[go: up one dir, main page]

WO2025166431A1 - Procédé de recyclage de batteries de phosphate - Google Patents

Procédé de recyclage de batteries de phosphate

Info

Publication number
WO2025166431A1
WO2025166431A1 PCT/BR2024/050046 BR2024050046W WO2025166431A1 WO 2025166431 A1 WO2025166431 A1 WO 2025166431A1 BR 2024050046 W BR2024050046 W BR 2024050046W WO 2025166431 A1 WO2025166431 A1 WO 2025166431A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
iron
batteries
solution
fact
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.)
Pending
Application number
PCT/BR2024/050046
Other languages
English (en)
Portuguese (pt)
Inventor
Denise Crocce Romano ESPINOSA
Jorge Alberto Soares TENÓRIO
David da Silva VASCONCELOS
Amilton Barbosa BOTELHO JUNIOR
Luciana Assis GOBO
Elio Augusto KUMOTO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universidade de Sao Paulo USP
Tupy SA
Original Assignee
Universidade de Sao Paulo USP
Tupy SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Universidade de Sao Paulo USP, Tupy SA filed Critical Universidade de Sao Paulo USP
Priority to PCT/BR2024/050046 priority Critical patent/WO2025166431A1/fr
Publication of WO2025166431A1 publication Critical patent/WO2025166431A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals

