Method for recycling positive electrode active material and positive electrode active material recycled thereby

Abstract

The present invention relates to a method for recycling a positive electrode active material and a positive electrode active material recycled thereby and, more specifically, the present invention can provide a method for recycling a positive electrode active material and a positive electrode active material recycled thereby, the method comprising the steps of: thermally treating a waste positive electrode, including a current collector and a positive electrode active material layer formed on the surface thereof, under an oxidative atmosphere to recover a positive electrode active material; adding a coating agent to the recovered positive electrode active material, followed by firing under a reductive atmosphere, to convert a trivalent iron compound in the positive electrode active material into a divalent iron compound and convert polycrystalline particles into a single-crystal cathode active material, while forming a coating layer on the surface of the positive electrode active material; and milling the positive electrode active material, which has the coating layer formed thereon and has undergone conversion into the divalent iron compound, to control the particle size of the positive electrode active material, so that during the recycling process, synthesis into a single crystal structure is achieved along with the conversion of trivalent iron into divalent iron to eliminate the remaining of trivalent iron inside the recycled positive electrode active material, thereby preventing battery performance degradation, and the positive electrode material exhibits excellent lifespan characteristics in a high-voltage environment, high thermal stability, and low gas generation resulting from charging and discharging.

Description

Method for regenerating positive electrode active material and positive electrode active material regenerated therefrom

[0001] 〔Cross-citation with the applicant(s)〕

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2024-0029457, filed February 29, 2024, and Korean Patent Application No. 10-2024-0029458, filed February 29, 2024, and Korean Patent Application No. 10-2025-0001945, filed January 7, 2025, which are refiled based on the Korean Patent Application No. 10-2025-0001945, the entire contents of which are incorporated herein by reference.

[0003] The present invention relates to a method for regenerating a positive electrode active material and a positive electrode active material regenerated therefrom, and more particularly, to a method for regenerating a positive electrode active material and a positive electrode active material regenerated therefrom, which controls the atmosphere and temperature conditions in the step of removing and recovering a positive electrode active material from a spent positive electrode and the step of applying a coating agent to the recovered positive electrode active material and firing it, thereby synthesizing a single crystal structure during the regeneration process and simultaneously converting trivalent iron into divalent iron, so that trivalent iron does not remain inside the regenerated positive electrode active material, thereby preventing degradation of battery performance, having excellent life characteristics in a high-voltage environment, high thermal stability, and a small amount of gas generated during charge and discharge.

[0004] Demand for lithium secondary batteries has steadily increased since the 1990s alongside the portable electronic device market, and has recently surged further worldwide due to the rapid growth of the electric vehicle market. This could lead to instability in the lithium resource supply and demand in the near future, and the continuous accumulation of spent batteries at the end of their useful life could also pose significant environmental problems. To address these issues, recycling spent lithium secondary batteries is a critical technological challenge.

[0005] Lithium secondary batteries are largely composed of a cathode in which a cathode active material layer is coated on a metal foil such as aluminum, a cathode in which a cathode active material layer is coated on a metal foil such as copper, a separator that prevents the cathode and anode from mixing with each other, and an electrolyte that allows lithium ions to move between the cathode and anode. The cathode is manufactured by applying a cathode composition including a cathode active material, a binder, a conductive agent, and a solvent to a current collector made of a metal foil such as aluminum, drying the composition, and then pressurizing and molding the resulting composition.

[0006] The cathode accounts for more than 60% of the cost of a lithium secondary battery, and the active materials of these cathodes include lithium cobalt oxide (LiCoO2), lithium nickel cobalt manganese oxide (LiNiMnCoO2), lithium manganese oxide (LiMnO2), and lithium iron phosphate (LiFePO4). Among these, lithium iron phosphate is increasingly being used in large-capacity lithium secondary batteries for electric vehicles due to its low unit price and supply stability. Accordingly, much research is being conducted on recycling processing technologies that selectively recover valuable metals from the cathodes of lithium secondary batteries that are discarded after use or cathode scrap generated in the lithium secondary battery manufacturing process (hereinafter referred to as “waste cathodes”), or to directly recover cathode active materials.

[0007] There are four methods introduced as direct recycled methods for directly regenerating the positive electrode active material without decomposing it from the waste positive electrode: calcination, solvent dissolution, aluminum foil dissolution, and crushing and screening.

[0008] However, although the above-mentioned firing method is a simple process, it has the disadvantages of generating foreign substances on the surface of the regenerated positive electrode active material that reduce the output performance of the battery, generating waste gas, and consuming a lot of energy.

[0009] In addition, the above solvent dissolution method can obtain a regenerated positive electrode active material with a relatively clean surface, but has the disadvantage of poor stability due to the solvent such as N-methyl-2-pyrrolidone (NMP) used to dissolve the binder being a toxic gas and having a risk of explosion, and requiring an expensive solvent recovery process.

[0010] In addition, the above aluminum foil melting method has good process stability, low process cost, and easy binder removal, but has the disadvantages of generating foreign substances that are difficult to remove on the surface of the regenerated positive electrode active material, and generating hydrogen gas during the process of removing the aluminum foil, which poses a risk of explosion.

[0011] Lastly, although the above crushing and screening method has the advantage of being the simplest process, it has the disadvantages of being difficult to completely separate the current collector and the positive electrode active material, changing the particle size distribution of the positive electrode active material during the crushing process, and deteriorating the battery characteristics of the regenerated positive electrode active material due to the remaining binder.

[0012] In particular, among the above-mentioned waste positive electrodes, the waste positive electrode containing lithium iron phosphate as a positive electrode active material has a disadvantage in that, during the regeneration process, particles with a polycrystalline structure are synthesized and trivalent iron particles are incorporated into the lithium iron phosphate, thereby lowering the performance of the battery.

[0013] [Prior Art Literature]

[0014] [Patent Document]

[0015] Japanese Patent Publication No. 2024-503575

[0016] In order to solve the problems of the prior art as described above, the present invention provides a method for regenerating a positive electrode active material and a regenerated positive electrode active material, which control the atmosphere and temperature conditions in the step of removing and recovering a positive electrode active material from a waste positive electrode and the step of applying a coating agent to the recovered positive electrode active material and firing it, thereby synthesizing it into a single crystal structure during the regeneration process and simultaneously converting trivalent iron into divalent iron so that trivalent iron does not remain inside the regenerated positive electrode active material, thereby preventing degradation of battery performance, having excellent life characteristics in a high-voltage environment, high thermal stability, and low gas generation due to charge and discharge.

[0017] The above and other objects of the present invention can all be achieved by the present invention described below.

[0018] In order to achieve the above purpose, the present invention comprises the steps of: I)(a) heat-treating a waste positive electrode including a current collector and a positive electrode active material layer formed on the surface thereof under an oxidizing atmosphere to recover the positive electrode active material;

[0019] (b) a step of adding a coating agent to the recovered positive electrode active material and firing it under a reducing atmosphere to form a coating layer on the surface of the positive electrode active material, thereby converting the trivalent iron compound in the positive electrode active material into a divalent iron compound and converting the polycrystalline particles into a single-crystal positive electrode active material; and

[0020] (c) A method for regenerating a positive electrode active material is provided, characterized by including a step of controlling the particle size of the positive electrode active material by milling the positive electrode active material on which a coating layer is formed and converted into a divalent iron compound.

[0021] II) In the above I), the step (a) may include a step of performing a first heat treatment at 300 to 500°C in an oxidizing atmosphere; and a step of performing a second heat treatment at 500 to 700°C in an oxidizing atmosphere after the first heat treatment.

[0022] III) In the above I) to II), the first heat treatment step can be performed for 30 minutes to 10 hours, and the second heat treatment step can be performed for 30 minutes to 10 hours.

[0023] IV) In the above I) to III), the step (b) may include a step of adding a coating agent to the recovered positive electrode active material and pre-milling it; a step of spray-drying the pre-milled positive electrode active material; and a step of calcining the spray-dried positive electrode active material at 710 to 900°C under a reducing atmosphere.

[0024] V) In the above I) to IV), the coating agent may include at least one of a metal, an organic metal, or a carbon component, preferably a carbon component, and more preferably at least one selected from among sucrose, glucose, graphite, PVDF (polyvinylidene fluoride), PEG (polyethylene glycol), citric acid, PVA (polyvinyl alcohol), graphene, and fructose.

[0025] VI) In the above I) to V), the firing can be performed for 1 to 24 hours.

[0026] VII) In the above I) to VI), the pre-milling can be performed using a ball mill, a high-energy ball mill, a vibration mill, or a roll mill.

[0027] VIII) In the above I) to VII), the pre-milling can be performed for 2 to 24 hours at a stirring speed of 50 to 500 rpm.

[0028] IX) In the above I) to VIII), the milling in the step (c) can be performed using a jet mill.

[0029] X) In the above I) to IX), the milling in the step (c) can be performed in air or an inert atmosphere.

