Although the Li-ion conductivity of Li2CO3 was extremely low (about 10-12 S cm-1 at room temperature), the ion-blocking impurities were hardly formed at the electrode/Li2CO3 electrolyte interface since Li2CO3 could be sintered at lower temperatures below 973 K. Li2+xC1-xBxO3, which is isostructural with Li2CO3, is also a Li-ion conductive oxide. According to the literature, the Li-ion conductivity was enhanced dramatically from 10-7 to 10-3 S cm-1 at 473 K as x in Li2+xC1-xBxO3 changes from 0 to 0.25.  We used Li2.2C0.8B0.2O3 as electrolyte material and assembled ASS-LIB by SPS method for reducing impurities under sintering.
Li2.2C0.8B0.2O3 was synthesized using Li2CO3, LiOH·H2O, and H3BO3 as the starting materials via a conventional solid-state reaction. The required amount of starting materials was ground and heated at 873 K for 10 h in air. The obtained powder was cold-pressed into a pellet and re-heated at 923 K for 10 h in air twice. A single phase of Li2.2C0.8B0.2O3 was identified by a powder XRD pattern of the synthesized product. For ion conductivity measurements, the prepared Li2.2C0.8B0.2O3 was firstly put in a 80 mL ZrO2 cap with five of 5 mm ZrO2 disks, and was crushed by disk mill. Samples for AC impedance measurement were prepared by two sintering methods; conventional furnace sintering (CFS) of uniaxial pressing powder and SPS of Au/ Li2.2C0.8B0.2O3 powder/Au. (Both sides were polished and coated with Au after the CFS method.) The sintering temperature and time at CFS and SPS were 923 K, 2h and 723 K, 1 min, respectively, for densification over 90%. Total Li-ion conductivities for Li2.2C0.8B0.2O3 SPS pellet was 2.1 x 10-6 S cm-1at 303 K, which was higher than that of CFS pellet: 6.7 x 10-7 S cm-1. The growth of Li2.2C0.8B0.2O3 grain was less observed at SEM image of the SPS pellet. The total conductivity was enhanced about three times by suppressing the grain growth via the SPS method, due probably to reducing the high-resistive layer near the grain boundary, which would be formed by long-term duration via the CFS method.
Composite electrode powder was prepared from a mixture of 70 wt% LiCoO2 and 30 wt% Li2.2C0.8B0.2O3 electrolyte. Au/composite electrode powder/Li2.2C0.8B0.2O3 powder was assembled by SPS method under the same condition for the sample of AC impedance measurement. Lithium foil was used as a reference/counter electrode. A poly(ethylene oxide)-based polymer electrolyte film was inserted between the lithium foil and the Li2.2C0.8B0.2O3 electrolyte as a separator to reduce the interfacial resistance with adhesion as possible. Electrochemical charge-discharge test was performed at a constant current of 10 μA cm-2 at 333 K between 4.2 and 2.0 V vs. Li/Li+. The ASS-LIB showed an initial charge-discharge profile which is similar to the liquid electrolyte case, and the discharge capacity was 118 mAh g-1. No impurity peak was observed in the powder XRD pattern of the LiCoO2-Li2.2C0.8B0.2O3 composite electrode after SPS method. Thus, we have successfully prepared the oxide-based ASS-LIB, working with demonstrating the comparable discharge capacity to the LIB using liquid electrolyte, by the combination of the low-melting Li2.2C0.8B0.2O3 and the rapid sintering method.
 A. Aboulaich et al., Adv. Energy Mater., 2011, 1, 179.
 R. D. Shannon et al., Electrochem. Acta, 22 (1977) 783.