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Biomass-Derived Hard Carbon Anodes for Sodium-Ion Batteries: From Structure Engineering to Sustainable Production
KTH, School of Industrial Engineering and Management (ITM), Materials Science and Engineering, Process.ORCID iD: 0000-0001-8160-6634
2026 (English)Doctoral thesis, comprehensive summary (Other academic) [Artistic work]
Sustainable development
SDG 12: Responsible consumption and production, SDG 13: Climate action, SDG 7: Affordable and clean energy
Abstract [en]

Hard carbon (HC) is currently one of the most promising anode materials for sodium-ion batteries (SIBs). For commercial applications, HC anodes require a high initial Coulombic efficiency (ICE) and a high reversible capacity, which are closely related to a low open-pore volume and a high closed-pore volume in the HC structure. In parallel, HC requires production routes with lower energy consumption and smaller environmental footprints in order to support a circular economy. However, current HC production predominantly relies on conventional resistance-heated carbonization, in which heat is supplied externally and transferred indirectly to the material. This leads to high energy consumption and typically requires extreme carbonization temperatures to induce closed-pore formation. Therefore, additional chemical treatments or post-modification processes are often required, further increasing energy demand and environmental impact. These limitations collectively restrict the scalable and sustainable application of HC anodes.

This thesis aims to develop feasible and energy-efficient modification and carbonization processes for HC production to enhance material resource circularity. Accordingly, fundamental studies combining data-driven modeling, laboratory-scale experiments, and process simulations are conducted. The thesis is based on four different studies that together establish a systematic understanding of the process–structure–performance relationships in biomass-derived HC and propose an energy-efficient pore-engineering strategy enabled by bio-oil modification and induction heating carbonization (IC).

First, through comprehensive literature data analysis and machine-learning modeling, carbonization temperature and HC structure are identified as the dominant factors for HC electrochemical performance. Low open-pore structures and surface defect densities are found to be critical for achieving high ICE, while large interlayer spacing and closed-pore volumes are beneficial for a high plateau capacity. Importantly, the analysis reveals the limitation of conventional carbonization in simultaneously achieving low open porosity and promoting closed-pore formation.

To overcome these limitations, a sustainable bio-oil surface engineering strategy is developed to suppress open pores and surface defects. This approach reduces the specific surface area of HC from 28 to 9 m²/g and increases the ICE from 84.4% to 89.9%. By combining bio-oil surface engineering, a novel IC route is further developed. IC enables direct volumetric heating through eddy currents, which simultaneously minimizes open porosities and promotes closed-pore formation. As a result, optimal IC-derived HC exhibits open-pore volume below 0.003 cm³/g and closed-pore volume of up to 0.23 cm³/g, with an ultra-high ICE value exceeding 95%, and plateau capacity above 260 mAh/g.

Finally, energy analysis and life cycle assessment demonstrate that IC reduces the carbonization energy consumption by approximately 60% and lowers overall environmental impacts by approximately 35% compared with conventional routes. Overall, this thesis demonstrates that the combination of bio-oil modification and IC provides an energy-efficient and low-carbon pathway for producing high-performance biomass-derived HC anodes, supporting the sustainable development of next-generation sodium-ion batteries.

Abstract [sv]

Hårt kol (HC) utgör för närvarande ett av de mest lovande anodmaterialen för natriumjonbatterier (SIB). För kommersiella tillämpningar krävs att HC-anoder uppvisar en hög initial Coulombisk verkningsgrad (ICE) och en hög reversibel kapacitet, vilka är nära kopplade till en HC-struktur med en låg öppen porvolym och en hög sluten porvolym. Parallellt kräver HC produktionsvägar med låg a energiförbrukningar och en reducerad miljöpåverkan för att stödja en cirkulär ekonomi. Emellertid baseras dagens HC-produktion huvudsakligen på konventionell resistansuppvärmd karbonisering, där värme tillförs externt och överförs indirekt till materialet. Detta leder till en hög energiförbrukning och kräver vanligtvis extrema karboniseringstemperaturer för att inducera bildning av slutna porer. Därför används ofta ytterligare kemiska behandlingar eller eftermodifieringsprocesser, vilket ytterligare ökar energibehovet och miljöpåverkan. Dessa begränsningar sammantaget hindrar den skalbara och hållbara tillämpningen av HC-anoder.

