Advancing Battery Research with In-situ and Operando XRD Solutions

Webinar summary

The webinar opens by framing X-ray diffraction as a central tool for understanding how crystalline battery materials behave under real operating conditions. The presenter, Dr. Stephan Wollstadt, an XRD applications specialist, explains that XRD is not just for phase ID: it lets you distinguish crystalline and amorphous content, quantify phases, refine lattice parameters and atomic positions, and even probe local structure via PDF. That’s directly tied to battery performance, because lithiation and delithiation show up as reversible lattice distortions, phase transitions, and sometimes the formation of parasitic products. With modern diffractometers you can follow these changes in situ and operando while the cell is actually being cycled, instead of destroying cells point-by-point for ex situ measurements.

Stephan then introduces Rigaku’s SmartLab floor-standing diffractometer as a high-end platform for this kind of work. The system uses a high-power PhotonMax rotating-anode source, up to 9 kW, which can deliver roughly an order of magnitude more intensity than a sealed tube in practical configurations. That extra brightness is important when you want short time slices and still need enough counts to see minor phases or subtle peak shifts. For battery work the instrument is configured with harder radiation such as Mo or Ag for transmission measurements on pouch cells, combined with a convergent beam geometry and a large-area 2D HyPix-3000 detector. At a short detector distance the detector covers tens of degrees in 2θ, so in a “snapshot” mode with the detector fixed you can record a rich diffraction pattern in about one second and repeat that continuously during cycling. All instrument control, operando data acquisition, and analysis (including Rietveld and lattice-parameter tracking) are handled in one environment, SmartLab Studio II, which also manages optical configurations and auto-alignment so users can switch between standard powder work and battery experiments without rebuilding the system from scratch.

The core technical example is an operando pouch-cell study on LiMn₂O₄ spinel cathode material. The talk focuses on the 111 reflection of the spinel, because that plane intersects the tetrahedral Li sites, and on the graphite 002 peak on the anode side. During charge and discharge, the Li leaves and re-enters the spinel, and intercalates into graphite, which shows up as systematic peak shifts and, at higher angles, coherent changes across multiple hkl reflections. With the snapshot setup, you can watch these reflections slide back and forth in real time in a waterfall or heat-map representation. Using Rietveld refinement over the time-resolved series, the speaker shows how to convert the lattice-parameter evolution into a capacity estimate; in the example data set the calculated capacity is about 93 mAh g⁻¹ over roughly 7.4 hours of cycling. The point isn’t that this is a record cell, but that you can connect structural metrics directly to electrochemical performance from a single operando experiment.

To get closer to realistic use conditions, the webinar then moves to a non-ambient pouch-cell holder that combines temperature control and electrical connections. This stage seals the cell behind a thin X-ray window and allows operation from about −10°C to 110°C under nitrogen or vacuum, with integrated thermocouples. Using the same LiMn₂O₄ system at different temperatures, the speaker shows that as temperature increases the lattice-parameter swing during cycling becomes larger, reflecting easier Li mobility and faster structural response. When this is translated back into electrochemistry, the capacity nearly doubles between 0°C and 50°C, from about 63 to 110 mAh g⁻¹. That’s used to argue that temperature-dependent operando XRD is a powerful way to see why a cell behaves differently in winter versus in a hot car, rather than just measuring a change in the voltage curve and guessing at the underlying mechanism.

The second half of the webinar addresses labs that don’t have a floor-standing rotating-anode diffractometer. Stephan shows that a benchtop MiniFlex 600, equipped with a high-energy-resolution XSPA-200 ER detector and a coin-cell stage, can still do serious operando work in reflection geometry using standard Cu radiation. The energy-discriminating detector suppresses fluorescence from transition-metal cathodes like NCM, giving a clean peak-to-background ratio even though Cu Kα strongly excites elements such as Co, Ni, Fe, and Mn. An example operando NCM vs Li coin cell is used to highlight phase transitions and lattice-parameter evolution; by tracking the change in maximum lattice expansion over multiple cycles, you can see structural degradation as a shrinking amplitude of the parameter swing. The talk also compares conventional Kapton-window coin cells with a new low-background coin-cell design using a polymer window supplied by Rigaku. Electrochemically, both behave similarly, but in XRD the new window gives a very flat background with only a small polymer bump, instead of the strong Kapton scattering that can obscure weaker reflections. The webinar closes by emphasizing that between the SmartLab platform with hard-radiation transmission and non-ambient capability, and the MiniFlex with improved coin-cell hardware and a high-resolution detector, you can cover everything from routine QC to advanced operando and degradation studies, all within a single software ecosystem that makes setting up and analyzing battery XRD experiments straightforward for non-specialists as well as experts.