[0030] XI) In the above I) to X), the positive electrode active material may be represented by the following chemical formula 1.

[0031] [Chemical Formula 1]

[0032] Li 1-a M a Fe 1-b N b P 1-c X c O 4-d Y d

[0033] (In the above chemical formula 1, M includes at least one element selected from the group consisting of Nb, Al, Na, Ti, Zr, and K, N includes at least one element selected from the group consisting of Mo, V, Mn, Sm, Eu, Yb, Cu, Mg, Ni, and Co, X includes Si, Y includes at least one element selected from the group consisting of F, S, and N, and a, b, c, and d are 0≤a<1, 0≤b<1, 0≤c<1, and 0≤d<4, respectively.)

[0034] XII) In the above I) to XI), the positive electrode active material may be composed of 99 mol% or more or 100 mol% of a single crystal.

[0035] XIII) In the above I) to XII), the positive electrode active material may have a trivalent iron compound of less than 1 mol% or 0 mol% based on 100 mol% of the total of divalent and trivalent iron compounds based on XRD analysis or EPR (Electron Paramagnetic Resonance) analysis.

[0036]

[0037] In addition, the present invention provides a regenerative positive electrode active material represented by the following chemical formula 1 (XIV) and characterized by being composed of 99 mol% or more or 100 mol% of a single crystal.

[0038] [Chemical Formula 1]

[0039] Li 1-a M a Fe 1-b N b P 1-c X c O 4-d Y d

[0040] (In the above chemical formula 1, M includes at least one element selected from the group consisting of Nb, Al, Na, Ti, Zr, and K, N includes at least one element selected from the group consisting of Mo, V, Mn, Sm, Eu, Yb, Cu, Mg, Ni, and Co, X includes Si, Y includes at least one element selected from the group consisting of F, S, and N, and a, b, c, and d are 0≤a<1, 0≤b<1, 0≤c<1, and 0≤d<4, respectively.)

[0041]

[0042] In addition, the present invention provides a secondary battery characterized by including XV) the above-described regenerative positive electrode active material.

[0043] According to the present invention, there is provided a method for regenerating a cathode active material, which is synthesized into a single crystal structure during a regeneration process and simultaneously converts trivalent iron into divalent iron, so that trivalent iron does not remain inside the regenerated cathode active material, thereby preventing degradation of battery performance, and has excellent life characteristics in a high-voltage environment, high thermal stability, and low gas generation during charge and discharge.

[0044] In addition, it has the effect of providing a method for regenerating positive electrode active materials with greatly improved economic efficiency and productivity, as it directly regenerates positive electrode active materials without decomposing them in a simple and environmentally friendly manner.

[0045] Figure 1 is a scheme of the positive electrode active material regenerated in Example 2 and Comparative Examples 3 and 4 according to the present invention.

[0046] Figure 2 is a drawing showing TEM photographs of the positive electrode active material regenerated in Example 1 and Comparative Examples 1 and 2.

[0047] Figure 3 is a drawing comparing the TEM image and the Electron Diffraction Pattern (EDP) image of the positive electrode active material regenerated in Example 2 and Comparative Example 3.

[0048] Figure 4 is a drawing showing a TEM photograph and a TEM-EDS mapping image of the positive electrode active material regenerated in Comparative Example 4.

[0049] Figure 5 is a drawing comparing the XRD graphs of the positive electrode active materials produced in Example 2 and Comparative Examples 3 and 4.

[0050] Figure 6 is a drawing comparing the XPS graphs of the positive electrode active materials regenerated in Example 2 and Comparative Examples 3 and 4.

[0051] Figure 7 is a drawing comparing the EPR graphs of the positive electrode active materials regenerated in Example 2 and Comparative Examples 3 and 4.

[0052] Figure 8 is a drawing comparing the electrochemical performance, such as rated voltage, energy capacity, CHC capacity retention rate, and 45°C life capacity, of the positive electrode active materials regenerated in Example 1 and Comparative Examples 1 and 2.

[0053] Figure 9 is a drawing comparing the electrochemical performance, such as energy capacity and CHC capacity retention rate, of the regenerated or newly produced positive electrode active materials in Example 2 and Comparative Examples 3 and 4.

[0054] In the above drawings, Ref represents Comparative Example 1, 700C represents Comparative Example 2, 800C represents Example 1, a) represents Example 2, b) represents Comparative Example 3, and c) represents Comparative Example 4, respectively.

[0055] The present inventors, while studying a method for directly regenerating waste cathode materials into cathode materials with excellent battery performance without decomposing them (direct recycled method), found that when the atmosphere and temperature conditions of the step of removing and recovering cathode active materials from waste cathodes and the step of applying a coating agent to the recovered cathode active materials and firing them are controlled, the cathode active material is synthesized into a single crystal structure during the regeneration process and at the same time, trivalent iron is converted into divalent iron, so that trivalent iron does not remain inside the regenerated cathode active material, and thus the battery does not deteriorate in performance, has excellent life characteristics in a high-voltage environment, has high thermal stability, and generates little gas during charge and discharge, and based on this, they further devoted themselves to research and completed the present invention.

[0056] In the present invention, the active material layer of the positive electrode may include a positive electrode active material, a binder, and a conductive material.

[0057] In this description, “oxidizing atmosphere” may specifically be air or an atmosphere having an oxygen purity of 30% or more.

[0058] In this description, “trivalent iron compound” may be, but is not limited to, Li3Fe(PO4)3 and Fe2O3, unless otherwise specified.

[0059] In this description, fresh positive electrode active material means a positive electrode active material newly synthesized and manufactured, rather than obtained through recovery and regeneration from a spent battery.

[0060]

[0061] Hereinafter, the cathode active material, cathode active material regeneration method, and secondary battery of the present invention are described in detail.

[0062] However, the terms or words used in this specification and claims cannot be interpreted as limited to their usual or dictionary meanings, and should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention based on the principle that the inventor can appropriately define the concept of the term to explain his or her own application in the best way. Therefore, the embodiments described in this specification and the configurations illustrated in the drawings are only one embodiment of the present invention and do not represent all of the technical idea of ​​the present invention, and it should be understood that there may be various equivalents and modified examples that can replace them, and that they can be arranged, replaced, combined, separated, or designed in various other configurations.

[0063] All technical and scientific terms used in this document, unless otherwise defined, have the same meaning as commonly understood by a person of ordinary skill in the art to which the present invention pertains.

[0064]

[0065] Method for regenerating positive electrode active material

[0066] The method for regenerating a positive electrode active material of the present invention comprises the steps of: (a) heat-treating a waste positive electrode including a current collector and a positive electrode active material layer formed on the surface thereof under an oxidizing atmosphere to recover the positive electrode active material; (b) adding a coating agent to the recovered positive electrode active material and firing the recovered positive electrode active material under a reducing atmosphere to form a coating layer on the surface of the positive electrode active material while converting a trivalent iron compound in the positive electrode active material into a divalent iron compound and converting polycrystalline particles into a single-crystal positive electrode active material; and (c) milling the positive electrode active material on which the coating layer has been formed and which has been converted into a divalent iron compound to control the particle size of the positive electrode active material. In this case, the crystal structure of the single crystal is recovered, and at the same time, the trivalent iron generated during the regeneration process is completely converted into divalent iron, thereby realizing excellent charge capacity, resistance characteristics, and capacity characteristics.

[0067]

[0068] Below, the method for regenerating the positive electrode active material is described in detail step by step.

[0069]

[0070] (a) Positive electrode active material recovery step

[0071] In the present invention, the method for regenerating a positive electrode active material includes a step of heat-treating a waste positive electrode including a current collector and a positive electrode active material layer formed on the surface thereof under an oxidizing atmosphere, and in this case, recovery is easy and the purity of the recovered positive electrode active material is improved.

[0072]

[0073] The above-mentioned waste positive electrode may preferably be a positive electrode separated from a secondary battery discarded after use, or a positive electrode sheet or positive electrode scrap discarded after defects or cutting occurring in the secondary battery manufacturing process. For example, in the case of positive electrode scrap occurring in the manufacturing process, there is an advantage in that better battery characteristics can be realized because there is no loss of lithium ions in the positive electrode active material.

[0074] The above secondary battery may preferably be a lithium secondary battery.

[0075]

[0076] The olivine structure in this paper is a type of crystal structure of a cathode active material, and its lattice structure is a 3D hexahedron, and since PO (phosphorus-oxygen) is strongly bonded, the structure can be maintained even when all lithium ions are lost, so there is little performance degradation due to charge and discharge, and it is a structure with excellent thermal stability. This has the disadvantage of having a lower energy density than other cathode active materials and low electrical conductivity and lithium ion diffusion, but it has great economic advantages because it uses inexpensive iron instead of expensive cobalt.

[0077] The above olivine structure can be confirmed by a measurement method generally practiced in the technical field to which the present invention belongs, and as a specific example, can be confirmed through X-ray diffraction analysis (XRD).

