Progress 10/01/23 to 09/30/24
Outputs
Target Audience:The target audiences include 3 PhD students, 1 MS student, and 46 undergraduate students. The graduate students were trained in a highly interdisciplinary environment, involving mechanical engineering, materials science, computer science and chemistry. They are supervised by both PI and Co-PI to do this project for their dissertation/thesis. One of the three PhD students and the MS student focus on experimental studies, and the other two PhD students focus on theoretical/numerical simulation work in materials design for energy applications. 13 undergraduate students taking the course Polymeric Materials and 33 undergraduate students taking the course Engineering Composites (both were taught by the PI) learned the knowledge on this research project Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?Training activities: one-on-one trainings were provided to 3 PhD students and 1 MS student in labs. These graduate students in conducting this project received training in a highly interdisciplinary environment, involving mechanical engineering, materials science, computer science and chemistry. They are supervised by both PI and Co-PI to do this project for their dissertation/thesis. One of the three PhD students and the MS student primarily focus on experimental studies, and the other two PhD students mainly focus on theoretical/numerical simulation work in materials design for energy applications. Professional development: the two post-doctoral fellows learned how to supervise graduate students to do polymeric materials and assembly batteries in labs in conducting this project. They also learned how to write research proposals based on the training of the PIs. One PhD student and one post-doc attended an ACS local conference by presenting two posters of the research results. How have the results been disseminated to communities of interest?One PhD student and one post-doc presented two posters of the research results obtained from this project in an ACS local conference. What do you plan to do during the next reporting period to accomplish the goals?In the past two years we conducted studies on the simulation and experimental investigations on "protein-based separator" and "protein-based binders" for enhancing performance of Li-S batteries (goal # 1, 2, 3 and 4). Next year, we plan to continue studies on combining the protein-based separators and binders to further enhance the battery performance. Specifically, we will: Setup and perform AbInitia DFT simulations to explore the binding mechanisms between different types of amino acids and lithium polysulfides. Provide guidance for optimal design amino acids-based binders and separators. Conduct experimental studies on amino acids-based binder for sulfur cathode based on simulation studies as amino acids are critical structural structures of proteins; Conduct simulation and experimental studies on amino acids-modified separators for Li-S batterie based on simulation studies. Conduct experimental studies on combining protein-/amino acid-derived binders and separators to advance Li-S battery performance.
Impacts
What was accomplished under these goals?
1.The issue or problem that ourproject addresses: Lithium-sulfur (Li-S) batteries hold great potential in satisfying increasing demands for green energy. However, critical scientific, technical and fabrication issues, such as insufficient energy density, short service life and safety hazards, must be resolved before practical applications. 2. What will be most immediately helped by your work, and how? Applying abundant natural proteins (such as soy or corn proteins) has great potential in resolving the issues to advance the battery performance. To solve the problems for enhancing performance of the batteries will be significant for development of high performance batteries. 3. For each major goal listed in our project initiation form, describtionsfor Year 2: Research Goal #1: Simulation studies on protein structures and their interactions with polysulfides and with ions: 1. Protein-graphene Composite for Anchoring Lithium Polysulfides in Li-S Batteries. Our calculations revealed a strong binding affinity between the composite material and lithium polysulfides, particularly for positively charged AA like Arg, which exhibited a dual binding mechanism involving electrostatic attraction and hydrogen bonding. Overall, our computational findings suggest that graphene-protein composite materials hold great promise as effective anchoring materials for lithium polysulfides in Li-S batteries. The proposed composite structure offers both strong electronic conductivity and anchoring capability, which could contribute to improved battery performance and cycling stability. Research Goal #2: Study of processing of protein "Janus" separator for trappingpolysulfides and regulating Li+: Zein protein-functionalized separator through a viable method for trapping polysulfides and regulating ion transport in Li-S batteries:We successfully demonstrated efficacy of preparing zein-functionalized separator to address the challenges of polysulfide shuttling and lithium dendrite growth in Li-S batteries. By employing a simple soaking method to coat zein onto commercial separator, we achieved significant improvements in the performance and stability of Li-S batteries. Soy protein as a dual-functional bridge enabling high performance solid electrolyte for Li metal batteries:We applied soy protein as a dual-functional bridge for preparation of a hybrid SiO2 nanofabric/PEO electrolyte. The remarkable