CN111509192B - Method for recycling positive electrode material from waste lithium battery, obtained product and application - Google Patents
Method for recycling positive electrode material from waste lithium battery, obtained product and application Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to a method for recycling a positive electrode material from a waste lithium battery, an obtained product and application. The method comprises the following steps: (1) screening a positive electrode material obtained by crushing and disassembling waste batteries, and dividing the particle size of the positive electrode material into a first particle size, a second particle size and a third particle size, wherein the first particle size is smaller than the second particle size and smaller than the third particle size; (2) analyzing and adjusting the molar ratio of elements in the positive electrode material with the second particle size, and performing first calcination to obtain a positive electrode material; (3) dissolving the positive electrode material with the first particle size and the positive electrode material with the third particle size, adjusting the element molar ratio, precipitating to obtain a positive electrode material precursor, and performing second calcination to obtain the positive electrode material. According to the invention, the anode material is firstly screened according to the particle size, so that the anode material is recycled in a targeted manner, the waste of resources is reduced, the recycling cost is reduced, and the maximum economic benefit is achieved.
Description
Technical Field
The invention belongs to the field of recycling of waste lithium batteries, and particularly relates to a method for recycling a positive electrode material from a waste lithium battery, an obtained product and application.
Background
With the economic development, people have more and more requirements on energy, the continuous shortage and non-regeneration of energy promote the development of novel energy, and novel automobiles develop rapidly in 2009 with the support of national policies, and more than 200 thousands of automobiles are expected in 2020.
When the capacity of the battery is reduced to about 60-80% of the initial capacity, the battery needs to be replaced, the average service life of the lithium iron phosphate power battery is 4-6 years, and the service life of the ternary material power battery is 2-4 years, so that the high-efficiency recycling of the waste lithium battery is not slow when the decommissioning tide of the power battery comes.
The waste lithium battery contains various metals such as nickel, cobalt, manganese, lithium, aluminum, copper and the like, and valuable metals are recycled and directly used for manufacturing the lithium battery cell, so that the method has great significance for constructing an industrial chain closed loop. The method can relieve the economic pressure of people, effectively recycle limited natural resources and protect the environment, so that the method is extremely important for efficiently recycling the waste lithium batteries.
In the current recycling of waste lithium batteries, two ways of wet method and dry method recycling are available conventionally. The dry method is to disassemble the lithium battery, detect the element content, adjust the proportion, and directly calcine and crush to obtain the anode material. The wet method is to disassemble the lithium battery, dissolve the anode material with acid, and then precipitate lithium salt, nickel-cobalt-manganese and other metal salts or ternary precursors by chemical precipitation, solvent extraction, electrodeposition, salting-out, ion exchange and the like. However, the quality of the anode material obtained by dry recovery is poor, and the wet recovery process is complex and has high cost.
CN109309266A discloses a method for recycling a waste lithium ion battery anode material, which comprises the following steps: a) soaking a positive plate of a waste lithium ion battery in water, and separating an active material layer and a current collector to obtain a recovered positive material; b) and after the content of the metal elements in the recovered anode material is detected, adding the metal elements to a preset value to obtain a first raw material, and performing first roasting to obtain the regenerated anode material. But the quality of the cathode material obtained by the method is poor.
CN110828887A discloses a method for recycling waste lithium iron phosphate anode materials and the obtained lithium iron phosphate anode materials. The method comprises the following steps: 1) separating the waste lithium iron phosphate positive pole piece, and removing the aluminum current collector to obtain a powdery lithium iron phosphate positive pole recycled material; 2) adding a lithium source, an iron source and a phosphorus source, or adding a reducing agent, adding a binder used for swelling the lithium iron phosphate anode recovery material, dissolving or dispersing an organic solvent of the lithium source, the iron source, the phosphorus source and the reducing agent, uniformly mixing the materials, and drying to obtain a lithium iron phosphate precursor; 3) correspondingly, sintering in a reducing or inert gas atmosphere to obtain the repaired and regenerated lithium iron phosphate cathode material. But the recovery process is complex and costly.
Therefore, there is a need in the art to develop a method for efficiently recycling waste lithium battery materials, which is simple in process and gives battery materials having excellent electrochemical properties.