Definitions

  • This invention relates to the process of recycling lithium iron phosphate Li-ion batteries, LFP (LiFePO4), from the electronics and automotive sector using mechanical processing and hydrometallurgical route for pouch, cylindrical and prismatic type batteries.
  • LFP Li-ion batteries
  • Li-ion batteries are the main technology for use in electronic equipment and electric vehicles. Due to the shift towards a society with lower greenhouse gas emissions, the consumption of these batteries for electric vehicles could increase in capacity up to 10 times by 2030. Global consumption of Li-ion batteries is estimated to reach US$221 billion from 2015 to 2024.
  • Lithium is considered a critical and strategic element in the world's major economies. Demand for lithium will grow to the point where current production from mining will no longer be sufficient to meet market demand, especially for Li-ion batteries. Therefore, the search for other sources of lithium is crucial, with recycling playing an important role in promoting the circular economy.
  • Another important aspect of Li-ion batteries as a secondary source of lithium is the higher concentration of this element in batteries than in primary sources, such as spodumene and lepidolite.
  • Document US10919775 refers to the production of lithium carbonate from the recycling of LFP batteries.
  • the discarded battery is ground and the aluminum foil is separated from the active material (cathode).
  • an acid leaching step using mineral acids
  • the iron is not leached, resulting in only a lithium solution.
  • Document CN106848473B presents calcination (heat treatment) steps as a pretreatment for LFP batteries to remove aluminum, and the material containing lithium and iron undergoes grinding steps in a ball mill. The resulting material is leached in an acidic medium with the addition of an oxidizing agent.
  • the recycling process for LFP Li-ion batteries has particularities in relation to other lithium batteries, such as the processing of aluminum present in the composition of the electron collector.
  • the most selective leaching steps for lithium still contain some of the leached iron. Therefore, separation and purification steps are necessary to remove the aluminum and iron before obtaining lithium as a product.
  • lithium precipitation step 106 in which lithium is precipitated with the addition of NaaPC or Na2CO3.
  • Lithium precipitation is carried out with the addition of the amount of Na2CÜ3 that is between the stoichiometric and 20% excess, with a reaction time of up to 2.0 hours, in a temperature range of 20°C to 80°C, and with a yield of at least 10% lithium precipitation.
  • the precipitated lithium passes through a filtration step 117 and the water used for filtration can then be recirculated in the process, and can return and feed the grinding step 103.
  • the external structure of the battery cells (without plastic parts), graphite, active material, the aluminum and copper foils that are present in the solution from the grinding step 103, go to the leaching step 107.
  • the acids Sulfuric and citric acids can be used, preferably sulfuric acid. Acid concentrations range from 0.2 mol/L to 4.0 mol/L over a temperature range of 25°C to 90°C.
  • the reaction time can range from 0.5 to 5.0 hours.
  • No oxidizing agent is used in the leaching step.
  • the efficiency of the leaching process of the present invention can reach 99% of the metals present in the active material, even without the presence of an oxidizing agent, due to the presence of the metallic aluminum foil of the battery cells.
  • the efficiency of the leaching step 107 of the present invention can be seen in Table 1, which shows a comparison between the results obtained with the process claimed herein and prior art processes that use an oxidizing agent or another type of acid different from those employed in the present process.
  • a filtration step 108 to remove solid material from the solution (external structure of the battery cells, aluminum, copper and graphite sheets).
  • the liquor obtained (aqueous phase) goes to the separation (purification) step of the metals present, and the solid material (leaching residue) goes to the sieving and elutriation step 109 (physical separation).
  • a screening step is performed to recover the graphite, while the outer structure of the battery cells, the aluminum foils, and the copper foils are recovered through an elutriation step.
  • the electrodialysis separation 112B to separate the aluminum from the solution prior to the aluminum precipitation step 112A, shown in the embodiment illustrated in Figure 2, is performed with cationic and anionic membranes, in a range of 200 mA to 400 mA of electric current for a reaction period of up to 30 hours.
  • the aluminum-concentrated solution then proceeds to the aluminum precipitation step 112A to obtain aluminum hydroxide, aluminum carbonate, or aluminum oxide, as previously explained.
  • Different types of lithium product can be obtained from the solution after precipitation of iron and aluminum.
  • the remaining lithium precipitation step 113 can obtain, for example, i) lithium sulfate, from crystallization of the solution in a temperature range of 80°C to 110°C, for a reaction period of 1.0 to 5.0 hours; ii) lithium phosphate, from the addition of sodium phosphate, in an amount between stoichiometric and 40% excess, in the solution under stirring in a temperature range of 25 to 90°C for a reaction period of 1.0 to 5.0 hours; iii) lithium carbonate, with addition of solid sodium carbonate or in solution in a concentration of 50 to 200g/L, under stirring, in a temperature range of 25°C to 90°C for a reaction period of 1.0 to 5.0 hours; iv) lithium hydroxide, from the lithium carbonate previously obtained with the addition of calcium hydroxide at a concentration of 0.2 g/L to 1.0 g/L, in a temperature range of 25°C to 90°C, for a reaction period of 1.0 to 5.0 hours.
  • the iron phosphate obtained after the separation of iron 1 10 and removal of remaining iron 11 1 is added to a lithium solution, with the pH corrected to 5.0, and addition of ascorbic acid at a concentration of up to 0.05 mol/L.
  • the ratio of Li:Fe:PCU in solution is adjusted with the addition of LiOH, Fe(OH)2 or LiPC .
  • the solution is then taken to a pressure reactor, where the mixture is stirred and heated at a temperature of approximately 200°C, for a reaction period of up to 6 hours.

Landscapes

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

Abstract

La présente invention concerne une nouvelle voie de recyclage de batteries utilisées dans le secteur des équipements électriques/électroniques et dans le secteur automobile. Cette invention trouve une application particulière dans les batteries avec matériau actif à base de phosphate de lithium et de fer, LFP (LiFePO4), des types prismatique, cylindrique et poche. Le procédé comprend les étapes suivantes : décharge des batteries, démontage et séparation des composants de la batterie, broyage des éléments des batteries, précipitation du fluor et du lithium, lixiviation avec de l'acide, séparation du fer par précipitation et résine échangeuse d'ions, précipitation de l'aluminium, et précipitation du lithium restant. La présente invention introduit une étape de lixiviation acide sans utilisation d'agent oxydant, pouvant atteindre des valeurs proches de 99 % d'efficacité pour le Li et le Fe, ainsi qu'un traitement mécanique sans aucun traitement thermique pour concentrer les métaux d'intérêt des cathodes des batteries.
PCT/BR2024/050046 2024-02-08 2024-02-08 Procédé de recyclage de batteries de phosphate Pending WO2025166431A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/BR2024/050046 WO2025166431A1 (fr) 2024-02-08 2024-02-08 Procédé de recyclage de batteries de phosphate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/BR2024/050046 WO2025166431A1 (fr) 2024-02-08 2024-02-08 Procédé de recyclage de batteries de phosphate

