KR100717389B1 - A valuable material recovery method of a scrapped Lithium ion battery - Google Patents
A valuable material recovery method of a scrapped Lithium ion battery Download PDFInfo
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- KR100717389B1 KR100717389B1 KR20050103486A KR20050103486A KR100717389B1 KR 100717389 B1 KR100717389 B1 KR 100717389B1 KR 20050103486 A KR20050103486 A KR 20050103486A KR 20050103486 A KR20050103486 A KR 20050103486A KR 100717389 B1 KR100717389 B1 KR 100717389B1
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- lithium ion
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 67
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000011084 recovery Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 title description 2
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 239000002699 waste material Substances 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002739 metals Chemical class 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 239000002893 slag Substances 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims 1
- 238000002844 melting Methods 0.000 abstract description 19
- 230000008018 melting Effects 0.000 abstract description 19
- 239000002994 raw material Substances 0.000 abstract description 11
- 238000004064 recycling Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 18
- 229910017052 cobalt Inorganic materials 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 229910000531 Co alloy Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- -1 graphite Chemical compound 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 206010011906 Death Diseases 0.000 description 1
- 229910003307 Ni-Cd Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 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
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/025—Obtaining nickel or cobalt by dry processes with formation of a matte or by matte refining or converting into nickel or cobalt, e.g. by the Oxford process
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- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
개시된 본 발명은 고온열처리방법 중 하나인 건식용융방식을 이용하여 부가가치가 높은 코발트, 리튬 등 폐리튬이온전지 및 리튬이온전지 제조공정의 스크랩내 포함된 유가금속을 농축하고 회수하여 재활용 할 수 있도록 한 폐리튬이온전지의 유가금속 회수방법에 관한 것으로, 폐리튬이온전지 및 리튬이온전지 제조공정 스크랩을 단순한 전처리(파쇄와 분쇄)공정을 통한후 SiO2, MgO, Al2O3 이 포함된 CaO계 용제와 혼합한 후 가열로에 장입시켜 1,300℃ ~ 1,700℃의 고온에서 용융처리하며, 상기 용융처리된 원료물질을 10-17atm 이상의 산소분압하에서 30분에서 3시간 동안 유지시킨 후 자연 냉각시켜 유가금속과 불순물이 분리 회수될 수 있도록 한 것을 구성의 요지로 한다.The present invention discloses a method for concentrating, recovering and recycling valuable metals contained in scraps of a lithium ion battery and a process of manufacturing lithium ion batteries having high added value by using a dry melting method, which is one of high temperature heat treatment methods. The present invention relates to a valuable metal recovery method of waste lithium ion battery, and to a method of recovering waste lithium ion battery and lithium ion battery through a simple pretreatment (crushing and crushing) process, including Ca 2 based on SiO 2 , MgO, and Al 2 O 3. After mixing with the solvent, it is charged into a heating furnace and melted at a high temperature of 1,300 ° C to 1,700 ° C. The molten raw material is kept at 30 minutes to 3 hours under an oxygen partial pressure of 10 -17 atm or higher, and then naturally cooled. The main point of the configuration is that metal and impurities can be separated and recovered.
폐리튬이온전지, 용융환원, 유가금속, 회수, 재활용 Waste Lithium Ion Battery, Melt Reduction, Valuable Metals, Recovery, Recycling
Description
도 1은 본 발명에 따른 리튬이온전지 유가금속 회수과정을 개략적으로 보인 흐름도.1 is a flow chart schematically showing a recovery process of a valuable metal lithium ion battery according to the present invention.
본 발명은 폐리튬이온전지를 재활용하기 위해 폐리튬이온전지 및 리튬이온전지의 처리 및 제조공정에서 발생한 물질로부터 유가금속을 농축하여 회수하는 방법에 관한 것으로, 이는 특히, 고온열처리방법 중 하나인 건식용융방식을 이용하여 부가가치가 높은 코발트, 리튬 등 전지내 포함된 유가금속을 농축하고 회수하여 재활용 할 수 있도록 한 리튬이온전지의 유가금속 회수방법에 관한 것이다.The present invention relates to a method for concentrating and recovering valuable metals from materials generated during the processing and manufacturing process of waste lithium ion batteries and lithium ion batteries to recycle waste lithium ion batteries. The present invention relates to a valuable metal recovery method of a lithium-ion battery, which enables to concentrate, recover, and recycle valuable metals contained in batteries such as cobalt and lithium having high added value using a melting method.
