KR20240048982A - Method for collecting LiCO3 from ceramic container having cathode material - Google Patents
Method for collecting LiCO3 from ceramic container having cathode material Download PDFInfo
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- ncm
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- cathode material
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- 239000000919 ceramic Substances 0.000 title claims abstract description 27
- 239000010406 cathode material Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000000843 powder Substances 0.000 claims abstract description 51
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 35
- 238000002386 leaching Methods 0.000 claims abstract description 31
- 238000010304 firing Methods 0.000 claims abstract description 29
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000002699 waste material Substances 0.000 claims abstract description 23
- 239000012153 distilled water Substances 0.000 claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 19
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000011572 manganese Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 9
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000010405 anode material Substances 0.000 claims abstract description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005191 phase separation Methods 0.000 abstract description 5
- 238000010306 acid treatment Methods 0.000 abstract description 4
- 239000013067 intermediate product Substances 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- 239000004568 cement Substances 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 3
- 230000008020 evaporation Effects 0.000 abstract description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910012573 LiSiO Inorganic materials 0.000 description 1
- -1 NiO Chemical class 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/22—Purification
-
- 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
-
- 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
Abstract
본 발명은 양극재 폐 세라믹 소성용기에서 탄산리튬 회수방법에 관한 것으로서, 양극재 폐 세라믹 소성용기로부터 수집한 Li(리튬), Ni(니켈), Co(코발트), Mn(망간)을 포함하는 NCM(NixMnxCox)계 분말을 열처리로 내에 장입한 상태에서, 열처리로로 CO2를 주입하면서 800℃ 이상의 열반응처리를 수행하여 NiO(산화니켈), CoO(산화코발트), MnO(산화망간)를 포함하는 유가금속 산화물상과 Li2CO3(탄산리튬) 으로 상분리하는 제1 단계 및 상분리된 NCM계 분말을 증류수를 이용한 수침출처리를 수행하여 액체상태의 Li2CO3과 고체상태의 유가금속 산화물 분말로 분리된 혼합물을 생성하는 제2 단계 및 수침출처리를 통해 생성된 혼합물을 감압여과기를 통해 감압여과하여 액체상태의 Li2CO3과 고체상태의 고체상태의 유가금속 산화물 분말을 분리 회수하는 제3 단계 및 분리된 액체상태의 Li2CO3을 증발농축기를 통해 105℃에서 2시간 건조하여 탄산리튬분말을 회수하는 제4 단계를 포함하여 이루어진다.
상기와 같은 본 발명에 의하면, 강산성의 용매를 사용하지 않고 열분해와 수침출을 이용하는 건식회수법을 통해 양극재 폐 세라믹 소성용기의 양극재인 NCM(NixCoxMnx)계 분말로부터 순도 높은 탄산리튬(Li2CO3)을 회수할 수 있으므로, 산 처리 공정 및 중간생성물의 수세공정에 요구되는 비용을 크게 절감할 수 있다.
또한, 본 발명은 NCM계 분말을 수집하고 남은 폐 세라믹 소성용기는 분쇄하여 시멘트 제조에 이용함으로써, 순환자원으로 활용이 가능하다.The present invention relates to a method for recovering lithium carbonate from a waste cathode material ceramic firing container. NCM containing Li (lithium), Ni (nickel), Co (cobalt), and Mn (manganese) collected from a waste anode material ceramic firing container. (NixMnxCox)-based powder is charged into the heat treatment furnace, and a heat reaction treatment of over 800°C is performed while injecting CO 2 into the heat treatment furnace to contain NiO (nickel oxide), CoO (cobalt oxide), and MnO (manganese oxide). The first step is phase separation into the valuable metal oxide phase and Li 2 CO 3 (lithium carbonate), and the phase-separated NCM-based powder is subjected to water leaching treatment using distilled water to produce Li 2 CO 3 in liquid state and valuable metal oxide in solid state. The second step of producing a mixture separated into powder and the mixture produced through water leaching treatment are filtered under reduced pressure through a reduced pressure filter to produce Li 2 CO 3 in liquid state and It includes a third step of separating and recovering valuable metal oxide powder in a solid state and a fourth step of recovering lithium carbonate powder by drying the separated liquid Li 2 CO 3 at 105°C for 2 hours through an evaporation concentrator. This is done.
According to the present invention as described above, high purity lithium carbonate (Li 2 CO 3 ) can be recovered, thereby significantly reducing the cost required for the acid treatment process and the water washing process of the intermediate product.
In addition, the present invention can be utilized as a circular resource by collecting NCM-based powder and crushing the remaining waste ceramic firing containers to manufacture cement.