Denna avhandling syftar till att utveckla genomförbara och energieffektiva modifierings- och karboniseringsprocesser för HC-produktion för att förbättra materialresursernas cirkularitet. I detta syfte genomförs grundläggande studier som kombinerar datadriven modellering, laboratorieexperiment och processimuleringar. Avhandlingen baseras på fyra olika studier som tillsammans etablerar en systematisk förståelse av sambanden mellan process, struktur och prestanda i biomassabaserat HC samt föreslår en energieffektiv por-ingenjörsstrategi möjliggjord av bio-oljemodifiering och induktionsuppvärmd karbonisering (IC).

För det första identifieras, genom en omfattande litteraturanalys och maskininlärningsmodellering, karboniseringstemperatur och HC-struktur som de dominerande faktorerna som påverkar den elektrokemiska prestandan hos HC. Undertryckta öppna porstrukturer och låg ytdefekttäthet visar sig vara avgörande för att uppnå hög ICE, medan större interlagringsavstånd och hög sluten porvolym är gynnsamma för hög platåkapacitet. Analysen visar dessutom den inneboende begränsningen hos konventionell karbonisering när det gäller att samtidigt uppnå låg öppen porositet och främja bildning av slutna porer.

För att övervinna dessa begränsningar utvecklas en hållbar ytmodifieringsstrategi baserad på bio-olja för att minska andelen öppna porer och ytdefekter. Denna metod reducerar den specifika ytan hos HC från 28 till 9 m²/g och ökar ICE från 84,4 % till 89,9 %. Genom att kombinera bio-oljebaserad ytmodifiering utvecklas vidare en ny IC-process. IC möjliggör direkt volymetrisk uppvärmning via virvelströmmar, vilket samtidigt minimerar den öppen porositeten och främjar bildningen av slutna porer. Som ett resultat uppvisar en optimerat IC-framställd HC anod en öppen porvolym under 0,003 cm³/g och en sluten porvolym upp till 0,23 cm³/g, med mycket höga ICE-värden över 95 % samt platåkapaciteter över 260 mAh/g.

Slutligen visar energi- och livscykelanalyser att IC reducerar energiförbrukningen vid karbonisering med cirka 60 % och minskar den totala miljöpåverkan med cirka 35 % jämfört med konventionella processer. Sammantaget visar denna avhandling genom att använda kombinatione av en bio-oljemodifiering och en induktionsuppvärmd karbonisering är möjligt att åstadkomma en energieffektiv och koldioxidsnål väg för en produktion av högpresterande biomassabaserade HC-anoder, vilket stödjer en hållbar utveckling av nästa generations natriumjonbatterier.

Place, publisher, year, edition, pages
Stockholm: Kungliga Tekniska högskolan, 2026. , p. xx, 84
Series
TRITA-ITM-AVL ; 2025:22
Keywords [en]
Hard Carbon, Biomass, Induction heating carbonization, Pore engineering, Surface engineering.
National Category
Materials Engineering
Research subject
Materials Science and Engineering
Identifiers
URN: urn:nbn:se:kth:diva-382837ISBN: 978-91-8106-663-0 (print)OAI: oai:DiVA.org:kth-382837DiVA, id: diva2:2079695
Public defence
2026-09-18, Kollegiesalen / https://kth-se.zoom.us/j/65097205815, Brinellvägen 8, Stockholm, 09:00 (English)
Opponent
Supervisors
Funder
Vinnova, 2021-03735Available from: 2026-06-30 Created: 2026-06-25 Last updated: 2026-09-11Bibliographically approved
List of papers
1. From Waste Biomass to Hard Carbon Anodes: Predicting the Relationship between Biomass Processing Parameters and Performance of Hard Carbons in Sodium-Ion Batteries
Open this publication in new window or tab >>From Waste Biomass to Hard Carbon Anodes: Predicting the Relationship between Biomass Processing Parameters and Performance of Hard Carbons in Sodium-Ion Batteries
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2023 (English)In: Processes, E-ISSN 2227-9717, Vol. 11, no 3, article id 764Article, review/survey (Refereed) Published
Abstract [en]

