium generation, the surface structure can affect the safety performance and the electrical performance, and the surface structure of the lithium battery anode recycled material can be recovered by performing secondary sintering, so that the residual lithium amount is reduced.
In the technical scheme, the scheme of firstly supplementing lithium and then sintering is adopted, and the time required by sintering is obviously shortened compared with the conventional dry sintering lithium supplementing process because the crystal form of the material is approximately and completely remolded in the lithium supplementing process.
According to the technical scheme, the lithium supplement of the lithium battery anode recycled material is realized through the technology of combining the impurity removal/lithium supplement of the molten salt and the regeneration of the high-temperature solid phase. The obtained lithium battery anode regenerated material has high purity and good performance, can be directly used as a lithium battery anode material, and has good performance.
Specifically, in the step 1), the powder of the lithium battery anode recycling material is as follows:
the method comprises the following steps of (1) processing powder obtained after a pole piece made of a lithium battery positive electrode material fails, for example, the powder obtained after the failed waste pole piece is processed, wherein the processing step can comprise separating a current collector;
alternatively, the powder obtained after processing the leftover materials of the positive electrode materials of the lithium battery, for example, the powder obtained after processing the leftover materials without contacting the electrolyte, and the processing step can comprise separating the current collector.
Specifically, in step 1):
the positive electrode material of the lithium battery is layered LiMeO2Me is Ni, Co or Mn; or the positive electrode material of the lithium battery is olivine-structured LiMePO4Me is Fe or Mn;
the lithium supplement salt comprises but is not limited to any one or more of lithium nitrate, lithium hydroxide, lithium carbonate, lithium acetate or lithium sulfate;
the fluxing agent includes, but is not limited to, an alkali metal nitrate or a strong base;
the weight ratio of the lithium battery positive electrode recycled material to the lithium supplement agent is 2: 1-1: 5.
Based on the technical scheme, lithium supplement can be realized.
The principle and reaction of lithium supplement are as follows:
the molten salt environment provides a high-pressure-like environment for the cathode material, so that the lithium intercalation reaction which is not easy to occur at normal temperature and normal pressure and the conversion reaction of rock salt phase to layered phase can occur, wherein the ion reaction equation of the lithium intercalation reaction is as follows:
Li++MexOy→LiMeO2
in the step 2), the mixture obtained in the step 1) is heated to be molten salt at the temperature of 170-300 ℃, and lithium supplement is carried out, or lithium supplement and impurity removal are carried out.
Since the lowest eutectic temperature of the molten salt is related to the kind and ratio of the lithium supplement salt and/or the flux, the optimum temperature is slightly different. Based on the temperature range of the technology, the fused salt eutectic melting of various compositions can be realized and the lithium supplement reaction can be carried out under the condition of the lowest temperature, namely the lowest energy consumption, so that the crystal form of the recovered anode powder is remolded.
Specifically, in step 3), constant weight treatment is performed after washing and drying.
In the technical scheme, the constant weight treatment can ensure complete drying of the material.
Specifically, the constant weight treatment method comprises the step of drying at 80-150 ℃ until the weight change is less than 0.3%.
According to the technical scheme, the material can be completely dried by constant weight at the temperature of 80-150 ℃, and the problem of performance reduction such as increase of residual lithium on the surface caused by moisture in the preservation process is avoided.
Specifically, in the step 4):
the sintering atmosphere is air, oxygen, nitrogen or the mixture of any one or more of inert gases;
the sintering temperature is 600-900 ℃;
the sintering time is 1-8 h.
Based on the technical scheme, the crystal form of the recycled material of the positive electrode of the mixed lithium battery can be recovered, and compared with the conventional dry sintering method, the lithium supplement method has the advantages that the sintering temperature is reduced, the sintering time is reduced, and the universality is enhanced.
The invention also provides a lithium battery anode regeneration material obtained by the molten salt regeneration repair method of the lithium battery anode material.
The lithium battery anode regenerated material obtained by the technical scheme has high purity and good performance, can be directly used as a lithium battery anode material, and has good performance.
