Research at Argonne National Laboratory was funded by U.S. Department of Energy, FreedomCAR and Vehicle Technologies Office. Use of the Advanced Photon Source and research carried out in the Electron Microscopy Center at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.

Por favor, consultar todas as Fichas de Dados de Segurança do Material relevantes (MSDS) antes do uso. Muitos dos produtos químicos usados ​​nestas sínteses são altamente tóxicos e cancerígenos. Nanomateriais podem ter riscos adicionais em comparação com o seu homólogo granel. Por favor, use todas as práticas de segurança adequadas ao executar uma reação nanocristais incluindo o uso de controles de engenharia (exaustor, glovebox) e equipamentos de proteção individual (óculos de segurança, luvas, jaleco, calça de corpo inteiro, fechou-toe sapatos). Partes dos seguintes procedimentos envolvem técnicas de manuseio livre de ar padrão. 1. Síntese de materiais de cátodo Nota: materiais de cátodo pode ser sintetizado por qualquer uma de deposição da camada atómica ou reacção química húmida. <ol><li> Atomic camada de deposição (ALD) <ol><li> Dispersa-se 5 g de carvão poroso em 100 ml de 1 M de solução de KMnO4 sob agitação magnética durante 12 h. </li><li> Espalhe 100 mg de the pó de carvão oxidado para um tabuleiro de aço inoxidável o instrumento de ALD e prender uma tampa de malha de aço inoxidável sobre a bandeja. </li><li> Segurar o pó de carbono na bandeja a 200 ° C sob fluxo contínuo de 300 sccm-ultra-elevado grau de pureza do gás transportador de azoto a uma pressão Torr durante 30 min. </li><li> Tratar o pó de carbono com um ciclo de ALD completa como se segue. Nota: Tome nanopartículas de Pd como um exemplo dos eletrocatalisadores neste protocolo. Os reagentes podem ser alterados de acordo com requisitos específicos. Todos os reagentes são utilizados como recebidos sem qualquer purificação adicional. <ol><li> Expor o substrato de carbono (100 mg) para hexafluoroacetilacetonato de paládio (Pd (hfac) 2, 99,9%) a 200 ° C durante 100 min. </li><li> Purga-se o tabuleiro com o fluxo contínuo de 300 sccm-ultra-elevado grau de pureza do gás transportador de azoto a uma pressão de 300 Torr durante min. </li><li> Expor o substrato de carbono a formalina (HCHO a 37 wt.% Em H2O) a 200 ° C durante 100 min. </li><li> purge tele bandeja com o fluxo contínuo de 300 sccm-ultra-elevado grau de pureza do gás transportador de azoto a uma pressão de 300 Torr durante min. </li></ol></li><li> ciclo de ALD Repita conforme necessário. Normalmente 3-10 repetições. </li></ol></li><li> Wet-química Reacção Nota: Tome nanopartículas de Fe como um exemplo do eletrocatalisador neste protocolo. Os reagentes podem ser alterados de acordo com requisitos específicos. Todos os reagentes são utilizados como recebidos sem qualquer purificação adicional. <ol><li> Dispersa-se 5 g de carvão poroso em 100 ml de 1 M de solução de KMnO4 sob agitação magnética durante 12 h. </li><li> Lavar o carbono oxidado com água de s ionizada. </li><li> Filtra-se o carbono lavou-se com um filtro de balão equipado com uma fibra de vidro, e em seguida secá-lo numa estufa a 110 ° C durante 12 h. </li><li> Dispersa-se o carvão seco em 100 ml de água desionizada, em seguida adicionar 1 g de FeCl3 sob agitação magnética. </li><li> Ajustar o valor de pH a cerca de 9, utilizando uma solução 1 M de NaOH. </li><li> Agita-se a resulting suspensão durante 5 horas, e, em seguida, filtrar a suspensão com um filtro de balão equipado com uma fibra de vidro. </li><li> Lavar o produto com água desionizada e etanol. Em seguida, secá-lo numa estufa a 110 ° C durante a noite. </li><li> Tratar termicamente o produto a 450 ° C com o fluxo contínuo de mistura de H 2 / Ar (4% de H 2) num forno de tubo de quartzo. Utilize uma taxa de fluxo de 100 ml / min durante 5 horas. </li></ol></li></ol> 2. Preparação de eletrodos e eletrólitos <ol><li> Cátodo <ol><li> Misturar o material do cátodo como poli-preparado e ligante (fluoreto de vinilideno) (PVDF) em uma proporção de 4: 1 em peso. Nota: O total da mistura depende da quantidade dos cátodos. A carga do material de cátodo em cada pedaço está na gama de 0,1-1 mg. </li><li> Adicionar 1-metil-2-pirrolidinona (NMP) à mistura, e agita-se bem para fazer uma suspensão uniforme-texturizados. Adicionar NMP a cerca de três vezes o peso da mistura. </li><li> Brasão da lama em carboN papel por uma lâmina de médico, com uma espessura de cerca de 100 uM. </li><li> Seca-se o laminado numa estufa de vácuo a 100 ° C durante a noite. </li><li> Perfura o laminado em discos com um furador de diâmetro de 7/16 polegadas, e pesá-lo. </li></ol></li><li> aprótico Electrolyte <ol><li> Trifluorometanossulfonato de lítio seco (LiCF 3 SO 3) num forno de vácuo a 100 ° C durante a noite. </li><li> Adicionar seca LiCF 3 SO 3 em éter dimetílico de tetraetilenoglicol (TEGDME; H2O ~ 10 ppm) com uma concentração de 1 mol / L, em seguida, agita-se a solução com agitação magnética até o sal se dissolver. </li><li> Mantenha o electrólito numa caixa de luvas cheia com Ar. </li></ol></li><li> anódio <ol><li> Perfurar os lítio folha / chips em discos com um furador de diâmetro de 7/16 polegadas. </li></ol></li></ol> 3. Electrochemical Testing <ol><li> Assembleia da Swagelok celular &lt;/ Strong&gt; Nota: Todos os passos da montagem são operados numa caixa de luvas cheia com Ar, exceto 3.1.9. <ol><li> Montar o conjunto de Swagelok como se mostra na Figura 1a. Aperte a extremidade do ânodo, e afrouxe o fim cátodo. </li><li> Coloque um pedaço de chip de lítio metálico (diâmetro de 7/16 polegadas) na parte superior da barra de aço inoxidável da extremidade do ânodo. </li><li> Coloque um pedaço de separador de fibra de vidro (diâmetro de 1/2 polegadas) na parte superior do ânodo