[0078]

[0079] The positive electrode active material having the above olivine structure may include, for example, a compound represented by the following chemical formula 1, and in this case, it has the advantages of excellent high-temperature stability and lifespan characteristics and excellent economic efficiency.

[0080] [Chemical Formula 1]

[0081] Li 1-a M a Fe 1-b N b P 1-c X c O 4-d Y d

[0082] (In the above chemical formula 1, M includes at least one element selected from the group consisting of Nb, Al, Na, Ti, Zr, and K, N includes at least one element selected from the group consisting of Mo, V, Mn, Sm, Eu, Yb, Cu, Mg, Ni, and Co, X includes Si, Y includes at least one element selected from the group consisting of F, S, and N, and a, b, c, and d are 0≤a<1, 0≤b<1, 0≤c<1, and 0≤d<4, respectively.)

[0083] In the above chemical formula 1, a, b, c, and d may be 0≤a≤0.5, 0≤b≤0.5, 0≤c≤0.5, and 0≤d≤0.1, respectively.

[0084] The compound represented by the above chemical formula 1 may preferably be lithium iron phosphate, in which case it has the advantages of excellent high-temperature stability and lifespan characteristics and excellent economic efficiency.

[0085] The above lithium iron phosphate may preferably include LiFePO4 having an olivine structure, in which case it has the advantages of excellent high-temperature stability and lifespan characteristics and excellent economic efficiency.

[0086]

[0087] The above conductive material may be, for example, a carbon-based conductive material, and preferably, carbon black, CNT, or a mixture thereof.

[0088] The binder may be, for example, a polymer binder, preferably polyvinylidene fluoride (PVdF), acrylonitrile-butadiene rubber (NBR) or a mixture thereof, and more preferably polyvinylidene fluoride.

[0089] The active material layer of the positive electrode may include, for example, a solvent, and the solvent may be a solvent generally used in the technical field to which the present invention pertains for mixing the positive electrode active material, binder, and / or conductive agent. The solvent may be, for example, at least one selected from the group consisting of dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methyl-2-pyrrolidone (NMP), acetone, and water.

[0090] The active material layer of the above-mentioned positive electrode may further include, for example, a dispersant.

[0091] The above dispersant is, for example, a cellulose compound, polyalkylene oxide, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetal, polyvinyl ether, polyvinyl sulfonic acid, polyvinyl chloride (PVC), polyvinylidene fluoride, chitosan, starch, amylose, polyacrylamide, poly-N-isopropylacrylamide, poly-N,N-dimethylacrylamide, polyethyleneimine, polyoxyethylene, poly(2-methoxyethoxyethylene), poly(acrylamide-co-diallyldimethylammonium chloride), acrylonitrile-butadiene-styrene (ABS) copolymer, an acrylate-styrene-acrylonitrile (ASA) copolymer, a mixture of an acrylate-styrene-acrylonitrile (ASA) copolymer and propylene carbonate, It may be at least one selected from the group consisting of styrene-acrylonitrile (SAN) copolymers and methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) copolymers.

[0092]

[0093] The above (a) positive electrode active material recovery step may include, for example, (a1) a step of performing a first heat treatment at 300 to 440° C. in an oxidizing atmosphere; and (a2) a step of performing a second heat treatment at 500 to 650° C. in an oxidizing atmosphere after the first heat treatment. In this case, foreign substances such as binders and conductive agents included in the active material of the waste positive electrode can be easily removed, and the positive electrode active material precursor can be recovered at a high yield, which can be simply referred to as a 'desorption process'.

[0094] In this description, the cathode active material precursor is proposed to be distinguished from the final regenerated cathode active material after the calcination and milling process following desorption, and means a material that can provide the final regenerated cathode active material by calcination and milling.

[0095] The above heat treatment is not particularly limited if it is a method commonly performed in the technical field to which the present invention belongs, and the heating rate and heating time can be appropriately adjusted as needed.

[0096]

[0097] The above (a) positive electrode active material recovery step may include, as a preferred example, (a1) a step of performing a first heat treatment at 350 to 440° C. in an oxidizing atmosphere; and (a2) a step of performing a second heat treatment at 520 to 630° C. in an oxidizing atmosphere after the first heat treatment; more preferably, the temperature of the first heat treatment may be lower than the temperature of the second heat treatment. In this case, in the process of recovering the positive electrode active material from the waste positive electrode, foreign substances such as metals introduced from the current collector, such as aluminum, as well as the binder and conductive agent, are smoothly removed, so that there is an advantage in that a high-purity positive electrode active material can be recovered.

[0098] In a preferred embodiment of the present invention, after preliminary desorption by oxidizing heat treatment of a waste positive electrode at a low temperature range as described above, the positive electrode active material powder including the preliminarily desorbed positive electrode active material can be again oxidized heat treated at a high temperature to complete the desorption. In this case, the amount of residual metal introduced from the current collector is greatly reduced without a separate pretreatment process for separating or removing the current collector, thereby improving the purity of the positive electrode active material and simplifying the process.

[0099] More specifically, in the recovery process for desorption and recovery of the positive electrode active material from the waste positive electrode, heat treatment can be performed in two stages under a predetermined temperature condition and a higher temperature condition as described above, in which case, in the first heat treatment process (preliminary desorption process), metal-based foreign substances that may flow from the current collector are removed, and in the process of secondary oxidation heat treatment at a high temperature (desorption process), carbon-based foreign substances such as binders, conductive agents, and positive electrode active material surface coating agents are removed, so that the residual amount of foreign substances other than the components constituting the positive electrode active material can be significantly reduced, and through this, a high-purity positive electrode active material can be recovered through a simple process.

[0100] In addition, the positive electrode active material in the waste positive electrode may be coated with a coating agent containing, for example, a metal and / or carbon. In this way, the positive electrode active material may often be coated with a coating agent containing various metals and / or carbon for the purpose of improving battery performance. However, in the process of recovering the positive electrode active material from the waste positive electrode, the structure of this coating layer is destroyed, and if it is reused in a battery without being removed, it may cause a decline in battery performance. Therefore, if the positive electrode active material in the waste positive electrode is coated, it is advantageous to remove it. In the second heat treatment step (a2), the carbon coating on the surface of the positive electrode active material can be removed, and therefore, in this case, the purity of the recovered positive electrode active material is improved and there is an advantage of preventing a decline in battery performance.

[0101]

[0102] The above first heat treatment and second heat treatment can be performed, for example, in an oxidizing atmosphere including an air atmosphere or an oxygen atmosphere, in which case, foreign substances such as metals introduced from the binder, conductive material, and current collector are smoothly removed, so that the desired positive electrode active material can be recovered with high purity and high yield.

[0103] The above oxygen atmosphere may have an oxygen purity of, for example, 30% or more or 50% or more, preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, and even more preferably 90 to 99%, and within this range, there is an advantage in that the desired positive electrode active material can be recovered with high purity and high yield.

[0104] The purity % of the above oxygen can be volume % or mol %.

[0105] The purity of the oxygen of this invention is not particularly limited when measured by a measurement method commonly used in the technical field to which the present invention belongs.

[0106] The above first heat treatment can be preferably performed at 330 to 440°C, more preferably at 350 to 440°C, even more preferably at 360 to 440°C, and even more preferably at 360 to 420°C, and within this range, there is an advantage in that the purity and recovery yield of the positive electrode active material precursor are greatly improved without excessive energy consumption.

[0107] The heating rate until reaching the above first heat treatment temperature may be, for example, 1 to 10°C / min, preferably 2 to 9°C / min, and more preferably 3 to 7°C / min, and within this range, there is an advantage in that the desired positive electrode active material can be recovered with high purity and high yield.

[0108] The above first heat treatment time may be, for example, 30 minutes to 10 hours, preferably 40 minutes to 8.5 hours, more preferably 1 to 8 hours, and even more preferably 3 to 6 hours, and within this range, there is an advantage in that the desired positive electrode active material can be recovered with high purity and high yield.

[0109] In the first heat treatment step (a1) above, for example, the active material layer of the waste positive electrode can be separated from the current collector. In addition, during this process, some of the binder and conductive material included in the positive electrode active material layer can be removed. However, the remaining binder and conductive material may remain in the positive electrode material preliminarily removed in the first heat treatment step (a1), and thus, the positive electrode material recovered in the first heat treatment step (a1) above may include the positive electrode active material, residual binder, and residual conductive material.

[0110] The cathode material preliminarily removed in the first heat treatment step (a1) above can be recovered in powder form.

[0111] The above-described positive electrode active material recovery step may include, for example, a step of cooling the positive electrode active material powder recovered in the first heat treatment step between the (a1) first heat treatment step and the (a2) second heat treatment step, in which case the mixing ratio of the current collector constituent metal is minimized, thereby enabling recovery of a high-purity positive electrode active material precursor with a high yield, and at the same time, the crystallinity of the regenerated positive electrode active material obtained after the regeneration process is increased, thereby improving battery characteristics when used in a secondary battery.

