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WO2019198972A1 - Procédé de production de monohydrate d'hydroxyde de lithium à l'aide d'un matériau de cathode résiduaire d'une batterie secondaire au lithium-ion - Google Patents

Procédé de production de monohydrate d'hydroxyde de lithium à l'aide d'un matériau de cathode résiduaire d'une batterie secondaire au lithium-ion Download PDF

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Publication number
WO2019198972A1
WO2019198972A1 PCT/KR2019/003988 KR2019003988W WO2019198972A1 WO 2019198972 A1 WO2019198972 A1 WO 2019198972A1 KR 2019003988 W KR2019003988 W KR 2019003988W WO 2019198972 A1 WO2019198972 A1 WO 2019198972A1
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WO
WIPO (PCT)
Prior art keywords
cathode material
lithium
waste cathode
secondary battery
ion secondary
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2019/003988
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English (en)
Korean (ko)
Inventor
박석준
박종선
이명규
서범석
이민우
김다모아
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Ecopro Innovation Co Ltd
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Ecopro Innovation Co Ltd
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Filing date
Publication date
Application filed by Ecopro Innovation Co Ltd filed Critical Ecopro Innovation Co Ltd
Publication of WO2019198972A1 publication Critical patent/WO2019198972A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/02—Oxides; Hydroxides
    • 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
    • Y02W30/20—Waste processing or separation
    • 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

