Hello,

there are commercially available cells from the company "EL-CELL" in Germany (Link below). However, in the as-delivered condition they are not useful in my experience, as they provide a "window" which is way to thick for x-ray penetration. Maybe you can try to modify/improve them. What I found in literature (although i dont't recall the references) is as follows:

• Transmission and reflection geometries have been constructed.
• Transmission measurements were done with a synchrotron source
• For the reflection geometry, it may be possible to replace the metal current collector (which is the may attenuation) with polymer sheet that was metallized with a thin film of Cu or Al (depending on the electrode).
• Check out the works of Petr Novak and his group at the PSI (this may give some ideas) and also the links below

regards, Alfred

http://el-cell.com/

http://www.icdd.com/resources/axa/vol42/v42_31.pdf

Hello,

there are commercially available cells from the company "EL-CELL" in Germany (Link below). However, in the as-delivered condition they are not useful in my experience, as they provide a "window" which is way to thick for x-ray penetration. Maybe you can try to modify/improve them. What I found in literature (although i dont't recall the references) is as follows:

• Transmission and reflection geometries have been constructed.
• Transmission measurements were done with a synchrotron source
• For the reflection geometry, it may be possible to replace the metal current collector (which is the may attenuation) with polymer sheet that was metallized with a thin film of Cu or Al (depending on the electrode).
• Check out the works of Petr Novak and his group at the PSI (this may give some ideas) and also the links below

regards, Alfred

http://el-cell.com/

http://www.icdd.com/resources/axa/vol42/v42_31.pdf

Also RIGAKU provides a in-situ xrd cell

Thanks Alfred for sharing your experiences and valuable information. Earlier, I tried to purchase Rigaku in-situ cell only, but they did not sell without XRD machine..few years ago and possible changed since then.

Also, regarding the "thick window" issue of "EL-CELL," is it for glass window or Beryllium window? I found they have a Beryllium window option in their cell, which may solve the issue, but hope to hear your experience.

Again, thank you for your suggestions!!!

I am talking about the beryllium window. It is 2mm thick. This is way too thick for penetration in my opinion. Also it is very brittle and breaks easily. We were not able to perform a measurement with it. Maybe a self made window could be a work around.

Before buying a cell I would suggest you to request a set of data that was measured with it from the company. Apparently, not all equipment is tested properly before it is offered for sale.

For laboratory XRD, we use coin cells with x-ray transparent windows. The cell design is described in detail in Rhodes et al., Rev Sci Instrum, 82, 075107

Note that we later switched to using Mo radiation instead of Cu on this diffractometer to achieve better depth of penetration and less fluorescence from the transition metals. 

http://dx.doi.org/10.1063/1.3607961

As i was recently informed, beryllium and glassy carbon Windows with thickness below 180 um have been successfully used with laboratory copper radiation.

Alfred Amon is correct regarding the thick Be window. Remember if you are working in reflection geometry (i.e., not transmission geometry) then the beam path through the Be at shallow angles will be very significant, so very little beam will get through.

I can recomment polymer windows - you may also make use of a thin-layer geometry which is e.g. described in the X-ray standing wave and surface X-ray diffraction works of Jörg Zegenhagen and coworkers, e.g.

Surf. Sci. 352-354 (1996) 346, DOI: 10.1016/0039-6028(95)01158-7

And there are cells developed by other groups using similar designs. Using the thin layer geometry, the crucial factor is the absorption of the electrolyte and not the windows. However, in general higher X-ray energies are beneficial. I personally prefer transmission mode cells (see e.g. Surf. Sci. 365 (1996) 263, DOI:  DOI: 10.1016/0039-6028(96)00710-8, because of the much easier cell construction and handling.

Furthermore, using e.g. Mo or Ag Kalpha radiation, the electrolyte and the windows absorb only about 10% of the intensity if the cell is not too thick (several mm can be handled properly), so applying photon counting techniques with "conventional" detector equipment should work well usually.

You may calculate the parasitic absorption of windows, electrolyte etc using the centre of X-ray optics website: http://henke.lbl.gov/optical_constants/filter2.html, there you may learn that even 20 mm of water at 20 keV will still transmit ca. 25% at 20 keV photon energy, making diffraction experiments feasible.