[0112] The above cooling may be, as a specific example, natural cooling in which the heat supply to the heating furnace in which the first heat treatment is performed is stopped and the furnace is left at room temperature. In this case, there is an advantage in that subsequent processes can be easily performed without additional energy consumption.

[0113] In this document, room temperature refers to a point within 20 ± 5 ℃.

[0114]

[0115] The above secondary heat treatment can be performed at 500 to 650°C, preferably 520 to 630°C, more preferably 530 to 620°C, and even more preferably 520 to 610°C, and within this range, there is an advantage in that the purity and recovery yield of the positive electrode active material precursor are greatly improved without excessive energy consumption.

[0116] The heating rate until the secondary heat treatment temperature is reached may be, for example, 1 to 10°C / min, preferably 5 to 10°C / min, more preferably 7 to 9°C / min, and within this range, there is an advantage in that the desired positive electrode active material can be recovered with high purity and high yield.

[0117] The above secondary heat treatment time may be, for example, 30 minutes to 10 hours, preferably 40 minutes to 8.5 hours, more preferably 1 to 8 hours, and even more preferably 3 to 6 hours, and within this range, there is an advantage in that the desired positive electrode active material can be recovered with high purity and high yield.

[0118] The positive electrode active material recovered after the above secondary heat treatment can be naturally cooled, for example, and in this case, there is an advantage in that it can be easily input into a subsequent process.

[0119]

[0120] The recovered positive electrode active material (positive electrode active material precursor) after completion of the above (a) positive electrode active material recovery step may include, for example, a compound represented by the above chemical formula 1, preferably an LFP-based positive electrode active material, and as a specific example, may include Fe2O3 and Li3Fe2(PO4)3, and in this case, a high-purity regenerated positive electrode active material with significantly reduced residual metal-based foreign substances such as aluminum and carbon-based foreign substances can be provided through subsequent regeneration treatment. The regenerated positive electrode active material has high purity and can provide good battery characteristics when applied as a positive electrode active material of a secondary battery.

[0121] In this description, the LFP-based positive electrode active material is not particularly limited as long as it is an LFP-based positive electrode active material commonly defined or used in the technical field to which the present invention belongs.

[0122]

[0123] After the above (a) positive electrode active material recovery step is completed, the recovered positive electrode active material precursor may have a content of metal introduced from the current collector remaining therein of, for example, 390 ppm or less, preferably 250 ppm or less, more preferably 240 ppm or less, even more preferably 230 ppm or less, and even more preferably 225 ppm or less, and the lower limit thereof is not particularly limited, but may be 10 ppm or more, or 50 ppm or more, in terms of the balance between the positive electrode active material purity and recovery rate and the process efficiency. In this case, there is an advantage in that a high-purity positive electrode active material can be recovered.

[0124] The metal introduced from the above-mentioned collector is not particularly limited as long as it is a metal commonly applied to a collector in the technical field to which the present invention belongs, and a specific example thereof may be aluminum.

[0125] In this description, the measurement of the metal element content is not particularly limited to a method commonly practiced in the technical field to which the present invention belongs, and as a specific example, it can be measured by ICP (Inductively Coupled Plasma) analysis.

[0126]

[0127] After the above (a) positive electrode active material recovery step is completed, the recovered positive electrode active material precursor may have, for example, a carbon element (C) content of 1.0 wt% or less, preferably 0.5 wt% or less, more preferably 0.1 wt% or less, even more preferably 0.08 wt% or less, and even more preferably 0.06 wt% or less, and the lower limit thereof is not particularly limited, but may be 0.001 wt% or more, or 0.01 wt% or more, in terms of the balance between the purity and recovery rate of the positive electrode active material and the process efficiency. In this case, there is an advantage in that a high-purity positive electrode active material can be recovered.

[0128] In this description, the measurement of the carbon element content is not particularly limited to a method commonly practiced in the technical field to which the present invention belongs, and as a specific example, it can be measured by quantitative analysis using a CS analyzer (Carbon / Sulfur Determinator).

[0129]

[0130] (b) Recovery step of the 3-valent iron compound-free 2-valent structure within the positive electrode active material

[0131] In the present invention, the method for regenerating a positive electrode active material includes the step of (b) adding a coating agent to the recovered positive electrode active material and firing the recovered positive electrode active material under a reducing atmosphere to form a coating layer on the surface of the positive electrode active material while converting a trivalent iron compound in the positive electrode active material into a divalent iron compound and converting polycrystalline particles into a single-crystal positive electrode active material. In this case, a coating layer is formed on the surface of the particles of the regenerated positive electrode active material, and when this is applied to a secondary battery, the output characteristics, charge / discharge performance, and life performance of the battery are improved, which is advantageous in providing good battery characteristics equivalent to those of the case where a fresh positive electrode active material is applied. In addition, since the trivalent iron compound-free divalent structure is restored similarly to the crystal structure of the fresh positive electrode active material before forming the coating layer, the coating layer can be uniformly formed on the surface of the particles, and agglomeration of the positive electrode active material particles is prevented, which is advantageous in improving battery performance.

[0132]

[0133] The step (b) above may include a step of adding a coating agent to the recovered positive electrode active material (precursor) and pre-milling; a step of spray-drying the pre-milled positive electrode active material; and a step of calcining the spray-dried positive electrode active material at 710 to 900° C. under a reducing atmosphere; in which case, while making the particle size uniform, a coating layer having a uniform thickness is manufactured, and by having a divalent iron compound without a trivalent iron compound in the positive electrode active material, there is an effect of restoring a structure similar to the crystal structure of a fresh positive electrode active material.

[0134]

[0135] The coating agent may be, for example, a coating agent including at least one of a metal, an organic metal, and a carbon component, and preferably, a coating agent including a carbon component configured to form a carbon coating, in which case there is an advantage of even better battery characteristics.

[0136] The above carbon component is not particularly limited as long as it is a carbon component commonly used in the technical field to which the present invention belongs, and as a specific example, it may be at least one selected from the group consisting of sugars such as sucrose, glucose, and fructose, graphite, and polyvinylidene fluoride, preferably sugars, and more preferably sucrose, in which case there is an advantage of easy coating and economical efficiency, and when applied to a battery, there is an advantage of an excellent effect of improving battery characteristics.

[0137] The coating agent including the above metal is preferably a coating agent including at least one selected from the group consisting of B, W, Al, Ti, Mg, Ni, Co, Mn, Si, Zr, Ge, Sn, Cr, Fe, V, Nb and Y, more preferably a coating agent including at least one selected from the group consisting of B, W, Al, Ti and Mg, and even more preferably a coating agent including boron (B), tungsten (W) or a mixture thereof, and even more preferably a coating agent containing tungsten (W) and / or boron (B), and a specific example is a coating agent containing tungsten boride (WB), in which case there is an effect of improving resistance characteristics and life characteristics.

[0138] The above metal may include, for example, an oxide or acid containing a metal element as an element within a molecule.

[0139] The coating agent containing the above organic metal is not particularly limited as long as it is an organic metal commonly used as a coating agent in the technical field to which the present invention belongs, and a specific example thereof may be a metal alkoxide, etc.

[0140] The coating agent may be, for example, a coating solution prepared by mixing a metal, organometallic or carbon component with an appropriate solvent. The solvent is not particularly limited as long as it is a commonly used solvent, and a specific example thereof may be an aqueous solvent, more specifically, deionized water. The solid content ratio in the coating solution may be 20 wt% or less, preferably 1 to 15 wt%, and more preferably 2 to 10 wt%, relative to the total weight of the coating solution. In this case, the coating efficiency is excellent, and the subsequent milling process proceeds smoothly, so that the coating layer ultimately formed on the surface of the positive electrode active material particles is advantageously formed uniformly.

[0141] The method for applying the above coating agent to the recovered positive electrode active material (precursor) is not particularly limited as long as it is a coating method commonly used in the technical field to which the present invention belongs, and as a specific example, it may be appropriately selected from the group consisting of a liquid method in which a liquid coating agent is prepared and mixed with the positive electrode active material, a mechanochemical method using the high mechanical energy of ball milling, a fluidized bed coating method, a spray drying method, a precipitation method in which a coating agent is precipitated onto the surface of the positive electrode active material in an aqueous solution state, a method utilizing the reaction between a gaseous coating agent and the positive electrode active material, or a sputtering method.

[0142] The method for drying the positive electrode active material to which the above coating agent has been applied may preferably be a spray drying method, in which case the coating is uniformly formed, agglomeration of positive electrode active material particles is prevented, and the coating process is smoothly performed, resulting in excellent productivity.