Description
본 발명은에 탄산리튬 회수방법에 관한 것으로서, 보다 상세하게는 강산성의 용매를 사용하지 않고 열분해와 수침출을 이용하는 건식회수법을 통해 양극재 폐 세라믹 소성용기로부터 수집된 양극재인 NCM(NixCoxMnx)계 분말로부터 순도 높은 탄산리튬(Li2CO3)을 회수할 수 있는 방법에 관한 것이다.The present invention relates to a method for recovering lithium carbonate, and more specifically, to the NCM (NixCoxMnx) system, which is a cathode material collected from a waste cathode material ceramic firing vessel through a dry recovery method using thermal decomposition and water leaching without using a strongly acidic solvent. It relates to a method of recovering high purity lithium carbonate (Li 2 CO 3 ) from powder.
일반적으로 많이 사용되고 있는 층상구조의 양극재는 니켈(Ni), 망간(Mn), 코발트(Co)가 포함된 전구체 분말과 리튬(Li)이 혼합된 혼합분말을 소성하여 제조되며, 이러한 양극재는 리튬(Li), 니켈(Ni), 코발트(Co), 망간(Mn)을 포함하는 NCM계 분말로 이루어진다.Commonly used cathode materials with a layered structure are manufactured by firing a mixed powder of precursor powder containing nickel (Ni), manganese (Mn), and cobalt (Co) and lithium (Li), and these cathode materials are made of lithium ( It is made of NCM-based powder containing Li), nickel (Ni), cobalt (Co), and manganese (Mn).
또한, 위와 같은 양극재는 이차전지로 제조하기 위해서는 이를 수용할 수 있는 세라믹 소성용기가 요구되는데, 이러한 세라믹 소성용기는 알루미나(Al2O3) 함량이 70% 이상이면서 실리카 등이 함유된 코런덤(corundum), 뮬라이트(Mullite), 코디어라이트(Cordierite) 재질을 사용하고 있으며, 크기는 업체별 차이가 있으나 통상 330×330×75의 크기를 사용하고 있다.In addition, in order to manufacture the above cathode material into a secondary battery, a ceramic firing vessel that can accommodate it is required. Such a ceramic firing vessel is made of corundum (corundum) containing more than 70% of alumina (Al 2 O 3 ) and silica, etc. Corundum, Mullite, and Cordierite materials are used, and the size varies depending on the company, but the size is usually 330 × 330 × 75.
한편, 상기한 세라믹 소성용기는 이차전지의 제조를 위한 양극재의 소성과정에서 고온에 반복적으로 노출되면서 기계적, 열적 특성이 저하되고, 사용과정에서 NCM계 분말과의 반응으로 인한 표면 부식 및 박리로 인해 수명을 다하게 된다.Meanwhile, the mechanical and thermal properties of the ceramic firing container deteriorated as it was repeatedly exposed to high temperatures during the firing process of the cathode material for the production of secondary batteries, and surface corrosion and peeling occurred due to reaction with NCM-based powder during use. Life comes to an end.
이에 따라 수명이 다한 폐 세라믹 소성용기는 NCM계 분말로 이루어진 양극재와 함께 버려지게 되는데, 이러한 폐 세라믹 소성용기에는 리튬 포함 양극재 잔류량이 2~3%에 이르며, 특히, 산화알루미늄(Al2O3) 또는 산화규소(SiO2) 재질의 소성용기가 리튬원료(LiCO3, LiOH·H2O)와 반응하여 생성된 리튬화합물(LiALO2, LiSiO4 등)이 다량 축적되어 있다.Accordingly, waste ceramic firing containers that have reached the end of their life are discarded together with the anode material made of NCM-based powder. In these waste ceramic firing containers, the residual amount of anode material containing lithium reaches 2 to 3%, and in particular, aluminum oxide (Al 2 O 3 ) Or a firing container made of silicon oxide (SiO 2 ) reacts with lithium raw materials (LiCO 3 , LiOH·H 2 O), thereby accumulating a large amount of lithium compounds (LiALO 2 , LiSiO 4 , etc.).
이에 따라, 폐 세라믹 소성용기에는 회수 가능한 리튬원료(LiCO3, LiOH·H2O)가 1,500 톤, NCM(NixMnxCox)계 분말이 100 톤에 달하는 것으로 예상되나, 현재 전량 매립 폐기되므로 이에 대한 친환경적인 처리 방안 마련 및 재활용 기술 개발이 시급한 실정이다.Accordingly, the waste ceramic firing vessel is expected to contain 1,500 tons of recoverable lithium raw materials (LiCO 3 , LiOH·H 2 O) and 100 tons of NCM (NixMnxCox)-based powder. However, since all of this is currently landfilled and disposed of, it is environmentally friendly. There is an urgent need to prepare treatment methods and develop recycling technologies.
