Identification of discharge products of ATO


To investigate the processes involved in the discharge and charge of ATO cells, which are expected to differ from those in cells with carbon cathodes judging from the fundamentally different voltage profiles, the quantification of Li2O2 and Li2O content at different SOC is pursued using three complementary analytical methods: (i) The sum of all potential discharge products such as Li2O2, Li2O, LiOH, and Li2CO3 (partly also Li acetate and Li formate) is determined by acid-base titration (see also Fig. S1 in the SI). (ii) The amount of Li2O2 is quantified by photometric detection in the UV-vis range of a colored [Ti(O2−)]2+ complex formed by the reaction of titanium(IV) oxysulfate with H2O2, which is exclusively generated by the hydrolysis of Li2O2. (iii) The absence or presence of discharge products other than Li2O2 and Li2O is verified by ATR-FTIR of discharged electrode samples by the absence of their distinct infrared absorption bands. The ATR-FTIR spectra of fresh and discharged ATO cathodes, several reference samples (left panel), and the quantification of discharge products were calculated from titration and UV-vis photometry (mid and right panels). The SOC used for product analysis is marked as #1 discharged, #2 charged to 5 V, and #3 charged to the 1st discharge capacity. Product analyses at each SOC are taken from at least two different cells. All given amounts are mean values with their standard deviation (SD), taking into consideration the error propagation when subtracting (ii) from (i). To compensate for different cathode loadings in different cells, all amounts are normalized to μmol of Li per As of 1st discharge capacity of each cell. The resulting fractions of the discharge capacity chemically stored in each product are visualized. For the upcoming comparison with Baratron/OEMS data in the next section of this work, an additional normalization of the Li2O2 and Li2O fractions to μmol of O2 equivalents contained in each product per As of 1st discharge capacity is carried out. The results reflect that a 2e−/O2 process produces Li2O2, while Li2O is formed in a 4e−/O2 reaction. If you are looking for high quality, high purity, and cost-effective ATO, or if you require the latest price of ATO, please feel free to email contact mis-asia.

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