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Cellulose-assisted electrodeposition of zinc for morphological control in battery metal recycling
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Polymeric Materials.
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Polymeric Materials.
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Polymeric Materials.ORCID iD: 0000-0002-2073-7005
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Biocomposites.ORCID iD: 0000-0002-1591-5815
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2022 (English)In: Materials Advances, E-ISSN 2633-5409, Vol. 3, no 13, p. 5304-5314Article in journal (Refereed) Published
Abstract [en]

Cellulose nanofibers (CNF) are demonstrated as an effective tool for converting electrodeposits into more easily detachable dendritic deposits useful in recycling zinc ion batteries via electrowinning. The incorporation of CNF at concentrations ranging from 0.01 to 0.5 g/L revealed a progressively extensive formation of a nacre-like dendritic zinc structure that did not form in its absence. Increasing CNF-concentrations from 0.01 to 0.5 g/L resulted in more extensive dendritic structures forming. The explanation to the observed phenomenon is the CNFs ability to strongly interact with the metal ions, i.e., restricting the mobility of the ions towards the electrowinning electrode. At the highest concentration of CNF (0.5 g/L), in combination with the lowest current density (150 A/m2), the electrodeposition was limited to the extent that formed deposits were almost non-existent. The electrodeposition in the presence of CNF was further evaluated at different temperatures: 20, 40 and 60°C. The dendritic formation was increasingly suppressed with increasing temperatures, and at a temperature of 60°C, the electrodeposited morphologies could not be differentiated from the morphologies formed in the absence of the cellulose. The results stemmed from a greater mobility of the metal ions at elevated temperatures, while at the same time suggests an inability of the CNF to strongly associate the metal ions at the elevated temperatures. High-pressure blasted titanium electrodes were used a reference material for accurate comparisons, and electron microscopy (FE-SEM) and X-ray diffraction were used to characterize the zinc morphologies and crystallite sizes, respectively. The article reports the first investigation on how dispersions of highly crystalline cellulose nanofibers can be used as a renewable and functional additive during the recycling of battery metal ions. The metal-ion/cellulose interactions may also allow for structural control in electrodeposition for other applications. 

 

Place, publisher, year, edition, pages
Royal Society of Chemistry (RSC) , 2022. Vol. 3, no 13, p. 5304-5314
National Category
Materials Engineering
Identifiers
URN: urn:nbn:se:kth:diva-311141DOI: 10.1039/d2ma00249cISI: 000790418300001Scopus ID: 2-s2.0-85134295028OAI: oai:DiVA.org:kth-311141DiVA, id: diva2:1652579
Note

Correction in DOI 10.1039/D3MA90041J

QC 20260108

Available from: 2022-04-19 Created: 2022-04-19 Last updated: 2026-01-08Bibliographically approved
In thesis
1. Exploring cellulose as a biomacromolecule for enhanced battery metal ion recovery/recycling
Open this publication in new window or tab >>Exploring cellulose as a biomacromolecule for enhanced battery metal ion recovery/recycling
2023 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The research focused on the effects of integrating nanocellulose in the solidification of metal ions into metal oxide particles or metallic electrodeposits.  Firstly, the cellulose was isolated as highly crystalline ca. 15-25 nm thick and 500 nm long fibers from bacterial cellulose using acid hydrolysis and had a negative surface charge. Positively charged nanocellulose was also explored using cationic functional groups substituted onto the nanofiber surface.  The effect of the isolated nanocellulose when preparing metal oxides via enforced precipitation of zinc metal ions into zinc oxide particles was investigated at ultra-low nanocellulose content ≤0.01 %. The result indicated that increased reaction yields of ~15 % and a reduction of particle sizes by up to 50 % could occur at nanocellulose concentrations of 0.01 %. The kinetics was studied and showed that the presence of cellulose consistently increased the consumption rates of zinc ions. If the reaction consumed a large fraction of the zinc-ions (>80%) within the first 15 min, continued growth of ZnO was also suppressed by the presence of nanocellulose. This was observed during the synthesis of sheet-like ZnO-particles, where an increase in reaction yield from 81 to 95 % hindered the growth of additional nanorods, which otherwise had formed after 15 min of the reaction. Further, nanocellulose was then evaluated for metal recovery reactions of Zn, Cd, and Ni using electrodeposition. Zinc and cadmium, which generally form separate, faceted metal particles during electrodeposition, grew large dendrites when nanocellulose was present in the electrolyte. In the case of cadmium, the formation of dendrites was correlated with increases in yield by up to 15 %. For nickel, which always deposited as uniform and non-faceted layers, the presence of nanocellulose did not result in dendritic deposits. While the presence of 0.05 % of nanocellulose did not affect the yield for negatively charged nanocellulose, positively charged nanocellulose decreased the deposited amount by up to ca. 20 %. The temperature was also used to tune the dendritic formation during the zinc deposition. The major finding was that while the zinc electrodeposition in the presence of nanocellulose at 20 or 40°C induced dendritic growth, a similar deposition at 60 °C did not, reverting the deposition towards promoting dense and faceted zinc particles. The research on integrating nanocellulose in metal oxide particle solidification and metal recovery using electrodeposition aligns with the United Nations' Sustainable Development Goals (SDGs), particularly Goal 12: Responsible Consumption and Production, and Goal 1: End poverty in all its forms everywhere, but also Goal 13: Climate Action. The use of nanocellulose as an additive can contribute to sustainable consumption and production practices, reducing waste and conserving natural resources. This approach can help to address the challenge of meeting growing demands for metals used in various industrial applications, particularly those associated with battery manufacturing. Recycling valuable metals using nanocellulose can reduce the environmental impact of mining and processing ores, contributing to sustainable resource management and contribute to poverty reduction for creating job opportunities. Furthermore, the use of nanocellulose in electrodeposition reactions will help to combat climate change by promoting more efficient and environmentally friendly metal recovery methods, potentially reducing the carbon footprint associated with traditional metal recovery and mitigate the environmental impacts of metal extraction and mining. Overall, the research on integrating nanocellulose in metal oxide particle solidification and metal recovery using electrodeposition demonstrates innovative and sustainable solutions for resource management, contributing to the UN's SDGs.

