Applikationer

Lithium hexafluorophosphate (LiPF6) is used as an electrolyte in rechargeable batteries. Its high solubility in non-polar solvents and its non-coordinating character in particular make lithium hexafluorophosphate the ideal salt for use in lithium-ion cells. This Application describes the determination of cation traces in LiPF6 with conductivity detection following sequential suppression.

The commercialization of Li-ion batteries in 1991 was the culmination of in-depth R&D conducted by scientists and engineers around the globe over the preceding few decades. Further development of Li-ion batteries and alternative rechargeable batteries has continued until today. As the world is rapidly moving towards a new era defined by green technologies, more practical and accurate R&D is required in order to meet the increasing demands for energy storage systems, specifically from the automotive industry. This white paper presents the basics of the Li-ion battery technology and guides the reader through the relevant techniques and terminologies in Li-ion battery research.

The FOS/TAC value is an important characteristic to assess the status of the fermenter before costly problems arise. The new Eco Titrator from Metrohm allows the determination of this quotient in a fast, cost-efficient, and precise way.

This White Paper introduces the principles of cyclic voltammetry (CV) and the various ways it can be used for catalyst investigation. A case study and helpful glossary are provided to support your understanding.

White paper about Raman spectroscopy and electrochemistry and their combination (electrochemical Raman).

With Hydranal™ NEXTGEN FA reagents, the water content in ketones can be determined quickly and reliably. Compared to other existing KF reagents for ketones on the market, the side reactions are measurably better suppressed.

Raman spectroscopy’s use for process analytics in the pharmaceutical and chemical industries continues to grow due to its nondestructive measurements, fast analysis times, and ability to do both qualitative and quantitative analysis. Spectral preprocessing algorithms are routinely applied to quantitative spectroscopic data in order to enhance spectral features while minimizing variability unrelated to the analyte in question. In this technical note we discuss the main preprocessing options pertinent to Raman spectroscopy with real applications examples, and to review the algorithms available in B&W Tek and Metrohm software so that the reader becomes comfortable applying them to build Raman quantitative models.

Raman spectroscopy is a valuable tool for the characterization of carbon nanomaterials due to its selectivity, speed, and ability to measure samples nondestructively. Carbon materials typically have simple Raman spectra, but they contain a wealth of information about internal microcrystalline structures in peak position, shape, and relative intensity.

This bulletin deals with the automated determination of mixtures of HNO3, HF and H2SiF6 in the range of approximately 200-600 g/L HNO3, 50-160 g/L HF, and 0-185 g/L H2SiF6 using thermometric titration.Etch acid mixtures containing HNO3, HF and H2SiF6 from the etching of silicon substrates can be analyzed in a sequence of two determinations using the 859 Titrotherm. The first determination involves a direct titration with standard c(NaOH) = 2 mol/L, followed by a back titration with c(HCl) = 2 mol/L. This determination yields the H2SiF6 content plus a value for the combined (HNO3+HF) contents. The second determination consists of a titration with c(Al3+) = 0.5 mol/L to determine the HF content. For freshly made up mixtures of HNO3 and HF containing no H2SiF6, a linked two-titration sequence is employed. Results from the two determinations are used by tiamoTM to yield individual results for HNO3, HF and H2SiF6.

Two separate titration sequences are required to analyze the mixture:- titration of the HF content with Al(NO3)3 (the «elpasolite» reaction)- titration of the H2SO4 with BaCl2 followed by titration with NaOH to determine the «total acids» contentThe HF, H2SO4, and «total acids» contents are converted to a HNO3 equivalent, with the HNO3 content found by subtracting the HF and H2SO4 from the «total acids» content.

Determination of ferrous ions in heat exchanger and vessel acid wash solutions, for measuring the effectiveness of acid inhibitors used in the solutions. Depending on the condition of the sample, the lower practical limit for the determination will vary from approximately 20-100mg/Kg Fe2+. Samples with high silicic acid contents require relatively large amounts of dilution water to render them mobile, and this limits the aliquot size and hence the amount of Fe2+ which can be analyzed.

