CN112054265A - Method for recycling and reusing anode material of waste ternary lithium ion battery - Google Patents
Method for recycling and reusing anode material of waste ternary lithium ion battery Download PDFInfo
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- CN112054265A CN112054265A CN202011064180.1A CN202011064180A CN112054265A CN 112054265 A CN112054265 A CN 112054265A CN 202011064180 A CN202011064180 A CN 202011064180A CN 112054265 A CN112054265 A CN 112054265A
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a method for recycling a waste ternary lithium ion battery anode material, which comprises the following steps: separating a current collector and positive electrode slurry from a waste ternary lithium ion battery positive electrode piece through a separating agent; filter-pressing the positive electrode slurry to obtain a filter cake, carrying out vacuum drying on the filter cake, and then carrying out air separation to separate out a positive electrode material and a conductive agent; and mechanically crushing the separated anode material, screening to obtain anode particles with a proper particle size range, supplementing lithium to the anode particles, and calcining to obtain the ternary single crystal anode material. The recycling method is environment-friendly in process and simple in operation, and the ternary single crystal anode material prepared again is excellent in performance.
Description
Technical Field
The invention belongs to the technical field of waste battery regeneration, and particularly relates to a method for recycling a waste ternary lithium ion battery anode material.
Background
In recent years, under the encouragement and support of national policies, the new energy automobile industry in China is rapidly developed, and the development of the new energy automobile industry also promotes the development of lithium ion batteries. Along with the rapid development, the lithium ion battery also faces a plurality of challenges, and the recycling treatment of the lithium ion battery faces problems due to the large use amount of the lithium ion battery.
The waste lithium ion battery contains a large amount of valuable metal elements such as nickel, cobalt, manganese, iron, lithium, aluminum, copper and the like and organic solvents such as electrolyte, and if the waste lithium ion battery is directly discarded, not only can the resource waste be caused, but also the environmental pollution can be caused. Therefore, how to treat and recycle the waste lithium ion battery on a large scale becomes a great challenge currently. According to the knowledge, the power battery carried by the new energy automobile in China is expected to meet the large-scale retirement surge for the first time in 2020. The search for a commercially viable, economically viable and environmentally friendly recycling solution is currently a focus of research in lithium ion batteries.
The recycling of the anode material, which is the most economically valuable component of lithium ion batteries, particularly ternary lithium ion batteries, is of great significance, so that the recycling of waste lithium ion batteries is mainly focused on the treatment of anode plates and the recycling of anode materials.
Currently, the recovery of the anode material is often combined with the recovery by a pyrometallurgical or/and hydrometallurgical process. Metallurgy aims at obtaining metal simple substances, oxides or ionic solutions, which tend to destroy the original crystal structure of the anode material and cannot realize direct reutilization. If the waste water is recycled, the waste water needs to be processed into a precursor, so that the waste water is time-consuming and labor-consuming, and environmental pollutants are generated again. Although various schemes are proposed for recycling the positive electrode material in the prior art, such as directly recycling and re-preparing the positive electrode material, a large amount of harmful and toxic organic solvent is adopted in the stripping process of the positive electrode material and the aluminum foil, so that the green environmental protection is not facilitated; for example, the positive electrode material is directly recovered by adopting a full-dry purification method, although the process is simple and economical and feasible, a large amount of harmful gas is generated in the process of low-temperature heating of the binder to lose efficacy, and the environment is polluted.
Disclosure of Invention
In view of the above, the present invention provides a recycling method for a waste ternary lithium ion battery positive electrode material, wherein the recycling method selects a low-toxicity or slightly-toxic solvent, has an environment-friendly process and a simple operation, and is used for preparing a ternary single crystal positive electrode material with excellent performance by performing high temperature lithium supplement after mechanical crushing and screening after air separation, so as to solve the above problems.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for recycling a waste ternary lithium ion battery anode material, which comprises the following steps:
placing the waste ternary lithium ion battery positive pole piece in a separating agent for ultrasonic heating, and separating out a current collector and positive pole slurry;
filter-pressing the positive electrode slurry to obtain a filter cake, carrying out vacuum drying on the filter cake, and then carrying out air separation to separate out a positive electrode material and a conductive agent;
mechanically crushing and screening the separated anode material to obtain a particle size range D502-5 μm of positive electrode particles;
and after lithium is supplemented to the anode particles, calcining the anode particles to obtain the ternary single crystal anode material.
