Different models for class implementation:
1. Professor-led student discussion; monitor quantity and quality of individual student input.
2. Student-led presentation and discussion (pairs work well); grading of presentation and quality of question answers.
3. Student written report answering Literature Discussion questions.
We have not implemented this Literature Discussion in class yet.
Lithium battery technology is an evolving field as commercial requirements for storage and use of energy demand smaller, safer, more efficient and longer-lasting batteries. Copper ferrite, CuFe2O4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe2O4. The results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging. Students learn about normal and inverse spinel structures, solid cathode electrochemical processes and the use of X-ray absorption spectroscopy to figure out local structure, oxidation state and coordination environment.
1. Students should become familiar with the parts and charging/discharging of a solid-state lithium battery, and relate to introductory discussions of redox chemistry.
2. Student should learn about spinel and inverse spinel structures, and be able to relate to cubic unit cell types presented in General Chemistry.
3. Students should learn how X-ray absorption spectroscopy can be used to evaluate oxidation state and local coordination environment in a solid.
The powerpoint presentation about X-ray absorption spectroscopy can be used to provide background for the analytical techniques used in this research. The classic spinel structure should be discussed in class. Otherwise, this can be implemented like any other Literature Discussion.
Students will gain experience interpreting the basic features of cyclic voltammograms, including: half-potential, electrochemical reversibility, chemical reversibility, and scan rate dependence
Students will learn the physical origins of the "duck" shape of a reversible CV using the Nernst equation and diffusion concepts
Students will learn what analytical methods are available using CV
None yet. I'm considering creating an activity using the information in this website, but for now I just wanted to share this resource.
I do not grade this activity, but if I did, I would look for class participation in the discussion or assign several of the questions to be turned in at a later date.
My impression of this activity is that it really helps students see the value of redox chemistry. In my experience, the aspects of redox chemistry we teach students (balancing equations, calculating cell potentials, etc.) seem both difficult and esoteric. This activity reinforces these concepts while demonstrating their importance to modern life. One of the biggest realizations the students come to is the relationship between cell voltage and the mass of the materials involved in the redox reaction.
This In-Class Activity is a series of instructor-guided discussion questions that explore lithium-ion batteries through the lens of simple redox chemistry. I use this exercise as a review activity in my Descriptive Inorganic Chemistry course to help prepare for examinations. However, my primary purpose with this exercise is to impress upon students how basic concepts in redox chemistry and solid-state structure are directly relevant to technologies they use everyday. I do not focus too heavily on the design or operation of the batteries themselves, as other exercises published on VIPEr already do a very good job of that. My intention is to demonstrate how a basic knowledge of redox chemistry is the first step in understanding seemingly complex technologies.
The primary goal of this In-Class Activity is for students to solidify their understanding of redox reactions, cell voltages and the relationship between electrical energy and potential. The exercise is also designed to show students how these considerations are part of the design of modern batteries. A secondary aspect of the activity explores the solid-state structure of metal-oxides and how these materials are important to the operation of the battery. At the conclusion of the activity, the student should be familiar enough with calculaing cell voltages and free energy changes that they can critically evaluate the components of a standard battery.
I display the pdf file on screen and use the white board to work out simple arithmetic aspects of the exercise, while soliciting responses from the class.
The problems presented here represented half the points on the final exam – I have included point totals to give an idea of the weight assigned to each problem.
Twelve students were enrolled in my course in the fall 2016. The average overall score for these problems was 78%.
For problem 1b, I calculated the oxidation numbers using the familiar general chemistry method of assigning oxygen as –2 and hydrogen as +1. Students recently coming through organic may have some other way to do it, and you may need to provide directions for your students about your preferred method. I think I could have worded part (c) better to try to emphasize the redox processes involved. I wanted them to think of combustion, but I think they needed to be specifically prompted, such as "Give an example of the combustion processes that generate CO2 and trace the oxidation state of carbon through the reaction." Overall my students scored 86% on problem 1.
The second problem (about another method that could be used to measure d-spacing) was fairly hit or miss. Five students got full credit, six students got 3 points, and one got zero. Eleven out of twelve did answer part (a) correctly. I realized as I made this LO that the article says the carbon-based material doesn’t diffract X-rays, but doesn’t actually directly explain whether or not the Cu nanoparticles diffracted X-rays, so you may need to adjust the question to be technically accurate.
Question three (re: surfactants in nanoparticle synthesis) referred back to knowledge from earlier in the course. The overall score was 61%.
Question 4 (define and describe electrodes) was fairly straightforward, and students scored 85%.
Question 5 caused some confusion, as some students missed that I was looking for “carbon-containing” products only. I didn’t count off for that mistake, but it made the problem harder for students who included hydrogen in each box. Overall, students did very well on this problem (89% correct).
Question 6 – again, not too much trouble here (84% correct).
Question 7 – I was surprised that students didn’t do better on this question, as I thought that water reduction was mentioned often in the article. Only three (of 12) students scored 5 points on this problem, and the average score was 53%. This was probably my favorite question, as it foreshadows electrochemistry topics I cover in my inorganic course.
This literature discussion is based on an article describing the use of copper nanoparticles on an N-doped textured graphene material to carry out the highly selective reduction of CO2 to ethanol (Yang Song et al., “High-Selectivity Electrochemical Conversion of CO2 to Ethanol using a Copper Nanoparticle / N-Doped Graphene Electrode” ChemistrySelect 2016, 1, 6055-6061. DOI: 10.1002/slct.201601169). The article provides a good introduction to the concepts of electrochemical reduction, selectivity and recycling of fossil fuels. The literature discussion assignment shared here was used as half of the final exam in a half-credit nanomaterials chemistry course, but could be adapted for use as a take-home or in-class assignment.
After reading this paper and working through the problems, a student will be able to:
- assign oxidation states to carbon and trace the oxidation and reduction of carbon through fossil fuel combustion and CO2 conversion
- describe the role of control experiments in studying the CO2 conversion presented in the article
- define the word “selective” in the context of this research
- use the proposed mechanism to explain why the electrode studied produces ethanol in such a high proportion
- identify the primary reaction competing with CO2 reduction for available electrons
These questions comprised half of the final exam for my half-credit nanomaterials chemistry course in the fall of 2016. I gave the article to the students one week ahead of time. They were encouraged to read the article, make any small notes they liked, and meet with me in office hours with questions. At the final exam they were allowed to use their copy of the article, but they were also required to hand in their copy with their exam so that I could make sure they hadn't written lots of extraneous information on the exam copy.
The nanomaterials course features near-weekly homework assignments centered around articles from the literature. Because I used this article at the end of the course, students were already familiar with nanomaterials synthesis and characterization techniques. Thus, some of the questions I asked relied on previous knowledge.
Please feel free to adapt these questions and add some of your own. Leave comments describing any new questions you’ve added.