CN117855657A - Method for directly regenerating NCM positive electrode by ternary molten salt, regenerated NCM positive electrode active material and application thereof - Google Patents
Method for directly regenerating NCM positive electrode by ternary molten salt, regenerated NCM positive electrode active material and application thereof Download PDFInfo
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for directly regenerating an NCM positive electrode by ternary molten salt, a regenerated NCM positive electrode active material and application thereof, and belongs to the technical field of battery materials. The invention provides a direct regeneration method, which is characterized in that positive NCM material is recovered from waste lithium ion batteries by means of simple disassembly, heat treatment and ultrasonic separation, and NiO and MnO are added into the waste NCM material 2 、Co 3 O 4 Adjusting the element proportion and in LiOH-Li 2 SO 4 ‑Na 2 SO 4 And sintering the ternary fused salt at a medium and high temperature. At last molten saltThe treated material is washed with water, ball-milled and sintered for the second time to obtain a new NCM523 material. With the LiOH-Li 2 SO 4 ‑Na 2 SO 4 The ternary molten salt directly regenerates the waste positive electrode material, and the structural defects of lithium loss, particle breakage, irreversible phase change, serious Li/Ni disorder and the like are effectively repaired. The electrochemical performance of the NCM523 after direct regeneration is close to the level of commercial materials, and a new way is provided for the regeneration and utilization of the NCM positive electrode of the waste lithium ion battery.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a method for directly regenerating an NCM positive electrode by ternary molten salt, a regenerated NCM positive electrode active material and application thereof.
Background
Since the successful commercialization of lithium ion batteries in 1991, the lithium ion batteries have been widely applied to the fields of consumer electronics, electric automobiles, energy storage devices and the like due to the advantages of high energy density, long cycle life and the like. The service life of the lithium ion battery is only 3-8 years, and along with the rapid increase of the use amount of the lithium ion battery in recent years, a large number of scrapped lithium ion batteries are expected to be generated, which causes people to worry about resource shortage and environmental pollution. Therefore, it is important to recycle the waste lithium ion batteries.
At present, traditional recovery methods of waste lithium ion batteries are pyrometallurgical and hydrometallurgical processes, but the processes involve complicated steps or high energy consumption and generate a large amount of liquid/gas pollutants. The direct regeneration method eliminates the way of completely destroying particles in the traditional metallurgical process, and restores the waste cathode material by supplementing lost elements and restoring the structure thereof. The direct regeneration method has simple process, and reduces the environmental pollution and the secondary damage to the structure of the material in the recovery process. The direct regeneration methods which have been developed at present include solid state sintering, hydrothermal treatment, molten salt treatment, electrochemical treatment, chemical and physical chemistry and the like.
However, most reported direct regeneration methods are effective with only one or two less damaged spent positive electrodes, especially for direct regeneration of severely capacity fade positive electrode materials, which is challenging.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for directly regenerating an NCM positive electrode by ternary molten salt, a regenerated NCM positive electrode active material and application thereof. The invention aims to provide a ternary molten salt method, which directly regenerates different waste NCM positive electrode materials into new NCM523 and is applied to a lithium ion battery. The method effectively solves the structural defect of the waste NCM material, and realizes the recombination and regeneration of NCM morphology and crystal structure, and the like.
The first object of the invention is to provide a method for directly regenerating NCM positive electrode active material by ternary molten salt, which comprises the following steps:
s1: recovering waste NCM materials in the positive electrode plate from the waste lithium ion battery by using a roasting and ultrasonic treatment method;
s2: mixing the waste NCM material obtained in the step S1 with a nickel source, a manganese source and a cobalt source, adding ternary molten salt, mixing to obtain a mixture, and carrying out primary heating sintering on the obtained mixture in an oxygen-containing atmosphere;
s3: and (3) washing, drying and grinding the solid matters obtained in the step (S2) subjected to primary heating sintering, and carrying out secondary heating sintering on the ground powder in an atmosphere containing oxygen to obtain the regenerated NCM523 positive electrode active material.
