Innovations in Li-ion Battery Recycling: Advanced Physical Separation, Characterization, and Industrial Process Integration

Tommi Rinne

Innovations in Li-ion Battery Recycling: Advanced Physical Separation, Characterization, and Industrial Process Integration

Julkaisun otsikon käännös: Innovaatioita Li-ioniakkujen kierrätyksen saralla: uuden sukupolven karakterisointi- ja erotusmenetelmät, sekä näkökulmia teolliseen prosessi-integraatioon

Tommi Rinne

Tutkimustuotos: Doctoral Thesis › Collection of Articles

Abstrakti

Sähköajoneuvomarkkinoiden eksponentiaalinen kasvu ja kestävien energianvarastointiratkaisujen kasvava kysyntä ovat johtaneet litiumioniakkujen tuotannon merkittävään lisääntymiseen. Tämän seurauksena akkutuotannossa välttämättömien kriittisten raaka-aineiden, kuten Co, Ni, Cu, grafiitti ja Li kysynnän ennustetaan tulevina vuosina kasvavan räjähdysmäisesti. Jäteakkujen ns. mustan massan käsittelyssä nykyisin hyödynnettävät teolliset kierrätysteknologiat (pyrometallurgia ja hydrometallurgia) ovat osin rajoittuneita ja sisältävät haittavaikutuksia. Tästä syystä tässä väitöstyössä tutkittiin vaahdotusta erotusprosessina akkujen ns. "suorakierrätyksen" mahdollistamiseksi. Suorakierrätyksessä akun anodi ja katodiaktiivimineraalit (KAM) otetaan talteen korkean jalostusasteen tuotteena. Työ sisälsi useita tutkimussuuntia, käsitellen esim. vaahdotusmekanismien ymmärtämistä sekä teollista prosessi-integraatiota. Työssä mm. kehitettiin uudenlainen röntgentomografiaan (xRCT) perustuva menetelmä vaahtojakeiden karakterisoimiseksi, jolla kiintoaineiden sijoittumista vaahdon eri kantajafaaseissa (ilma, vesi) kyettiin havainnoimaan. Tämän avulla osoitettiin, että kerosiini (yleisesti käytetty grafiittikerääjä) adsorboituu epäselektiivisesti litiumkobolttioksidi (LCO) partikkelien pintaan. Toisessa hankkeessa tutkittiin KAM-partikkelien flokkulaatiota. Tässä hankkeessa havaittiin, että tietyissä prosessiolosuhteissa LCO on mahdollista flokkuloida selektiivisesti grafiitti–LCO-seoksista. Näiden havaintojen pohjalta tutkittiin yhdistettyä flokkulaatio–vaahdotus-prosessia ja osoitettiin, että vaahdottamalla talteenotetun grafiitin puhtauteen voidaan vaikuttaa positiivisesti LCO-partikkeleja flokkuloimalla. Lisäksi väitöstyössä tutkittiin akkukierrätyksen integrointia teollisiin kuonankäsittelyprosesseihin. Tässä hankkeessa osoitettiin, että mustasta massasta voidaan ns. sitojapolymeerien läsnä ollessa vaahdottamalla erottaa tehokkaasti aktiivimineraalikonsentraatti sekä Cu–Al-konsentraatti. Näiden konsentraattien jatkojalostus demonstroitiin sekoitettuna nikkeli- ja kuparikuonaan, joiden pyrometallurginen käsittely mahdollisti arvometallien (Co, Ni, Cu, Fe) talteenoton ilman tarvetta lisätylle pelkistimelle. Al, Li ja Mn havaittiin kuitenkin päätyvän sekundäärikuonaan. Yhteenvetona, tämä väitöstyö esittelee tutkimuksen jäteakkujen karakterisointi- ja erotustekniikoista (xRCT, vaahdotus, flokkulaatio), sekä näkökulmia teolliseen prosessiintegraatioon. Havainnot edistävät kustannustehokkaampien ja kestävämpien kierrätysmenetelmien kehittämistä. Tutkittujen menetelmien pohjalta voidaan tulevaisuudessa vastata kriittisten akkumineraalien kasvavaan kysyntään.

