Hydrometallurgical process for the recovery of high value metals from spent lithium nickel cobalt aluminum oxide based lithium-ion batteries

Joulié, M.; Laucournet, Richard; Billy, Emmanuel

doi:10.1016/j.jpowsour.2013.08.128

Cited by 361 publications

(167 citation statements)

References 29 publications

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“…1,2,9,[14][15][16] A maior parte dos processos descritos na literatura envolve lixiviação dos componentes eletroativos (catodo, anodo e eletrólito) por um meio ácido contendo um agente redutor para permitir a redução de Co(III) a Co(II), estável e solúvel em meio aquoso ácido. O meio ácido normalmente é inorgânico forte (principalmente H 2 SO 4 ), 7,8,17,18 mas ácidos orgânicos vem sendo igualmente testados por suas propriedades complexantes em um meio menos corrosivo. 7,11,16 O redutor é, frequentemente, H 2 O 2 .…”

Section: 10unclassified

Lixiviação Ácida De Baterias Íon-Lítio

Silva¹,

Afonso²,

Mahler³

2018

Quim. Nova

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publicado na web em 22/02/2018 ACIDIC LEACHING OF Li-ION BATTERIES. This paper describes a route for recovering cobalt and lithium from spent Li-ion batteries via acidic leaching. Sulfuric, hydrochloric, hydrofluoric and formic acids were used as leachants. Hydrogen peroxide was added as reductant, except for formic acid since it is itself a reductant. Experiments were run at [25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40] o C for 1-3 h. Under the best optimal conditions, the leaching efficiency order was HCl ≈ HF > H 2 SO 4 > HCOOH. Over 90 wt.% of cobalt and lithium were leached by the inorganic acids. The insoluble matter corresponds mainly to the carbon from the cathode. Co(II) was extracted with D2EHPA 16 vol.% diluted in n-hexane at pH ~5 (A/O ratio 1/1 vol/vol, one stage, 25 °C). Co(II) striping was possible using a dilute leachant (1-2 mol L -1 HCl or H 2 SO 4 , 4-5 mol L -1 HF or HCOOH). Lithium was isolated from the raffinate by precipitation as carbonate or phosphate.Keywords: lithium-ion battery; metals recovery; solvent extraction; cobalt; lithium. INTRODUÇÃOAs baterias de íon-lítio por apresentarem uma elevada densidade de energia, vida útil longa, massa reduzida, taxa de descarga baixa e menor toxicidade em relação a outros tipos de baterias (níquel-cád-mio, níquel hidreto metálico), são hoje muito utilizadas em telefones celulares, câmeras fotográficas e outros equipamentos eletroeletrônicos (EEE) portáteis.1,2 O desenvolvimento de novas versões tecnológicas desses equipamentos e a maior facilidade de acesso dos mesmos a mais camadas da população levam a uma inevitável elevação da produção e do consumo de EEE e, consequentemente, de suas baterias. Mais de 60% do mercado da energia potátil é hoje preenchido por baterias de íon-lítio.3-6 Suas características o colocam na dianteira do desenvolvimento de veículos híbridos e elétricos. [6][7][8] Essas baterias apresentam em sua composição um ânodo, um cátodo, coletores de corrente, um separador, um eletrólito, um invó-lucro externo e peças de vedação. O ânodo é composto de grafite, lítio, carbono e fluoreto de polivinilideno (PVDF), que fixa os demais componentes ao coletor de corrente, que é uma lâmina de cobre; o eletrólito é tipicamente hexafluorfosfato de lítio (LiPF 6 ) em solvente orgânico, normalmente carbonato de etileno (CE), carbonato de dietila (DEC), carbonato de dimetila (DMC) ou misturas deles. O separador é feito de polipropileno (PP) ou polietileno (PE). O cátodo é feito de carbono (grafita), um óxido misto contendo lítio e cobalto (como o LiCoO 2 , que detém ~40% do mercado 6 ) e PVDF, que fixa os componentes ao coletor de corrente do cátodo, que é uma lâmina de alumínio. Hoje, cerca de 25% do cobalto produzido no mundo se destina à manufatura de baterias.8 A expansão do mercado de EEE portáteis pressiona o preço desse metal nos mercados internacionais. 9,10Além disso, devido a problemas relacionados à disponibilidade de cobalto (as principais fontes primárias se localizam em regiões de forte instabilidade geopolítica...