Furthermore, the anode plate of the waste ternary lithium ion battery is made of a nickel-cobalt-manganese or nickel-cobalt-aluminum ternary anode material, and the binder is PVDF.
Further, the separating agent is one or a mixture of more than two of dichloromethane, ethyl acetate, thiourea solution and ethanol.
Further, the mass ratio of the waste ternary lithium ion battery positive pole piece to the separating agent is 1: 2-10.
Further, the specific steps of the ultrasonic heating are as follows: ultrasonic treating at 50-80 deg.C for 0.5-10 hr.
Further, before the lithium supplement of the positive electrode particles, ICP elemental analysis is carried out on the positive electrode particles, and the total molar ratio of lithium to the transition metal element M is obtained.
Further, the lithium supplement is a lithium source supplement according to the total molar ratio Li/M of lithium to the transition metal element M of 1: 1.01-1.24.
Further, the lithium source is one or a mixture of two or more of lithium carbonate, lithium hydroxide, lithium nitrate, lithium citrate and lithium acetate.
Further, the calcining step is as follows: presintering for 3-6h at the temperature of 400-600 ℃ in the air or oxygen atmosphere with the pressure of 20-100MPa, then heating to the temperature of 700-1000 ℃ and sintering for 15-20 h.
Compared with the prior art, the invention has the following beneficial effects:
the method for recycling the waste ternary lithium ion battery anode material has the advantages of simple process, economy, feasibility, environmental protection and large-scale application.
The recycling method can successfully recycle the anode material from the anode plate of the waste ternary lithium ion battery, utilizes the characteristic that a large number of cracks exist in the material after failure, prepares the material into a particle size suitable for synthesizing the ternary single crystal anode material by mechanical crushing, and finally prepares the ternary single crystal anode material by a method of supplementing a lithium source and sintering at high temperature and high pressure, so that the obtained ternary single crystal anode material has excellent performance.
Drawings
FIG. 1 is a flow chart of the recycling of the anode material of the waste ternary lithium ion battery of the present invention;
FIG. 2 is an XRD spectrum of a ternary single crystal positive electrode material prepared by a recycling method in example 1 of the present invention;
FIG. 3 is a cross-sectional view of a ternary single-crystal positive electrode material produced by a recycling method in example 1 of the present invention;
fig. 4 is a cross-sectional view of the ternary cathode material directly recovered in comparative example 1.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention discloses a method for recycling a waste ternary lithium ion battery anode material, which has a specific flow shown in figure 1 and comprises the following steps:
placing the waste ternary lithium ion battery anode material in a separating agent for ultrasonic heating, and separating out a current collector and anode slurry;
filter-pressing the positive electrode slurry to obtain a filter cake, carrying out vacuum drying on the filter cake, and then carrying out air separation to separate out a positive electrode material and a conductive agent;
mechanically crushing and screening the separated anode material to obtain a particle size range D502-5 μm of positive electrode particles;
and after lithium is supplemented to the anode particles, calcining the anode particles to obtain the ternary single crystal anode material.