Julkaisun otsikon käännös	Innovaatioita Li-ioniakkujen kierrätyksen saralla: uuden sukupolven karakterisointi- ja erotusmenetelmät, sekä näkökulmia teolliseen prosessi-integraatioon
Alkuperäiskieli	Englanti
Pätevyys	Tohtorintutkinto
Myöntävä instituutio	Aalto-yliopisto
Valvoja/neuvonantaja	Serna Guerrero, Rodrigo, Vastuuprofessori Serna Guerrero, Rodrigo, Ohjaaja
Kustantaja	Aalto University
Painoksen ISBN	978-952-64-2000-4
Sähköinen ISBN	978-952-64-2001-1
Tila	Julkaistu - 2024
OKM-julkaisutyyppi	G5 Artikkeliväitöskirja

Tutkimusalat

vaahdotus
selektiivinen flokkulaatio
kiertotalous
grafiitti
röntgentomografia

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http://urn.fi/URN:ISBN:978-952-64-2001-1

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Karppinen, M. (Manager)
Kemian tekniikan korkeakoulu
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@phdthesis{5e07fab654f142c5aa0f656fc55f0112,

title = "Innovations in Li-ion Battery Recycling: Advanced Physical Separation, Characterization, and Industrial Process Integration",

abstract = "The exponential growth in the electric vehicle market and the rising demand for sustainable energy storage solutions have resulted in a significant increase in the production rates of lithium-ion batteries (LIBs). Consequently, the demand for critical raw materials needed for LIB manufacturing (e.g., Co, Ni, Cu, graphite, and Li) is projected to increase rapidly in the coming years.Current industrial-scale recycling technologies, namely pyrometallurgy and hydrometallurgy, face limitations in processing end-of-life LIBs and recovering valuables from their active component mixtures (a.k.a., black mass). To overcome these limitations, this Thesis investigated the potential of froth flotation as a separation process for direct recycling of LIBs, an approach aimed at preserving the structural and chemical integrity of the anode and cathode active minerals (CAMs).The research comprised multiple campaigns ranging from fundamental understanding of flotation mechanisms to the integration of flotation in industrial processes. Firstly, a novel tomographybased methodology was developed to characterize flotation froths, thus providing insights into the extraction mechanisms of solid particles. A previously overlooked phenomenon was uncovered, where binder-free lithium cobalt oxide (LCO) particles were observed to be hydrophobized by a common oily collector – indicating a lack of collector selectivity. Another campaign focused on flocculation of CAMs, specifically demonstrating the potential for selectively flocculating LCO particles in mixtures with graphite. Building on these insights, a combined approach of selective flocculation and froth flotation was studied, showing promise in improving the selectivity of graphite separation from black mass through a CAM-selective flocculation pretreatment .Lastly, the integration of LIB recycling into existing industrial slag cleaning processes was studied. It was demonstrated that, in the presence of binder polymers, flotation can effectively separate an industrial black mass into a froth concentrate rich in active minerals and an underflow concentrate comprising current collector metals. Furthermore, the refining of these concentrates was successfully integrated with industrial Ni slag cleaning and Cu slag cleaning processes, revealing synergistic benefits. The integrated processes were found to be chemically self-sustaining, requiring no additional reductants for refining valuable metals Cu, Co, Ni, and Fe, although loss of Li, Al, and Mn to the slag phase was observed. In summary, this thesis presents a comprehensive investigation into advanced characterization and physical separation techniques for LIB recycling, with perspectives on industrial process integration. The findings contribute to the development of more efficient, cost-effective, and environmentally sustainable recycling methods. The studied methods are expected to address existing concerns associated with the growing demand for critical battery materials.",

keywords = "froth flotation, selective flocculation, circular economy, graphite, x-ray computed tomography, vaahdotus, selektiivinen flokkulaatio, kiertotalous, grafiitti, r{\"o}ntgentomografia, froth flotation, selective flocculation, circular economy, graphite, x-ray computed tomography",

author = "Tommi Rinne",

year = "2024",

language = "English",

isbn = "978-952-64-2000-4",

series = "Aalto University publication series DOCTORAL THESES",

publisher = "Aalto University",

number = "182",

address = "Finland",

school = "Aalto University",

}

TY - BOOK

T1 - Innovations in Li-ion Battery Recycling: Advanced Physical Separation, Characterization, and Industrial Process Integration