Generally, the molten salt regeneration repair method for providing the lithium ion battery cathode material provided by the invention has the following advantages:
1) on the basis of not damaging the original structure of the anode powder, the step of separating and mixing the anode material is saved, and the regeneration of two or more mixed powders is realized by a fused salt lithium supplement method, so that the performance of the mixed powders reaches the level of commercial materials.
2) As the pyrometallurgical temperature is about 1000-1200 ℃, and the equal weight/several times weight of the furnace slag needs to be heated simultaneously, compared with the traditional pyrometallurgical method, the method of the invention does not damage the original structure of the material, has low sintering temperature, short time and energy saving of more than 50 percent. Compared with the traditional hydrometallurgy, the method does not introduce an organic solvent required by solvent extraction, and is environment-friendly. Compared with the dry sintering lithium supplement, the temperature for lithium supplement is reduced to below 300 ℃ from 800-900 ℃; the required time is reduced from more than 10h to less than 4 h.
3) The content of Al impurities can be reduced to be close to 0 by supplementing lithium with molten salt; the content of C is reduced to 0.03%, and compared with the traditional methods such as flotation, the content of C is reduced by one order of magnitude.
4) Thermodynamically, the rock salt phase Ni oxide generated in the circulation process is difficult to be converted into a layered structure by a simple sintering method. The process of lithium supplement by molten salt is beneficial to the process, and the Li/Ni mixed discharge is effectively reduced.
5) The fused salt lithium supplement has a saturation value, and the lithium can be supplemented to the mixed material in a balanced manner, after the lithium is supplemented fully, the Li/Me ratio is about 1.0-1.1, and the Li/Me ratio cannot be changed along with the increase of the time length and the increase of the temperature.
6) And the step of recovering the crystal form by heat treatment mainly aims at remolding the surface, and the lithium is not needed to be supplemented, so that the sintering time is short, the damage to the mixed material is neglected, and on the contrary, the crystal form can be effectively molded to a layered structure, and the mixed cation discharge is reduced.
Drawings
FIG. 1 is a SEM comparison of the material to be regenerated and the regenerated material 1 in example 1.
Fig. 2 is a comparison XRD of the material to be regenerated in example 1 and the regenerated material 1.
FIG. 3 is a graph comparing electrochemical performance of the material to be regenerated and the regenerated material 1 in example 1.
FIG. 4 is a SEM comparison of the material to be regenerated and the regenerated material 2 in example 2.
Fig. 5 is a XRD comparison pattern of the material to be regenerated in example 2 with that of regenerated material 2.
FIG. 6 is a graph comparing the electrochemical performance of the material to be regenerated with that of regenerated material 2 in example 2.
FIG. 7 is a graph comparing electrochemical performances of the material to be regenerated and the regenerated material 3 in example 3.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
1) 1.5g of anhydrous LiOH and 6.5g of LiNO were weighed out32g of the material to be reconstituted (waste material obtained by mixing NCM111 and LCO at a mass ratio of 3: 1), was thoroughly ground and mixed in a mortar, and then charged with Al2O3A crucible is provided.
2) Under the oxygen atmosphere, lithium is supplemented by fused salt in a tube furnace, the temperature rising speed is 3 ℃/min, the temperature is kept at 300 ℃/2h, and the lithium is naturally cooled to the room temperature and then taken out.
3) And stirring and dissolving the cooled molten salt by using deionized water, and filtering to obtain the lithium-supplemented anode powder. The filter cake was rinsed with deionized water until the filtrate had a pH < 11, and then dried at 130 ℃ until the weight difference was below 0.3%.
4) And sintering and remolding the surface crystal form at the heating speed of 5 ℃/min and 680 ℃/4h in the dry air atmosphere. And (3) taking the material out of the furnace at the temperature of below 150 ℃, and directly sieving the material through a 300-mesh sieve to obtain the lithium battery anode regeneration material 1.
