Reciclagem química e eletroquímica de baterias exauridas de Ni-MH

Detalhes bibliográficos
Autor(a) principal: Dixini, Pedro Vitor Morbach
Data de Publicação: 2014
Tipo de documento: Dissertação
Idioma: por
Título da fonte: Repositório Institucional da Universidade Federal do Espírito Santo (riUfes)
Texto Completo: http://repositorio.ufes.br/handle/10/1610
Resumo: Here in, new technology has been developed for recycling of metals from the cathodes and anodes of spent Ni-MH batteries. The cathodes recycling occurred through the electrodeposition of metals in galvanostatic conditions; also the mechanism of simultaneous electrodeposition of Ni, Co, Zn and Mn was studied in potentiodynamic, potentiostatic and galvanostatic conditions. Aluminium and vitreous carbon electrodes were used in electrodeposition. From cyclic voltammetry experiments at scan rates of 1, 5 and 10 mV.s-1, it was observed that the metals deposition occurs from the precipitation of hydroxides on the electrode surface, in which they are formed after alkalinization of the electrode/solution interface, due the hydrogen evolution reaction. From SEM analysis it was observed that in potentiostatic conditions, only the nucleation process takes place and there is no film growth, the nuclei were dissolved and analyzed by ICP OES, Ni, Co and Zn were detected as traces. In galvanostatic conditions the following current densities, were used, -20, -25 , -30 , -35 and -40 mA.cm-2 and the charge density was fixed in -50 C.cm-2. The greatest charge efficiency was observed for current densities of -25 and -40 mA.cm-2 in Al and -35 and -40 mA.cm-2 in the vitreous carbon. From the micrographs it was found that all electrodeposits presents a heterogeneous surface. XRD measurements identified Ni, Co, Ni(OH)2 and Mn3O4 at all electrodeposits. Using EIS, equivalent circuits were determined for all electrodeposits. All of them are of the form R1(R2Q)W, where R1 is the solution resistance across the pores and R2, Q and W are relative to the pores. The recycled films were analyzed by cyclic voltammetry in alkaline solution. A charge efficiency of 85 % was obtained, showing good suitability of the material as an electrochemical capacitor and electrochromic cells. The lanthanides presents at the anodes spent Ni-MH batteries were recovered as a mixture of Ln2(SO4)3, where Ln = La , Ce and Nd , and an efficiency of 99,9 % was found. The synthesis of (La.Nd)2O2S.CeO2 have been carried out by subjecting a mixture of La2(SO4)3, Ce2(SO4)3, and Nd2(SO4)3 to a heat treatment in a reducing atmosphere up to1000 °C. The (La.Nd)O2SO4.CeO2 compounds have been obtained after thermal treatment of (La.Nd)O2S.CeO2 in a synthetic air atmosphere. The oxysulfide/oxysulfate compounds have been subjected to thermal cycles, respectively, in synthetic air as well as in an N2-CO atmosphere. The thermogravimetric plot (TG) for (La.Nd)2O2S.CeO2 shows a mass gain of 14,98 % w/w in atemperature range of 300-550 °C, which is due to the oxidation of (La.Nd)2O2S.CeO2 to(La.Nd)2O2SO4CeO2, where 2 mol of O2 are added. Likewise, in the (La.Nd)2O2SO4CeO2 thermogravimetric plot, a mass loss of 17.16 % w/w is observed in the range of 500-750 °C. This loss of mass can be associated with output of 2 moles of O2 forming again the (La.Nd)2O2S.CeO2. The transformation of the (La.Nd)2.O2S.CeO2 to (La.Nd)2O2SO4CeO2 causes an increase in the macropores.