Abstract [sv]

Denna avhandling fokuserar på effekten av att integrera nanocellulosa under kondensationen av metall-joner till antingen metalloxid-partiklar eller elektrodeponerad metall. Cellulosan erhölls som ca. 15-25 nm tjocka och 500 nm långa fibrer via syrahydrolys av bakteriell cellulosa, vilket resulterade i nanofibrer med en negativ ytladdning. Även positivt laddad nanocellulosa utforskades genom att substituera in katjoniska funktionella grupper på nanofiber-ytan.När det gäller bildandet av metalloxider så undersöktes effekten av den isolerade nanocellulosan på utfällningen av zinkjoner till zinkoxidpartiklar (ZnO) vid ultra-låga koncentrationer kring 0.01 % eller lägre. Resultaten pekade på att cellulosans närvaro resulterade i ca. 15 % högre reaktionsutbyten samt en minskning av partikelstorlekarna på upp till 50% vid en cellulosakoncentration av 0.01%. Reaktionskinetiken studerades och visade att cellulosans närvaro alltid ökade konsumtionshastigheten av zink-joner. I de fall när en stor del av de närvarande zinkjonerna konsumerades (>80%) inom reaktionens första 15 min, visade resultaten att den fortsatta tillväxten ströps i samband med nanocellulosans närvaro. Detta observerades i samband med syntesen av partiklar bestående av ZnO-flak, då en ökning från 81 till 95 % hindrade tillväxten av nano-stavar som annars hade bildats efter 15 min av reaktionens gång. Cellulosan utvärderades även i metallåtervinningsreaktioner av zink, kadmium och nickel via elektrodeponering.  Zink och kadmium, som i regel bildar separata och facetterade metallpartiklar, deponerade i form av stora dendriter när nanocellulosan var närvarande i elektrolyten. I fallet av kadmium sammanföll bildandet av dendriter med en ökning i utbytet med upp till 15%. När det gäller nickel, som alltid deponerades i form av ett jämt täckande lager utan facetterade ytor, resulterade närvaron av nanocellulosa inte i någon dendritisk tillväxt. Istället så ledde en liknande tillsats av negativt laddad nanocellulosa inte till någon påverkan på utbytet, medan en positivt laddad nanocellulosa minskade utbytet med upp till ca. 20 %. Temperaturen kunde användas styra tillväxten av dendriter i samband med zink-elektrodeponering. Medans zinkdendriter tenderade att bildas i närvaron av nanocellulosa vid 20 och 40°C, motverkades tillväxten av dendriter helt vid 60°, vilket återigen resulterade i att massiva och facetterade zinkpartiklar bildades.Forskning som fokuserar på att integrera nanocellulosa i metallåtervinning genom utfällningsreaktioner och elektrodeponering sammanfaller med FN:s mål kring hållbar utveckling, framförallt mål 12, som gäller en hållbar konsumtion och produktion, mål 1 som fokuserar på att motverka fattigdom, samt mål 13 som går in på att motverka klimatförändringar och dess påföljder. Användandet av nanocellulosa kan bidra till att utveckla hållbara konsumtions- och produktionsstrategier på ett sätt som reducerar avfall och minskar förbrukningen av naturliga resurser. Detta bidrar med att adressera utmaningarna med att möta den ökande efterfrågan på metaller som används i flertalet industriella applikationer, framförallt batteritillverkning. Skapandet av återvinningsstrategier som utnyttjar nanocellulosa skulle minska utvinningen och hanterandet av malmer, vilket i sig bidrar till en mer hållbar resurshantering samtidigt som nya jobbmöjligheter kan skapas genom utvecklandet av nya återvinningsstrategier. Användandet av nanocellulosa inom metallåtervinning kan dessutom bidra till att motverka klimatförändringar i och med att fler miljövänliga återvinningsstrategier kan utvecklas, något som kan minska det ekologiska fotavtrycket som tillkommer med mer konventionella återvinningsstrategier och en intensifierad utvinning via gruvindustrin. I överlag så demonstrerar användandet av nanocellulosa vid utfällning av metalloxider samt elektrodeponering av metall-joner möjligheterna till att utveckla innovativa och hållbara lösningar för resurshantering som i sig bidrar till att uppfylla flera av FN:s hållbarhetsmål.

Place, publisher, year, edition, pages
KTH Royal Institute of Technology, 2023. p. 85
Series
TRITA-CBH-FOU ; 2023:27
Keywords
Biomacromolecules, Nanocellulose, metal oxide nanoparticle synthesis, electrodeposition, battery recycling
National Category
Polymer Chemistry Inorganic Chemistry
Research subject
Fibre and Polymer Science
Identifiers
urn:nbn:se:kth:diva-327014 (URN)978-91-8040-615-4 (ISBN)978-91-8040-630-7 (ISBN)
Public defence
2023-06-09, D3, Lindstedtsvägen 9, Stockholm, 14:00 (English)
Opponent
Supervisors
Funder
Wallenberg Foundations
Note

QC 2023-05-17

Available from: 2023-05-17 Created: 2023-05-17 Last updated: 2023-06-07Bibliographically approved

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Hoogendoorn, Billy W.Jesus Parra Gil, MarianoCapezza, Antonio JoseLi, YuanyuanForsberg, KerstinXiao, XiongOlsson, Richard

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