In the invention, after the anode plate of the waste ternary lithium ion battery is placed in a separating agent for ultrasonic heating, the separating agent is used for dissolving a binder in the anode plate, so that the viscosity of the binder is ineffective, and the separation of a current collector and an anode material is realized; the method comprises the steps of enriching and drying a filter-pressed anode material, separating the anode material from a conductive agent through air separation, mechanically crushing and screening the anode material according to the characteristic that a large number of cracks exist in the failed anode material to obtain particles suitable for synthesizing the ternary single crystal anode material, and finally obtaining the ternary single crystal anode material with excellent performance by lithium supplement and high-temperature high-pressure sintering. The method has the advantages of simple process and environment-friendly process, and the ternary single crystal anode material obtained after recycling has excellent performance. It can be understood that the composition of the waste ternary lithium ion battery positive electrode piece is not particularly limited, and the waste ternary lithium ion battery may be any conventional waste ternary lithium ion battery in the art, and the waste ternary lithium ion battery positive electrode piece is generally obtained by disassembling and sorting the waste ternary lithium ion battery, and since the disassembling and sorting process is known in the art, the process is not specifically described here.
Further, the anode material of the waste ternary lithium ion battery is a nickel-cobalt-manganese or nickel-cobalt-aluminum ternary anode material, and the binder of the waste ternary lithium ion battery is PVDF.
Further, the separating agent in the invention is preferably a separating agent with low toxicity and environmental protection, in some specific embodiments of the invention, the separating agent is selected from one or a mixture of more than two of dichloromethane, ethyl acetate, thiourea solution and ethanol, thereby avoiding the problem of environmental pollution caused by the adoption of a large amount of toxic and harmful organic solvents in the process of stripping the positive electrode material from the current collector, wherein preferably, 5-10 wt% of the thiourea solution.
Further, the ratio of the waste ternary lithium ion battery positive electrode piece to the separating agent is not particularly limited, so that the waste ternary lithium ion battery positive electrode piece is completely immersed in the separating agent, preferably, in some embodiments of the present invention, the mass ratio of the waste ternary lithium ion battery positive electrode piece to the separating agent is 1: 2-10.
Further, the specific steps of the ultrasonic heating are as follows: ultrasonic treating at 50-80 deg.C for 0.5-10 hr. It will be appreciated that the parameters of the ultrasonic heating are not particularly limited and may be adjusted as desired, but that the appropriate elevated temperature facilitates dissolution failure of the binder, and thus, some embodiments of the present invention are preferred.
Further, before the lithium supplement is performed on the positive electrode particles, ICP element analysis is performed on the positive electrode particles to obtain a total molar ratio of lithium to a transition metal element M, and the positive electrode particles are subjected to element analysis to accurately supplement a lithium source, so that a subsequently prepared ternary single crystal positive electrode material meets requirements.
Further, the purpose of supplementing the lithium source is to make the ratio of the lithium element to other elements in the material meet the requirement, and the proportion relationship is adopted in the conventional proportion relationship in the field, wherein the lithium is supplemented according to the molar ratio of lithium to the total transition metal element M, in some specific embodiments of the invention, the lithium source is supplemented according to the molar ratio of lithium to the total transition metal element M Li/M being 1:1.01-1.24, and preferably, the molar ratio of Li/M is 1: 1.05.
further, the lithium source may be any conventionally employed lithium source in the art, and specific examples that may be mentioned include, but are not limited to, one or a mixture of two or more of lithium carbonate, lithium hydroxide, lithium nitrate, lithium citrate, and lithium acetate.
Further, the calcining step is as follows: presintering for 3-6h at the temperature of 400-600 ℃ in the air or oxygen atmosphere with the pressure of 20-100MPa, then heating to the temperature of 700-1000 ℃ and sintering for 15-20 h.
The technical solution of the present invention will be more clearly explained below with reference to specific examples.
