SE543505C2 - Process for the recovery of cathode materials in the recycling of lithium ion batteries - Google Patents

Process for the recovery of cathode materials in the recycling of lithium ion batteries

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Publication number
SE543505C2
SE543505C2 SE1950468A SE1950468A SE543505C2 SE 543505 C2 SE543505 C2 SE 543505C2 SE 1950468 A SE1950468 A SE 1950468A SE 1950468 A SE1950468 A SE 1950468A SE 543505 C2 SE543505 C2 SE 543505C2
Authority
SE
Sweden
Prior art keywords
fepo4
process according
precipitation
aipo4
leachate
Prior art date
Application number
SE1950468A
Other languages
Swedish (sv)
Other versions
SE1950468A1 (en
Inventor
Cristian Tunsu
Emma Nehrenheim
Ingrid Karlsson
Mahmood Alemrajabi
Martina Petranikova
Ragnar Sjödahl
Original Assignee
Northvolt Ab
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.)
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Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=70295111&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=SE543505(C2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Northvolt Ab filed Critical Northvolt Ab
Priority to SE1950468A priority Critical patent/SE543505C2/en
Priority to EP24159949.7A priority patent/EP4372112A3/en
Priority to HUE20719981A priority patent/HUE066510T2/en
Priority to JP2021560619A priority patent/JP7612604B2/en
Priority to ES20719981T priority patent/ES2980579T3/en
Priority to US17/601,865 priority patent/US11509000B2/en
Priority to PCT/EP2020/060487 priority patent/WO2020212363A1/en
Priority to CN202511227047.6A priority patent/CN121046640A/en
Priority to CA3135949A priority patent/CA3135949C/en
Priority to PL20719981.1T priority patent/PL3956487T3/en
Priority to HRP20240522TT priority patent/HRP20240522T1/en
Priority to EP20719981.1A priority patent/EP3956487B1/en
Priority to CN202080028603.6A priority patent/CN113924374A/en
Priority to KR1020217036676A priority patent/KR20220031997A/en
Publication of SE1950468A1 publication Critical patent/SE1950468A1/en
Publication of SE543505C2 publication Critical patent/SE543505C2/en
Priority to US17/967,424 priority patent/US12381268B2/en

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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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
    • 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
    • C22B1/005—Preliminary treatment of 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • 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
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • 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
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • 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
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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
    • C22B47/00—Obtaining manganese
    • 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
    • C22B47/00—Obtaining manganese
    • C22B47/0018—Treating ocean floor nodules
    • C22B47/0045—Treating ocean floor nodules by wet processes
    • C22B47/0081—Treatment or purification of solutions, e.g. obtained by leaching
    • 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
    • C22B7/006—Wet processes
    • 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
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B2101/00—Type of solid waste
    • B09B2101/15—Electronic waste
    • B09B2101/16—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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • 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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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Oceanography (AREA)
  • Ocean & Marine Engineering (AREA)
  • Toxicology (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Processing Of Solid Wastes (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

A process for removal of aluminium and iron in the recycling of rechargeable batteries comprising the extraction of copper from a leachate from black mass producing a first leachate, adding phosphoric acid (H3PO4) to the leachate from step a) and adjusting the pH to form iron phosphate (FePO4) and aluminium phosphate (AIPO4), precipitating and removing the formed FePO4 and AIPO4, and forming a filtrate for further recovery of cathode metals, mainly NMC-metals and lithium.

Description

190271SE Process for the recovery of cathode materials in the recycling of lithium ion batteries Technical field id="p-1" id="p-1" id="p-1" id="p-1" id="p-1" id="p-1" id="p-1" id="p-1" id="p-1" id="p-1" id="p-1" id="p-1" id="p-1"
[001] The present disclosure relates to the recycling of batteries, and in particularprocess steps in the recovery of cathode materials such as lithium (Li), nickel (Ni), manganese (I\/ln), and cobalt (Co), the latter three frequently referred to as NMC metals.