[0143] The above spray drying is not particularly limited when performed using spray drying equipment commonly used in the technical field to which the present invention belongs, and for example, an ultrasonic spray drying device, an air nozzle spray drying device, an ultrasonic nozzle spray drying device, a filter expansion droplet generating device, or an electrostatic spray drying device may be used, and as a specific example, it may be performed using equipment such as PSD-05 (manufactured by Eugene Tech Co., Ltd.), but is not limited thereto.

[0144] In addition, the spraying pressure, the supply speed of the coating solution, etc. can be appropriately selected considering the amount of coating agent to be coated on the surface of the final regenerated positive electrode active material.

[0145]

[0146] After the spray drying, the temperature at which the positive electrode active material to which the coating agent is applied is fired under a reducing atmosphere may be 710 to 900°C, preferably 710 to 850°C, more preferably 710 to 800°C, and even more preferably 710 to 750°C. In this case, there is an advantage in that the coating agent is stably coated on the surface of the positive electrode active material while maintaining the inherent properties of the positive electrode active material. From Examples 1 and 2 described below, it can be confirmed that the firing process atmosphere and its temperature conditions are one variable that can restore the trivalent iron compound-free divalent structure and recover the active material in a single crystal state.

[0147] The interior of a regenerated positive electrode active material according to the present invention and a regenerated positive electrode active material not according to the present invention is schematically shown in Figure 1 below.

[0148] The following Figure 1 is a schematic diagram schematically showing the positive electrode active material regenerated in Example 2 according to the present invention and Comparative Examples 3 and 4 that do not. As shown in Comparative Example 4 on the right side of Figure 1, when heat treatment is performed under an oxidizing atmosphere and then firing treatment is not applied under a reducing atmosphere, a trivalent iron compound exists inside, and even when firing is performed under a reducing atmosphere, Comparative Example 3 in the middle of Figure 1, where the firing temperature conditions are inappropriate, also has some trivalent iron compounds that are not converted to divalent iron compounds remaining, but in Example 2 on the left side of Figure 1, where both the heat treatment conditions and the firing temperature conditions are according to the present invention, it is confirmed that no trivalent iron compounds exist and all are converted to divalent iron compounds.

[0149] The above-mentioned firing has the advantage that the heating rate to reach the above-mentioned firing temperature can be, for example, 1 to 20°C / min, preferably 1 to 10°C / min, and more preferably 2 to 7°C / min, and the desired firing effect can be sufficiently expressed within this range.

[0150] The above firing can be performed, for example, at the above firing temperature for 1 to 24 hours, preferably 1 to 16 hours, more preferably 3 to 16 hours, and has the advantage of sufficiently expressing the desired firing effect within this range.

[0151] The reducing atmosphere may be, for example, an argon (Ar) or nitrogen (N2) atmosphere. Preferably, the reducing atmosphere may have a nitrogen purity of 80% or more, preferably 90% or more, more preferably 90 to 99.8%, and even more preferably 95 to 99.8%. In this case, oxidation of the coating agent is prevented during the firing process, and a coating layer is stably formed on the surface of the positive electrode active material.

[0152] The purity % of the above nitrogen can be volume % or mol %.

[0153] The purity of the nitrogen of this invention is not particularly limited when measured by a measurement method commonly used in the technical field to which the present invention belongs.

[0154]

[0155] The amount of the coating layer formed on the surface of the above-described regenerated positive electrode active material particles may be, for example, 0.1 to 15 wt%, preferably 0.2 to 10 wt%, more preferably 0.5 to 5 wt%, even more preferably 0.7 to 3 wt%, and even more preferably 0.8 to 2 wt%, based on the total weight of the regenerated positive electrode active material including the weight of the coating layer, and there is an advantage in that the desired coating effect can be sufficiently expressed within this range.

[0156] The amount of the coating layer formed on the surface of the above-mentioned regenerative positive electrode active material particles can be measured by a method commonly practiced in the technical field to which the present invention pertains, and as a specific example, can be measured by quantitative analysis using thermogravimetric analysis (TGA) or a CS analyzer (Carbon / Sulfur Determinator).

[0157] The thickness of the coating layer coated on the surface of the above-described regenerative positive electrode active material particles can be appropriately controlled depending on the desired coating amount. In the present disclosure, the thickness of the coating layer can be measured by a method commonly practiced in the technical field to which the present invention pertains, and for example, the major diameters of 5 to 100 positive electrode active material particles observed using a transmission electron microscope (TEM) or a scanning electron microscope (SEM) can be measured and then the arithmetic average can be obtained.

[0158]

[0159] The above step (b) may include a pre-milling step, in which case, by controlling the particle size of the recovered positive electrode active material within a predetermined range before inputting it into a subsequent regeneration process, the particle size and particle size distribution of the finally obtained regenerated positive electrode active material are evenly controlled, and the particles are controlled in a state favorable for restoring the crystal structure of the positive electrode active material in the subsequent step, so that there is an advantage in that the battery characteristics are greatly improved.

[0160]

[0161] The above pre-milling can be performed using, for example, a ball mill, a high energy ball mill, a vibrating mill, or a roll mill, and is preferably performed using a ball mill. In this case, it is easy to control the particle size distribution of the regenerated positive electrode active material and the average particle diameter of the finally obtained regenerated positive electrode active material, and there is an advantage in that it is advantageous for restoring the crystal structure of the positive electrode active material in a subsequent step.

[0162]

[0163] The above pre-milling can be performed for, for example, 2 to 24 hours, preferably 2 to 20 hours, more preferably 5 to 16 hours, and has the advantage of suppressing the generation of fine particles within this range and smoothly controlling the particle size distribution of the regenerated positive electrode active material within a narrow range.

[0164]

[0165] The above pre-milling can be performed under conditions of, for example, 50 to 500 rpm, preferably 100 to 450 rpm, more preferably 150 to 420 rpm, even more preferably 180 to 410 rpm, still more preferably 200 to 400 rpm, and particularly more preferably 250 to 320 rpm, and in this case, there is an advantage in that the generation of fine particles can be suppressed, the crystal structure of the positive electrode active material can be maintained, and the desired effect can be sufficiently expressed.

[0166]

[0167] The average particle diameter (D) of the positive electrode active material powder obtained after the above pre-milling 50 ) may be 0.3 to 0.7 ㎛, preferably 0.3 to 0.65 ㎛, more preferably 0.35 to 0.65 ㎛, even more preferably 0.4 to 0.6 ㎛, and even more preferably 0.45 to 0.55 ㎛, and in this case, there is an advantageous advantage in that the particle size of the finally obtained regenerated positive electrode active material can be controlled within the desired range while suppressing the generation of fine particles and maintaining the crystal structure of the positive electrode active material.

[0168]

[0169] (c) Single crystal particle synthesis step

[0170] The method for regenerating a positive electrode active material of the present invention may include, for example, a step of (c) milling a positive electrode active material in which a three-phase iron compound-free two-phase structure has been restored, in which case agglomeration, particle breakage, and fine particle generation of the finally obtained regenerated positive electrode active material are prevented, and the particle size distribution is controlled to a narrow range, so that the positive electrode active material can be manufactured as a single crystal particle (single particle), thereby preventing degradation of battery performance due to fine particles and further improving the thermal stability and life characteristics of the battery. In addition, when the regenerated positive electrode active material is ultimately applied to the positive electrode of a secondary battery, there is an advantage in that it can provide good battery characteristics equivalent to or superior to those of a fresh positive electrode active material.

[0171]

[0172] The above single particle may be a particle composed of, for example, 30 or fewer nodules, preferably 1 to 20 nodules, more preferably 1 to 10 nodules, even more preferably 1 to 5 nodules, and most preferably 1 nodule. In this case, there is an effect of preventing degradation of battery performance during the electrode manufacturing process and providing a positive electrode active material with excellent battery thermal stability and lifespan characteristics.

[0173] In this description, a nodule refers to a particle unit body that constitutes a single particle, and may refer to a single crystal lacking a crystalline grain boundary, or a polycrystal in which no grain boundary exists in appearance when observed at a magnification of 5,000 to 20,000 times using a scanning electron microscope (SEM) or an electron backscatter diffraction pattern analyzer (EBSD).

[0174] In this description, the number of nodules means the average number of nodules of positive electrode active material particles, and a positive electrode including positive electrode active material is cut by an ion milling method, and a cross-sectional image in the thickness direction of the cut positive electrode is obtained using a scanning electron microscope (SEM), and then at least 30 particles are selected for each of the largest positive electrode active material particle and the smallest positive electrode active material particle in the cross-sectional image, and then the number of nodules in the cross-section of each positive electrode active material particle is measured through SEM image analysis, and the arithmetic mean is obtained.

[0175] In this description, a secondary particle means a particle that is an aggregate formed by the agglomeration of multiple single particles and contains more than 30 nodules.

[0176]

[0177] In the above step (c), the milling may be, for example, a jet mill, in which case, while preventing damage to the crystal structure of the positive electrode active material, the particle size and particle distribution of the finally obtained regenerated positive electrode active material can be precisely controlled within a narrow range, and further, the inflow of foreign substances that may occur during the milling process is prevented, thereby improving the purity of the regenerated positive electrode active material.

