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.
This failed, but it did not deter him from making a miraculous "animal oil" and releasing it upon an unsuspecting public. The concoction, distilled from the ground up remains of animals, was so foul it was believed it must be good for you (like any good medicine right?)
What does this have to do with a dye maker? Diesbach is said to have been preparing his dyes in Dippels laboratories. His potash shortage was solved by buying from Dippel. Now, Dippel was not a great alchemist and a terrible chemist so of course the potash was contaminated
And so, unsuspectingly using the potash contaminated with animal remains Diesbach tried to produce his red dye. He did not get a red dye. He produced a very blue powder instead.
Keep in mind that obtaining vibrant blue colours for paint or clothing in these times was not easy, and not cheap. Diesbach knew this and quickly attempted to recreate the recipe and sell his new blue pigment to the world leading to several famous paintings.
The original recipe called for dried ox blood as a key ingredient. Of course, they can't have known what was really going on at the time because the discovery of several key elements had not yet happened (like nitrogen in 1772). So what did they really make?
The key ingredients are iron and cyanide. The cyanide, which originated from various alkyl cyanides in the animal remains, dramatically changed the reaction leading to what is now known as Prussian blue. But it took a few hundred years to figure this out rdcu.be/cm3vx
Finally, using X-ray diffraction, it was determined that Prussian blue was a coordination framework compound consisting of iron centers bridged together by cyanide ligands. Each iron can be coordinated by six cyanides giving the porous cubic structure.
This was just the beginning. Prussian blue is one member of a family of compounds known as Prussian blue analogues. They share the same coordination environment of CN bridges, but the transition metal can change and the pores in the structure can host many different species.
Many different compositions leads to a variety of properties and applications. Prussian blue analogues are more than just pretty colours. They can be used for treating Cesium and thallium poisoning, CO2 capture, in electrochromic windows and of course, in batteries! (and more)
For more detail on the history of Prussian blue, I recommend the work by Alexander Kraft, who has written a few times on the history of the pigment (acshist.scs.illinois.edu/bulletin_open_…) and also a nice perspective by Andreas Ludi: pubs.acs.org/doi/10.1021/ed…

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More from @RealSci_Nano

23 Jun
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…
Read 22 tweets
23 Jun
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
Read 5 tweets
23 Jun
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.
Read 10 tweets
22 Jun
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. Image
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). ImageImage
Read 8 tweets
22 Jun
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 ImageImageImage
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. ImageImageImage
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! ImageImage
Read 12 tweets
22 Jun
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. Image
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.
Read 7 tweets

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