What is X-ray fluorescence (XRF) and how does it work?

X-ray fluorescence (XRF) is a non-destructive elemental analysis technique used to determine the basic building blocks, or elements, that make up a material. It works by exciting a sample with primary X-rays from an X-ray tube. These primary X-rays cause electrons in the sample's atoms to be ejected from their shells. Electrons from higher energy shells then drop down to fill these vacancies, releasing energy in the form of fluorescence, which is detected and measured as distinct peaks (spectra) by the spectrometer. Each element emits X-rays at characteristic wavelengths, allowing for identification and quantification.

What are the main types of XRF techniques and their differences?

The two primary types of XRF techniques are energy dispersive X-ray fluorescence (EDXRF) and wavelength dispersive X-ray fluorescence (WDXRF). EDXRF units are typically smaller, more portable (handheld or benchtop), and operate at lower power. They have an analysis range from sodium to uranium. WDXRF units are generally larger (benchtop or floor models), operate at much higher power, and offer a wider analysis range from beryllium through curium. WDXRF also uses analyzing crystals and multiple detectors, leading to more complex mechanics but often higher precision, especially for trace elements and light elements. EDXRF systems are generally more affordable and "plug-and-play," requiring less setup.

What are the key benefits of using XRF for material analysis compared to traditional techniques like ICP-MS?

XRF offers several significant advantages over traditional techniques like inductively coupled plasma-mass spectrometry (ICP-MS ): Non-destructive and sample recovery: XRF is a non-destructive technique, allowing for 100% recovery of the sample, which can then be reused for other analyses or if the material is valuable. ICP-MS typically requires sample digestion, making recovery impossible. Simplified sample preparation: XRF sample preparation is significantly easier and faster, often taking only 5 to 15 minutes for solids, powders, or liquids. It doesn't require hazardous acids, extensive heating, or complex digestion processes common in ICP-MS. Speed of analysis: XRF analysis times are very quick, ranging from less than a minute to about 30 minutes, compared to potentially hours for ICP-MS. Wide range of analytes: XRF can analyze most elements on the periodic table, making it versatile for various applications. While ICP-MS is better for quantifying lithium and parts per billion (PPB) trace levels, XRF excels at parts per million (PPM) and mass percent. Ease of use and calibration: XRF instruments are generally easier to operate and calibrate. A single calibration can often cover all elements, and recalibration is typically only recommended every six months or even longer, unlike ICP-MS, which may require daily recalibrations. This allows for open access and operation by a wider range of personnel.

What types of analyses can XRF provide?

XRF can provide three main types of analyses: Qualitative analysis (scanning): This answers the question "what is in the sample?" without any prior calibration. It provides a general overview of the elements present. Semi-quantitative analysis: This combines qualitative scanning with a factory-installed calibration to provide a reasonable estimation of element concentrations. It's useful for initial screening or when standards are not available, offering good comparisons for materials like NCM powders. While not as precise as quantitative analysis, it's quick and requires no additional calibration work. Quantitative analysis: This is the most precise form, requiring calibration with standard materials that have certified values (or trusted in-house values from other techniques like ICP-MS). The goal is to match the matrix of the standards to the unknown materials, allowing for accurate determination of element concentrations.

When should one choose between EDXRF and WDXRF for battery analysis?

The choice between EDXRF and WDXRF for battery analysis depends on specific needs: EDXRF is suitable if light element analysis is not critical and detection limits for trace level elements are not extremely low (e.g., not parts per billion). Its portability and lower cost make it ideal for quick screenings or on-the-go analysis. WDXRF is preferred when analyzing light elements (like beryllium) or if high precision for trace level elements (parts per million or lower) is required due to its higher power and wider analysis range.

How are detection limits determined in XRF, and how do they vary?

The detection limit for an XRF spectrometer is typically determined as three times the standard deviation of the background signal from a blank material. It's important to note that the detection limit is not a fixed value and will vary depending on the material being analyzed. For instance, the detection limit for nickel in a powder cathode material will be different from that in a liquid bath material because the X-rays escape differently from each matrix.

Where in the battery lifecycle can XRF be effectively used?

XRF can be used throughout the entire battery lifecycle: Mining: For rough screening of ore materials and checking the grades of mined materials, often using handheld or benchtop/floor model units. Refining: For elemental analysis to ensure quality control of incoming products, identify contaminants, and monitor for process killers. Mixing: To ensure correct elemental ratios in materials, such as NCM powders (nickel, cobalt, manganese). Coating, drying, and calendaring: Inline XRF systems can be used for quality control monitoring during these processes. Recycling: At the end of a battery's life, XRF assists in determining the elements present in black mass or other recycled materials, aiding in material identification for reuse or further processing.