Background id="p-2" id="p-2" id="p-2" id="p-2" id="p-2" id="p-2" id="p-2" id="p-2" id="p-2" id="p-2" id="p-2" id="p-2" id="p-2"
[002] The transition from fossil fuels towards renewable energy has gainedconsiderable momentum. One ofthe most important contributing factors is thedevelopment of better and cheaper rechargeable batteries. Currently, lithium-ion batteriesare becoming increasingly popular. They represent a type of rechargeable battery in which lithium ions move from the negative electrode to the positive electrode duringdischarge and back when charging. As a consequence of this popularity, the demand forelements necessary in lithium ion batteries is increasing exponentially. Such elementsinclude, apart from lithium, also NMC metals, and in particular cobalt. The global sources ofcobalt appear to be depleting, which in turn shifts the focus from extraction to recovery ofcobalt. ln addition, cobalt mining is in some countries associated with serious negative environmental and social impact such as pollution, child labor etc. id="p-3" id="p-3" id="p-3" id="p-3" id="p-3" id="p-3" id="p-3" id="p-3" id="p-3" id="p-3" id="p-3" id="p-3" id="p-3"
[003] Economical and environmentally friendly recycling of lithium batteries isnecessary to conserve natural resources and minimize pollution. Additionally, recycling willalso provide a sustainable source for the production of new batteries. Currently, lithium-ionbattery recycling is still in its early stages of development. At this stage, one of the majorobstacles is the lack of a steady supply. Once the amount of expired batteries has increased,it will be easier to develop a cost-effective technology and a global standardized process.Also, the high cost of recycling creates a profitability barrier that inhibits the development ofa large-scale market. Another problem to consider is that lithium-ion batteries from differentmanufacturers use different chemical processes to store and release energy, which makes it difficult to create a standardized recycling procedure. 190271SE id="p-4" id="p-4" id="p-4" id="p-4" id="p-4" id="p-4" id="p-4" id="p-4" id="p-4" id="p-4" id="p-4" id="p-4" id="p-4"
[004] To conclude, the forecasted increase in demand for raw materials for lithiumion batteries, the critical reserves of cobalt and the instability in supply and price of lithium, make it highly desirable to develop efficient and cost-effective recycling processes. id="p-5" id="p-5" id="p-5" id="p-5" id="p-5" id="p-5" id="p-5" id="p-5" id="p-5" id="p-5" id="p-5" id="p-5" id="p-5"
[005] US2011059339 (H. Yamasaki et al.) discloses a method for treating lithiumbatteries. The method includes an acid solution treatment process wherein an acid solution,namely aqueous phosphoric acid solution, aqueous carbonic acid water or aqueoushydrogen sulfide, is brought into contact with the surface of the positive active materiallayer and the positive current collector which constitute the positive electrode member.Then the positive active material layer is separated from the positive current collector andsubjected to an oxalic acid treatment process wherein the material for treatment containingmetal components originating from the positive active material layer is reacted with aqueous oxalic acid solution. id="p-6" id="p-6" id="p-6" id="p-6" id="p-6" id="p-6" id="p-6" id="p-6" id="p-6" id="p-6" id="p-6" id="p-6" id="p-6"
[006] DE102014014894 (Adensis GmbH) discloses a method for the recovery ofmaterial from the cathode of lithium ion batteries. The method comprises acidic detachmentof the cathode material from the substrate material through the use of oxidizing or non-oxidizing acids. As oxidizing acids, preferably nitric acid and/or phosphoric acid and/or sulfuric acid can be used. id="p-7" id="p-7" id="p-7" id="p-7" id="p-7" id="p-7" id="p-7" id="p-7" id="p-7" id="p-7" id="p-7" id="p-7" id="p-7"
[007] EP2532759 (SARP Industries) discloses a method for separating materials fromlithium batteries, wherein the process comprises leaching a ground material in an acidmedium so as to dissolve a part ofthe ground material to obtain a solution containing metalions and a portion of insoluble ground material and separating the metal ions present in thesolution. The acid used in the leaching step is selected from mineral acids, such as sulfuricacid, hydrochloric acid, phosphoric acid, nitric acid and mixtures of a or more thereof. The preferred acid is sulfuric acid. id="p-8" id="p-8" id="p-8" id="p-8" id="p-8" id="p-8" id="p-8" id="p-8" id="p-8" id="p-8" id="p-8" id="p-8" id="p-8"
[008] EP2450991 (Eco Recycling S.R.L.) discloses a process for treatlng all the end-of-life accumulator and battery types except the alkaline, zânc-carbon ones and leadaccumulators, The process comprises a first phase of physical operatlons and a second phaseof chemical operations which all together allow the recovery of crappel" and rslastlc rnateršalstyplcally crahtalned ln hlckel-rraetal lfytlride accurnulators, lithium ion batteries and accumulators, primary lithium batteries. The process is characterlzed by the use of a 190271SE purification operation by means of a solvent which allows obtaining Eithiunt rsrraducts (Lšzíïüg), cobalt (Co/CoSO4 jíïraíïüg) and nickel (Ni/NiCOg) of high purity. id="p-9" id="p-9" id="p-9" id="p-9" id="p-9" id="p-9" id="p-9" id="p-9" id="p-9" id="p-9" id="p-9" id="p-9" id="p-9"
[009] WO 2018/209164 (Worcester Polytechnic Institute) concerns the extraction ofCo (cobalt), Ni (nickel), Al (aluminium) and I\/|n (manganese) for the production of activecathode materials for new batteries. LiFePO4 forms as a waste stream and is often discardeddue to infeasibility of recycling. WO 2018/209164 teaches the precipitation of LiFePO4 asFePO4 forming a by-product, along with graphite and carbon, which are not dissolved intothe solution. FePO4 can then be separated from graphite and carbon, and used to synthesize LiFePO4 as cathode material whereas graphite can be regenerated as anode material.