Disclosure of Invention
Aiming at the defects of poor quality of the anode material obtained by dry recovery, complex wet recovery process and high cost in the prior art. The invention aims to provide a method for recycling a positive electrode material from waste lithium batteries, an obtained product and application.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a method for recycling a positive electrode material from waste lithium batteries, which comprises the following steps:
(1) screening a positive electrode material obtained by crushing and disassembling waste batteries, and dividing the particle size of the positive electrode material into a first particle size, a second particle size and a third particle size, wherein the first particle size is smaller than the second particle size and smaller than the third particle size;
(2) analyzing and adjusting the molar ratio of elements in the positive electrode material with the second particle size, and performing first calcination to obtain a positive electrode material;
(3) dissolving the positive electrode material with the first particle size and the positive electrode material with the third particle size, adjusting the element molar ratio, precipitating to obtain a positive electrode material precursor, coating the positive electrode material precursor with a conductive agent, and carrying out secondary calcination to obtain the positive electrode material.
The order of step (2) and step (3) in the present invention can be changed.
Before dry or wet recovery, the positive electrode material is screened, the positive electrode material with a moderate particle size (within a second particle size range) can be recovered by the dry method, and the positive electrode material with the particle size has a good crystal form and a good specific surface area and is suitable for compaction; and agglomerates formed by the conductive agent, the adhesive agent and the like may be adhered to the positive electrode material with the larger particle size (the third particle size), and the possible material with the smaller particle size (the first particle size) is cracked and the crystal form is damaged, so that the positive electrode material with the first particle size and the third particle size needs to be recovered by a dissolving wet method.
The invention can be recycled in a targeted manner, reduces the waste of resources, reduces the recycling cost, and achieves the maximization of economic benefit and environmental protection.
In the step (2), the molar ratio of elements in the positive electrode material with the second particle size is adjusted to be: detecting the content of different elements according to different types of batteries, and adjusting the element proportion according to the optimal preparation conditions. The molar ratio of the elements is adjusted in the step (3).
Preferably, the process of crushing and dismantling the waste batteries in the step (1) comprises the following steps: classifying the waste batteries, then carrying out discharge treatment until the voltage is 0V, then putting the waste batteries into a crusher for crushing and disassembling, and realizing the separation of copper powder, aluminum powder diaphragms, cathode materials and anode materials in the batteries through screening equipment.
Preferably, the screening device comprises any one or a combination of at least two of vibratory screening, air-flow sorting electromagnetic screening and liquid screening.
Preferably, the waste battery comprises any one of lithium iron phosphate series, ternary lithium battery series and lithium cobaltate battery or a combination of at least two of the lithium iron phosphate series, the ternary lithium battery series and the lithium cobaltate battery.
Preferably, the second particle diameter D50 is 1-15 μm, such as 1.1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, or 5 μm.
Preferably, the waste battery is a lithium iron phosphate series, the first particle size D50 is <1 μm (e.g., 0.01 μm, 0.05 μm, 0.08 μm, 0.1 μm, 0.3 μm, 0.5 μm, 0.6 μm, 0.8 μm, or 0.9 μm, etc.), the second particle size D50 is 1 to 8 μm (e.g., 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, or 7.5 μm, etc.), and the third particle size D50>8 μm (e.g., 9 μm, 10 μm, 12 μm, 14 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 25 μm, 30 μm, 40 μm, or 50 μm, etc.).
Preferably, the waste battery is a ternary lithium battery series, the first particle size D50 is <5 μm (e.g. 0.01 μm, 0.05 μm, 0.1 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, or 4.5 μm, etc.), the second particle size D50 is 5 to 15 μm (e.g. 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, or 14 μm, etc.), and the third particle size D50 is >15 μm (e.g. 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 25 μm, 30 μm, 40 μm, or 50 μm, etc.).
The invention limits different particle size ranges for different waste battery materials, because the optimal particle size ranges of different battery materials are different, only the battery materials in the optimal particle size range can achieve the optimal performance.
Preferably, the screening in step (1) is vibration screening and/or negative pressure screening.
Preferably, a ball milling process is further included before the sieving in the step (1).
Preferably, the rotation speed of the ball mill is 100-300 rpm, such as 120rpm, 150rpm, 160rpm, 180rpm, 200rpm, 220rpm, 250rpm or 280rpm, and the like.
Preferably, the ball milling time is 2-6 h, such as 2.5h, 2.8h, 3h, 3.5h, 4h, 4.5h, 5h or 5.5 h.