5) The obtained lithium battery anode regenerated material 1 and the material to be regenerated are subjected to comparative test, and the results are as follows:
the morphology is shown in figure 1, which is an SEM comparison of the material to be regenerated and the regenerated material 1. The SEM picture shows that the material to be regenerated is composed of secondary spheres with a particle size of about 10 μm mixed with single crystals with a particle size of about 2 μm, and the surfaces of the components have obvious flocculent impurities. After the regeneration of each step, the obtained regenerated material 1 is almost unchanged, wherein the sphericity of the secondary spheres is good and is consistent with that of the single crystal, the cracking and crushing conditions are avoided, and the flocculent impurities (the binder and the conductive agent) shown by each component are reduced, which shows that the material has good impurity removal after the regeneration and meets the requirements in terms of macroscopic morphology.
The crystal form is shown in figure 2, which is an XRD comparison graph of the material to be regenerated and the regenerated material 1. The XRD pattern shows that the 003/104 peak strength of the powder after regeneration is obviously enhanced, which shows that the Li/Me mixed discharge is obviously reduced; meanwhile, the 006/012 and 018/110 peaks are clearer, the splitting degree between each group of peaks is more obvious, and the material is more obvious in layered structure and better in crystallinity.
Electrochemical properties are shown in fig. 3, which is a comparison of the electrochemical properties of the material to be regenerated and the regenerated material 1 in example 1. The comparison graph shows that under the cut-off voltage of 2.8-4.2V, the performance of the material to be regenerated is seriously attenuated, and only has the specific charge capacity of 155mAh/g and the specific discharge capacity of 132mAh/g, and the first charge-discharge efficiency is lower than 85%; the electrochemical performance after the regeneration is obviously improved, the charging performance of 165mAh/g and the discharging specific capacity of 141mAh/g are achieved, and the first cycle charging and discharging efficiency reaches more than 85.3 percent.
Example 2
1) 1.5g of anhydrous LiOH and 6.5g of LiNO were weighed out32g of a material to be regenerated (NCM 523 secondary ball edge material doped with NCM523 single crystal) was sufficiently ground and mixed in a mortar, and then Al was charged2O3A crucible is provided.
2) Under the oxygen atmosphere, lithium is supplemented by molten salt in a tube furnace, the temperature rise speed is 3 ℃/min, and the constant temperature is 280 ℃/3 h. Naturally cooling to room temperature and taking out.
3) And stirring and dissolving the cooled molten salt by using deionized water, and filtering to obtain the lithium-supplemented anode powder. The filter cake was rinsed with deionized water until the filtrate had a pH < 11, and then dried at 130 ℃ until the weight change was less than 0.3%.
4) And sintering and remolding the surface crystal form at the heating speed of 5 ℃/min and the heating speed of 650 ℃/4h in the dry air atmosphere. And (3) taking the material out of the furnace at the temperature of below 150 ℃, and directly sieving the material through a 300-mesh sieve to obtain the lithium battery anode regeneration material 2.
5) The obtained lithium battery anode regenerated material 2 and the material to be regenerated are subjected to comparative test, and the results are as follows:
the appearance is shown in figure 4, from left to right, the material to be regenerated, the material after molten salt treatment and the material after final sintering are arranged in sequence. As can be seen from the SEM image, the raw material is a mixed material of single crystals and secondary spheres, and the flocculent binder, the conductive agent, and the tubular conductive agent remain on the surface of the material. Because the scrap is adopted, the macroscopic morphology is not damaged; after the materials are treated by a molten salt method, cleaned and dried, the impurities on the surface of the materials are reduced, and the appearance is not damaged; after final sintering at 650 ℃, surface impurities are removed completely, and the structural appearance is kept intact.
The crystal form is shown in figure 5, the material is a mixed leftover material, so that the crystal form is not greatly damaged, after molten salt and washing, part of the surface structure is actually damaged, but after dry sintering and reshaping, the 003/104 strength of the material is obviously improved, and the ion mixed-exclusion degree is low; 006/012 and 018/110 peaks are clearer, and the splitting degree between each group of peaks is more obvious, which indicates that the material has more obvious layered structure and better crystallinity.