AU - Rinne, Tommi

PY - 2024

Y1 - 2024

N2 - The exponential growth in the electric vehicle market and the rising demand for sustainable energy storage solutions have resulted in a significant increase in the production rates of lithium-ion batteries (LIBs). Consequently, the demand for critical raw materials needed for LIB manufacturing (e.g., Co, Ni, Cu, graphite, and Li) is projected to increase rapidly in the coming years.Current industrial-scale recycling technologies, namely pyrometallurgy and hydrometallurgy, face limitations in processing end-of-life LIBs and recovering valuables from their active component mixtures (a.k.a., black mass). To overcome these limitations, this Thesis investigated the potential of froth flotation as a separation process for direct recycling of LIBs, an approach aimed at preserving the structural and chemical integrity of the anode and cathode active minerals (CAMs).The research comprised multiple campaigns ranging from fundamental understanding of flotation mechanisms to the integration of flotation in industrial processes. Firstly, a novel tomographybased methodology was developed to characterize flotation froths, thus providing insights into the extraction mechanisms of solid particles. A previously overlooked phenomenon was uncovered, where binder-free lithium cobalt oxide (LCO) particles were observed to be hydrophobized by a common oily collector – indicating a lack of collector selectivity. Another campaign focused on flocculation of CAMs, specifically demonstrating the potential for selectively flocculating LCO particles in mixtures with graphite. Building on these insights, a combined approach of selective flocculation and froth flotation was studied, showing promise in improving the selectivity of graphite separation from black mass through a CAM-selective flocculation pretreatment .Lastly, the integration of LIB recycling into existing industrial slag cleaning processes was studied. It was demonstrated that, in the presence of binder polymers, flotation can effectively separate an industrial black mass into a froth concentrate rich in active minerals and an underflow concentrate comprising current collector metals. Furthermore, the refining of these concentrates was successfully integrated with industrial Ni slag cleaning and Cu slag cleaning processes, revealing synergistic benefits. The integrated processes were found to be chemically self-sustaining, requiring no additional reductants for refining valuable metals Cu, Co, Ni, and Fe, although loss of Li, Al, and Mn to the slag phase was observed. In summary, this thesis presents a comprehensive investigation into advanced characterization and physical separation techniques for LIB recycling, with perspectives on industrial process integration. The findings contribute to the development of more efficient, cost-effective, and environmentally sustainable recycling methods. The studied methods are expected to address existing concerns associated with the growing demand for critical battery materials.

AB - The exponential growth in the electric vehicle market and the rising demand for sustainable energy storage solutions have resulted in a significant increase in the production rates of lithium-ion batteries (LIBs). Consequently, the demand for critical raw materials needed for LIB manufacturing (e.g., Co, Ni, Cu, graphite, and Li) is projected to increase rapidly in the coming years.Current industrial-scale recycling technologies, namely pyrometallurgy and hydrometallurgy, face limitations in processing end-of-life LIBs and recovering valuables from their active component mixtures (a.k.a., black mass). To overcome these limitations, this Thesis investigated the potential of froth flotation as a separation process for direct recycling of LIBs, an approach aimed at preserving the structural and chemical integrity of the anode and cathode active minerals (CAMs).The research comprised multiple campaigns ranging from fundamental understanding of flotation mechanisms to the integration of flotation in industrial processes. Firstly, a novel tomographybased methodology was developed to characterize flotation froths, thus providing insights into the extraction mechanisms of solid particles. A previously overlooked phenomenon was uncovered, where binder-free lithium cobalt oxide (LCO) particles were observed to be hydrophobized by a common oily collector – indicating a lack of collector selectivity. Another campaign focused on flocculation of CAMs, specifically demonstrating the potential for selectively flocculating LCO particles in mixtures with graphite. Building on these insights, a combined approach of selective flocculation and froth flotation was studied, showing promise in improving the selectivity of graphite separation from black mass through a CAM-selective flocculation pretreatment .Lastly, the integration of LIB recycling into existing industrial slag cleaning processes was studied. It was demonstrated that, in the presence of binder polymers, flotation can effectively separate an industrial black mass into a froth concentrate rich in active minerals and an underflow concentrate comprising current collector metals. Furthermore, the refining of these concentrates was successfully integrated with industrial Ni slag cleaning and Cu slag cleaning processes, revealing synergistic benefits. The integrated processes were found to be chemically self-sustaining, requiring no additional reductants for refining valuable metals Cu, Co, Ni, and Fe, although loss of Li, Al, and Mn to the slag phase was observed. In summary, this thesis presents a comprehensive investigation into advanced characterization and physical separation techniques for LIB recycling, with perspectives on industrial process integration. The findings contribute to the development of more efficient, cost-effective, and environmentally sustainable recycling methods. The studied methods are expected to address existing concerns associated with the growing demand for critical battery materials.

KW - froth flotation

KW - selective flocculation

KW - circular economy

KW - graphite

KW - x-ray computed tomography

KW - vaahdotus

KW - selektiivinen flokkulaatio

KW - kiertotalous

KW - grafiitti

KW - röntgentomografia

KW - froth flotation

KW - selective flocculation

KW - circular economy

KW - graphite

KW - x-ray computed tomography

M3 - Doctoral Thesis

SN - 978-952-64-2000-4

T3 - Aalto University publication series DOCTORAL THESES

PB - Aalto University

ER -

Innovations in Li-ion Battery Recycling: Advanced Physical Separation, Characterization, and Industrial Process Integration

Abstrakti

Tutkimusalat

YK:n kestävän kehityksen tavoitteet

Pääsy asiakirjaan

Sormenjälki

Laitteet

Raaka-aineiden tutkimusinfrastruktuuri

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