The ball milling process is carried out before screening, and the agglomerated anode material can be crushed, so that the screening of the particle size is more accurate.
Preferably, the temperature of the first calcination in the step (2) is 700 to 800 ℃, such as 710 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃, 770 ℃, 780 ℃, 790 ℃ or the like.
Preferably, the time of the first calcination in the step (2) is 1 to 3 hours, such as 1.2 hours, 1.5 hours, 1.8 hours, 2 hours, 2.2 hours, 2.5 hours or 2.8 hours.
Preferably, the dissolving in the step (3) includes any one or a combination of at least two of acid dissolution, volume reduction, electrochemical dissolution and organic solvent dissolution.
Preferably, the precipitation in step (3) is direct coprecipitation or indirect coprecipitation.
The raw materials and the process adopted in the precipitation process are not particularly limited, and the skilled person can select the raw materials and the process according to actual experience.
Preferably, step (3) further includes, before the second calcining, a process of doping the positive electrode material precursor with a conductive agent.
Preferably, the temperature of the second calcination in the step (3) is 700 to 800 ℃, such as 710 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃, 770 ℃, 780 ℃, 790 ℃ or the like.
Preferably, the time of the second calcination in the step (3) is 8 to 12 hours, such as 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours or 11.5 hours.
As a preferred technical scheme, the method for recycling the positive electrode material from the waste lithium battery comprises the following steps:
(1) classifying the waste batteries, then carrying out discharge treatment until the voltage is 0V, then putting the waste batteries into a crusher for crushing and disassembling, and separating copper powder, aluminum powder diaphragms, negative electrode materials and positive electrode materials in the batteries through screening equipment;
(2) ball-milling the positive electrode material obtained by crushing and disassembling the waste batteries in the step (1) at the rotating speed of 100-300 rpm for 2-6 hours, and screening to divide the particle size of the positive electrode material into a first particle size, a second particle size and a third particle size, wherein the first particle size is smaller than the second particle size and smaller than the third particle size;
(3) analyzing and adjusting the content of elements in the positive electrode material with the second particle size, and performing first calcination at 700-800 ℃ for 1-3 h to obtain a positive electrode material;
(4) dissolving the positive electrode material with the first particle size and the positive electrode material with the third particle size, adjusting element content, precipitating to obtain a positive electrode material precursor, doping the positive electrode material precursor with a conductive agent, and calcining for 8-12 hours at 700-800 ℃ for the second time to obtain the positive electrode material.
Fig. 1 is a process flow diagram of the present invention for recycling a positive electrode material from a waste lithium battery, and it can be seen from the diagram that the present invention separates the positive electrode material by discharging, disassembling, roasting, and crushing the waste lithium battery, performs ball milling and screening on the positive electrode material to separate the positive electrode material with a moderate particle size (a second particle size), and performs calcination (ball milling may be performed after the calcination) after adjusting the element content (supplementing a lithium source, a carbon source, and the like) to obtain a positive electrode material product; the positive electrode material with the first particle size and the positive electrode material with the third particle size (larger and smaller particle size) need to be prepared through dissolving and precipitating processes (calcining).
It is a second object of the present invention to provide a positive electrode material obtained by the method according to the first object.
The cathode material obtained by the recovery method has excellent electrochemical performance, and effectively solves the problems of poor quality of the cathode material obtained by dry recovery, complex wet recovery process and high cost in the prior art.
The third object of the present invention is to provide a lithium ion battery comprising the positive electrode material of the second object.
Compared with the prior art, the invention has the following beneficial effects:
before dry or wet recovery, the positive electrode material is screened, and the positive electrode material with a good crystal form and a moderate particle size (the second particle size) can be recovered by the dry method; and wet recovery (first particle size positive electrode material and third particle size) is performed when the crystal form is not good and the particle size is larger or smaller. The invention can be recycled in a targeted manner, reduces the waste of resources, reduces the recycling cost, and achieves the maximization of economic benefit and environmental protection.