일반적으로 리튬전지(lithium battery)는, 높은 에너지 밀도와 경량의 특성을 지니고 있기 때문에 소형 휴대장비의 전력원으로 사용되고 있으며, 최근 들어 리튬이온전지의 사용량이 급증하고 있는 실정이다. 상기 리튬이온전지는, 양극과 음극, 유기전해질(organic electrolyte) 및 분리막(organic separator)으로 구성되 어 있으며, 양극활물질(active materials)로는 가역성(reversibility)이 우수하고, 낮은 자가방전율, 고용량, 고에너지밀도 및 합성이 용이한 리튬코발트 산화물이 상용화 되어 있다.In general, lithium batteries are used as power sources for small portable devices because they have high energy density and light weight characteristics, and the use of lithium ion batteries is increasing rapidly in recent years. The lithium ion battery is composed of a positive electrode and a negative electrode, an organic electrolyte (organic electrolyte) and an organic separator (organic separator), the positive active material (active material) is excellent in reversibility (reversibility), low self-discharge rate, high capacity, high Energy density and easy synthesis of lithium cobalt oxide is commercialized.
이와 같은 리튬이온 전지는 충전후 재사용이 가능한 고성능 2차 전지(Secondary Battery)로 분류할 수 있다. 특히 니카드(Ni-Cd), 니켈수소(Ni-MH), 리튬이온 전지와 같은 고성능 2차 전지는 5백회 이상 충, 방전이 가능하다. 양극, 음극, 전해질, 분리막 등으로 구성되어 있는 리튬이온 전지의 양극에는 LiCoO₂가, 음극에는 흑연 등 탄소가 주로 사용된다. 이들 전극 물질은 이온 상태의 리튬(Li+ , Li-Ion)이 내부에 가역적으로 이동을 용이하게 할 수 있는 구조를 가지고 있다. 즉 LiCoO₂의 내부에 위치하는 리튬이 빠져 나와 전해질을 따라 이동해 탄소 내부로 들어가는 현상이 리튬이온 전지에서는 충전에 해당되며, 그 반대 방향으로 이동은 방전에 해당된다. Such a lithium ion battery may be classified into a high performance secondary battery capable of being reused after being charged. In particular, high-performance secondary batteries such as Ni-Cd, Ni-MH, and lithium ion batteries can be charged and discharged more than 500 times. LiCoO2 is used for the positive electrode of a lithium ion battery composed of a positive electrode, a negative electrode, an electrolyte, a separator, and carbon, such as graphite, for the negative electrode. These electrode materials have a structure that allows lithium (Li +, Li-Ion) in an ionic state to be easily reversibly moved inside. In other words, lithium in LiCoO₂ escapes and moves along the electrolyte and enters carbon, which is a charge in a lithium ion battery, and movement in the opposite direction corresponds to discharge.
상기 리튬이온전지에 대해 구체적으로 설명하면, 현재까지 리튬코발트 산화물을 양극활물질로 사용하고 탄소류와 유기결합제가 혼합되어 전기집전 금속판인 알루미늄 판에 도포되는 양극; 음극활물질인 흑연(graphite)과 탄소류가 유기결합제와 혼합되어 전기집전 금속판인 구리판에 도포 되어있는 음극; 그리고 유기분리막과 리튬염(lithium salt)이 유기용매에 용해되어 있는 유기전해액으로서 단위전지(unit cell)를 구성하고, 1개에서 수 개의 단위전지가 조합되어 충전보호 집적회로칩(IC chip)과 함께 플라스틱으로 패키지(package)화 한 것이다. 상기와 같은 구성으로 이루어진 리튬이온전지는, 충방전이 가능하고, 비교적 긴 수명을 가지나 그 역시 수명이 충방전 500회 정도인 소모품이기 때문에 사용량의 증가와 함께 폐기량도 증가하고 있는 실정이며, 이러한 폐리튬 이온전지는 성상이 간단하고, 비교적 고가인 리튬과 코발트 등의 유가금속이 다량 함유되어 있어, 경제적인 가치가 있는 폐자원으로 인식되고 있다. The lithium ion battery will be described in detail. Up to now, lithium cobalt oxide is used as a positive electrode active material, and carbon and an organic binder are mixed to be coated on an aluminum plate which is an electrical current collecting plate; A cathode in which graphite and carbon, which are negative electrode active materials, are mixed with an organic binder and coated on a copper plate, which is an electrical current collecting plate; An organic electrolyte in which an organic separator and a lithium salt are dissolved in an organic solvent forms a unit cell, and one to several unit cells are combined to form a charge protection integrated circuit chip (IC chip) and It is packaged together with plastic. The lithium ion battery having the above configuration is a consumable that can be charged and discharged and has a relatively long lifespan, but also has a lifespan of about 500 charge / discharge cycles. Lithium ion batteries are recognized as waste resources of economic value because they are simple in appearance and contain a large amount of valuable metals such as lithium and cobalt which are relatively expensive.
