APPLYING ABUNDANT PLANTS TO DEVELOP BATTERY MATERIALS AND BENEFITS TO THE AGRICULTURAL ECONOMY

• Sponsoring Institution: National Institute of Food and Agriculture
• Project Status: COMPLETE
• Funding Source: AFRI COMPETITIVE GRANT
• Reporting Frequency: Annual
• Accession No.: 1005250
• Grant No.: 2015-67021-22911
• Cumulative Award Amt.: $494,805.00
• Proposal No.: 2014-04184
• Project Start Date: Jan 1, 2015
• Project End Date: Dec 31, 2018
• Grant Year: 2015
• Program Code: [A1521]- Agricultural Engineering

Recipient Organization
WASHINGTON STATE UNIVERSITY
240 FRENCH ADMINISTRATION BLDG
PULLMAN,WA 99164-0001

Performing Department
Mechanical & Materials Engrg.

Non Technical Summary
Battery disposal causes deteriorating effects on theenvironment and human health, as released harmful substances are easily consumed by plant roots and accumulated in fruits, vegetables and grass, and thus by human beings. Recycling batteries is a much better option than disposing ofthem in landfills, but it is expensive involving time/energy consuming processes.If we coulddevelop bio-based battery materials,with thecreation of solid electrolytes and removing the liquid electrolytes,we could eliminateleakage, spillage, or damageto the environment and economy as well as to agriculture.The approach is to apply abundant plants, such as soy and canola, as the base component to develop safe andrenewable battery electrolyte materials through research in both fundamental and applied sciences. The project team is focused directly on integrating the technologiesneeded to convert this agricultural feedstock into bio-battery materials. The project will contribute to the industries producing bio-battery materials from wood residuals derived from thebiomass industry including soybean, an abundant plant, canola meals, a low-value byproduct from thebiodiesel industry. This contributes to adding value and profit for those agriculture relevant industries and creates new technologies for thebattery industry. The team will link and engage related industries in our outreach and education efforts and involve them in the development of bio-based battery materials and finally bio-based batteries.The ultimate goal of the proposed project is to develop bio-energy storage materials that can help promote sustainable agriculture and a benign environment. This cutting-edge research will lead to significant benefits to society, specifically: (1) advancing the agricultural economy through the use of bio-based materials for energy, a new market; and (2) reducing deleterious impacts to the environment through enabling more-electric platforms using environmentally sustainable materials.

Animal Health Component

60%

Research Effort Categories

Basic

40%

Applied

60%

Developmental

(N/A)

Classification

Knowledge Area (KA)	Subject of Investigation (SOI)	Field of Science (FOS)	Percent
511	1848	2020	20%
511	0650	2020	15%
511	1820	2020	25%
601	1848	3010	15%
601	0650	3010	10%
601	1820	3010	15%

Knowledge Area
601 - Economics of Agricultural Production and Farm Management; 511 - New and Improved Non-Food Products and Processes;

Subject Of Investigation
0650 - Wood and wood products; 1820 - Soybean; 1848 - Canola;

Field Of Science
2020 - Engineering; 3010 - Economics;

Keywords

plant

agriculture economy

battery material

energy storage

Goals / Objectives
Goal: to extend the application ofabundant agricultural byproducts to the efficient energy storage field, boosting the agricultural economy and improving efficiency in the energy field.Specific objectives: Our multi-disciplinary team proposes a project aiming to: (1) apply soy and canola products, in order to develop novel battery materials: solid-state electrolyte materials, for advanced lithium batteries. (2) Define the cost efficiency of the soy-based bio-material technologies and analyze the impact of the use of abundant plants as raw materials for fabricating batteries on the agricultural economy.

Project Methods
Protein extraction and kinetics: Canola protein will be isolated from canola meal with alkaline extraction. Canola meal is first dried in an oven at 49°C for 24 hours. The effects of different operation parameters (alkaline concentration of pH7-12, time 5-120min, and particle size of 20-80 mesh) on the kinetic coefficients in the model will be studied. Two parallel processes, one faster and one slower, will be considered in a two-site kinetic model. Protein content will be measured according to AOAC method 990.03 (AOAC 1995a). The chemical profile of canola protein will be correlated to the properties studied for solid electrolytes in order tounderstand the interaction between protein and PEO.Lignin separation and kinetics: The lignin from Douglas fir sawdust will be isolated by an organosolv delignification process developed at Dr. Lei's lab. We will apply Cellulolytic Enzyme Lignin (CEL) treatment and the FTIR spectra will be analyzed to ensure that all carbohydrates have been removed from the lignin. The content of aliphatics methoxyl and phenolics, as well as other functional groups and the content of different linkages between the lignins will be quantified by 13C-NMR and 1H NMR. Their molecular weight will be determined by Gel Permeation Chromatography (GPC) for acetylated lignin. Kinetics analysis will be conducted to understand the mechanism of delignification and chemical reactions of the organosolv process. The development of kinetics models for extractions can be used to optimize the lignin and protein extraction processes. These quantified functional groups and the molecular weight of lignin will be correlated to the results of mechanical properties of solid electrolytes.Fabrication of the bio-SPEs and study of their structures: (1) denaturation for the protein will be exploited first. The denaturation conditions, i.e., pH values, temperature, ionic strength (adjusted by LiClO4) will be studied. (2)The structure of the protein based film, including the morphology (crystallinity (using XRD), interaction/miscibility between denatured protein and PEO, and glass transition temperature Tg (using DSC), will be examined. (3) Strengthening the resulting SPEs using lignin will be realized. Films of different ratios of denatured soy/canola-PI/PEO and LiClO4 with organosolv lignin will be synthesized by dissolving the appropriate amounts in tetrahydrofuran (THF) at 60 °C with stirring for 12hr. Dielectric spectroscopy and nuclear magnetic resonance (NMR) will be used to study the polymer segment mobility. A set of Li ion conductive films will be prepared; in particular, the flexibility of the films can be adjusted. The effects of denatured SPI (structure and ratios) on the structure of the resulted films will be determined.Property studies of the soy/canola protein-based polymer films: The ionic conductivities (σ) of the films will be measured by the AC impedance method at room temperature and then will be calculated from the bulk electrolyte resistance value (Rb) found in the complex impedance diagram. Tensile tests of soy-based SPEs will be performed using an Instron and a laser extensometer. Machine stretching of the soy/canola-based films will be carried out at different temperatures at a constant rate of 10.6 mm/min. The ionic conductivity will be tested parallel and perpendicular the axis of stretching. The ionic conductivity as a function of the stretching and the temperature will be discussed.Cost estimation and analysis of effects on economy: A complete "/protein/lignin-to-bio-battery materials" analysis will be completed and continuously updated throughout the project's life. Economic data will be generated and full economic costs and returns will be quantified. Life cycle costs for this bio-materials for battery application pathway will be compared with petroleum analogs. Breakeven profitability of using alternative feedstocks (protein/lignin) will be compared with current petroleum analogs. Expected outcomes: (1) New econometric and statistical measures (e.g., elasticities) for understanding of protein, starch, and lignin markets; (2) Novel framework for assessing economic and environmental impacts of the proposed technology; (3) New generation of researchers trained to analyze such problems. From (2) we will have direct measures of the economic feasibility of the product to the firm and to society.Efforts: formal classroom instruction (new course lectures/sessions in BSysE 593 Renewable Energy Technologies, MSE 402 Polymeric Materials, and Envr_Sci 490 Biomass conversions to Bioproducts and Biofuels), laboratory instruction (new lab sessions in Envr_Sci 490 Biomass conversions to Bioproducts and Biofuels); development of curricula (new lecture sessions and new lab sessions on biomass conversion and separation); innovative new case studies to be created for formal classroom instruction. Trained graduate and undergraduate students who work on this project will eventually join the workforce and contribute to the effort of developing new battery technology for future energy needs. Seminars to local chapters of societies, such as MRS WSU student chapter, SAMPE WSU student chapter and Seattle chapter and at regional and national conferences (annual campus-wide Academic Showcase at WSU; Annual International Conference: American Society of Agricultural and Biological Engineers (ASABE), Materials Research Society (MRS) and American Chemical Society (ACS), etc.); new experiential learning opportunities for students; extension and outreach (outreach communications and presentations to biomass industrial companies, battery and related industries).Evaluation: The following evaluation studies will be conducted for the project: Our formative evaluation will assess initiatives and resource allocations which will ultimately influence the success of the project. We will make sure that the project is being implemented as intended with appropriate resources available for project implementation; Identify aspects of the project which are most effective and least effective; identify the challenges associated with project implementation and address them; we will collect quantitative and qualitative data related to project activities, analyze and report to the PI/Co-PIs team in a timely fashion to inform project modifications and improvements as necessary. Our summative evaluation will examine the extent to which the PI and Co-PIs have achieved each of the goals stated in this proposal. A comprehensive review of the objectives and evaluation findings - particularly the outputs/products/milestones, but also a summary of the inputs and processes - will be used to determine the extent to which the project has achieved its goals.Other evaluations include: To facilitate accountability and overall evaluation, each task is required to develop a set of outputs/products/milestones; the team members will collaborate to create a set of baseline metrics and provide data needed to evaluate project outcomes and impacts; annual progress and final impact reports will be communicated to the project team and USDA on an annual basis; the team members will be required to communicate their findings to both scientific and public audiences including biomass industrial companies, battery and related industries; the research team will create posters to showcase their findings in the annual campus-wide Academic Showcase at WSU, and PI/Co-PIs and the graduate students will be expected to present research findings in annual scientific meetings; the research findings will be communicated to the general public via news releases; The studentsand PI/Co-PIs willpublish their results in peer-reviewed high-impact journals.