이러한 이유로 최근에는 양극재 폐 세라믹 소성용기로부터 수집된 양극재인 NCM계 분말을 수집하여 이로부터 리튬, 니켈, 코발트, 망간, 알루미늄 등과 같은 희유금속을 회수 및 고순도화하여 소재화하기 위한 노력이 시도되고 있다.For this reason, efforts have recently been made to collect NCM powder, which is a cathode material collected from waste cathode material ceramic firing containers, and recover and purify rare metals such as lithium, nickel, cobalt, manganese, aluminum, etc. into materials. there is.
널리 알려진 리튬 화합물 회수 방법으로는 질산, 황산, 염산 등의 강산을 사용하여 양극재인 NCM계 분말을 용해한 뒤 중화반응을 행하여 리튬과 기타 금속화합물을 분리 회수하는 방법이 있다.A widely known method for recovering lithium compounds is to use strong acids such as nitric acid, sulfuric acid, and hydrochloric acid to dissolve NCM-based powder, which is a cathode material, and then perform a neutralization reaction to separate and recover lithium and other metal compounds.
그러나, 상기와 같은 회수 방법은 비싼 약품을 사용하여야 하고, 산을 사용함으로써 발생되는 환경적인 문제를 해결하기 위해 추가로 산 처리 공정을 추가해야 함은 물론, 중간생성물이 다량 발생하여 불순물로 작용하기 때문에 다수의 수세공정이 요구되므로 비경제적이라는 문제점이 지적되고 있다.However, the above recovery method requires the use of expensive chemicals, requires the addition of an additional acid treatment process to solve environmental problems arising from the use of acid, and generates a large amount of intermediate products, which act as impurities. Therefore, a problem has been pointed out that it is uneconomical because multiple washing processes are required.
특히 리튬의 경우 향 후 수요가 공급을 넘어설 것으로 전망되기 때문에 양극재 폐 세라믹 소성용기와 함께 버려지는 양극재인 NCM계 분말로부터 리튬을 포함하는 유가금속의 회수는 더욱 절실히 요구되는 실정이다.In particular, in the case of lithium, since demand is expected to exceed supply in the future, recovery of valuable metals including lithium from NCM powder, which is a cathode material that is discarded along with waste cathode material ceramic firing containers, is more urgently required.
본 발명은 상기와 같은 문제점을 해결하기 위해 안출된 것으로서, 본 발명의 목적은 강산성의 용매를 사용하지 않고 열분해와 수침출을 이용하는 건식회수법을 통해 양극재 폐 세라믹 소성용기로부터 수집된 양극재인 NCM(NixCoxMnx)계 분말로부터 순도 높은 탄산리튬(Li2CO3)을 회수할 수 있는 방법을 제공함에 있다.The present invention was developed to solve the above problems, and the purpose of the present invention is to collect NCM, which is a cathode material collected from a waste cathode material ceramic firing container through a dry recovery method using thermal decomposition and water leaching without using a strongly acidic solvent. The aim is to provide a method for recovering high purity lithium carbonate (Li 2 CO 3 ) from (NixCoxMnx)-based powder.
상기 목적을 달성하기 위한 본 발명에 따르면, 양극재 폐 세라믹 소성용기로부터 수집한 Li(리튬), Ni(니켈), Co(코발트), Mn(망간)을 포함하는 NCM(NixMnxCox)계 분말을 열처리로 내에 장입한 상태에서, 열처리로로 CO2를 주입하면서 800℃ 이상의 열반응처리를 수행하여 NiO(산화니켈), CoO(산화코발트), MnO(산화망간)를 포함하는 유가금속 산화물상과 Li2CO3(탄산리튬) 으로 상분리하는 제1 단계 및 상분리된 NCM계 분말을 증류수를 이용한 수침출처리를 수행하여 액체상태의 Li2CO3과 고체상태의 유가금속 산화물 분말이 포함된 혼합물을 생성하는 제2 단계 및 수침출처리를 통해 생성된 혼합물을 감압여과기를 통해 감압여과하여 액체상태의 Li2CO3과 고체상태의 유가금속 산화물 분말을 분리 회수하는 제3 단계 및 분리된 액체상태의 Li2CO3을 증발농축기를 통해 105℃에서 2시간 건조하여 탄산리튬분말을 회수하는 제4 단계를 포함하는 것을 특징으로 하는 양극재 폐 세라믹 소성용기에서 탄산리튬 회수방법이 제공된다.According to the present invention to achieve the above object, NCM (NixMnxCox)-based powder containing Li (lithium), Ni (nickel), Co (cobalt), and Mn (manganese) collected from a waste cathode material ceramic firing container is heat treated. In the state of charging into the furnace, a heat reaction treatment of over 800°C is performed while injecting CO 2 into the heat treatment furnace to produce valuable metal oxide phases including NiO (nickel oxide), CoO (cobalt oxide), and MnO (manganese oxide) and Li. 2 The first step is phase separation into CO 3 (lithium carbonate) and the phase-separated NCM-based powder is subjected to water leaching treatment using distilled water to produce a mixture containing Li 2 CO 3 in liquid state and valuable metal oxide powder in solid state. The mixture produced through the second step and water leaching treatment is filtered under reduced pressure through a reduced pressure filter to produce Li 2 CO 3 in liquid state and A third step of separating and recovering solid valuable metal oxide powder and a fourth step of recovering lithium carbonate powder by drying the separated liquid Li 2 CO 3 at 105°C for 2 hours through an evaporation concentrator. A method for recovering lithium carbonate from a waste cathode material ceramic firing vessel is provided.
