CN114830408A - Method for preparing regenerated positive active material using waste secondary battery - Google Patents
Method for preparing regenerated positive active material using waste secondary battery Download PDFInfo
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- CN114830408A CN114830408A CN202180003928.3A CN202180003928A CN114830408A CN 114830408 A CN114830408 A CN 114830408A CN 202180003928 A CN202180003928 A CN 202180003928A CN 114830408 A CN114830408 A CN 114830408A
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 85
- 239000002699 waste material Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 35
- 239000000126 substance Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 239000011148 porous material Substances 0.000 claims description 17
- -1 Li 2 CO 3 Inorganic materials 0.000 claims description 9
- 239000004020 conductor Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 claims description 5
- 229910013553 LiNO Inorganic materials 0.000 claims description 4
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000013543 active substance Substances 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 24
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 19
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- 239000010941 cobalt Substances 0.000 description 15
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- 229940044175 cobalt sulfate Drugs 0.000 description 2
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- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
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- 206010021143 Hypoxia Diseases 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
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- 239000003273 ketjen black Substances 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 239000010450 olivine Substances 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of a regenerated positive active substance, which comprises the following steps: (S1) forming Co on the positive electrode plate separated from the waste secondary battery by heat treatment x O y A step of matter; (S2) adding the solution to the generated Co x O y A step of mixing a substance containing lithium into the substance; (S3) a step of forming a regenerated positive electrode active material by heat-treating the mixed material in Co x O y Wherein x and y each have a value between 0 and 10.
Description
Technical Field
The present invention relates to a method for preparing a regenerated positive electrode active material using a waste secondary battery, and more particularly, to a method for preparing a regenerated positive electrode active material which can be regenerated at a high generation rate and can provide an efficiency similar to that of an original secondary battery.
Background
As the technical development and demand for mobile devices increase, the demand for secondary batteries as an energy source also increases sharply. Among such secondary batteries, lithium secondary batteries having high energy density and voltage characteristics, long cycle life and low self-discharge rate have been commercialized and are now widely used.
The positive active material of the lithium secondary battery uses lithium transition metal oxide, and lithium cobalt oxide (LiCoO) is mainly used as the lithium transition metal oxide 2 ) Lithium manganese oxide (LiMnO) 2 、LiMn 2 O 4 Etc.), lithium iron phosphate compound (LiFePO) 4 Etc.), lithium nickel oxide (LiNiO) 2 Etc.) and the like. However, the positive electrode active material of such a lithium secondary battery includes, for example: transition metals forming lithium cobalt oxide or NCM-based lithium oxide are very expensive, especially cobalt is a strategic metal, and supply and demand are of particular concern to countries in the world. In addition, such transition metals may cause environmental problems, and therefore, environmental regulations are also required.
A conventional method of recycling waste lithium secondary batteries is to selectively concentrate only waste positive electrode active materials through processes such as pulverization, magnetic separation, classification, and the like, and then leach cobalt through a sulfuric acid leaching method using hydrogen peroxide as a reducing agent. Then, in order to recover cobalt from the leaching solution, after a process of selectively separating and recovering cobalt by using oxalic acid and a process of adjusting a pH value and removing impurities, the waste lithium secondary battery is reused by preparing cobalt sulfate by using a solvent extraction method. However, such conventional reuse methods are limited to the use of Lithium Cobalt Oxide (LCO) in the waste positive electrode active material, and it is difficult to effectively leach lithium nickel cobalt manganese oxide (NCM) or lithium ion manganese oxide (LMO) for electric vehicles, which is a trend of increasing use, from the LCO only with sulfuric acid. In the conventional recycling method, when cobalt is produced from oxalic acid, cobalt sulfate is obtained by decomposing oxalic acid with carbon dioxide after baking, and then re-dissolving cobalt oxide in sulfuric acid, which is not a preferable method from the viewpoint of cost. In addition, in the conventional reuse method, an excessive amount of oxalic acid is added to selectively separate cobalt, thereby causing considerable difficulties in wastewater treatment.
As another prior art, there is a technology of leaching the aluminum-removed positive electrode active material powder with an acid, and then reusing it in the form of a hydroxide mixed with nickel, cobalt, and manganese or a single hydroxide by alkali precipitation. However, when the positive electrode active material regenerated in this manner is used as a precursor material for a secondary battery having a high added value, the content of impurities is high, and therefore, the positive electrode active material lacks its value as a complete material and has a substantial commercial value.