Following the addition of caustic soda, hexafluorosilic acid can be determined through back titration of excess hydroxide with hydrochloric acid. Hydrofluoric acid (hydrogen fluoride) is determined by precipitation with aluminum in the presence of sodium and potassium ions. Nitric acid is determined by subtracting the equivalence concentrations of hexafluorosilic acid and hydrofluoric acid from the total acid concentration.

Coal contains a certain amount of fluorine, chlorine, and sulfur compounds. During combustion of the coal, these components release corrosive acids (e.g., fluorine compounds form hydrofluoric acid). Thermal power plants therefore request low-fluorine coal to avoid massive hydrofluoric acid production. In this application note, fluorine content in coal is determined by ion chromatography after pyrohydrolysis.

In pressurized water reactors (PWRs), light water is used as coolant in the primary side. Boron (as boric acid) is added to the coolant to absorb neutrons, thus controlling reactivity. Lithium hydroxide assures the alkaline pH value to prevent corrosion. This application allows to measure lithium content besides high boric acid concentrations. AN-C-138 shows the respective trace metal determination on the same system setup.

N-methyldiethanolamine and piperazine are used in scrubber solutions, e.g., in the natural gas process. Testing this type of samples by ion chromatography requires a good resolution and the separation of amines from standard cations. The separation is achieved on a Metrosep C 4 - 150/4.0 column applying direct conductivity detection.

Determination of nickel, zinc, cobalt, iron(II), and manganese in lithium bromide using cation chromatography with UV/VIS detection (520 nm) after post-column reaction with PAR.

Determination of traces of zinc and iron(II) in the presence of lithium, sodium, ammonium, potassium, calcium, and magnesium in boiler water using cation chromatography with direct conductivity detection.

Water in steel-based cooling systems requires a pH value slightly above 7 to prevent corrosion. Often ammonium or organic amines are applied for pH adjustement. This application shows the separation of typical amines besides inorganic cations. Sample preconcentration applies combined Inline Preconcentration and Matrix Elimination (MiPCT-ME).

The water content of coal dust is determined according to Karl Fischer. Because of the low water content of the voluminous sample, the oven method (nitrogen, 270 °C) and coulometric titration have to be used.

Determination of silicate and borate and their limits of determination (LOD) and quantification (LOQ) according to the EPA procedure for method detection limit (MDL) using anion chromatography with direct conductivity detection and Metrohm Inline Calibration.

Scrubber solutions for scrubbing flue gas often contain amines for absorbing acid gases, e.g., sulfur dioxide (SO2). 1-(2-hydroxyethyl)piperazine and 1,4- Bis(2-hydroxyethyl)piperazine from gas scrubber solutions are separated in the Metrosep Carb 2 - 150/4.0 column and then determined using pulsed amperometric detection.

A combination of the 850 Professional IC and the 872 Extension Module Liquid Handling opens the field of Metrohm’s online monitoring by IC. In this application, Inline Preconcentration is coupled to Matrix Elimination (MiPCT-ME). By removing excess matrix components, corrosive anions can be sensitively determined. Additionally, this technique allows automated calibration using a single multi-ion standard solution. Online trace analysis for chloride and sulfate is possible for several different sample lines.

Boiler feed water is a working medium in thermal power plant. To keep corrosion low, the pH value should be in the slightly alkali range, which is why amines are added to the feed water. This addition must be monitored regularly. Also important is the monitoring of the sodium concentration, because an increase of this indicates that cooling water is seeping into the condenser. Ion chromatography with conductivity detection following sequential suppression is the optimum system for monitoring, particularly in combination with intelligent Sample Preconcentration and Matrix Elimination.

The Metrosep C Supp 2 column family is polystyrene/divinylbenzene based and therefore sequential cation suppression may be applied. This AN shows the separation and detection of different amines on the 150 mm version of the column with subsequent conductivity detection after sequential cation suppression.

Determination of Al in alkaline ZnO solution with Eriochrome Blue Black R at 60 °C.

Excessive silica concentrations in the boiler feed water can lead to deposits on turbine blades and must therefore be avoided. Silica analysis is carried out via differential photometry using a leading-edge technology thermostatic cuvette module for non-sample contact at the detector. Typical concentration ranges for silica are 0–50 ppb and 0–1 ppm or higher.

