Performing Department
(N/A)
Non Technical Summary
This project will demonstrate the use of pine wood derived graphene oxidematerials for two diverse applications: lithium-ion batteries and paving blocks. Additionally, the project will include further research into how changes in processing affect the finalproducts. This research is critical for scale-up and commercialization to improve the effectiveness of the process and provide scale-up feasibility.Wood feedstock is first converted to biochar, then to graphene oxide,a viable product. The materials produced in this way have similar properties to graphene materials produced via graphite but have different structural characteristics. The differences offer advantages for particular applications, such as battery anode materials. Further treatment produces reduced graphene oxideand highly reduced graphene nanosheets, also viable products.The end use sectors for project materials include battery manufacturing, pharmaceuticals, concrete manufacturing, optics, filtration, and composites. These materials, depending on the level of processing, can cost thousands of dollars per kilogram, but the development proposed in this project can reduce these costs and increase availability of these powerful materials. It is important to utilize the abundant woody biomass available annually, not only to help with climate change mitigation, but to produce a value-added product from forest resources and wood waste. The synthesis method is an improvement over other known methods since it is faster, easier to perform, and uses fewer reagents. This patented process has proven successful with biochar as feedstock.
Animal Health Component
0%
Research Effort Categories
Basic
(N/A)
Applied
50%
Developmental
50%
Goals / Objectives
The overall goal of this project is to utilize woody biomass to produce high-value products while simultaneously expanding graphene use via lower cost and increased availability. The high-value products to be examined in this project are graphene oxide materials for use in lithium ion batteries and as concrete block paver additives. The Objectives of this Phase II SBIR project are:1.Determine how autothermal fast pyrolysis affects the synthesized material performance2. Determine the effect of heating rate under air and argon on material properties3. Demonstrate feasibility of recycling and reuse of process acid4. Demonstrate feasibility for conversion of process NOx to nitric acid for re-use5. Further optimize the synthesis process by examining important time, temperature, concentration, and sonication parameters6. Demonstrate ability to produce LIB anodes using biochar derived rGO materials7. Fabricate and test LIBs using half coin cell, full coin cell, and pouch cell configurations8. Examine the use of biochar with GO as aggregate replacement in paving blocks.
Project Methods
The methods for this Phase II project are described in the following Tasks.Task 2. Perform autothermal fast vs. slow pyrolysis study - Biochar will produced using the autothermal fast pyrolysis method at ~500°C by Dr. Bakshi at the Iowa State University Bioeconomy Institute. This material will be characterized using various instrumentation which includes but not limited to elemental analyzer (EA), TGA, inductively coupled plasma optical emission spectroscopy (ICP-OES), and FTIR. The biochar will be transferred to ARD for conversion to rGO products and characterization, then will be transferred to ISU for battery testing.Task 3. Synthesize materials & characterize3.1 Biochar Synthesis - Biochar will be synthesized by charring pine wood under N2 atmosphere at a temperature of 600? and using a heating rate of 10?/min with two hours dwell. After charring, the material is milled before GO synthesis. Biochar synthesis will be performed by ARD.3.2 GO Synthesis - Graphene oxide will be synthesized using biochar via the nitric acid synthesis method. Briefly, this method involves adding biochar to the nitric acid solution, and the reaction takes place at 70? under continuous stirring and sonication for 4 hours. Solution is then filtered and the GO is dried at ~80?. GO synthesis will be performed by ARD.3.3 rGO Synthesis - Reduced graphene oxide will be synthesized via thermal treatment of the GO under inert atmosphere. Reduction temperatures of 1100?, 1400?, 1700?, 2000?, 2200? and 2500? will be used to determine the effect of reduction temperature on battery performance. The 1100? rGO will be reduced using a tube furnace, while all other temperatures will use a graphite furnace. Synthesis of rGO will be performed by ARD.3.4 Material Characterization - All materials will be characterized using Raman spectroscopy, FTIR, XRD, TGA, N2 gas sorption by ARD. XPS and SEM will be performed by ISU.Task 4. Examine effect of heating and reduction ramp rate on GO materials - Biochar derived GO will be examined under various heating ramp rates. Small samples will be examined using a thermogravimetric analyzer (TGA) under argon and air atmosphere. Heating rates from 10?/min to 50?