Therefore, the present inventors have recognized that it is urgently necessary to develop an effective method for regenerating a positive electrode active material of a secondary battery in order to solve the problems, and have completed the present invention.
[ Prior art documents ]
(patent document 1) Korean registered patent publication No. 10-2064668
(patent document 2) Japanese laid-open patent publication No. 1999-006020
Disclosure of Invention
Technical problem to be solved
The purpose of the present invention is to provide a method for producing a regenerated positive electrode active material that can be easily regenerated from a waste secondary battery, can ensure economical efficiency, and can provide excellent electrochemical characteristics.
The technical problems to be solved by the present invention are not limited to the above-mentioned technical problems, and other technical problems not yet mentioned may be clearly understood by those having ordinary knowledge in the art through the description of the present invention.
Technical scheme for solving technical problem
In order to achieve the object, the present invention provides a method for preparing a regenerated positive electrode active material using a waste secondary battery.
Next, a method for producing the regenerated positive electrode active material according to the present invention will be described in detail.
The preparation method of the regenerated positive active material comprises the following steps:
(S1): heat treating the positive electrode plate separated from the waste secondary battery to produce Co x O y A step of matter;
(S2): to the generated Co x O y A step of mixing a substance containing lithium into the substance;
(S3): and a step of subjecting the mixed substance to heat treatment to form a regenerated positive electrode active material.
In the Co x O y Wherein x and y each have a value between 0 and 10.
In the present invention, the positive electrode plate separated from the waste secondary battery of the (S1) step may include an active material, a conductive material, and a binder.
In the present invention, the heat treatment of the (S1) step may be performed under an inert gas or a reducing gas atmosphere.
In the present invention, the heat treatment of the (S1) step is performed at a temperature ranging from 510 ℃ to 750 ℃, and the positive electrode plate is reduced by the heat treatment performed in the (S1) step, thereby generating Co x O y A substance.
In the present invention, the Co generated in the (S1) step x O y Comprises from CoO, Co 2 O 3 And Co 3 O 4 1 or more selected from the group consisting of.
In the present invention, the Co generated in the (S1) step x O y The substance is CoO.
In the present invention, the Co generated in the (S1) step x O y The substance is formed as a porous structure.
In the present invention, the Co generated in the (S1) step x O y The substance comprises 0.001 to 10.0cm 3 Pores in the range of/g.
In the present invention, the Co generated in the (S1) step x O y The substance has a thickness of 0.3 to 50.0m 2 Specific surface area in g.
In the present invention, the lithium-containing substance mixed in the (S2) step includes: from LiOH, Li 2 CO 3 、LiNO 3 And Li 3 PO 4 1 or more selected from the group consisting of.
In the present invention, the lithium-containing substance mixed in the (S2) step is directed to the Co produced in the (S1) step x O y Co contained in the material is mixed in such a manner that the molar ratio of lithium to Co is 1.0 to 1.06.
In the present invention, the heat treatment of the (S3) step may be performed at a temperature ranging from 800 ℃ to 1,050 ℃.
In the present invention, the heat treatment of the (S3) step may be performed by dry heat treatment or wet heat treatment.
In addition, the present invention provides a regenerated positive electrode active material formed according to the foregoing preparation method.
All of the above-mentioned matters are equally applicable as long as they are not contradictory, with respect to the method for producing a regenerated positive electrode active material using the waste secondary battery and the regenerated positive electrode active material produced by this method.
Effects of the invention
The method for producing a regenerated positive electrode active material for a waste secondary battery according to the present invention can ensure economical efficiency and easily regenerate a positive electrode active material from a waste secondary battery, and can exhibit excellent impedance characteristics, conductivity characteristics, and capacity characteristics without degrading electrochemical performance of the positive electrode active material during regeneration.
The effects of the present invention are not limited to the above-mentioned effects, and other effects not yet mentioned can be clearly understood by those skilled in the art from the description of the claims.
Drawings
Fig. 1 is a block diagram roughly showing a method for producing a regenerated positive electrode active material using a waste secondary battery of the present invention.
