Thanks Dr. Braun for your answer. Will go through those papers.

To Dr. Braun. Lithium carbon LixC has a non-constant potential, unlike metallic lithium, which makes its use as a reference electrode meaningless.

For Dr. Braun.

Not directly, but in case of quick read of two neighboring phrases, this opinion can arise ...

"The lithium metal usually would be the counter electrode.

As an alternative one can use lithium carbon LixC."

But if one read it carefully, then lot of interpretations of meaning can be found ...

Yes, you can avoid Li metal - and in fact, although not convenient at times, this would be the ideal case.

Li is very reactive with the electrolyte, and will inevitably introduce small alterations in electrolyte composition. If you are studying the electrochemistry of additives that are reactive and present in small concentrations, this may become significant.

This same reactivity also brings caveats to its activity as a reference: the voltage output of Li as reference varies to some extent with the specific properties of the surface layer it develops in the cell. The properties of this surface layer depend on electrolyte composition and concentration - so if you want to compre very diverse systems, it would bring you a bit of trouble (if you are very concerned with accuracy). There are many papers reporting the use of non-aqueous reference electrodes, or even pseudo-reference electrodes (Pt + a redox indicator, as ferrocene, with the latter added at the end of the test to “calibrate” the scale), so this should not be an issue.

But the most important part if you are investigating electrolytes is to be concerned with moisture. Certain electrolyte components (specially LiPF6) present notable instabilities when in contact with even small concentrations of water, what can also trigger some changes in their behavior (chemical and electrochemical). Even components that are stable towards hydrolysis may have drastic changes in behavior (ionic liquids become less electrochemicaly stable when in contact with moisture, for example). In this sense, it is extremely important to consider not only the environment where you carry the experiments, but also the long term storage, as well. A glove bag, as suggested above, could be a good idea if you don’t have access to a glove box, but you should try to minimize the exposure of your samples to moisture during storage and handling to avoid interference.

Dear Bharath,

To evaluate a novel lithium battery electrolyte you can completely avoid the use of lithium foil. For this purpose you can use capacitively oversized (over your working electrode) LiFePO4 electrode in a two-electrode coin-cell configuration. This cell configuration offers several advantages, namely: (i) in this case there is no need for using of globe box (all manipulations can be carried out in the air except for work with aprotic electrolyte); (ii) a stable reference potential of 3.45 V vs. Li/Li+; (iii) to provide a defined Li-reservoir, without a capacity loss due to the depletion of cyclable Li (https://doi.org/10.1134/S1070427210040130, https://doi.org/10.1134/S1023193512110080, and https://doi.org/10.1134/S1023193514060068); and (iv) to minimize side reactions of the electrolyte, which would alter the electrolytedecomposition and thus influence its quantification.

Good luck!

Dear Bharath Ravikumar,

in a two electrode set-up you could try a proposal coin-cell configuration:

(C-LiFePO4) // your electrolyte // C(-MWCNTs).

For a three electrode set-up, you could add, in your electrolyte, a thin metallic wire of pure Cu (or Pt) as a RE, for short time tests.

Dear Dr. Samaras,

Thank you for your time.

Can you elaborate the second part of your answer?

If I am using pure Pt as RE in three electrode set-up, what can be the choices for WE and CE?

The electrolyte let's say, is as mentioned in the question .

Dear Bharath Ravikumar,

what are your favorite electrodes for WE and CE ?