Rigaku Corporation

This application note demonstrates the measurement by X-ray diffraction (XRD) of positive electrode material from lithium ion batteries during the charge/discharge process.

	Lithium ion secondary batteries are widely used in small portable devices such as mobile phones. Research and development of lithium ion batteries for use in automobiles and larger machines is an active field. To develop lithium ion secondary batteries with high capacity, high stability and long life, it is essential to evaluate the stability of the positive electrode material during the charge/discharge process. Operando X-ray diffraction measurements using an attachment that reproduces the charge/discharge environment and a 2D detector that can perform high-speed measurements enables detailed observation of crystal phase changes while a battery is in use, making it suitable for studying battery performance and life.


	Figure 1: Figure 1 shows a picture and an illustration of the cross-sectional structure of a battery cell attachment. The positive electrode material was LiMn

. Measurement using an exposure time of 15 s was repeated while charging/discharging the electrode at a charge and discharge rate 1C = 132 mAh/g. Changes to the X-ray diffraction profile over time were investigated.

	X-ray diffraction measurements of the positive electrode material during high-speed charging and discharging were carried out with a battery cell attachment and a HyPix-3000 2D detector on a Rigaku SmartLab X-ray diffractometer.


	Figure 2: Figure 2 shows the multiple 1D XRD profiles, 2D profile maps and voltage graphs. Two steps of a two-phase coexistence reaction occurred with charging and discharging. After charging and discharging, the electrode material returned to the same crystal phase as before the measurement started.

	The Rigaku SmartLab Automated multipurpose X-ray diffractometer with HyPix-3000Hybrid pixel array multi-dimensional detector can perform high-speed Operando measurements of crystal phase changes of lithium ion batteries to evaluate battery performance and life.


	Figure 3: Rigaku SmartLab automated multipurpose X-ray diffractometer (XRD) with Guidance software.


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	tel. (281) 362-2300, fax (281) 364-3628
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Articles

Operando Measurement of Li Ion Battery Positive Electrode in Charge/Discharge Process by X-ray Diffraction

This application note demonstrates the capabilities of a low-cost, benchtop WDXRF spectrometer for rapid quantitative elemental analysis of cement raw meal.

	Cement is one of the most important materials in the construction industry. Since its physical properties and those of the concrete ultimately made from it depend on its composition, it is important to monitor the composition of the raw meal used to make the clinker.

	Thanks to simple sample preparation and routine operation, short measurement times and high precision, X-ray fluorescence (XRF) spectrometry has become the technique of choice for elemental analysis at all points in cement production: from alternative fuels, raw materials and raw meal to clinker and final certification. Wavelength-dispersive (WD) XRF is the most commonly utilized analytical technique in the cement industry because it offers the highest throughput, precision and sensitivity, especially for essential light elements, such as Na, S, and K.

	Traditionally, WDXRF spectrometers used in cement plants have been large, floor-standing models with substantial installation requirements and ownership expenses. As the industry strives for greater efficiency, operators have increasingly sought equipment that is less expensive to acquire and less costly to maintain.

	The Supermini200 is a benchtop sequential wavelength-dispersive X-ray fluorescence (WDXRF) spectrometer designed specifically to deliver high performance while eliminating typical installation requirements, such as cooling water, special power supply, large floor space, etc.

	Featuring a unique air-cooled 200W X-ray tube, two detectors and three analyzing crystals, the Supermini200 can analyze all relevant elements in just minutes with full spectral separation of all peaks, high sensitivity for light elements, such as Na, Mg, P and Cl, and exceptional repeatability.

	The Windows-based software running the Supermini200 is shared with Rigaku's higher- power Primus series of WDXRF systems.

	The pressed powder method is the most common sample preparation technique in XRF because it does not require an expensive flux, fusion machine, or highly-trained operators. For this report, cement raw meal powders were pulverized and pressed into aluminum rings at 120 kN.

	Measurements were performed in vacuum on the Supermini200 with the 200W Pd target X-ray tube operating at 50 kV and 4.0 mA and using the standard crystals: LiF(200), PET, and RX25. The total analysis time for all of the analytes was about four min per sample.

	A series of reference materials of cement raw meal certified by CSBTS (China State Bureau of Technical Supervision) was used for calibration. The calibration results are presented in Table I.