Example 1
The method for recycling the anode material of the waste ternary lithium ion battery in the embodiment comprises the following specific steps:
mixing the NCM811 waste ternary lithium ion positive pole piece with a thiourea solution according to a mass ratio of 1:5, completely soaking the positive pole piece in the thiourea solution, heating to 60 ℃, and carrying out ultrasonic treatment for 8 hours. Then fishing out the aluminum foil;
and (3) carrying out filter pressing on the slurry with the aluminum foil removed, wherein the pressure of the filter press is 0.12MPa, and respectively obtaining filtrate and filter cakes. Then, the filter cake is placed in a drying oven at 200 ℃ for vacuum drying, and the ternary cathode material and the conductive agent are separated from the dried filter cake in a winnowing mode;
mechanically crushing and screening the separated ternary cathode material to obtain the particle size D50Particles of 3.5 μm;
ICP element analysis is carried out on the screened ternary anode particles, the proportion of the total mass of lithium and a transition metal element is obtained, LiOH is supplemented according to the molar ratio of the lithium to the transition metal element M being Li/M1: 1.05, the mixture is placed in a muffle furnace, the box pressure is kept at 50MPa, the temperature is raised to 500 ℃ from room temperature in an oxygen atmosphere, the temperature is raised to 850 ℃ after 5 hours of heat preservation, the temperature is maintained for 15 hours, and finally the mixture is naturally cooled to room temperature, so that the NCM811 ternary single crystal anode material is obtained.
The NCM811 ternary single crystal positive electrode material obtained in the embodiment, a conductive agent SP and a binder PVDF are prepared into a pole piece by taking NMP as a solvent according to the mass ratio of 8:1:1, the pole piece is coated on a carbon-coated aluminum foil, the carbon-coated aluminum foil is dried for 5 hours at the temperature of 100 ℃, and the positive electrode is obtained by compacting on a roller press. A button cell is assembled by using a metal lithium sheet as a negative pole piece, a 1M LiPF6 solution as an electrolyte and a cell gard2300 as a diaphragm and the positive pole, and the performance test results are shown in Table 1.
Comparative example 1
The NCM811 ternary positive electrode material obtained in the air flotation of example 1 was recovered without treatment. The other steps are the same as in example 1. A button cell was assembled in the same manner as in example 1, and the electrochemical performance test results are shown in table 1.
Comparative example 2
The NCM811 positive electrode material obtained in example 1 by the air separation was directly subjected to ICP elemental analysis without crushing to obtain the ratio of the total amount of lithium to the transition metal element, and LiOH was added in the molar ratio of lithium to the transition metal element of Li/M1: 1.03. Raising the temperature from room temperature to 500 ℃ in an oxygen atmosphere, preserving the heat for 5h, raising the temperature to 800 ℃ again, and preserving the heat for 15 h. And finally, naturally cooling to room temperature to obtain the NCM811 ternary cathode material. The other steps are the same as in example 1. A button cell was assembled in the same manner as in example 1, and the electrochemical performance test results are shown in table 1.
Example 2
The NCM811 waste ternary lithium ion positive electrode piece in the example 1 is replaced by the NCM523 waste ternary lithium ion positive electrode piece, and the steps of stripping with aluminum foil, filter pressing, air separation and mechanical crushing are carried out in sequence in the same way as the example 1. Then, the particle size after mechanical crushing meets the requirement (D)502-5 μ M) to obtain the ratio of the total mass of the lithium and the transition metal element, and then obtaining the molar ratio Li/M of the lithium to the transition metal element as 11.13 ratio for Li supplementation2CO3Then, the mixture is placed in a muffle furnace, and the temperature is raised to 500 ℃ from the room temperature in the air atmosphere, and is kept for 5h, and then the temperature is raised to 970 ℃ and is kept for 15 h. And finally, naturally cooling to room temperature to obtain the NCM523 ternary single crystal cathode material. A button cell was assembled in the same manner as in example 1, and the electrochemical performance test results are shown in table 1.
Example 3
In this embodiment, the NCM622 waste ternary lithium ion positive electrode sheet is soaked in a dichloromethane solution, heated and ultrasonically treated, and then subjected to filter pressing, air separation, mechanical pulverization and ICP elemental analysis in sequence, which are the same as those in embodiment 1. Then, Li is supplemented at a ratio of 1:1.09 of the total molar ratio of lithium to transition metal elements2CO3Then placing the mixture into a muffle furnace, keeping the pressure of the box at 60MPa, raising the temperature from room temperature to 500 ℃ in an air atmosphere, preserving the heat for 5 hours, then raising the temperature to 950 ℃ and preserving the heat for 15 hours. And finally, naturally cooling to room temperature to obtain the NCM622 ternary single crystal cathode material. A button cell was assembled in the same manner as in example 1, and the electrochemical performance test results are shown in table 1.