In one embodiment of the present invention, in step S1, the baking temperature is 500-600 ℃ for 1-3 hours;
the ultrasonic time in the ultrasonic treatment method is 15-45min;
NCM in the waste NCM material is LiNi x Co y Mn z ，x+y+z＝1；
In one embodiment of the present invention, in step S2, the metal element content of the waste NCM material is obtained by inductively coupled plasma spectroscopy (ICP-AES) detection. And determining whether a nickel source, a manganese source and a cobalt source are added or not according to the metal element content of the waste NCM material and the adding amount of the nickel source, the manganese source and the cobalt source. Ni of a mixture of the waste NCM material, a nickel source, a manganese source and a cobalt source: co: the mole ratio of Mn element is 5:2:3, a step of;
the nickel source is selected from NiO, ni (OH) 2 And Ni (CH) 3 COO) 2 One or more of the following;
the manganese source is selected from MnO 2 And/or Mn 2 O 3 ；
The cobalt source is selected from Co 2 O 3 And/or CoO。
In one embodiment of the present invention, in step S2, the ternary molten salt includes a lithium supplementing agent and a fluxing agent; the lithium supplementing agent is selected from LiOH; the cosolvent comprises sulfate.
In one embodiment of the invention, the lithium supplementing agent is in an excess of 20-50mol%, the excess referring to the sum of the amounts of Ni, co, mn substances in the mixture; the addition amount of the fluxing agent is 10mol%, which refers to the sum of the amounts of substances of Ni, co and Mn in the mixture;
the sulfate is selected from Li 2 SO 4 、Na 2 SO 4 The method comprises the steps of carrying out a first treatment on the surface of the The Li is 2 SO 4 And Na (Na) 2 SO 4 The molar ratio of (2) is 0.6:0.4 to 0.8:0.2;
in one embodiment of the present invention, in step S2, the gas of the atmosphere containing oxygen is air;
the temperature of the primary heating sintering is 950-850 ℃, the time is 8-15h, and the heating rate is 5-10 ℃/min.
In one embodiment of the present invention, in step S3, the grinding time is 20-60min, and the rotation speed is 200-400r/min;
the temperature of the secondary heating sintering is 650-750 ℃ and the time is 2-5h.
A second object of the present invention is to provide a regenerated NCM positive electrode active material including a regenerated NCM positive electrode active material obtained by the above-described method of regenerating an NCM positive electrode active material.
A third object of the present invention is to provide a positive electrode sheet comprising the above-described regenerated NCM positive electrode active material.
A fourth object of the present invention is to provide a lithium ion battery, including the positive electrode sheet.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the invention firstly recovers the abandoned NCM anode by simple disassembly, heat treatment and ultrasonic separation methods, and then recovers the abandoned NCM anode by simple ternary fused salt (LiOH-Li 2 SO 4 -Na 2 SO 4 ) The method of (2) repair the structural defect of NCMThe spinel phase and the rock phase existing on the surface of the NCM are restored to a layered structure, and the novel NCM523 material is successfully prepared.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which,
FIG. 1 is an XRD spectrum of SNCM, RNCM523 and CNCM523 in example 1 of the present invention, scanning speed is 5 °/min, scanning range is 10-90 °;
fig. 2 is an SEM image of SNCM (a) and RNCM523 (b) in example 1 of the present invention;
fig. 3 is a graph showing the cycle performance of SNCM, RNCM523 and CNCM523 as positive electrodes of lithium ion batteries in example 1 of the present invention;
fig. 4 is a graph showing the rate performance of SNCM, RNCM523 and CNCM523 as positive electrodes of lithium ion batteries in example 1 of the present invention;
wherein SNCM in fig. 1-4 represents a ternary cathode material recovered from a waste lithium ion battery, RNCM523 represents a recovered regenerated NCM523 material, and CNCM523 represents a commercial NCM523 material.
Detailed Description
In order to solve the technical problems pointed out in the background art, the invention provides a method for directly regenerating an NCM positive electrode by ternary molten salt, a regenerated NCM positive electrode active material and application thereof.
The aim of the invention is achieved by the following scheme:
the invention provides a method for regenerating NCM positive electrode active material, which comprises the following steps:
s1: recovering waste NCM materials in the positive electrode plate from the waste lithium ion battery by using a roasting and ultrasonic treatment method;
s2: mixing the waste NCM material obtained in the step S1 with a nickel source, a manganese source and a cobalt source, adding ternary molten salt, mixing to obtain a mixture, and carrying out primary heating sintering on the obtained mixture in an oxygen-containing atmosphere;
s3: and (3) washing, drying and grinding the solid matters obtained in the step (S2) subjected to primary heating sintering, and carrying out secondary heating sintering on the ground powder in an atmosphere containing oxygen to obtain the regenerated NCM positive electrode active material.