de metal de lítio. </li><li> Adicionar 5-7 gotas de electrólito para molhar completamente o separador de fibra de vidro. Pressione suavemente o separador para remover as bolhas. </li><li> Coloque um pedaço de cátodo na parte superior do separador de molhada, com o material activo voltado para o ânodo. </li><li> Cobrir o cátodo com um pedaço de malha de alumínio (diâmetro de 7/16 polegadas). </li><li> Pressione as camadas acima mencionadas com o tubo de alumínio, em seguida, aperte o fim cátodo. </li><li> Selar a célula inteira Swagelok em uma câmara de vidro, e fixar a câmara com um grampo, como mostrado nas <strong&gt; Figura 1. </li><li> Leve toda a célula fora do porta-luvas. Ligue a câmara de vidro para um tanque de oxigênio ultra-alta pureza, e limpá-lo com um fluxo contínuo de oxigênio à pressão de 1 atm por 30 min. </li></ol></li><li> Teste de Desempenho da bateria <ol><li> Definir um termostato a 25 ° C. </li><li> Coloque as células e eletrodos (grampos eletrônicos conectados ao equipamento através de um cabo) para o termostato, e corrigi-los. </li><li> Prenda o cátodo eo ânodo na câmara de vidro com grampos eletrônicos correspondente. </li><li> Abra o software de operação do sistema de teste de bateria, e selecione o canal conectado com o cabo. </li><li> Definir um procedimento do teste eletroquímico. Nota: Defina a densidade de corrente de material activo 100 mA / g, e faixa de tensão de 2,2-4,5 V. <ol><li> Defina a tensão de descarga de corte de 2,2 V para teste de descarga. </li><li> Defina a descarga / carga etapa em tempo de 5 ou 10 horas, para a prova de ciclismo de controle de capacidade. </li&gt; <li> Defina a tensão de descarga de corte de 2,2 V e carga de tensão de corte de 4,5 V para o ensaio de ciclagem de tensão controlada. </li></ol></li><li> Executar o procedimento clicando no botão &quot;Run&quot; na interface do software. </li></ol></li><li> A desmontagem e limpeza da célula <ol><li> Desmontar células numa caixa de luvas. </li><li> Mantenha os eletrodos em frascos de vidro para as seguintes caracterizações. Transferir outras partes da célula para fora do porta-luvas. </li><li> Coloque as partes Swagelok, hastes de aço inoxidável, tubos de alumínio, e malhas de alumínio em solução em acetona (~ 20%) ou de água desionizada numa proveta, e limpá-los com ultra-sons durante 15-30 minutos. </li><li> Secam-se as peças de vidro e as câmaras em um termostato regulado para 60-80 ° C. </li></ol></li></ol> 4. Preparação de Amostras de caracterização Nota: As amostras são preparadas de um exaustor (como para materiais preparados) ou uma caixa de luvas cheia com Ar (para arespécimes sensível). <ol><li> As amostras para MEV e XPS <ol><li> Cole uma fita de carbono no cenário de exemplo. A fita de carbono pode ser tão grande como a plataforma da amostra, ou tão pequenas como o pedaço de amostra. </li><li> Corte um pedaço de amostra de cerca de 5 mm 2, e colá-la na fita de carbono. Nota: A amostra pode ser qualquer amostra não magnéticos. Para os espécimes após ensaios eletroquímicos, lavá-los com o solvente de eletrólitos antes da vara para a fita de carbono. </li><li> Selar as amostras sensíveis ao ar em um frasco de pedreiro antes da medição. </li><li> Operar o SEM 34-36 ou XPS 37,38 de acordo com as instruções do fabricante. </li></ol></li><li> As amostras para TEM <ol><li> Moinho 1 mg do pó da amostra. Nota: Para amostras de eléctrodos, raspar os materiais activos off papel carbono antes da moagem. </li><li> Carregar o pó para amostra numa grelha de cobre, e remover o pó solto. </li><li> Carregar o cobre glivrar ao titular da amostra de TEM. Nota: Obter esta etapa feito tão rápido quanto possível para amostras sensíveis ao ar. </li><li> Execute TEM. 39-41 </li></ol></li><li> As amostras de DRX de alta energia <ol><li> amostras de pó <ol><li> Selar uma extremidade de um tubo de poliimida por argila ou uma cola. </li><li> Carregar o pó para o tubo. </li><li> Selar a outra extremidade do tubo. </li></ol></li><li> espécimes de disco Nota: Para medir os materiais activos no eletrodo, outra opção é para raspar-los fora de papel carbono e siga o passo 4.3.1. <ol><li> Selar as peças de amostra com um pedaço de fita de poliamida. Selar, colocando as amostras em meio de um pedaço de fita adesiva, e cobrindo-os com outro pedaço de fita adesiva. Nota: Para os espécimes após ensaios eletroquímicos, lavá-los com o solvente de eletrólitos antes de selar. </li></ol></li><li> Operar o DRX-alta energia 42-44 in Advanced PhFontes Oton em Argonne National Laboratory. </li></ol></li><li> As amostras para XANES <ol><li> amostras de pó <ol><li> Dilui-se as amostras se a concentração dos elementos de medição é elevada, utilizando quer o nitreto de boro (BN) ou negro de carbono como agente diluído. Aqui, diluir a 3-5 em peso. %. </li><li> Pressionar o pó em disco com o diâmetro de 7 mm e a espessura de cerca de 1 mm, utilizando um Kit de KBr Prima e 7 mm Die Set. </li><li> Selar o disco com filme de janela. </li></ol></li><li> espécimes de disco <ol><li> Selar a amostra com filme de janela. </li></ol></li><li> Operar a alta energia XANES 45-47 no avançada do fotão Fontes em Argonne National Laboratory. </li></ol></li><li> As amostras de ATR-FTIR <ol><li> Limpar a unidade de diamante reflexão total atenuada (ATR) antes e após a medição. </li><li> Coloque as amostras no aparelho de diamante para todas as amostras interessadas. </li><li> Execute ATR-FTIR espectrometria. 48,49 </li></ol></li><li> As amostras para Raman Spectra <ol><li> Coloque as amostras em uma placa plana (vidro, aço inoxidável, etc.). </li><li> Cubra o espécime com uma cobertura deslizante. </li><li> Selar o conjunto de amostras sensíveis ao ar. </li><li> Execute espectrometria Raman 50,51. </li></ol></li></ol>