Progress 01/01/15 to 12/31/18

Outputs
Target Audience:Biomass industrial companies, battery materials and battery related industries, lignin, starch, and protein producers, processors, wholesalers, and retailers: Carbon Cycle Crush LLC, Creative Energy Systems Inc., Gen-X Energy Group Inc., North America Green Pulp Inc., Washington Bio-oils Inc., Archer Danieis Midland Co., and State and Federal policy makers. Efforts: Formal classroom instruction (new course lectures/sessions) about the project in BSysE 593 Renewable Energy Technologies, BSYSE 552 Advanced Biological Systems Engineering Topics, MSE 402 Polymeric Materials, MSE 404 Engineering Composites, MSE 508 Polymeric Nanocomposites and Functionalities, and EconS 351 Introduction to Food and Agricultural Markets; Development of curriculum (new lecture sessions on biomass conversion and separation; bio-material based electrolytes; economic science and agricultural markets); Trained graduate and undergraduate students who work on this project will eventually join the workforce and contribute to the effort of utilizing biomass and developing new battery technology for the future energy needs: PhD students Xiaolu Zhu, Lei Zhu, Elmar Villota, Xuewei Fu, Youngran Choi, Wendy Mateo, Marie Qian, Kuan-Ju Chen; MS students: Gayatri Yadavalli, Yupeng Liu, Allen Eyler, Xiaolin Wang, Min Zheng; undergraduate students: Noah Taylor, Chris Glusac, Jacqueline Reeve, James Tuba ,Lucas Kovatch, Katie Tran. Involved students in the project gained new experiential learning opportunities. They conducted various experiments on utilizing several species of proteins, to make several kinds of battery materials, including electrolytes, binders and separator coatings. The experiments include denaturation of the proteins, fabrication of the materials and characterization of the materials. Characterization includes wettability studies of the battery materials using contact angle analyzer, ionic conductivity using impedance tester, and battery performance test. Seminars to local chapter of societies, such as Materials Research Society WSU student chapter, Materials Research Society (MRS) Annual Conference and American Chemical Society (ACS) Annual Conference, Electrochemical Society (ECS) Meeting, Pacific Northwest American Vacuum Society (AVS) Annual Symposium, Bio-Environmental Polymer Society (BEPS), regional and national conferences (see session of publication list in Product and the following outreach communications and presentations); Extension and outreach includes outreach communications and presentations to biomass industrial companies, battery and related industries. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Training activities: The funding received from this project has been used to support 3 post-docs, 8 PhD candidates, 5 MS students, and 6 undergraduate students in the WSU Biological Systems Engineering Program, Material Science and Engineering Program, and Economic Science Program. 8 PhD students, 5 MS students, and 6 undergraduate students, and 3 post-doc research associates learned to develop new technologies, new processes, new materials, new econometric techniques, protocols, and market analysis. Post-docs and graduate students have developed the experience assisting undergraduate students attaining greater proficiency in developing new technologies and conducting experiments. PIs incorporated the research results from this project in teaching BSysE 593 Renewable Energy Technologies, BSYSE 552 Advanced Biological Systems Engineering Topics, MSE 402 Polymeric Materials, MSE 404 Engineering Composites, MSE 508 Polymeric Nanocomposites and Functionalities, and EconS 351 Introduction to Food and Agricultural Markets. Professional development activities: PIs had a monthly conference calls and active collaborations among each other, and their research group had weekly meetings to make sure the good progress of the project. PIs and their research teams had updates presented at group meetings. Students developed collaboration skills and exchanged technical information cross group knowledge. Graduate students and Post-docs have participated and presented papers at American Society of Agricultural and Biological Engineers (ASABE) 2016, 2017, and 2018 Annual International Meetings, 2015 Pacific Northwest Chapter of the AVS, 2016 American Vacuum Society (AVS) Annual Symposium, and 2017 Bio-Environmental Polymer Society (BEPS) Annual Meetings, 2017 Western Education and Research Activities Committee on Agribusiness (WERA-72), 2018 Agricultural and Applied Economics Association, and 2018 Agricultural and Applied Economics Association meeting. How have the results been disseminated to communities of interest?The PIs and their students and post-docs created posters and/or made oral presentations to showcase findings and present the study results at industrial meetings and conferences. The research findings were communicated to the general public via national and international conferences, such as American Society of Agricultural and Biological Engineers (ASABE) Annual International Conferences, Bio-Environmental Polymer Society (BEPS) Annual Meetings, Agricultural and Applied Economics Association meetings. The published and submitted journal papers and proceedings can be found in previous sessions in this final report. We also disseminated our research results to communities by presenting to industrial delegations and academic communities. Our outreach dissemination efforts includes: seminar of Natural Protein Materials for Functional Applications, seminar of Bio-composites for Energy Applications, seminar of Biomass conversions for biofuels and bioproducts, and seminar of Consumer Willingness to Pay for Bio-based Batteries. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? Impact: Battery disposal causes deteriorating effects on environment and human health, as the released harmful substances are easily consumed by plant roots and accumulated in fruits, vegetables and grass. This USDA supported project is to develop bio-based battery materials and create a "green" solution for solid electrolytes in order to remove the liquid electrolyte from batteries to get rid of leakage, spillage, or damage, which is important to the environment and economy as well as agriculture. The project team is focused directly on integrating the technologies employed to convert the agricultural feedstock into bio-battery materials. The project provides a novel renewable energy storage system to the industries for sustainably producing bio-battery, and directly contributes to adding value and profit for those industries and creating new technology for battery industry. The team is lining and engaging related industries in our outreach and education efforts and involved them in the development of a biobased battery. Major activities completed / experiments conducted / data collected / results / key outcomes: Specific objective (1): Task 1: Protein extraction and kinetics (Dr. Lei's team) The effect of various protein extraction conditions on the parameters of a two-site kinetic model and Peleg's model were determined for extraction from canola meal. Particle size had the greatest effect on equilibrium yield with a 269.68 mg·g-1 increase in yield between particle ranges of 16-35 mesh and 60-120 mesh. At a higher temperature of 55 °C, the faster process dominated the rate and protein was released at an initial rate of 2858.42 mg·g-1·s-1, which was a tenfold increase from room temperature. The maximum equilibrium protein yield (779.90 mg·g-1) was obtained at a particle size of 60-120 mesh and 0.06 M sodium hydroxide concentration at 25 ºC. Protein isolated from canola meal was supplied to Dr. Zhong for electrolyte synthesis. Task 2: Lignin separation and kinetics (Dr. Lei's team) Technical lignin oligomers from dilute alkali separation at mild conditions were optimized for kinetics studies with the effects of pH, extraction temperature and time. The range of acid insoluble lignin yield varied from 19.1 to 71.5 %wt, and the acid soluble lignin was from 29.0 to 58.6 %wt. Influence of different extraction conditions on the FTIR spectra of alkaline lignin was elucidated by the structure, characterization of chemical reactivity and functional properties of lignin. Base reaction at alkali treatment consists of cleavage of aryl-ether bonds which brings about an increase of phenolic hydroxyl content. The lignin yield and the extraction conditions were strongly related (R2=0.96). The lignin with the highest purity was supplied to Dr. Zhong for electrolyte synthesis. Task 3: Development of soy/canola protein based solid electrolytes (Drs. Zhong and Scudiero's teams) We studied various protein denaturation methods including thermal treatment, acidic solvent treatment and dialysis, and found that morphology and properties of the composite polymer electrolytes (CPEs) are strongly affected by the protein denaturation conditions. Choosing a polyethylene oxide (PEO)-soluble salt results in a more amorphous matrix with stretchable behavior, while choosing a PEO-insoluble salt preserves the PEO crystalline structure and leads to an increase in fracture toughness. By selecting salts with the appropriate combination of solubility in water and solubility in PEO, the characteristics of both the protein and matrix can be customized for the desired application. The difference in denaturation degree is demonstrated in their dielectric and mechanical properties. Task 4: Study of protein-reinforced adhesive composite electrolytes (Drs. Zhong and Scudiero's teams) We developed a high-performance protein-based solid electrolyte with high ionic conductivity, high transference number and good mechanical properties. The higher formation temperature resulted in much more flexible and expansive protein configuration, which allowed sufficient interactions between protein and ions. The positively charged amino acid residues showed strong interactions with anions from lithium salts to immobilize the anions. The ion transport of protein was decoupled with chain movement, and improve ionic conductivity significantly without sacrificing mechanical properties. A high-performance solvent-free composite polymer electrolytes (CPEs) with novel protein-ceramic hybrid nanofillers was demonstrated. By fabricating core-shell structured protein/TiO2 nanowires, the ionic conductivity and mechanical properties of the resulting composite electrolytes were further improved. Task 5: Structure and properties from different constituents of the electrolyte (Dr. Scudiero's teams) Spectroscopic and microscopic methods were used to understand the interaction between the different constituents of the solid polymer electrolyte. AFM, FTIR, UV-Vis and XPS are utilized to characterize the solid polymer electrolyte films. We emphasize the results obtained on solutions and on films based on the result obtained for the ionic conductivity. Drying the films with this composition showed the highest ionic conductivity. The addition of protein and then LiClO4 made the film more electrically conducting. Specific objective (2): Task 6: Cost estimation (Drs. Tozer and Marsh's team) We examined how consumers' characteristics and preferences for product attributes and environmentally friendly practices vary across regions of the U.S. and influence consumers' willingness to pay (WTP) for bio-based batteries. We obtained nationwide data via an online survey platform and used a dichotomous-choice contingent valuation method to estimate the WTP. We estimate that consumers on average are willing to pay US$7.91 for the bio-based batteries made from agricultural by-products. A long-run equilibrium of price relationship is found between corn and lignin, and similarly for soybean meal and lignin. By identifying the co-varying movement between biomaterial and agricultural commodities, we understand the market interconnections among starch, protein, and agricultural lignin by-products and the impact on the agricultural economy. Change in Knowledge: Improved understanding of separation kinetics for protein from canola and lignin from biomass, and their roles in solid electrolytes and bio-battery; Improved understanding of the strategies of manipulating protein's structure and the relationship between protein's configuration and its ion-conduction behavior; Improved understanding of effects of nanoparticles on molecular structures of protein and the benefits for ion-transportation for SPEs; Improved understanding of the advantages of applying proteins as bio-nanofillers for enhancing polymer electrolytes over applying inorganic nanofillers; Improved understanding of protein's multifunctionality in development of various battery materials; Increased the knowledge of the structural economic relationships between bio-battery materials and agricultural inputs; Provided empirical evidence from about 1500 consumers on their preferences and characteristics for bio-batteries. Change in Action: A new way to fabrication of solid electrolytes and lay foundation for achieving bio-battery by using biomass derived lignin and proteins from canola and soybean. Change in Condition: Positive impact on the agricultural economy and on the use of the abundant plants as raw materials for fabricating bio-battery materials; The bio- based solid electrolytes are renewable and non-polluting to solve the central challenge of leakage, spillage, or deteriorating effects of current rechargeable liquid lithium batteries on environment and human health to be faced worldwide.