Summary id="p-10" id="p-10" id="p-10" id="p-10" id="p-10" id="p-10" id="p-10" id="p-10" id="p-10" id="p-10" id="p-10" id="p-10" id="p-10"
[010] ln view of an increasing demand for metals used in rechargeable lithium ionbatteries, and a growing concern for the environment, it remains to develop improved processes for the recovery of cathode metals. id="p-11" id="p-11" id="p-11" id="p-11" id="p-11" id="p-11" id="p-11" id="p-11" id="p-11" id="p-11" id="p-11" id="p-11" id="p-11"
[011] A first aspect of the present disclosure is a process for removal of aluminiumand iron in the recycling of rechargeable batteries, preferably rechargeable lithium ion batteries, said process comprising the following steps: a) extracting copper from a leachate from black mass producing a first leachate, b) adding phosphoric acid (H3PO4) to the leachate from step a), c) adjusting the pH to form iron phosphate (FePO4) and aluminium phosphate (AIPO4), d) precipitating and removing the formed FePO4 and AIPO4, and e) forming a filtrate for recovery of cathode metals. id="p-12" id="p-12" id="p-12" id="p-12" id="p-12" id="p-12" id="p-12" id="p-12" id="p-12" id="p-12" id="p-12" id="p-12" id="p-12"
[012] According to an embodiment of said aspect, the precipitation is performed in two separate steps at different pH. id="p-13" id="p-13" id="p-13" id="p-13" id="p-13" id="p-13" id="p-13" id="p-13" id="p-13" id="p-13" id="p-13" id="p-13" id="p-13"
[013] ln the first precipitation step the pH is adjusted, optionally with alkali, to aninterval of pH 1.5 to 4, such as pH 1.5 to 3.5, preferably pH 1.5 to 3. ln a second step the pH is adjusted to an interval of pH 3 to 6.5, such as pH 3 to 6, preferably pH 3 to 5.5. 190271SE4 id="p-14" id="p-14" id="p-14" id="p-14" id="p-14" id="p-14" id="p-14" id="p-14" id="p-14" id="p-14" id="p-14" id="p-14" id="p-14"
[014] According to an embodiment, freely combinable with the above, crystallization seeds are added to precipitate FePO4 and AIPO4 in the first precipitation step. id="p-15" id="p-15" id="p-15" id="p-15" id="p-15" id="p-15" id="p-15" id="p-15" id="p-15" id="p-15" id="p-15" id="p-15" id="p-15"
[015] Preferably, the crystallization seeds comprise aluminium and iron phosphatecrystals, said seeds added in an amount of 0.05-0.3 g/L, such as 0.05-0.2 g/L, and preferably0.05-0.15 g/L. id="p-16" id="p-16" id="p-16" id="p-16" id="p-16" id="p-16" id="p-16" id="p-16" id="p-16" id="p-16" id="p-16" id="p-16" id="p-16"
[016] The precipitation steps are, preferably, conducted at a temperature in the interval of 55-95 °C, such as 55-85 °C, and preferably 65-75 °C. id="p-17" id="p-17" id="p-17" id="p-17" id="p-17" id="p-17" id="p-17" id="p-17" id="p-17" id="p-17" id="p-17" id="p-17" id="p-17"
[017] Preferably, the precipitation steps each have a residence time in the interval of 2 - 24 h, such as 2 - 12 h, preferably 2 - 6 h. id="p-18" id="p-18" id="p-18" id="p-18" id="p-18" id="p-18" id="p-18" id="p-18" id="p-18" id="p-18" id="p-18" id="p-18" id="p-18"
[018] According to an embodiment, freely combinable with the above aspect andembodiments, a higher amount of FePO4 and AIPO4 is precipitated in the first precipitationstep than in the second precipitation step. The first precipitate is removed by filtration, andthe |eachate comprising traces of aluminium and iron is led to a second precipitation stepwhere the pH is adjusted to an interval of pH 3 to 6.5, such as pH 3 to 6, preferably pH 3 to5.5. A second precipitate is formed and removed by filtration. The resulting |eachate is substantially free from copper, aluminium and iron and rich in NI\/IC-metals and lithium. id="p-19" id="p-19" id="p-19" id="p-19" id="p-19" id="p-19" id="p-19" id="p-19" id="p-19" id="p-19" id="p-19" id="p-19" id="p-19"
[019] Optionally, this |eachate is subjected to further treatment to separate lithium and precipitate NMC metals in the form of hydroxides. id="p-20" id="p-20" id="p-20" id="p-20" id="p-20" id="p-20" id="p-20" id="p-20" id="p-20" id="p-20" id="p-20" id="p-20" id="p-20"
[020] According to an embodiment, freely combinable with the above aspect andembodiments, the precipitates comprising FePO4 and AIPO4 are washed with an acidaqueous solution, preferably an aqueous solution having a pH in the interval of pH 1.5 - 5.5,preferably pH 1.5 - 2.5. The precipitate formed in the first precipitation step, as well as inthe second precipitation step, is washed with said acid aqueous solution, and the acid filtrate is recirculated to the black mass leaching unit.
