Tag Archives: open source

A low cost, open source, Cu/Mn rechargeable static battery

Building a rechargeable battery is not an easy task. Although many great technologies are available (like LiFePO4 or even lead acid batteries), building these batteries isn’t trivial because of the technological hurdles, manufacturing requirements, chemical substances, knowledge and safety requirements. It would be ideal if we had access to an open source rechargeable battery technology that was easy to construct in practice with readily available materials, robust and at low cost.

This is a sample 0.5mL cell using a copper anode and a carbon felt cathode (0.3mm). A polypropylene felt separator is used between both. The cell is 1cmx1cmx0.5cm in volume.

In a previous post I talked about Cu/Mn batteries and how several different papers describe batteries using Cu sulfate and Mn sulfate along with sulfuric acid to create robust batteries with significant capacities, even above 40Ah/L. Such batteries would be close to ideal as they are easy to build, use earth abundant materials and – in theory – are very robust. However, my efforts to reproduce these batteries were plagued with failure as I was unable to reproduce both their reversibility and their capacities.

Furthermore, this Cu/Mn technology using sulfuric acid has been patented by a French company (years before the Chinese articles started sharing the chemistry in 2017). This means that this chemistry is not open source and significant battles could arise from the use of this technology at a wide scale. This also explains why the patent applications mentioned by some of the Chinese researchers in their papers cannot be found (probably the patents were denied because of the preceding French patent).

Experimental results of the Cu/Mn cell using methylsulfonic acid. The electrolyte was prepared with 0.05g of FeSO4.7H2O, 2g CuSO4.5H2O, 1.8g of MnSO4.4H2O, 2mL of 70% CH3SO3H and 8mL of RO water. Cycling was done at 5mA/cm2

To tackle my problems reproducing this chemistry, the hurdles with intellectual property and some issues dealing with the solubility limit of copper/manganese sulfate mixes, I have modified this technology to use methansulfonic acid (CH3SO3H) instead of sulfuric acid. Methanesulfonic acid is easier to get than sulfuric acid – because it has no regulatory restrictions – and the solubility of both copper and manganese mesylates is higher than that of their sulfates, meaning that even higher capacities than with sulfuric acid should be possible.

The above experimental results show cycling of the cell shown in the first picture. This chemistry achieves a CE above 90% with an EE above 65%, the cycling is also very stable with very reversible MnO2 formation in the highly acidic media. The electrolyte tested is roughly 0.8m Cu, 0.8m Mn and 1m CH3SO3H. I haven’t tried changing the acid concentration or preparing more highly concentrated electrolytes yet, as I am still fine tuning the cell fabrication process to enhance reproducibility. The cells right now can be charged to 20Ah/L, which is already an interesting level of capacity, although 40Ah/L should be possible.

Image of dendrites due to electric field abnormalities around the edges of the Cu anode.

A very important issue I’ve noticed is that dendrites tend to appear around the edges of my Cu anodes due to electric field instabilities, as the Cu prefers to grow in the free solution rather than through the polypropylene separator. This can cause the battery to short when charging to very high capacities). Cells without separators – with just the electrodes hanging parallel as in the case of some of the Chinese papers – could help alleviate the issue. I am also trying passivating the edges using nail polish, to see if this fully solves the issue.

While the Cu/Mn battery chemistry using H2SO4 is clearly patented, the innovation using CH3SO3H is not protected, neither covered by the scope of the current patent nor previously published anywhere else (my innovation to the best of my knowledge). The publication of this blog post should ensure that this technology will remain patent-free.

Update:

The results above show the cell being charged to 1.45V (This is likely the Nernst limit of the cell). I got a discharge capacity of 33.6Ah/L at 10mA/cm2. Electrolyte is identical to the one mentioned before. The CE and EE are still the same at higher capacity. Dendrites do not seem to get worse provided enough space is left between the edge of the copper electrode and the edge of the separator.

Building a machine to test and research batteries at home

As a chemist who loves electro-chemistry, battery technology has always seemed incredibly interesting, especially since it’s within the group of potential topics that could be researched with some degree of success at home. This is because batteries can be made within a very wide array of chemistries, some of which use very easy-to-find materials and the equipment necessary to research batteries at a small scale should not be hard to build.

Public PCB project at OshPark

However, after looking at a lot of people sharing their DIY batteries at their own houses on the internet, it seems clear that most of them don’t do any proper characterization of their batteries at all and those who do – who appear to be very few – seem to use relatively expensive pieces of equipment to do so, probably the lower end of what would be used within a regular university research environment.

The options available to minimally characterize batteries, which means at least measuring their charge/discharge curves seem to all be expensive and there is no commercial option I could find that would allow you to perform these tests for less than 1000 USD.

However, I did find a very interesting publication (here) where the researchers share the PCB, software, firmware and bill of materials for a cheap galvanostat/potentiostat that can be used for the characterization of small batteries. Given its limited current +/25mA, it cannot be used for the characterization of any larger batteries, but it should allow for some very interesting and well-done research of small batteries at home.

I added this PCB to OshaPark (you can order it here) and I have ordered the materials from Digikey using the bill of materials provided by the author within the paper (you can use this file to upload to dikigey directly) . The microcontroller used within this project also requires to be programmed using a PicKit3, so you will need to get one here. Note that due to COVID related supply constraints I had to order the MCP3550-50E/SN microchip from microchipdirect.com instead of digikey and I also changed the mini-USB port for a micro-USB port (609-4053-1-ND).

Current progress of my order at pcbway

As backup plan I have also ordered a fully assembled PCB board from pcbway.com, which charged me a total of 154 USD for the entire production of the PCB and mounting all the surface components. This is all done in China and the exported to the US, so it will take around a month for the entire process to go through. I want to compare the quality of my own assembly with the product I obtain from China.

In this process I also got quotes for several different US manufacturers for the production of these boards, but came to the conclusion that it is not economical unless I wanted to get at least 10-20 manufactured. This is because the price is often in the 1200-1500 USD range, independently of whether I get 1 or 10-12 boards done.

I still haven’t received everything I need from oshpark and digikey to assemble the board but once I do I will update you on my progress building/programming/testing this open source galvanostat/potentiostat.