<ol>
	<li>Abraham, K. M., Jiang, Z. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+polymer+electrolyte-based+rechargeable+lithium/oxygen+battery.">A polymer electrolyte-based rechargeable lithium/oxygen battery.</a> J. Electrochem. Soc. 143, 1-5 (1996).</li><li>Bruce, P. G., Freunberger, S. A., Hardwick, L. J., Tarascon, J. -. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Li-O2+and+Li-S+batteries+with+high+energy+storage.">Li-O2 and Li-S batteries with high energy storage.</a> Nat. Mater. 11, 19-29 (2012).</li><li>Lu, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Aprotic+and+Aqueous+Li-O2+Batteries.">Aprotic and Aqueous Li-O2 Batteries.</a> Chem. Rev. 114, 5611-5640 (2014).</li><li>Black, R., Adams, B., Nazar, L. F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Non-Aqueous+and+Hybrid+Li-O2+Batteries.">Non-Aqueous and Hybrid Li-O2 Batteries.</a> Adv. Energy Mater. 2, 801-815 (2012).</li><li>Bruce, P. G., Hardwick, L. J., Abraham, K. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Lithium-air+and+lithium-sulfur+batteries.">Lithium-air and lithium-sulfur batteries.</a> MRS Bull. 36, 506-512 (2011).</li><li>Christensen, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+Critical+Review+of+Li/Air+Batteries.">A Critical Review of Li/Air Batteries.</a> J. Electrochem. Soc. 159, 1-30 (2012).</li><li>Girishkumar, G., McCloskey, B., Luntz, A. C., Swanson, S., Wilcke, W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Lithium-Air+Battery:+Promise+and+Challenges.">Lithium-Air Battery: Promise and Challenges.</a> J. Phys. Chem. Lett. 1, 2193-2203 (2010).</li><li>Lu, J., Amine, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recent+Research+Progress+on+Non-aqueous+Lithium-Air+Batteries+from+Argonne+National+Laboratory.">Recent Research Progress on Non-aqueous Lithium-Air Batteries from Argonne National Laboratory.</a> Energies. 6, 6016-6044 (2013).</li><li>Ding, N., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Influence+of+carbon+pore+size+on+the+discharge+capacity+of+Li-O2+batteries.">Influence of carbon pore size on the discharge capacity of Li-O2 batteries.</a> J. Mater. Chem. A. 2, 12433 (2014).</li><li>Nimon, V. Y., Visco, S. J., De Jonghe, L. C., Volfkovich, Y. M., Bograchev, D. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Modeling+and+Experimental+Study+of+Porous+Carbon+Cathodes+in+Li-O2+Cells+with+Non-Aqueous+Electrolyte.">Modeling and Experimental Study of Porous Carbon Cathodes in Li-O2 Cells with Non-Aqueous Electrolyte.</a> ECS Electrochem. Lett. 2, 33-35 (2013).</li><li>Ottakam Thotiyl, M. M., Freunberger, S. A., Peng, Z., Bruce, P. G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+Carbon+Electrode+in+Nonaqueous+Li-O2+Cells.">The Carbon Electrode in Nonaqueous Li-O2 Cells.</a> J. Am. Chem. Soc. 135, 494-500 (2012).</li><li>Park, J. -. B., Lee, J., Yoon, C. S., Sun, Y. -. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ordered+Mesoporous+Carbon+Electrodes+for+Li-O2+Batteries.">Ordered Mesoporous Carbon Electrodes for Li-O2 Batteries.</a> Acs Appl. Mater. Interfaces. 5, 13426-13431 (2013).</li><li>Lei, Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+of+porous+carbon+supported+palladium+nanoparticle+catalysts+by+atomic+layer+deposition:+application+for+rechargeable+lithium-O2+battery.">Synthesis of porous carbon supported palladium nanoparticle catalysts by atomic layer deposition: application for rechargeable lithium-O2 battery.</a> Nano Lett. 13, 4182-4189 (2013).</li><li>Lu, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Effect+of+the+size-selective+silver+clusters+on+lithium+peroxide+morphology+in+lithium-oxygen+batteries.">Effect of the size-selective silver clusters on lithium peroxide morphology in lithium-oxygen batteries.</a> Nat. Commun. 5, 4895 (2014).</li><li>Lu, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+nanostructured+cathode+architecture+for+low+charge+overpotential+in+lithium-oxygen+batteries.">A nanostructured cathode architecture for low charge overpotential in lithium-oxygen batteries.</a> Nat. Commun. 4, 2383 (2013).</li><li>Lu, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+and+characterization+of+uniformly+dispersed+Fe3O4/Fe+nanocomposite+on+porous+carbon:+application+for+rechargeable+Li-O2+batteries.">Synthesis and characterization of uniformly dispersed Fe3O4/Fe nanocomposite on porous carbon: application for rechargeable Li-O2 batteries.</a> RSC Adv. 3, 8276-8285 (2013).</li><li>Luo, X., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Pd+nanoparticles+on+ZnO-passivated+porous+carbon+by+atomic+layer+deposition:+an+effective+electrochemical+catalyst+for+Li-O2+battery.">Pd nanoparticles on ZnO-passivated porous carbon by atomic layer deposition: an effective electrochemical catalyst for Li-O2 battery.</a> Nanotechnology. 26, 164003 (2015).</li><li>Freunberger, S. A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+Lithium-Oxygen+Battery+with+Ether-Based+Electrolytes.">The Lithium-Oxygen Battery with Ether-Based Electrolytes.</a> Angew. Chem. Int. Ed. 50, 8609-8613 (2011).</li><li>Laoire, C. O., Mukerjee, S., Abraham, K. M., Plichta, E. J., Hendrickson, M. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Influence+of+Nonaqueous+Solvents+on+the+Electrochemistry+of+Oxygen+in+the+Rechargeable+Lithium-Air+Battery.">Influence of Nonaqueous Solvents on the Electrochemistry of Oxygen in the Rechargeable Lithium-Air Battery.</a> J. Phys. Chem. C. 114, 9178-9186 (2010).</li><li>McCloskey, B. D., Bethune, D. S., Shelby, R. M., Girishkumar, G., Luntz, A. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Solvents'+Critical+Rope+in+Nonaqueous+Lithium-Oxygen+Battery+Electrochemistry.">Solvents' Critical Rope in Nonaqueous Lithium-Oxygen Battery Electrochemistry.</a> J. Phys. Chem. Lett. 2, 1161-1166 (2011).</li><li>Assary, R. S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Molecular-Level+Insights+into+the+Reactivity+of+Siloxane-Based+Electrolytes+at+a+Lithium-Metal+Anode.">Molecular-Level Insights into the Reactivity of Siloxane-Based Electrolytes at a Lithium-Metal Anode.</a> ChemPhysChem. 15, 2077-2083 (2014).