여기서, 상기 제2 단계에서 증류수와 NCM계 분말을 30:1의 중량비로 혼합하여 5시간 동안 수침출처리를 수행하는 것을 특징으로 한다.Here, in the second step, distilled water and NCM-based powder are mixed at a weight ratio of 30:1 and water leaching treatment is performed for 5 hours.
그리고, 상기 제2 단계에서 증류수의 온도는 0~60℃ 인 것을 특징으로 한다.And, in the second step, the temperature of distilled water is 0 to 60°C.
상기와 같은 본 발명에 의하면, 강산성의 용매를 사용하지 않고 열분해와 수침출을 이용하는 건식회수법을 통해 양극재 폐 소성용기로부터 수집된 양극재인 NCM(NixCoxMnx)계 분말로부터 순도 높은 탄산리튬(Li2CO3)을 회수할 수 있으므로, 산 처리 공정 및 중간생성물의 수세공정에 요구되는 비용을 크게 절감할 수 있다.According to the present invention as described above, high purity lithium carbonate (Li 2 Since CO 3 ) can be recovered, the costs required for the acid treatment process and the washing process of the intermediate product can be greatly reduced.
또한, 본 발명은 양극재인 NCM(NixCoxMnx)계 분말을 수집하고 남은 폐 세라믹 소성용기는 파쇄 및 분쇄하여 시멘트 제조에 이용함으로써, 순환자원으로 활용이 가능하다.In addition, the present invention collects NCM (NixCoxMnx)-based powder, which is a cathode material, and crushes and pulverizes the remaining waste ceramic firing containers to use them for cement production, making it possible to utilize them as circular resources.
도 1은 양극재 폐 세라믹 소성용기에서 탄산리튬 회수방법을 설명하기 위한 도면.
도 2는 건조 공정을 통해 회수된 분말의 XRD 분석 결과를 나타낸 도면.1 is a diagram illustrating a method of recovering lithium carbonate from a waste cathode material ceramic firing vessel.
Figure 2 is a diagram showing the results of XRD analysis of powder recovered through a drying process.
이하에서는 도면을 참조하여 본 발명을 보다 상세하게 설명한다. 도면들 중 동일한 구성요소들은 가능한 어느 곳에서든지 동일한 부호들로 나타내고 있음에 유의해야 한다. 또한 발명의 요지를 불필요하게 흐릴 수 있는 공지기능 및 구성에 대한 상세한 설명은 생략한다.Hereinafter, the present invention will be described in more detail with reference to the drawings. It should be noted that like elements in the drawings are represented by like symbols wherever possible. Additionally, detailed descriptions of known functions and configurations that may unnecessarily obscure the gist of the invention are omitted.
도 1은 양극재 폐 세라믹 소성용기에서 탄산리튬 회수방법을 설명하기 위한 도면이다.Figure 1 is a diagram for explaining a method of recovering lithium carbonate from a waste cathode material ceramic firing vessel.
도 1을 참조하면, 본 발명의 일 실시예에 따른 양극재 폐 세라믹 소성용기에서 탄산리튬 회수방법은 먼저 양극재 폐 세라믹 소성용기로부터 Li(리튬), Ni(니켈), Co(코발트), Mn(망간)을 포함하는 NCM(NixMnxCox)계 분말을 준비하였다.Referring to FIG. 1, the method of recovering lithium carbonate from a waste cathode material ceramic firing vessel according to an embodiment of the present invention first collects Li (lithium), Ni (nickel), Co (cobalt), and Mn from the waste cathode material ceramic firing vessel. NCM (NixMnxCox)-based powder containing (manganese) was prepared.