Can XRF replace ICP-MS entirely for battery material analysis, especially concerning pass/fail thresholds?

XRF generally cannot replace ICP-MS entirely, as the two techniques are often complementary. Pass/fail thresholds: When switching from ICP-MS to XRF, pass/fail thresholds for elemental concentration in battery materials may not need significant adjustment if you are looking at parts per million (ppm) or mass percent levels. XRF can provide very good precision in these ranges. Limitations: However, for ultra-trace level elements in the parts per billion (ppb) detection range, ICP-MS remains the preferred technique. Additionally, for quantifying lithium, ICP-MS is still the recommended method, as XRF cannot directly analyze lithium. Therefore, a laboratory often benefits from having both techniques to cover a comprehensive range of analytical needs.

Webinar Summary: Non-Destructive Elemental Analysis of Batteries Using XRF

Presenter: Amber Quevy

Rigaku

Co-Presenter: Tim Bradow

Rigaku

Sr. Business Development Manager

Webinar summary

The webinar, part of a series focused on X-ray analysis of battery materials, offers a thorough introduction to how X-ray fluorescence (XRF) spectroscopy can be leveraged across the battery production lifecycle. Aimed at researchers and professionals working with battery materials, the session walks through both the theory and practical applications of XRF, emphasizing its role as a non-destructive, versatile tool for elemental analysis. The presenters highlight the technique’s strengths in speed, simplicity, sample preservation, and broad elemental coverage, positioning it as an attractive alternative or complement to more established techniques like inductively coupled plasma mass spectrometry (ICP-MS) and X-ray photoelectron spectroscopy (XPS).

XRF’s primary advantage lies in its minimal sample preparation and ability to analyze solids, powders, and liquids with little or no modification. The speakers detail the two major types of XRF instruments: energy dispersive (EDXRF), which is lower-cost, compact, and often portable; and wavelength dispersive (WDXRF), which is higher powered and suitable for broader elemental range and better detection limits. These options allow labs to tailor their analytical approach depending on needs such as detection limits, sample types, and throughput requirements. For battery materials, EDXRF might suffice for bulk screening and quality checks, while WDXRF would be favored for trace analysis or when lighter elements need detection.

Throughout the session, the presenters provide battery-specific examples, including analyses of NCM cathode powders, graphite anodes, and black mass from recycling processes. In these cases, XRF was used to assess key elements like nickel, manganese, cobalt, and iron, sometimes revealing unexpected contaminants such as sulfur or iron in materials marketed as high purity. The ability to generate both qualitative and semi-quantitative data out of the box—without custom calibration—makes XRF particularly powerful for quick screening or preliminary checks. However, for situations demanding tighter precision or regulatory compliance, full quantitative calibration using certified standards or correlated ICP-MS data is recommended.

Another core theme is workflow efficiency. Unlike ICP-MS, which requires complex digestion steps involving acids and hazardous waste, XRF analysis can often be completed in minutes, with no loss of sample, making it ideal for high-value or limited-quantity materials. Sample prep options include pressing powders into pellets, pouring into cups with films, or direct measurement of solids—all of which retain sample integrity. The technique also lends itself to broad accessibility, as systems can be operated with minimal training, eliminating reliance on specialized chemists.

XRF is shown to be valuable across the battery manufacturing chain, from mining and refining to electrode mixing, quality control, and recycling. Whether for verifying raw material purity, ensuring correct stoichiometry in cathode blends, screening for contaminants, or characterizing recycled content, the technique fills a growing need for fast, reliable elemental insights. The speakers encourage users to start with semi-quantitative analysis and escalate to full calibration only if accuracy demands exceed typical tolerances—generally within ±10%, though often much tighter in practice.

The webinar concludes by reinforcing that XRF is not a standalone solution but a robust component in a toolkit that may also include ICP-MS, XPS, and other methods. The full recording and a battery-focused application eBook were made available for follow-up, wrapping up the final session in a broader webinar series on X-ray-based analytical techniques in battery research. For anyone evaluating materials characterization workflows in battery development, especially where turnaround time, simplicity, and sample conservation are critical, this session makes a compelling case for integrating XRF.

Key questions answered in the webinar

: X-ray fluorescence (XRF) is a non-destructive elemental analysis technique used to determine the basic building blocks, or elements, that make up a material. It works by exciting a sample with primary X-rays from an X-ray tube. These primary X-rays cause electrons in the sample's atoms to be ejected from their shells. Electrons from higher energy shells then drop down to fill these vacancies, releasing energy in the form of fluorescence, which is detected and measured as distinct peaks (spectra) by the spectrometer. Each element emits X-rays at characteristic wavelengths, allowing for identification and quantification.
: The two primary types of XRF techniques are energy dispersive X-ray fluorescence (EDXRF) and wavelength dispersive X-ray fluorescence (WDXRF).

