2017 Summer Program Success

Each summer we ask for anonymous feedback from our researchers.  Below are a few comments we received:

  • I loved the work environment here at MSUBI.  All the employees here were great and very helpful.  My favorite part was meeting new people and making some life long friendships.
  • The project was geared towards my general understanding experience and future use of skills.  It was definitely assigned in the direction of my interests.
  • Communication was on-going, so if changes needed to be made or difficulties with the project were present then adjustments were made.
  • The experience provided a valuable practice for graduate school lab practices.  Work was independent but help from those with more experience could be sought out.
  • I enjoyed my colleagues the most out of the internship.  They are all very intelligent and great for advice and seeking information.  The tours were also super interesting because I had never seen this type of chemistry application before.  I loved it.
  • Science takes time.  Reactions will run and fail, staying optimistic is the real skill to develop with the research because it does not go perfectly according to plan.
  • This was a great 10 week program.  I loved working here and will be very sad to leave.  Working here has been the best experience I have ever had.
  • I will be letting my department know about the program.

Suggestions for improvement?

  • Maybe go kayaking or mini golfing.

Great suggestion.  I like the way you think.

Thanks to all of our summer researchers.  Some great advances were made this summer and it was due to your hard work.  We are excited about the future applications of your research, and we are also very excited about your futures!  We had a great summer and I’m glad to hear from your comments that you did too.  Please keep in touch, you know where to find us…

Amber Dood and Nick Mortimer

Amber and Nick collaborated on a poster for presenting at the Schaap Symposium…

High Potential Organic Redox Shuttles for Overcharge Protection in Lithium Ion Batteries;  Amber J. Prins, Nicholas J. Mortimer and Thomas F. Guarr*

Lithium ion batteries are universally used today, but unsafe conditions can occur if expensive electronics are not used to prevent overcharging. These electronics can double the price of the battery pack, so it is important to find a more economical way to control charging. “Redox shuttles” are potential additives to batteries to shunt the excess current and allow the battery to be safely used to its full capacity. When overcharge current flows through a battery, the redox shuttle is oxidized to form the radical cation which diffuses across the cell and is reduced at the anode. This effectively turns overcharge current into thermal energy which can be readily controlled, thereby preventing battery degradation. Numerous organic compounds have been investigated as shuttle candidates, but finding materials that possess the following qualities proves challenging: 1) high oxidation potential (generally > 4.2 V vs. Li/Li +); 2) solubility in battery electrolytes; 3) compatibility with other electrolyte components; 4) high stability in both reduced and oxidized forms (leading to long cycle life).

This project is made possible in part by a grant from the Community Foundation of the Holland/Zeeland area, as well as through financial support from a Michigan Strategic Fund grant through Lakeshore Advantage to MSU.

Tom Guarr also presented similar posters at the 68th Annual International Society of Electrochemistry in Providence, RI on August 30 and at the 232nd Electrochemical Society meeting in National Harbor, MD on October 5, 2017.

Shane Mann

Shane joined us in January this year from Central Michigan University.  He has been researching and synthesizing full time for us ever since.

Multifunctional pyridinium systems for non-aqueous redox flow batteries;  Shane Mann, Nick Mortimer, Anthony Petty II, Jessica Scott, Dr. Tom Guarr*

Long-term, reliable energy storage on an industrial scale requires a battery system that is both incredibly cost efficient while also exceptionally simple to maintain over time. A proposed solution to large-scale energy storage is to reduce the cost and environmental impact of grid storage through the use of sustainable electrochemically active organic compounds.

The development of stable catholyte and anolyte materials for organic redox flow batteries (ORFB) minimizes the proliferation of toxic transition metal compounds, while simultaneously affording added assurance to nearby population centers in the event of any spill or leak. In order to maximize power output and meet modern electrical demands, we have developed a series of multi-electron, quinoidal systems. Using substituted polycyclic heterocycles such as phenothiazines or carbazoles in conjunction with extended bispyridinium anolytes, practical ORFBs have been developed.

Great work Shane, keep on developing new compounds and keeping us busy.

Korey Cook

Korey started at MSUBI early in 2017.  He is a man of many talents and interests.  He was the  lone engineer in the lab this summer and managed to create a working redox flow battery prototype system.  Outside of our lab, he came very close to installing a working river turbine in the Grand River and got engaged to his girlfriend this summer.