Definitions

  • the present invention relates to a method for producing lithium hydroxide monohydrate using a waste cathode material of a lithium ion secondary battery, and more specifically, by injecting water vapor in an inert atmosphere and pre-treating the waste cathode material containing lithium by water leaching
  • the present invention relates to a method for producing lithium hydroxide monohydrate using a waste cathode material of a lithium ion secondary battery capable of recovering lithium ions at a high recovery rate and producing high purity lithium hydroxide monohydrate.
  • Lithium-ion secondary battery has the advantage of having a small size and high-density energy, and is manufactured for each product use is used in various ways as well as smart phones, battery cars.
  • the lithium ion secondary battery battery includes a cathode material, an anode material, a separator, an electrolyte, and the cathode material contains valuable metals such as lithium, nickel, cobalt, and manganese.
  • lithium is the main raw material that enables the storage or release of electrical energy in the battery.
  • the existing technology of recycling lithium using waste lithium ion secondary battery is to recover valuable metals such as nickel and cobalt first through sulfuric acid leaching and solvent extraction process, and then recover lithium with residual impurities. have.
  • an object of the present invention is to recover the lithium ion with a high recovery rate by using the waste cathode material of the lithium ion secondary battery, high-purity lithium hydroxide work by minimizing impurities It is to provide a method for producing lithium hydroxide monohydrate using the waste cathode material of a lithium ion secondary battery capable of producing a hydrate.
  • the present invention provides a waste cathode material preparation step of preparing a waste cathode material of a lithium ion secondary battery;
  • the waste cathode material of the lithium ion secondary battery is lithium nickel cobalt aluminum oxide (LiNiCoAlO 2 , NCA), lithium nickel cobalt manganese oxide (LiNiCoMnO 2 , NCM), oxides of lithium iron (LiFePO 4 , LFP), Group consisting of lithium manganese iron oxides (LiMnFePO 4 , LMFP), lithium manganese oxides (LiMn 2 O 4 , LMO), lithium nickel manganese spinel (LiNi 0.5 Mn 1.5 O 4 , LNMO), lithium cobalt oxide (LiCoO 2 , LCO) At least one selected from.
  • the waste cathode material pretreatment step is reacted by Scheme 1 shown below.
  • Me is at least one selected from the group consisting of Ni, Co, Mn, Al.
  • the waste cathode material pretreatment step is nitrogen, carbon dioxide or hydrogen is injected at 0.1 to 1,000 LPM (Liter per minute) per 1g of the waste cathode material to form the inert atmosphere, the water vapor is the waste anode It is injected at 0.1 to 1,000 LPM (Liter per minute) per 1 g of ash, and is heat-treated at 500 ° C. to 1,000 ° C. for 100 to 600 minutes.
  • the water leaching step is mixed with 1 to 10 times the water based on the weight of the pretreatment result to the pretreatment result is stirred for 1 to 5 hours at a temperature of 20 °C to 100 °C .
  • the residue is used to separate Ni, Co, Mn or Al.
  • the crystallization step is concentrated by evaporation in a vacuum at a temperature of 60 °C to 120 °C for 30 minutes to 10 hours.
  • the present invention has the following excellent effects.
  • lithium is discharged by pre-treating the waste cathode material containing lithium in an inert atmosphere and then pre-treated with water There is an effect that can be recovered at a high recovery rate.
  • 1 is a step for explaining a method of manufacturing lithium hydroxide monohydrate using the waste cathode material of a lithium ion secondary battery according to an embodiment of the present invention.
  • NCA lithium nickel cobalt oxide
  • 3 is an XRD analysis result of the pretreatment result after the pretreatment step according to an embodiment of the present invention.
  • 1 is a step for explaining a method for producing lithium hydroxide monohydrate using the waste cathode material of a lithium ion secondary battery according to the present invention.
  • a method of manufacturing lithium hydroxide monohydrate using waste cathode materials of a secondary battery recovers lithium from waste cathode materials of a lithium ion secondary battery and converts the lithium hydroxide into lithium hydroxide monohydrate.
  • a waste cathode material of a lithium ion secondary battery is prepared (S100).
  • the waste cathode material is not limited as long as it is a cathode material containing lithium element, preferably lithium nickel cobalt aluminum oxide (LiNiCoAlO 2 , NCA), lithium nickel cobalt manganese oxide (LiNiCoMnO 2 , NCM), lithium iron oxide (LiFePO 4 , LFP), lithium manganese oxides (LiMnFePO 4 , LMFP), lithium manganese oxides (LiMn 2 O 4 , LMO), lithium nickel manganese spinel (LiNi 0.5 Mn 1.5 O 4 , LNMO), lithium cobalt oxide (LiCoO 2 , LCO) may be any one or more selected from the group consisting of.
  • lithium nickel cobalt aluminum oxide LiNiCoAlO 2 , NCA
  • LiNiCoMnO 2 , NCM lithium iron oxide
  • LiMnFePO 4 , LMFP lithium manganese oxides
  • the pretreatment step (S200) is a process for deforming the structure of the waste cathode material to transform lithium into the form of a water-soluble material, and is reacted by Scheme 1 shown below.
  • Me is at least one selected from the group consisting of Ni, Co, Mn, Al.
  • nitrogen, carbon dioxide or hydrogen may be injected at 0.1 to 1,000 LPM (Liter per minute) per 1g of the waste cathode material.
  • the water vapor is injected at 0.1 to 1,000 LPM (Liter per minute) per 1g of the waste cathode material, and induces physicochemical decomposition of the waste cathode material through a hydrolysis reaction by high temperature saturated steam.
  • the temperature is maintained in the range of 500 °C to 1,000 °C, heat treatment for 100 minutes to 600 minutes.
  • the water is added 1 to 10 times on the basis of the weight of the pretreatment result, it is stirred at 200rpm to 1,000rpm for 1 to 5 hours at a temperature of 20 °C to 100 °C.
  • a solid-liquid separation step (S400) of separating the water-leached mixture into solids and separating the leachate and residues is performed.
  • metallic elements such as nickel, cobalt, manganese, and aluminum, are separated into a cake residue, and lithium is dissolved and separated in a leach solution.
  • the residue is separated separately and recovered as elements such as nickel, cobalt, manganese, aluminum through sulfuric acid leaching or solvent extraction process, and synthesized as a precursor of a secondary battery cathode material using this as a raw material. Can be recycled.
  • the leachate is concentrated by evaporation at a temperature of 60 ° C to 120 ° C for 30 minutes to 10 hours in a vacuum to form lithium hydroxide monohydrate crystals.
  • LiNiCoAlO 2 , NCA lithium nickel cobalt aluminum oxide
  • Table 1 shows the results of ICP chemical component content analysis of the lithium nickel cobalt aluminum oxide
  • Figure 2 shows the lithium nickel cobalt aluminum oxide XRD analysis results.
  • the prepared waste cathode material powder was introduced into a tube kiln, and then heated to 800 ° C. ⁇ 10 ° C. at a temperature rising rate of 10 ° C. per minute, and then maintained for 120 minutes.
  • nitrogen gas was injected at 30cc per minute, and steam was injected at 650cc per minute.
  • natural cooling was performed to obtain a pretreatment result, and nitrogen and steam were not injected in the cooling section.
  • FIG. 3 shows the XRD analysis results of the pretreatment result.
  • the intensity value is reduced at 19 degrees. It was observed that the deformation of the intermolecular bonding structure in the waste cathode material was confirmed.
  • the leachate was concentrated by evaporation and crystallization, and the obtained crystals were washed with water and dried to obtain lithium hydroxide monohydrate that can be used in a secondary battery battery.
  • Lithium nickel cobalt aluminum oxide was prepared as a waste cathode material in the same manner as in Example, and the prepared waste cathode material powder was introduced into a tube kiln, and then heated up to 800 ° C. ⁇ 10 ° C. at a temperature rising rate of 10 ° C. per minute, and then 5. After cooling for an hour, it was naturally cooled.
  • the lithium concentration in the leachate obtained by solid-liquid separation of the solution from which the water leach was completed was analyzed, and the result confirmed that the lithium recovery was 11.6%.
  • Lithium component can be recovered with high recovery rate, and by leaching water without using acid, only lithium ions can be selectively extracted without nickel, cobalt, manganese or aluminum ions, thereby producing high purity lithium hydroxide monohydrate. It has the advantage to do it.
  • nickel, cobalt, manganese, or aluminum can be separated by using the residue separated from the water-leached mixture and recycled as a precursor of the secondary battery cathode material.
  • Recovering lithium from the waste cathode material it can be used as a raw material of the lithium ion secondary battery, it can be applied to various fields using lithium hydroxide monohydrate as a raw material.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention concerne un procédé de production de monohydrate d'hydroxyde de lithium à l'aide d'un matériau de cathode résiduaire d'une batterie secondaire au lithium-ion et, plus spécifiquement, un procédé de production de monohydrate d'hydroxyde de lithium à l'aide d'un matériau de cathode résiduaire d'une batterie secondaire au lithium-ion, le matériau de cathode résiduaire contenant du lithium prétraité par injection de vapeur dans une atmosphère inerte, puis étant soumis à une lixiviation à l'eau, ce par quoi des ions de lithium peuvent être récupérés à un taux élevé et un monohydrate d'hydroxyde de lithium de grande pureté peut être produit.
PCT/KR2019/003988 2018-04-12 2019-04-04 Procédé de production de monohydrate d'hydroxyde de lithium à l'aide d'un matériau de cathode résiduaire d'une batterie secondaire au lithium-ion Ceased WO2019198972A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2018-0042642 2018-04-12
KR1020180042642A KR102043711B1 (ko) 2018-04-12 2018-04-12 리튬이온 2차전지의 폐 양극재를 이용한 수산화리튬 일수화물의 제조방법