[0178] The above jet milling can be performed, for example, using air or an inert gas, at a temperature of -30°C to 30°C, preferably -20°C to 20°C, and a pressure of 0.8 to 10 bar. In this case, damage to the crystal structure of the positive electrode active material can be prevented, while the particle size and particle distribution of the final obtained regenerated positive electrode active material can be precisely controlled within a narrow range. In addition, the inflow of foreign substances that may occur during the milling process is prevented, thereby improving the purity of the regenerated positive electrode active material.

[0179] In particular, when jet milling is performed using an inert gas that does not react with the above-described regenerated cathode active material, it is preferable because it can prevent the regeneration of a trivalent iron compound by jet milling energy. The inert gas may be, for example, argon (Ar), nitrogen (N2), etc.

[0180] The jet milling can be performed for 5 minutes or less under conditions where the pressure of the feeding line is 2 to 8 bar, preferably 2.5 to 6 bar, more preferably 3 to 5 bar, and the pressure of the grinding line is 0.8 to 2 bar, preferably 0.9 to 1.5 bar, more preferably 1 to 1.3 bar, more specifically, within this range, it is advantageous in preventing damage to the crystal structure of the positive electrode active material, precisely controlling the particle size and particle distribution of the finally obtained regenerated positive electrode active material within a narrow range, and implementing a single particle structure.

[0181]

[0182] The average particle size (D) of the regenerated positive electrode active material finally recovered in the above step (c) 50 ) may be, for example, 0.6 to 3.0 ㎛, preferably 0.7 to 2.0 ㎛, more preferably 0.8 to 1.5 ㎛, even more preferably 0.9 to 1.2 ㎛, and even more preferably 0.955 to 1.255 ㎛, and in this case, there is an advantage in that excellent battery characteristics are exhibited.

[0183] In this paper, the average particle diameter (D) of the positive electrode active material 50 ) is not particularly limited if it is a measurement method commonly performed in the technical field to which the present invention belongs, and for example, it may be the average particle diameter based on the cumulative 50% of the particle diameter distribution measured using laser diffraction.

[0184]

[0185] The regenerated positive electrode active material recovered in the above step (c) may have a crystal size measured by XRD (X-Ray Diffraction) of, for example, 120 to 180 nm, preferably 125 to 170 nm, more preferably 130 to 167 nm, even more preferably 140 to 166 nm, and even more preferably 150 to 165 nm. In this case, there is an advantage that the structure of the regenerated positive electrode active material is restored to the structure of a fresh positive electrode active material, thereby providing good battery characteristics.

[0186] In addition, the final recovered regenerated positive electrode active material in the above step (c) has a cell volume of 291.00 to 291.12 Å as measured by XRD, for example. 3 may be, preferably 291.02 to 291.12 Å 3 , more preferably 291.15 to 291.11 Å 3 This can be done, and in this case, the regenerated cathode active material structure can be restored to its original state as a fresh cathode active material structure, which has the advantage of providing good battery characteristics.

[0187]

[0188] Regenerated cathode active material

[0189] The regenerated positive electrode active material of the present invention is characterized by being regenerated by the positive electrode active material regeneration method of the present invention, and in this case, it has an eco-friendly advantage and simultaneously synthesizes a single crystal structure, converts trivalent iron into divalent iron, so that no trivalent iron compound remains inside the regenerated positive electrode active material, and when it is applied as a positive electrode active material of a secondary battery, it has the advantage of excellent charge / discharge characteristics, cycle characteristics, and life characteristics of the battery, and excellent thermal stability, thereby improving high-temperature performance. In addition, because the regenerated positive electrode active material of the present invention can ultimately provide battery characteristics equivalent to or superior to those of a secondary battery using a fresh positive electrode active material, it has the advantage of being able to replace a fresh positive electrode active material.

[0190]

[0191] The above-mentioned regenerative positive electrode active material may be, for example, a compound represented by Chemical Formula 1, preferably a lithium iron phosphate (LFP)-based positive electrode active material, and more preferably may include LiFePO4 having an olivine structure, in which case it has the advantages of excellent high-temperature stability and lifespan characteristics and excellent economic efficiency.

[0192] [Chemical Formula 1]

[0193] Li 1-a M a Fe 1-b N b P 1-c X c O 4-d Y d

[0194] (In the above chemical formula 1, M includes at least one element selected from the group consisting of Nb, Al, Na, Ti, Zr, and K, N includes at least one element selected from the group consisting of Mo, V, Mn, Sm, Eu, Yb, Cu, Mg, Ni, and Co, X includes Si, Y includes at least one element selected from the group consisting of F, S, and N, and a, b, c, and d are 0≤a<1, 0≤b<1, 0≤c<1, and 0≤d<4, respectively.)

[0195] In the above chemical formula 1, it is preferable that a, b, c, and d are 0≤a≤0.5, 0≤b≤0.5, 0≤c≤0.5, and 0≤d≤0.1, respectively.

[0196]

[0197] The above-mentioned regenerative positive electrode active material has, for example, a crystal size of 120 to 180 nm as measured by XRD, and a cell volume of 291.00 to 291.12 Å as measured by XRD. 3It may be, preferably, a crystal size of 125 to 170 nm, more preferably 130 to 167 nm, even more preferably 140 to 166 nm, and even more preferably 150 to 165 nm, and a cell volume of 291.02 to 291.12 Å. 3 , more preferably 291.15 to 291.11 Å 3 This can be advantageous in that it can provide good battery characteristics.

[0198]

[0199] The above-mentioned regenerative positive electrode active material may preferably be a single particle in which no boundary layer is observed within the particle, more preferably a single particle composed only of a single crystal and not including secondary particles, and in this case, during the electrode manufacturing process, it is converted into a positive electrode active material containing only a divalent iron compound, thereby providing a positive electrode active material that does not cause a decrease in battery performance, has excellent life characteristics in a high-voltage environment, has high thermal stability, and generates little gas during charge and discharge.

[0200]

[0201] The above-mentioned regenerated positive electrode active material may include, for example, a positive electrode active material composed of 99 mol% or more or 100 mol% of a single crystal, preferably a compound represented by the above-mentioned chemical formula 1, more preferably a lithium iron phosphate compound, and in this case, by synthesizing single crystal particles during the positive electrode active material regeneration process, there is an effect of providing a regenerated positive electrode active material that does not cause a decrease in battery performance, has excellent life characteristics in a high-voltage environment, has high thermal stability, and has a low amount of gas generated during charge and discharge.

[0202]

[0203] The above-mentioned regenerated positive electrode active material may have a trivalent iron compound of less than 1 mol% or 0 mol% based on 100 mol% of the total of divalent and trivalent iron compounds as determined by XRD analysis or EPR (Electron Paramagnetic Resonance) analysis, and more preferably, it is 0 mol%. In this case, by synthesizing positive electrode active material particles containing only divalent iron compounds during the electrode manufacturing process, there is an effect of providing a regenerated positive electrode active material that does not cause a decrease in battery performance, has excellent life characteristics in a high-voltage environment, has high thermal stability, and has a low amount of gas generated during charge and discharge.

[0204] In the present invention, mole % may be referred to as volume % if necessary.

[0205]

[0206] The above-mentioned regenerative positive electrode active material may have a fluorine (F) content of, for example, 250 mg / kg or less, preferably 200 mg / kg or less, more preferably 10 to 200 mg / kg, and within this range, the particle strength is improved, thereby providing advantages in terms of excellent charging capacity, resistance characteristics, and capacity characteristics.

[0207] In this paper, the fluorine (F) content can be measured using an ICP analyzer, and at this time, it can be measured using a general ICP analyzer widely used in laboratories, but there is no deviation depending on the measuring device or method.

[0208]

[0209] The above-mentioned regenerated positive electrode active material may have, for example, an average crystal size of 50 to 500 nm, preferably 50 to 300 nm, and more preferably 50 to 200 nm, and within this range, the conductivity of the regenerated positive electrode active material is improved, thereby providing an advantage of extending the battery life.

[0210] In this paper, the average crystal size can be measured by XRD crystal analysis, and there is no deviation depending on the measuring device or method. Specifically, it can be obtained by placing 5 g of positive electrode active material particles in a holder, irradiating the particles with X-rays, and analyzing the resulting diffraction grating. At this time, the calculation method can be obtained from the half-width of the main peak or three or more peaks, and this can be regarded as the average crystal size of the primary particles of the positive electrode active material particles.

[0211] In addition, the regenerative positive electrode active material of the present invention includes a lithium iron phosphate compound coated with a coating agent containing carbon, and is characterized in that no peak of a trivalent iron compound appears in XRD analysis and EPR (Electron Paramagnetic Resonance) analysis, and in this case, there is an excellent effect in battery performance such as charge capacity, resistance characteristics, and capacity characteristics.