Fig. 2 is a spectrum diagram of X-ray photoelectron spectroscopy (XPS) for analyzing components of the positive electrode plate that can be used in the method for producing a regenerated positive electrode active material according to the present invention.
FIG. 3 is a Scanning Electron Microscope (SEM) image showing the confirmation of pores formed in the CoO produced in example 1 of the present invention.
Fig. 4 is a view showing an X-ray diffraction (XRD) pattern of a material prepared by performing (S1) the process under (a) air and (b) argon atmosphere in the method for preparing a regenerated positive active material using a waste secondary battery according to the present invention.
Fig. 5 is a view showing an X-ray diffraction (XRD) pattern of a material prepared by performing the heat treatment of the step (S1) under the conditions of 500 c, 600 c and 700 c in the method for preparing a regenerated positive electrode active material using a waste secondary battery according to the present invention.
FIG. 6 shows X-ray diffraction patterns (XRD) of CoO produced in example 1 of the present invention and a regenerated positive electrode active material ((LCO)1) produced using the same.
Fig. 7 is a graph showing the evaluation of electrochemical properties using 3.0 to 4.3V for the regenerated positive active material and the common positive active material prepared according to the present invention.
Detailed Description
Terms used in the present specification are selected as much as possible from general terms that are currently widely used in consideration of functions of the present invention, but may be changed according to intentions or examples of a person skilled in the art who works in the field, the appearance of new technology, and the like. In addition, there may be terminology arbitrarily selected by the inventor in certain cases, and in such cases, the meanings thereof will be described in detail in the description part of the corresponding invention. Therefore, the terms used in the present invention are not defined solely by their names, but should be defined based on the meanings of the terms and the overall contents of the present invention.
Unless defined otherwise, all terms used herein include technical and scientific terms having the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms having the same meaning as defined in a general dictionary should be interpreted as having a meaning consistent with the context of the related art. Unless expressly defined otherwise herein, it is not intended to be construed in an idealized or overly formal sense.
Numerical ranges include the numbers defined within the range. All maximum numerical limitations given throughout this specification are to be understood as if any numerical limitation were explicitly recited, including all lower numerical limitations. All minimum numerical limitations given throughout this specification are to be understood as if any higher numerical limitations were expressly written, including all higher numerical limitations. All numerical limitations given throughout this specification are to be understood as if such limitations were expressly written herein, including all numerical ranges where such limitations are more pronounced than others.
Although the following examples of the present invention are described in detail, it is obvious that the present invention is not limited to the following examples.
The method for preparing the regenerated positive active material according to the present invention
The present invention provides a method for preparing a regenerated positive electrode active material including the following steps.
(S1) heat-treating the positive electrode plate separated from the waste secondary battery to produce Co x O y A step of matter;
(S2) adding the solution to the generated Co x O y A step of mixing a substance containing lithium into the substance;
(S3) a step of heat-treating the mixed substance to form a regenerated positive electrode active material.
In the Co x O y In (3), x and y may have values of 0 to 10, respectively.
The "positive electrode active material" is a main component that generates electricity by a chemical reaction in the secondary battery, and generally refers to an active material containing lithium oxide. If the positive electrode active material is used in the present invention, the positive electrode active material as a positive electrode active material containing lithium and cobalt may preferably be a lithium secondary battery composed of LCO (LiCoO) 2 )、LCA(LiCoAlO 2 )、LCM(LiCoMnO 2 ) And LCMA (LiCoMnAlO) 2 ) The positive electrode active material having a layered structure formed, LMO (LiMn) 2 O 4 ) Spinel-structured positive electrode active material and LFP (LiFePO) 4 ) The positive electrode active material may be 1 or more selected from the group consisting of olivine-structured positive electrode active materials, and preferably, may be 1 or more layered-structured positive electrode active materials selected from the group consisting of NCO, NCA, NCM, and NCMA.
The LCO is in the form of oxides of lithium and cobalt with a layered structure, and has the advantages of very high stability and very long lifetime.
The LCA is in the form of oxides of lithium, cobalt and aluminum with a layered structure, reduces the content of expensive cobalt, and has the advantages of easy industrial application and long service life.
The LCM is in the form of oxides of lithium, cobalt and manganese with a layered structure, reduces the content of expensive cobalt, and has the advantages of easy industrial application and high stability.