Research and Development of a Highly Efficient and Cost Effective Redox Flow Battery; Korey Cook, Dr. Tom Guarr, Shane Mann and Brian Chiou

Renewable energy generation technology is growing rapidly and increasingly relies on energy storage systems to balance fluctuating energy demand.  The high manufacturing cost and limited life cycle of current commercial battery technologies inhibits large-scale grid storage.  This research project focused on creating an organic redox flow battery prototype that demonstrates significantly lower manufacturing cost and minimal electrolyte degradation to increase total charge cycles.  The developed prototype system includes electrolyte tanks, pumps, and a reactor that continuously and evenly distributes electrolyte solutions across an ion exchange membrane.  This battery system demonstrates a flow battery that can be scaled for long-term energy storage.

Korey is a Mechanical Engineer from Hope College, class of 2016.  This fall, he will continue to work with us, and he will begin his MS in Engineering program at Michigan State University with Tom Guarr and Andre Benard as his advisors.  We are very excited to watch him continue his work developing new-generation redox flow batteries.

Anthony Porath

Anthony is an undergraduate at Alma College.  He is a Chemistry major with emphasis in Organic Synthesis.

Synthesis of Tri-functional Pyridinium Compounds for Electrochemical Applications; Anthony Porath, Dr. Thomas Guarr

Quaternary salts of tri-functional pyridinium compounds could offer small, multi-electron organic components to be used in electrochemical processes. Not many organic molecules of this type are in common use. The methyl and hydrogen substituted versions have been successfully prepared utilizing Suzuki coupling. The phenyl substituted variety is in progress using a pyrylium intermediate. Future work will involve inserting a p-phenylene bridge between the pyridine and the central ring, and working on hexa-functional pyridinium complexes.

Anthony worked very hard in our lab this summer.  He has a bright future ahead.  He will graduate from Alma College next spring and move on to great things.  Remember to keep in touch and let us know what your future holds.

Rachel Beltman

A graduate of University of Detroit Mercy, with a degree in Biochemistry, Rachel synthesized many compounds for us this summer.

Extended Bispyridines: an Approach to Molecular Wires; Rachel Beltman and Dr. Thomas Guarr

Recently, redox flow batteries (RFBs) have been intensively researched for grid-level energy storage applications. In addition to offering an inexpensive option for long term storage, this technology also provides a means to achieve the load leveling required to effectively utilize renewable sources of energy. Bispyridinium compounds are of interest in RFBs because they offer reasonable voltages, good stability, and relatively high energy densities. We have developed a series of extended bispyridinium systems that incorporate p-phenylene (or longer) bridges can also be used as anolyte materials.

The extension of the π system in such compounds allows for an increase in cell voltage, along with a corresponding improvement in energy density. Stability is also improved because the ability to accept two electrons and achieve a stable, closed shell reduced state helps to avoid the buildup of less stable radical intermediates. In this study, the effects of substituent choice and bridge length on cell potential, molecular weight, durability, and ease of synthesis are explored.

Rachel has proven herself to be quite talented at organic synthesis, and she is continuing her studies at Wayne State this fall to pursue a doctorate in Organic Chemistry.  We appreciate all of your contributions this summer, Rachel.  Enjoy your time at Wayne State.

Anna-Catharina Wilhelm

Anna-Catharina came to the OESL with a degree in Biochemistry and Molecular Biology from Michigan Technological University.  She spent time this summer pinning down the degradation pathways of some of our redox shuttle compounds.

Fragmentation Analysis of Labeled Phenothiazines via Ion Trap Mass Spectrometry; Anna-Catharina Wilhelm and Thomas F. Guarr

The incorporation of organic compounds that display reversible electrochemical oxidation at very high potentials into lithium batteries has been shown to prevent dangerous overcharge conditions.  In order to better understand possible degradation pathways of such compounds (typically called “redox shuttles”), their breakdown was examined by mass spectrometry.  Previous studies of shuttle stability have been limited to empirical testing, modeling, or very limited analysis of reaction products.  In this project, ion trap mass spectrometry was used to explore the sequential fragmentation of several deuterium labeled compounds that are good candidates for such applications.  Using this approach, it was possible to selectively isolate and fragment both the oxidized (cation radical) and protonated forms of the parent compound.  Careful analysis of the data clearly shows that these two species break down by different mechanisms.  The results will aid in the design of more durable second-generation redox shuttles.

Anna-Catharina is beginning her PhD pursuit at the University of British Columbia this fall.  Best wishes for your future Anna!  Keep on running and enjoy our neighbor to the north.