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spelling Freitas, Marcos Benedito José Geraldo deDixini, Pedro Vitor MorbachGarcia, Eric MarsalhaFerreira, Rafael de Queiroz2015-11-17T12:51:42Z2016-06-24T06:00:07Z2014-01-012014-03-14Here in, new technology has been developed for recycling of metals from the cathodes and anodes of spent Ni-MH batteries. The cathodes recycling occurred through the electrodeposition of metals in galvanostatic conditions; also the mechanism of simultaneous electrodeposition of Ni, Co, Zn and Mn was studied in potentiodynamic, potentiostatic and galvanostatic conditions. Aluminium and vitreous carbon electrodes were used in electrodeposition. From cyclic voltammetry experiments at scan rates of 1, 5 and 10 mV.s-1, it was observed that the metals deposition occurs from the precipitation of hydroxides on the electrode surface, in which they are formed after alkalinization of the electrode/solution interface, due the hydrogen evolution reaction. From SEM analysis it was observed that in potentiostatic conditions, only the nucleation process takes place and there is no film growth, the nuclei were dissolved and analyzed by ICP OES, Ni, Co and Zn were detected as traces. In galvanostatic conditions the following current densities, were used, -20, -25 , -30 , -35 and -40 mA.cm-2 and the charge density was fixed in -50 C.cm-2. The greatest charge efficiency was observed for current densities of -25 and -40 mA.cm-2 in Al and -35 and -40 mA.cm-2 in the vitreous carbon. From the micrographs it was found that all electrodeposits presents a heterogeneous surface. XRD measurements identified Ni, Co, Ni(OH)2 and Mn3O4 at all electrodeposits. Using EIS, equivalent circuits were determined for all electrodeposits. All of them are of the form R1(R2Q)W, where R1 is the solution resistance across the pores and R2, Q and W are relative to the pores. The recycled films were analyzed by cyclic voltammetry in alkaline solution. A charge efficiency of 85 % was obtained, showing good suitability of the material as an electrochemical capacitor and electrochromic cells. The lanthanides presents at the anodes spent Ni-MH batteries were recovered as a mixture of Ln2(SO4)3, where Ln = La , Ce and Nd , and an efficiency of 99,9 % was found. The synthesis of (La.Nd)2O2S.CeO2 have been carried out by subjecting a mixture of La2(SO4)3, Ce2(SO4)3, and Nd2(SO4)3 to a heat treatment in a reducing atmosphere up to1000 °C. The (La.Nd)O2SO4.CeO2 compounds have been obtained after thermal treatment of (La.Nd)O2S.CeO2 in a synthetic air atmosphere. The oxysulfide/oxysulfate compounds have been subjected to thermal cycles, respectively, in synthetic air as well as in an N2-CO atmosphere. The thermogravimetric plot (TG) for (La.Nd)2O2S.CeO2 shows a mass gain of 14,98 % w/w in atemperature range of 300-550 °C, which is due to the oxidation of (La.Nd)2O2S.CeO2 to(La.Nd)2O2SO4CeO2, where 2 mol of O2 are added. Likewise, in the (La.Nd)2O2SO4CeO2 thermogravimetric plot, a mass loss of 17.16 % w/w is observed in the range of 500-750 °C. This loss of mass can be associated with output of 2 moles of O2 forming again the (La.Nd)2O2S.CeO2. The transformation of the (La.Nd)2.O2S.CeO2 to (La.Nd)2O2SO4CeO2 causes an increase in the macropores.Neste trabalho foram desenvolvidas tecnologias para a reciclagem de metais provenientes dos cátodos e ânodos de baterias Ni-MH exauridas. A reciclagem do cátodo se deu via a eletrodeposição dos metais em condições galvanostáticas, também foi estudado o mecanismo de deposição simultânea de Ni, Co, Zn e Mn em condições potenciodinâmicas, potenciostáticas e galvanostáticas em eletrodos de Al e carbono vítreo. A partir de experimentos de voltametria cíclica com velocidades de 1, 5 e 10 mV.s-1, observou-se que a deposição dos metais ocorre a partir de hidróxidos precipitados na superfície, aonde estes são formados após a alcalinização da interface eletrodo/solução devido a reação de desprendimento de hidrogênio. A partir de análises de MEV foi observado que em condições potenciostáticas, somente o processo de nucleação ocorre, não havendo o crescimento do filme, os núcleos foram