Publications

• Type: Journal Articles Status: Accepted Year Published: 2019 Citation: Y. Wang, X. Fu, M. Zheng, W. H. Zhong, G. Cao. 2019. Strategies for Building Robust Traffic Networks in Advanced Energy Storage Devices: A Focus on Composite Electrodes, Adv. Mater., accepted.
• Type: Journal Articles Status: Accepted Year Published: 2019 Citation: Y. Li, X. Fu, Y. Wang, R. Li, W. H. Zhong. 2019.See the Invisibles: Inspecting Defects in Battery Separators by Pressure Drop. Energy Storage Mater. in press.
• Type: Journal Articles Status: Published Year Published: 2019 Citation: G. Yadavalli, H. Lei, Z. Yang, Y. Zhang, E. Villota, M. Qian. 2018. Alkaline Separation of Protein from Canola Meal and Its Kinetic Study. SF Journal of Material and Chemical Engineering, 2(1): 1011.
• Type: Journal Articles Status: Published Year Published: 2018 Citation: X. Fu, C. Li, Y. Wang, L. Kovatch, L. Scudiero, J. Liu, W. H. Zhong. 2018. Building Ion-conduction Highways in Polymeric Electrolytes by Manipulating Protein Configuration, Building Ion-Conduction Highways in Polymeric Electrolytes by Manipulating Protein Configuration. ACS Appl. Mater. Interface 10 (5), 47264736.
• Type: Journal Articles Status: Published Year Published: 2018 Citation: X. Fu, C. Li, Y. Wang, M. Zheng, L. Scudiero, J. Liu, W. H. Zhong. 2018. A Self-Assembled Polysulfides Nanofilter for Electrochemical and PM2.5 Filtration, J. Phys. Chem. Lett. 9, 2450-2459.
• Type: Journal Articles Status: Published Year Published: 2018 Citation: X. Fu, Y. Wang, X. Fan, L. Scudiero, W. H. Zhong. 2018. CoreShell Hybrid Nanowires with Protein Enabling Fast Ion Conduction for High-Performance Composite Polymer Electrolytes, Small 1803564.
• Type: Journal Articles Status: Published Year Published: 2018 Citation: X. Fu, Y. Wang, L. Scudiero, W. H. Zhong. 2018. A Polymeric Nanocomposite Interlayer as Ion-Transport-Regulator for Trapping Polysulfides and Stabilizing Lithium Metal. Energy Storage Mater. 15, 447-457.
• Type: Journal Articles Status: Published Year Published: 2018 Citation: X. Fu, Y. Wang, J. Tuba, L. Scudiero, W. H. Zhong. 2018. Small Molecules Make a Big Difference: A Solvent-Controlled Strategy for Building Robust Conductive Network Structures in High-Capacity Electrode Composites. Small Methods 2, 1800066.
• Type: Journal Articles Status: Published Year Published: 2018 Citation: M. Zheng, X. Fu, Y. Wang, J. Reeve, L. Scudiero, W. H. Zhong. 2018. Poly(vinylidene fluoride)-Based Blends as New Binders for Lithium-Ion Batteries. ChemElectroChem 5, 2288 2294.
• Type: Journal Articles Status: Published Year Published: 2018 Citation: X. Fu; Y. Wang; L. Scudiero and W. H. Zhong. 2018. A Review: Natrual Polymer Electrolytes for Lithium Ion Batteries, Journal of Harbin Institute of Technology 25, 1.
• Type: Journal Articles Status: Published Year Published: 2017 Citation: X. Fu, Y. Wang, J. Liu, W. H. Zhong, G. Cao. 2017. A Multifunctional Protein Coating for Self-Assembled Porous Nanostructured Electrodes, ACS Omega 2 (4), 16791686.
• Type: Journal Articles Status: Published Year Published: 2017 Citation: Y. Wang, A. Gozen and L. Chen and W. H. Zhong. 2017. Gum-like Nanocomposites as Conformable, Conductive and Adhesive Electrode Matrix for Energy Storage Devices, Adv. Energy Mater. 7, 1601767.
• Type: Journal Articles Status: Published Year Published: 2016 Citation: X. Fu, Y. Jewel, Y. Wang, J. Liu, W. H. Zhong. 2016. Decoupled Ion-Transport in a Protein-Based Solid Ion Conductor, J. Phys. Chem. Lett. 7, 4304?4310.
• Type: Journal Articles Status: Published Year Published: 2016 Citation: X. Wang, X. Fu, Y. Wang, W. H. Zhong. 2016. A Protein-Reinforced Adhesive Composite Electrolyte, Polymer 106, 43-52.
• Type: Journal Articles Status: Published Year Published: 2015 Citation: A. Eyler, Y. Wang, T. Liu, B. Li, W. H. Zhong. 2015. Ion-Induced Effective Control of Morphologies of Soy Protein Biocomposites, J. Mater. Sci. 50, 26912699.
• Type: Journal Articles Status: Submitted Year Published: 2019 Citation: Y. Choi, K. J. Chen, and T. L. Marsh. 2018. Consumer preference for bio-based batteries. revised and resubmitted at Energy Economics.
• Type: Journal Articles Status: Other Year Published: 2019 Citation: K. J. Chen, T. L. Marsh, and T. R. Fortenbery. 2019. An impact of EISA on the relationship between biomaterial and agricultural commodity markets. To be submitted to Applied Energy.
• Type: Journal Articles Status: Other Year Published: 2019 Citation: M. Qian, H. Lei, X. Zhang, E. Villota, Y. Zhang, D. Duan. 2019. The structural and chemical functionality of sulfur-free acid insoluble and acid-soluble lignins affected by the alkaline extraction from Douglas fir. To be submitted to Biomass and Bioenergy.
• Type: Book Chapters Status: Published Year Published: 2017 Citation: Y. Wang; W.-H. Zhong, Nanomaterials and Nanostructures for Regulating Ion and Electron Transport in Advanced Energy Storage Devices. In Nanomaterials for Energy Storage and Conversion, Cao, G.; Wei, D., Eds. 2017.
• Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: G. Yadavalli, H. Lei, Z. Yang, Y. Zhang, E. Villota, M. Qian, L. Zhu. 2017. The effect of canola protein extraction conditions on the kinetic parameters of a two-site extraction model. 2017 ASABE Annual International Meeting, Paper#1701289, doi:10.13031/aim.201701289
• Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: X. Fu; C. Li; Y. Jewel; Y. Wang; J. Liu and W.H. Zhong, Manipulating Protein Configuration for High-Performance Solid Polymer Electrolytes, 233rd ECS Meeting, Seattle, Washington, 05/13-05/17/2018.
• Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: X. Fu, Protein as a Multifunctional Material for Energy Storage Applications, September 7, 2018, Washington State University, Washington
• Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: M. Qian, H. Lei, E. Villota, W. Mateo, Z. Yang, Y. Zhang, K. Qian. 2018. Microwave-assisted catalytic and acidic depolymerization of alkaline lignin for production of aromatic hydrocarbons. 2018 ASABE Annual International Meeting, Detroit, Michigan, July 29 - August 01, 2018.
• Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: W. Mateo, H. Lei, E. Villota, Z. Yang, Y. Zhang, M. Qian, K. Qian, D. Duan. 2018. Synthesis and Performance of Carbon-based Solid Acid Catalyst for Organosolv Fractionation. 2018 ASABE Annual International Meeting, Detroit, Michigan, July 29 - August 01, 2018.
• Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: K. Chen, R. Fortenbery, and T. L. Marsh. 2018. The Relationship Between Biomaterial and Agricultural Commodity Markets. 2018 Agricultural and Applied Economics Association.
• Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Y. Choi, K. Chen, and T. L. Marsh. 2018. Consumer preference for bio-based batteries. 2018 Agricultural and Applied Economics Association, Washington DC.
• Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Y. Choi, K. Chen, T. L. Marsh. 2017. Consumer Willingness to Pay for Bio-based Batteries. Western Education and Research Activities Committee on Agribusiness (WERA-72), June 14, 2017.
• Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: G. Yadavalli, H. Lei, Z. Yang, Y. Zhang, E. Villota, M. Qian, L. Zhu. 2017. The effect of canola protein extraction conditions on the kinetic parameters of a two-site extraction model. 2017 ASABE Annual International Meeting, Spokane, WA, Jul 16-19, 2017
• Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: X. Fu; Y. Jewel; Y. Wang; J. Liu and W.H. Zhong, A Protein Solid Electrolyte with Decoupled Ion Transport, BEPS 24th Annual Meeting, Berkeley, California, 09/20-09/22/2017.
• Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Choi, Y., Chen, K., and Marsh, T. L., (2017). Consumer willingness to pay for bio-based batteries. WERA-72 Annual Meeting, Western Education and Research Activities Committee on Agribusiness, June 12-13, 2017 / Boise, Idaho, The Future of Agribusiness Research, Teaching and Extension.
• Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: X. Fu; Y. Jewel; Y. Wang; J. Liu and W.H. Zhong, A Natural Electrolyte with Adjustable Ion-Transportation, American Vacuum Society (AVS) Annual Symposium, Richland, Washington, 09/14-09/16/2016.
• Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: M. Qian, X. Zhang, H. Lei, L. Zhu, J. C. Chan, X. Zhu, Y. Liu, G. Yadavalli, D. Yan. 2016. Catalytic separation and depolymerization of lignin for effective production of aromatic hydrocarbons. 2016 ASABE Annual International Meeting, Orlando, Florida, July 17 - 20, 2016
• Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: X. Zhu, G. Yadavalli, H. Lei, X. Zhang, M. Qian, J. C. Chan, L. Zhu, Y. Liu, , D Yan. Protein based solid electrolyte from abundant Canola meal protein. 2016 ASABE Annual International Meeting, Orlando, Florida, July 17 - 20, 2016
• Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: A. Eyler, T. Liu, Y. Wang, L. Scudiero, Safe and Flexible Battery Materials by Applying Natural Plants, 2015 Pacific Northwest Chapter of the AVS, Mount Hood, Oregon, 09/30-10/2/2015.