</li><li>Du, P., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Compatibility+of+lithium+salts+with+solvent+of+the+non-aqueous+electrolyte+in+Li-O2+batteries.">Compatibility of lithium salts with solvent of the non-aqueous electrolyte in Li-O2 batteries.</a> Phys. Chem. Chem. Phys. 15, 5572-5581 (2013).</li><li>Aleshin, G. Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Protected+anodes+for+lithium-air+batteries.">Protected anodes for lithium-air batteries.</a> Solid State Ion. 184, 62-64 (2011).</li><li>Assary, R. S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+Effect+of+Oxygen+Crossover+on+the+Anode+of+a+Li-O2+Battery+using+an+Ether-Based+Solvent:+Insights+from+Experimental+and+Computational+Studies.">The Effect of Oxygen Crossover on the Anode of a Li-O2 Battery using an Ether-Based Solvent: Insights from Experimental and Computational Studies.</a> ChemSusChem. 6, 51-55 (2013).</li><li>Aurbach, D., Zinigrad, E., Cohen, Y., Teller, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+short+review+of+failure+mechanisms+of+lithium+metal+and+lithiated+graphite+anodes+in+liquid+electrolyte+solutions.">A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions.</a> Solid State Ion. 148, 405-416 (2002).</li><li>Dey, A. N. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Lithium+Anode+Film+And+Organic+And+Inorganic+Electrolyte+Batteries.">Lithium Anode Film And Organic And Inorganic Electrolyte Batteries.</a> Thin Solid Films. 43, 131-171 (1977).</li><li>Lau, K. C., Lu, J., Luo, X., Curtiss, L. A., Amine, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Implications+of+the+Unpaired+Spins+in+Li-O2+Battery+Chemistry+and+Electrochemistry:+A+Minireview.">Implications of the Unpaired Spins in Li-O2 Battery Chemistry and Electrochemistry: A Minireview.</a> ChemPlusChem. 80, 336-343 (2015).</li><li>Lau, K. C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Theoretical+Exploration+of+Various+Lithium+Peroxide+Crystal+Structures+in+a+Li-Air+Battery.">Theoretical Exploration of Various Lithium Peroxide Crystal Structures in a Li-Air Battery.</a> Energies. 8, 529-548 (2015).</li><li>Black, R., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Screening+for+Superoxide+Reactivity+in+Li-O2+Batteries:+Effect+on+Li2O2/LiOH+Crystallization.">Screening for Superoxide Reactivity in Li-O2 Batteries: Effect on Li2O2/LiOH Crystallization.</a> J. Am. Chem. Soc. 134, 2902-2905 (2012).</li><li>Gallant, B. M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Influence+of+Li2O2+morphology+on+oxygen+reduction+and+evolution+kinetics+in+Li-O2+batteries.">Influence of Li2O2 morphology on oxygen reduction and evolution kinetics in Li-O2 batteries.</a> Energy Environ. Sci. 6, 2518-2528 (2013).</li><li>Lu, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Magnetism+in+Lithium-Oxygen+Discharge+Product.">Magnetism in Lithium-Oxygen Discharge Product.</a> ChemSusChem. 6, 1196-1202 (2013).</li><li>Xu, J. -. J., Wang, Z. -. L., Xu, D., Zhang, L. -. L., Zhang, X. -. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Tailoring+deposition+and+morphology+of+discharge+products+towards+high-rate+and+long-life+lithium-oxygen+batteries.">Tailoring deposition and morphology of discharge products towards high-rate and long-life lithium-oxygen batteries.</a> Nat. Commun. 4, 2438 (2013).</li><li>Zhong, L., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=In+Situ+Transmission+Electron+Microscopy+Observations+of+Electrochemical+Oxidation+of+Li2O2.">In Situ Transmission Electron Microscopy Observations of Electrochemical Oxidation of Li2O2.</a> Nano Lett. 13, 2209-2214 (2013).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Hitachi S-4700 SEM Training &amp; Reference Guide. , (2015).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> SEM Hitachi S4700 User Manual. , (2015).</li><li>Goldstein, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Scanning Electron Microscopy and X-ray Microanalysis. , (2003).</li><li>. X-Ray Photoelectron Spectrometer Operation Procedure Available from: <a target="_blank" href="https://nanofabrication.4dlabs.ca">https://nanofabrication.4dlabs.ca</a> (2015)</li><li>Haasch, R. T., Sardela, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Practical Materials Characterization. , 93-132 (2014).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> JEM-2100F Field Emission Transmission Electron Microscope. , (2015).</li><li>Wen, J. -. G., Sardela, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Practical Materials Characterization. , 189-229 (2014).</li><li>Williams, D. B., Carter, C. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Transmission Electron Microscopy. , (2009).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Beamline 11-ID-C: High-energy Diffraction Beamline. , (2015).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Beamline 11-ID-D: Sector 11 - Time Resolved X-ray Spectroscopy and Scattering. , (2015).</li><li>Sardela, M. R., Sardela, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Practical Materials Characterization. , 1-41 (2014).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Beamline 9-BM-B,C: X-ray Absorption Spectroscopy Beamline. , (2015).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Beamline 20-BM-B: X-ray Absorption Spectroscopy Beamline. , (2015).</li><li>Bunker, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Introduction to XAFS: A Practical Guide to X-ray Absorption Fine Structure Spectroscopy. , (2010).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Nicolet FT-IR User's Guide. , (2015).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Nicolet iS5 User Guide. , (2015).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Renishaw inVia Raman Microscope Training Notebook. , (2015).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Renishaw InVia Quick Operation Summary. , (2015).</li><li>Mitchell, R. R., Gallant, B. M., Thompson, C. V., Shao-Horn, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=All-carbon-nanofiber+electrodes+for+high-energy+rechargeable+Li-O2+batteries.">All-carbon-nanofiber electrodes for high-energy rechargeable Li-O2 batteries.</a> Energy Environ. Sci. 4, 2952-2958 (2011).</li></ol>