Short description of the drawings id="p-21" id="p-21" id="p-21" id="p-21" id="p-21" id="p-21" id="p-21" id="p-21" id="p-21" id="p-21" id="p-21" id="p-21" id="p-21"
[021] Different aspects are now described, by way of example, with reference to the accompanying drawings, in which: 190271SE id="p-22" id="p-22" id="p-22" id="p-22" id="p-22" id="p-22" id="p-22" id="p-22" id="p-22" id="p-22" id="p-22" id="p-22" id="p-22"
[022] Figure 1 is a schematic flow chart illustrating a process for recovery of cathodemetals in the recycling of batteries. ln the flow chart, a leaching step (A) is followed by afiltration step (B) from which the leach residue is led to a washing step (W). The filtrate fromB is led to a copper extraction step (C) with an associated copper recovery step (D), e.g.solvent extraction of copper with one or more (mixtures) of copper-specific extractingcompounds, followed by copper electroextraction or electrowinning, producing coppermetal. A substantially copper free leachate is then led to an aluminium and iron precipitationunit (E). After removal of copper, aluminium and iron, the NMC metals are precipitated instep (F) together with minimal amounts of lithium. ln step (G) the lithium is selectivelydissolved, producing an NMC hydroxide cake. The lithium rich solution from step F is led to alithium recovery unit (H). Wash solutions from steps W and G are recirculated back to the initial leaching step A. id="p-23" id="p-23" id="p-23" id="p-23" id="p-23" id="p-23" id="p-23" id="p-23" id="p-23" id="p-23" id="p-23" id="p-23" id="p-23"
[023] Figure 2 is a schematic flow chart illustrating the Al and Fe phosphateprecipitation operation. A leachate (I) containing substantially no copper or only smallamounts of copper enters a first precipitation tank 200 via a pH adjustment unit 100. After acertain residence time, the content of the tank 200 is filtered in a filter 300, producing aprecipitate and a leachate. The precipitate is led to a washing unit 310 to be subjected to anacid washing solution, while the leachate is led to a second precipitation tank 500 via a pHadjustment unit 400. After another residence time, which can be the same or different as inthe previous step, the content of the tank 500 is filtered in the filter 600, producing aleachate IV which is substantially free from copper, aluminium and iron, and rich in NI\/|C-metals and lithium, and a precipitate, that is washed in unit 610, comprising residual aluminium and iron in the form of phosphates.
Description id="p-24" id="p-24" id="p-24" id="p-24" id="p-24" id="p-24" id="p-24" id="p-24" id="p-24" id="p-24" id="p-24" id="p-24" id="p-24"
[024] Before the present invention is described, it is to be understood that theterminology employed herein is used for the purpose of describing particular embodimentsonly and is not intended to be limiting, since the scope ofthe present invention will be limited only by the appended claims and equivalents thereof. id="p-25" id="p-25" id="p-25" id="p-25" id="p-25" id="p-25" id="p-25" id="p-25" id="p-25" id="p-25" id="p-25" id="p-25" id="p-25"
[025] Batteries can coarsely be divided into disposable and rechargeable batteries.
Disposable batteries are mainly alkaline, meaning that the cathode is made of manganese 190271SE oxide, the anode is a zinc powder, and the electrolyte is potassium hydroxide. Currently avery large proportion ofall disposable batteries end up as landfill. Rechargeable batteriescan be based on different Chemistry, illustrated by the increasingly popular lithium ionbattery, where lithium cobalt oxide is used as the cathode and carbon as the anode. Anotherexample is the nickel-cadmium battery, nickel-zinc, and the nickel-metal hydride batteries.While rechargeable batteries can be recharged hundreds or even thousands of times, andused for a long time, they will eventually need to be discarded. ln order to minimize wasteand to conserve the earth's resources, it is necessary to recycle both disposable and rechargeable batteries and to recover their components. id="p-26" id="p-26" id="p-26" id="p-26" id="p-26" id="p-26" id="p-26" id="p-26" id="p-26" id="p-26" id="p-26" id="p-26" id="p-26"
[026] ln the present disclosure, the term "battery" is intended to comprise both disposable and rechargeable batteries. id="p-27" id="p-27" id="p-27" id="p-27" id="p-27" id="p-27" id="p-27" id="p-27" id="p-27" id="p-27" id="p-27" id="p-27" id="p-27"
