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WO2016129732A1 - Procédé de régénération de déchets de précurseur de matériau actif d'électrode positive pour batterie rechargeable au lithium au moyen d'un broyeur à boulets - Google Patents

Procédé de régénération de déchets de précurseur de matériau actif d'électrode positive pour batterie rechargeable au lithium au moyen d'un broyeur à boulets Download PDF

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Publication number
WO2016129732A1
WO2016129732A1 PCT/KR2015/001699 KR2015001699W WO2016129732A1 WO 2016129732 A1 WO2016129732 A1 WO 2016129732A1 KR 2015001699 W KR2015001699 W KR 2015001699W WO 2016129732 A1 WO2016129732 A1 WO 2016129732A1
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WO
WIPO (PCT)
Prior art keywords
ball mill
positive electrode
active material
electrode active
secondary battery
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/KR2015/001699
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English (en)
Korean (ko)
Inventor
권순모
권오상
강동구
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E&d CO Ltd
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E&d CO Ltd
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Filing date
Publication date
Application filed by E&d CO Ltd filed Critical E&d CO Ltd
Publication of WO2016129732A1 publication Critical patent/WO2016129732A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the present invention relates to a method for recovering and recovering manganese, cobalt, and nickel from waste precursors generated during the production of a precursor used in a lithium secondary battery positive electrode active material, and more specifically, a recovery time can be improved by using a ball mill.
  • the technology can be reduced to.
  • a lithium secondary battery is a battery in which carbon such as graphite is used as a negative electrode active material, a metal oxide containing lithium is used as a positive electrode active material, and a nonaqueous solvent is used as an electrolyte.
  • Lithium is a metal that has a high tendency to ionize and is a material that is attracting attention in a battery having high energy density because it can express high voltage.
  • a lithium transition metal oxide containing lithium is mainly used as a positive electrode active material for a lithium secondary battery, and a layered lithium transition metal composite oxide such as cobalt / nickel / tricomponent (cobalt, nickel, and manganese coexist) This is used more than 90%.
  • a layered lithium transition metal composite oxide such as cobalt / nickel / tricomponent (cobalt, nickel, and manganese coexist)
  • Li 2 CO 3 and Ni x Co y Mn 1-xy (OH) 2 -based precursors are mixed and plasticized to be used as a positive electrode material.
  • Ni x Co y Mn 1-xy (OH) 2 precursor is prepared by coprecipitation method.
  • Ni x Co y Mn 1-xy (OH) 2 is synthesized and precipitated.
  • the present invention relates to a method for recovering nickel, cobalt and manganese by regenerating a Ni x Co y Mn 1-xy (OH) 2- based waste precursor.
  • Ni x Co y Mn 1-xy (OH) 2- based waste precursor conventionally, they are simply cut and leached in a sulfuric acid solution, and then regenerated by removing impurities (iron, etc.).
  • impurities iron, etc.
  • the present invention provides a regeneration method using a low cost and high efficiency process capable of simultaneously regenerating nickel, cobalt, and manganese from waste precursors [Ni x Co y Mn 1-xy (OH) 2 ] generated during the production of a cathode of a lithium ion battery. It aims to do it.
  • the present invention comprises the steps of grinding a waste precursor for a lithium secondary battery positive electrode active material using a ball mill; Solvent leaching step; And it provides a method for regenerating the waste precursor for a lithium secondary battery positive electrode active material comprising a step of removing impurities.
  • the waste precursor is preferably Ni x Co y Mn 1-xy (OH) 2 .
  • the solvent leaching step is preferably using sulfuric acid as a solvent.
  • the solvent leaching step is preferably made at pH 1.5 ⁇ 3.1.
  • the impurity extraction removal step is preferably made by a mixture solution of kerosene and di-2-ethylhexyl-phosphoric acid (D2EHPA).
  • D2EHPA di-2-ethylhexyl-phosphoric acid
  • the kerosene is 70 to 80% by weight
  • D2EHPA is preferably 20 to 30% by weight.
  • the impurity extracting step is preferably cocurrent multistage extraction.
  • the present invention regenerates the waste cathode material from the waste precursor through simple cutting and subsequent processing to regenerate the waste precursor.
  • the present invention uses a ball mill to grind the waste precursor to reduce particle size. During solvent leaching, the leaching rate can be dramatically lowered.
  • 1 is a ball mill particle size distribution diagram of a closed precursor.
  • FIG. 2 is a particle size distribution diagram after ball milling of a closed precursor.