advantages of this dual functional bridge enabled by natural protein open up a new and sustainable avenue to achieve long-lifespan, safe and high-energy-density all-solid-state lithium metal batteries. Research Goal #3: Study of processing of protein binder for high-loading S cathode: Enabling bio-cathode with graphene coating via networking soy-protein (SP) and polydopamine (PDA) for Li-S batteries: The bio-binder SP-PDA with an interpenetrated network was successfully prepared for improving the high performance by reducing the shuttle effect of polysulfides. The assembled Li-S batteries with the bio-cathode demonstrate excellent rate performance and long cycling capabilities. High-performance S cathode through a decoupled ion-transport mechanism: We successfully fabricated a multifunctional SP-PEO-Gr binder for the S cathode with mitigated shuttle effect and excellent dual-conductive capabilities, i.e., high electronic and ionic conductivities. The resulting S cathode shows uniform structure, good wettability to electrolyte, enhanced mechanical properties and good battery cycling stability. An amino acid as functional cathode additives for efficient Li-S batteries: We investigated the role of arginine (Arg) as a functional additive in sulfur cathodes for Li-S batteries. Our findings demonstrate that the incorporation of Arg into cathode enhances the performance of Li-S batteries. Research Goal #4: Analysis of the Li-S battery performance. 1.Zein protein-functionalized separator through a viable method for trapping polysulfides and regulating ion transport in Li-S batteries: The Li-S cell with the zein-soaked separator demonstrate the potential of zein-functionalized separator as a promising approach to address the key challenges hindering the widespread adoption of Li-S batteries in various energy storage applications. 2. Soy protein as a dual-functional bridge enabling high performance solid electrolyte for Li metal batteries: The remarkable advantages of the dual functional bridge enabled by natural protein provides long-lifespan, safe and high-energy-density all-solid-state lithium metal batteries. 3. Enabling bio-cathode with graphene coating via networking soy-protein and polydopamine for Li-S batteries:The remarkable advantages of the dual functional bridge enabled by natural protein provides long-lifespan, safe and high-energy-density all-solid-state lithium metal batteries. 4. High-performance S cathode through a decoupled ion-transport mechanism: The assembled Li-S batteries with the SP-PEO-Gr cathode demonstrate enhanced rate and long cycling capacities. This work is of great significance for introducing an unconventional ion-transport mechanism into electrodes to prepare high-performance batteries. 5. Enabling bio-cathode with graphene coating via networking soy-protein and polydopamine for Li-S batteries: The long-term cycling performance of the batteries was obtained. The enhanced performance of the Arg-PAA cathode demonstrated the significant contribution of Arg to the overall performance of Li-S batteries. 4. The key outcomes or other accomplishments realized. Our computational findings suggest that graphene-protein composite materials hold great promise as effective anchoring materials for lithium polysulfides in Li-S batteries. The proposed composite structure offers both strong electronic conductivity and anchoring capability, which could contribute to improved battery performance and cycling stability. By employing a simple soaking method to coat zein onto commercial separator, we achieved significant improvements in the performance and stability of Li-S batteries. the scalable and straightforward soaking process used for the zein modification offers a practical approach for the possible commercial production of functional separators for Li-S batteries. The remarkable advantages of the dual functional bridge enabled by natural soy protein open up a new and sustainable avenue to achieve long-lifespan, safe and high-energy-density all-solid-state lithium metal batteries. The assembled Li-S batteries the bio-binder SP-PDA with an interpenetrated network demonstrate excellent rate performance and long cycling capabilities. This study provides a sustainable strategy for enhancing performance of Li-S batteries through making bio-based S cathode. The soy protein-based S cathode with mitigated shuttle effect and excellent dual-conductive capabilities, i.e., high electronic and ionic conductivities. provides the battery performance with facilitated Li+ transport and good cycling stability. The incorporation of arginine (Arg) into cathode enhances the performance of Li-S batteries. This study provides valuable insights for the development of high-performance, long-lasting Li-S batteries and opens new avenues for the use of amino acide being a biomolecule in advanced battery technologies. Based our studies, we have had four journal papers published. The other three manuscripts are being reviewed, and two more are in preparation for journals.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2024
Citation:
C. H. Ying, C. Wang, W.H. Zhong, J. Liu, "Dual Anchoring Mechanism of Protein-Based Binder for Lithium?Sulfur Batteries", Journal of Physical Chemistry Part C, https://doi.org/10.1021/acs.jpcc. 4c03939, 128, 34, 1452214528, 2024
- Type:
Journal Articles
Status:
Published
Year Published:
2024
Citation:
C. Wang, L. Ren, C. Ying, J. Liu and W.H. Zhong, An amino acid-enabled separator for effective stabilization of Li anode", ACS Applied Materials & Interfaces, https://doi.org/10.1021/acsami.4c01256 2024.