/min will be examined for sudden material expansion as indicated by a rapid weight change. This testing will be performed by ARD.Task 5. Examine recycling of recovered acid5.1 Optimize ratio of recycled acid to makeup acid - ARD will investigate the impact of recycling process acid by replacing fresh acid at 30%, 60%, and 90% and performing synthesis five times with the used acid collected and used as the recycled acid for the next synthesis. The best candidate is continued for an additional five syntheses. The GO produced at every step will be examined using FTIR, Raman, and XRD. This task will be performed by ARD.5.2 Examine contaminant buildup and recycled acid quality - After every synthesis in Task 5.1, the acid will be examined for quality and buildup of contaminants via ICP-OES, FTIR, and pH measurement. This task will be performed by ARD.Task 6. Determine effect of process acid dilution - GO synthesis will be performed using varying levels of dilution from 70% to 30% (as received) nitric acid. All other synthesis parameters as described in Task 3.2 will be used. The GO products will also be converted to rGO, and all materials will be characterized as described in Task 3.4. Analysis of results will be used to determine acceptable dilution of process acid, which is a critical parameter for scale-up. Task 6 will be performed at ARD.Task 7. Examine capture and recycling of NOx - The acid produced in the scrubber system will be examined via pH measurement and FTIR to determine concentration and quality. Distillation will be used as needed for increasing concentration. To determine if the recovered acid is suitable for use, GO synthesis will be performed using the recovered acid and synthesis parameters as described in Task 3.2. rGO will also be produced and all materials will be characterized as described in Task 3.4, namely Raman, FTIR, XRD, and BET, while XPS and SEM will be performed on selected samples. Results will be compared to synthesis using fresh acid to determine if recovered acid is suitable for use in the synthesis process. Task 7 will be performed by ARD.Task 8. Determine effect of reaction time - GO synthesis will be performed using reaction times of 0.5, 1, 2, and 3 hours, with all other synthesis parameters as described in Task 3.2. Also, rGO will be produced, and all materials will be characterized as described in Task 7 for comparison to results from the standard 4-hour synthesis. Effective shorter reaction time can increase capacity at production scale and is important for scale-up. Task 8 will be performed at ARD.Task 9. Determine effect of sonication time - GO synthesis will be performed using sonication times of 0, 1, 2, and 3 hours while using a standard 4-hour total reaction time. Synthesis will otherwise be performed as described in Task 3.2, and the GO and subsequent rGO will be characterized as described in Task 7. Results will determine the amount of sonication needed to produce an equivalent product, which can reduce operating costs and energy consumption for the process. Task 9 will be performed at ARD.Task 10. Produce and test lithium-ion batteries using biochar derived anode material10.1 Produce anodes and assemble LIBs - Anodes for this project will be produced using rGO in different combinations. Anodes will be constructed both with and without 10% conductive carbon additive to determine if an additive is necessary with the rGO material. All anodes produced will also use 10% PVDF binder. Similar anode configurations using graphite rather than rGO will also be produced for performance comparisons. Using rGO from the six different reduction temperatures, the anode material combinations (all with 10% PVDF binder) will examine 90% rGO, 80% rGO/10% conductive carbon, and 90% graphite and 80% graphite/10% conductive carbon for comparison. The anodes will be made by casting slurries of the above combinations onto copper foil, drying the slurries, and cutting to the necessary dimensions. The anodes will then be used in assembly of the LIBs in half coin cell, full coin cell, and pouch cell battery formats. rGO materials will be provided by ARD to Johnson group at ISU where anode fabrication and battery assembly will be performed.10.2 Test LIBs - The Johnson group at ISU will test the assembled lithium-ion batteries for galvanostatic (constant current) charge - discharge measurements and cyclic voltammetry measurements where the cells are swept through a voltage range. Additionally, Electrochemical Impedance Spectroscopy (EIS) will be utilized. This involves applying an alternating voltage and then the alternating current response is recorded and analyzed.Task 11. Produce biochar/GO block pavers with varied biochar and GO content - Biochar contents of 20 to 40% along with cement as a binder, and GO contents of 0%, 0.25%, and 0.5% of cement will be used for mixes. Adequate water-cement ratios will be determined to provide good workability for fabricating paving blocks and obtain adequate engineering properties. Paving block samples will be prepared at 200 mm x 100 mm x 60 mm which meets the ASTM C936 (2023), followed by curing in a wet room for at least 28 days. Samples will be tested for bulk density and compressive strength for a minimum of 7 and 28 days (ASTM C140 (2023)). Design mixes that meet or exceed the strength requirements specified in ASTM C140 (2023) will be selected for water absorption test - ASTM C140 (2023), abrasion resistance test - ASTM C418 (2020), and freeze-thaw durability test - ASTM C1645 (2022). Selected samples will also be selected for microstructural analysis using SEM. Task 11 will be performed by UW.?