[027] A battery comprises many different materials, such as plastic and metal thatmakes up its housing, the cathode and anode materials, and an electrolyte. The recycling ofbatteries starts by sorting waste batteries according to their chemical composition, and thencrushing or shredding them. The shredded batteries are then moved along a conveyer beltto a shaker, where they pass through a series of filters. Plastic and metal shreds areseparated, washed and collected for recycling. This shredding and refining process results ina product called 'black mass', which contains electrolyte, cathode and anode materials, andother components. As the sorting of batteries difficult, and sometimes neglected, thecomposition of the black mass will vary. Examples of different compositions of black mass (BM) rich in either nickel, NMC or cobalt is given in Table 1 below. 190271SE Table 1. Compositions of black mass (BM) Al Co Ni I\/|n Li Fe Cu Graphite Nickel rich Bl\/l (wt%) 12.01 2.67 21.13 2.47 3.71 0.90 3.89 26.69 Nl\/lCrich Bl\/l(wt%) 14.16 9.4 9.61 9.12 3.95 0.12 4.25 29.13 Cobaltrich Bl\/l(wt%) 12.97 26.41 0.10 0.10 3.70 0.90 3.89 26.71 id="p-28" id="p-28" id="p-28" id="p-28" id="p-28" id="p-28" id="p-28" id="p-28" id="p-28" id="p-28" id="p-28" id="p-28" id="p-28"
[028] ln the present description and claims, the term "black mass" is thus used todescribe the crushed or shredded inner contents of batteries, fed to a recycling process, after the removal of plastic, solid metal parts etc. id="p-29" id="p-29" id="p-29" id="p-29" id="p-29" id="p-29" id="p-29" id="p-29" id="p-29" id="p-29" id="p-29" id="p-29" id="p-29"
[029] The term "cathode materials" and "cathode metals" are used interchangeablyto describe the materials or metals constituting the cathode in a battery. Common cathodematerials are lithium cobalt oxide (also referred to as lithium cobaltate), lithium manganeseoxide (also known as spinel or lithium manganate), lithium iron phosphate, as well as lithiumnickel manganese cobalt (frequently abbreviated NMC) and lithium nickel cobalt aluminium oxide (NCA). id="p-30" id="p-30" id="p-30" id="p-30" id="p-30" id="p-30" id="p-30" id="p-30" id="p-30" id="p-30" id="p-30" id="p-30" id="p-30"
[030] The vast majority of lithium-ion batteries use graphite powder as an anodematerial. The term "anode material" however comprises natural and artificial graphite,activated carbon, carbon black, conductive additives, LTO (lithium titanate), surface-functionalized silicon, and high-performance powdered graphene. id="p-31" id="p-31" id="p-31" id="p-31" id="p-31" id="p-31" id="p-31" id="p-31" id="p-31" id="p-31" id="p-31" id="p-31" id="p-31"
[031] Finally, it must be noted that, as used in this specification and the appended claims, the singular forms a, an," and "the" include plural referents unless the context clearly dictates otherwise.[032] A first aspect of the present disclosure relates to a process for the recovery ofaluminium and iron in the recycling of rechargeable batteries, wherein said processcomprises the following steps:a) extracting copper from a leachate from black mass producing a first leachate,b) adding phosphoric acid (H3PO4) to the leachate from step a), c) adjusting the pH to form iron phosphate (FePO4) and aluminium phosphate (AIPO4), 190271SE8 d) precipitating and removing the formed FePO4 and AIPO4, ande) forming a filtrate for recovery of cathode metals. id="p-33" id="p-33" id="p-33" id="p-33" id="p-33" id="p-33" id="p-33" id="p-33" id="p-33" id="p-33" id="p-33" id="p-33" id="p-33"
[033] The first leachate typically has a pH below 1.5, such as below 1, and preferablybelow 0.7, such as about pH 0.5. id="p-34" id="p-34" id="p-34" id="p-34" id="p-34" id="p-34" id="p-34" id="p-34" id="p-34" id="p-34" id="p-34" id="p-34" id="p-34"
[034] Iron and aluminium have low solubility as phosphates in their trivalent stateand the addition of H3PO4 to the first leachate, thus, efficiently precipitates iron andaluminium for further recovery. The precipitation of Fe and Alin the form of phosphates isadvantageous compared to the precipitation in the form of hydroxides, as Al and Fehydroxides tend to absorb NMC metals and lithium. Further, Al and Fe phosphates are easier to separate by filtration and also easier to wash than the corresponding hydroxides. id="p-35" id="p-35" id="p-35" id="p-35" id="p-35" id="p-35" id="p-35" id="p-35" id="p-35" id="p-35" id="p-35" id="p-35" id="p-35"
[035] According to an embodiment of said aspect, the precipitation is performed intwo separate steps at different pH, which is advantageous because a higher efficiency in the removal of aluminium and iron is achieved. id="p-36" id="p-36" id="p-36" id="p-36" id="p-36" id="p-36" id="p-36" id="p-36" id="p-36" id="p-36" id="p-36" id="p-36" id="p-36"