dissolvidos e analisados por ICP OES, e Ni, Co e Zn foram detectados na forma de traços. Em condições galvanostáticas, utilizou-se as seguintes densidades de corrente: -20, -25, -30, -35 e -40 mA.cm-2 e densidade de carga fixa de -50 C.cm-2. A maior eficiência de carga foi observada para as densidades de corrente de -25 e -40 mA.cm-2 para o substrato de Al e -35 e -40 mA.cm-2 para o substrato de carbono vítreo. A partir das micrografias constatou que todos os eletrodepósitos se formaram de maneira bastante heterogênea. Medidas de DRX identificaram Ni, Co, Ni(OH)2 e Mn3O4 em todos os eletrodepósitos. Utilizando a EIE, foram determinados os circuitos equivalentes dos eletrodepósitos para todas as densidades de corrente. Todos eles são da forma R1(R2Q)W, onde R1 é a resistência da solução ao redor dos poros e R2, Q e W são relativos aos poros do depósito. Os filmes reciclados foram analisados por voltametria cíclica em solução alcalina. Uma eficiência de carga de 85 % foi obtida, demonstrando boa aplicabilidade do material como um capacitor eletroquímico e em células eletrocrômicas. Os lantanídeos presentes nos ânodos de baterias Ni-MH exauridas, foram recuperados na forma de uma mistura de Ln2(SO4)3, onde Ln = La, Ce e Nd, e uma eficiência de 99.9 % foi encontrada.A síntese do (La.Nd)O2S.CeO2 foi realizada submentendo a mistura de Ln2(SO4)3 a um tratamento térmica em atmosfera redutora até 1000 ºC. Para a síntese do (La.Nd)O2SO4.CeO2, submeteu-se a mistura de oxisulfetos a um tratamento térmico em atmosfera de ar sintético. Os materiais, oxisulfetos/oxisulfatos, foram submetidos a ciclos térmicos, respectivamente, em atmosfera de ar e N2-CO. O termograma para o (La.Nd)2O2S.CeO2 mostra um ganho de massa de 14,98 % w/w, em uma faixa de temperatura entre 300 – 550 ºC, que é devido a oxidação para a fase oxisulfato, onde 2 mols de O2 são adicionados a molécula. Da mesma maneira, no termograma dos oxisulfatos, uma perda de massa de 17,16 % é observada na faixa de temperatura entre 500 – 750 ºC. Essa perda é associada a saída de 2 mols de O2, regenerando assim os oxisulfetos. Imagens de MEV demonstram que a transformação oxisulfeto para oxisulfato leva a um aumento do tamanho dos macroporos na molécula.CapesTexthttp://repositorio.ufes.br/handle/10/1610porUniversidade Federal do Espírito SantoMestrado em QuímicaPrograma de Pós-Graduação em QuímicaUFESBRCentro de Ciências ExatasQuímicaEletroquímicaBaterias elétricasProdutos recicladosQuímica54Reciclagem química e eletroquímica de baterias exauridas de Ni-MHinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da Universidade Federal do Espírito Santo (riUfes)instname:Universidade Federal do Espírito Santo (UFES)instacron:UFESCapesORIGINALReciclagem Química e Eletroquímica de Baterias Exauridas de Ni-MH..pdfReciclagem Química e Eletroquímica de Baterias Exauridas de Ni-MH..pdfapplication/pdf3085521http://repositorio.ufes.br/bitstreams/2b5615d9-3a1f-4bb3-a83e-a50db8935235/download9a9996556b4cec5ed8329acdccfccf51MD5110/16102024-06-28 17:52:30.014oai:repositorio.ufes.br:10/1610http://repositorio.ufes.brRepositório InstitucionalPUBhttp://repositorio.ufes.br/oai/requestopendoar:21082024-06-28T17:52:30Repositório Institucional da Universidade Federal do Espírito Santo (riUfes) - Universidade Federal do Espírito Santo (UFES)false
dc.title.none.fl_str_mv Reciclagem química e eletroquímica de baterias exauridas de Ni-MH
title Reciclagem química e eletroquímica de baterias exauridas de Ni-MH
spellingShingle Reciclagem química e eletroquímica de baterias exauridas de Ni-MH
Dixini, Pedro Vitor Morbach
Química
Eletroquímica
Baterias elétricas
Produtos reciclados
Química
54
title_short Reciclagem química e eletroquímica de baterias exauridas de Ni-MH
title_full Reciclagem química e eletroquímica de baterias exauridas de Ni-MH
title_fullStr Reciclagem química e eletroquímica de baterias exauridas de Ni-MH
title_full_unstemmed Reciclagem química e eletroquímica de baterias exauridas de Ni-MH
title_sort Reciclagem química e eletroquímica de baterias exauridas de Ni-MH
author Dixini, Pedro Vitor Morbach
author_facet Dixini, Pedro Vitor Morbach
author_role author