[0212]

[0213] secondary battery

[0214] The secondary battery of the present invention includes the above-described regenerated positive electrode active material, and in this case, by completely converting the trivalent iron compound within the regenerated positive electrode active material into a divalent iron compound and simultaneously implementing a single crystal structure, there is no deterioration in the performance of the battery, and there is an advantage of excellent life characteristics in a high-voltage environment, high thermal stability, and low gas generation due to charge and discharge.

[0215] The secondary battery of the present invention may include all of the contents of the above-described regenerative positive electrode active material and the regeneration method thereof. Therefore, redundant description thereof is omitted herein.

[0216] The method for manufacturing a secondary battery according to the present invention is not particularly limited if it is a method for manufacturing a lithium secondary battery commonly used in the technical field to which the present invention belongs.

[0217]

[0218] Hereinafter, preferred examples are presented to help understand the present invention, but the following examples are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and technical idea of ​​the present invention, and it is also natural that such changes and modifications fall within the scope of the appended patent claims.

[0219]

[0220] [Example]

[0221] Example 1

[0222] A waste cathode material having a cathode active material layer including an LFP cathode active material having an olivine structure, a binder, and a conductive material applied on an aluminum current collector was prepared by crushing cathode scrap remaining after cathode plate pressing into a size of 2 cm x 2 cm.

[0223] Next, the temperature was increased at a rate of 5°C / min under an oxygen atmosphere, and then the primary heat treatment was performed by heating at 390°C for 5 hours. At this time, 95% pure oxygen gas was supplied at 3 L / min. During this process, the binder in the waste positive electrode was thermally decomposed, and the positive electrode active material powder separated from the current collector was recovered.

[0224] After the first heat treatment, the heat supply was stopped, the recovered positive electrode active material powder was completely cooled to room temperature, and then heated again at a heating rate of 8 ℃ / min in an air atmosphere, and then heated at 580 ℃ for 5 hours to perform a second heat treatment. At this time, oxygen gas was supplied at a rate of 3 L / min.

[0225] After the above secondary heat treatment, the heat supply was stopped and the powder was cooled to room temperature, and then a coating composition (solvent water) was added to the recovered positive electrode active material (precursor) powder, in which sucrose was mixed with deionized water as a coating agent so that the carbon content was 4.4 parts by weight per 100 parts by weight of the positive electrode active material, and the powder was pre-milled using a ball mill at 300 rpm for 12 hours, and then the positive electrode active material to which the coating agent was applied was dried by spray drying. The average particle diameter (D) of the spray-dried positive electrode active material powder 50 ) was 0.5 μm.

[0226] The above spray-dried positive electrode active material was heated at a heating rate of 3°C / min in a furnace under a nitrogen atmosphere, and then fired at 800°C for 12 hours to form a carbon (C) coating layer on the surface of the positive electrode active material. At this time, the nitrogen supply rate during the firing was 3 L / min, and the CS analysis result after the firing was completed showed that the coating amount was 1.43 wt%.

[0227] The above-mentioned coated positive electrode active material was milled using a jet mill under an air atmosphere at a feeding line pressure of 4 bar and a grinding line pressure of 1 bar to obtain a regenerated positive electrode active material having a final particle size of 200 to 1500 nm.

[0228]

[0229] Example 2

[0230] A regenerated positive electrode active material was manufactured by repeating the same process as in Example 1, except that milling was performed under an inert (Ar) atmosphere using a jet mill at a feeding line pressure of 4 bar and a grinding line pressure of 1 bar.

[0231]

[0232] Comparative Example 1

[0233] Fresh LFP cathode active material, not recycled cathode active material, was used. The fresh LFP cathode active material was analyzed by ICP analysis and confirmed to be LFP (LiFePO4) cathode active material with an element ratio of Li / Fe: 1.06, Li / P: 1.00, and P / Fe: 1.06.

[0234]

[0235] Comparative Example 2

[0236] In the above Example 1, a regenerated positive electrode active material was manufactured in the same manner as in the above Example 1, except that the firing after spray drying was performed at 700°C.

[0237]

[0238] Comparative Example 3

[0239] In the above Example 2, a regenerated positive electrode active material was manufactured in the same manner as in the above Example 2, except that the firing after spray drying was performed at 600°C.

[0240]

[0241] Comparative Example 4

[0242] In the above Example 2, only the second heat treatment step was performed to manufacture a regenerated positive electrode active material.

[0243]

[0244] [Experimental Example I: TEM Analysis]

[0245] TEM analysis was performed on the regenerated or newly produced positive electrode active materials obtained in Examples 1 to 2 and Comparative Examples 1 to 4.

[0246] Specifically, scanning electron microscopy images of the positive electrode active material were obtained using a scanning electron microscope (TITAN G2 800-200) and are shown in FIG. 1 and FIG. 2 below.

[0247] The following drawing 1 is a drawing showing a TEM photograph of a regenerated or newly produced positive electrode active material in Example 1 and Comparative Examples 1 and 2 according to the present invention.

[0248] As shown in the following Figure 1, Example 1 and Comparative Example 2 appear similar when looking at the carbon coating layer and its interface, but as a result of confirming the spot structure (corresponding to a single-particle crystal structure) and the ring structure (corresponding to a multi-particle crystal structure) in the Electron Diffraction Pattern (EDP) drawing on the right, in Comparative Example 2, the ring structure, which is a single-particle crystal structure, and the spot structure, which is a multi-particle crystal structure, are clearly observed simultaneously, confirming the coexistence of single crystals and polycrystals, while in the case of Example 1, only the spot structure, which is a single-particle crystal structure, is observed, confirming that particles composed only of single crystals were manufactured.

[0249] From this, it was confirmed that a single particle regenerated positive electrode active material with a single crystal structure was synthesized according to the regeneration process of the present invention.

[0250]

[0251] [Experimental Example II: TEM Analysis]

[0252] TEM analysis was performed on the regenerated or newly produced positive electrode active materials obtained in Examples 1 to 2 and Comparative Examples 1 to 4.

[0253] Specifically, TEM images of the positive electrode active material were obtained using TEM (TITAN G2 800-20) equipment.

[0254] The following Figure 3 is a drawing comparing a TEM photograph and an Electron Diffraction Pattern (EDP) photograph of a positive electrode active material regenerated in Example 2 according to the present invention and a positive electrode active material regenerated in Comparative Example 3, and the following Figure 4 is a TEM photograph and a TEM-EDS mapping image of a positive electrode active material regenerated in Comparative Example 4.

[0255] As shown in Fig. 3 below, in Example 2 and Comparative Example 3, the reduction reaction of Fe3+ is properly performed and no grain boundary is observed, whereas in Comparative Example 4 of Fig. 4, in the regenerated positive electrode active material, a grain boundary is observed because trivalent iron compounds (Fe2O3 and Li3Fe2(PO4)3) exist within the particles.

[0256] It is inferred that the similarity between the images of Example 2 and Comparative Example 3 is due to the fact that a local foreign substance (iron trivalent compound) that is difficult to observe in a TEM image remains in Comparative Example 3.

[0257] Looking at the TEM-EDS mapping image of Comparative Example 4 in Fig. 4 below, it is observed that P element is present in large quantities on the inside and Fe is present in large quantities on the particle surface. Here, P indicates the presence of a trivalent iron compound Li3Fe2(PO4)3, and it is inferred that Fe on the surface is Fe2O3.

[0258] Therefore, since Comparative Example 4 did not go through a reduction calcination process, it mostly exists as an Fe oxide compound of a trivalent iron compound and shows a core / shell form, and according to the TEM-EDS mapping of Figure 3, both Example 2 and Comparative Example 3 show a shape in which P and Fe are mixed. This is inferred to be because most of the trivalent iron compounds (Li3Fe2(PO4)3 and Fe2O3) were reduced to the divalent iron compound LFP form.

[0259]

[0260] [Experimental Example III: XRD Analysis]

[0261] XRD analysis was performed on the regenerated or newly produced positive electrode active materials obtained in Examples 1 to 2 and Comparative Examples 1 to 4, and XRD graphs were obtained.

[0262] Specifically, the following Figure 5 is a drawing comparing the XRD graphs of the regenerated positive electrode active materials of Example 2 and Comparative Examples 3 to 4 according to the present invention.

[0263] As shown in Figure 5 below, in the case of Example 2 and Comparative Examples 3 to 4 according to the present invention, the reduction reaction of the trivalent iron compound to the divalent iron compound proceeded appropriately and an XRD graph consistent with the fresh LFP was obtained.

[0264] On the other hand, in the case of Comparative Example 4, it was confirmed that the reduction reaction of the trivalent iron compound to the divalent iron compound did not occur well, and thus Fe2O3 and Li3Fe2(PO4)3 were observed.

[0265]

[0266] [Experimental Example IV: XPS Analysis]

[0267] XPS analysis was performed on the regenerated or newly produced positive electrode active materials obtained in Examples 1 to 2 and Comparative Examples 1 to 4, and XPS graphs were obtained.