One way to maximize heat transfer efficiency and reduce costs in a power plant is by controlling the water chemistry in the cooling circuit. This cooling water is kept alkaline to maintain the protective oxide layer on the metal piping throughout the water circuit. However alkalinity above the recommended range increases the probability of scale formation (deposition), so it is buffered with carbonate (CO32-) and bicarbonate ions (HCO3-). Titration of the cooling water to pH 4.5 gives the so-called "M-Alkalinity" (methyl orange alkalinity), a measure of total alkalinity. Below this pH, there is no more alkalinity present, only free acid (H+), carbonic acid (H2CO3), and CO2.

Thermal power plants require enormous amounts of water, using high purity steam at high pressure to rotate turbines. A separate cooling water circuit is implemented, which helps to form a vacuum when the steam condenses after the turbines. Maintaining this vacuum with optimal condensation parameters is critical for the power plant efficiency. The copper condensers are susceptible to corrosion by ammonia, leading to an upper limit of 2 mg/L NH3 set by EPRI in cooling water. Small cracks in the condenser combined with the large pressure differential between the steam circuit and the cooling water circuit will contaminate the high purity water in the boiler, causing major problems and necessitating a shutdown for plant maintenance. Monitoring NH3 online in cooling water with a process analyzer can signal early problems in a plant before significant intermediation is necessary.

Neutralizing amines are added to adjust pH levels within the water-steam circuit of power plants to avoid corrosion-inducing conditions. This preventive maintenance can reduce costly and critical downtimes due to corrosion, however frequent monitoring of the amine chemistry is necessary to ensure conditions stay optimal. The 2060 IC Process Analyzer featuring the Metrohm intelligent Partial Loop Technique (MiPT) option is ideal for this application, with the ability to measure trace amounts of the analytes precisely and reliably through an automated method. The benefit of using IC is that multiple analytes can be monitored simultaneously, and here the ability to measure the presence of sodium next to the high ammonium or amine concentrations could indicate that cooling water is seeping into the circuit, indicating a problem upstream.

Copper is used widely in industrial cooling water systems for its heat transfer properties, although it is susceptible to corrosion. Corrosion can cause a loss of efficiency and eventually a failure of equipment, leading to costly maintenance, replacement, and downtime. Corrosion inhibitors (triazoles) can be added to the water chemistry, which form sparingly soluble protective layers on the surface of the metal. Triazole concentrations must be maintained to protect the copper, which necessitates regular concentration determinations in cooling water. The 2060 IC Process Analyzer with UV/VIS detection is well-suited for this application, able to precisely and reliably measure multiple ionic and UV-active compounds simultaneously in cooling water.

In power plants, corrosion is the greatest enemy. If corrosive impurities are present in the circuit streams (e.g., chlorides and hydroxides), deposition of an insulating layer of scale on the heat transfer surfaces occurs, resulting in costly and critical downtimes. To ensure high throughput of power plants, online analysis of critical parameters such as sodium is highly advantageous for safety, protection, and process optimization. With the 2035 Process Analyzer from Metrohm Process Analytics, operators gain the information they need to accurately identify trends, reduce downtimes, and address operational issues before costly problems arise.

Lithium is a soft alkali metal that is typically obtained from salt lake brines. Lithium is used for many applications, but especially for production of lithium-ion batteries in electric cars, mobile phones, and more. This Process Application Note presents a method to monitor lithium as well as other cations in brines by online process ion chromatography (IC), a multiparameter analytical technique that can measure ionic analytes in a wide range of concentrations.

Incineration flue gas requires treatment such as wet scrubbing. The 2060 VA Process Analyzer monitors heavy metals in the scrubbing water, ensuring compliance.

This application note shows how it is possible with Metrohm Autolab PGSTATs and the Metrohm Autolab Optical Bench, to retrieve information about the mechanism and the kinetics of the back reaction, a side reaction which limits the performances of dye-sensitized solar cells.

Electrochemical impedance spectroscopy (EIS) is a powerful technique which provides information about the processes occurring at the electrode-electrolyte interface. The data collected with EIS are modeled with a suitable electrical equivalent circuit. The fitting procedure will change the values of the parameters until the mathematical function matches the experimental data within a certain margin of error. In this Application Note, some suggestions are given in order to get acceptable initial parameters and to perform an accurate fitting.