NCM계 분말은 양극재 폐 세라믹 소성용기에 표면에 묻어있는 있으므로 이를 별도의 도구를 이용하여 긁어냄으로써 얻을 수 있다.(S1)NCM-based powder can be obtained by scraping it off using a separate tool since it is stuck on the surface of the anode material waste ceramic firing container. (S1)
이어 열분해 반응을 이용하여 NCM계 분말을 Li2CO3(탄산리튬)과 유가금속의 산화물상인 NixMnyCozOxide 상분리하는 상분리 공정을 수행하였다.Next, a phase separation process was performed using a thermal decomposition reaction to separate the NCM-based powder into Li 2 CO 3 (lithium carbonate) and NixMnyCozOxide, an oxide phase of a valuable metal.
즉, NCM계 분말을 도가니에 수납하여 열처리로 내에 장입한 후, 열처리로 내부로 CO2가스를 주입하여 CO2 분위기를 형성한 상태에서 열처리로의 온도를 승온시키는 열분해 반응처리를 수행한다.That is, after the NCM-based powder is stored in a crucible and charged into the heat treatment furnace, CO 2 gas is injected into the heat treatment furnace to form a CO 2 atmosphere, and a thermal decomposition reaction treatment is performed to raise the temperature of the heat treatment furnace.
이 때, 열처리로는 외부와의 분위기가 완전히 차단되며 1000℃까지 승온 가능한 전기로를 사용한다. 그리고, 열처리로 내부는 CO2분위기로, CO2가스유량은 분당 300cc로 설정되고, 온도조건은 승온 및 감온을 10℃/min 단위로 수행하되, 기 설정된 상분리 온도에서 2시간 동안 유지한다. 여기서, 상분리 온도는 800℃ 이상으로 설정하는 것이 바람직하다.At this time, the heat treatment furnace uses an electric furnace that is completely blocked from the outside atmosphere and can raise the temperature up to 1000℃. In addition, the inside of the heat treatment furnace is set to a CO 2 atmosphere, the CO 2 gas flow rate is set to 300 cc per minute, and temperature conditions are such that temperature increase and decrease are performed in units of 10°C/min, and the preset phase separation temperature is maintained for 2 hours. Here, the phase separation temperature is preferably set to 800°C or higher.
열처리로에서의 CO2 반응 메카니즘은 하기 화학식1과 같다.The CO 2 reaction mechanism in the heat treatment furnace is shown in Chemical Formula 1 below.
<화학식 1><Formula 1>
여기서, (s)는 고체상태, (g)는 기체상태를 의미한다.Here, (s) means solid state and (g) means gaseous state.
즉, 화학식 1과 같이 NCM계 분말을 CO2 분위기의 열반응을 통해 상분리를 진행함으로써, LiCO3(탄산리튬)과 NiO(산화니켈), CoO(산화코발트), MnO(산화망간)의 유가금속 산화물상을 획득하였다.(S2)In other words, as shown in Chemical Formula 1, the NCM-based powder is phase separated through a thermal reaction in a CO 2 atmosphere, thereby producing valuable metals of LiCO 3 (lithium carbonate), NiO (nickel oxide), CoO (cobalt oxide), and MnO (manganese oxide). The oxide phase was obtained (S2).
이어, 상분리된 NCM계 분말을 증류수를 이용한 수침출처리를 수행하여 액체상태의 Li2CO3(탄산리튬)과 고체상태의 유가금속 산화물 분말이 포함된 혼합물을 생성하였다.Next, the phase-separated NCM-based powder was subjected to water leaching treatment using distilled water to produce a mixture containing liquid Li 2 CO 3 (lithium carbonate) and solid valuable metal oxide powder.
수침출은 Magnetic bar를 이용할 수 있고, 용매는 불순물이 들어있지 않는 증류수를 사용하며, 수침출 시간 및 분말과 증류수의 비율은 Li2CO3(탄산리튬)과 증류수와의 반응을 고려하여 최적 조건으로 설정될 수 있다. 이 때, 분말에 대한 증류수의 비율이 높을수록, 수침출 시간이 길수록 Li2CO3의 반응률이 높아진다.A magnetic bar can be used for water leaching, distilled water containing no impurities is used as the solvent, and the water leaching time and ratio of powder to distilled water are optimized considering the reaction between Li 2 CO 3 (lithium carbonate) and distilled water. It can be set to . At this time, the higher the ratio of distilled water to powder and the longer the water leaching time, the higher the reaction rate of Li 2 CO 3 .
이하에서 열반응에 의해 상분리된 NCM계 분말과 증류수의 비율을 1:10. 1:20. 1:30 의 중량비로 설정하여 각각 수침출을 진행하였으며, 수침출 시간은 1시간, 2시간, 3시간을 진행하였다.Below, the ratio of NCM-based powder phase-separated by thermal reaction and distilled water is 1:10. 1:20. Water leaching was performed at a weight ratio of 1:30, and the water leaching times were 1 hour, 2 hours, and 3 hours.