- Type:
Journal Articles
Status:
Published
Year Published:
2024
Citation:
C. Wang; L. Ren; C.H. Ying; J. Shang; J. McCloy, J. Liu; W.H Zhong, "Soy protein as a dual-functional bridge enabling high performance solid electrolyte for Li metal batteries", J. of Power Sources, https://doi.org/10.1016/j.jpowsour.2024.235260, Vol. 620, 15, 235260, 2024.
- Type:
Journal Articles
Status:
Published
Year Published:
2024
Citation:
4. L. Ren, C. Ying, C. Wang, Y. Guo, J. Liu and W.H. Zhong, "Zein protein-functionalized separator through a viable method for trapping polysulfides and regulating ion transport in Li-S batteries" J. of Energy Storage, Vol. 100, Part A, 113547, https://doi.org/10.1016/j.est. 2024.113547. 2024.
- Type:
Journal Articles
Status:
Under Review
Year Published:
2024
Citation:
Y. Guo, P. Sireesha, C. Wang, L. Ren, C. Ying, J. Liu and W.H. Zhong, "An interpenetrated protein-polar polymer interlayer for suppressing shuttle effect in Li-S batteries", Journal of Power Sources, under review, 2024
- Type:
Journal Articles
Status:
Under Review
Year Published:
2024
Citation:
Y. Guo, C. Ying, L. Ren, J. Zhong, J. Liu and W.H. Zhong, "Enabling bio-cathode with graphene coating via networking soy-protein and polydopamine for Li-S batteries", Journal of Energy Chemistry, under review, 2024
- Type:
Journal Articles
Status:
Under Review
Year Published:
2024
Citation:
Y. Guo, C. Ying, L. Ren, J. Zhong, S. Yu, Q. Zhang, J. Liu and W.H. Zhong, "High-performance S cathode through a decoupled ion-transport mechanism", Chem Eng J., under review, 2024
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Progress 10/01/22 to 09/30/23
Outputs
Target Audience:The target audiences include three PhD students, 1 MS student, and 52 undergraduate students. In addition, more than 20 undergraduates of Society of Women Engineers of WSU. The graduate students were trained in a highly interdisciplinary environment, involving mechanical engineering, materials science, computer science and chemistry. They are supervised by both PI and Co-PI to do this project for their dissertation/thesis. One of the three PhD students and the MS student focus on experimental studies, and the other two PhD students focus on theoretical/numerical simulation work in materials design for energy applications. 21 undergraduate students taking the course Polymeric Materials and 31 undergraduate students taking the course Engineering Composites (both were taught by the PI) learned the knowledge on this research project; In addition to the formal classroom and laboratory instructions, the PIs put special efforts of recruiting under-represented students to do the research project. For example, the PI made a presentation at the meeting Undergraduate Research Mixer organized by Society of Women Engineers of WSU, for promoting undergraduate students' participating in this research project in Feb 2023. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?Training activities: one-on-one trainings were provided to 3 PhD students and 1 MS student in labs. These graduate students in conducting this project received training in a highly interdisciplinary environment, involving mechanical engineering, materials science, computer science and chemistry. They are supervised by both PI and Co-PI to do this project for their dissertation/thesis. One of the three PhD students and the MS student primarily focus on experimental studies, and the other two PhD students mainly focus on theoretical/numerical simulation work in materials design for energy applications. Professional development: the post-doctoral fellow learned how to supervise graduate students to do polymeric materials and assembly batteries in labs in conducting this project. One PhD student attended two national conferences by presenting posters of the research results; Another PhD student was invited to give a seminar in the School of Mechanical and Materials Engineering at WSU. How have the results been disseminated to communities of interest?The PIs will publish journal papers. Those papers will have broader impacts nationally and internationally. Currently, four manuscirpts are being prepared for submission to high quality and high impact journals. The PIs' group members also presented the results of this project in two conferences and on campus to more students. The information on their presentations and seminars are listed in "Other Products". The PI introduced this research project at the meeting Undergraduate Research Mixer organized by Society of Women Engineers, WSU in Feb 2023. Those students were