[036] ln the first precipitation step the pH is adjusted, optionally with alkali, to aninterval of pH 1.5 to 4, such as pH 1.5 to 3.5, preferably pH 1.5 to 3. ln a second step the pHis adjusted, optionally with alkali, to an interval of pH 3 to 6.5, such as pH 3 to 6, preferablypH 3 to 5.5. id="p-37" id="p-37" id="p-37" id="p-37" id="p-37" id="p-37" id="p-37" id="p-37" id="p-37" id="p-37" id="p-37" id="p-37" id="p-37"
[037] Preferably, crystallization seeds are added to precipitate FePO4 and AIPO4 inthe first precipitation step. Adding crystallization seeds promotes crystallization andfacilitates agglomeration of FePO4 and AIPO4 and, thus, allows efficient separation by filtration. id="p-38" id="p-38" id="p-38" id="p-38" id="p-38" id="p-38" id="p-38" id="p-38" id="p-38" id="p-38" id="p-38" id="p-38" id="p-38"
[038] Preferably, the crystallization seeds comprise aluminium and iron phosphatecrystals, and said seeds are added in an amount of 0.05-0.3 g/L, such as 0.05-0.2 g/L, andpreferably 0.05-O.15 g/L. id="p-39" id="p-39" id="p-39" id="p-39" id="p-39" id="p-39" id="p-39" id="p-39" id="p-39" id="p-39" id="p-39" id="p-39" id="p-39"
[039] Performing the first precipitation at a low pH has the advantage of minimizingthe co-precipitation of lithium and NMC metals. When the second precipitation step isperformed, less solids are present. This is advantageous, as this counteracts the higher tendency for co-precipitation at higher pH. 190271SE9 id="p-40" id="p-40" id="p-40" id="p-40" id="p-40" id="p-40" id="p-40" id="p-40" id="p-40" id="p-40" id="p-40" id="p-40" id="p-40"
[040] The precipitation steps are typically conducted at a temperature in the intervalof 55-95 °C, such as 55-85 °C, and preferably 65-75 °C. An advantage is that the efficiency of the precipitation is higher at an increased temperature. id="p-41" id="p-41" id="p-41" id="p-41" id="p-41" id="p-41" id="p-41" id="p-41" id="p-41" id="p-41" id="p-41" id="p-41" id="p-41"
[041] The precipitation steps typically have a residence time in the interval of 2 - 24h, such as 2 - 12 h, preferably 2 - 6 h, and advantageously, this allows a high amount of FePO4 and AlPO4to form and agglomerate. id="p-42" id="p-42" id="p-42" id="p-42" id="p-42" id="p-42" id="p-42" id="p-42" id="p-42" id="p-42" id="p-42" id="p-42" id="p-42"
[042] Preferably, a higher amount of FePO4 and AIPO4 are precipitated at the firstprecipitation step than in the second precipitation step since more FePO4 and AIPO4 are present in the first |eachate that can be precipitated. id="p-43" id="p-43" id="p-43" id="p-43" id="p-43" id="p-43" id="p-43" id="p-43" id="p-43" id="p-43" id="p-43" id="p-43" id="p-43"
[043] Preferably, the precipitate comprising FePO4 and AlPO4is washed with anaqueous solution having a pH in the interval of pH 1.5 - 5.5, preferably pH 1.5 - 2.5, for efficient washing. id="p-44" id="p-44" id="p-44" id="p-44" id="p-44" id="p-44" id="p-44" id="p-44" id="p-44" id="p-44" id="p-44" id="p-44" id="p-44"
[044] ln a preferred embodiment, the filtrate contains lithium, nickel, manganeseand cobalt in amounts suitable for recovery, and is substantially free of aluminium, copper,and iron, such as containing less than 10 ppm, preferably less than 5 ppm ofaluminium and/or iron and/or copper. id="p-45" id="p-45" id="p-45" id="p-45" id="p-45" id="p-45" id="p-45" id="p-45" id="p-45" id="p-45" id="p-45" id="p-45" id="p-45"
[045] The process disclosed herein results in a more effective removal of iron andaluminium, while minimizing co-precipitation ofthe valuable NMC metals, nickel,manganese and cobalt. Simultaneously, the process results in the production of a lithiumrich filtrate which is substantially free from copper, iron and aluminium, and which therefore is well suited both for the precipitation of NMC metals and for the recovery of lithium.
Examples Example 1: Al and Fe phosphate precipitation id="p-46" id="p-46" id="p-46" id="p-46" id="p-46" id="p-46" id="p-46" id="p-46" id="p-46" id="p-46" id="p-46" id="p-46" id="p-46"
[046] A |eachate (I) from which substantially all copper has been removed, is led intoa precipitation unit 100 as schematically shown in Fig. 2. ln this example, the flow of|eachate is about 60 L/h and the pH of this initial |eachate is about 0.5. ln a first step, the pH is adjusted to about 2.5 by the addition of 85 % phosphoric acid (H3PO4) and sodium l90271SE hydroxide (NaOH, solid). The leachate is collected in a first precipitation tank 200, to whichcrystallization seeds (Al and Fe phosphate crystals) are added, to a concentration of about0.1 g/l in said tank. The residence time in the first precipitation tank is preferably about 24 hat a temperature of at least 70 °C, following which the contents are led to a separation unit 300, for example a filter, and separated into a precipitate and a filtrate. id="p-47" id="p-47" id="p-47" id="p-47" id="p-47" id="p-47" id="p-47" id="p-47" id="p-47" id="p-47" id="p-47" id="p-47" id="p-47"