Drawings
FIG. 1 is a process flow diagram of the present invention for recycling cathode materials from used lithium batteries.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
(1) Pretreatment of the waste battery: discharging the waste lithium iron phosphate battery until the voltage is 0V, crushing and disassembling the waste lithium iron phosphate battery in a crusher, and separating copper powder, aluminum powder diaphragms, negative electrode materials and positive electrode materials in the battery through vibration screening, airflow separation electromagnetic screening and liquid screening equipment;
(2) performing ball milling on the obtained positive electrode material at the rotating speed of 200rpm for 4h again, and screening to obtain a positive electrode material with a first particle size of D50 being less than 1 mu m, a second particle size of D50 being 1-8 mu m and a third particle size of D50 being more than 8 mu m;
(3) analyzing the content of elements in the anode material with the second particle size, adjusting the molar ratio of the elements, calcining at 760 ℃ for 2h, and performing ball milling to obtain a first anode material;
(4) dissolving the positive electrode materials with the first particle size and the third particle size, adjusting the element proportion, precipitating to obtain a positive electrode material precursor, doping a conductive agent (graphene) accounting for 2 wt% of the final product, calcining for 10 hours at 760 ℃, and performing ball milling to obtain a second positive electrode material.
Example 2
(1) Pretreatment of the waste battery: performing discharge treatment on a waste ternary lithium battery (NCM811) until the voltage is 0V, then putting the waste ternary lithium battery into a crusher for crushing and disassembling, and separating copper powder, aluminum powder diaphragm, negative electrode material and positive electrode material in the battery through vibration screening, airflow separation electromagnetic screening and liquid screening equipment;
(2) performing ball milling on the obtained positive electrode material at the rotating speed of 120rpm for 5h again, and screening to obtain a positive electrode material with a first particle size of D50 being less than 5 microns, a second particle size of D50 being 5-15 microns and a third particle size of D50 being more than 15 microns;
(3) analyzing the content of elements in the anode material with the second particle size, adjusting the molar ratio of the elements, calcining at 720 ℃ for 3h, and ball-milling to obtain a first anode material;
(4) dissolving the anode materials with the first particle size and the third particle size, adjusting the element proportion, precipitating to obtain an anode material precursor, doping a conductive agent (carbon nano tube) accounting for 3 wt% of the final product, calcining for 12 hours at 720 ℃, and ball-milling to obtain a second anode material.
Comparative example 1
The difference from example 1 is that the particle size classification process of step (2) is not performed, i.e., the positive electrode material obtained in step (1) is subjected to only dry recovery of step (3).
Comparative example 2
The difference from example 2 is that the size classification process of step (2) is not performed, i.e., the positive electrode material obtained in step (1) is only subjected to dry recovery of step (3).
And (3) performance testing:
the positive electrode materials obtained in the examples and comparative examples were used as positive electrode active materials, and the following were added to the positive electrode active material: conductive carbon black: mixing the PVDF binder at a mass ratio of 90:5:5, removing NMP as a solvent, mixing the slurry, coating the slurry on an aluminum foil, and performing vacuum drying at 90 ℃ to obtain a positive pole piece;
then the negative pole piece (lithium piece), the positive pole piece and electrolyte (1mol/L LiPF)6EC: EMC 1:1) and a separator were assembled into a battery.
The obtained battery is subjected to charge and discharge tests on a charge and discharge tester at the temperature of 25 +/-2 ℃, the charge and discharge voltage of example 1 and comparative example 1-2 is 2.0-3.65V, the charge and discharge voltage of example 2 is 2.5-4.3V, the current density is 1C, the first-cycle discharge specific capacity is respectively tested, and the test results are shown in table 1:
TABLE 1
As can be seen from table 1, the cathode material obtained by the method of the present invention has excellent electrochemical properties, and effectively overcomes the problems of poor quality of the cathode material obtained by dry recovery, complex wet recovery process and high cost in the prior art.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (21)
1. A method for recycling a positive electrode material from waste lithium batteries is characterized by comprising the following steps:
(1) screening a positive electrode material obtained by crushing and disassembling waste batteries, and dividing the particle size of the positive electrode material into a first particle size, a second particle size and a third particle size, wherein the first particle size is smaller than the second particle size and smaller than the third particle size;
(2) analyzing and adjusting the molar ratio of elements in the positive electrode material with the second particle size, and performing first calcination to obtain a positive electrode material;
(3) dissolving the positive electrode material with the first particle size and the positive electrode material with the third particle size, adjusting the element molar ratio, precipitating to obtain a positive electrode material precursor, and performing second calcination to obtain the positive electrode material.