not aware of such research project that are conducted on campus, and the PI's introduction initiated their interests and promoted undergraduate students' participating in this research project, as several students contacted the PI currently. What do you plan to do during the next reporting period to accomplish the goals?In the past year (Year 1) we primarily focused on the simulation and experimental investigations on "protein-based separator" in Li-S batteries (goal # 1, 2 and 4). Next year, we plan to conduct research on "protein-based binder" for high-loading sulfur cathode (goal #3). Specifically, we will: Setup and perform Ab initio DFT simulations for a binder system including peptides, graphene sheet and polysulfides. Investigate the fundamental interactions mechanisms among protein functional groups, graphene sheet and polysulfides. Provide guidance for optimal design of protein-graphene binder for sulfur cathodes. Conduct experimental studies on protein-based binder for sulfur cathode based on above simulation work; Conduct experimental studies on protein-graphene binder for sulfur cathode based on simulation studies.
Impacts
What was accomplished under these goals?
1.The issue or problem that ourproject addresses: Lithium-sulfur (Li-S) batteries hold great potential in satisfying increasing demands for green energy. However, critical technical and fabrication issues, such as insufficient energy density, short service life and safety hazards, must be resolved before practical applications. 2. What will be most immediately helped by your work, and how? Applying abundant natural proteins (such as soy or corn proteins) has great potential in resolving the issues to advance the battery performance. To solve the problems for enhancing performance of the batteries will be significant for development of high performance batteries. 3. For each major goal listed in our project initiation form, describtionsfor Year 1: Research Goal #1: Simulation studies on protein structures and their interactions with polysulfides and with ions 1.. Dual anchoring functions of protein-based binder in Li-S batteries through DFT calculations. 1.1 Binding of LiPSs with peptides with and without charged functional groups; 1.2 Electron charge transfer analysis during protein-LiPSs binding; 1.3 Morphological analysis; 1.4Conclusions: We identified a novel binding mechanism to improve the anchoring affinity in protein-based binder and efficiently regulate the active material at S cathode for Li-S batteries. The DFT calculations show the LiPSs can be not only strongly attracted by the oxygen donor atom at the protein backbone but also by the positively charged functional groups. Through Bader charge analysis, we found a strong hydrogen bonding between the S atom of the LiPSs with the hydrogen atoms of guanidino group. Compared to the peptide chain without charged group, the total binding energy of all LiPSs are nearly doubled, and final binding energy is at the edge of the recommend binding strength range. As a result, the active materials at S cathode will be mostly robustly refined without being decomposed into soluble ions. Research Goal #2: Study of processing of protein "Janus" separator for trapping polysulfides and regulating Li+ 1. Protein amino acid-enabled separator for enhancing performance of lithium metal batteries 1.1 Synthesis process and morphology of the amino acide-modified separator (Leu-P); 1.2 Surface compositional analysis; 1.3 Wetting behavior; 1.4 Electochemical performance; 1.5 Conclusions:The amino acid-based coating (Leu-P)for modifying the commerical separator is successfully prepared, and the performance of LMBs is effectively improved. Leu-P participates in the formation of the multifunctional SEI, whicheffectively guided Li+deposition forpreventingthe formation of Li dendrite and dead Li particles. 2. Modifying commercial separator with a protein-polar polymer coating for enhancing performance of L-Sbatteries. 2.1 Fabrication of interpenetrated protein-polar polymer hybrid; 2.2 Compositional and thermal analysis; 2.3 Morphological analysis; 2.4 Surface wettability; 2.5 DFT calculations and experiments on polysulfides trapping ability; 2.6 Electrochemical Performance; 2.7 Conclusions: we engineered a hybrid coating (ZPH) with maximized denaturation for zein, effectively mitigating the detrimental polysulfide shuttle effect. The optimized ZPH coating on the commercialseparator exhibitsmarkedly enhanced electrochemical performance in terms of cycling stability, capacity retention, and rate capability. Simulation studies for elucidating the mechanisms, including cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy, are carried out. 3. Corn protein (zein)-enabled multifunctional Janus separator for enhancing performance of Li-S Batteries. 