The authors have nothing to disclose.

Considerando a sensibilidade do sistema de baterias de Li-O 2 para o ar, especialmente CO2 e humidade, em muitos passos do protocolo são necessárias a fim de reduzir os interferentes e para evitar reacções secundárias. Por exemplo, a célula-tipo Swagelok é montado numa caixa de luvas cheia com Ar com O 2 &lt;0,5 ppm e H2O &lt;0,5 ppm; e todos os materiais de cátodo, solvente e electrólito de sal, fibra de vidro, peças Swagelok, e as câmaras de vidro são secos antes...

Em 1996, Abraham e Jiang 1 relatou o primeiro não aquoso Li-O 2 bateria reversível que consiste em um cátodo poroso de carbono, um eletrólito orgânico, e um ânodo de Li-metal. Desde então, devido ao seu extremamente alta densidade de energia teórica superior a de qualquer outro sistema de armazenamento de energia existentes, a bateria de Li-O 2, que induz um fluxo de corrente através da oxidação de lítio no ânodo e de redução do oxigénio no cátodo ( Li reação global + + O 2 + e - ↔ Li 2 O 2), tem recebido um interesse significativo recentemente 1-8. Um material de cátodo com os seguintes requisitos seria capaz de atender às necessidades de alta performance de Li-O 2 da bateria: (1) a difusão de oxigênio rápido; (2) boa condutividade elétrica e iônica; (3) área superficial específica elevada; e (4) estabilidade. Tanto a área de superfície e porosidade do cátodo é crítico para o. eficácia electroquímica de Li-O 2 baterias 9-12 A estrutura porosa permite a deposição de produtos de descarga de sólidos gerados a partir da reacção de Li catiões com O2; e áreas de superfície maiores fornecem locais mais activos para acomodar partículas eletrocatalíticas que aceleram as reações eletroquímicas. Tais electrocatalisadores são adicionados ao material do cátodo por certos métodos de deposição, que proporcionam uma forte adesão ao substrato e um bom controlo das partículas de catalisador, com preservação da estrutura de superfície porosa original do substrato. 13-17 Os materiais como preparadas são testados em células Swagelok do tipo como o cátodo de aprótico bateria Li-o 2. No entanto, o desempenho da célula não só depende da natureza dos materiais de cátodo, mas também do tipo de electrólito aprótico 18-22 e ânodo Li-metal. 23-26 Mais influências incluem a quantidade e concentração dos materiais ea pPROCEDIMENTO utilizado nos testes de carga / descarga. condições e protocolos adequados iria otimizar e melhorar o desempenho geral de materiais de bateria. Para além dos resultados do teste electroquímico, o desempenho da bateria pode ser também avaliada pela caracterização dos materiais cristalinos e os produtos de reacção. 27-33 microscopia electrónica de varredura (SEM) é usado para investigar a microestrutura de superfície do material do cátodo e a morfologia evolução dos produtos de descarga. A microscopia electrónica de transmissão (TEM), absorção de raios-X perto estrutura da extremidade (XANES), e espectroscopia de fotoelectrão de raios-X (XPS) pode ser usado para determinar a ultra-estrutura, estado químico, e o componente de elementos, especialmente para a de nanopartículas de catalisador. De alta energia de difracção de raios-X (XRD) é utilizada para identificar directamente os produtos de descarga cristalino. decomposição possível electrólito pode ser determinada por Fourier de reflexão total atenuada transformadaInfravermelhos (ATR-FTIR) e espectros de Raman. Este artigo é um protocolo que demonstra uma disposição sistemática e eficiente de testes de rotina do aprótico bateria Li-O 2, incluindo a preparação de materiais de bateria e acessórios, o teste de desempenho eletroquímico, e caracterização de materiais virgens e produtos de reacção. O protocolo de vídeo detalhada destina-se a ajudar os novos profissionais da área a evitar muitas armadilhas comuns associados com o teste de desempenho e caracterização de Li-S 2 baterias.

<table><tbody><tr><td>1-Methyl-2-pyrrolidinone (NMP), 99.5%</td><td>Sigma-Aldrich</td><td>328634</td><td></td></tr><tr><td>Battery test system</td><td>MACCOR</td><td>Series 4000 Automated Test System</td><td></td></tr><tr><td>Dimethyl carbonate (DMC), &amp;ge;99%</td><td>Sigma-Aldrich</td><td>517127</td><td></td></tr><tr><td>Ethyl alcohol, &amp;ge;99.5%</td><td>Sigma-Aldrich</td><td>459844</td><td></td></tr><tr><td>Formaldehyde solution, 37 wt. % in H&lt;sub&gt;2&lt;/sub&gt;O</td><td>Sigma-Aldrich</td><td>252549</td><td></td></tr><tr><td>Graphitized Carbon black, &gt;99.95%</td><td>Sigma-Aldrich</td><td>699632</td><td></td></tr><tr><td>Iron(III) chloride (FeCl&lt;sub&gt;3&lt;/sub&gt;), 97%</td><td>Sigma-Aldrich</td><td>157740</td><td></td></tr><tr><td>Kapton polyimide tubing</td><td>Cole-Parmer</td><td>EW-95820-09</td><td></td></tr><tr><td>Kapton polymide tape</td><td>Cole-Parmer</td><td>EW-08277-80</td><td></td></tr><tr><td>Kapton window film</td><td>SPEX Sample Prep</td><td>3511</td><td></td></tr><tr><td>Lithium Chip (99.9% Lithium)</td><td>MTI Corporation</td><td>EQ-Lib-LiC25</td><td></td></tr><tr><td>Lithium trifluoromethanesulfonate (LiCF&lt;sub&gt;3&lt;/sub&gt;SO&lt;sub&gt;3&lt;/sub&gt;)</td><td>Sigma-Aldrich</td><td>481548</td><td></td></tr><tr><td>Palladium hexafluoroacetylacetonate (Pd(hfac)&lt;sub&gt;2&lt;/sub&gt;), 99.9%</td><td>Aldrich</td><td>401471</td><td></td></tr><tr><td>Poly(vinylidene fluoride) (PVDF)</td><td>Aldrich</td><td>182702</td><td></td></tr><tr><td>Potassium permanganate (KMnO&lt;sub&gt;4&lt;/sub&gt;), &amp;ge;99.0%&amp;nbsp;</td><td>Sigma-Aldrich</td><td>223468</td><td></td></tr><tr><td>Sodium hydroxide (NaOH), &amp;ge;97.0%</td><td>Sigma-Aldrich</td><td>221465</td><td></td></tr><tr><td>Tetraethylene glycol dimethyl ether (TEGDME), &amp;ge;99%</td><td>Aldrich</td><td>172405</td><td></td></tr><tr><td>Toray 030 carbon paper</td><td>ElectroChem Inc.</td><td>590637</td><td></td></tr></tbody></table>

protocol of electrochemical test and characterization of aprotic li-o2 battery

We demonstrate a method for electrochemical testing of an aprotic Li-O2 battery. An aprotic Li-O2 battery is made of a Li-metal anode, an aprotic electrolyte, and an O2-breathing cathode. The aprotic electrolyte is a solution of lithium salt with aprotic solvent; and porous carbon is commonly used as the cathode substrate. To improve the performance, an electrocatalyst is deposited onto the porous carbon substrate by certain deposition methods, such as atomic layer deposition (ALD) and wet-chemistry reaction. The as-prepared cathode materials are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray absorption near edge structure (XANES). A Swagelok-type cell, sealed in a glass chamber filled with pure O2, is used for the electrochemical test on a battery test system. The cells are tested under either capacity-controlled mode or voltage controlled mode. The reaction products are investigated by electron microscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, and Raman spectroscopy to study the possible pathway of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). This protocol demonstrates a systematic and efficient arrangement of routine tests of the aprotic Li-O2 battery, including the electrochemical test and characterization of battery materials.