In a specific embodiment, in the step S1, the roasting temperature is 500-600 ℃ and the roasting time is 1-3h;
the ultrasonic time in the ultrasonic treatment method is 15-45min;
NCM in the waste NCM material is LiNi x Co y Mn z ，x+y+z＝1；
In a specific embodiment, the recovery steps of the used NCM material are as follows:
and disassembling the waste lithium ion battery subjected to soaking discharge in the sodium chloride solution, and separating out the positive pole piece, the negative pole piece, the diaphragm and the shell. Roasting the positive electrode plate in an air atmosphere, soaking in water, treating with ultrasonic waves, carrying out solid-liquid separation to obtain a solid phase after powder on the current collector falls off, and drying the obtained solid phase to obtain the waste NCM material.
In a specific embodiment, in step S2, the content of the metal element in the waste NCM material is obtained by inductively coupled plasma spectroscopy (ICP-AES) detection. And determining whether a nickel source, a manganese source and a cobalt source are added or not according to the metal element content of the waste NCM material and the adding amount of the nickel source, the manganese source and the cobalt source. Ni of a mixture of the waste NCM material, a nickel source, a manganese source and a cobalt source: co: the mole ratio of Mn element is 5:2:3, a step of;
the nickel source is selected from NiO, ni (OH) 2 Or/and Ni (CH) 3 COO) 2 One or more of the following;
the manganese source is selected from MnO 2 And/or Mn 2 O 3 ；
The cobalt source is selected from Co 2 O 3 And/or Co 3 O 4 。
In a specific embodiment, in step S2, the ternary molten salt includes a lithium supplementing agent and a fluxing agent; the lithium supplementing agent is selected from LiOH; the cosolvent is sulfate;
in a specific embodiment, the lithium supplement is in excess of 20-50mol%; the addition amount of the fluxing agent is 10mol%;
the sulfate is selected from Li 2 SO 4 、Na 2 SO 4 The Li is 2 SO 4 And Na (Na) 2 SO 4 The molar ratio of (2) is 0.6:0.4 to 0.8:0.2;
in the invention, ternary molten salt is utilized to promote ion diffusion so as to supplement positive electrode material components, and a lithium-rich environment is provided for the aspect of crystal grain regeneration; smaller oxide particles can be effectively dissolved by using a sulfate-based co-solvent.
In a specific embodiment, in step S2, the gas in the atmosphere containing oxygen is air;
the temperature of the primary heating sintering is 950-850 ℃, the time is 8-15h, and the heating rate is 5-10 ℃/min.
In a specific embodiment, in step S2, the method further includes cleaning and drying the solid material after the primary heating and sintering, wherein the cleaning solution is selected from deionized water, and the drying temperature is 80-120 ℃. The cleaning and drying step is a conventional method in the field, residual lithium salt can be removed by using a cleaning liquid, and the method can also assist in ultrasonic treatment, so that the residual lithium salt can be removed efficiently.
In a specific embodiment, in step S3, the grinding time is 20-60min, and the rotation speed is 200-400r/min. In a specific milling, an agate pot with agate balls is used in a high speed planetary mill, the milling mode can be clockwise and counterclockwise to obtain a material with a more uniform particle size distribution.
The secondary heating sintering temperature is 650-750 ℃, 650-700 ℃,700-750 ℃, specifically 650 ℃, 660 ℃, 670 ℃, 680 ℃, 690 ℃,700 ℃, or any value between any two values, the time is 2-5h, 2-4h, 3-5h and the like, and 1, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h or any value between any two values.
In the present invention, the surface of the positive electrode material is recrystallized and regrown by secondary heating sintering in an oxygen atmosphere. The process is favorable for repairing surface damage possibly caused in the water washing process, improves the crystallinity of the material, and can further remove residual moisture and impurities on the surface of the material.
In the invention, waste NCM material is added in LiOH-Li 2 SO 4 -Na 2 SO 4 Ternary molten salt, niO and Co 2 O 3 And MnO 2 In the presence of the combination of additives, various structural defects in the waste NCM (nickel cobalt lithium manganate) material are successfully repaired by the proposed two-step heating strategy, including the problems of lithium loss, particle breakage, irreversible phase change, li/Ni disorder and the like. In the first step of high temperature heat treatment, the repair of the waste material is realized by supplementing lithium ions, promoting the recrystallization and growth of particles, eliminating or relieving irreversible phase change and improving the distribution of Li/Ni. The second step of high temperature heat treatment further promotes the crystallization process, helping to form a more complete layered structure. The resulting RNCM523 has a complete layered structure, exhibiting good electrochemical performance, including improved capacity, cycle life, and charge-discharge efficiency.