Example 4
In this embodiment, the NCM651520 waste ternary lithium ion positive electrode sheet is placed in an ethyl acetate solution, and subjected to heating and ultrasonic treatment to separate the NCM651520 positive electrode material from an aluminum foil, and then subjected to filter pressing, sorting, mechanical crushing and ICP element analysis in the same manner as in embodiment 1. And then supplementing LiOH according to the molar ratio of the total lithium to the transition metal elements of 1:1.07, placing the mixture in a muffle furnace, keeping the pressure of the furnace at 60MPa, heating the mixture to 500 ℃ from room temperature in an air atmosphere, preserving the heat for 5 hours, raising the temperature to 900 ℃ and preserving the heat for 15 hours. And finally, naturally cooling to room temperature to obtain the NCM651520 ternary single crystal cathode material. A button cell was assembled in the same manner as in example 1, and the electrochemical performance test results are shown in table 1.
Test example
The electrochemical performance of the button cell assembled in the examples and comparative examples was tested at a cut-off voltage ranging from 2.8 to 4.3V, and the results are shown in table 1. Meanwhile, XRD characterization is carried out on the ternary single crystal anode material prepared in the example 1, and the result is shown in figure 2The diffraction pattern of the ternary positive electrode material is corresponding to a typical space group R3m and a layered structure, the diffraction peaks are relatively sharp, and the bifurcations of the diffraction peaks (108)/(110) are obvious, so that the prepared ternary positive electrode material is relatively good in crystallinity. In addition, cross sections of the ternary single crystal positive electrodes obtained in example 1 and comparative example 1 were also characterized, as shown in fig. 3 and 4, and it can be seen that a large number of cracks existed inside the ternary material secondary particles directly recovered in comparative example 1, whereas it was mechanically crushed to produce D in example 150The particle size is 2-5 μm, and after high-temperature and high-pressure lithium supplement calcination, cracks in the material disappear, and the material becomes more compact. The successful production of the ternary single crystal cathode material is illustrated by combining fig. 2 and fig. 3.
Table 1 electrochemical performance test results of assembled batteries in examples and comparative examples
As can be seen from table 1, when comparing example 1, comparative example 1 and comparative example 2, the first effect and capacity of the product are improved in comparative example 2 compared with the NCM811 ternary cathode material directly recovered in comparative example 1, but the cycle performance is poorer than that of example 1, and the cycle performance in example 1 is as high as 98.5%, which is mainly due to the fact that a large number of cracks exist in the failed ternary cathode material particles, and after the lithium supplement sintering is directly performed, a large number of cracks still exist in the particles, and the cracks can continuously expand and collapse in the cycle process, and side reaction with the electrolyte occurs, and lithium is continuously consumed, so that the cycle performance of the material is poor. The ternary positive electrode material failed in the embodiment 1 is crushed and then subjected to lithium supplement and high-temperature sintering to synthesize the ternary single crystal positive electrode material, so that the number of cracks can be effectively reduced, the structure is stabilized, and the cycle performance of the material is favorably improved. As can be seen from the data in Table 1, the NCM811 material recovered in comparative example 2 is not good for the performance of the cycle performance after the lithium supplement calcination because a large number of cracks still exist in the material, and therefore the cycle performance is inferior to that of example 1. Compared with comparative examples 1 and 2, the capacity and the cycle performance of the embodiment 1 are greatly improved, which shows that the capacity and the cycle performance of the NCM811 material which fails are recovered and even improved by preparing the NCM811 material into a ternary single crystal material.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. A method for recycling a waste ternary lithium ion battery anode material is characterized by comprising the following steps:
placing the waste ternary lithium ion battery positive pole piece in a separating agent for ultrasonic heating, and separating out a current collector and positive pole slurry;
filter-pressing the positive electrode slurry to obtain a filter cake, carrying out vacuum drying on the filter cake, and then carrying out air separation to separate out a positive electrode material and a conductive agent;
mechanically crushing and screening the separated anode material to obtain a particle size range D502-5 μm of positive electrode particles;
and after lithium is supplemented to the anode particles, calcining the anode particles to obtain the ternary single crystal anode material.