Figura 1a mostra a configuração da célula Swagelok-tipo do teste de bateria Li-O 2. Um pedaço de película de lítio é colocado sobre uma haste de aço inoxidável na extremidade do ânodo. O cátodo poroso é aberta para O2 puro através de um tubo de alumínio. A fibra de vidro é usado como um separador e um absorvedor de electrólito aprótico; e Al-malha é usado como uma corrente de colector. Toda a célula-tipo Swagelok é selado numa c?...

Watch this Scientific Journal Video about Protocol of Electrochemical Test and Characterization of Aprotic Li-O2 Battery at JoVE.com

Protocol of Electrochemical Test and Characterization of Aprotic Li-O2 Battery

A protocol for the electrochemical testing of an aprotic Li-O2 battery with the preparation of electrodes and electrolytes and an introduction of the frequently used methods of characterization is presented here.

Protocolo de Eletroquímica Teste e Caracterização de aprótico Li-O<sub&gt; 2</sub&gt; bateria

We demonstrate a method for electrochemical testing of an aprotic Li-O2 battery. An aprotic Li-O2 battery is made of a Li-metal anode, an aprotic ...

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Universidad de Cartagena UDEC

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Engineering

Protocol of Electrochemical Test and Characterization of Aprotic Li-O2 Battery

11.4K visualizações.  Argonne National Laboratory. A protocol for the electrochemical testing of an aprotic Li-O2 battery with the preparation of electrodes and electrolytes and an introduction of the frequently used methods of characterization is presented here. 

Vídeo: Protocol of Electrochemical Test and Characterization of Aprotic Li-O2 Battery

Construction and Testing of Coin Cells of Lithium Ion Batteries

Rechargeable lithium ion batteries have wide applications in electronics, where customers always demand more capacity and longer lifetime. Lithium ion batteries have also been considered to be used in electric and hybrid vehicles1 or even electrical grid stabilization systems2. All these applications simulate a dramatic increase in the research and development of battery materials3-7, including new materials3,8, doping9, nanostructuring10-13, coatings or surface modifications14-17 and novel binders18. Consequently, an increasing number of physicists, chemists and materials scientists have recently ventured into this area. Coin cells are widely used in research laboratories to test new battery materials; even for the research and development that target large-scale and high-power applications, small coin cells are often used to test the capacities and rate capabilities of new materials in the initial stage. 
 In 2010, we started a National Science Foundation (NSF) sponsored research project to investigate the surface adsorption and disordering in battery materials (grant no. DMR-1006515). In the initial stage of this project, we have struggled to learn the techniques of assembling and testing coin cells, which cannot be achieved without numerous help of other researchers in other universities (through frequent calls, email exchanges and two site visits). Thus, we feel that it is beneficial to document, by both text and video, a protocol of assembling and testing a coin cell, which will help other new researchers in this field. This effort represents the "Broader Impact" activities of our NSF project, and it will also help to educate and inspire students.
In this video article, we document a protocol to assemble a CR2032 coin cell with a LiCoO2 working electrode, a Li counter electrode, and (the mostly commonly used) polyvinylidene fluoride (PVDF) binder. To ensure new learners to readily repeat the protocol, we keep the protocol as specific and explicit as we can. However, it is important to note that in specific research and development work, many parameters adopted here can be varied. First, one can make coin cells of different sizes and test the working electrode against a counter electrode other than Li. Second, the amounts of C black and binder added into the working electrodes are often varied to suit the particular purpose of research; for example, large amounts of C black or even inert powder were added to the working electrode to test the "intrinsic" performance of cathode materials14. Third, better binders (other than PVDF) have also developed and used18. Finally, other types of electrolytes (instead of LiPF6) can also be used; in fact, certain high-voltage electrode materials will require the uses of special electrolytes7.

A protocol to construct and test coin cells of lithium ion batteries is described. The specific procedures of making a working electrode, preparing a counter electrode, assembling a cell inside a glovebox and testing the cell are presented.

Construção e Teste de Pilhas da moeda de baterias de lítio

Rechargeable lithium ion batteries have wide applications in electronics, where customers always demand more capacity and longer lifetime.  Lithium ion ...

Engenharia

Characterization of Electrode Materials for Lithium Ion and Sodium Ion Batteries Using Synchrotron Radiation Techniques

Intercalation compounds such as transition metal oxides or phosphates are the most commonly used electrode materials in Li-ion and Na-ion batteries. During insertion or removal of alkali metal ions, the redox states of transition metals in the compounds change and structural transformations such as phase transitions and/or lattice parameter increases or decreases occur. These behaviors in turn determine important characteristics of the batteries such as the potential profiles, rate capabilities, and cycle lives. The extremely bright and tunable x-rays produced by synchrotron radiation allow rapid acquisition of high-resolution data that provide information about these processes. Transformations in the bulk materials, such as phase transitions, can be directly observed using X-ray diffraction (XRD), while X-ray absorption spectroscopy (XAS) gives information about the local electronic and geometric structures (e.g.&#160;changes in redox states and bond lengths). In situ experiments carried out on operating cells are particularly useful because they allow direct correlation between the electrochemical and structural properties of the materials. These experiments are time-consuming and can be challenging to design due to the reactivity and air-sensitivity of the alkali metal anodes used in the half-cell configurations, and/or the possibility of signal interference from other cell components and hardware. For these reasons, it is appropriate to carry out ex situ experiments (e.g.&#160;on electrodes harvested from partially charged or cycled cells) in some cases. Here, we present detailed protocols for the preparation of both ex situ and in situ samples for experiments involving synchrotron radiation and demonstrate how these experiments are done.

We describe the use of synchrotron X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) techniques to probe details of intercalation/deintercalation processes in electrode materials for Li-ion and Na-ion batteries. Both in situ and ex situ experiments are used to understand structural behavior relevant to the operation of devices

Caracterização de Materiais de Eletrodo de íons de lítio e íon sódio Baterias Utilizando Técnicas Synchrotron Radiation

Intercalation compounds such as transition metal oxides or phosphates are the most commonly used electrode materials in Li-ion and Na-ion batteries. ...

