After our initial work on Li2MnO3, we discovered that there was a debate in the literature for a related compound. The more promising Li1.2Mn0.54Ni0.13Co0.13O2. It is the Li and Mn rich analogue to the Li[NiMnCo]O2 oxides used in commercial batteries.
What was this debate? It was whether the material existed as a solid solution or if it was an intergrowth or mix of Li2MnO3 and Li[NiMnCo]O2. Ie, if the composition crystallised as one or two phases. Here is an excerpt highlighting the debate pubs.acs.org/doi/10.1021/cm…
And here is what the two proposed models are. In the multi-phase model the hexagonal ordering occurs exclusively for Li and Mn whereas in the single phase Li in the transition metal layer can also have Ni and Co as nearest neighbours.
Why does this matter? It has been argued that the additional capacity, specifically the anionic redox capacity, originated from the Li2MnO3 phase. Thus, its presence is necessary for that additional capacity.
So why is this so difficult? Surely a diffraction experiment can tell you whether multiple phases are present. Lets play a game of spot the difference🙂. Below are diffraction patterns (X-rays and neutrons) from a confirmed "single" and "multi" phase samples
Aside from intensity differences in the neutron diffraction pattern, they look pretty similar. Figuring out this puzzle is further complicated since the compound has disorder over several length scales. Short to long: Atomic site mixing, stacking faults and phase segregation
Disorder over multiple length scales means to answer this question multiple characterisation tools are needed. This is what we did, looking at both local and long range information. The methods were diffraction, raman spectroscopy, magnetic susceptibility, and STEM measurements
What did we learn? Is the material one or two phases?? The answer is: both and it depends on how you synthesise the material. Similar to the first paper, solid state gives an inhomogeneous distribution of elements whereas the sol gel method is more homogeneous
It is not too surprising that this has led to conflicting results over the years. It does raise some interesting ideas about tailoring phase intergrowth via different synthetic pathways however.
The story of how @Altris_ab came to be and my involvement in PBA research is also a nice one. It was really a combination of the right people meeting at the right time and at the right place.
It began with Ronnie Mogensen, who was working on polymer electrolytes at the time and just needed a reliable positive electrode that was easy to make. He tried NaFePO4 which didn't always function. Then he turned to NaxFe[Fe(CN)6]. This always worked to a reasonable degree
He then stumbled upon a paper where the group of John Goodenough (Nobel laureate in chemistry for Li-ion #batteries) made rhombohedral Prussian white. pubs.acs.org/doi/10.1021/ja…
So how about Prussian blue analogues (PBAs) in batteries? In addition to @Altris_ab there are a number of other companies developing this class of compounds for energy storage applications. What makes them so attractive?
PBAs are commonly used as the positive electrode in beyond Li-ion batteries (sodium, potassium). They have an open structure leading to fast cation insertion. Additionally, due to the strong bonding of the cyanide ligand transition metals like iron have a decent voltage output.
Indeed, the performance metrics of PBAs, in particular the iron-based Na2Fe[Fe(CN)6], are quite similar to those of LiFePO4 (LFP). However, PBAs have the additional advantage of a simple and low cost synthesis making them very interesting to develop cheap sustainable batteries
Now to talk about Prussian blue analogues! To begin I have to tell the story behind them because it is one of my favourite pieces of chemical history. It is a tale of alchemists, theologians, famous paintings and about 200 years of wondering what Prussian blue was.
It all began in Berlin in 1704 with an enterprising dye maker by the name of Heinrich Diesbach. He was most interested in producing a red dye by the name of Cochineal red lake. The ingredients were iron sulphate, potash and crushed up beetles #alchemy
But Diesbach was running low on potash. Enter the scene one Johann Conrad Dippel. Master theologian, physician, alchemist. Dippel was captured by the allure of alchemy and like any good alchemist began his attempts at transmuting gold.
We just got back from a group lunch/farewell to @ashok_menon12. I will use this opportunity to talk a little bit about what Ashok has done during his PhD. Ashok has worked with what is known as Li and Mn-rich layered oxides.
The Li and Mn rich oxide materials are interesting as they have the potential to store a lot more energy compared to regular battery cathodes.
The reason is due to the excess lithium which sits in the transition metal layer. The presence of Li in this layer creates local Li-O-Li bonding environments allowing of anionic redox due to unhybridised O orbitals. Below I show the regular LiCoO2 (yellow) and Li2MnO3 (purple).
Ok lets take a look through the @StructuralChem1 lab! Development of new technologies begins with synthesis of new materials. This synthesis is carried out in many of the fumehoods that we have available
For synthesis of many ceramic materials we share a number of high temperature furnaces with other groups. Including tube furnaces for synthesis under various inert or reactive gases.
Additionally, a lot of synthetic work takes place inside our gloveboxes which are filled with Argon. Many chemicals we use for battery research (like Li metal) are air or moisture sensitive and so well maintained gloveboxes are a must!
But first, I think it is good to generally introduce what a Li or Na-ion #battery is built up from. While I am not an electrochemist by any stretch, I do work a lot with batteries and will mention them often.
A battery is comprised of four key components. Two electrodes connected to an external circuit: a positive (high potential) and a negative (lower potential) electrode. These are electrically isolated from each other by a separator soaked in electrolyte allowing ions to pass.
The electrons pass via an external circuit where they perform work during battery use. Both the positive and negative electrode materials need to accept both electrons and ions (such as Li+) reversibly. Designing materials which can do this is quite challenging.