Periodic Reporting for period 1 - REALSEI (opeRando chEmical spAce- and time-resoLved quantification of Solid Electrolyte Interphase in hard carbon anode for sustainable sodium-ion batteries)
Okres sprawozdawczy: 2021-06-01 do 2023-05-31
Problem/Issue Being Addressed:
REALSEI aims to pioneer real-time visualization of the Solid Electrolyte Interphase (SEI) formation on hard carbon anodes in sodium-ion batteries, a process largely unexplored at the local electrochemical level.
Importance for Society:
The urgency of our work is evident in the need to limit global warming to 2.7°C by 2100, requiring a tripling of global grid energy storage capacity by 2050. A transformative breakthrough is imperative, and that lies in the development of a low-cost, sustainable alternative to lithium-ion batteries. The 'Beyond-Lithium' batteries, specifically sodium-ion-based systems, hold immense promise. Bio-waste mesoporous hard carbon (BHC) emerges as a leading candidate—an abundant, low-cost, and recyclable anode material. BHC's adoption in beyond-lithium batteries could usher in the next generation of sustainable energy storage solutions.
Overall Objectives:
REALSEI's primary mission is to establish a comprehensive operando time- and space-resolved characterization methodology. This transition from bulk to surface analytical characterization relies on high-resolution X-ray techniques, both lab-based and synchrotron-based. The ultimate goal is the real-time visualization and quantification of SEI species on hard carbon. The project unfolds in three main objectives:
• O1: Optimization of HC materials synthesis and characterization.
• O2: Evaluation of HC electrode performance in sodium-ion batteries.
• O3: Visualization of operando SEI growth using High Resolution X-ray Spectrometry and protocol validation.
These objectives have been successfully met within the project timeline.
REALSEI aims to pioneer real-time visualization of the Solid Electrolyte Interphase (SEI) formation on hard carbon anodes in sodium-ion batteries, a process largely unexplored at the local electrochemical level.
Importance for Society:
The urgency of our work is evident in the need to limit global warming to 2.7°C by 2100, requiring a tripling of global grid energy storage capacity by 2050. A transformative breakthrough is imperative, and that lies in the development of a low-cost, sustainable alternative to lithium-ion batteries. The 'Beyond-Lithium' batteries, specifically sodium-ion-based systems, hold immense promise. Bio-waste mesoporous hard carbon (BHC) emerges as a leading candidate—an abundant, low-cost, and recyclable anode material. BHC's adoption in beyond-lithium batteries could usher in the next generation of sustainable energy storage solutions.
Overall Objectives:
REALSEI's primary mission is to establish a comprehensive operando time- and space-resolved characterization methodology. This transition from bulk to surface analytical characterization relies on high-resolution X-ray techniques, both lab-based and synchrotron-based. The ultimate goal is the real-time visualization and quantification of SEI species on hard carbon. The project unfolds in three main objectives:
• O1: Optimization of HC materials synthesis and characterization.
• O2: Evaluation of HC electrode performance in sodium-ion batteries.
• O3: Visualization of operando SEI growth using High Resolution X-ray Spectrometry and protocol validation.
These objectives have been successfully met within the project timeline.
Work Performed and Main Results
The project's journey began with an extensive literature review and meticulous planning of activities, including year one planning and risk assessment (D5.1 and D5.2).
Synthesis of Bio-Waste Derived Hard Carbon:
We initiated the scientific endeavor with the preparation of bio-waste derived hard carbon. Hazelnut shells from a local source were ball-milled to achieve a fine powder with a size distribution of 10 to 100 microns. Subsequent steps involved a two-step synthesis process, involving citric acid digestion at 200°C for 14 hours and pyrolysis at 1000°C. Variations in acid concentration and temperature yielded notable structural variations, impacting electrochemical performance. More than 10 samples were synthesized and tested in half sodium cells, with the standout performer named C05-1100.
Period at HZB, Berlin, Germany:
The following six months saw a crucial phase at HZB, Berlin, Germany. Replicating the performance achieved in Rome, we optimized electrode preparation for angular resolved X-ray fluorescence (XRF) measurements. Ex-situ XRF analysis on aged electrodes provided insights into SEI evolution during cycling. Furthermore, a custom test cell, tailored for ultra-high vacuum experiments such as High-Resolution X-ray Fluorescence (HRXRF), was developed. A 500 nm SiN window facilitated low-energy X-ray penetration. The subsequent operando experiments elucidated key aspects, including X-ray damage, electrochemical stability, X-ray penetration depth, and angular resolution. These tests furnished reliable measurements of SEI dynamics during cycling, revealing Na accumulation, nucleation, and solid-phase transitions.
Second Year Planning and Risk Assessment
During this phase, the project adhered to the second-year planning and risk assessment (D5.3 and D5.4). Internal seminars and an international conference on sodium-ion batteries organized by Prof. Adelhelm at HZB allowed the dissemination of preliminary results within the research community.
Last 8 Months at La Sapienza:
In the final eight months, comprehensive data extraction, processing, and result evaluation took place. The methodological procedure was validated through experiments, including impedance and SEM at the Helmholtz Institute Ulm. The PI presented research findings at international conferences, including E-MRS in Strasbourg (May 2023) and the Italian School of Synchrotron Light Facilities (SILS) in Rome (August 31, 2023). The culmination was a final seminar at La Sapienza on September 21, 2023.