The invention also provides a regenerated NCM positive electrode active material, which comprises the regenerated NCM positive electrode active material obtained by the method for regenerating the NCM positive electrode active material.
The invention provides a positive electrode sheet comprising the regenerated NCM positive electrode active material.
In a specific embodiment, the preparation method of the positive electrode sheet is a synthesis method conventional in the art, and is not particularly limited.
The invention provides a lithium ion battery, which comprises the positive plate.
In a specific embodiment, the lithium ion battery further comprises an electrolyte, a separator and a negative electrode sheet.
In a specific embodiment, the electrolyte and the separator are conventional materials in the field, without limitation, the separator can be one or more layers of composite films commonly used in the field, or an organic coating or an inorganic coating can be coated on the surface of a base film of the separator, and the base film of the separator is a polymer separator of at least one of polyethylene, polypropylene, polyacrylonitrile, polyvinyl alcohol, polyarylethersulfone and polyvinylidene fluoride.
In a specific embodiment, the negative electrode material of the negative electrode sheet is a material conventional in the art, and is not particularly limited, and may be one or a combination of several of metallic lithium, metallic lithium alloy, carbon-silicon composite material, graphite, lithium metal nitride, antimony oxide, carbon-germanium composite material.
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
The values disclosed in the embodiments of the present invention are approximate values and are not determined values. Where the error or experimental conditions allow, all values within the error range may be included without limiting the specific values disclosed in the embodiments of the present invention.
Example 1
The embodiment provides a method for directly regenerating NCM positive electrode by ternary molten salt, which comprises the following steps:
(1) And manually disassembling the abandoned lithium ion battery, separating the positive electrode plate from the negative electrode plate, adding the positive electrode plate into a tubular furnace for roasting for 3 hours at 500 ℃ (together with an aluminum foil current collector), soaking the positive electrode plate in deionized water after roasting, treating the positive electrode plate with ultrasonic waves for 20 minutes, collecting the black powder on the aluminum foil by a suction filtration method after the black powder on the aluminum foil falls off, and drying the obtained solid substance to obtain stripped powder. The obtained exfoliated powder was passed through a screen (screen 200 mesh) to obtain recovered positive electrode powder SNCM.
(2) ICP testing was performed on the cathode material SNCM recovered in this example, and the metal element content of the SNCM is shown in table 1. 0.8g of recovered positive electrode powder SNCM material is weighed, and 0.3984g of NiO and 0.054g of Co are added 3 O 4 And (5) mixing. Mixing in a mortar manually for 60min to obtain a mixture. Ni of the obtained mixture: co: the mole ratio of Mn element is 5:2:3.
(3) Adding excess LiOH-Li to the mixture 2 SO 4 -Na 2 SO 4 And (3) fully mixing the ternary molten salt to obtain a mixture. Wherein the ternary fused salt is in accordance with 0.48g LiOH H 2 O、0.0529gLi 2 SO 4 、0.0412gNa 2 SO 4 Mixing and preparing.
(4) And (3) sintering the mixture, heating to 900 ℃ at a speed of 5 ℃/min, preserving heat, sintering for 10 hours, and cooling to room temperature at a speed of 10 ℃/min to obtain the sintered material. The sintered material is washed by deionized water to dissolve residual lithium salt, and then is filtered and dried in vacuum to obtain a sintered product.
(5) And (3) placing the sintered product obtained in the step (4) into an agate tank with agate balls, and operating on a high-speed planetary mill for 30min at a rotating speed of 300 r/min. The milling mode is clockwise and counterclockwise to produce a material with a more uniform particle size distribution.