2. The method for recycling the anode material of the waste ternary lithium ion battery according to claim 1, wherein the anode plate of the waste ternary lithium ion battery is a nickel-cobalt-manganese or nickel-cobalt-aluminum ternary anode material, and the binder is PVDF.
3. The method for recycling the anode material of the waste ternary lithium ion battery according to claim 1, wherein the separating agent is one or a mixture of more than two of dichloromethane, ethyl acetate, thiourea solution and ethanol.
4. The method for recycling the anode material of the waste ternary lithium ion battery according to claim 1, wherein the mass ratio of the anode plate of the waste ternary lithium ion battery to the separating agent is 1: 2-10.
5. The method for recycling the anode material of the waste ternary lithium ion battery according to claim 1, wherein the specific steps of ultrasonic heating are as follows: ultrasonic treating at 50-80 deg.C for 0.5-10 hr.
6. The method for recycling the anode material of the waste ternary lithium ion battery according to claim 1, wherein the method further comprises performing ICP elemental analysis on the anode particles before the anode particles are subjected to lithium supplement to obtain the total molar ratio of lithium to the transition metal element M.
7. The method for recycling the anode material of the waste ternary lithium ion battery according to claim 1 or 6, wherein the lithium supplement is a lithium source supplement according to the total molar ratio Li/M of lithium to the transition metal element M of 1: 1.01-1.24.
8. The method for recycling the positive electrode material of the waste ternary lithium ion battery according to claim 7, wherein the lithium source is one or a mixture of more than two of lithium carbonate, lithium hydroxide, lithium nitrate, lithium citrate and lithium acetate.
9. The method for recycling the anode material of the waste ternary lithium ion battery according to claim 1, wherein the calcining comprises the following steps: presintering for 3-6h at the temperature of 400-600 ℃ in the air or oxygen atmosphere with the pressure of 20-100MPa, then heating to the temperature of 700-1000 ℃ and sintering for 15-20 h.
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| CN113437377A (en) * | 2021-06-15 | 2021-09-24 | 昆明理工大学 | Single crystallization regeneration method for waste ternary positive electrode material |
| CN113735196A (en) * | 2021-11-04 | 2021-12-03 | 北京胜能能源科技有限公司 | Recycling method of waste ternary precursor and ternary cathode material obtained by recycling |
| 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 |
| CN114068909A (en) * | 2021-11-10 | 2022-02-18 | 中南大学 | Method for regenerating NCMA (non-volatile memory MA) cathode material from retired NCM cathode material |
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| WO2022166197A1 (en) * | 2021-02-05 | 2022-08-11 | 哈尔滨工业大学 | Direct repair method for waste lithium-ion battery ternary positive electrode material |
| CN115367812A (en) * | 2022-07-11 | 2022-11-22 | 河南师范大学 | Method for preparing single crystal ternary cathode material by using waste lithium ion battery ternary cathode material |
| CN116285482A (en) * | 2023-03-31 | 2023-06-23 | 芜湖天弋能源科技有限公司 | Reagent for removing oily electrode coating and application method thereof |
| CN116588995A (en) * | 2023-07-17 | 2023-08-15 | 宁德时代新能源科技股份有限公司 | Echelon utilization method of waste ternary cathode material |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103311537A (en) * | 2012-03-16 | 2013-09-18 | 宁波杉杉新材料科技有限公司 | Recycling method of battery positive material, positive pole piece and preparation method thereof |