Electrochemical performance as shown in fig. 6, the points of each row are, from top to bottom, the commercial 523, the regenerated material, and the virgin material. As can be seen from fig. 6, the three materials have similar specific discharge capacities under the 0.1C test condition, but due to impurities on the surface of the original material and structural changes caused by long-term retention in the environment, the specific discharge capacity is significantly reduced to about 5C under the high-rate condition, and only about 60mAh/g of discharge capacity is far from the commercial requirement. The material treated by the scheme has similar performance to commercial materials under various multiplying power conditions.
Example 3
1) Weighing 1.5g KNO3 and 6.5g LiNO32g of a material to be regenerated (NCM 523 secondary ball edge material doped with NCM523 single crystal) was sufficiently ground and mixed in a mortar, and then Al was charged2O3A crucible is provided.
2) Under the oxygen atmosphere, lithium is supplemented by molten salt in a tube furnace, the temperature rise speed is 3 ℃/min, and the constant temperature is 150 ℃/2 h. Naturally cooling to room temperature and taking out.
3) And stirring and dissolving the cooled molten salt by using deionized water, and filtering to obtain the lithium-supplemented anode powder. The filter cake was rinsed with deionized water until the filtrate had a pH < 11, and then dried at 130 ℃ to a weight change of less than 0.3%.
4) And sintering and remolding the surface crystal form at the heating speed of 5 ℃/min and the heating speed of 650 ℃/4h in the dry air atmosphere. And (3) taking the material out of the furnace at the temperature of below 150 ℃, and directly sieving the material through a 300-mesh sieve to obtain the lithium battery anode regeneration material 3.
5) The obtained lithium battery anode regenerated material 3 and the material to be regenerated are subjected to comparative test, and the results are as follows:
as shown in fig. 7, the electrochemical performance of the sample is shown in fig. 7, the commercial 523, the recycled material and the original material are arranged in sequence from top to bottom, and although strong base is not used as a flux, impurities in the scrap, particularly Al impurities, cannot be completely removed, so that the alkaline system with stronger rate performance is slightly reduced, but the performance of the sample is still remarkably improved compared with that of an untreated sample.
Effect example 1
A 2025 button cell was assembled with the regenerated material 2 obtained in example 2 as active positive electrode powder and a lithium plate as negative electrode, and the cell was subjected to rate test:
in the rate test, electrochemical performance of the material at 0.1C, 0.5C, 1.0C, 2.0C and 5.0C rates was tested after 0.1C activation cycle, respectively.
The test results are electrochemical performance in reference example 2.
The results show that the obtained repair material has good performance due to complete impurity removal and good recovery of the laminated structure, and ensures that the battery device obtains the first-week efficiency and excellent performance under high rate. The lithium battery material meets the requirements of circulation and quick charge of the commercial lithium battery material.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (8)
1. A molten salt regeneration and repair method for a lithium ion battery anode material is characterized by comprising the following steps:
1) mixing powder of a lithium battery anode recycled material with a lithium supplement agent to obtain a mixture, wherein the lithium supplement agent comprises or does not comprise a fluxing agent;
2) heating the mixture obtained in the step 1) into molten salt, and supplementing lithium, or supplementing lithium and removing impurities to obtain a lithium battery anode recycled material after lithium is supplemented;
3) washing and drying the lithium battery anode recycled material after lithium supplement obtained in the step 2) to obtain a lithium battery anode recycled material to be sintered;
4) sintering the lithium battery anode recycled material to be sintered obtained in the step 3) to obtain a crystal-type remolded lithium battery anode regenerated material.
2. The molten salt regeneration repair method for a lithium ion battery positive electrode material according to claim 1, characterized in that: in the step 1), the powder of the lithium battery positive electrode recycling material is obtained by processing a pole piece made of the lithium battery positive electrode material after failure, or is obtained by processing leftover materials of the lithium battery positive electrode material.
