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Exploring cellulose as a biomacromolecule for enhanced battery metal ion recovery/recycling
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Polymeric Materials. Wallenberg Wood Science Center. (Polymera material)ORCID iD: 0000-0002-7261-746X
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 [en]
Biomacromolecules, Nanocellulose, metal oxide nanoparticle synthesis, electrodeposition, battery recycling
National Category
Polymer Chemistry Inorganic Chemistry
Research subject
Fibre and Polymer Science
Identifiers
URN: urn:nbn:se:kth:diva-327014ISBN: 978-91-8040-615-4 (electronic)ISBN: 978-91-8040-630-7 (print)OAI: oai:DiVA.org:kth-327014DiVA, id: diva2:1757756
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
List of papers
1. Ultra-low Concentration of Cellulose Nanofibers (CNFs) for Enhanced Nucleation and Yield of ZnO Nanoparticles
Open this publication in new window or tab >>Ultra-low Concentration of Cellulose Nanofibers (CNFs) for Enhanced Nucleation and Yield of ZnO Nanoparticles
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2022 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 38, no 41, p. 12480-12490Article in journal (Refereed) Published
Abstract [en]

Cellulose nanofibers (CNFs) were used in aqueous synthesis protocols for zinc oxide (ZnO) to affect the formation of the ZnO particles. Different concentrations of CNFs were evaluated in two different synthesis protocols producing distinctly different ZnO morphologies (flowers and sea urchins) as either dominantly oxygen-or zinc-terminated particles. The CNF effects on the ZnO formation were investigated by implementing a heat-treatment method at 400 degrees C that fully removed the cellulose material without affecting the ZnO particles made in the presence of CNFs. The inorganic phase formations were monitored by extracting samples during the enforced precipitations to observe changes in the ZnO morphologies. A decrease in the size of the ZnO particles could be observed for all synthesis protocols, already occurring at small additions of CNFs. At as low as 0.1 g/L CNFs, the particle size decreased by 50% for the flower-shaped particles and 45% for the sea-urchin-shaped particles. The formation of smaller particles was accompanied by increased yield by 13 and 15% due to the CNFs' ability to enhance the nucleation, resulting in greater mass of ZnO divided among a larger number of particles. The enhanced nucleation could also be verified as useful for preventing secondary morphologies from forming, which grew on the firstly precipitated particles. The suppression of secondary growths' was due to the more rapid inorganic phase formation during the early phases of the reactions and the faster consumption of dissolved salts, leaving smaller amounts of metal salts present at later stages of the reactions. The findings show that using cellulose to guide inorganic nanoparticle growth can be predicted as an emerging field in the preparation of functional inorganic micro/nanoparticles. The observations are highly relevant in any industrial setting for the large-scale and resource-efficient production of ZnO.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2022
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-321261 (URN)10.1021/acs.langmuir.2c01713 (DOI)000874223000001 ()36200128 (PubMedID)2-s2.0-85139961062 (Scopus ID)
Note

QC 20221111

Available from: 2022-11-11 Created: 2022-11-11 Last updated: 2023-05-17Bibliographically approved
2. Cellulose-assisted electrodeposition of zinc for morphological control in battery metal recycling
Open this publication in new window or tab >>Cellulose-assisted electrodeposition of zinc for morphological control in battery metal recycling
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2022 (English)In: Materials Advances, E-ISSN 2633-5409Article 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
National Category
Materials Engineering
Identifiers
urn:nbn:se:kth:diva-311141 (URN)10.1039/d2ma00249c (DOI)000790418300001 ()2-s2.0-85134295028 (Scopus ID)
Note

Correction in DOI 10.1039/D3MA90041J

QC 20220503

Available from: 2022-04-19 Created: 2022-04-19 Last updated: 2023-07-25Bibliographically approved
3. Formation of Different Zinc Oxide Crystal Morphologies Using Cellulose as Nucleation Agent in the Waste Valorization and Recycling of Zn-Ion Batteries
Open this publication in new window or tab >>Formation of Different Zinc Oxide Crystal Morphologies Using Cellulose as Nucleation Agent in the Waste Valorization and Recycling of Zn-Ion Batteries
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2023 (English)In: Rare Metal Technology 2023, Springer, 2023Conference paper, Published paper (Refereed)
Abstract [en]

The formation of zinc oxide particles of different hierarchical morphologies was investigated. By performing elemental analysis on samples extracted from the supernatant solution during precipitations yielding two distinctly different morphologies, the consumption of zinc ions was used to follow the liquid-to-solid phase formation. While a rapid Zn-ion consumption was synonymous with the formation of predominantly oxygen terminated flower-shaped ZnO-particles, with half of the zinc ions being precipitated during the first minute, less than 10% of the zinc ions were converted to sea urchin-shaped ZnO-particles (with mixed terminations) after 1 min of the reaction. The unique ZnO-particle morphologies may therefore be related to the precipitation rates, which can be further explored as a tool for understanding how ZnO-particles with differently facetted surfaces form. Interestingly, the different formation rates remained with identical patterns when 0.5 g/L cellulose (0.005 wt%) was added to the reactions as nucleating agent for improved yields. The controlled formation of specific functional ZnO-particle surfaces is an important method for recycling inexpensive zinc waste from batteries to high value materials useful in a variety of catalytic applications.

Place, publisher, year, edition, pages
Springer, 2023
Keywords
ZnO-particle synthesis, Hydrometallurgy, Precipitation Cellulose, Battery recycling
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-323839 (URN)10.1007/978-3-031-22761-5_20 (DOI)2-s2.0-85151047420 (Scopus ID)
Conference
TMS
Note

QC 20230221

Available from: 2023-02-14 Created: 2023-02-14 Last updated: 2023-06-08Bibliographically approved
4. The Impact of Cellulose Nanofibers (CNFs) on the Electrodeposition of Nickel and Cadmium in Ni-Cd Battery Recycling
Open this publication in new window or tab >>The Impact of Cellulose Nanofibers (CNFs) on the Electrodeposition of Nickel and Cadmium in Ni-Cd Battery Recycling
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(English)Manuscript (preprint) (Other academic)
Keywords
cellulose nanofibers, electrodeposition, battery metal recycling, nickel, cadmium
National Category
Polymer Chemistry Inorganic Chemistry
Research subject
Fibre and Polymer Science
Identifiers
urn:nbn:se:kth:diva-326965 (URN)
Funder
Wallenberg FoundationsVinnova, 2021-03738
Note

QC 20230522

Available from: 2023-05-16 Created: 2023-05-16 Last updated: 2023-05-22Bibliographically approved

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Hoogendoorn, Billy W.

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