	One of the reference materials, used in the calibration, was measured consecutively 10 times to determine the short-term stability of the method and instrument. The results show that it is possible to analyze pressed pellets of cement raw meal with high repeatability on a 200W WDXRF instrument that is small enough to fit on a bench.

	This report demonstrates that cement raw meal samples can be routinely analyzed by the pressed powder method with excellent accuracy and precision on the Rigaku Supermini200 low-cost benchtop sequential WDXRF spectrometer that does not require cooling water or special facility accommodations.


	9009 New Trails Drive, The Woodlands TX 77381
	tel. (281) 362-2300, fax (281) 364-3628
	Website: 

Cement Raw Meal Analysis by the Pressed Powder Method on Supermini200 Benchtop WDXRF

Semi-quantitative analysis in modern XRF instruments is a unique method which is performed without reference materials for the unknown samples. This report demonstrates determination of chemical composition in geological samples using semi-quantitative analysis by the pressed powder method on a WDXRF spectrometer.

Semi-Quantitative Analysis for Geological Samples

The permitted sulfur limit in fuel oils has been decreased to 10 ppm in many regions. This application note demonstrates that the performance of the Rigaku Micro-Z ULS meets the requirement of ASTM D2622-10, in the analysis of ultra-low sulfur in automotive fuels.

Recent developments in ultra-low sulfur (ULS) fuel have improved fuel efficiency and created cleaner exhaust gas. Globally, the permitted sulfur limit in fuel oils has been decreased to 10 ppm in many countries and regions. 

For compliance verification, X-ray fluorescence (XRF) spectrometry is the definitive analysis tool for use at distribution terminals and refineries, as well as mobile or stationary testing laboratories. In recent years, there has been an increasing need for an instrument which does not require the use of helium gas, for instances when acquisition or delivery of helium to the analysis site is difficult. 

The Micro-Z ULS (ultra-low sulfur) is a newly developed sulfur analyzer which does not require helium gas in operation. This application note demonstrates that Micro-Z ULS can meet the requirements of ASTM D2622-10. 

The Micro-Z ULS is a benchtop wavelength dispersive X-ray fluorescence (WDXRF) spectrometer with fixed optics optimized for sulfur analysis. The atmosphere in the optics path of the Micro-Z ULS is a vacuum, so that helium gas is not required. The spectrometer is designed to minimize the restrictions in installation such as the need for cooling water, a special power supply, and installation space. The Micro-Z ULS is equipped with an air-cooled 40 W Cr-target X-ray tube and a doubly curved RX-9 analyzing crystal optimized for low concentration sulfur. 

The Micro-Z ULS has a built-in operation panel, which enables simple and easy operation for daily analysis. The counting time was 300 s for peak and background measurements in this experiment. 

Approximately, 4 mL of each sample was poured into a liquid cell with sample film of 2.5 µm Mylar® film (Chemplex® 100). 

"Number 2 diesel fuel" standards and isooctane-based standards provided by VHG Labs, Inc. were used for calibrations of diesel fuel and gasoline respectively. 

 Figure 1: Calibration curve for each material of Micro-Z ULS; (a) diesel fuel, (b) isooctane (for gasoline).			

Repeatability tests were carried out using a representative sample for each material. For each sample, two aliquots were prepared and analyzed using the calibration Figure 1; this process was repeated 20 times. The term "r" represents "repeatability" defined by the following formula in ASTM D2622-10 (1): 

The difference between successive test results obtained by the same operator with the same apparatus under constant operation conditions on identical test material would exceed the values calculated by equation 1 only in one case in every 20. 

The test results, where the maximum value for each fuel is smaller than r, prove that the performance of the Micro-Z ULS meets the requirement of ASTM D2622-10 for diesel fuel and gasoline. 

Low concentration sulfur in petroleum-based fuel can be routinely analyzed with high accuracy and precision on the Micro-Z ULS, a benchtop WDXRF spectrometer with fixed optics, which does not require He gas, external water for cooling the X-ray tube, or special power supply. This application note demonstrates that the performance of the Micro-Z ULS meets the requirement of ASTM D2622-10, which has become strict in the recent versions of ASTM D2622. 

(1) ASTM D2622-10(2010), "Standard Test Method for Sulfur in Petroleum Products by Wavelength Dispersive X-ray Fluorescence Spectrometry," 

9009 New Trails Drive, The Woodlands TX 77381

The permitted sulfur limit in fuel oils has been decreased to 10 ppm in many regions.