Progress 01/01/17 to 12/31/17

Outputs
Target Audience:Biomass industrial companies, battery materials and battery related industries, lignin, starch, and protein producers, processors, wholesalers, and retailers: Carbon Cycle Crush LLC, Creative Energy Systems Inc., Gen-X Energy Group Inc., North America Green Pulp Inc., Washington Bio-oils Inc., Archer Danieis Midland Co., and State and Federal policy makers. Efforts: Formal classroom instruction (new course lectures/sessions) about the project in BSysE 593 Renewable Energy Technologies, BSYSE 552 Advanced Biological Systems Engineering Topics, MSE 402 Polymeric Materials, MSE 404 Engineering Composites, MSE 508 Polymeric Nanocomposites and Functionalities, and EconS 351 Introduction to Food and Agricultural Markets; Development of curriculum (new lecture sessions on biomass conversion and separation; bio-material based electrolytes; economic science and agricultural markets); Trained graduate and undergraduate students who work on this project will eventually join the workforce and contribute to the effort of utilizing biomass and developing new battery technology for the future energy needs: PhD students Xuewei Fu, Youngran Choi, Wendy Mateo, Marie Qian; MS students: Gayatri Yadavalli; undergraduate students: Jacqueline Reeve, James Tuba; New experiential learning opportunities for involved students in the project: Jacqueline Reeve and James Tuba (undergraduate students) gained experiential learning opportunities. They conducted various experiments on utilizing several species of proteins, to make several kinds of battery materials, including electrolytes, binders and separator coatings. The experiments include denaturation of the proteins, fabrication of the materials and characterization of the materials. Characterization includes wettability studies of the battery materials using contact angle analyzer, ionic conductivity using impedance tester, and battery performance test. Seminars to local chapter of societies, such as Materials Research Society WSU student chapter, Pacific Northwest American Vacuum Society (AVS) Annual Symposium, Bio-Environmental Polymer Society (BEPS), regional and national conferences (see session of publication list in Product and the following outreach communications and presentations); Extension and outreach (outreach communications and presentations to biomass industrial companies, battery and related industries): H. Lei, G. Yadavalli, K. Qian. 2017. Biomass conversions for biofuels and bioproducts. 2017 Meeting with MSS Sustainable LLC/ USS International LLP/ North America Green Pulp Inc., Richland, WA, May 25, 2017 Y. Choi, K. Chen, T. L. Marsh, "Consumer Willingness to Pay for Bio-based Batteries," Western Education and Research Activities Committee on Agribusiness (WERA-72), June 14, 2017. W. H. Zhong, Natural Protein Materials for Functional Applications, August 1, 2017, Huazhong Agricultural University, Wuhan, Hubei Province, China W. H. Zhong, Bio-composites for Energy Applications, August 2, 2017, Huazhong University of Science and Technology, Wuhan, Hubei Province, China Changes/Problems:None. What opportunities for training and professional development has the project provided?Training activities: The funding received from this project has been used to support 3 post-docs, 4 PhD candidates, and 2 undergraduate students in the WSU Biological Systems Engineering Program, Material Science and Engineering Program, and Economic Science Program. 4 PhD students, 2 undergraduate students, and 3 post-doc research associates learned to develop new technologies, new processes, new materials, new econometric techniques, protocols, and market analysis. Post-docs and PhD students have developed the experience assisting undergraduate students attaining greater proficiency in developing new technologies and conducting experiments. PIs incorporated the research results from this project in teaching BSysE 593 Renewable Energy Technologies, BSYSE 552 Advanced Biological Systems Engineering Topics, MSE 402 Polymeric Materials, MSE 404 Engineering Composites, MSE 508 Polymeric Nanocomposites and Functionalities, and EconS 351 Introduction to Food and Agricultural Markets. Professional development activities: PIs had a monthly conference calls and active collaborations among each other, and their research group had weekly meetings to make sure the good progress of the project. PIs and their research teams had updates presented at group meetings. Students developed collaboration skills and exchanged technical information cross group knowledge. PhD Students and Post-docs have participated and presented papers at American Society of Agricultural and Biological Engineers (ASABE) 2017 Annual International Meeting at Spokane, Washington, July 16 - 19, 2017, and Bio-Environmental Polymer Society (BEPS) 2017 Annual Meeting, Berkeley, California, September 20-22, 2017, and 2017 Western Education and Research Activities Committee on Agribusiness (WERA-72), June 14, 2017. How have the results been disseminated to communities of interest?The PIs and their students and post-docs created posters and/or made oral presentations to showcase findings and present the study results at industrial meetings and conferences. The research findings were communicated to the general public via national and international conferences, such as American Society of Agricultural and Biological Engineers (ASABE) Annual International Conference, and Bio-Environmental Polymer Society (BEPS) 2017 Annual Meeting. The published and submitted journal papers and proceedings can be found in previous sessions in this progress report. We also disseminated our research results to communities by presenting to industrial delegations and academic communities. Our outreach dissemination efforts includes: 2017 seminar of Natural Protein Materials for Functional Applications, 2017 seminar of Bio-composites for Energy Applications, Huazhong Agricultural University, Wuhan, China, August 1-2, 2017. 2017 seminar of Biomass conversions for biofuels and bioproducts with MSS Sustainable LLC/ USS International LLP/ North America Green Pulp Inc., Richland, WA, May 25, 2017, and 2017 seminar of Consumer Willingness to Pay for Bio-based Batteries with Western Education and Research Activities Committee on Agribusiness (WERA-72), June 14, 2017. What do you plan to do during the next reporting period to accomplish the goals?Based on our previous studies, protein is of great potential to fabricate three-dimensional nanostructure of carbon black (CB) via the surface protein coating. It is also a multifunctional "green" binder with ion-conductive properties. Therefore, during the next year of 2018, we will continue the task which aims to develop protein's broad application for fabricating electrodes as well as studying protein-directed self-assembly behavior towards nanoparticle-shaped electrodes. The morphology of the nanostructure and electrochemical performance of the resultant samples will be evaluated and optimized via varying the critical parameters. Due to the fact that our composite polymer electrolytes (CPEs) based on UHMWPEO is a soft and adhesive material, conventional cell assembly technique is not suitable for the CPEs. To assemble cells, a new cell assembly technique is demanded to get rid of high compression forces from assembly. Film-like cells will be assembled with no or less stress during fabrication. To acquire satisfactory battery performance, binder materials will also be optimized. The desired binder should obtain high ionic conductivity and electric conductivity simultaneously. Therefore, the introduction of carbon black (CB) will be evaluated based on the CPEs. The loading of CB can be varied from 5 to 15 wt% to finally result in desired adhesion properties and integral electrode configuration. We will finish working on understanding of protein separation with functional analysis experiments, and lignin separation with understanding of structure and functional groups which are related to lignin separation efficiency. We will also finish analysis of a consumer survey on the willingness to pay for bio-batteries, and also, we will complete an assessment of economic impacts along the supply chain.

