Carbon-polymer membranes

Long-term stability and contamination is a problem with both alkaline and polymer membrane electrolysis electrolytes. Alkaline electrolytes adsorb carbon dioxide readily and form carbonates. Polymer membrane systems must use very pure de-ionized water or they will accumulate cations that displace protons and increase the cell resistance over time. 

Besides zeolites and traditional silica, carbon molecular sieves have been investigated as dispersed phases. Mixed-matrix membranes have been created using carbon molecular sieves dispersed in polyetherimide (Ultem) and Matrimid, separately. These mixed-matrix membranes displayed an increase in both permeability and selectivity over their neat polymer counterparts." The effect of trace amounts of toluene impurity in the feed stream of these carbon-polymer membranes was tested, and the membranes showed promising stability over time against the impurity. Zeolite-carbon mixed-matrix membranes have recently been developed where the carbonized polymer matrix is derived from a pure Matrimid membrane." These mixed-matrix membranes double the CO2/CH4 selectivity of the pure carbonized Matrimid membranes tested but lose over half of their productivity in the process. While these properties are well above Robeson s upper bound, other researchers have achieved better separation properties using only pure carbonized Matrimid membranes. ... 

The preparation and properties of a novel, commercially viable Li-ion battery based on a gel electrolyte has recently been disclosed by Bellcore (USA) [124]. The technology has, to date, been licensed to six companies and full commercial production is imminent. The polymer membrane is a copolymer based on PVdF copolymerized with hexafluoropropylene (HFP). HFP helps to decrease the crystallinity of the PVdF component, enhancing its ability to absorb liquid. Optimizing the liquid absorption ability, mechanical strength, and processability requires optimized amorphous/crystalline-phase distribution. The PVdF-HFP membrane can absorb plasticizer up to 200 percent of its original volume, especially when a pore former (fumed silica) is added. The liquid electrolyte is typically a solution of LiPF6 in 2 1 ethylene carbonate dimethyl car-... 

A second surface modification has been reported by Yamamoto et al. These workers added stearic acid to their carbon paste mixture. This produced an electrode which was relatively insensitive to ascorbic acid and DOPAC relative to dopamine. It is theorized that this electrode works because of electrostatic repulsion of the anionic ascorbate and DOPAC by surface stearate groups. Ionic repulsion has also been employed by covering the surface of the working electrode with an anionic polymer membrane. Gerhardt et al. used Nafion, a hydrophobic sulfonated perfluoro-polymer, to make a dopamine selective electrode. This electrode exhibited selectivity coefficients as large as 250 1 for dopamine and norepinephrine over ascorbic acid, uric acid, and DOPAC. 

The presence of -S02(OH) groups reduced the carbon dioxide permeability by a factor of three. This can be explained (15) by the decrease in local segmental mobility of the polymer chains due to the interactions arising from hydrogen bonding. However, the overall transport process for this polymer membrane is more complicated and involves a more pronounced discrimination against methane molecules due to the highly polar nature of the polymer. 

Electrolyte Potassium hydroxide Polymer membrane Immobilized liquid molten carbonate Immobilized hquid phosphoric acid Ion exchange membrane Ceramic... 

The PEMFCs require expensive polymer membrane (e.g., Nation ), and operate at a low temperature (e.g., 80°C). Although low temperature reduced the cost of material, the heat generated at low temperatures is more difficult to remove. Alternate proton conducting membranes (e.g., inorganic polymer composites) that will operate at a high temperature (e.g., 200°C) are required. The expensive platinum catalyst used for electrochemical reactions can be poisoned by even trace amounts of carbon monoxide in the hydrogen fuel stream. Hence, a more tolerant catalyst material needs to be developed. 

Redox potential pH Ionic activities Inert redox electrodes (Pt, Au, glassy carbon, etc.) pH-glass electrode pH-ISFET iridium oxide pH-sensor Electrodes of the first land and M" /M(Hg) electrodes) univalent cation-sensitive glass electrode (alkali metal ions, NHJ) solid membrane ion-selective electrodes (F, halide ions, heavy metal ions) polymer membrane electrodes (F, CN", alkali metal ions, alkaline earth metal ions)... 

New polymer membrane-based ISEs for nitrate and carbonate exhibit detection limits and selectivities that may be applicable for ocean measurements. In addition, a number of these ISEs can be used as internal transducers for the design of useful potentiometric gas sensors. For example, dissolved C02 can be detected potentiometrically by using either a glass membrane electrode or a polymer-based carbonate ISE, in conjunction with an appropriate reference electrode, behind an outer gas permeable membrane. Novel differential pC02 sensors based on two polymer membrane-type pH sensors have also been developed recently. 

It is inappropriate to pursue here optimization of the electrolyte design for a PEM cell. The essentials of the cell are a thin polymer membrane coated on each surface with carbon mixed with platinum particles acting as the catalyst. 

Yoshikawa M, Ezaki T, Sanui K, and Ogata N. Selective permeation of carbon dioxide through synthetic polymer membranes having pyridine moiety as a fixed carrier. J. Appl. Polym. Sci. 1988 35 145-154. 

PEM fuel cells use a solid proton-conducting polymer as the electrolyte at 50-125 °C. The cathode catalysts are based on Pt alone, but because of the required tolerance to CO a combination of Pt and Ru is preferred for the anode [8]. For low-temperature (80 °C) polymer membrane fuel cells (PEMFC) colloidal Pt/Ru catalysts are currently under broad investigation. These have also been proposed for use in the direct methanol fuel cells (DMFC) or in PEMFC, which are fed with CO-contaminated hydrogen produced in on-board methanol reformers. The ultimate dispersion state of the metals is essential for CO-tolerant PEMFC, and truly alloyed Pt/Ru colloid particles of less than 2-nm size seem to fulfill these requirements [4a,b,d,8a,c,66j. Alternatively, bimetallic Pt/Ru PEM catalysts have been developed for the same purpose, where nonalloyed Pt nanoparticles <2nm and Ru particles <1 nm are dispersed on the carbon support [8c]. From the results it can be concluded that a Pt/Ru interface is essential for the CO tolerance of the catalyst regardless of whether the precious metals are alloyed. For the manufacture of DMFC catalysts, in... 

The most important fuel cells that are in use nowadays are the polymer electrolyte membrane fuel ceU (PEMFC), the molten carbonate fuel cell (MCFC), and the solid oxide fuel cell (SOFC). In a PEMFC, the electrolyte is a polymer membrane that conducts protons, in an MCFC the electrolyte is a carbonate melt in which oxygen is conducted in the form of carbonate ions, CO , and in an SOFC the electrolyte is a solid oxide that conducts oxygen ions, While a PEMFC can be operated at low temperatures of about 80 °C, an MCFC works at intermediate temperatures of about 650 °C, and an SOFC needs relatively high temperatures of 800-1000 °C (see next sections). 

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