따라서, 최근에는 인위적 또는 기술적으로 수명이 다한 리튬이온전지를 효과적으로 폐기 처리를 통한 환경오염 방지 및 화재,폭발성을 제거하는 동시에, 폐기 시 리튬이온전지에 포함된 부가가치가 높은 유가금속을 회수하여 재활용함으로써 자원을 효율적으로 이용할 수 있도록 리튬이온전지의 재활용기술에 대한 연구가 활발히 진행되고 있다.Therefore, in recent years, artificially or technically end-of-life lithium ion batteries are effectively disposed of to prevent environmental pollution, fire and explosiveness, and to recover and recycle valuable metals of high value contained in lithium ion batteries. In order to use resources efficiently, researches on recycling technology of lithium ion batteries are being actively conducted.
현재 일반적으로 알려진 폐리튬이온전지 처리방법은 전지를 해체하여 코발트를 회수하는 공정이 주된 공정으로 폐 리튬이온전지를 파쇄한 후 자력선별로 철 성분을 제거하고 공기분급 등으로 비금속성분, 구리호일과 알루미늄 호일을 각각 분리하여 코발트 성분이 농축된 파쇄산물을 대상으로 산 침출공정을 거쳐 침전법, 전해채취법, 용매추출법 등으로 코발트를 회수하는 공정으로 이루어져 있다. 이러한 공정은 물리적 분리방법과 습식 농축방법의 두가지 단계로 나눌 수 있는데, 물리적인 분리 시에 공정이 복잡하여 코발트(Co)의 손실 가능성이 높으며, 습식 농축공정은 일반적으로 저온공정으로 고순도화에 유리한 반면 대량 처리가 곤란하고 늦은 반응속도가 단점으로 지적되고 있다.The currently known method of waste lithium ion battery treatment is to disassemble the battery and recover the cobalt. The main process is to crush the waste lithium ion battery, remove iron components by magnetic lines, and classify nonmetals, copper foil and aluminum. The foils are separated from each other, and the cobalt is recovered by an acid leaching process with a cobalt component concentrated, followed by an precipitation method, an electrolytic extraction method, and a solvent extraction method. These processes can be divided into two stages: physical separation and wet concentration. The process is complicated at the time of physical separation, which leads to high loss of cobalt (Co), and wet concentration is generally low temperature, which is advantageous for high purity. On the other hand, mass processing is difficult and slow reaction speed is pointed out as a disadvantage.
본 발명은 상기와 같은 종래 기술 구조의 복잡성으로 야기되는 공정상의 문제점을 감안하여 이를 해결하고자 제안한 것으로, 폐리튬이온전지의 재활용에 있어 고온열처리방법 중 하나인 건식용융공정을 도입함으로써, 기존의 방법에 비해 공정이 간단하고, 처리속도가 빠르면서도 코발트 및 구리 등 부가가치가 높은 유가금속을 친환경일 뿐 만 아니라 공정적으로도 효율적으로 농축, 회수할 수 있는 폐리튬이온전지의 유가금속 회수방법을 제공하는 데에 그 목적이 있다.The present invention has been proposed to solve this problem in consideration of the process problems caused by the complexity of the prior art structure, by introducing a dry melting process which is one of the high temperature heat treatment method in the recycling of waste lithium ion battery, the existing method Compared with the simpler process, faster processing speed, and high value-added valuable metals such as cobalt and copper, it is not only eco-friendly but also efficiently recovers and recovers valuable metals from waste lithium ion batteries. Its purpose is to.
상기한 목적을 달성하기 위한 구체적인 수단으로서 본 발명은, 충전식 폐리튬이온전지 및 리튬이온전지 제조공정 스크랩으로부터 고가의 코발트와 구리 등의 유가금속과 불필요한 원소를 분리하여 유가 금속만을 농축하여 회수하는 건식용융정련공정에 있어서, 폐리튬이온전지 및 리튬이온전지 제조공정 스크랩을 단순한 전처리(파쇄와 분쇄)공정을 통한후 SiO2, MgO, Al2O3 이 포함된 CaO계 용제와 혼합한 후 가열로에 장입시켜 1,300℃ 이상의 고온에서 용융처리하며, 상기 용융처리된 원료물질을 10-17atm 이상의 산소분압하에서 30분에서 3시간 동안 유지시킨 후 자연 냉각시켜 유가금속과 불순물이 분리 회수될 수 있도록 한 것을 특징으로 하는 폐리튬이온전지의 유가금속 회수방법을 마련함에 의한다.As a specific means for achieving the above object, the present invention is a dry type to recover the valuable metals such as expensive cobalt and copper and unnecessary elements from the waste scrap lithium ion battery and the lithium ion battery scraps to concentrate and recover only the valuable metals. In the smelting and refining process, waste lithium ion battery and lithium ion battery manufacturing scraps are processed through a simple pretreatment (crushing and grinding) process, and then mixed with CaO solvents containing SiO 2 , MgO and Al 2 O 3 , followed by heating. The molten raw material was melted at a high temperature of 1,300 ° C. or higher, and the molten raw material was kept for 30 minutes to 3 hours at an oxygen partial pressure of 10 −17 atm or higher, and then naturally cooled to separate and recover valuable metals and impurities. By providing a valuable metal recovery method of the waste lithium ion battery, characterized in that.