하기 표1는 NCM계 분말과 증류수 비율에 따른 수침출 후 혼합물 내 리튬 함량을 실험한 결과이고, 표2는 시간에 따른 수침출 후 혼합물 내 리튬 함량을 실험한 결과이며, 표3은 온도에 따른 수침출 후 혼합물 내 리튬 함량을 실험한 결과로서, ICP 분석법을 통해 분석하였다.Table 1 below shows the results of testing the lithium content in the mixture after water leaching according to the ratio of NCM powder and distilled water, Table 2 shows the results of testing the lithium content in the mixture after water leaching according to time, and Table 3 shows the results of testing according to temperature. The lithium content in the mixture after water leaching was tested and analyzed using ICP analysis.
시간 : 1hr
1:10(분말:증류수)
시료량 : 10g
Time: 1hr
1:10 (powder:distilled water)
Sample amount: 10g
표1은 수침출 시간을 1시간으로 고정하여 실험한 결과로서, NCM계 분말과 증류수의 비율을 1:10으로 했을 때의 혼합물 내 리튬 함량은 2333ppm, 1:20의 경우 혼합물 내 리튬 함량은 2340ppm, 1:30의 경우 혼합물 내 리튬 함량은 2349ppm으로 증류수의 양이 증가할수록 리튬이 더 많이 침출되는 것을 확인할 수 있었다.Table 1 shows the results of an experiment with the water leaching time fixed at 1 hour. When the ratio of NCM powder and distilled water is 1:10, the lithium content in the mixture is 2333ppm, and at 1:20, the lithium content in the mixture is 2340ppm. , In the case of 1:30, the lithium content in the mixture was 2349 ppm, confirming that as the amount of distilled water increases, more lithium is leached.
그리고, 표2는 NCM계 분말과 증류수의 비율을 1:30으로 고정하여 실험한 결과로서, 1hr 수침출 시 혼합물 내 리튬 함량은 2321ppm, 3hr 수침출시 혼합물 내 리튬 함량은 2348ppm, 5hr 수침출시 혼합물 내 리튬 함량은 2366ppm으로 수 침출시간이 증가할수록 리튬이 더 많이 침출되는 것을 확인할 수 있었다.Table 2 shows the results of an experiment with the ratio of NCM powder and distilled water fixed at 1:30. The lithium content in the mixture after 1 hour water leaching was 2321 ppm, the lithium content in the mixture after 3 hours water leaching was 2348 ppm, and the lithium content in the mixture after 5 hours water leaching was 2321 ppm. The lithium content was 2366ppm, confirming that as water leaching time increases, more lithium is leached.
또한, 표3은 NCM계 분말 10g에 대해 NCM계 분말과 증류수의 비율을 1:10으로 고정하고, 수침출 시간을 1시간으로 고정하여 실험한 결과로서, 0℃의 경우 혼합물 내 리튬 함량은 2700pm, 20℃의 경우 혼합물 내 리튬 함량은 2400ppm, 40℃의 경우 혼합물 내 리튬 함량은 2400ppm, 60℃의 경우 혼합물 내 리튬 함량은 1800ppm, 80℃의 경우 혼합물 내 리튬 함량은 500ppm으로 수 침출 온도가 증가할 수록 침출되는 리튬의 양이 감소하는 것을 확인할 수 있었다.In addition, Table 3 shows the results of an experiment in which the ratio of NCM-based powder and distilled water was fixed at 1:10 for 10 g of NCM-based powder, and the water leaching time was fixed at 1 hour. At 0°C, the lithium content in the mixture was 2700 pm. , at 20℃, the lithium content in the mixture is 2400ppm, at 40℃, the lithium content in the mixture is 2400ppm, at 60℃, the lithium content in the mixture is 1800ppm, and at 80℃, the lithium content in the mixture is 500ppm, increasing the water leaching temperature. It was confirmed that the amount of lithium leached decreased as time went on.
특히, 80℃의 경우는 침출되는 리튬의 양이 현저한 폭으로 감소하는 것으로 나타났다.In particular, at 80°C, the amount of lithium leached was found to decrease significantly.
따라서, NCM계 분말과 증류수의 비율은 1:30, 수침출 시간은 5hr, 수침출 온도는 0~60℃로 설정하는 것이 가장 효율적인 것을 확인할 수 있었다.Therefore, it was confirmed that it was most efficient to set the ratio of NCM-based powder to distilled water at 1:30, water leaching time at 5 hr, and water leaching temperature at 0 to 60°C.