The LCMA is an oxide form of lithium, cobalt, manganese and aluminum with a layered structure, and can be said to be a combination of the LCA and the LCM, so that the advantages of the LCA and the LCM can be simultaneously embodied.
The LMO is in the form of spinel-structured oxides of lithium and manganese, has a very high stability and at the same time does not contain expensive cobalt, and therefore has the advantage of being very inexpensive on an economic level.
The LFP is an olivine structured material containing lithium, iron, phosphorus and oxygen, in contrast to the LCO (LiCoO) 2 )、LCA(LiCoMnO 2 )、LCM(LiCoMnO 2 ) And LMO (LiMn) 2 O 4 ) Compared with the prior art, the composite material has the highest stability and long service life, and can be used in various fields.
The (S1) step is to reduce the positive electrode plate separated from the waste secondary battery to heat-treat to generate Co x O y The step (2).
The positive electrode plate separated from the waste secondary battery used in the (S1) step includes: positive electrode active material, conductive material, binder, and the like. That is, the positive electrode plate separated from the waste secondary battery used in the (S1) step may be used as it is in a state of being used in the secondary battery (i.e., a state of being coated with an active material, a conductive material, a binder, etc., and then being re-pressed). When the heat treatment is performed in the (S1) step using such a positive electrode plate,since the conductive material and the binder substance are adhered to the positive electrode plate, Co can be generated x O y A substance.
The binder is a component for assisting the binding of the positive electrode active material to the conductive material, etc. and the current collector, and may be selected from the group consisting of Polyvinylidene fluoride (PVDF), Polyvinyl alcohol (pvvinyl alcohol, PVOH, PVA, PVAI), carboxymethyl Cellulose (CMC), starch, Hydroxypropyl Cellulose (HPMC), polyvinylpyrrolidone (polyvinylpyrrolidone), Polytetrafluoroethylene (PTFE), Polyethylene (PE), polypropylene (PP), Ethylene-Propylene-Diene terpolymer (Ethylene, Propylene, Non-conjugated Diene, Ethylene Propylene polymers, EPDM), styrene-butadiene rubber, fluorine rubber, and copolymers thereof, as long as 1 or more of them is used, but there is no limitation.
The conductive material is not particularly limited as long as it has conductivity without inducing chemical changes in the secondary battery. For example: graphite such as natural graphite or artificial graphite; carbon blacks such as carbon Black, acetylene Black, ketjen Black, channel Black, furnace Black, lamp Black and Summer Black (Summer Black); conductive fibers such as carbon fibers and metal fibers; metal powders such as carbon fluoride, aluminum, and nickel powders; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and conductive materials such as polystyrene (Polyphenylene) derivatives.
Preferably, the heat treatment of the (S1) step may be performed with the positive electrode plate at a temperature ranging from 510 ℃ to 750 ℃, and most preferably, may be performed at a temperature ranging from 550 ℃ to 660 ℃. If the heat treatment of the (S1) step is performed in a temperature range less than 510 ℃, it is possible to maintain the phase of the initial active material since sufficient reduction cannot be performed.
The (S1) step may be performed in an environment where the reduction reaction can be more easily performed due to oxygen deficiency. Preferably, it can be in an inert gas environment or reducingPerformed in a gaseous environment. More preferably, the reaction solution may be in argon (Ar) or nitrogen (N) 2 ) Carbon dioxide (CO) 2 ) Carbon monoxide (CO) or hydrogen (H) 2 ) And (4) executing under the environment. Most preferably, it can be performed under an argon or nitrogen atmosphere.
Co produced in the step (S1) x O y The substance comprises: from CoO, Co 2 O 3 And Co 3 O 4 1 or more selected from the group consisting of. Preferably, the Co generated in the (S1) step x O y The substance may be CoO.
For reference, the substance produced in the (S1) step in this specification, i.e., Co x O y Refers to the main species generated by heat treatment, and does not exclude the case where a small amount of other species is contained together with this species.
Co produced in the step (S1) x O y The substance may have a porous structure with pores formed therein. Preferably, Co x O y The substance comprises 0.001 to 10.0cm 3 Pores per gram.