Impacts
What was accomplished under these goals? Impact: Battery disposal causes deteriorating effects on environment and human health, as the released harmful substances are easily consumed by plant roots and accumulated in fruits, vegetables and grass, which are consumed by human beings. Recycling batteries is a much better option than dumping them in landfills, but it is expensive involving time/energy consuming processes. This USDA supported project is to develop bio-based battery materials and create a "green" solution for solid electrolytes in order to remove the liquid electrolyte from batteries to get rid of leakage, spillage, or damage, which is important to the environment and economy as well as agriculture. The approach is to apply abundant plants, such as soy and canola, as the base component to develop safe, renewable and battery electrolyte materials in both fundamental and applied sciences. The project team is focused directly on integrating the technologies employed to convert this agricultural feedstock into bio-battery materials. The project provides a novel renewable energy storage system to the industries for sustainably producing bio-battery, and directly contributes to adding value and profit for those industries and creating new technology for battery industry. The team is lining and engaging related industries in our outreach and education efforts and involved them in the development of a biobased battery. Major activities completed / experiments conducted / data collected / results / key outcomes: Specific objective (1): Task 1: Protein extraction and kinetics (Dr. Lei's team) The effect of various protein extraction conditions (alkaline concentration, particle size and temperature) on the parameters of a two-site kinetic model and Peleg's model were determined for extraction from canola meal. Particle size had the greatest effect on equilibrium yield with a 269.68 mg·g-1 increase in yield between particle ranges of 16-35 mesh and 60-120 mesh. At a higher temperature of 55 °C, the faster process dominated the rate and protein was released at an initial rate of 2858.42 mg·g-1·s-1, which was a tenfold increase from room temperature. Protein isolated from canola meal was supplied to Dr. Zhong for electrolyte synthesis. Task 2: Lignin separation and kinetics (Dr. Lei's team) Technical lignin oligomers from dilute alkali separation at mild conditions were optimized for kinetics studies with the effects of pH, extraction temperature and time. The range of acid insoluble lignin yield varied from 19.1 to 71.5 %wt, and the acid soluble lignin was from 29.0 to 58.6 %wt. Influence of different extraction conditions on the FTIR spectra of alkaline lignin was elucidated by the structure, characterization of chemical reactivity and functional properties of lignin. Base reaction at alkali treatment consists of cleavage of aryl-ether bonds which brings about an increase of phenolic hydroxyl content. The lignin yield and the extraction conditions were strongly related (R2=0.96). The lignin with the highest purity was supplied to Dr. Zhong for electrolyte synthesis. Task 3: Development of soy protein based solid electrolytes (Drs. Zhong and Scudiero's teams) A high-performance solvent-free composite polymer electrolytes (CPEs) with novel protein-ceramic nanofillers was demonstrated. We found that the ion-conduction of the TiO2-Protein nanofillers was sensitive to the protein structures as revealed by both experimental and simulation studies. The elevated structural flexibility promotes protein-TiO2 interactions and helps to form ion conductive pathways. The ionic conductivity of the resultant CPEs has been significantly improved from 5 x 10-6 to 6 x 10-5 S/cm at room temperature. Other properties, such as electrochemical stability, mechanical properties and even adhesion properties, all are improved. The studies bring a facile strategy based on controlling the structures and functions of natural proteins for design and fabrication of new organic-inorganic nanofillers to address the challenging issues in conventional solid polymer electrolytes. Task 4: Study of protein-reinforced adhesive composite electrolytes (Drs. Zhong and Scudiero's teams) A multifunctional protein surface coating of electrode nanoparticles to fabricate 3D porous nanostructured electrodes via self-assembly was demonstrated. The protein surface coating can play three roles simultaneously: a surfactant of the electrode nanoparticles that drives self-assembly during evaporation, an ionic conductive coating that facilitates the ion-transfer between electrolyte and electrode and finally a stable binder that maintains the structures for stable cycling. Benefiting from its multi-functionalities, the capacity, cycle stability and rate capability of the resultant self-assembled porous electrode are significantly improved as compared with traditional electrodes. This study provides a cost-effective and important strategy for fabrication of porous nanostructured electrodes via the self-assembly of electrode nanoparticles. Task 5: Structure and properties from different constituents of the electrolyte (Dr. Scudiero's teams) Spectroscopic and microscopic methods were used to probe the following systems, PEO, Protein-PEO and Protein-PEO-LiClO4 films to understand the interaction between the different constituents of the solid polymer electrolyte. AFM, FTIR and XPS were the main techniques utilized to characterize the solid polymer electrolyte films. We emphasized the results obtained only on films dried at 40°C in air and with 30 wt% LiClO4 loading. These conditions were selected based on the result obtained for the ionic conductivity. Drying the films with this composition showed the highest ionic conductivity of ~ 10-5S/cm. The addition of protein and then LiClO4 made the film more electrically conducting. Specific objective (2): Task 6: Cost estimation (Drs. Tozer and Marsh's team) We examined how consumers' characteristics and preferences for product attributes and environmentally friendly practices vary across regions of the U.S. and influence consumers' willingness to pay (WTP) for bio-based batteries. We obtained nationwide data via an online survey platform and used a dichotomous-choice contingent valuation method to estimate the WTP. The results suggest that the estimated WTP increases in the Midwest and South when consumers receive more information about the product. Consumers concerned with green production and recycling practices are willing to pay a premium for the product. Our results provide essential information to quantitatively assess the market impact of the product and develop effective management and marketing strategies to reach various consumer groups. Change in Knowledge: Increased understanding of the effects of extraction conditions on separation kinetics for protein from canola and lignin from biomass, and their roles in solid electrolytes and bio-battery; Increased our understanding of effects of nanoparticles on molecular structures of plant protein and the benefits for ion-transportation for SPEs; Increased our knowledge of electrode and battery fabrication and evaluation on SPEs through device performance; Provided empirical evidence from about 1500 consumers on their preferences and characteristics for bio-batteries; Change in Action: A new way to fabrication of solid electrolytes and lay foundation for achieving bio-battery by using biomass derived lignin and proteins from canola and soybean. Change in Condition: Positive impact on the agricultural economy and on the use of the abundant plants as raw materials for fabricating bio-battery materials; The bio- based solid electrolytes are renewable and non-polluting to solve the central challenge of leakage, spillage, or deteriorating effects of current rechargeable liquid lithium batteries on environment and human health to be faced worldwide.

Publications

• Type: Journal Articles Status: Published Year Published: 2017 Citation: X. Fu, Y. Wang, J. Liu, W.H. Zhong, G. Cao, A Multifunctional Protein Coating for Self-Assembled Porous Nanostructured Electrodes, 2017, ACS Omega 2 (4), 16791686.
• Type: Journal Articles Status: Accepted Year Published: 2017 Citation: X. Fu; Y. Wang; L. Scudiero and W.H. Zhong, A Review: Natrual Polymer Electrolytes for Lithium Ion Batteries, Journal of Harbin Institute of Technology, in press, 2017.
• Type: Journal Articles Status: Submitted Year Published: 2017 Citation: X. Fu, C. Li, Y. Wang, L. Kovatch, L. Scudiero, J. Liu, W.H. Zhong, Building Ion-conduction Highways in Polymeric Electrolytes by Manipulating Protein Configuration, submitted to ACS Applied Materials and Interfaces, Nov 2017.
• Type: Journal Articles Status: Submitted Year Published: 2017 Citation: X. Fu, C. Li, Y. Wang, M. Zheng, L. Scudiero, J. Liu, W.H. Zhong, A Self-Assembled Polysulfides Nanofilter for Electrochemical and PM2.5 Filtration, submitted to Journal of Materials Chemistry A, Dec 2017.
• Type: Journal Articles Status: Submitted Year Published: 2017 Citation: G. Yadavalli, H. Lei, Z. yang, Y. Zhang, E. Villota, M. Qian. 2017. Kinetic study of alkaline extraction of protein from canola meal, submitted to Biotechnology and Bioengineering, Dec 2017.
• Type: Book Chapters Status: Published Year Published: 2017 Citation: Y. Wang; W.-H. Zhong, Nanomaterials and Nanostructures for Regulating Ion and Electron Transport in Advanced Energy Storage Devices. In Nanomaterials for Energy Storage and Conversion, Cao, G.; Wei, D., Eds. 2017.
• Type: Other Status: Published Year Published: 2017 Citation: G. Yadavalli, H. Lei, Z. Yang, Y. Zhang, E. Villota, M. Qian, L. Zhu. 2017. The effect of canola protein extraction conditions on the kinetic parameters of a two-site extraction model. 2017 ASABE Annual International Meeting, Paper#1701289, doi:10.13031/aim.201701289
• Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: X. Fu; Y. Jewel; Y. Wang; J. Liu and W. H. Zhong. 2017. A Protein Solid Electrolyte with Decoupled Ion Transport, Bio-Environmental Polymer Society (BEPS) 24th Annual Meeting, Berkeley, California, 09/20-09/22/2017
• Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: G. Yadavalli, H. Lei, Z. Yang, Y. Zhang, E. Villota, M. Qian, L. Zhu. 2017. The effect of canola protein extraction conditions on the kinetic parameters of a two-site extraction model. 2017 ASABE Annual International Meeting, Spokane, WA, Jul 16-19, 2017