3.1 Preparation of zein (corn protein) enabled Janus separator; 3.2 Morphology analysis;3.3 Compositional and thermal analysis ; 3.4 Wettability and surface interaction; 3.5 Polysulfides trapping test for the protein-enabled separator; 3.6 Electrochemical performance of the Li-S battery with the Janus separator; 3.7 Conclusions: A zein-enabled Janus separator with multifunctional capabilities, including trapping polysulfides, stabilizing Li+ deposition, and facilitating Li+ transport, were successfully fabricated. The Janus protein zein-enabled separator effectively reduces polysulfide shuttling and thenpromotes the development of stable, long-life, and safe Li- S batteries. Research Goal #3: Study of processing of protein binder for high-loading S cathode. None. The research group will work for this research goal next year. Research Goal #4: Analysis of the Li-S battery performance. (1). The amino acid-based coating (Leu-P) for commercial separator modification effectively improved the performance of the lithium meal batteries. The symmetrical Li Li cells with Leu-P exhibits a prolonged lifespan of over 280 h (vs. 185 h of pristine cell). The Li Cu cell with Leu-P shows a higher Coulombic efficiency of 91.98% at the 36th cycle compared to that of pristine cell (78.4%). The LiFePO4 Li full cell with Leu-P displays a high capacity of 127.5 mAh g−1 after 200 cycles at 1 C, while the pristine cell fails under the same cycling process. (2). The zein-polar polymer coating on the commercial separator exhibits markedly enhanced electrochemical performance in terms of cycling stability, capacity retention, and rate capability. The cell with the zein-polar polymer coated separator exhibits higher discharge capacities at different current densities compared to that of the commerical separator. In the long-cycling performance, the Li-S battery with the zein-modifed separator shows a higher discharge capacity (~450 mAh g-1) and capacity retention (~42%) than that of the battery with Celgard, which are ~150 mAh g-1 and 16%, respectively. (3). The protein zein-enabled Janus separator with multifunctional capabilities, including trapping polysulfides, stabilizing Li+ deposition, and facilitating Li+ transport, were successfully fabricated. The Janus separator facilitates the Li+ transport and stabilizes Li+ deposition throughout the charge-discharge processes for longer cycles. The Li/Li cells with the Janus separator present ultralong cycle life >900 h and stable and low polarization. The Li- S battery with the P/ZP Janus separator delivers extraordinary long-cycle stability for 500 cycles at 0.5 mA.g-1. 4. The key outcomes and other accomplishments realized; We studied a novel binding mechanism to improve the anchoring affinity in protein-based binder and efficiently regulate the active material at sulfur cathode for Li-S batteries. The simulation results laid foundation for the experimental studies. We appliedprotein materials to successfully fabricate two types of coatings for modifying the commercial separator. One is the primaryamino acid of protein,Leu-based coatingfor commercialseparator modification, and the outcome of it effectively improved the performance of the lithium meal batteries. The other one is thezein-polar polymer coatingon the commercial separator; the resulting Li-S battery exhibits markedly enhanced electrochemical performance in terms of cycling stability, capacity retention, and rate capability. We also fabricated an independent separator using zein protein and a polar polymer. Thezein-enabled Janus separatorpresents multifunctional capabilities, including trapping polysulfides, stabilizing Li+deposition, and facilitating Li+transport, thus effectively improves the performance of the Li-S batteries. Based on these outcomes, we are preparing four journal paper manuscripts currently as shown below: Protein-based Binder with Dual Anchoring Functions for High Energy L-SBatteries. Protein amino acid-enabled separator for enhancing performance of LMBs. An novel separator with an interpenetrated structure of protein-polar polymer for constructive suppression of shuttle effectinL-S batteries. Corn protein-initiated multifunctional Janus separator for enhancing performance of Li-S batteries.
Publications
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