여기에서, 상기 용제는 염기도(CaO와 SiO2의 비율)가 0.8 ~ 1.5 이내이며, MgO과 AL2O3가 용제의 총 중량대비 20%이내의 함량을 갖도록 정련제를 배합하여 사 용하는 것이 바람직하다.Here, the solvent has a basicity (ratio between CaO and SiO 2 ) of 0.8 to 1.5 or less, and MgO and AL 2 O 3 are preferably used in combination with a refining agent to have a content of less than 20% of the total weight of the solvent. Do.
그리고, 상기 용제는 슬래그비(최종슬래그 중량/금속중량)가 0.05 이상이 되도록 함량을 조절하여 혼합하는 것이 바람직하다.In addition, the solvent is preferably mixed by adjusting the content so that the slag ratio (final slag weight / metal weight) is 0.05 or more.
이하, 첨부도면에 의거하여 본 발명의 바람직한 실시예를 상세히 설명한다.Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
도 1은 본 발명에 따른 리튬이온전지 유가금속 회수과정을 개략적으로 보인 흐름도로서, 본 발명은 폐리튬이온전지 및 리튬이온전지 제조공정 스크랩을 단순한 전처리(파쇄와 분쇄)공정을 통한후 CaO계 용제와 혼합하여 가열로에 장입시킨 후 고온에서 용융처리하며, 용융처리된 원료물질을 10-17atm 이상의 산소분압하에서 일정시간 동안 유지시킨 후 자연 냉각시켜 유가금속과 불순물이 분리 회수될 수 있도록 한 것이다.
여기서, 상기 산소분압란 전체압력 분의 산소의 압력의 비를 의미하며, 상기 10-17atm이상의 산소분압은 진공상태에서의 전체 공기의 압력이 아닌, CO 가스의 전체 압력 중 산소가 차지하는 압력의 비를 의미한다. 또한, 상기 CO가스가 유입되는 가열로는 유도절류를 이용하여 온도를 올리는 것으로 탄소내화재를 사용하여 발열하며, 상기 CO가스를 렌스를 통하여 상기 가열로에 불어 넣어주면 상기 가열로의 전체적인 압력은 대기압인 1atm이 된다. 이때, 다음의 열역학적 반응을 통하여 일정한 온도에서의 산소 포텐셜이 발생한다. 이때, 다음의 열역학적 반응을 통하여 일정한 온도에서의 산소 포텐셜이 발생하게 된다.
상기 수식에서 Go는 반응이 일어날 때의 에너지 변화량이고, K는 평형상수, a는 활동도, p는 분압, R은 기체상수, T는 조업온도를 나타냅니다. 그러므로, C(s)의 활동도는 탄소내화재를 사용하였으므로 1이 되고, p CO는 CO 가스 1atm이므로 1이 된다. 따라서, 가열 온도인 1723K(1500oC)에서는 10-17atm의 평형산소분압이 존재하게 된다.
구체적으로 살펴보면, 도 1에 도시된 바와 같이 발명은 폐리튬이온전지 및 충전된 리튬이온전지 제조공정 스크랩의 경우에는 용융로에 장입하기 전에 전처리공정을 거쳐 완전 방전시킨다. 이는 용융과정에서 우려되는 전지의 폭발을 미연에 방지하기 위함이며, 방전방법으로는 충전전지를 소금물에 담그는 습식방전방법 또는 열처리 후 분쇄하는 건식방전방법 등 어느 것이나 적용 가능하다. 1 is a flow chart schematically showing a process of recovering a lithium-ion battery valuable metal according to the present invention, the present invention is a CaO-based solvent after a simple pre-treatment (crushing and grinding) process of the waste lithium ion battery and lithium ion battery manufacturing process scrap It is mixed with and charged into a furnace and melted at high temperature, and the melted raw material is kept under oxygen partial pressure of 10 -17 atm for a predetermined time and then naturally cooled to recover valuable metals and impurities separately. .
Here, the oxygen partial pressure means a ratio of the pressure of the oxygen of the total pressure, the oxygen partial pressure of 10 -17 atm or more is the ratio of the pressure occupied by the oxygen of the total pressure of the CO gas, not the pressure of the total air in a vacuum state. Means. In addition, the heating furnace in which the CO gas is introduced is heated to increase the temperature by using induction current, and generates heat using carbon refractory material, and when the CO gas is blown into the heating furnace through a lance, the overall pressure of the heating furnace is atmospheric pressure. It becomes 1atm which is. At this time, oxygen potential at a constant temperature is generated through the following thermodynamic reaction. At this time, the oxygen potential at a constant temperature is generated through the following thermodynamic reaction.