  • the present invention comprises the steps of grinding a waste precursor for a lithium secondary battery positive electrode active material using a ball mill; Solvent leaching step; And it provides a method for regenerating the waste precursor for a lithium ion battery positive electrode material comprising a step of removing impurities.
  • Ni x Co y Mn 1-xy (OH) 2 waste precursors which are precursors for lithium anode electrodes mixed with nickel, cobalt, and manganese
  • a grinding step such as a conventional cutting or grinder is used.
  • the metal component is leached into the solvent through a subsequent process (solvent extraction, etc.) through the bay, and the entire regeneration process time is prolonged due to the problem that the leaching process takes a very long time.
  • the present invention is characterized by grinding the waste precursor with a ball mill in order to solve this problem.
  • the ball mill crusher generates high collision energy in the ball of the jar by the three kinetic forces of rotation, vibration, and oscillation generated in the jar.
  • This equipment is used for crushing, dispersing, or mixing particles in liquid samples, crushing plant and animal tissues, crushing microbial cells and extracting effective substances.
  • the ball mill crusher can be put into the waste precursor that needs to be regenerated to reduce the particle size of the waste precursor through the ball mill.
  • Nickel, cobalt and manganese are leached from the precursor particles pulverized by the ball mill using a solvent, in particular sulfuric acid as a solvent, and leached in the sulfate state of the respective components.
  • the ball mill pulverized precursor powder is added to a reaction tank, and sulfuric acid is slowly added to the metal to leach into an aqueous sulfuric acid solution.
  • the reaction tank temperature is preferably performed at about 70 °C, stirring speed 200 ⁇ 220 rpm.
  • a mixed solution of di-2-ethylhexyl-phosphoric acid (D2EHPA) diluted with kerosene is removed using a mixed solution of di-2-ethylhexyl-phosphoric acid (D2EHPA) diluted with kerosene.
  • D2EHPA di-2-ethylhexyl-phosphoric acid
  • the reaction temperature is 20 ⁇ 25 °C
  • mixing time is less than 10 minutes
  • separation time is preferably within 30 minutes.
  • the mixed solution of kerosene and D2EHPA it is preferable to use a mixture of kerosine at 70 to 80% by weight and D2EHPA at a ratio of 20 to 30% by weight.
  • FIG. 1 is a particle size distribution diagram of a precursor precursor Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 used in the embodiment of the present invention. As shown in FIG. 1, the median size was 7.4 ⁇ m. Meanwhile, in order to analyze the components of the precursor, the components of the waste precursor powder were analyzed by leaching the waste precursor powder into the aqua regia by inductively coupled plasma emission spectrometer (ICP-Atomic Emission Spectrometer) analysis. The results were as shown in Table 1 below.
  • ICP-Atomic Emission Spectrometer inductively coupled plasma emission spectrometer
  • the waste precursor was pulverized in a ball mill grinder for at least 10 hours, and then the particle size distribution was measured. As shown in the result of FIG. 2, the particle size is 1.4 ⁇ m, and the particle size decreases by about 80% compared to 7.4 ⁇ m before the ball mill, thereby increasing the reactivity in the leaching step, thereby significantly reducing the leaching time than the prior art.
  • the results of measuring the leaching time and leaching rate when not using the ball mill and used are shown in Figure 3 and Table 4.
  • the leaching rate was much higher at the same leaching time when the ball mill was used. For example, 120 minutes was sufficient to show a leaching rate of 99% when using a ball mill, but only a leaching rate of 71% was shown even at 120 minutes when a ball mill was not used.
  • the first composite sulfate solution After the impurity washing, the first composite sulfate solution has insufficient content of each metal component to be used as a precursor.
  • Table 6 is a specification of the raw material for the NCM-based 523 precursor.
  • nickel sulfate, cobalt sulfate, and manganese sulfate were further added to meet the specifications of Table 6, thereby preparing a secondary composite sulfate solution.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention concerne un procédé de régénération de déchets d'un précurseur de matériau d'électrode positive pour batterie au lithium-ion, procédé dans lequel des déchets de précurseur sont broyés au moyen d'un broyeur à boulets, ce qui permet de réduire la taille des particules et de réduire le temps de lixiviation par solvant qui est une procédure suivante. Par conséquent, la durée de l'ensemble de la procédure de régénération peut être réduite.
PCT/KR2015/001699 2015-02-13 2015-02-23 Procédé de régénération de déchets de précurseur de matériau actif d'électrode positive pour batterie rechargeable au lithium au moyen d'un broyeur à boulets Ceased WO2016129732A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2015-0022112 2015-02-13
KR20150022112 2015-02-13