EDXRF units are typically smaller, more portable (handheld or benchtop), and operate at lower power. They have an analysis range from sodium to uranium.

WDXRF units are generally larger (benchtop or floor models), operate at much higher power, and offer a wider analysis range from beryllium through curium. WDXRF also uses analyzing crystals and multiple detectors, leading to more complex mechanics but often higher precision, especially for trace elements and light elements. EDXRF systems are generally more affordable and "plug-and-play," requiring less setup.
: XRF offers several significant advantages over traditional techniques like inductively coupled plasma-mass spectrometry (ICP-MS ):

Non-destructive and sample recovery: XRF is a non-destructive technique, allowing for 100% recovery of the sample, which can then be reused for other analyses or if the material is valuable. ICP-MS typically requires sample digestion, making recovery impossible.

Simplified sample preparation: XRF sample preparation is significantly easier and faster, often taking only 5 to 15 minutes for solids, powders, or liquids. It doesn't require hazardous acids, extensive heating, or complex digestion processes common in ICP-MS.

Speed of analysis: XRF analysis times are very quick, ranging from less than a minute to about 30 minutes, compared to potentially hours for ICP-MS.

Wide range of analytes: XRF can analyze most elements on the periodic table, making it versatile for various applications. While ICP-MS is better for quantifying lithium and parts per billion (PPB) trace levels, XRF excels at parts per million (PPM) and mass percent.

Ease of use and calibration: XRF instruments are generally easier to operate and calibrate. A single calibration can often cover all elements, and recalibration is typically only recommended every six months or even longer, unlike ICP-MS, which may require daily recalibrations. This allows for open access and operation by a wider range of personnel.
: XRF can provide three main types of analyses:

Qualitative analysis (scanning): This answers the question "what is in the sample?" without any prior calibration. It provides a general overview of the elements present.

Semi-quantitative analysis: This combines qualitative scanning with a factory-installed calibration to provide a reasonable estimation of element concentrations. It's useful for initial screening or when standards are not available, offering good comparisons for materials like NCM powders. While not as precise as quantitative analysis, it's quick and requires no additional calibration work.

Quantitative analysis: This is the most precise form, requiring calibration with standard materials that have certified values (or trusted in-house values from other techniques like ICP-MS). The goal is to match the matrix of the standards to the unknown materials, allowing for accurate determination of element concentrations.
: The choice between EDXRF and WDXRF for battery analysis depends on specific needs:

EDXRF is suitable if light element analysis is not critical and detection limits for trace level elements are not extremely low (e.g., not parts per billion). Its portability and lower cost make it ideal for quick screenings or on-the-go analysis.

WDXRF is preferred when analyzing light elements (like beryllium) or if high precision for trace level elements (parts per million or lower) is required due to its higher power and wider analysis range.
: The detection limit for an XRF spectrometer is typically determined as three times the standard deviation of the background signal from a blank material. It's important to note that the detection limit is not a fixed value and will vary depending on the material being analyzed. For instance, the detection limit for nickel in a powder cathode material will be different from that in a liquid bath material because the X-rays escape differently from each matrix.
: XRF can be used throughout the entire battery lifecycle:

Mining: For rough screening of ore materials and checking the grades of mined materials, often using handheld or benchtop/floor model units.

Refining: For elemental analysis to ensure quality control of incoming products, identify contaminants, and monitor for process killers.

Mixing: To ensure correct elemental ratios in materials, such as NCM powders (nickel, cobalt, manganese).

Coating, drying, and calendaring: Inline XRF systems can be used for quality control monitoring during these processes.

Recycling: At the end of a battery's life, XRF assists in determining the elements present in black mass or other recycled materials, aiding in material identification for reuse or further processing.
: XRF generally cannot replace ICP-MS entirely, as the two techniques are often complementary.

Pass/fail thresholds: When switching from ICP-MS to XRF, pass/fail thresholds for elemental concentration in battery materials may not need significant adjustment if you are looking at parts per million (ppm) or mass percent levels. XRF can provide very good precision in these ranges.

Limitations: However, for ultra-trace level elements in the parts per billion (ppb) detection range, ICP-MS remains the preferred technique. Additionally, for quantifying lithium, ICP-MS is still the recommended method, as XRF cannot directly analyze lithium. Therefore, a laboratory often benefits from having both techniques to cover a comprehensive range of analytical needs.

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Beneath the Surface: X-ray Analyses of Battery Materials and Structures

5. Non-Destructive Elemental Analysis of Batteries Using XRF

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Webinar summary

Key questions answered in the webinar

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