The pores are formed by oxygen (O) during the reduction of the waste secondary battery 2 ) The pores increase the specific surface area of the positive electrode active material due to the elution of gas and lithium (Li) ions, and thus have an effect of improving the diffusion of lithium during the production of the regenerated LCO.
Further, Co produced in the step (S1) x O y The substance has a thickness of 0.3 to 50.0m 2 Specific surface area in g.
The step (S2) is as follows x O y A step of mixing with a lithium-containing substance, the lithium-containing substance mixed in the step (S2) including: from LiOH, Li 2 CO 3 、LiNO 3 And Li 3 PO 4 1 or more selected from the group consisting of. Preferably, it comprises: from Li 2 CO 3 、LiNO 3 And Li 3 PO 4 1 or more selected from the group consisting of. Most preferably, it comprises: from Li 2 CO 3 And Li 3 PO 4 Composition of1 or more selected from the group of (1).
The lithium-containing material mixed in the (S2) step is mixed in such a manner that lithium is opposed to Co produced in the (S1) step x O y The molar ratio of Co contained in (1.0) to (1.06) (Li/Co).
The heat treatment of the (S3) step may be performed at 800 to 1,050 ℃.
In addition, the heat treatment of the (S3) step may be performed by dry heat treatment performed by putting in an oven, a furnace, a pipe, or the like in a state where moisture is not present, or by wet heat treatment performed by hydrothermal treatment.
Advantages and features of the present invention and methods of accomplishing the same may be understood more readily by reference to the following detailed description of exemplary embodiments. However, the present invention is not limited to the following embodiments, and can be realized in various forms different from each other, and the following embodiments are only provided to make the explanation of the present invention more complete, and to enable a person having ordinary knowledge in the art to which the present invention pertains to more clearly understand the present invention.
Example 1 preparation of regenerated cathode active Material 1
After separating the positive electrode plate including the active material and the additive from the waste lithium secondary battery, the positive electrode plate was reduced by heat treatment at 600 ℃ in an atmosphere of argon (Ar), which is an inert gas, to prepare CoO having pores. Then, the resulting CoO was added at a ratio of 1.02:1 (Li) 2 CO 3 : CoO) by adding (mixing) Li 2 CO 3 Subsequently, heat treatment was performed at 850 ℃ at 158mAh/g, thereby preparing a regenerated positive electrode active material (LCO) 1.
Example 2 preparation of regenerated cathode active Material 2
Separating positive plate containing active material and additive from waste lithium secondary battery, and performing heat treatment reduction at 700 deg.C in inert gas argon (Ar) environment to obtain productA porous CoO. Then, the resulting CoO was mixed in a ratio of 1.04: 1 (Li) 2 CO 3 : CoO) by adding (mixing) Li 2 CO 3 Subsequently, heat treatment was performed at 850 ℃ at 158mAh/g, thereby preparing regenerated cathode active material (LCO) 2.
Experimental example 1 confirmation of separated Positive plate Components
In order to confirm the components contained in the positive electrode plate separated from the waste lithium secondary battery, the separated positive electrode plate was measured by X-ray photoelectron spectroscopy (XPS), and the measurement results are shown in fig. 2.
Referring to fig. 2, it can be confirmed that the positive electrode plate separated from the waste lithium secondary battery includes: lithium containing an active material, a binder (PVDF) as an additive, an electrolyte, and the like.
Experimental example 1 confirmation of pores on the surface of the CoO produced
1.1. Specific surface area Analyzer (Brunauer Emmett Teller, BET)
In order to confirm that the CoO having pores was formed by performing the heat treatment reduction after separating the positive electrode plate from the waste secondary battery according to the present invention at step (S1), the specific surface areas of the CoO prepared in example 1, the regenerated positive electrode active material (LCO)1, and the common positive electrode active material (LCO) were analyzed using a specific surface area analyzer (BET), and the results are shown in [ table 1 ].
[ Table 1]
Referring to the [ table 1], it was confirmed that, compared to the regenerated positive electrode active material 1 and the general positive electrode active material, the CoO generated in the (S1) step according to the present invention had pores formed therein, which had a denser pore size and a high specific surface area.