In the above formula, G o is the change in energy when the reaction takes place, K is the equilibrium constant, a is the activity, p is the partial pressure, R is the gas constant, and T is the operating temperature. Therefore, the activity of C (s) is 1 because carbon refractory material is used, and p CO is 1 since CO is 1 atm of CO gas. Therefore, at a heating temperature of 1723 K (1500 ° C.), an equilibrium oxygen partial pressure of 10 −17 atm exists.
Specifically, as shown in FIG. 1, the invention completely discharges the waste lithium ion battery and the charged lithium ion battery through a pretreatment process before charging to a melting furnace. This is to prevent the explosion of the battery that is concerned during the melting process, and the discharge method may be any of a wet discharge method of immersing a rechargeable battery in salt water, or a dry discharge method of grinding after heat treatment.
삭제delete
방전이 완료된 폐리튬이온전지 및 충전된 리튬이온전지제조공정스크랩과 미충전 리튬이온전지제조공정스크랩은 용융로에 장입시켜 고온용융처리하여 고가의 코발트와 구리를 분리 농축하게 되는데, 그 용융조건은 다음과 같다.Discharged lithium ion battery and charged lithium ion battery manufacturing process scrap and uncharged lithium ion battery manufacturing process scrap are charged into a melting furnace and hot melted to separate and concentrate expensive cobalt and copper. Same as
원료의 용융온도 저하 및 불순물 제거를 위해 원료와 함께 용융로에 투입되는 용제(flux)는 폐리튬이온전지 및 리튬이온전지제조공정스크랩에 다량 함입되어 있는 불순물인 알루미늄에 대한 제거효율이 높으면서 용융조업 온도에서 충분한 점성을 가지는 SiO2, MgO, Al2O3 등이 포함된 CaO계 슬래그를 사용한다. 바람직하게는, CaO 와 SiO2의 비율인 염기도(CaO/SiO2)가 0.8 ~ 1.5, MgO와 Al2O3가 용제의 총 중량대비 20%이내의 함량을 갖는 용제를 사용하는 것이 바람직하다. 상기 염기도가 0.8미만일 경우에는 높은 점성으로 인하여 조업안정성 떨어지며 염기도가 1.5 초과일 경우에는 융점이 높아져 역시 조업안정성이 떨어진다는 점을 감안하여 본 발명에서는 염기도를 0.8 ~ 1.5 범위로 한정한 것이며, MgO와 Al2O3가 용제의 총중량 대비 20%이상이 되면 슬래그 중 Al2O3의 포화가 되어 금속 중 알루미늄이 슬래그 중으로 정련되지 않으므로 이를 감안하여 MgO와 Al2O3가 용제의 총중량 대비 20%이내에 있도록 한 것이다.To reduce the melting temperature of the raw material and remove impurities, the flux injected into the melting furnace together with the raw material has a high removal efficiency for the aluminum, which is a large amount of impurities contained in the waste lithium ion battery and the lithium ion battery manufacturing process scrap, and the melting operation temperature. CaO-based slag containing SiO 2 , MgO, Al 2 O 3, etc. having sufficient viscosity at is used. Preferably, it is desirable that the CaO and SiO in a ratio of 2 basicity (CaO / SiO 2) is 0.8 ~ 1.5, MgO and Al 2 O 3 using a solvent having a content of less than 20% of the total weight of the solvent compared. When the basicity is less than 0.8, the operation stability is lowered due to the high viscosity, and when the basicity is higher than 1.5, the melting point is increased and the operation stability is also lowered, so that the basicity is limited to the range of 0.8 to 1.5 in the present invention. When Al 2 O 3 is more than 20% of the total weight of the solvent, Al 2 O 3 is saturated in the slag and aluminum is not refined in the slag. Therefore, MgO and Al 2 O 3 are within 20% of the total weight of the solvent. It would be.
상기 장입되는 용제의 양은 폐리튬이온전지의 불순물로 작용하는 Al, Fe, 망간, 탄소와 같은 불순원소의 제거효율과 조업 후 코발트 합금의 순도를 고려하여 용융 후 분리되는 코발트와 구리등의 금속중량과 발생되는 슬래그 중량과의 비율인 슬래그비에 의해 결정되는데, 본 발명에서는 슬래그비(슬래그 중량/금속중량)가 0.05이상이 되도록 조절한 상태에서 용제를 장입한다. 이 때, 금속과 슬래그의 슬래그비가 0.05미만이면 최소한의 반응조차 일어나지 않으므로 슬래그비가 최소한 0.05이상은 되어야 한다.The amount of the charged solvent is a metal weight such as cobalt and copper separated after melting in consideration of the removal efficiency of impurities such as Al, Fe, manganese, carbon, and the purity of the cobalt alloy after operation, which acts as an impurity of the waste lithium ion battery. It is determined by the slag ratio, which is a ratio of the generated slag weight, and in the present invention, the solvent is charged while the slag ratio (slag weight / metal weight) is adjusted to be 0.05 or more. At this time, if the slag ratio of the metal and slag is less than 0.05, the minimum reaction does not occur, so the slag ratio should be at least 0.05.