Progress 01/01/16 to 12/31/16

Outputs
Target Audience:Biomass industrial companies, battery materials and battery related industries, lignin, starch, and protein producers, processors, wholesalers, and retailers: Carbon Cycle Crush LLC, Creative Energy Systems Inc., Gen-X Energy Group Inc., North America Green Pulp Inc., Washington Bio-oils Inc., Archer Danieis Midland Co. Efforts: Formal classroom instruction (new course lectures/sessions) about the project in BSysE 593 Renewable Energy Technologies, BSYSE 552 Advanced Biological Systems Engineering Topics, MSE 402 Polymeric Materials, MSE 404 Engineering Composites, and EconS 351 Introduction to Food and Agricultural Markets; Development of curriculum (new lecture sessions on biomass conversion and separation; bio-material based electrolytes; economic science and agricultural markets); Trained graduate and undergraduate students who work on this project will eventually join the workforce and contribute to the effort of utilizing biomass and developing new battery technology for the future energy needs: PhD students Xuewei Fu, Youngran Choi, Kuan Chen, Xiaolu Zhu, Lei Zhu, Elmar Villota, Marie Qian; MS students: Allen Eyler, Gayatri Yadavalli, Di Yan; undergraduate students: Jacqueline Reeve, Lucas P. Kovatch, Katie Tran; New experiential learning opportunities for involved students in the project; Seminar to local chapter of societies, such as Materials Research Society WSU student chapter, Pacific Northwest American Vacuum Society (AVS) Annual Symposium, regional and national conferences (see session of publication list in Product and the following outreach communications and presentations); Extension and outreach (outreach communications and presentations to biomass industrial companies, battery and related industries): Invited presentation: W. H. Zhong, Protein for Energy Application, Beijing University of Chemical Technology, Beijing, China, Nov 2, 2016. Invited presentation: H Lei, Processes, biofuels, and bioproducts from biomass, China University of Mining and Technology (Beijing), Beijing, July 6, 2016. H. Lei. 2016. Bioprocesses for biofuels and bioproducts. 2016 Meeting with MSS Sustainable LLC/ USS International LLP/ Qilu University of technology / North America Green Pulp Inc., Richland, WA, May 29, 2016 H. Lei. 2016. Biofuels and bioproducts from lignocellulose biomass. 2016 Meeting with Creative Energy Systems Inc. / Washington Bio-oils Inc. / NC RJ Reynolds Tobacco Co. Richland, WA, December 15, 2016 Changes/Problems:None. What opportunities for training and professional development has the project provided?Training activities: The funding received from this project has been used to support 1 post-docs, 7 PhD candidates, 3 MS students, and 3 undergraduate students in the WSU Biological Systems Engineering Program, Material Science and Engineering Program, and Economic Science Program. 7 PhD students, 3 MS students, 3 undergraduate students, and 1 post-doc research associates learned to develop new technologies, new processes, new materials, new econometric techniques, protocols, LCA and market analysis. Post-docs and PhD students have developed the experience assisting MS and undergraduate students attaining greater proficiency in developing new technologies and conducting experiments. PIs incorporated the research results from this project in teaching BSysE 593 Renewable Energy Technologies, BSYSE 552 Advanced Biological Systems Engineering Topics, MSE 402 Polymeric Materials, and EconS 351 Introduction to Food and Agricultural Markets. Professional development activities: PIs had a monthly conference calls and active collaborations among each other, and their research group had weekly meetings to make sure the good progress of the project. PIs and their research teams had updates presented at group meetings. Students developed collaboration skills and exchanged technical information cross group knowledge. PhD Students and Post-docs have participated and presented papers at American Society of Agricultural and Biological Engineers (ASABE) 2016 Annual International Meeting at Orlando, Florida, July 17 - 20, 2016, and 2016 Pacific Northwest American Vacuum Society (AVS) Annual Symposium, Richland, Washington, 09/14-09/16/2016, and 2016 annual meeting of Agricultural and Applied Economics Association, Boston, Massachusetts, July 31-August 2, 2016. How have the results been disseminated to communities of interest?The PIs and their students and post-docs created posters and/or made oral presentations to showcase findings and present the study results at Pacific Northwest American Vacuum Society (AVS) Annual Symposium. The research findings were communicated to the general public via national and international conferences, such as American Society of Agricultural and Biological Engineers (ASABE) Annual International Conference, and annual meeting of Agricultural and Applied Economics Association. The published and submitted journal papers and proceedings can be found in previous sessions in this progress report. We also disseminated our research results to communities by presenting to industrial delegations and academic communities. Our outreach dissemination efforts includes: 2016 seminar of protein for energy application, Beijing University of Chemical Technology, Beijing, China, Nov 2, 2016. 2016 seminar of Processes, Biofuels, and Bioproducts from Lignocellulosic Biomass with China University of Mining and Technology (Beijing), Beijing, July 6, 2016; 2016 Meeting of biofuels and bioproducts with MSS Sustainable LLC/ USS International LLP/ Qilu University of technology / North America Green Pulp Inc., Richland, WA, May 29, 2016; 2016 Meeting of Biofuels and bioproducts with Creative Energy Systems Inc. / Washington Bio-oils Inc. / NC RJ Reynolds Tobacco Co. Richland, WA, December 15, 2016. What do you plan to do during the next reporting period to accomplish the goals?During the next year of 2017, we will continue working on understanding of protein separation with functional analysis experiments, and lignin separation with understanding of microscopic structure and identification and controlling of functional groups which are related to lignin separation efficiency. We will continue developing and fabricating the protein-based SPEs. We will adjust the protein structure by incorporating NPs to eventually achieve high-performance protein electrolyte. We will study and optimize the protein-NP complexes as polymer electrolyte hosts, incorporate inorganic NPs with protein and introduce the protein-NP complexes to PEO host, and study the interaction between protein and NPs. We will continue market analysis (e.g., farm, wholesale, retail levels) for inputs and batteries that will provide input into the cost model and the partial equilibrium model, as well as model development. We anticipate that we will meet the objectives of the proposed work in a timely manner.

Impacts
What was accomplished under these goals? Impact: Battery disposal causes deteriorating effects on environment and human health, as the released harmful substances are easily consumed by plant roots and accumulated in fruits, vegetables and grass, which are consumed by human beings. Recycling batteries is a much better option than dumping them in landfills, but it is expensive involving time/energy consuming processes. This USDA supported project is to develop bio-based battery materials and create a "green" solution for solid electrolytes in order to remove the liquid electrolyte from batteries to get rid of leakage, spillage, or damage, which is important to the environment and economy as well as agriculture. The approach is to apply abundant plants, such as soy and canola, as the base component to develop safe, renewable and battery electrolyte materials in both fundamental and applied sciences. The project team is focused directly on integrating the technologies employed to convert this agricultural feedstock into bio-battery materials. The project provides a novel renewable energy storage system to the industries for sustainably producing bio-battery from wood residuals derived from biomass industry, and canola meals, a low-value byproduct from biodiesel industry, and directly contributes to adding value and profit for those industries and creating new technology for battery industry. The team is lining and engaging related industries in our outreach and education efforts and involved them in the development of a biobased battery. Major activities completed / experiments conducted / data collected / results / key outcomes: Specific objective (1): Task 1: Protein extraction and kinetics (Dr. Lei's team) Canola protein was extracted from expeller pressed canola meal in alkaline conditions. Two models were fit to the kinetic data, namely a two-site kinetic model, and a second order model. The two site kinetic model indicates that 65 % of protein extracted from <16 mesh particles size canola meal, comes from a slower extraction process from bigger particles in the meal. The second order model gave a better fit to the data (R2=0.94). Water and oil absorption capacity of the protein concentrate was greater than that of the meal. The protein concentrate absorbed both oil and water, indicating the presence of both hydrophobic and hydrophilic groups. Protein isolated from canola meal was supplied to Dr. Zhong for electrolyte synthesis. Task 2: Lignin separation and kinetics (Dr. Lei's team) Technical lignin oligomers from dilute alkali depolymerization at low temperature of 60-90°C were extracted and optimized for kinetics studies with the effects of pH, extraction temperature and time. The infrared spectrum of the extracted lignin were recorded with Shimadzu IRPrestige FTIR Spectrometer and each functional group were compared. Solubility of the lignin samples was performed in various organic solvents such as methanol, ethanol, ethyl acetate, acetone and hexane. The lignin with the highest purity was supplied to Dr. Zhong for electrolyte synthesis. Task 3: Development of soy protein based solid electrolytes (Drs. Zhong and Scudiero's teams) The project is motivated by the good solubility of lithium salt in protein which has abundant functional groups derived from its assorted amino acid side groups which are potentially reactive with the solvated ions. A high-performance protein based solid electrolyte with high ionic conductivity, high transference number and good mechanical properties was fabricated via adjusting the protein structure by formation temperature. Via molecular dynamic simulation, it was found that the ion transport mechanism of protein is distinctive from conventional SPEs but similar to ceramic electrolytes. The ion transport of protein is decoupled with chain movement, and therefore provides the opportunity to improve ionic conductivity significantly without sacrificing mechanical properties. Task 4: Study of protein-reinforced adhesive composite electrolytes (Drs. Zhong and Scudiero's teams) In composite electrolytes, the fillers are usually rigid inorganic nanoparticles with limited functional groups contributing to mechanical properties and/or adhesion properties. In this study, wax particles with similar particle size with protein but much less functional groups were applied for parallel experiment for comparison. The natural proteins have been demonstrated as promising multifunctional bio-fillers for reinforcing the mechnical properties and adhesive property of the PEO based composite electrolytes. Further, this study also shows that the mechanical properties of the composite electrolytes can be notably improved by protein without sacrificing ionic conductivity, which indicates an effective way to solve the critical issues in gel electrolytes; that is, the trade-off between ionic conductivity and mechanical properties. Task 5: Structure and properties from different constituents of the electrolyte (Dr. Scudiero's teams) Spectroscopic methods were used to probe the following systems, spi-peo and spi-peo-LiClO4 (liquid and solid) to understand the interaction between the different constituents of the electrolyte. UV-Vis, FTIR and X-ray photoelectron spectroscopy (XPS) were the main techniques utilized to characterize the electrolytes at room temperature and as a function of increasing temperature from 20 to 95°C. In addition, viscosity measurements were conducted to correlate ionic conductivity of the SPE and viscosity as a function of salt loading and temperature. Specific objective (2): Task 6: Cost estimation (Drs. Tozer and Marsh's team) Literature review was completed. Completed retail survey on WTP for batteries to assess final demand. Econometrically evaluated trade and commodities prices analysis of lignin, starch, and protein. Currently pretesting retail survey. Will field survey immediately after analyzing pretest data. Completed a flow diagram of the supply chain process and markets. Continued examination of lignin, corn starch, and soybean meal data using monthly data 2002 to 2015. Completed consumer survey to assess retail market. A consistent public time data series of battery price data for the U.S. domestic market is limited. To assess the retail market, we developed a survey. These data are important to understand past, current, and future price trends that feed into calculating cost estimates and outcomes from the partial equilibrium model. Change in Knowledge: Increased understanding of the effects of extraction conditions on separation kinetics for protein from canola and lignin from biomass, and their roles in solid electrolytes and bio-battery; Increased our understanding of the effects of protein structure and formation temperature on high-performance protein based solid electrolyte; Enhanced our knowledge of the natural proteins for reinforcing the mechnical properties and adhesive property of electrolytes; Improved the understanding of cost estimates and outcomes from the partial equilibrium model, which will improve our ability to project impacts on the agricultural economy. Change in Action: A new way to fabrication of solid electrolytes and lay foundation for achieving bio-battery by using biomass derived lignin and proteins from canola and soybean. Change in Condition: Positive impact on the agricultural economy and on the use of the abundant plants as raw materials for fabricating bio-battery materials; The bio- based solid electrolytes are renewable and non-polluting to solve the central challenge of leakage, spillage, or deteriorating effects of current rechargeable liquid lithium batteries on environment and human health to be faced worldwide.