Publications (1)

Publication Number Publication Date
WO2016129732A1 true WO2016129732A1 (fr) 2016-08-18

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106921000A (zh) * 2017-04-14 2017-07-04 中南大学 一种废旧锂离子电池正极活性材料的球磨酸浸方法
CN108390118A (zh) * 2018-03-12 2018-08-10 上海第二工业大学 一种利用NCNTs修饰电极联合微生物浸出锂电池中钴的方法
CN109897968A (zh) * 2019-04-21 2019-06-18 湖南金源新材料股份有限公司 一种采用超细磨机处理锂电池再生料提高浸出率的方法
WO2019117411A1 (fr) * 2017-12-15 2019-06-20 주식회사 포스코 Procédé de préparation de précurseur de matériau actif de cathode pour batterie secondaire et appareil de préparation l'employant
CN111455171A (zh) * 2019-01-22 2020-07-28 深圳市金航深海矿产开发集团有限公司 一种海底多金属结核提取有价金属并联产锂电正极材料前驱体及掺钛正极材料的方法
WO2022191634A1 (fr) * 2021-03-11 2022-09-15 에스케이이노베이션 주식회사 Réacteur à lit fluidisé et procédé de recyclage de précurseur de lithium faisant appel à celui-ci
CN115124011A (zh) * 2022-07-22 2022-09-30 宁夏汉尧富锂科技有限责任公司 一种废旧磷酸铁除杂提纯工艺及其应用
DE102023205153A1 (de) * 2023-06-02 2024-12-05 Volkswagen Aktiengesellschaft Verfahren zur Verwertung von Abfall aus der Herstellung von Lithium-Ionen-Akkumulatoren

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KR100709268B1 (ko) * 2006-05-04 2007-04-19 한국지질자원연구원 폐망간전지 및 알카라인전지 재활용 장치 및 방법
KR20110117024A (ko) * 2010-04-20 2011-10-26 한국지질자원연구원 폐배터리의 유가금속 재활용방법
KR101392616B1 (ko) * 2012-10-30 2014-05-07 (주)이엠티 리튬 이온 전지의 폐 양극재를 이용한 전구체 원료의 재생 방법, 그 방법에 의해 재생된 원료를 사용하여 제조한 전구체, 양극재 및 리튬 이온 전지
JP2014156649A (ja) * 2013-02-18 2014-08-28 Jx Nippon Mining & Metals Corp 廃正極材及び廃電池からの金属回収方法
KR101441421B1 (ko) * 2014-02-26 2014-09-23 타운마이닝리소스주식회사 폐 리튬 이온 전지를 이용한 전구체 원료의 회수 방법

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KR100709268B1 (ko) * 2006-05-04 2007-04-19 한국지질자원연구원 폐망간전지 및 알카라인전지 재활용 장치 및 방법
KR20110117024A (ko) * 2010-04-20 2011-10-26 한국지질자원연구원 폐배터리의 유가금속 재활용방법
KR101392616B1 (ko) * 2012-10-30 2014-05-07 (주)이엠티 리튬 이온 전지의 폐 양극재를 이용한 전구체 원료의 재생 방법, 그 방법에 의해 재생된 원료를 사용하여 제조한 전구체, 양극재 및 리튬 이온 전지
JP2014156649A (ja) * 2013-02-18 2014-08-28 Jx Nippon Mining & Metals Corp 廃正極材及び廃電池からの金属回収方法
KR101441421B1 (ko) * 2014-02-26 2014-09-23 타운마이닝리소스주식회사 폐 리튬 이온 전지를 이용한 전구체 원료의 회수 방법

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106921000A (zh) * 2017-04-14 2017-07-04 中南大学 一种废旧锂离子电池正极活性材料的球磨酸浸方法
WO2019117411A1 (fr) * 2017-12-15 2019-06-20 주식회사 포스코 Procédé de préparation de précurseur de matériau actif de cathode pour batterie secondaire et appareil de préparation l'employant
US11827524B2 (en) 2017-12-15 2023-11-28 Posco Holdings Inc. Method for preparing cathode active material precursor for secondary battery, and preparation apparatus using same
CN108390118A (zh) * 2018-03-12 2018-08-10 上海第二工业大学 一种利用NCNTs修饰电极联合微生物浸出锂电池中钴的方法
CN111455171A (zh) * 2019-01-22 2020-07-28 深圳市金航深海矿产开发集团有限公司 一种海底多金属结核提取有价金属并联产锂电正极材料前驱体及掺钛正极材料的方法
CN111455171B (zh) * 2019-01-22 2021-10-08 深圳市金航深海矿产开发集团有限公司 一种海底多金属结核提取有价金属并联产锂电正极材料前驱体及掺钛正极材料的方法
CN109897968A (zh) * 2019-04-21 2019-06-18 湖南金源新材料股份有限公司 一种采用超细磨机处理锂电池再生料提高浸出率的方法
WO2022191634A1 (fr) * 2021-03-11 2022-09-15 에스케이이노베이션 주식회사 Réacteur à lit fluidisé et procédé de recyclage de précurseur de lithium faisant appel à celui-ci
JP2024510990A (ja) * 2021-03-11 2024-03-12 エスケー イノベーション カンパニー リミテッド 流動層反応器及びそれを用いたリチウム前駆体の再生方法
CN115124011A (zh) * 2022-07-22 2022-09-30 宁夏汉尧富锂科技有限责任公司 一种废旧磷酸铁除杂提纯工艺及其应用
DE102023205153A1 (de) * 2023-06-02 2024-12-05 Volkswagen Aktiengesellschaft Verfahren zur Verwertung von Abfall aus der Herstellung von Lithium-Ionen-Akkumulatoren

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