상기와 같이 폐리튬이온전지 등의 원료와 용제가 혼합된 혼합물은 용융로에 투입한 후 가열하여 용융시킨다. 이때, 용융온도가 너무 높으면 알루미늄 등 불순물제거 성능이 떨어지므로, 1,300℃이상의 온도 범위 내에서 용융을 실시하도록 한다. 또한, 폐리튬이온전지 등 원료의 용융시간, 그리고 최소한의 반응시간을 고려하여, 용융온도에서 1시간 이상을 유지하는 것이 바람직하다.As described above, a mixture of raw materials and a solvent such as a waste lithium ion battery is added to a melting furnace, and then heated and melted. At this time, if the melting temperature is too high, since the impurity removal performance such as aluminum is poor, it is to be carried out within the temperature range of 1,300 ℃ or more. In addition, in consideration of the melting time and the minimum reaction time of the raw materials such as waste lithium ion batteries, it is preferable to maintain at least one hour at the melting temperature.
마지막으로, 상기 용융처리된 원료물질을 10-17atm 이상의 산소분압하에서 일정시간 동안 유지시킨 후 자연상태에서 냉각시켜 유가금속을 포함한 슬래그 층과 불순물이 함유된 괴상 금속매트 층이 분리 형성되도록 한다.Finally, the molten raw material is maintained for 10 hours under an oxygen partial pressure of 10 -17 atm or more, and then cooled in a natural state so that a slag layer including valuable metals and a bulk metal mat layer containing impurities are formed.
여기에서, 알루미늄을 포함한 폐리튬이온전지 내 불순물의 슬래그를 통한 제거효율은 용융로 내 산소분압에 크게 영향을 받기 때문에, 용융로 내 산소분압이 증가할수록 불순물의 제거 및 코발트와 구리금속의 농축효과는 커지나, Al 정련을 위해 본 발명에서는 10-17 atm 이상을 유지할 것을 권장한다. Here, since the slag removal efficiency of impurities in the waste lithium ion battery including aluminum is greatly influenced by the oxygen partial pressure in the melting furnace, as the oxygen partial pressure in the melting furnace increases, the effect of removing impurities and the concentration of cobalt and copper metal increases. For the refining of Al, it is recommended to maintain more than 10 -17 atm in the present invention.
이하, 구체적인 실시예를 통하여 본 발명을 더욱 상세히 살펴본다.Hereinafter, the present invention will be described in more detail with reference to specific examples.
<실시예><Example>
먼저, 폐리튬이온전지 및 리튬이온전지 제조공정 스크랩을 습식방전방법 또는 열처리 후 분쇄하는 건식방전방법 등을 이용하여 방전시킨다. 본 발명에서 원료로 사용한 방전된 전지의 조성은 아래 <표 1>과 같다. First, the waste lithium ion battery and the lithium ion battery manufacturing process scraps are discharged using a wet discharge method or a dry discharge method that is pulverized after heat treatment. The composition of the discharged battery used as a raw material in the present invention is shown in Table 1 below.
다음으로, 코발트, 구리, 리튬, 철, 알루미늄 및 유기물이 함유되어 있는 전지를 SiO2, MgO 및 Al2O3가 포함되어 있는 CaO계 용제와 혼합한 다음, 1,300℃ 이상의 고온으로 가열한다. Next, a battery containing cobalt, copper, lithium, iron, aluminum, and organics is mixed with a CaO-based solvent containing SiO 2 , MgO, and Al 2 O 3 , and then heated to a high temperature of 1,300 ° C. or higher.