Sodium-ion batteries (SIBs) serve as the most promising next-generation commercial batteries besides lithium-ion batteries (LIBs). Hard carbon (HC) from renewable biomass resources is the most commonly used anode material in SIBs. In this contribution, we present a review of the latest progress in the conversion of waste biomass to HC materials, and highlight their application in SIBs. Specifically, the following topics are discussed in the review: (1) the mechanism of sodium-ion storage in HC, (2) the HC precursor's sources, (3) the processing methods and conditions of the HCs production, (4) the impact of the biomass types and carbonization temperature on the carbon structure, and (5) the effect of various carbon structures on electrochemical performance. Data from various publications have been analyzed to uncover the relationship between the processing conditions of biomass and the resulting structure of the final HC product, as well as its electrochemical performance. Our results indicate the existence of an ideal temperature range (around 1200 to 1400 degrees C) that enhances the formation of graphitic domains in the final HC anode and reduces the formation of open pores from the biomass precursor. This results in HC anodes with high storage capacity (>300 mAh/g) and high initial coulombic efficiency (ICE) (>80%).

Place, publisher, year, edition, pages
MDPI AG, 2023
Keywords
waste biomass, hard carbon, sodium ion batteries, sodium-ion storage, anode material
National Category
Materials Chemistry
Identifiers
urn:nbn:se:kth:diva-326634 (URN)10.3390/pr11030764 (DOI)000967839300001 ()2-s2.0-85151727689 (Scopus ID)
Note

QC 20230509

Available from: 2023-05-09 Created: 2023-05-09 Last updated: 2026-06-25Bibliographically approved
2. Unveiling the role of lignin in biomass-derived hard carbon anodes via machine learning
Open this publication in new window or tab >>Unveiling the role of lignin in biomass-derived hard carbon anodes via machine learning
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2025 (English)In: Journal of Power Sources, ISSN 0378-7753, E-ISSN 1873-2755, Vol. 631, article id 236323Article in journal (Refereed) Published
Abstract [en]

Biomass-derived hard carbon is a sustainable and promising anode material for sodium-ion batteries. Variations in biomass precursors lead to substantial differences in capacity, necessitating a deeper understanding of the underlying mechanisms. This study collected data from 149 relevant literature in the past decade. We used machine learning models to analyze the impact of lignin content and its structure in biomass precursors on the specific capacity of the derived hard carbon. The tree-based ensemble algorithms, particularly XGB and GBDT, showed superior performance, with the optimal model having a R2value of up to 0.99 for training and 0.60 for testing. Interpretable machine learning models identified lignin content and its structure as crucial factors, Shapley value analysis highlighted that higher lignin content and well-defined lignin structures positively influence capacity. Also, it is found that optimal pyrolysis temperatures (1000-1400 degrees C) and appropriate retention times are critical for enhancing performance. This work provides insights into optimizing biomass precursor selection and processing for high-performance hard carbon anodes.

Place, publisher, year, edition, pages
Elsevier BV, 2025
Keywords
Biomass hard carbon, Sodium-ion battery, Machine learning, XGB, Precursor selection, Lignin
National Category
Materials Chemistry
Identifiers
urn:nbn:se:kth:diva-360068 (URN)10.1016/j.jpowsour.2025.236323 (DOI)001412618000001 ()2-s2.0-85215766440 (Scopus ID)
Note