(6) O of the material obtained in the step (5) in a tube furnace 2 Heating to 700 ℃ at a heating rate of 5 ℃ in atmosphere, and sintering for 2 hours to obtain a secondary sintering product, namely the regenerated material RNCM523 of the NCM positive electrode material; subjecting the obtained SNCM material, regenerated material RNCM523 and commercial CNCM523 material to structural characterization, see in particular FIGS. 1 and 2; as can be seen from FIG. 1, all three materials have alpha-NaFeO 2 The (006)/(102) and (108)/(110) peaks of RNCM523, CNCM523 are clearly separated by the structure, but compared to SNCM, indicating that the regenerated sample has a good layered structure as commercial materials. As can be seen from fig. 2, the SNCM is subjected to volume changes and internal mechanical stresses during lithium ion extraction/intercalation after a long period of cycling, resulting in possible cracking or even chipping of the particles. These microcracks and broken particles further contact the electrolyte causing more side effects that further erode the particle surface. While the surface of regenerated RNCM523 was smooth, and microcracked and broken particles were successfully repaired.
Table 1 shows the metal element content of the NCM material recovered in example 1 of the present invention
Example 2
The embodiment provides a method for directly regenerating NCM positive electrode by ternary molten salt, which comprises the following steps:
(1) And manually disassembling the abandoned lithium ion battery, separating the positive electrode plate from the negative electrode plate, placing the positive electrode plate in a tubular furnace for roasting for 2 hours at 550 ℃ (together with an aluminum foil current collector), soaking the positive electrode plate in deionized water after roasting, treating the positive electrode plate with ultrasonic waves for 30 minutes, collecting the black powder on the aluminum foil by a suction filtration method after the black powder on the aluminum foil is removed, and drying the obtained solid substance to obtain stripped powder. The obtained exfoliated powder was passed through a screen (screen 200 mesh) to obtain recovered positive electrode powder SNCM.
(2) ICP testing was performed on the cathode material SNCM recovered in this example, and the metal element content of the SNCM is shown in table 2. Weighing 0.8g of recovered positive electrode powder SNCM material, adding 0.4058g of NiO and 0.03446g of Co 3 O 4 Mixing materials, and mixing materials for 30min at 150rpm by using a mixer to obtain a mixture. Ni of the final mixture: co: the mole ratio of Mn element is 5:2:3.
(3) Adding excess LiOH-Li to the mixture 2 SO 4 -Na 2 SO 4 And (3) fully mixing the ternary molten salt to obtain a mixture. Wherein the ternary fused salt is in accordance with 0.453g LiOH H 2 O、0.0576gLi 2 SO 4 、0.044.8gNa 2 SO 4 Mixing and preparing.
(4) And (3) sintering the mixture, heating to 900 ℃ at a speed of 5 ℃/min, preserving heat, sintering for 10 hours, and cooling to room temperature at a speed of 10 ℃/min to obtain the sintered material. And soaking the reaction product in deionized water for 30 minutes under the ultrasonic action to dissolve residual lithium salt, and then carrying out vacuum filtration and drying to obtain a sintered product.
(5) And (3) placing the sintered product obtained in the step (4) into an agate tank with agate balls, and operating at a rotating speed of 200r/min for 60min on a high-speed planetary mill. The milling mode is clockwise and counterclockwise to produce a material with a more uniform particle size distribution.
(6) NCM523 Material O in tube furnace 2 And (3) heating to 700 ℃ at a heating rate of 5 ℃ in atmosphere, and sintering for 2 hours to obtain a secondary sintering product, namely the regenerated material RNCM523 of the NCM positive electrode material.
Table 2 shows the metal element content of the NCM material recovered in example 2 of the present invention
Test case
(1) The directly regenerated NCM523 material in examples 1-2 was applied to a lithium ion battery positive electrode material, specifically as follows:
according to 8:1:1, weighing RNCM523, conductive carbon black and polyvinylidene fluoride (PVDF) according to the mass ratio, dropwise adding a proper amount of N-methylpyrrolidone (NMP) into an agate mortar, mixing and grinding uniformly to obtain slurry, coating the slurry on the surface of an aluminum foil, performing vacuum drying at 80 ℃, performing tabletting treatment by a roller press, cutting into wafers by a slicer, transferring into a glove box in an argon atmosphere, taking RNCM523 as a working electrode, taking a metal lithium sheet as a counter electrode, and taking a polyethylene/polypropylene film (Celgard 2400) as a diaphragm, wherein 1M LiPF 6 DMC: DEC (volume ratio 1:1:1, 5wt% FEC was added) solution to assemble CR2032 button cell as electrolyte and cycle and rate performance tests were performed on a Neware battery testing system.
(2) Electrochemical performance tests were performed on the half-cells described above with the RNCM523 as the working electrode. The results are shown in FIGS. 3-4.