Summary of Results:
The project yielded remarkable results that push the boundaries of current scientific knowledge:
1. In-depth investigation of synthetic parameters' impact on material structure.
2. Advanced characterization of C05-1100 compared to HC-com using SAXS, SEM, and WAXS.
3. Dynamic bulk behavior of Na+ insertion observed through operando SAXS.
4. Ex-situ analysis of electrodes stopped at different state-of-charge.
5. HRXRF characterization of aged electrodes (up to 100 cycles).
6. Operando HRXRF analysis of C05-1100 and the benchmark for the first two cycles.
These results represent a significant advancement beyond the current state of the art, particularly in the field of operando characterization.
The project's journey began with an extensive literature review and meticulous planning of activities, including year one planning and risk assessment (D5.1 and D5.2).
Synthesis of Bio-Waste Derived Hard Carbon:
We initiated the scientific endeavor with the preparation of bio-waste derived hard carbon. Hazelnut shells from a local source were ball-milled to achieve a fine powder with a size distribution of 10 to 100 microns. Subsequent steps involved a two-step synthesis process, involving citric acid digestion at 200°C for 14 hours and pyrolysis at 1000°C. Variations in acid concentration and temperature yielded notable structural variations, impacting electrochemical performance. More than 10 samples were synthesized and tested in half sodium cells, with the standout performer named C05-1100.
Period at HZB, Berlin, Germany:
The following six months saw a crucial phase at HZB, Berlin, Germany. Replicating the performance achieved in Rome, we optimized electrode preparation for angular resolved X-ray fluorescence (XRF) measurements. Ex-situ XRF analysis on aged electrodes provided insights into SEI evolution during cycling. Furthermore, a custom test cell, tailored for ultra-high vacuum experiments such as High-Resolution X-ray Fluorescence (HRXRF), was developed. A 500 nm SiN window facilitated low-energy X-ray penetration. The subsequent operando experiments elucidated key aspects, including X-ray damage, electrochemical stability, X-ray penetration depth, and angular resolution. These tests furnished reliable measurements of SEI dynamics during cycling, revealing Na accumulation, nucleation, and solid-phase transitions.
Second Year Planning and Risk Assessment
During this phase, the project adhered to the second-year planning and risk assessment (D5.3 and D5.4). Internal seminars and an international conference on sodium-ion batteries organized by Prof. Adelhelm at HZB allowed the dissemination of preliminary results within the research community.
Last 8 Months at La Sapienza:
In the final eight months, comprehensive data extraction, processing, and result evaluation took place. The methodological procedure was validated through experiments, including impedance and SEM at the Helmholtz Institute Ulm. The PI presented research findings at international conferences, including E-MRS in Strasbourg (May 2023) and the Italian School of Synchrotron Light Facilities (SILS) in Rome (August 31, 2023). The culmination was a final seminar at La Sapienza on September 21, 2023.
Summary of Results:
The project yielded remarkable results that push the boundaries of current scientific knowledge:
1. In-depth investigation of synthetic parameters' impact on material structure.
2. Advanced characterization of C05-1100 compared to HC-com using SAXS, SEM, and WAXS.
3. Dynamic bulk behavior of Na+ insertion observed through operando SAXS.
4. Ex-situ analysis of electrodes stopped at different state-of-charge.
5. HRXRF characterization of aged electrodes (up to 100 cycles).
6. Operando HRXRF analysis of C05-1100 and the benchmark for the first two cycles.
These results represent a significant advancement beyond the current state of the art, particularly in the field of operando characterization.
Progress Beyond the State of the Art:
REALSEI has made significant strides in advancing the understanding of Solid Electrolyte Interface (SEI) formation in sodium-ion batteries. The application and validation of a systematic experimental methodology, utilizing High-Resolution X-ray Spectrometry, have enabled real-time visualization and rationalization of SEI formation processes, pushing the boundaries of current scientific knowledge.
Expected Results until the End of the Project:
The project's final phase aims to consolidate the gathered knowledge and continue monitoring SEI dynamics. We anticipate obtaining a comprehensive view of SEI behavior during extended cycling, further enriching our understanding of sodium-ion battery performance and longevity.
Potential Impacts:
The impact of REALSEI extends beyond scientific boundaries:
1. Enhanced Career Prospects: The PI secured a permanent position at ENEA agency and applied for an ERC consolidator grant. Additionally, the PI secured a SAPIexcellence grant, highlighting the career benefits of this project.
2. Advancements in Sustainable Energy: The project contributes to the development of sustainable sodium-ion batteries, a key player in addressing climate change and fostering renewable energy integration.
In conclusion, REALSEI's success in achieving its objectives and pushing the boundaries of scientific knowledge marks a significant milestone toward sustainable energy storage solutions.
REALSEI has made significant strides in advancing the understanding of Solid Electrolyte Interface (SEI) formation in sodium-ion batteries. The application and validation of a systematic experimental methodology, utilizing High-Resolution X-ray Spectrometry, have enabled real-time visualization and rationalization of SEI formation processes, pushing the boundaries of current scientific knowledge.
Expected Results until the End of the Project:
The project's final phase aims to consolidate the gathered knowledge and continue monitoring SEI dynamics. We anticipate obtaining a comprehensive view of SEI behavior during extended cycling, further enriching our understanding of sodium-ion battery performance and longevity.
Potential Impacts:
The impact of REALSEI extends beyond scientific boundaries:
1. Enhanced Career Prospects: The PI secured a permanent position at ENEA agency and applied for an ERC consolidator grant. Additionally, the PI secured a SAPIexcellence grant, highlighting the career benefits of this project.
2. Advancements in Sustainable Energy: The project contributes to the development of sustainable sodium-ion batteries, a key player in addressing climate change and fostering renewable energy integration.
In conclusion, REALSEI's success in achieving its objectives and pushing the boundaries of scientific knowledge marks a significant milestone toward sustainable energy storage solutions.