[0268] Specifically, the following Figure 6 is a drawing comparing the XPS graphs of the regenerated positive electrode active materials of Example 2 and Comparative Examples 3 to 4 according to the present invention. The XPS analysis is O 1s The differences were analyzed.

[0269] As shown in Figure 6 below, no difference could be found between the graphs of the reference (fresh LFP) and Comparative Example 3. This is understood to be because the oxygen element present in the positive electrode active material is located within the same crystal.

[0270] However, a shoulder is observed near 530 eV in Comparative Example 4. This is believed to be because, as seen in the EDP image of Fig. 3, Comparative Example 4 exists in a core / shell form in which the outside of the particle is in the form of Fe2O3 and a large amount of Li3Fe2(PO4)3 exists inside the particle.

[0271] As with the XRD of the above Figure 5, if a trivalent iron compound exists in the new positive electrode active material of Comparative Example 1 in trace amounts, it is not observed in XPS either, so the XPS analysis results of Example 2 and Comparative Example 3 are similar.

[0272]

[0273] [Experimental Example V: EPR Analysis]

[0274] EPR analysis was performed on the regenerated or newly produced positive electrode active materials obtained in Examples 1 to 2 and Comparative Examples 1 to 4, and EPR graphs were obtained.

[0275] Specifically, the following Figure 7 is a drawing comparing the EPR graphs of the regenerated positive electrode active materials of Example 2 and Comparative Examples 3 to 4 according to the present invention.

[0276] As shown in Figure 7 below, in the case of Comparative Example 4, peaks due to tertiary iron compounds present in Li3Fe2(PO4)3 and Fe2O3 were significantly observed.

[0277] However, in Example 2, the corresponding peak was not observed because all trivalent iron compounds were reduced and converted to divalent iron compounds.

[0278] In addition, unlike the above XRD and XPS results, EPR analysis showed that Comparative Example 3 also had a graph showing a different slope shape from Example 2. It is believed that this is because a trace amount of trivalent iron compound that was not observed in XRD and XPS remained in Comparative Example 3, resulting in a slope-shaped graph in EPR.

[0279] Through this, it was confirmed that, unlike Comparative Examples 3 and 4, in Example 2, the trivalent iron compound was completely converted and a regenerated positive electrode active material containing only a divalent iron compound was produced.

[0280]

[0281] [Experimental Example VI: CHC Cell Evaluation]

[0282] The electrochemical performance of the regenerated or newly produced positive electrode active materials obtained in Examples 1 to 2 and Comparative Examples 1 to 4 was measured through the following CHC cell evaluation.

[0283] * CHC cell evaluation: 97.5 wt% of recycled or newly produced positive electrode active material, 1 wt% of carbon black as a conductive agent, and 1.5 wt% of PVdF as a binder were weighed and mixed with LFP to make a slurry. This was coated on aluminum foil to manufacture a positive electrode, and then a cell (Coin Half Cell, CHC) was manufactured. The voltage was set to 3-4.3 V, and charge / discharge was performed at 0.1 C / 0.1 C. The electrochemical performance (charge capacity, discharge capacity, and efficiency) was evaluated under the conditions of ethylene carbonate (EC): ethyl methyl carbonate (EMC) = 3:7 (weight ratio) as an electrolyte and including other additives.

[0284]

[0285] The evaluation results are shown in Figures 8 and 9, respectively.

[0286] The following Figure 8 is a drawing comparing electrochemical performances such as rated voltage, energy capacity, CHC capacity retention rate, and 45°C life capacity of the regenerated or newly produced positive electrode active materials in Example 1 and Comparative Examples 1 and 2, and the following Figure 9 is a drawing comparing electrochemical performances such as energy capacity, CHC capacity retention rate, and the like of the regenerated or newly produced positive electrode active materials in Example 2 and Comparative Examples 3 and 4.

[0287]

[0288] As shown in the upper right drawing of FIG. 8 below, in the case of Example 1 indicated with blue ink, it was confirmed that the charge / discharge capacity was equivalent to or improved compared to the fresh positive electrode active material of Comparative Example 1 indicated with black ink and the regenerated positive electrode active material of Comparative Example 2 indicated with red ink.

[0289] As shown in FIG. 9 below, it was confirmed that Example 2, marked with blue ink, exhibited overall superior cell characteristics compared to Comparative Example 3, marked with black ink. In particular, as shown in the lower right drawing of FIG. 9, Example 2 was found to be significantly superior in high-temperature (45°C) life characteristics, but Comparative Example 4 exhibited significantly inferior cell characteristics to the extent that it was difficult to measure them.

Claims

1. (a) A step of recovering a positive electrode active material by heat-treating a waste positive electrode including a current collector and a positive electrode active material layer formed on the surface thereof under an oxidizing atmosphere; (b) a step of adding a coating agent to the recovered positive electrode active material and firing it under a reducing atmosphere to form a coating layer on the surface of the positive electrode active material, thereby converting the trivalent iron compound in the positive electrode active material into a divalent iron compound and converting the polycrystalline particles into a single-crystal positive electrode active material; and (c) a step of forming a coating layer and milling the positive electrode active material converted into a divalent iron compound to control the particle size of the positive electrode active material; characterized in that it includes; Method for regenerating positive electrode active material.

2. In paragraph 1, The step (a) above is characterized by including a step of performing a first heat treatment at 300 to 440°C under an oxidizing atmosphere; and a step of performing a second heat treatment at 500 to 650°C under an oxidizing atmosphere after the first heat treatment. Method for regenerating positive electrode active material.

3. In paragraph 1, In the above step (a), the first heat treatment is performed for 30 minutes to 10 hours, and the second heat treatment is performed for 30 minutes to 10 hours. Method for regenerating positive electrode active material.

4. In paragraph 1, The step (b) is characterized by including a step of adding a coating agent to the recovered positive electrode active material and pre-milling; a step of spray-drying the pre-milled positive electrode active material; and a step of calcining the spray-dried positive electrode active material at 710 to 900° C. under a reducing atmosphere. Method for regenerating positive electrode active material.

5. In paragraph 1 or paragraph 4, The coating agent is characterized in that it contains at least one of a metal, an organometallic or a carbon component. Method for regenerating positive electrode active material.

6. In paragraph 1 or paragraph 4, In the above step (b), the firing is characterized in that it is performed for 1 to 24 hours. Method for regenerating positive electrode active material.

7. In paragraph 4, The above pre-milling is characterized in that it is performed using a ball mill, a high-energy ball mill, a vibration mill or a roll mill. Method for regenerating positive electrode active material.

8. In paragraph 7, The above pre-milling is characterized in that it is performed for 2 to 24 hours at a stirring speed of 50 to 500 rpm. Method for regenerating positive electrode active material.

9. In paragraph 1, In the above step (c), milling is characterized in that it is performed using a jet mill. Method for regenerating positive electrode active material.

10. In paragraph 1, The above positive electrode active material is characterized by being represented by the following chemical formula 1. Method for regenerating positive electrode active material. [Chemical Formula 1] Li 1-a M a Fe 1-b N b P 1-c X c O 4-d Y d (In the above chemical formula 1, M includes at least one element selected from the group consisting of Nb, Al, Na, Ti, Zr, and K, N includes at least one element selected from the group consisting of Mo, V, Mn, Sm, Eu, Yb, Cu, Mg, Ni, and Co, X includes Si, Y includes at least one element selected from the group consisting of F, S, and N, and a, b, c, and d are 0≤a<1, 0≤b<1, 0≤c<1, and 0≤d<4, respectively.) 11. In paragraph 1, The above positive electrode active material is characterized in that it is composed of 99 mol% or more or 100 mol% of a single crystal. Method for regenerating positive electrode active material.

12. In paragraph 1, The above cathode active material is characterized in that the trivalent iron compound is less than 1 mol% or 0 mol% based on 100 mol% of the total of divalent and trivalent iron compounds based on XRD analysis or EPR (Electron Paramagnetic Resonance) analysis. Method for regenerating positive electrode active material.

13. A compound represented by the following chemical formula 1, characterized in that it is composed of 99 mol% or more or 100 mol% of a single crystal. Regenerated cathode active material. [Chemical Formula 1] Li 1-a M a Fe 1-b N b P 1-c X c O 4-d Y d (In the above chemical formula 1, M includes at least one element selected from the group consisting of Nb, Al, Na, Ti, Zr, and K, N includes at least one element selected from the group consisting of Mo, V, Mn, Sm, Eu, Yb, Cu, Mg, Ni, and Co, X includes Si, Y includes at least one element selected from the group consisting of F, S, and N, and a, b, c, and d are 0≤a≤0.5, 0≤b≤0.5, 0≤c≤0.5, and 0≤d≤0.1, respectively.) 14. Characterized in that it includes the regenerative positive electrode active material of Article 13. Secondary battery.

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