Publications (1)

Publication Number Publication Date
WO2025166431A1 true WO2025166431A1 (fr) 2025-08-14

Family

ID=96698771

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/BR2024/050046 Pending WO2025166431A1 (fr) 2024-02-08 2024-02-08 Procédé de recyclage de batteries de phosphate

Country Status (1)

Country Link
WO (1) WO2025166431A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017006209A1 (fr) * 2015-07-06 2017-01-12 Attero Recycling Pvt. Ltd. Procédé de récupération de métaux à partir de batteries li-ion épuisées
CN107043116A (zh) * 2017-04-24 2017-08-15 北京化工大学 从除镁卤水中提取锂并制备电池级碳酸锂的方法
BR112018074702A2 (pt) * 2016-07-07 2019-03-19 Grst International Limited método para reciclar baterias de íon de lítio
US20220136079A1 (en) * 2020-11-04 2022-05-05 Nanyang Technological University Method of extracting metal ions from batteries
US20230050044A1 (en) * 2020-11-23 2023-02-16 Hunan Jin Yuan New Materials Joint Stock Company Limited Comprehensive recycling method for waste lithium iron phosphate battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017006209A1 (fr) * 2015-07-06 2017-01-12 Attero Recycling Pvt. Ltd. Procédé de récupération de métaux à partir de batteries li-ion épuisées
BR112018074702A2 (pt) * 2016-07-07 2019-03-19 Grst International Limited método para reciclar baterias de íon de lítio
CN107043116A (zh) * 2017-04-24 2017-08-15 北京化工大学 从除镁卤水中提取锂并制备电池级碳酸锂的方法
US20220136079A1 (en) * 2020-11-04 2022-05-05 Nanyang Technological University Method of extracting metal ions from batteries
US20230050044A1 (en) * 2020-11-23 2023-02-16 Hunan Jin Yuan New Materials Joint Stock Company Limited Comprehensive recycling method for waste lithium iron phosphate battery

Similar Documents

Publication Publication Date Title
US12412941B2 (en) Method for recycling lithium batteries
JP7253538B2 (ja) リチウムイオン電池リサイクル方法
EP4481074A1 (fr) Procédé de récupération de lithium à partir de batterie au lithium-ion usagée
JP2000015216A (ja) リチウムイオン２次電池からの正極活物質の再生方法
JP6330949B2 (ja) リン及び／又はフッ素の除去方法、並びに、有価金属の回収方法
JP2016003382A (ja) リン及び／又はフッ素の除去方法、並びに、有価金属の回収方法
WO2023195533A1 (fr) Procédé de récupération de lithium à partir de batteries au lithium-ion usagées
US12024755B2 (en) Process and system for recovering lithium from lithium-ion batteries
KR102396644B1 (ko) Ncm, nca, ncma계 폐배터리 리튬이차전지 및 양극재 공정스크랩을 이용한 황산니켈6수화물, 황산코발트, 및 인산리튬 제조 방법
US20250188566A1 (en) Method for processing lithium ion secondary battery
CN117897508A (zh) 从废旧锂离子电池中回收锂的方法
WO2025166431A1 (fr) Procédé de recyclage de batteries de phosphate
US20170317391A1 (en) Method for Recovering Lithium from Lithium-Sulfur Accumulators
WO2024178482A1 (fr) Procédé de recyclage de batteries
WO2025040555A1 (fr) Procédé d'extraction de lithium à partir de batteries contenant du lithium
AU2023343511A1 (en) Production of hydrogen and solid lithium hydroxide
JP2025068412A (ja) リチウム塩水溶液からリチウムを回収する方法
CN119768953A (zh) 用于从废锂离子电池回收金属的方法及系统
OA20995A (en) Method for recycling lithium batteries.

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24922692

Country of ref document: EP

Kind code of ref document: A1