1.2. Scanning Electron Microscope (SEM)
In order to reduce the CoO formed with the pores in the step (S1) after the positive electrode plate is separated from the waste secondary battery according to the present invention, the CoO formed in example 1 was measured by a scanning electron microscope, and a pore formation image was confirmed, and the result is shown in fig. 3.
Referring to fig. 3, (a) when CoO produced in example 1 of the present invention was enlarged, (b) it was confirmed that pores were formed in the produced CoO, and (c) it was confirmed that pores were also formed in the cross section of the produced CoO. The air hole may be oxygen (O) during the reduction of the waste secondary battery 2 ) From the results of the elution of gas and lithium (Li) ions, it was confirmed that pores were formed in the CoO of the present invention on the whole of the inner and outer portions (surfaces).
Experimental example 2 comparison of Effect of Heat treatment according to step S1
2.1. Comparison of the atmosphere of the heat treatment gas according to the (S1) step
In the method for preparing a regenerated positive electrode active material according to the present invention, in order to compare the heat treatment environments (gas environments) according to the step (S1), comparative regenerated positive electrode active materials 1 to 3 were prepared by heat-treating the step (S1) at 500 ℃, 600 ℃ and 700 ℃ in an oxygen atmosphere through the above-mentioned examples 1 and 2 and comparative groups thereof, and the X-ray diffraction patterns were measured, and the results thereof are shown in fig. 4.
Referring to fig. 4, it was confirmed that (a) the comparative regenerated positive electrode active materials 1 to 3 heat-treated at 500 ℃ to 600 ℃ to 700 ℃ in an oxygen atmosphere had an X-ray diffraction pattern in which only the initial active material was present, regardless of the temperature range. On the contrary, (b) the regenerated positive electrode active materials 1 and 2 obtained by performing the step (S1) at 600 ℃ and 700 ℃ respectively in an argon atmosphere exhibited an X-ray diffraction pattern in which all the active materials were reduced and only the CoO-form cobalt oxide existed.
2.2. Comparing temperatures according to the step (S1)
In the method for preparing a regenerated positive electrode active material according to the present invention, in order to perform comparison according to the temperature range of the (S1) step, a comparative regenerated positive electrode active material 4 was prepared by the examples 1 and 2 and the comparative group thereof under the same conditions as the example 1 except that the heat treatment temperature of the (S1) step was changed to 500 ℃, and the X-ray diffraction pattern was measured, the result of which is shown in fig. 5.
Referring to fig. 5, it was confirmed that the comparative regenerated positive electrode active material 4 in which the step (S1) was performed at 500 ℃ had an X-ray diffraction pattern in which CoO coexisted with the active material regardless of the temperature range. In contrast, the regenerated positive electrode active materials 1 and 2 according to the present invention, in which the step (S1) was performed at 600 ℃ and 700 ℃, exhibited an X-ray diffraction pattern in which all of the active materials were reduced and only CoO existed.
From the results, it can be confirmed that, most preferably, in order to prepare pure CoO completely removing impurities through the (S1) step, the heat treatment of the (S1) step should be performed with the temperature limited within the range of 510 ℃ to 750 ℃ under an inert gas, i.e., argon atmosphere.
Experimental example 3 confirmation of regenerated cathode active material having layered structure
In order to confirm the structural characteristics of the regenerated positive electrode active material prepared according to the present invention, X-ray diffraction patterns were measured for CoO produced in example 1 and regenerated positive electrode active material (LCO)1 prepared using the CoO produced, and the results are shown in fig. 6.
Referring to fig. 6, it can be confirmed that the regenerated cathode active material (example 1) prepared using the porous CoO prepared according to the present invention has a layered structure.
Experimental example 3 evaluation of electrochemical Properties of regenerated Positive electrode active Material
In order to evaluate the electrochemical properties of the regenerated cathode active material prepared according to the present invention, the electrochemical properties were evaluated at 3.0 to 4.3V for a commonly used cathode active material (LCO), and the results thereof are shown in [ table 2] and fig. 7.
