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Molecules 2017, 22, 403 7 of 21 5. Carbon Dioxide and Its Extraction Properties Besides being infamous as greenhouse gas [129–132], CO2 is substantial to many chemical reactions. These reactions include the application as a monomer in materials synthesis [133] or as a C1 block in the fabrication of polycarbonates [134] or other organic compounds [135]. Furthermore, CO2 is involved in the synthesis of linear and cyclic carbonates for LIB electrolytes as well [136–139]. It has been applied for lithium metal and lithium ion batteries as a SEI forming additive [140] and graphite anode surface modifications [141,142]. Additionally, due to the reduction or oxidation of the electrolyte CO2 is produced and present in LIBs [143,144]. Aside from the standard phases (solid, liquid and gaseous), the supercritical phase is reached relatively non-elaborate. Temperature and pressure need to be increased above the critical point of 31 °C and 74 bar (Figure 5) [145]. In this state, supercritical CO2 has the density of liquid CO2 and the viscosity of gaseous CO2. The physical properties are between those of the liquid and gaseous phase with greatly enhanced dissolution characteristics [146]. In combination with additional solvents, a wide variety of organic substances can be extracted and, therefore, supercritical carbon dioxide is the most applied supercritical medium for extraction [147]. It is normally used in food chemistry, with the well-known example of coffee decaffeination [148–152]. Other application areas include as a reaction medium for metal nanoparticle synthesis [153] or olefin polymerization [154], as a drying aid for electrode material synthesis [155] and crack-free silica aerogel production [156,157]. In supercritical fluid chromatography it functions as the eluent [147]. Figure 5. Pressure and temperature phase diagram of CO2 [158,159]. K: Kelvin, p: pressure, T: temperature, sc: supercritical, l: liquid, g: gaseous, s: solid. For supercritical extraction, commercial flow-through units with a corresponding compressor for the generation of supercritical CO2 from liquid CO2 are available. However, helium head pressure carbon dioxide (HHPCO2) can be used as an alternative. Here, liquid carbon dioxide is compressed with a helium head pressure to 120 bar. Because of the different densities, in the two-phase system, supercritical carbon dioxide is available. Nevertheless, there are small deviations in the extraction behavior of HHPCO2 compared to supercritical CO2 due to little amounts of dissolved helium in thePDF Image | CO2 for Recycling and Sample Preparation of Lithium Ion Battery
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