한편, 본 발명에서 수침출은 물에 용해되는 Li2CO3과 물에 용해되지 않는 유가금속 산화물인 NiO, CoO, MnO의 용해도 차이로 분리되는 원리를 이용한다.Meanwhile, water leaching in the present invention uses the principle of separating water-soluble Li 2 CO 3 and water-insoluble valuable metal oxides such as NiO, CoO, and MnO.
즉, 용해도를 갖는 Li2CO3은 물에 녹아 액체상태로 변화되는 반면, 용해도가 없는 유가금속 산화물은 고체(분말)상태로 그대로 남아있게 된다.In other words, Li 2 CO 3 with solubility dissolves in water and changes into a liquid state, while the valuable metal oxide without solubility remains in a solid (powder) state.
Li2CO3이 물(증류수)에 녹을 때의 반응식은 하기 화학식 2와 같다.The reaction equation when Li 2 CO 3 is dissolved in water (distilled water) is as shown in Chemical Formula 2 below.
<화학식 2><Formula 2>
여기서, (s)는 고체상태, (aq)는 액체상태를 의미한다.(S3)Here, (s) means solid state and (aq) means liquid state. (S3)
이어, 수침출 처리를 통해 생성된 혼합물을 감압 여과기를 통해 감압 여과하여 액체상태의 Li2CO3과 고체상태의 유가금속 산화물 분말을 분리 회수한다.Next, the mixture produced through the water leaching treatment is filtered under reduced pressure through a vacuum filter to separate and recover the liquid Li 2 CO 3 and the solid valuable metal oxide powder.
위와 같이 감압 여과를 실시하는 이유는, 일반 여과를 실시하는 경우, 여과가 거의 진행되지 않을 뿐 아니라, Fe, Cu, Al 등과 같은 Ni, Co, Mn 이외의 다른 유가금속 산화물 분말이 거름종이와 여과기 사이의 틈을 통과하여 들어가 여과되는 Li2CO3의 순도를 낮추는 현상이 발생할 수 있기 때문이다.The reason for performing reduced-pressure filtration as described above is that when general filtration is performed, not only does filtration hardly proceed, but also other valuable metal oxide powders other than Ni, Co, and Mn, such as Fe, Cu, and Al, are deposited on the filter paper and filter. This is because a phenomenon may occur that lowers the purity of Li 2 CO 3 that passes through the gap and is filtered.
이를 고려하여 본 발명에서는 의 순도를 높이기 위해 다른 유가 금속 산화물 분말이 여과되지 않도록 감압 여과기의 적절한 감압 압력조건을 설정하여 감압여과를 수행할 수 있다.(S4)Considering this, in the present invention, in order to increase the purity of , reduced pressure filtration can be performed by setting appropriate reduced pressure conditions of the reduced pressure filter so that other valuable metal oxide powders are not filtered. (S4)
이어, 액체상태의 Li2CO3을 분말상으로 회수하기 위하여 증발농축기를 사용하여 물을 증발시킨 후, 105℃에서 2시간 동안 건조하여 탄산리튬 분말을 회수하였다.Next, in order to recover liquid Li 2 CO 3 in powder form, water was evaporated using an evaporation concentrator, and then dried at 105°C for 2 hours to recover lithium carbonate powder.
도 2는 건조 공정을 통해 회수된 탄산리튬 분말의 XRD 분석 결과를 나타낸 것으로서, XRD 분석 결과 대부분의 상이 Li2CO3상으로 나타난 바, Li2CO3이 분말상으로 회수된 것을 확인할 수 있었다. Figure 2 shows the results of an
또한, 하기 표4는 건조 공정을 통해 회수된 탄산리튬 분말을 순도를 분석한 결과로서, ICP 분석법을 통해 분석하였다.In addition, Table 4 below shows the results of analyzing the purity of lithium carbonate powder recovered through the drying process, which was analyzed using ICP analysis.
(wt%)Ca
(wt%)
(wt%)Mg
(wt%)
(wt%)P
(wt%)
(wt%)Zn
(wt%)
(wt%)Na
(wt%)
(wt%)K
(wt%)
(wt%)S
(wt%)
총량impurities
total amount
건조공정을 통해 회수된 탄산리튬 분말의 순도 분석 결과, 표 4에서 보는 바와 같이, 탄산리튬 이외의 Ca, Mg, P, Zn, Na, K, S를 포함하는 불순물 총량이 0.587로 나타나, 회수된 탄산리튬의 순도가 99.41로 매우 높은 것을 확인할 수 있었다.(S5)As a result of purity analysis of the lithium carbonate powder recovered through the drying process, as shown in Table 4, the total amount of impurities including Ca, Mg, P, Zn, Na, K, and S other than lithium carbonate was found to be 0.587, indicating that the recovered It was confirmed that the purity of lithium carbonate was very high at 99.41 (S5).