Failure Analysis of Batteries Using Synchrotron-based Hard X-ray Microtomography

Imaging morphological changes that occur during the lifetime of rechargeable batteries is necessary to understand how these devices fail. Since the advent of lithium-ion batteries, researchers have known that the lithium metal anode has the highest theoretical energy density of any anode material. However, rechargeable batteries containing a lithium metal anode are not widely used in consumer products because the growth of lithium dendrites from the anode upon charging of the battery causes premature cell failure by short circuit. Lithium dendrites can also form in commercial lithium-ion batteries with graphite anodes if they are improperly charged. We demonstrate that lithium dendrite growth can be studied using synchrotron-based hard X-ray microtomography. This non-destructive imaging technique allows researchers to study the growth of lithium dendrites, in addition to other morphological changes inside batteries, and subsequently develop methods to extend battery life.

Synchrotron-based hard X-ray microtomography is used to image the electrochemical growth of dendrites from a lithium metal electrode through a solid polymer electrolyte membrane.

Falha Análise de Baterias Usando baseado no Synchrotron microtomografia de raios-X dura

Imaging morphological changes that occur during the lifetime of rechargeable batteries is necessary to understand how these devices fail. Since the advent ...

Non-aqueous Electrode Processing and Construction of Lithium-ion Coin Cells

Research into new and improved materials to be utilized in lithium-ion batteries (LIB) necessitates an experimental counterpart to any computational analysis. Testing of lithium-ion batteries in an academic setting has taken on several forms, but at the most basic level lies the coin cell construction. In traditional LIB electrode preparation, a multi-phase slurry composed of active material, binder, and conductive additive is cast out onto a substrate. An electrode disc can then be punched from the dried sheet and used in the construction of a coin cell for electrochemical evaluation. Utilization of the potential of the active material in a battery is critically dependent on the microstructure of the electrode, as an appropriate distribution of the primary components are crucial to ensuring optimal electrical conductivity, porosity, and tortuosity, such that electrochemical and transport interaction is optimized. Processing steps ranging from the combination of dry powder, wet mixing, and drying can all critically affect multi-phase interactions that influence the microstructure formation. Electrochemical probing necessitates the construction of electrodes and coin cells with the utmost care and precision. This paper aims at providing a step-by-step guide of non-aqueous electrode processing and coin cell construction for lithium-ion batteries within an academic setting and with emphasis on deciphering the influence of drying and calendaring.

Non-aqueous electrode processing is central to the construction of coin cells and the evaluation of new electrode chemistries for lithium-ion batteries. A step-by-step guide to the basic practices needed as an electrochemical engineer working with batteries in an academic experimental setting is furnished.

Processamento Eletrodo não aquoso e Construção de iões de lítio Coin Cells

Research into new and improved materials to be utilized in lithium-ion batteries (LIB) necessitates an experimental counterpart to any computational ...

A Protocol for Electrochemical Evaluations and State of Charge Diagnostics of a Symmetric Organic Redox Flow Battery

Redox flow batteries have been considered as one of the most promising stationary energy storage solutions for improving the reliability of the power grid and deployment of renewable energy technologies. Among the many flow battery chemistries, non-aqueous flow batteries have the potential to achieve high energy density because of the broad voltage windows of non-aqueous electrolytes. However, significant technical hurdles exist currently limiting non-aqueous flow batteries to demonstrate their full potential, such as low redox concentrations, low operating currents, under-explored battery status monitoring, etc. In an attempt to address these limitations, we recently reported a non-aqueous flow battery based on a highly soluble, redox-active organic nitronyl nitroxide radical compound, 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (PTIO). This redox material exhibits an ambipolar electrochemical property, and therefore can serve as both anolyte and catholyte redox materials to form a symmetric flow battery chemistry. Moreover, we demonstrated that Fourier transform infrared (FTIR) spectroscopy could measure the PTIO concentrations during the PTIO flow battery cycling and offer reasonably accurate detection of the battery state of charge (SOC), as cross-validated by electron spin resonance (ESR) measurements. Herein we present a video protocol for the electrochemical evaluation and SOC diagnosis of the PTIO symmetric flow battery. With a detailed description, we experimentally demonstrated the route to achieve such purposes. This protocol aims to spark more interests and insights on the safety and reliability in the field of non-aqueous redox flow batteries.

We present the protocols for electrochemically evaluating a symmetric non-aqueous organic redox flow battery and for diagnosing its state of charge using FTIR.

Um protocolo para eletroquímicos Avaliações e estado de carga Diagnostics de um fluxo Redox Battery Symmetric Organic

Redox flow batteries have been considered as one of the most promising stationary energy storage solutions for improving the reliability of the power grid ...

Química

Synthesis of Ionic Liquid Based Electrolytes, Assembly of Li-ion Batteries, and Measurements of Performance at High Temperature

The chemical instability of the traditional electrolyte remains a safety issue in widely used energy storage devices such as Li-ion batteries. Li-ion batteries for use in devices operating at elevated temperatures require thermally stable and non-flammable electrolytes. Ionic liquids (ILs), which are non-flammable, non-volatile, thermally stable molten salts, are an ideal replacement for flammable and low boiling point organic solvent electrolytes currently used today. We herein describe the procedures to: 1) synthesize mono- and di-phosphonium ionic liquids paired with chloride or bis(trifluoromethane)sulfonimide (TFSI) anions; 2) measure the thermal properties and stability of these ionic liquids by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA); 3) measure the electrochemical properties of the ionic liquids by cyclic voltammetry (CV); 4) prepare electrolytes containing lithium bis(trifluoromethane)sulfonamide; 5) measure the conductivity of the electrolytes as a function of temperature; 6) assemble a coin cell battery with two of the electrolytes along with a Li metal anode and LiCoO2 cathode; and 7) evaluate battery performance at 100 &#176;C. We additionally describe the challenges in execution as well as the insights gained from performing these experiments.

Here, we describe protocols to prepare phosphonium-based ionic liquid and lithium bis(trifluoromethane)sulfonimide salt electrolytes, and assemble a non-flammable and high temperature functioning lithium-ion coin cell battery.

Síntese de líquidos iónicos baseados eletrólitos, Assembléia de baterias de iões de lítio, e as medições de desempenho em alta temperatura

The chemical instability of the traditional electrolyte remains a safety issue in widely used energy storage devices such as Li-ion batteries. Li-ion ...