[ Table 2]
| Charging capacity (mAh/g) | Discharge capacity (mAh/g) | Efficiency (%) | |
| Common positive electrode active material | 164.2 | 159.6 | 97.2 |
| Regenerated positive electrode active material 1 | 163.9 | 158.7 | 96.8 |
| Regenerated positive electrode active material 2 | 163.3 | 157.7 | 96.6 |
Referring to table 2 and fig. 7, it was confirmed that the charge capacity, discharge capacity, efficiency, and the like of the common positive electrode active material, the regenerated positive electrode active material 1, and the regenerated positive electrode active material 2 have almost the same characteristics within the error range. From these results, it was confirmed that the regenerated positive electrode active material prepared according to the present invention can realize excellent electrochemical characteristics without deterioration in electrochemical performance.
It will be understood from the foregoing description that a person having ordinary skill in the art to which the present invention pertains may embody other embodiments without changing the technical spirit or essential features of the present invention. It will thus be seen that the embodiments set forth above are illustrative in all respects, and are not limiting.
Claims (14)
1. A method for producing a regenerated positive electrode active material, comprising:
(S1) forming Co on the positive electrode plate separated from the waste secondary battery by heat treatment x O y A step of matter;
(S2) adding the solution to the generated Co x O y A step of mixing a substance containing lithium into the substance;
(S3) a step of forming a regenerated positive electrode active material by heat-treating the mixed material,
in the Co x O y In (b), x and y each have a value between 0 and 10.
2. The method for producing a regenerated positive electrode active material according to claim 1,
the positive electrode plate separated from the waste secondary battery of the (S1) step includes: a positive electrode active material, a conductive material, and a binder.
3. The method for producing a regenerated positive electrode active material according to claim 1,
the step (S1) is performed under an inert gas or reducing gas atmosphere.
4. The method for producing a regenerated positive electrode active material according to claim 3,
the heat treatment of the (S1) step is performed at a temperature ranging from 510 ℃ to 750 ℃,
the positive electrode plate is reduced by the heat treatment performed in the (S1) step, thereby generating Co x O y A substance.
5. The method for producing a regenerated positive electrode active material according to claim 1,
co produced in the step (S1) x O y The substance comprises: from CoO, Co 2 O 3 And Co 3 O 4 Composition of1 or more selected from the group of (1).
6. The method for producing a regenerated positive electrode active material according to claim 5,
co produced in the step (S1) x O y The substance is CoO.
7. The method for producing a regenerated positive electrode active material according to claim 1,
co produced in the (S1) step x O y The substance is formed as a porous structure.
8. The method for producing a regenerated positive electrode active material according to claim 7,
co produced in the step (S1) x O y The material is 0.001-10.0 cm 3 The range of/g includes pores.
9. The method for producing a regenerated positive electrode active material according to claim 1,
co produced in the step (S1) x O y The substance has a thickness of 0.3 to 50.0m 2 Specific surface area in g.
10. The method for producing a regenerated positive electrode active material according to claim 1,
the lithium-containing material mixed in the step (S2) includes: from LiOH, Li 2 CO 3 、LiNO 3 And Li 3 PO 4 1 or more selected from the group consisting of.
11. The method for producing a regenerated positive electrode active material according to claim 1,
the lithium-containing materials mixed in the (S2) step are mixed by,
with respect to Co generated in the (S1) step x O y The molar ratio of lithium to Co contained in the substance is 1.0 to 1.06.
12. The method for producing a regenerated positive electrode active material according to claim 1,
the heat treatment of the (S3) step is performed at a temperature ranging from 800 ℃ to 1,050 ℃.
13. The method for producing a regenerated positive electrode active material according to claim 12,
the heat treatment of the (S3) step is performed using a dry heat treatment or a wet heat treatment.
14. A regenerated positive electrode active material characterized in that,
formed by the production method according to any one of claims 1 to 13.
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| PCT/KR2021/017681 WO2022114868A1 (en) | 2020-11-27 | 2021-11-26 | Method for manufacturing recycled positive electrode active material using waste secondary battery |
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| KR101992715B1 (en) * | 2017-01-25 | 2019-06-25 | 주식회사 엘지화학 | Method for recovering positive electrode active material from lithium secondary battery |
| KR102064668B1 (en) | 2018-04-24 | 2020-01-09 | (주)이엠티 | A Method of Recycling Material for Precursor of Anode Active Material, Precursor of Anode Active Material, Anode Active Material, Anode, and Lithium Ion Secondary Battery Using The Same |
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- 2021-11-26 WO PCT/KR2021/017681 patent/WO2022114868A1/en active Application Filing
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