전술한 바와 같이, 본 발명은 강산성의 용매를 사용하지 않고 열분해와 수침출을 이용하는 건식회수법을 통해 양극재 폐 세라믹 소성용기로부터 수집된 NCM(NixCoxMnx)계 분말로부터 순도 높은 탄산리튬(Li2CO3)을 회수할 수 있으므로, 산처리 공정 및 중간생성물의 수세공정에 요구되는 비용을 크게 절감할 수 있다.As described above, the present invention provides high purity lithium carbonate (Li 2 CO 3) Since can be recovered, the cost required for the acid treatment process and the washing process of the intermediate product can be greatly reduced.
또한, 본 발명은 양극재인 NCM(NixCoxMnx)계 분말을 수집하고 남은 폐 세라믹 소성용기는 파쇄 및 분쇄하여 시멘트 제조에 이용함으로써, 순환자원으로 활용이 가능하다.In addition, the present invention collects NCM (NixCoxMnx)-based powder, which is a cathode material, and crushes and pulverizes the remaining waste ceramic firing containers to use them for cement production, making it possible to utilize them as circular resources.
비록 본 발명이 상기 바람직한 실시 예들과 관련하여 설명되어졌지만, 발명의 요지와 범위로부터 벗어남이 없이 다양한 수정이나 변형을 하는 것이 가능하다. 따라서, 첨부된 특허 청구범위는 본 발명의 요지에 속하는 이러한 수정이나 변형을 포함할 것이다.Although the present invention has been described in relation to the above preferred embodiments, various modifications and variations can be made without departing from the gist and scope of the invention. Accordingly, the appended patent claims are intended to cover such modifications or variations as fall within the subject matter of the present invention.
부호 없음unsigned
Claims (3)
상분리된 NCM계 분말을 증류수를 이용한 수침출처리를 수행하여 액체상태의 Li2CO3과 고체상태의 유가금속 산화물 분말이 포함된 혼합물을 생성하는 제2 단계와;
수침출처리를 통해 생성된 혼합물을 감압여과기를 통해 감압여과하여 액체상태의 Li2CO3과 고체상태의 유가금속 산화물 분말을 분리 회수하는 제3 단계와;
분리된 액체상태의 Li2CO3을 증발농축기를 통해 105℃에서 2시간 건조하여 탄산리튬분말을 회수하는 제4 단계를 포함하는 것을 특징으로 하는 양극재 폐 세라믹 소성용기에서 탄산리튬 회수방법.
NCM (NixMnxCox)-based powder containing Li (lithium), Ni (nickel), Co (cobalt), and Mn (manganese) collected from the anode material waste ceramic firing container was charged into the heat treatment furnace, and the CO An agent that performs a heat reaction treatment at over 800°C while injecting 2 to separate the phase into a valuable metal oxide phase including NiO (nickel oxide), CoO (cobalt oxide), and MnO (manganese oxide) and Li 2 CO 3 (lithium carbonate). Step 1 and;
A second step of performing water leaching treatment on the phase-separated NCM-based powder using distilled water to produce a mixture containing Li 2 CO 3 in a liquid state and valuable metal oxide powder in a solid state;
The mixture produced through water leaching treatment is filtered under reduced pressure through a vacuum filter to produce liquid Li 2 CO 3 and A third step of separating and recovering solid valuable metal oxide powder;
A method for recovering lithium carbonate from a waste cathode material ceramic firing vessel, comprising a fourth step of recovering lithium carbonate powder by drying the separated liquid Li 2 CO 3 at 105° C. for 2 hours through an evaporative concentrator.
상기 제2 단계에서 증류수와 NCM계 분말을 30:1의 중량비로 혼합하여 5시간 동안 수침출처리를 수행하는 것을 특징으로 하는 이차전지용 양극재 폐 세라믹 소성용기에서 탄산리튬 회수방법.
According to paragraph 1,
A method for recovering lithium carbonate from a waste ceramic firing container for cathode material for secondary batteries, characterized in that in the second step, distilled water and NCM-based powder are mixed at a weight ratio of 30:1 and water leaching treatment is performed for 5 hours.
상기 제2 단계에서 증류수의 온도는 0~60℃ 인 것을 특징으로 하는 양극재 폐 세라믹 소성용기에서 탄산리튬 회수방법.
According to paragraph 2,
A method of recovering lithium carbonate from a waste cathode material ceramic firing vessel, characterized in that the temperature of the distilled water in the second step is 0 to 60°C.
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