Publications

• Type: Journal Articles Status: Published Year Published: 2016 Citation: X. Fu, Y. Jewel, Y. Wang, J. Liu, W.H. Zhong, Decoupled ion transport in a protein-based solid ion conductor, J. Phys. Chem. Lett. 7, 4304?4310, 2016. X. Wang, X. Fu, Y. Wang, Wei-Hong Zhong. 2016. A protein-reinforced adhesive composite electrolyte, Polymer 106, 43-52.
• Type: Journal Articles Status: Published Year Published: 2016 Citation: Y. Wang, A. Gozen and L. Chen and W.H. Zhong. 2016. Gum-like Nanocomposites as Conformable, Conductive and Adhesive Electrode Matrix for Energy Storage Devices, Advanced Energy Materials, 1601767.
• Type: Journal Articles Status: Published Year Published: 2016 Citation: Q. Bu, H. Lei, M. Qian, G. Yadavalli. 2016. A thermal behavior and kinetics study of the catalytic pyrolysis of lignin. RSC Advances, 6, 100700-100707.
• Type: Journal Articles Status: Submitted Year Published: 2016 Citation: X. W. Fu, Y. Wang, W. H. Zhong and G. Z. Cao. 2016. A Multifunctional Protein Coating for Self-Assembled Porous Nanostructured Electrodes, submitted to Nanoenergy, Nov 2016.
• Type: Book Chapters Status: Submitted Year Published: 2016 Citation: Y. Wang and W. H. Zhong. 2016. Nanomaterials and Nanostructures for Regulating Ions and Electrons Transport in Advanced Energy Storage Devices, of the book Nanomaterials for Energy Conversion and Storage, submitted to Imperial College Press/World Scientific, 2016.
• Type: Theses/Dissertations Status: Published Year Published: 2016 Citation: X. L. Wang, Protein as Functional bio-filler for Enhancing Performance of Adhesive Composite Electrolyte, PhD Dissertation, Washington State University, January 2016.
• Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: X. Fu; Y. Jewel; Y. Wang; J. Liu and W. Zhong. 2016. A Protein Solid Electrolyte with Decoupled Ion Transport, American Vacuum Society (AVS) Annual Symposium, Richland, Washington, 09/14-09/16/2016
• Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: K. Chen, K. Chen, T. Marsh. 2016. Analysis of Energy and Agricultural Commodity Markets: A Vine Copula-Based ARMA-EGARCH Model, 2016 annual meeting of Agricultural and Applied Economics Association, Boston, Massachusetts, July 31-August 2, 2016
• Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: M. Qian, X. Zhang, H. Lei, L. Zhu, J. C. Chan, X. Zhu, Y. Liu, G. Yadavalli, D. Yan. 2016. Catalytic separation and depolymerization of lignin for effective production of aromatic hydrocarbons. 2016 ASABE Annual International Meeting, Orlando, Florida, July 17 - 20, 2016
• Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: X. Zhu, G. Yadavalli, H. Lei, X. Zhang, M. Qian, J. C. Chan, L. Zhu, Y. Liu, , D Yan. 2016. Protein based solid electrolyte from abundant Canola meal protein. 2016 ASABE Annual International Meeting, Orlando, Florida, July 17 - 20, 2016

Progress 01/01/15 to 12/31/15

Outputs
Target Audience:Biomass industrial companies, battery materials and battery related industries, lignin, starch, and protein producers, processors, wholesalers, and retailers: Carbon Cycle Crush LLC, Creative Energy Systems Inc., Gen-X Energy Group Inc., North America Green Pulp Inc., Washington Bio-oils Inc., Archer Danieis Midland Co. Efforts: Formal classroom instruction (new course lectures/sessions) about the project in BSysE 593 Renewable Energy Technologies (Fall 2015, 8 students), BSYSE 552 Advanced Biological Systems Engineering Topics (Spring 2015, 5 students), MSE 402 Polymeric Materials (fall 2015, 36 students), and EconS 351 Introduction to Food and Agricultural Markets (fall 2015, 45 students); Development of curriculum (new lecture sessions on biomass conversion and separation; bio-material based electrolytes; economic science and agricultural markets); Trained graduate and undergraduate students who work on this project will eventually join the workforce and contribute to the effort of utilizing biomass and developing new battery technology for the future energy needs: PhD students Xiaolu Zhu, Lei Zhu, Charlie Shaw, Allen Eyler, Xuewei Fu; MS students: Gayatri Yadavalli, Yupeng Liu, Xiaolin Wang; undergraduate students: Allison Ocudiero, Stephanie George; New experiential learning opportunities for involved students in the project; Seminar to local chapter of societies, such as MRS WSU student chapter, WSU ShowCase Conference, Pacific Northwest Chapter of the AVS, regional and national conferences (see session of publication list in Product and the following outreach communications and presentations); Extension and outreach (outreach communications and presentations to biomass industrial companies, battery and related industries): H. Lei, L. Zhu, X. Zhang, Y. Wei, Y. Liu, G. Yadavalli. Jet fuels of aromatics and cycloalkanes from integrated catalytic processes of diverse lignocellulosic biomasses. 2015 Inaugural Clean Technology Showcase, Washington Clean Technology Alliance, Bell Harbor Conference Center, Seattle, WA, June 22, 2015. Adult Contacts direct: 300 H. Lei. 2015. Biofuels and bioproducts from lignocellulose biomass. 2015 Meeting with Creative Energy Systems Inc. / Washington Bio-oils Inc. on June 11, 2015 at WSU TriCities. Adult Contacts direct: 6 H. Lei. 2015. Biofuels and bioproducts from lignocellulose biomass. 2015 Meeting with MSS Sustainable LLC/ USS International LLP/ Qilu University of technology / North America Green Pulp Inc. on May 29, 2015 at WSU TriCities. Adult Contacts direct: 5 Invited presentation: H. Lei. 2015. Green engineering of processes, from biomass. 2015 Delegation from Shanghai Environmental Protection Bureau, Academy of Environmental Sciences, and Shanghai Geodetic Institute, Puyallup, WA, April 10, 2015. Adult Contacts direct: 25: 11 from China, and others from WA Department of Ecology, Pierce County Public Works, Pacific Partners Environmental Consulting, LLC, GeoEngineers, Inc. X. Zhang, L. Zhu, G. Yadavalli, Y. Wei, Y. Liu, D. Yan, H. Lei. 2015. Cycloalkanes and aromatics for jet fuels from integrated catalytic processes of diverse lignocellulosic biomasses.2015 JCATI Research Symposium: Advancing Public-Private Partnerships in Aerospace, Seattle, WA, April 20, 2015. Adult Contacts direct: 250 Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Training activities: The funding received from this project has been used to support 2 post-docs, 7 PhD candidates, 2 MS students, and 2 undergraduate students in the WSU Biological Systems Engineering Program, Material Science and Engineering Program, and Economic Science Program. 7 PhD students, 2 MS students, 2 undergraduate students, and 2 post-doc research associates learned to develop new technologies, new processes, new materials, new econometric techniques, protocols, LCA and market analysis. Post-docs and PhD students have developed the experience assisting MS and undergraduate students attaining greater proficiency in developing new technologies and conducting experiments. PIs incorporated the research results from this project in teaching BSysE 593 Renewable Energy Technologies (Fall 2015, 8 students), BSYSE 552 Advanced Biological Systems Engineering Topics (Spring 2015, 5 students), MSE 402 Polymeric Materials (fall 2015, 36 students), and EconS 351 Introduction to Food and Agricultural Markets (fall 2015, 45 students). There were 94 students in the classes and learned our processes and research results. Professional development activities: PIs had a monthly conference calls and active collaborations among each other, and their research group had weekly meetings to make sure the good progress of the project. PIs and their research teams had updates presented at group meetings. Students developed collaboration skills and exchanged technical information cross group knowledge. PhD Students and Post-docs have participated and presented papers at American Society of Agricultural and Biological Engineers (ASABE) 2015 Annual International Meeting at New Orleans, Louisiana, July 26 - 29, 2015, and 2015 Pacific Northwest Chapter of the AVS, Mount Hood, Oregon, Sep. 30 - Oct. 2, 2015, and 2015 WSU ShowCase Conference, Pullman, WA, March 28, 2015. How have the results been disseminated to communities of interest?The PIs and their students and post-docs created posters and/or made oral presentations to showcase findings on and off campus: annual campus-wide Academic Showcase, and present the study results at the PNWAVS symposia fall 2015. The research findings were communicated to the general public via national and international conferences, such as American Society of Agricultural and Biological Engineers (ASABE) Annual International Conference. The published and submitted journal papers and proceedings can be found in previous sessions in this progress report. We also disseminated our research results to communities by attending industrial directed outreach conferences and presenting to industrial delegations. Our outreach dissemination efforts includes: 2015 Inaugural Clean Technology Showcase, Washington Clean Technology Alliance, Bell Harbor Conference Center, Seattle, WA, June 22, 2015, adult contacts direct: 300; 2015 JCATI Research Symposium: Advancing Public-Private Partnerships in Aerospace, Seattle, WA, April 20, 2015, adult contacts direct: 250; 2015 Meeting with Creative Energy Systems Inc. / Washington Bio-oils Inc. on June 11, 2015 at WSU TriCities, adult contacts direct: 6; 2015 Meeting with MSS Sustainable LLC/ USS International LLP/ Qilu University of technology / North America Green Pulp Inc. on May 29, 2015 at WSU TriCities. adult contacts direct: 5; 2015 Delegation from Shanghai Environmental Protection Bureau, Academy of Environmental Sciences, and Shanghai Geodetic Institute, Puyallup, WA, April 10, 2015, adult contacts direct: 25: 11 from China, and others from WA Department of Ecology, Pierce County Public Works, Pacific Partners Environmental Consulting, LLC, GeoEngineers, Inc. What do you plan to do during the next reporting period to accomplish the goals?During the next year of 2016, we will continue working on understanding of protein separation with functional analysis experiments, and lignin separation using the new biocarbon acid catalyst with understanding of microscopic structure and identification and controlling of functional groups which are related to lignin separation efficiency. We will continue developing and fabricating the soy/canola protein-based SPEs by controlling the denatured structure of proteins and studying their structures and properties of the soy/canola protein/lignin-based polymer electrolytes to improve mechanical and electrochemical properties. We will continue market analysis (e.g., farm, wholesale, retail levels) for inputs and batteries that will provide input into the cost model and the partial equilibrium model, as well as model development. We anticipate that we will meet the objectives of the proposed work in a timely manner.