We have applied those cells even at about 8-9 keV photon energy, the cell contained in the liquid was in those cases put in a pure He atmosphere to avoid contaminations of the electrolyte and the charge/discharge reactions (see Surface and Interface Analysis 38 (2006) 330; DOI: 10.1002/sia.2279). Provided that you have ports for electrolyte inlets, working and counter electrodes etc, such a setup does not need a glove box to be equipped. And the X-ray windows may be easily adapted to the desired incidence and exit angles.

Contact me if you need further input, Dirk

Not seeing the object I cannot say much, but Philippe Sarrazin and I developed a portable, noninvasive XRD/XRF instrument called DUETTO, that uses a Cu tube (see our paper in ResearchGate). There are other similar instruments quoted in that paper.

Good luck. Giacomo

Hello,

A simple cell has been published by Leriche et al (Journal of The Electrochemical Society - J ELECTROCHEM SOC 01/2010; 157(5). DOI: 10.1149/1.3355977).

It uses Be window, I am using it everyday  for XRD, XAS and Mössbauer spectroscopy and I do recommend it !

some of the authors are present in RG :

S. Hamelet

C. Masquelier

Bests

last : 

2 other solutions :

A) http://www.mtixtl.com/SplitFlatCellforRandDBattery-EQ-STC-QW.aspx

b) http://www.mtixtl.com/CR2016Casewith2sidesKaptonWindow-EQ-CR2016-Kapton-2s.aspx

please contact me if you wants to get more detailed solutions on in-situ battery test at a in-house XRD system. Thank you.

[email protected]

+82-10-4016-6760

EL-Cell offers an electrochemical test cell "ECC-Opto-Std" for  in-situ experiments in the reflective mode. With this design, the incident beam shines onto the backside of the working electrode which must therefore be free-standing or supported on a mesh type current collector. The cell can be used for different optical techniques including Raman and XRD. For XRD, a special kit is available containing a modified cell lid and a beryllium window (0.2 mm thick) replacing the standard glass window. The diameter of the active window area is 10 mm. Many other window materials such as polyimide (Kapton) and PET (Mylar) are available. Thickness is 0.2 or 0.3 mm.

http://el-cell.com/products/test-cells/ecc-opto-std/

http://el-cell.com/products/test-cells/ecc-opto-std/

Dear Matthias Hahn, can you give an example measurement (graphic), that was actually measured using the ECC-Opto-Cell with the Beryllium window?

I don't have. Did you have the chance to work with the cell? Or do you have concerns about the design? Thanks, Matthias

Fantastic compilation of information for modules related to XRD experimentation with "battery electrode" materials. I've learned a lot. Thanks to all the contributors for uninhibitedly sharing!

The most critical component in any XRD experimental arrangement after incident beam conditioning and proper sample positioning as well as environment would be the "data acquisition" (detector) system. There are generally several options including:

Some other sources of similar (not as high specs :-) detectors include Rigaku, Bruker, Panalytical, Dextrics (?), MARS, Pilatus etc. Please include others if known when possible. Actual experimental data with these 2D devices will be extremely helpful. Thanks!

I realize that there are some here that have an emotional attachment to the conventional "Jurassic" equatorial scan diffractogram who bristle at the mention of superseding it with modern 2D real time XRD methods. As is clear from this discussion, none yet believe that the data acquisition technique is the most critical component in any optimization of XRD experiment. I'd hope dissenters would have the gall to express their opinions rather than just a "knee jerk" reaction to a perceived self promotion. Do feel free to do some of your own self-promotion in this austere audience if it is meaningful to the advancement of XRD into the modern era with age old tried and tested 2D XRD techniques :-)

IDEAL SYSTEM SPECIFICATIONS/DESIGN SHOULD INCLUDE:

https://www.researchgate.net/post/What_is_better_for_XRD_rocking_curve_analyses_0D_1D_or_2D_detectors_Why/1

https://www.researchgate.net/post/What_is_the_conventional_alignment_procedure_critical_for_precision_in_XRD_for_sample_surface_positioning_collinear_to_the_diffractometer_axis?_tpcectx=profile_questions

https://www.flickr.com/photos/85210325@N04/22353456270/in/datetaken/

Dear Matthias,

do you not have any test-measurements from the development of this cell?

"if Cu-Ka XRD source is strong enough to penetrate the pouch and can obtain good signal/noise ratio using such laboratory XRD."