여기에서, 아래 <표 1>의 조성과 같은 폐리튬이온전지 및 리튬이온전지 제조공정 스크랩 1㎏과 0.05 이상의 SiO2, MgO 및 Al2O3가 포함되어 있는 CaO계 용제를 CaO 와 SiO2의 비율인 염기도(CaO/SiO2)가 0.8 ~ 1.5, MgO와 Al2O3이 20% 이내의 범위에서 적절히 조정하여, MgO 도가니에 장입하고 용융로에 넣은 다음, 1℃/분 이상의 가열 속도로 1,500℃까지 가열한 후, 10-17atm이상의 적절한 산소분압에서 30분에서 3시간 동안 유지한 후 자연 냉각하였다.Here, 1 kg of waste lithium ion battery and lithium ion battery manufacturing process scrap and the CaO-based solvent containing 0.05 or more of SiO 2 , MgO and Al 2 O 3 as shown in the following <Table 1> were selected from CaO and SiO 2 . The basicity (CaO / SiO 2 ), which is a ratio, is 0.8 to 1.5 and MgO and Al 2 O 3 are appropriately adjusted within 20%, charged into a MgO crucible, placed in a melting furnace, and then heated to 1,500 at a heating rate of 1 ° C./min or more. After heating to ℃, it was maintained for 30 minutes to 3 hours at an appropriate oxygen partial pressure of 10 -17 atm or more and then naturally cooled.
위와 같이 원료에 용제를 혼합한 상태에서 고온으로 가열하여 용융시키면, 코발트, 구리 등의 금속은 용융되어 용탕을 형성하게 되며, 폐리튬이온전지 및 리튬이온전지 내의 알루미늄, 철 등은 융점이 매우 높은 산화물의 형태로 용제에 흡수되지만, SiO2, MgO 및 Al2O3가 포함되어 있는 CaO계 용제와 혼합하여 혼합효과에 의한 낮은 융점의 산화물을 형성하게 된다. 이 때 알루미늄, 철 등의 산화물은 금속에 비해 비중이 낮기 때문에 용탕의 상부에 부유하게 된다. When heated and melted at a high temperature in a state in which a solvent is mixed with a raw material as described above, metals such as cobalt and copper are melted to form a molten metal, and aluminum and iron in waste lithium ion batteries and lithium ion batteries have a very high melting point. Although absorbed by the solvent in the form of an oxide, it is mixed with a CaO-based solvent containing SiO 2 , MgO and Al 2 O 3 to form an oxide having a low melting point due to the mixing effect. At this time, since the specific gravity is lower than that of the metal, oxides such as aluminum and iron are suspended above the molten metal.
따라서, 이러한 상태에서 용융된 코발트 및 구리 합금과 산화물 형태의 용제를 비중차를 이용하여 분리하여 냉각한다면 코발트 및 구리 합금의 금속상 괴상매트와 산화물상을 분리할 수 있다. Therefore, in this state, if the molten cobalt and copper alloys and the solvent in the form of oxides are separated and cooled by using a specific gravity difference, the metal bulk and the oxide phases of the cobalt and copper alloys may be separated.
냉각 후 상부는 SiO2, MgO 및 Al2O3가 포함되어 있는 CaO계 용제의 혼합물로 존재하였으며, 하부는 괴상 금속매트로 분리 용이한 상태가 되었다. After cooling, the upper part was present as a mixture of CaO-based solvents containing SiO 2 , MgO and Al 2 O 3 , and the lower part was easily separated by a bulk metal mat.
고온 처리에 의하여 폐리튬이온전지 및 리튬이온전지 제조공정 스크랩 내의 탄소류와 유기물류 및 리튬 그리고 알루미늄, 철과 같은 산화하기 용이한 원소들은 산화 제거 되었으므로 하부의 매트는 주로 코발트 및 구리의 합금이었다. Carbon and organic materials in the scrap manufacturing process of waste lithium-ion and lithium-ion batteries by high temperature treatment, and easily oxidized elements such as lithium, aluminum, and iron were oxidized and removed, so the bottom mat was mainly an alloy of cobalt and copper.
상기의 금속매트와 분말을 냉각한 후 각각의 화학성분을 분석하여 처리 전, 후의 성분을 아래 <표 1>에 나타내었다. After cooling the metal mat and powder, the respective chemical components were analyzed and the components before and after the treatment are shown in Table 1 below.
<표 1>TABLE 1
위 <표 1>을 통해서 알 수 있는 바와 같이, 괴상의 금속매트는 코발트와 구리의 성분이 각각 91.81%와 6.85%로 높은 코발트 성분비를 갖는 금속매트 형태로 분리됨을 알 수 있었다. 산화물의 주성분은 CaO, Al2O3, SiO2 이었다. As can be seen from Table 1, the bulk metal mat was found to be separated into a metal mat having a high cobalt component ratio of 91.81% and 6.85%, respectively. The main components of the oxide were CaO, Al 2 O 3 , and SiO 2 .
따라서, 상기와 같은 본 발명의 처리조건에 의하여 폐리튬이온전지 및 리튬이온전지 제조공정 스크랩으로부터 효과적으로 고가의 코발트 및 구리를 분리 농축하여 회수할 수 있었다. Therefore, expensive cobalt and copper were effectively separated and recovered from the waste lithium ion battery and the lithium ion battery scrap by the processing conditions of the present invention as described above.