QC 20250217

Available from: 2025-02-17 Created: 2025-02-17 Last updated: 2026-06-25Bibliographically approved
3. Development of biomass pyrolysis bio-oil as a renewable surface engineering agent for bio-based hard carbon production
Open this publication in new window or tab >>Development of biomass pyrolysis bio-oil as a renewable surface engineering agent for bio-based hard carbon production
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2025 (English)In: Journal of Power Sources, ISSN 0378-7753, E-ISSN 1873-2755, Vol. 641, article id 236824Article in journal (Refereed) Published
Abstract [en]

Sodium-ion batteries (SIBs) are emerging as a promising alternative to lithium-ion batteries due to their potential for efficient and sustainable energy storage. Thus, the demand for high-performance battery materials with a sustainable supply chain, particularly hard carbon (HC) as the primary anode material for SIBs, is rapidly increasing. This study focuses on enhancing the production and electrochemical performance of HC products by leveraging Sweden's abundant forestry resources and advanced biomass refining processes. Specifically, we propose a novel HC production process that compresses sawdust-derived biocarbon with bio-oil derived from the same pyrolysis process to produce HC with improved properties, where the bio-oil serves as both a binder and a surface engineering agent for the biocarbon. This approach effectively modifies surface defects, leading to increased initial Coulombic efficiency (ICE), reaching values of 90 % in half-cell tests. Moreover, laboratory measurements and Life Cycle Assessment (LCA) results quantified that this production method achieves nearly 50 % higher HC yields and reduces greenhouse gas (GHG) emissions by approximately 20 % compared to the conventional production method. As a result, this offers a potentially more sustainable and economically viable solution for advancing the SIB anode material production.

Place, publisher, year, edition, pages
Elsevier BV, 2025
National Category
Energy Engineering
Identifiers
urn:nbn:se:kth:diva-362046 (URN)10.1016/j.jpowsour.2025.236824 (DOI)001456247100001 ()2-s2.0-105000536182 (Scopus ID)
Note

QC 20250404

Available from: 2025-04-03 Created: 2025-04-03 Last updated: 2026-06-25Bibliographically approved
4. Energy‐Efficient Induction Carbonization: Tailoring Pore Structures in Hard Carbon Anodes Toward Enhanced Electrochemical Performance
Open this publication in new window or tab >>Energy‐Efficient Induction Carbonization: Tailoring Pore Structures in Hard Carbon Anodes Toward Enhanced Electrochemical Performance
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2026 (English)In: Carbon Energy, ISSN 2637-9368, article id e70243Article in journal (Refereed) Epub ahead of print
Abstract [en]

Hard carbon (HC) is currently the predominant anode material for sodium-ion batteries; however, its practical application is still limited by insufficient initial Coulombic efficiency (ICE) and plateau capacity. Meanwhile, conventional HC production relies on energy-intensive carbonization processes with considerable carbon emissions. Here, an induction heating carbonization strategy is developed for extruded biocarbon columns derived from biomass-based biochar and bio-oil, enabling simultaneous enhancement of electrochemical performance and production sustainability. Bio-oil combined with high-pressure extrusion suppresses open pores, whereas induction heating generates localized eddy currents and concentrated Joule heating that accelerate carbon rearrangement and promote closed pore formation. As a result, the closed-to-open pore volume ratio increases from 0.32 to 85.18, leading to improved ICE (95.0% vs. 84.4%) and plateau capacity ratio (77.6% vs. 64.7%) relative to conventional carbonized HC. Life-cycle assessment further indicates an approximately 35% reduction in global warming potential. Overall, this work presents an energy-efficient, low-emission route for producing high-performance HC anodes.

Place, publisher, year, edition, pages
Wiley, 2026
National Category
Materials Engineering Materials Chemistry Energy Systems Other Environmental Engineering
Identifiers
urn:nbn:se:kth:diva-382836 (URN)10.1002/cey2.70243 (DOI)001765537700001 ()2-s2.0-105038822179 (Scopus ID)
Funder
Vinnova, 2021‐03735German Research Foundation (DFG), 390874152
Note

QC 20260604

Available from: 2026-06-01 Created: 2026-06-01 Last updated: 2026-06-25Bibliographically approved

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