[047] The precipitate is led to a washing unit 310, producing a washed precipitate (II)of FePO4 and AlPO4with trace amounts of co-precipitated Li and NMC and a filtrate (III). Thisfiltrate (III) is preferably recycled, for example by leading it to a leaching unit up-stream in the recycling process (not shown). id="p-48" id="p-48" id="p-48" id="p-48" id="p-48" id="p-48" id="p-48" id="p-48" id="p-48" id="p-48" id="p-48" id="p-48" id="p-48"
[048] The pH ofthe filtrate from the precipitation tank 200 and the separation unit300 is adjusted to about pH 5, in unit 400, for example by the addition of NaOH and led to asecond precipitation tank 500. The residence time in the second precipitation tank ispreferably about 24 h at a temperature of at least 70 °C. Optionally, crystallization seeds (Aland Fe phosphate crystals) are added, to a concentration of about 0.1 g/l in said tank. Thecontents ofthe second precipitation tank are then led to a separation unit 600, for examplea filter, producing a lithium rich filtrate (IV) free of Cu, Al and Fe, and a solid precipitate. Thisprecipitate is preferably washed, in unit 610, producing a washed solid precipitate (VI)containing residual Al and Fe, and co-precipitated Ni, I\/In and Co, and a filtrate (VII) which is recirculated to wash the Al and Fe phosphate precipitate in unit 310. id="p-49" id="p-49" id="p-49" id="p-49" id="p-49" id="p-49" id="p-49" id="p-49" id="p-49" id="p-49" id="p-49" id="p-49" id="p-49"
[049] The Al-Fe-precipitation works without any organic solvents, using only bulkchemicals such as NaOH and H3PO4, and produces an aqueous NI\/IC-rich stream which issubstantially free from Cu, Al and Fe. The two precipitate streams are formed, a mainprecipitate consisting substantially of FePO4 and AIPO4 with minute amounts of co-precipitated Ni, I\/In and Co, and a second precipitate, comprising residual FePO4 and AIPO4and co-precipitated Ni, I\/In and Co. With an incoming flow of 60 l/h of a leachate having acomposition typical for battery recycling processes, and an estimated 60 l/h of lithium-richleachate /filtrate is produced. The main precipitate stream will be about 1.5 kg/h and thesecondary precipitate stream 0.3 kg/h indicating that the main precipitate is indeed the Al and few phosphates. l90271SE11 id="p-50" id="p-50" id="p-50" id="p-50" id="p-50" id="p-50" id="p-50" id="p-50" id="p-50" id="p-50" id="p-50" id="p-50" id="p-50"
[050] An acid aqueous solution is preferably added in washing unit 610, and thefiltrate led to washing unit 310. The consumption of water is minimized, as the filtrate fromunit 310 is recycled to unit operations up-stream in the recycling / recovery process.
Estimated process flows are shown in Table 3: Table 3. Estimated process flows in an Al-Fe-phosphate precipitation unit ln Out Cu-free leachate 60 l/h Phosphoric acid (85 %) 1.5 kg/h Sodium hydroxide 0.75 kg/h + 1.2 kg/h Water 3.6 l/h FePO4 and AIPO4 with trace 1.5 kg/hamounts of Li and NMCmetals NI\/IC-rich filtrate without 60 l/hCu, Al, Fe Residual Al and Fe 0.3 kg/hphosphate, co-precipitatedNMC metals Filtrate 3.6 l/h id="p-51" id="p-51" id="p-51" id="p-51" id="p-51" id="p-51" id="p-51" id="p-51" id="p-51" id="p-51" id="p-51" id="p-51" id="p-51"
[051] ln an industrial scale process, the first, copper free leachate is typically addedin an amount of 40 000-80 000 L/h, such as 50 000-70 000 L/h, or preferably 55 000-65 000L/h. Phosphoric acid, H3PO4 at a concentration of 85% is typically added to the first leachatein an amount of 500-2500 kg/h, such as 1000-2000 kg/h, preferably 1250-1750 kg/h to a pH of about 2.5 in the first precipitation step. id="p-52" id="p-52" id="p-52" id="p-52" id="p-52" id="p-52" id="p-52" id="p-52" id="p-52" id="p-52" id="p-52" id="p-52" id="p-52"
[052] ln a second precipitation step, NaOH (s) is typically added to the first leachatein an amount of 250-1500 kg/h, such as 500-1000 kg/h, preferably 700-800 kg/h in order to adjust the pH to about pH 5 for the second precipitation. id="p-53" id="p-53" id="p-53" id="p-53" id="p-53" id="p-53" id="p-53" id="p-53" id="p-53" id="p-53" id="p-53" id="p-53" id="p-53"
[053] The process disclosed herein has several advantages. The precipitation of Al and Fe in the form of phosphates minimizes the co-precipitation of lithium and NMC metals.