이상에서 살펴본 바와 같이 본 발명에 적용된 폐리튬이온전지의 유가금속회 수방법에 의하면, 폐리튬이온전지 및 리튬이온전지 제조공정 스크랩의 재활용에 건식용융방식을 적용함으로써 기존의 습식 처리법 및 물리적 처리법에 비해 공정이 간단하면서도 고가의 코발트 및 구리 등의 유가금속의 회수율이 매우 높으며, 폐리튬이온전지 및 리튬이온전지 제조공정 스크랩의 재활용으로 인해 폐기시 유발되는 환경오염을 최소화 하였을 뿐 아니라, 제조공정의 단순화와 효율성 제고에 따른 처리공정 및 환경 비용원가를 고려한 경제적인 측면에서도 효과가 있다.As described above, according to the valuable metal recovery method of the waste lithium ion battery applied to the present invention, by applying the dry melting method to the recycling of the scrap lithium ion battery and the lithium ion battery manufacturing process scrap to the existing wet treatment method and physical treatment method Compared with the simpler process, the high recovery rate of valuable metal such as cobalt and copper is very high. In addition to minimizing the environmental pollution caused by waste due to the recycling of scrap lithium ion battery and lithium ion battery manufacturing process, It is also economically effective considering the cost of processing and environmental costs due to simplicity and efficiency.
이상에서 본 발명은 상기 언급된 바람직한 실시 예와 관련하여 설명되어졌지만, 발명의 요지와 범위로부터 벗어남이 없이 다양한 수정이나 변형을 하는 것이 가능하다. 따라서 첨부된 특허청구의 범위는 본 발명의 요지에서 속하는 이러한 수정이나 변형을 포함할 것이다.Although the present invention has been described above with reference to the above-mentioned preferred embodiments, it is possible to make various modifications or changes without departing from the spirit and scope of the invention. Accordingly, the appended claims will cover such modifications and variations as fall within the spirit of the invention.
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KR20200017627A (en) | 2018-08-09 | 2020-02-19 | 기주현 | Method for recovering base materials from waste battery |
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KR102641852B1 (en) | 2023-01-30 | 2024-02-27 | 주식회사 영풍 | Method for recovering lithium from lithium battery |
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---|---|---|---|---|
KR100860972B1 (en) * | 2008-01-30 | 2008-09-30 | 한국지질자원연구원 | Safe method for dismantling spent lithium-ion secondary batteries |
KR101328585B1 (en) * | 2012-04-06 | 2013-11-12 | 한국과학기술연구원 | Fabricating method of cathode for lithium ion secondary battery by recycling cathode active material and a lithium ion secondary battery fabricated thereby |
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JP7226403B2 (en) * | 2020-07-09 | 2023-02-21 | 住友金属鉱山株式会社 | Methods of recovering valuable metals |
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KR102554465B1 (en) * | 2021-12-21 | 2023-07-12 | 포스코홀딩스 주식회사 | Valuable metal recovery alloy, valuable metal recovery composition, and method of recovering valuable metal |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08316532A (en) * | 1995-05-19 | 1996-11-29 | Hitachi Chem Co Ltd | Cooling unit structure |
JPH10158751A (en) | 1996-11-27 | 1998-06-16 | Sumitomo Metal Mining Co Ltd | Method for recovering valuable metal from used lithium secondary battery |
JP2001040431A (en) | 1999-07-30 | 2001-02-13 | Nippon Mining & Metals Co Ltd | Method for recovering valuable matter |
KR20010090551A (en) * | 2000-03-24 | 2001-10-18 | 미야무라 심뻬이 | Process of recovering valuable metal |
-
2005
- 2005-10-31 KR KR20050103486A patent/KR100717389B1/en not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08316532A (en) * | 1995-05-19 | 1996-11-29 | Hitachi Chem Co Ltd | Cooling unit structure |
JPH10158751A (en) | 1996-11-27 | 1998-06-16 | Sumitomo Metal Mining Co Ltd | Method for recovering valuable metal from used lithium secondary battery |
JP2001040431A (en) | 1999-07-30 | 2001-02-13 | Nippon Mining & Metals Co Ltd | Method for recovering valuable matter |
KR20010090551A (en) * | 2000-03-24 | 2001-10-18 | 미야무라 심뻬이 | Process of recovering valuable metal |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20200017627A (en) | 2018-08-09 | 2020-02-19 | 기주현 | Method for recovering base materials from waste battery |
KR102639566B1 (en) | 2022-11-10 | 2024-02-23 | 주식회사 영풍 | Method for recovering lithium |
KR20240068591A (en) | 2022-11-10 | 2024-05-17 | 주식회사 영풍 | Method for recovering lithium |
KR102641852B1 (en) | 2023-01-30 | 2024-02-27 | 주식회사 영풍 | Method for recovering lithium from lithium battery |
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