dc.contributor.advisor1.fl_str_mv Freitas, Marcos Benedito José Geraldo de
dc.contributor.author.fl_str_mv Dixini, Pedro Vitor Morbach
dc.contributor.referee1.fl_str_mv Garcia, Eric Marsalha
dc.contributor.referee2.fl_str_mv Ferreira, Rafael de Queiroz
contributor_str_mv Freitas, Marcos Benedito José Geraldo de
Garcia, Eric Marsalha
Ferreira, Rafael de Queiroz
dc.subject.por.fl_str_mv Química
Eletroquímica
Baterias elétricas
Produtos reciclados
topic Química
Eletroquímica
Baterias elétricas
Produtos reciclados
Química
54
dc.subject.cnpq.fl_str_mv Química
dc.subject.udc.none.fl_str_mv 54
description Here in, new technology has been developed for recycling of metals from the cathodes and anodes of spent Ni-MH batteries. The cathodes recycling occurred through the electrodeposition of metals in galvanostatic conditions; also the mechanism of simultaneous electrodeposition of Ni, Co, Zn and Mn was studied in potentiodynamic, potentiostatic and galvanostatic conditions. Aluminium and vitreous carbon electrodes were used in electrodeposition. From cyclic voltammetry experiments at scan rates of 1, 5 and 10 mV.s-1, it was observed that the metals deposition occurs from the precipitation of hydroxides on the electrode surface, in which they are formed after alkalinization of the electrode/solution interface, due the hydrogen evolution reaction. From SEM analysis it was observed that in potentiostatic conditions, only the nucleation process takes place and there is no film growth, the nuclei were dissolved and analyzed by ICP OES, Ni, Co and Zn were detected as traces. In galvanostatic conditions the following current densities, were used, -20, -25 , -30 , -35 and -40 mA.cm-2 and the charge density was fixed in -50 C.cm-2. The greatest charge efficiency was observed for current densities of -25 and -40 mA.cm-2 in Al and -35 and -40 mA.cm-2 in the vitreous carbon. From the micrographs it was found that all electrodeposits presents a heterogeneous surface. XRD measurements identified Ni, Co, Ni(OH)2 and Mn3O4 at all electrodeposits. Using EIS, equivalent circuits were determined for all electrodeposits. All of them are of the form R1(R2Q)W, where R1 is the solution resistance across the pores and R2, Q and W are relative to the pores. The recycled films were analyzed by cyclic voltammetry in alkaline solution. A charge efficiency of 85 % was obtained, showing good suitability of the material as an electrochemical capacitor and electrochromic cells. The lanthanides presents at the anodes spent Ni-MH batteries were recovered as a mixture of Ln2(SO4)3, where Ln = La , Ce and Nd , and an efficiency of 99,9 % was found. The synthesis of (La.Nd)2O2S.CeO2 have been carried out by subjecting a mixture of La2(SO4)3, Ce2(SO4)3, and Nd2(SO4)3 to a heat treatment in a reducing atmosphere up to1000 °C. The (La.Nd)O2SO4.CeO2 compounds have been obtained after thermal treatment of (La.Nd)O2S.CeO2 in a synthetic air atmosphere. The oxysulfide/oxysulfate compounds have been subjected to thermal cycles, respectively, in synthetic air as well as in an N2-CO atmosphere. The thermogravimetric plot (TG) for (La.Nd)2O2S.CeO2 shows a mass gain of 14,98 % w/w in atemperature range of 300-550 °C, which is due to the oxidation of (La.Nd)2O2S.CeO2 to(La.Nd)2O2SO4CeO2, where 2 mol of O2 are added. Likewise, in the (La.Nd)2O2SO4CeO2 thermogravimetric plot, a mass loss of 17.16 % w/w is observed in the range of 500-750 °C. This loss of mass can be associated with output of 2 moles of O2 forming again the (La.Nd)2O2S.CeO2. The transformation of the (La.Nd)2.O2S.CeO2 to (La.Nd)2O2SO4CeO2 causes an increase in the macropores.
publishDate 2014
dc.date.submitted.none.fl_str_mv 2014-03-14
dc.date.issued.fl_str_mv 2014-01-01
dc.date.accessioned.fl_str_mv 2015-11-17T12:51:42Z
dc.date.available.fl_str_mv 2016-06-24T06:00:07Z
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Mestrado em Química
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dc.publisher.department.fl_str_mv Centro de Ciências Exatas
publisher.none.fl_str_mv Universidade Federal do Espírito Santo
Mestrado em Química
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