The DuoCoin Cell Holder is introduced. EIS measurements on a commercial coin cell battery are performed. Differences in impedance between the four-terminal configuration and two-terminal configuration is highlighted, putting in evidence the importance of having a direct four-terminal configuration, when low-impedance DUTs are investigated.

This Application Note outlines GITT, a key technique for studying Li-ion battery kinetics, OCV, and diffusion, using INTELLO for streamlined control and analysis.

The ASTM B825 is used to determine the corrosion and tarnish film on metal surfaces. This is achieved by using the so-called cathodic reduction method. With the help of a Metrohm Autolab PGSTAT302N and a Metrohm Autolab 1 L corrosion cell, a procedure to replicate the ASTM B825 is shown.

This application explains ohmic iR drop in electrochemical cells, its causes, and strategies to minimize its impact for accurate and reliable potential measurements.

The way low-impedance devices, like fuel cells and battery, are connected to a load influences their performances. In this document, a comparison of EIS results on a commercial Li-ion battery is shown. Different EIS measurements have been performed, changing the way the battery has been connected to the potentiostat.

In this application note, the advantage of recording the raw time domain data for each individual frequency during an electrochemical impedance measurement is described.

A fuel cell is an electrochemical energy conversion device that produces electricity and heat by electrochemically combining a fuel (typically hydrogen) and an oxidant (typically oxygen). The higher efficiency also results in much lower carbon dioxide emissions and negligible amounts of SOx and NOx (when reformed fuel is used) compared with fossil fuel-based technologies for the same power output.

In this Application Note the use of Electrochemical Impedance Spectroscopy (EIS) for the characterisation of PEM fuel will be demonstrated. It will be shown that EIS is a powerful diagnostic tool for the determination of the following factors that can influence the performance of a PEM fuel cell.

A solar cell or photovoltaic cell is a device that converts light energy into electrical energy. Dye-sensitized solar cells (DSC) are currently the subject of intense research in the context of renewable energies as a low-cost photovoltaic (PV) device. Electricity generated from a PV produces zero emissions, is modular, and can produce energy anywhere the sun shines. The standard characterization technique of a PV device consists in the determination of the DC current-voltage curves under different incident light intensities.

The use of impedance measurements on fuel cells under load makes it possible to study the influence of the different fuel cell elements on the behavior and (if detectable) on the ageing of the fuel cell. To perform high current density measurements, the Autolab systems can be connected to a third party electronic load. This extends the measurable range of the instrument by several current decades.

The TSC SW closed and TSC battery cells are compact systems designed for measurement of air or moisture sensitive materials, such as those materials used in rechargeable batteries. These cells offer well-controlled environment for the in-temperature measurement of solid and gel like materials in contact with metal electrodes in planar geometry. For example, battery active materials, ionically conductive solid-state electrolytes and battery separators can be tested using these cells. In this experiment, standard resistors of 100 Ω are used in both cells to understand the cell effects, if any, on the measurements.

In this application note, we demonstrate how to determine the through-plane tortuosity τ of a commercial lithium ion battery cathode material with known porosity and coating thickness, based on the electrochemical impedance spectroscopy (EIS) method.

The ASTM standard G100 is an electrochemical method to test localized corrosion of aluminum 3003-H14 and other alloys. A cyclic galvanostatic staircase polarization (galvanostaircase) is composed of an upward and a downward scan. The potential values at the end of each step are collected and linearly fitted, and the potential values at zero current are found.

The rotating cylinder electrode (RCE) is a technique used in corrosion research to simulate in a laboratory environment the turbulent flow which usually occurs when liquids are transported through pipelines. The RCE is used to generate a turbulent flow at the surface of a sample, simulating the pipe flow conditions. Experiments that involve an RCE are regulated by the ASTM G185 standard. In this application note, The RCE with a 1018 carbon steel cylinder sample was used with the linear polarization (LP) measurement technique.

This Application Note details ASTM G61-compliant corrosion measurements performed with VIONIC powered by INTELLO using Metrohm’s ASTM-compliant corrosion cells.