Publications (1)

Publication Number Publication Date
WO2019198972A1 true WO2019198972A1 (fr) 2019-10-17

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KR (1) KR102043711B1 (fr)
WO (1) WO2019198972A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112267026A (zh) * 2020-10-13 2021-01-26 湖南金凯循环科技有限公司 一种以废金属锂为原料制备氢氧化锂的方法
GB2609212A (en) * 2021-07-22 2023-02-01 Mexichem Fluor Sa De Cv Process
CN115786731A (zh) * 2021-09-09 2023-03-14 釜庆大学校 从锂锰铁磷酸盐选择性地回收锂的方法

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KR20210054946A (ko) 2019-11-06 2021-05-14 주식회사 에코프로이노베이션 양극재 세척수로부터 배터리급 수산화리튬 일수화물을 제조하는 방법
KR102332465B1 (ko) * 2019-12-27 2021-11-30 (주)다원화학 폐 리튬이온전지의 양극재에서 유가금속 회수 방법
KR102751375B1 (ko) * 2020-02-10 2025-01-06 에스케이이노베이션 주식회사 리튬 이차 전지의 활성 금속 회수 방법
KR102520392B1 (ko) * 2020-12-22 2023-04-11 부경대학교 산학협력단 리튬망간산화물(lmo)로부터 산화리튬 회수방법
KR102350008B1 (ko) * 2021-07-05 2022-01-11 주식회사 에코프로이노베이션 폐전극소재를 이용한 리튬과 유가금속의 분리 회수방법
KR20230052569A (ko) * 2021-10-13 2023-04-20 에스케이이노베이션 주식회사 리튬 이차 전지로부터 리튬 전구체의 회수 방법
KR102444732B1 (ko) 2022-01-20 2022-09-16 이원희 양극재 제조 방법 및 제조방법으로 제조된 양극재
KR102643085B1 (ko) 2022-03-03 2024-03-05 (주)선영시스텍 양극재 제조 장치
KR20240071905A (ko) * 2022-11-16 2024-05-23 국립부경대학교 산학협력단 수산화리튬 제조 방법
KR20240071711A (ko) * 2022-11-16 2024-05-23 국립부경대학교 산학협력단 수산화리튬 제조 방법
KR102720096B1 (ko) * 2023-02-28 2024-10-22 (주)에코프로머티리얼즈 양극 활물질 제조용 사용 후 도가니로부터 고압 스팀을 활용한 유가금속 회수 시스템
KR20240160875A (ko) 2023-05-03 2024-11-12 고등기술연구원연구조합 폐배터리 양극재의 리튬선회수방법
KR20250040172A (ko) 2023-09-15 2025-03-24 주식회사 정수뉴테크 리튬 이차 전지의 리튬 회수 방법
KR20250090774A (ko) * 2023-12-13 2025-06-20 포스코홀딩스 주식회사 폐내화갑으로부터 리튬을 회수하는 방법

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JP2004011010A (ja) * 2002-06-11 2004-01-15 Sumitomo Metal Mining Co Ltd コバルト酸リチウムからのリチウムおよびコバルトの回収方法
KR20130069538A (ko) * 2009-10-14 2013-06-26 에스지엘 카본 에스이 Ｌｉ를 포함하는 벌크 재료의 처리를 위한 방법 및 반응로
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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN112267026A (zh) * 2020-10-13 2021-01-26 湖南金凯循环科技有限公司 一种以废金属锂为原料制备氢氧化锂的方法
GB2609212A (en) * 2021-07-22 2023-02-01 Mexichem Fluor Sa De Cv Process
CN115786731A (zh) * 2021-09-09 2023-03-14 釜庆大学校 从锂锰铁磷酸盐选择性地回收锂的方法

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KR102043711B1 (ko) 2019-11-12
KR20190119329A (ko) 2019-10-22

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