Focused Ion Beam Fabrication of LiPON-based Solid-state Lithium-ion Nanobatteries for In Situ Testing

Solid-state electrolytes are a promising replacement for current organic liquid electrolytes, enabling higher energy densities and improved safety of lithium-ion (Li-ion) batteries. However, a number of setbacks prevent their integration into commercial devices. The main limiting factor is due to nanoscale phenomena occurring at the electrode/electrolyte interfaces, ultimately leading to degradation of battery operation. These key problems are highly challenging to observe and characterize as these batteries contain multiple buried interfaces. One approach for direct observation of interfacial phenomena in thin film batteries is through the fabrication of electrochemically active nanobatteries by a focused ion beam (FIB). As such, a reliable technique to fabricate nanobatteries was developed and demonstrated in recent work. Herein, a detailed protocol with a step-by-step process is presented to enable the reproduction of this nanobattery fabrication process. In particular, this technique was applied to a thin film battery consisting of LiCoO2/LiPON/a-Si, and has further been previously demonstrated by in situ cycling within a transmission electron microscope.

Focused Ion Beam Fabrication of LiPON-based Solid-state Lithium-ion Nanobatteries for In Situ Testing

A protocol for the fabrication of electrochemically active LiPON-based solid-state lithium-ion nanobatteries using a focused ion beam is presented.

Fabricação de feixe de íon focalizado de estado sólido baseados em LiPON de lítio-íon Nanobatteries para In Situ testes

Solid-state electrolytes are a promising replacement for current organic liquid electrolytes, enabling higher energy densities and improved safety of ...

In Situ Lithiated Reference Electrode: Four Electrode Design for In-operando Impedance Spectroscopy

Extending operating voltage of Li-ion batteries results in higher energy output from these devices. High voltages, however, may trigger or accelerate multiple processes responsible for long-term performance decay. Given the complexity of physical processes occurring inside the cell, it is often challenging to achieve a full understanding of the root causes of this performance degradation. This difficulty arises in part from the fact that any electrochemical measurement of a battery will return the combined contributions of all components in the cell. Incorporation of a reference electrode can solve part of the problem, as it allows the electrochemical reactions of the cathode and the anode to be individually probed. A variation in the voltage range experienced by the cathode, for example, can indicate alterations in the pool of cyclable lithium ions in the full-cell. The structural evolution of the many interphases existing in the battery can also be monitored, by measuring the contributions of each electrode to the overall cell impedance. Such wealth of information amplifies the reach of diagnostic analysis in Li-ion batteries and provides valuable input to the optimization of individual cell components. In this work, we introduce the design of a test cell able to accommodate multiple reference electrodes, and present reference electrodes that are appropriate for each specific type of measurement, detailing the assembly process in order to maximize the accuracy of the experimental results.

The incorporation of reference electrodes in a Li-ion battery provides valuable information to elucidate degradation mechanisms at high voltages. In this article, we present a cell design that accommodates multiple reference electrodes, along with the assembly steps to assure maximum accuracy of the data obtained in electrochemical measurements.

No eletrodo de referência Lithiated Situ: Quatro eletrodos Design por espectroscopia de impedância no operando

Extending operating voltage of Li-ion batteries results in higher energy output from these devices. High voltages, however, may trigger or accelerate ...

The Effect of Charging and Discharging Lithium Iron Phosphate-graphite Cells at Different Temperatures on Degradation

The effect of charging and discharging lithium iron phosphate-graphite cells at different temperatures on their degradation is evaluated systematically. The degradation of the cells is assessed by using 10 charging and discharging temperature permutations ranging from -20 &#176;C to 30 &#176;C. This allows an analysis of the effect of charge and discharge temperatures on aging, and their associations. A total of 100 charge/discharge cycles were carried out. Every 25 cycles a reference cycle was performed to assess the reversible and irreversible capacity degradation. A multi-factor analysis of variance was used, and the experimental results were fitted showing: i) a quadratic relationship between the rate of degradation and the temperature of charge, ii) a linear relationship with the temperature of discharge, and iii) a correlation between the temperature of charge and discharge. It was found that the temperature combination for charging at +30 &#176;C and discharging at -5 &#176;C led to the highest rate of degradation. On the other hand, the cycling in a temperature range from -20 &#176;C to 15 &#176;C (with various combinations of temperatures of charge and discharge), led to a much lower degradation. Additionally, when the temperature of charge is 15 &#176;C, it was found that the degradation rate is nondependent on the temperature of discharge.

This article describes the effect of dissimilar charging/discharging temperatures on the degradation of lithium iron phosphate-graphite pouch cells, aiming at simulating close to real case scenarios. In total, 10 temperature combinations are investigated in the range -20 to 30 &#176;C in order to analyze the impact of temperature on degradation.

O efeito de carregamento e de descarregamento de lítio ferro fosfato-grafite células em diferentes temperaturas na degradação

The effect of charging and discharging lithium iron phosphate-graphite cells at different temperatures on their degradation is evaluated systematically. ...

Three-electrode Coin Cell Preparation and Electrodeposition Analytics for Lithium-ion Batteries

As lithium-ion batteries find use in high energy and power applications, such as in electric and hybrid-electric vehicles, monitoring the degradation and subsequent safety issues becomes increasingly important. In a Li-ion cell setup, the voltage measurement across the positive and negative terminals inherently includes the effect of the cathode and anode which are coupled and sum to the total cell performance. Accordingly, the ability to monitor the degradation aspects associated with a specific electrode is extremely difficult because the electrodes are fundamentally coupled. A three-electrode setup can overcome this problem. By introducing a third (reference) electrode, the influence of each electrode can be decoupled, and the electrochemical properties can be measured independently. The reference electrode (RE) must have a stable potential that can then be calibrated against a known reference, for example, lithium metal. The three-electrode cell can be used to run electrochemical tests such as cycling, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS). Three-electrode cell EIS measurements can elucidate the contribution of individual electrode impedance to the full cell. In addition, monitoring the anode potential allows the detection of electrodeposition due to lithium plating, which can cause safety concerns. This is especially important for the fast charging of Li-ion batteries in electric vehicles. In order to monitor and characterize the safety and degradation aspects of an electrochemical cell, a three-electrode setup can prove invaluable. This paper aims to provide a guide to constructing a three-electrode coin cell setup using the 2032-coin cell architecture, which is easy to produce, reliable, and cost-effective.

Three-electrode cells are useful in studying the electrochemistry of lithium-ion batteries. Such an electrochemical setup allows the phenomena associated with the cathode and anode to be decoupled and examined independently. Here, we present a guide for construction and use of a three-electrode coin cell with emphasis on lithium plating analytics.

Preparação de célula de moeda de três-elétrodo e eletrodeposição Analytics para baterias do lítio-íon

As lithium-ion batteries find use in high energy and power applications, such as in electric and hybrid-electric vehicles, monitoring the degradation and ...

Protocolo de Eletroquímica Teste e Caracterização de aprótico Li-O

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