The surface films formed on commercial LiNi0.8Co0.15Al0.05O2 cathodes (ATD Gen2) charged from 3.75V to 4.2V vs. Li/Li+ in EC:DEC - 1M LiPF6 were analyzed using ex-situ Fourier transform infrared spectroscopy (FTIR) with the attenuated total reflection (ATR) technique. A surface layer of Li2CO3 is present on the virgin cathode, probably from reaction of the active material with air during the cathode preparation procedure. The Li2CO3 layer disappeared even after soaking in the electrolyte, indicating that the layer dissolved into the electrolyte possibly even before potential cycling of the electrode. IR features only from the binder (PVdF) and a trace of polyamide from the Al current collector were observed on the surfaces of cathodes charged to below 4.2 V, i.e., no surface species from electrolyte oxidation. Some new IR features were, however, found on the cathode charged to 4.2 V and higher. An electrolyte oxidation product was observed that appeared to contain dicarbonyl anhydride and (poly)ester functionalities. The reaction appears to be an indirect electrochemical oxidation with overcharging (removal of > 0.6 Li ions) destabilizing oxygen in the oxide lattice resulting in oxygen transfer to the solvent molecules.

Lithium-ion cells, with graphite anodes and LiNi0.8Co0.15Al0.05O2 cathodes, were cycled for up to 1000 cycles over different ranges of SOC and temperatures. The decline in cell performance increases with the span of SOC and temperature during cycling. Capacity fade was caused by a combination of the loss of cycleable Li and degradation of the cathode. The room temperature anodes showed SEI compositions and degrees of graphite disorder that correlated with the extent of the Li consumption, which was linear in cell test time. TEM of the cathodes showed evidence of crystalline defects, though no major new phases were identified, consistent with XRD. No evidence of polymeric deposits on the cathode particles (FTIR) was detected although both Raman and TEM showed evidence of P-containing deposits from electrolyte salt degradation. Raman microscopy showed differences in relative carbon contents of the cycled cathodes, which is blamed for part of the cathode degradation.

The potential use of different iron phosphates as cathode materials in lithium-ion batteries has recently been investigated.1 One of the promising candidates is LiFePO4. This compound has several advantages in comparison to the state-of-the-art cathode material in commercial rechargeable lithium batteries. Firstly, it has a high theoretical capacity (170 mAh/g). Secondly, it occurs as mineral triphylite in nature and is inexpensive, thermally stable, non-toxic and non-hygroscopic. However, its low electronic conductivity (~;10-9 S/cm) results in low power capability. There has been intense worldwide research activity to find methods to increase the electronic conductivity of LiFePO4, including supervalent ion doping,2 introducing non-carbonaceous network conduction3 and carbon coating, and the optimization of the carbon coating on LiFePO4 particle surfaces.4 Recently, the Li doped LiFePO4 (Li1+xFe1-xPO4) synthesized at ARL has yield electronic conductivity increase up to 106.5 We studied electronic structure of LiFePO4 and Li doped LiFePO4 by synchrotron based soft X-ray emission (XES) and X-ray absorption (XAS) spectroscopies. XAS probes the unoccupied partial density of states, while XES the occupied partial density of states. By combining XAS and XES measurements, we obtained information on band gap and orbital character of both LiFePO4 and Li doped LiFePO4. The occupied and unoccupied oxygen partial density of states (DOS) of LiFePO4 and 5 percent Li doped LiFePO4 are presented in Fig. 1. Our experimental results clearly indicate that LiFePO4 has wide band gap (~; 4 eV). This value is much larger than what is predicted by DFT calculation. For 5 percent Li doped LiFePO4, a new doping state was created closer to the Fermi level, imparting p-type conductivity, consistent with thermopower measurement. Such observation substantiates the suggestion that high electronic conductivity in Li1.05Fe0.95 PO4 is due to available number of charge carriers in the material. Furthermore, Hall effect measurement on Li doped sample confirmed presence of free charge carriers, which are responsible for the observed electronic conductivity increase in Li doped LiFePO4. There is no evidence that Fe3+ valence is created by doping with excessive Li+ in Li1.05Fe0.95PO4, as shown by Fe-edge XAS. (Fig.2) Instead, charge-carrier holes reside primarily in unoccupied O 2p states, which compensate for the charge deficiency from Li+ substitution for Fe2+. The increased conductivity in Li1.05Fe0.95PO4 is attributed to the new charge carriers (doped holes) and the strong electron correlation between O 2p and Fe 3d states.