Analysis of Ultra-Low Sulfur in Automotive Fuels According to ASTM D2622-10 by Sulfur Analyzer Micro-Z ULS

This application note introduces an Application Package for quantitative analysis of additive elements in polymer. The Application Package includes calibration standards and drift correction samples required for the quantitative analysis, the step-by-step instruction manual, and more. This polymer Application Package makes it easy to set up the quantitative analysis application by the use of polyethylene disk specimens as calibration standards. 

The polymer Application Package is applicable to Rigaku sequential wavelength-dispersive XRF spec-trometer, ZSX Primus, ZSX PrimusII, and ZSX Pri-musIII+. For Mg, Na, and F analysis, an optional high-sensitivity crystal RX35 is required. In addition, an optional Ge crystal is needed for the ZSX PrimusIII+. The analysis area is 30 mm in diameter. 

Table I: Analysis element and calibration range			

Table I lists the analysis components (elements) and their calibration ranges of this Application Package. 

The measurement conditions shown in Table II, standard values of six set-up standard samples, various correction coefficients and conditions of two drift correction samples are automatically set by running the installation CD. After the installation, the instruction manual provides simple, step-by-step instructions on how to set up quantitative application, which enables less-experienced users to generate accurate calibration curves. Figure 1 shows the outline of this Application Package. 

Figure 1: Outline of polymer Application Package.			

Before measurement, the analysis surface of each sample is polished using sand paper and then cleaned with ethanol. 

Figure 2: Calibration curves and their accuracies for typical elements.			

Calibration curves and their accuracies for typical elements are shown in Figure 2. 

The Rigaku ZSX Primus series of sequential wavelength dispersive X-ray fluorescence spectrometers.  			

The accuracy of calibration is calculated by the following formula,

Table III shows the test results of 5-time measurements with sample preparation on the ZSX PrimusII. 

Polymer Application Package, introduced in this application note, makes it possible to easily set up calibration for additive elements in polyethylene-base samples. This Application Package is effective to analysis of polymers similar in composition to polyethylene. 

9009 New Trails Drive, The Woodlands, TX 77381

tel. (281) 362-2300, fax (281) 364-3628  

This application note introduces an Application Package for quantitative analysis of additive elements in polymer.

Analysis of Additive Elements in Polymer Using ZSX Primus Series/Application Package

Globally, the permitted sulfur limit in fuel oils has been decreased to 10 ppm in many countries and regions. For compliance verification, X-ray fluorescence (XRF) spectrometry is the definitive analysis tool for use at distribution terminal and refineries, as well as mobile or stationary testing laboratories

Rigaku Micro-Z ULS is a benchtop wavelength dispersive X-ray fluorescence (WDXRF) spectrometer with fixed optics optimized for sulfur analysis. The atmosphere in the optics path of the Micro-Z ULS is a vacuum so that helium gas is not required. The spectrometer is designed to minimize the restrictions  in installation such as cooling water, special power supply, installation space, etc. 

Micro-Z ULS is equipped with an air-cooled 40 W Cr-target X-ray tube and a doubly curved RX-9 analyzing crystal optimized for low concentration sulfur. The counting time was 300 s for peak  and background measurements. 4.0 mL of each diesel fuel sample was poured into a liquid XRF cup (inner diameter 35 mm) equipped with 2.5 μm Mylar® film.  

Figure 1: Calibration results for diesel fuel.			

Repeatability tests were carried out using a representative sample. For each, two aliquots were prepared and analyzed using the calibration shown in Figure 1; this process was repeated 20 times. The test results are tabulated in Table I for diesel fuel, in which the average and the difference of two aliquots are shown respectively. Lower-limit-of detection (LLD) was calculated as 0.3 ppm sulfur.  

Table I: Repeatibility results for diesel fuel			

Low concentration sulfur in petroleum-based fuel can be routinely analyzed with high accuracy and precision with the Micro-Z ULS, a benchtop WDXRF spectrometer with fixed optics, which does not require He gas, external water supply or special power supply. This application note demonstrates that the performance of the Micro-Z ULS meets the requirements of ASTM D2622-10.  

9009 New Trails Drive, The Woodlands, TX 77381  

Globally, the permitted sulfur limit in fuel oils has been decreased to 10 ppm in many countries and regions.