Further, Al and Fe phosphates are easier to filter and the precipitate formed is easier to wash than for example a precipitate of the corresponding hydroxides. id="p-54" id="p-54" id="p-54" id="p-54" id="p-54" id="p-54" id="p-54" id="p-54" id="p-54" id="p-54" id="p-54" id="p-54" id="p-54"
[054] Additionally, the process is very flexible and can handle incoming black mass leachates with varying amounts of aluminium and iron, as these are efficiently removed at l90271SE12 an early stage. This is particularly advantageous as large-scale recovery of rechargeablelithium ion batteries will involve the handling of black mass of varying composition. Theprocess disclosed herein will guarantee an efficient recovery ofthe NMC metals and lithium also when initial leachate composition varies. id="p-55" id="p-55" id="p-55" id="p-55" id="p-55" id="p-55" id="p-55" id="p-55" id="p-55" id="p-55" id="p-55" id="p-55" id="p-55"
[055] Without further elaboration, it is believed that a person skilled in the art can,using the present description, including the examples, utilize the present invention to itsfullest extent. Also, although the invention has been described herein with regard to itspreferred embodiments, which constitute the best mode presently known to the inventors,it should be understood that various changes and modifications as would be obvious to onehaving the ordinary skill in this art may be made without departing from the scope ofthe invention which is set forth in the claims appended hereto. id="p-56" id="p-56" id="p-56" id="p-56" id="p-56" id="p-56" id="p-56" id="p-56" id="p-56" id="p-56" id="p-56" id="p-56" id="p-56"
[056] Thus, while various aspects and embodiments have been disclosed herein,other aspects and embodiments will be apparent to those skilled in the art. The variousaspects and embodiments disclosed herein are for purposes of illustration and are notintended to be limiting, with the true scope and spirit being indicated by the following claims.

Claims (10)

l90271SE13
1. Claims1. A process for removal of aluminium and iron in the recycling of rechargeablelithium ion batteries, said process comprising:a) extracting copper from a leachate from black mass producing a first leachate,b) adding phosphoric acid (H3PO4) to the leachate from step a),c) adjusting the pH to form iron phosphate (FePO4) and aluminium phosphate (AIPO4),d) precipitating and removing the formed FePO4 and AIPO4, ande) forming a filtrate for recovery of cathode metals.
2. The process according to claim 1, wherein the precipitation is performed in two steps at different pH.
3. The process according to claim 2, wherein the pH in a first precipitation step isadjusted to an interval of pH 1.5 to 4, such as pH 1.5 to 3.5, preferably pH 1.5 to 3, andwherein the pH, in a second step, is adjusted to an interval of pH 3 to 6.5, such as pH 3 to 6, preferably pH 3 to 5.5.
4. The process according to claim 2 or 3, wherein crystallization seeds are added to precipitate FePO4 and AIPO4 in the first precipitation step.
5. The process according to claim 4, wherein the crystallization seeds comprisealuminium and iron phosphate crystals and wherein said seeds are added in an amount of 0.05-O.3 g/L, such as 0.05-0.2 g/L, preferably 0.05-O.15 g/L.
6. The process according to any one of the claims 3 - 5, wherein the precipitationsteps are conducted at a temperature in the interval of 55 - 95 °C, such as 55 - 85 °C, preferably 65 - 75 °C.
7. The process according to any one of the claims 3 - 6, wherein eachprecipitation step has a residence time in the interval of 2 - 24 h, such as 2 - 12 h, preferably 2-6h. l90271SE14
8. The process according to any one of the claims 3 - 7, wherein a higher amountof FePO4 and AIPO4 is precipitated in the first precipitation step than in the second precipitation step.
9. The process according to any one of the preceding claims, wherein theprecipitate comprising FePO4 and AIPO4 is washed with an aqueous solution having a pH in the interval of pH 1.5 - 5.5, preferably pH 1.5 - 2.5.
10. The process according to any one of the preceding claims, wherein the fi|tratecomprises lithium, nickel, manganese and cobalt, and less than 10 ppm, such as less than 5 ppm of aluminium and/or iron and/or copper.
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KR1020217036676A KR20220031997A (en) 2019-04-15 2020-04-14 Process for recovery of cathode material in battery recycling
PCT/EP2020/060487 WO2020212363A1 (en) 2019-04-15 2020-04-14 Process for the recovery of cathode materials in the recycling of batteries
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JP2021560619A JP7612604B2 (en) 2019-04-15 2020-04-14 Method for recovering cathode materials in battery recycling
ES20719981T ES2980579T3 (en) 2019-04-15 2020-04-14 Process for the recovery of cathode materials in battery recycling
US17/601,865 US11509000B2 (en) 2019-04-15 2020-04-14 Process for the recovery of cathode materials in the recycling of batteries by removing aluminum and iron
EP24159949.7A EP4372112A3 (en) 2019-04-15 2020-04-14 Process for the recovery of cathode materials in the recycling of batteries
CN202511227047.6A CN121046640A (en) 2019-04-15 2020-04-14 Method for recovering cathode material in battery recycling
HUE20719981A HUE066510T2 (en) 2019-04-15 2020-04-14 Process for the recovery of cathode materials in the recycling of batteries
PL20719981.1T PL3956487T3 (en) 2019-04-15 2020-04-14 METHOD OF RECOVERY OF CATHODE MATERIALS DURING BATTERY RECYCLING
HRP20240522TT HRP20240522T1 (en) 2019-04-15 2020-04-14 PROCEDURE OF RECOVERY OF CATHODE MATERIALS IN BATTERY RECYCLING
EP20719981.1A EP3956487B1 (en) 2019-04-15 2020-04-14 Process for the recovery of cathode materials in the recycling of batteries
CN202080028603.6A CN113924374A (en) 2019-04-15 2020-04-14 Method for recovering cathode material in battery recycling
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