Impacts
What was accomplished under these goals? Impact: Battery disposal causes deteriorating effects on environment and human health, as the released harmful substances are easily consumed by plant roots and accumulated in fruits, vegetables and grass, which are consumed by human beings. Recycling batteries is a much better option than dumping them in landfills, but it is expensive involving time/energy consuming processes. This USDA supported project is to develop bio-based battery materials and create a "green" solution for solid electrolytes in order to remove the liquid electrolyte from batteries to get rid of leakage, spillage, or damage, which is important to the environment and economy as well as agriculture. The approach is to apply abundant plants, such as soy and canola, as the base component to develop safe, renewable and battery electrolyte materials in both fundamental and applied sciences. The project team is focused directly on integrating the technologies employed to convert this agricultural feedstock into bio-battery materials. The project provides a novel renewable energy storage system to the industries for sustainably producing bio-battery from wood residuals derived from biomass industry, and canola meals, a low-value byproduct from biodiesel industry, and directly contributes to adding value and profit for those industries and creating new technology for battery industry. The team is lining and engaging related industries in our outreach and education efforts and involved them in the development of a biobased battery. Major activities completed / experiments conducted / data collected / results / key outcomes: Specific objective (1): Task 1: Protein extraction and kinetics (Dr. Lei's team) The direct alkaline method was used for protein extraction from expeller pressed canola meal. The sodium hydroxide concentration and time were varied during extraction. It was found in that varying time does not have a significant effect on the protein extraction rate. Results indicated that an increasing alkaline concentration increased the total protein yield. Based on a two site kinetic model, higher concentrations of alkaline also assist in breaking intact meal molecules, facilitating the release of protein. Protein isolated from canola meal was supplied to Dr. Zhong for electrolyte synthesis. Task 2: Lignin separation and kinetics (Dr. Lei's team) This task is developing a new biomass derived carbon (biocarbon) acid catalyst used to replace sulfuric acid in lignin separation. Biocarbon was produced from microwave pyrolysis of corn stover which demonstrated the influence of pyrolysis conditions on the production and surface functionality of biocarbon by FTIR spectra. A low-temperature process for a new biocarbon solid acid catalyst is being developed and we are optimizing the lignin separation process using the new biomass derived solid acid catalysts. Source of lignin influenced the lignin extraction yield as well as its Klason lignin and contaminants content. The total phenolic structures were detected in highest amounts which can give the lignin potential for oxidation which can enhance the chemical bonding in bio-battery application. The lignin with the highest purity was supplied to Dr. Zhong for electrolyte synthesis. Task 3: Effects of denaturation on the structure and properties of soy protein composites (Drs. Zhong and Scudiero's teams) The morphology and properties of the PEO/SPI composites are strongly affected by the SPI denaturation conditions. The dialysis-treated SPI has the smallest particles resulting from the greatest number of intermolecular bonds broken, and therefore the denaturation is most effective compared to thermal and mixed solvent treated samples. Results of the light-scattering experiment are in strong agreement with this result, very little scattering occurs when the laser beam is passed through the dialysis denatured SPI solution, indicating a small particle size. Furthermore, the difference in denaturation degree is demonstrated in their dielectric and mechanical properties. Both the smaller particle size and unique mechanical behavior for the dialysis-treated samples show that this denaturation technique is the most effective of the three methods studied here. Task 4: Effects of salt type on the structure of soy protein composites (Drs. Zhong and Scudiero's teams) In this task, the morphology of SPI has been controlled within a PEO matrix by adjusting the interactions within and between protein chains; this has been accomplished by adding different types of salts to the system. The interactions between the ions and SPI are determined by the availability of ions in the solution. Higher salt concentrations or salts with higher solubility in water result in a larger particle size. The matrix morphology and properties are also controlled by the salt type: choosing a PEO-soluble salt results in a more amorphous matrix with stretchable behavior, while choosing a PEO-insoluble salt preserves the PEO crystalline structure and leads to an increase in fracture toughness. The change in SPI morphology via the addition of salts may also influence the mechanical properties. Task 5: Effects of protein type on structure and properties of protein composites (Drs. Zhong Scudiero's teams) In this task, the mixed solvent-treated CP has more transparent solution, indicating a small particle size, and therefore the denaturation is most effective compared to pH 11 and DI treated samples. As the protein concentration increases, the ionic conductivity PEO/CP/salt is reduced. Compared to CP, electrolyte samples with SPI show higher ionic conductivity. Specific objective (2): Task 6: Cost estimation (Drs. Tozer and Marsh's team) We developed protocol to collect primary data on costs from experiments, initiated development of partial equilibrium model, and completed an overview of LCA for conventional and bio - batteries. We are in the process of collecting data for retail battery prices, collected secondary data (from U.S.D.A., U.S. Census, etc,) that is necessary to estimate cost and returns, including time series data on lignin, starch, and protein inputs, elasticities, etc. We initiated development of baseline prices for batteries from market data, and preliminary examination of trends for lignin, corn starch, and soybean meal data using monthly data 2002 to 2015. Time series data for corn starch and protein from soybean are readily available in both domestic and exports/imports, as well as future prices. These data are important to understand past, current, and future price trends that feed into calculating cost estimates and outcomes from the partial equilibrium model. Change in Knowledge: Increased understanding of separation kinetics for protein from canola and lignin from biomass, and their roles in solid electrolytes and bio-battery; Improved understanding of the behavior of soy/canola protein-based SPE at the microscopic and spectroscopic levels; Increased our knowledge and understanding of the effects of Li ions on molecular structures of soy/canola protein and enhance our knowledge of the interaction of the soy/canola protein-SPE with commercial electrodes; Improved the understanding of basic trends and structural changes underlying the cost structure, which will improve our ability to project impacts on the agricultural economy; Change in Action: A new way to fabrication of solid electrolytes and lay foundation for achieving bio-battery by using biomass derived lignin and proteins from canola and soybean. Change in Condition: Positive impact on the agricultural economy and on the use of the abundant plants as raw materials for fabricating bio-battery materials; The bio- based solid electrolytes are renewable and non-polluting to solve the central challenge of leakage, spillage, or deteriorating effects of current rechargeable liquid lithium batteries on environment and human health to be faced worldwide;

Publications

• Type: Journal Articles Status: Submitted Year Published: 2015 Citation: A. Eyler, T. Liu, W.H. Zhong, Effects of Denaturation on the Structure and Properties of Soy Protein Composites, Journal of Composites and Biodegradable Polymers, under review, Oct. 27, 2015
• Type: Journal Articles Status: Submitted Year Published: 2015 Citation: Q. Bu, H. Lei, L. Wang, X. Zhang, Y. Wei, L. Zhu, Y. Liu, G. Yadavalli. 2014. Phenols production and kinetics study of catalytic pyrolysis of lignin: comparison of microwave and conventional heating. Fuel, under review, Oct. 2015.
• Type: Journal Articles Status: Submitted Year Published: 2015 Citation: X. Zhang, H. Lei, L. Zhu, Y. Wei, Y. Liu, G. Yadavalli, D Yan, M. Qian, J. C. Chan, X. Zhu, J. Wu, S. Chen. 2015. Development of a catalytically green route from diverse lignocellulosic biomasses to renewable cycloalkanes for jet fuels. Catalytic Science & Technology, under review, Sep. 2015.
• Type: Journal Articles Status: Published Year Published: 2015 Citation: L. Zhu, H. Lei, L. Wang, G. Yadavalli, X. Zhang, Y. Wei, Y. Liu, S. Chen, and B. Ahring. 2015. Biochar of Corn Stover: Microwave-assisted Pyrolysis Condition Induced Changes in Surface Functional Groups and Characteristics. Journal of Analytical and Applied Pyrolysis, 115, 149-156. doi:10.1016/j.jaap.2015.07.012. Published Sep. 2015
• Type: Book Chapters Status: Submitted Year Published: 2015 Citation: I. Cybulska, G. Brudecki, H. Lei. 2015. Organosolv delignification of lignocellulosic materials, In Driving the Future: Advances in Cellulosic Ethanol and Advanced Drop-In Biofuels. Ed. B. Simmons. Future Science, under review, Feb. 2015
• Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Allen Eyler, Tian Liu, Yu Wang, Louis Scudiero, Safe and Flexible Battery Materials by Applying Natural Plants, 2015 Pacific Northwest Chapter of the AVS, Mount Hood, Oregon, Sep. 30  Oct. 2, 2015.
• Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: L. Zhu, H. Lei, X. Zhang, G. Yadavalli Y. Wei, Y. Liu. 2015. Preparation and Characterization of Biochar and Activated Carbon Based Solid Acid Catalysts for Catalytic Microwave Pyrolysis. 2015 ASABE Annual International Meeting, New Orleans, Louisiana, July 26 - 29, 2015
• Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: L. Zhu, H. Lei, X. Zhang, G. Yadavalli Y. Wei, Y. Liu. 2015. Production of hydrocarbons from biomass through in situ microwave-assisted catalytic pyrolysis using carbon catalyst. 2015 WSU ShowCase Conference, Pullman, WA, March 28, 2015