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Section: 10unclassified

Lixiviação Ácida De Baterias Íon-Lítio

Silva¹,

Afonso²,

Mahler³

2018

Quim. Nova

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“…e l s e v i e r . c o m / l o c a t e / w a s m a n et al., 2008;Sun and Qiu, 2011) and the separation of Co and Li (Joulié et al, 2014;Provazi et al, 2011;Wang et al, 2009). Among these studies, leaching of Co and Li from LiCoO 2 powder using hydrometallurgical techniques had attracted wide attention, besides inorganic acids Jha et al, 2013), organic oxalate (Sun and Qiu, 2012), organic citric acid (Li et al, 2010a), succinic acid , oxalic acid (Zeng et al, 2015), tartaric acid and ascorbic acid (Nayaka et al, 2016) were used as leaching agents with satisfactory achievements.…”

Section: Contents Lists Available At Sciencedirectmentioning

confidence: 99%

An environmental benign process for cobalt and lithium recovery from spent lithium-ion batteries by mechanochemical approach

2016

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a b s t r a c tIn the current study, an environmental benign process namely mechanochemical approach was developed for cobalt and lithium recovery from spent lithium-ion batteries (LIBs). The main merit of the process was that neither corrosive acid nor strong oxidant was applied. In the proposed process, lithium cobalt oxide (obtained from spent LIBs) was firstly co-grinded with various additives in a hermetic ball milling system, then Co and Li could be easily recovered by a water leaching procedure. It was found that EDTA was the most suitable co-grinding reagent, and 98% of Co and 99% of Li were respectively recovered under optimum conditions: LiCoO 2 to EDTA mass ratio 1:4, milling time 4 h, rotary speed 600 r/min and ball-to-powder mass ratio 80:1, respectively. Mechanisms study implied that lone pair electrons provided by two nitrogen atoms and four hydroxyl oxygen atoms of EDTA could enter the empty orbit of Co and Li by solid-solid reaction, thus forming stable and water-soluble metal chelates Li-EDTA and Co-EDTA. Moreover, the separation of Co and Li could be achieved through a chemical precipitation approach. This study provides a high efficiency and environmentally friendly process for Co and Li recovery from spent LIBs.

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“…Dissolution also takes part in many chemical processes in the mining industry [4][5][6][7], batteries [8,9], fertilizer production [10], or the recycling industry [11]. Among these chemical processes, the Purex process is a hydrometallurgical process involving the dissolution of spent nuclear fuels in nitric acid in the head-end steps, before carrying out solvent extraction steps allowing the recovery of uranium and plutonium [12].…”

Section: Introductionmentioning

confidence: 99%

A method for phenomenological and chemical kinetics study of autocatalytic reactive dissolution by optical microscopy. The case of uranium dioxide dissolution in nitric acid media

Marc¹,

Magnaldo²,

Godard³

et al. 2018

EPJ Nuclear Sci. Technol.

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Abstract. Dissolution is a milestone of the head-end of hydrometallurgical processes, as the stabilization rates of the chemical elements determine the process performance and hold-up. This study aims at better understanding the chemical and physico-chemical phenomena of uranium dioxide dissolution reactions in nitric acid media in the Purex process, which separates the reusable materials and the final wastes of the spent nuclear fuels. It has been documented that the attack of sintering-manufactured uranium dioxide solids occurs through preferential attack sites, which leads to the development of cracks in the solids. Optical microscopy observations show that in some cases, the development of these cracks leads to the solid cleavage. It is shown here that the dissolution of the detached fragments is much slower than the process of the complete cleavage of the solid, and occurs with no disturbing phenomena, like gas bubbling. This fact has motivated the measurement of dissolution kinetics using optical microscopy and image processing. By further discriminating between external resistance and chemical reaction, the "true" chemical kinetics of the reaction have been measured, and the highly autocatalytic nature of the reaction confirmed. Based on these results, the constants of the chemical reactions kinetic laws have also been evaluated.

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Hydrometallurgical process for the recovery of high value metals from spent lithium nickel cobalt aluminum oxide based lithium-ion batteries

Cited by 361 publications

References 29 publications

Lixiviação Ácida De Baterias Íon-Lítio

Lixiviação Ácida De Baterias Íon-Lítio

An environmental benign process for cobalt and lithium recovery from spent lithium-ion batteries by mechanochemical approach

A method for phenomenological and chemical kinetics study of autocatalytic reactive dissolution by optical microscopy. The case of uranium dioxide dissolution in nitric acid media

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