3. The molten salt regeneration repair method for the lithium ion battery positive electrode material according to claim 2, characterized in that in step 1):
the positive electrode material of the lithium battery is layered LiMeO2Me is Ni, Co or Mn; or the positive electrode material of the lithium battery is olivine-structured LiMePO4Me is Fe or Mn;
the lithium supplement salt comprises but is not limited to any one or more of lithium nitrate, lithium hydroxide, lithium carbonate, lithium acetate or lithium sulfate;
the fluxing agent includes, but is not limited to, an alkali metal nitrate or a strong base;
the weight ratio of the lithium battery positive electrode recycled material to the lithium supplement agent is 2: 1-1: 5.
4. The molten salt regeneration repair method for a lithium ion battery positive electrode material according to claim 1, characterized in that: in the step 2), the mixture obtained in the step 1) is heated to be molten salt at the temperature of 170-300 ℃, and lithium supplement is carried out, or lithium supplement and impurity removal are carried out.
5. The molten salt regeneration repair method for a lithium ion battery positive electrode material according to claim 1, characterized in that: in step 3), constant weight treatment is performed after washing and drying.
6. The molten salt regeneration repair method for a lithium ion battery positive electrode material according to claim 5, characterized in that: the constant weight treatment method comprises the step of drying at the temperature of 80-150 ℃ until the weight difference is less than 0.3%.
7. The molten salt regeneration repair method for the lithium ion battery positive electrode material according to any one of claims 1 to 6, characterized in that in step 4):
the sintering atmosphere is air, oxygen, nitrogen or the mixture of any one or more of inert gases;
the sintering temperature is 600-900 ℃;
the sintering time is 1-8 h.
8. A lithium battery positive electrode regeneration material obtained by the molten salt regeneration repair method of the lithium ion battery positive electrode material according to any one of claims 1 to 7.
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| CN112886084A (en) * | 2021-01-13 | 2021-06-01 | 上海紫剑化工科技有限公司 | Method for repairing layered oxide positive electrode material of sodium ion battery |
| CN113800575A (en) * | 2021-08-17 | 2021-12-17 | 广东邦普循环科技有限公司 | Method for recycling lithium battery positive electrode material |
| CN114204013A (en) * | 2021-12-15 | 2022-03-18 | 中南大学 | Direct repairing method for waste ternary lithium battery positive electrode material and ternary positive electrode material prepared by same |
| EP4152477A4 (en) * | 2020-09-28 | 2024-01-03 | LG Energy Solution, Ltd. | Method for reusing active material by using positive electrode scrap |
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| EP4117059A4 (en) * | 2020-03-06 | 2024-05-15 | Sumitomo Chemical Company, Limited | Method for manufacturing active material |
| CN111430830A (en) * | 2020-03-11 | 2020-07-17 | 中南大学 | Method for recovering valuable components in positive electrode of waste lithium battery based on molten salt system |
| CN111430830B (en) * | 2020-03-11 | 2021-07-27 | 中南大学 | Method for recovering valuable components in positive electrode of waste lithium battery based on molten salt system |
| EP4152477A4 (en) * | 2020-09-28 | 2024-01-03 | LG Energy Solution, Ltd. | Method for reusing active material by using positive electrode scrap |
| CN112886084A (en) * | 2021-01-13 | 2021-06-01 | 上海紫剑化工科技有限公司 | Method for repairing layered oxide positive electrode material of sodium ion battery |
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| CN112777645A (en) * | 2021-01-21 | 2021-05-11 | 昆明理工大学 | Method for regenerating waste lithium cobaltate cathode material at low temperature by double-effect molten salt |
| CN113800575A (en) * | 2021-08-17 | 2021-12-17 | 广东邦普循环科技有限公司 | Method for recycling lithium battery positive electrode material |
| CN113800575B (en) * | 2021-08-17 | 2022-11-15 | 广东邦普循环科技有限公司 | Method for recycling lithium battery positive electrode material |
| CN114204013A (en) * | 2021-12-15 | 2022-03-18 | 中南大学 | Direct repairing method for waste ternary lithium battery positive electrode material and ternary positive electrode material prepared by same |
| CN114204013B (en) * | 2021-12-15 | 2024-03-22 | 中南大学 | Direct repair method for waste ternary lithium battery positive electrode material and ternary positive electrode material prepared by same |
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