As shown in fig. 3, the positive electrode prepared in example 1 has a first-turn specific discharge capacity of 148mAh/g at a current density of 0.5C (1c=150 mAh/g) under a voltage window of 2.8-4.3V, and a reversible specific discharge capacity of 129.3mAh/g is maintained after 50 cycles.
As shown in fig. 4, in order to show the rate performance results of the RNCM523 material of example 1 at different current densities, it is understood that as the current density increases, the RNCM523 exhibits good rate performance. The reversible specific discharge capacities reached 159.3, 152.7, 138.8, 123.2 and 108.4mAh/g at current densities of 0.1, 0.2, 0.5, 1 and 2C, respectively, and increased back to 150.6mAh/g when the current densities were reduced again to 0.1C.
As can be seen from the above specific examples and characterization results, the present invention is carried out by discharging, disassembling, heat treatment, ultrasonic separation, etcThe step of obtaining the waste NCM anode material, and then passing through LiOH-Li 2 SO 4 -Na 2 SO 4 The ternary soluble salt of (2) repairs the waste NCM material at high temperature and regenerates the waste NCM material into NCM523 material.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The method for directly regenerating the NCM positive electrode active material by using the ternary molten salt is characterized by comprising the following steps of:
s1: recovering waste NCM materials in the positive electrode plate from the waste lithium ion battery by using a roasting and ultrasonic treatment method;
s2: mixing the waste NCM material obtained in the step S1 with a nickel source, a manganese source and a cobalt source, adding ternary molten salt, mixing to obtain a mixture, and carrying out primary heating sintering on the obtained mixture in an oxygen-containing atmosphere;
s3: and (3) washing, drying and grinding the solid matters obtained in the step (S2) subjected to primary heating sintering, and carrying out secondary heating sintering on the ground powder in an atmosphere containing oxygen to obtain the regenerated NCM523 positive electrode active material.
2. The method for regenerating an NCM positive electrode active material according to claim 1, wherein in step S1, the baking temperature is 500 to 600 ℃ for 1 to 3 hours;
the ultrasonic time in the ultrasonic treatment method is 15-45min;
NCM in the waste NCM material is LiNi x Co y Mn z ，x+y+z＝1。
3. The method for regenerating an NCM positive electrode active material according to claim 1, wherein in step S2, a mixture of the waste NCM material and a nickel source, a manganese source, and a cobalt source is Ni: co: the mole ratio of Mn element is 5:2:3, a step of;
the nickel source is selected from NiO, ni (OH) 2 And Ni (CH) 3 COO) 2 One or more of the following;
the manganese source is selected from MnO 2 And/or Mn 2 O 3 ；
The cobalt source is selected from Co 2 O 3 And/or CoO.
4. The method for regenerating an NCM positive electrode active material according to claim 1, wherein in step S2, the ternary molten salt includes a lithium supplementing agent and a flux; the lithium supplementing agent is selected from LiOH; the cosolvent is sulfate.
5. The method for regenerating an NCM positive electrode active material according to claim 4, wherein the excess amount of the lithium supplementing agent is 20 to 50mol%; the addition amount of the fluxing agent is 10-15mol%;
the sulfate comprises Li 2 SO 4 、Na 2 SO 4 ；
The Li is 2 SO 4 And Na (Na) 2 SO 4 The molar ratio of (2) is 0.6:0.4 to 0.8:0.2.
6. the method for regenerating an NCM positive electrode active material according to claim 1, wherein in step S2, the gas of the oxygen-containing atmosphere is air;
the temperature of the primary heating sintering is 950-850 ℃, the time is 8-15h, and the heating rate is 5-10 ℃/min.
7. The method for regenerating an NCM positive electrode active material according to claim 1, wherein in step S3, the grinding time is 20 to 60min and the rotation speed is 200 to 400r/min;
the temperature of the secondary heating sintering is 650-750 ℃ and the time is 2-5h.
8. A regenerated NCM positive electrode active material, characterized by comprising an NCM positive electrode active material obtained by the method for regenerating an NCM positive electrode active material according to any one of claims 1 to 7.
9. A positive electrode sheet comprising the regenerated NCM positive electrode active material according to claim 8.
10. A lithium ion battery comprising the positive electrode sheet of claim 9.
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| CN116924486A (en) * | 2023-07-24 | 2023-10-24 | 复旦大学 | Molten salt repairing and recycling method for waste ternary cathode material |
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