| CN105070970A (en) * | 2015-07-21 | 2015-11-18 | 河南科技学院 | Method for preparing lithium ion battery anode material by using mixed waste alkaline battery |
| CN106410147A (en) * | 2016-11-03 | 2017-02-15 | 长沙理工大学 | Preparation method of LiFePO4/graphene composite material |
| CN106981698A (en) * | 2017-04-07 | 2017-07-25 | 上海电气集团股份有限公司 | A kind of method that recovery prepares lithium titanate anode material from waste and old lithium titanate battery |
| CN107546437A (en) * | 2017-09-05 | 2018-01-05 | 华东理工大学 | Lithium, nickel, cobalt, the method for manganese are reclaimed from waste and old lithium ion battery |
| CN108546822A (en) * | 2018-03-14 | 2018-09-18 | 华东理工大学 | The method for recycling noble metal from discarded lithium battery using microorganism |
| CN108832216A (en) * | 2018-06-14 | 2018-11-16 | 合肥工业大学 | A kind of pre-treating method of waste power lithium battery recycling |
| CN109687051A (en) * | 2018-12-25 | 2019-04-26 | 云南能投汇龙科技股份有限公司 | A kind of method for recycling anode material of waste and old lithium ion battery |
| CN109713393A (en) * | 2018-12-30 | 2019-05-03 | 沈阳化工研究院有限公司 | A kind of isolated method of lithium battery active material |
| CN109904446A (en) * | 2019-02-26 | 2019-06-18 | 广东邦普循环科技有限公司 | A kind of regeneration positive electrode and preparation method thereof and the lithium ion battery comprising the regeneration positive electrode |
| EP3512031A1 (en) * | 2017-07-27 | 2019-07-17 | LG Chem, Ltd. | Cell recycling method |
| CN110808430A (en) * | 2019-11-15 | 2020-02-18 | 武汉瑞杰特材料有限责任公司 | Separation and purification method of lithium ion battery anode material and obtained lithium ion battery anode material |
-
2020
- 2020-09-30 CN CN202011064180.1A patent/CN112054265A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103311537A (en) * | 2012-03-16 | 2013-09-18 | 宁波杉杉新材料科技有限公司 | Recycling method of battery positive material, positive pole piece and preparation method thereof |
| CN105070970A (en) * | 2015-07-21 | 2015-11-18 | 河南科技学院 | Method for preparing lithium ion battery anode material by using mixed waste alkaline battery |
| CN106410147A (en) * | 2016-11-03 | 2017-02-15 | 长沙理工大学 | Preparation method of LiFePO4/graphene composite material |
| CN106981698A (en) * | 2017-04-07 | 2017-07-25 | 上海电气集团股份有限公司 | A kind of method that recovery prepares lithium titanate anode material from waste and old lithium titanate battery |
| EP3512031A1 (en) * | 2017-07-27 | 2019-07-17 | LG Chem, Ltd. | Cell recycling method |
| CN107546437A (en) * | 2017-09-05 | 2018-01-05 | 华东理工大学 | Lithium, nickel, cobalt, the method for manganese are reclaimed from waste and old lithium ion battery |
| CN108546822A (en) * | 2018-03-14 | 2018-09-18 | 华东理工大学 | The method for recycling noble metal from discarded lithium battery using microorganism |
| CN108832216A (en) * | 2018-06-14 | 2018-11-16 | 合肥工业大学 | A kind of pre-treating method of waste power lithium battery recycling |
| CN109687051A (en) * | 2018-12-25 | 2019-04-26 | 云南能投汇龙科技股份有限公司 | A kind of method for recycling anode material of waste and old lithium ion battery |
| CN109713393A (en) * | 2018-12-30 | 2019-05-03 | 沈阳化工研究院有限公司 | A kind of isolated method of lithium battery active material |
| CN109904446A (en) * | 2019-02-26 | 2019-06-18 | 广东邦普循环科技有限公司 | A kind of regeneration positive electrode and preparation method thereof and the lithium ion battery comprising the regeneration positive electrode |
| CN110808430A (en) * | 2019-11-15 | 2020-02-18 | 武汉瑞杰特材料有限责任公司 | Separation and purification method of lithium ion battery anode material and obtained lithium ion battery anode material |
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