2. The method of claim 1, wherein the step (1) of crushing and dismantling the used batteries comprises: classifying the waste batteries, then carrying out discharge treatment until the voltage is 0V, then putting the waste batteries into a crusher for crushing and disassembling, and realizing the separation of copper powder, aluminum powder diaphragms, cathode materials and anode materials in the batteries through screening equipment.
3. The method of claim 2, wherein the screening device comprises any one or a combination of at least two of vibratory screening, air-flow sorting electromagnetic screening, and liquid screening.
4. The method according to claim 1, wherein the waste battery comprises any one of lithium iron phosphate series, ternary lithium series and lithium cobalt oxide batteries or a combination of at least two of the foregoing.
5. The method according to claim 1, wherein the secondary particle size D50 is 1 to 15 μm.
6. The method of claim 4, wherein the waste batteries are lithium iron phosphate series, the first particle size D50 is less than 1 μm, the second particle size D50 is 1-8 μm, and the third particle size D50 is greater than 8 μm.
7. The method according to claim 4, wherein the waste batteries are ternary lithium batteries, the first particle size D50 is less than 5 μm, the second particle size D50 is 5-15 μm, and the third particle size D50 is greater than 15 μm.
8. The method of claim 1, wherein the screening of step (1) is vibratory screening and/or negative pressure screening.
9. The method of claim 1, wherein the step (1) of screening further comprises a ball milling process.
10. The method of claim 9, wherein the ball milling is performed at a speed of 100 to 300 rpm.
11. The method of claim 9, wherein the ball milling time is 2 to 6 hours.
12. The method of claim 1, wherein the temperature of the first calcining in step (2) is 700 to 800 ℃.
13. The method of claim 1, wherein the first calcining time in step (2) is 1 to 3 hours.
14. The method of claim 1, wherein the dissolving in the step (3) comprises any one of acid dissolution, alkali dissolution, electrochemical dissolution and organic solvent dissolution or a combination of at least two thereof.
15. The method of claim 1, wherein the precipitation in step (3) is direct co-precipitation or indirect co-precipitation.
16. The method according to claim 1, wherein step (3) further comprises doping the positive electrode material precursor with a conductive agent before the second calcination.
17. The method of claim 1, wherein the temperature of the second calcining in step (3) is 700 to 800 ℃.
18. The method of claim 1, wherein the time of the second calcination in step (3) is 8 to 12 hours.
19. The method of claim 1, wherein the method comprises the steps of:
(1) classifying the waste batteries, then carrying out discharge treatment until the voltage is 0V, then putting the waste batteries into a crusher for crushing and disassembling, and separating copper powder, aluminum powder diaphragms, negative electrode materials and positive electrode materials in the batteries through screening equipment;
(2) ball-milling the positive electrode material obtained by crushing and disassembling the waste batteries in the step (1) at the rotating speed of 100-300 rpm for 2-6 hours, and screening to divide the particle size of the positive electrode material into a first particle size, a second particle size and a third particle size, wherein the first particle size is smaller than the second particle size and smaller than the third particle size;
(3) analyzing and adjusting the content of elements in the positive electrode material with the second particle size, and performing first calcination at 700-800 ℃ for 1-3 h to obtain a positive electrode material;
(4) dissolving the positive electrode material with the first particle size and the positive electrode material with the third particle size, adjusting element content, precipitating to obtain a positive electrode material precursor, doping the positive electrode material precursor with a conductive agent, and calcining for 8-12 hours at 700-800 ℃ for the second time to obtain the positive electrode material.
20. A positive electrode material, characterized in that it is obtained by the method according to any one of claims 1 to 19.
21. A lithium ion battery comprising the positive electrode material according to claim 20.
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| CN112658000B (en) * | 2020-10-09 | 2022-11-25 | 武汉瑞科美新能源有限责任公司 | Method for recycling leftover materials of positive plate of lithium iron phosphate battery |
| CN112838205B (en) * | 2021-01-11 | 2021-11-30 | 厦门厦钨新能源材料股份有限公司 | Method for recovering fine powder of lithium ion battery cathode material |
| CN113270659A (en) * | 2021-05-12 | 2021-08-17 | 湖北融通高科先进材料有限公司 | Method for recycling lithium iron phosphate material by two-step method |
| CN113904021A (en) * | 2021-11-10 | 2022-01-07 | 苏州博萃循环科技有限公司 | Recycling method of waste lithium ion battery anode material and lithium ion battery anode material |
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