This would depend on the sensitivity and dynamic range of the data acquisition system. In the past year it has become abundantly clear to us that the majority of folks using XRD have never even seen their own "main beam" (incident beam or Io). Not even with a simple "dental film". In fact, we are routinely able to observe the direct beam past the slits and at times past the "shutter". So beware of closed "shutters" :-)

Using the wavelength/energy of the incident beam to penetrate varying sampling depths is rudimentary and ought to be taken advantage of like in the "old days". We would routinely switch tubes (target material Al, W, Cu, Mo, Cr etc.) and also switch from "point" to "line" source mode on-demand. Present day instrumentation has been deprived of such flexibility. Why? XRD manufacturers' self interest?

The real question is whether the data acquisition technique is sensitive enough to deconvolute the effects of:

• Incident beam intensity profile and shape.
• Slit edge scattering effects.
• Scattering from any filters and windows (Ni filter, or Kapton, Mylar etc.)
• Sampling volume.
• Flight path constituents.
• Preferred orientation.

Boldly going where others haven't yet :-)

"Is there any commercial in-situ electrochemical cells which I can purchase for this purpose?"

Plenty of viable well engineered commercial options exist and may be taken advantage of.

"in order to observe phase transition of electrode materials during charge/discharge."

This, I'd think is a dynamic phenomenon and you would need the following detector characteristics to successfully complete this requirement:

• High dynamic range
• High frame rate
• High sensitivity
• High spatial resolution, smaller pixel size
• Large data acceptance window size (active surface area)

Is there any commercial in-situ electrochemical cells which I can purchase for this purpose?

The Japanese company Rigaku offers a commercial in situ XRD cell, which might be interesting for you:

http://www.rigaku.com/downloads/journal/RJ27-2/RigakuJournal27-2_32-35.pdf

If you plan to use Beryllium as X-ray transparent window material, the purity of the Be affects the transmissivity. Materion (formerly Brush Wellman) offers high purity Be windows for X-ray applications.

You may also consider using glassy carbon (e.g. Sigradur), which is used by Argonne National Lab for synchrotron studies (AMPIX cell). Glassy carbon is pretty brittle, though.

https://materion.com/Products/Beryllium/BerylliumX-Ray.aspx

http://scripts.iucr.org/cgi-bin/paper?S0021889812042720

http://www.htw-germany.com/technology.php5?lang=en&nav0=2&nav1=0

Be windows may require some caution due to toxicity. There are other safer standard polymeric materials that are available as well. I would think, the ability to detect the 2D "background" signal from such "window" materials and having the ability to deconvolute the XRD signal of interest from the total image in 3D reciprocal space, to be key.

https://www.flickr.com/photos/85210325@N04/15649120475/in/album-72157645018820696/

Dear Jung-Hyun Kim

at PANalytical we have developed several solutions for battery research market. I agree with what is mentioned above, that in many cases the additional information that you can obtain using hard radiation (Mo or Ag) and transmission setup is a great advantage for this type of investigation. We do nevertheless support also reflection geometry, and among other solution we can integrate the solution from El-cell in our diffractometer.

We have several webinars available on our webpage on this topic, that you can see on demand:

http://www.panalytical.com/Event/In-situ-in-operando-XRD-characterization-of-lithiumion-batteries.htm

http://www.panalytical.com/Event/Solving-the-challenges-of-Naion-battery-electrodes.htm

We have also an application note related to the first webinar, that you can download (or please contact us on the website and we can send you a printed version of it):

http://www.panalytical.com/Application-notes/Highquality-in-operando-Xray-diffraction-analysis-of-pouch-bag-lithiumion-batteries.htm

Finally, a dedicated webpage linking to some recent results obtained from our users with the Empyrean diffractometer:

www.panalytical.com/Investigating-lithium-ion-battery-with-a-xray-diffractometer.htm

If you have further question, please do not hesitate in contacting me or the sales representative in your area.

With kind regards,

Fabio Masiello, Empyrean Product Manager at PANalytical

www.panalytical.com/Investigating-lithium-ion-battery-with-a-xray-diffractometer.htm

http://www.panalytical.com/Event/In-situ-in-operando-XRD-characterization-of-lithiumion-batteries.htm

http://www.panalytical.com/Event/Solving-the-challenges-of-Naion-battery-electrodes.htm

http://www.panalytical.com/Application-notes/Highquality-in-operando-Xray-diffraction-analysis-of-pouch-bag-lithiumion-batteries.htm