All-solid-state lithium batteries (ASSLBs) are receiving attention as a prospective next-generation secondary battery technology that can reduce the risk of commercial lithium-ion batteries by replacing flammable organic liquid electrolytes with non-flammable solid electrolytes. The practical application of ASSLBs requires developing robust solid electrolytes that possess ionic conductivity at room temperature on a par with that of organic liquids. These solid electrolytes must also be thermally and chemically stable, as well as compatible with electrode materials. Inorganic solid electrolytes, including oxide and sulfide-based compounds, are being studied as promising future candidates for ASSLBs due to their higher ionic conductivity and thermal stability than polymer electrolytes. Here, we present the challenges currently facing the development of oxide and sulfide-based solid electrolytes, as well as the research efforts underway aiming to resolve these challenges.
In order to prepare anode materials for high power lithium ion secondary batteries, carbon composites were fabricated with a mixture of petroleum pitch and coke (PC) and a mixture of petroleum pitch, coke, and natural graphite (PCNG). Although natural graphite has a good reversible capacity, it has disadvantages of a sharp decrease in capacity during high rate charging and potential plateaus. This may cause difficulties in perceiving the capacity variations as a function of electrical potential. The coke anodes have advantages without potential plateaus and a high rate capability, but they have a low reversible capacity. With PC anode composites, the petroleum pitch/cokes mixture at 1:4 with heat treatment at 1000 oC (PC14-1000C) showed relatively high electrochemical properties. With PC-NG anode composites, the proper graphite contents were determined at 10~30 wt.%. The composites with a given content of natural graphite and remaining content of various petroleum pitch/cokes mixtures at 1:4~4:1 mass ratios were heated at 800~1200 oC. By increasing the content of petroleum pitch, reversible capacity increased, but a high rate capability decreased. For a given composition of carbonaceous composite, the discharge rate capability improved but the reversible capacity decreased with an increase in heat treatment temperature. The carbonaceous composites fabricated with a mixture of 30 wt.% natural graphite and 70 wt.% petroleum pitch/cokes mixture at 1:4 mass ratio and heat treated at 1000 oC showed relatively high electrochemical properties, of which the reversible capacity, initial efficiency, discharge rate capability (retention of discharge capacity in 10 C/0.2 C), and charge capacity at 5 C were 330 mAh/g, 79 %, 80 %, and 60 mAh/g, respectively.
Cathode materials and their precursors are prepared with transition metal solutions recycled from the thewaste lithium-ion batteries containing NCM (nickel-cobalt-manganese) cathodes by a H2 and C-reduction process. Therecycled transition metal sulfate solutions are used in a co-precipitation process in a CSTR reactor to obtain the tran-sition metal hydroxide. The NCM cathode materials (Ni:Mn:Co=5:3:2) are prepared from the transition metal hydroxideby calcining with lithium carbonate. X-ray diffraction and scanning electron microscopy analyses show that the cathodematerial has a layered structure and particle size of about 10 µm. The cathode materials also exhibited a capacity ofabout 160 mAh/g with a retention rate of 93~96% after 100 cycles.
This study investigated the dependence of the various sputtering conditions (Ar pressure: 2~10 mTorr, Power: 50~150 W) and thickness (50~1200 nm) of Si thin film on the electrochemical properties, microstructural properties and the capacity fading of a Si thin film anode. A Si layer and a Ti buffer layer were deposited on Copper foil by RF-magnetron sputtering. At 10 mTorr, the 50 W sample showed the best capacity of 3323 mAh/g, while the 100 W sample showed the best capacity retention of 91.7%, also at 10 mTorr. The initial capacities and capacity retention in the samples apart from the 50W sample at 10 mTorr were enhanced as the Ar pressure and power increased. This was considered to be related to the change of the microstructure and the surface morphology by various sputtering conditions. In addition, thinner Si film anodes showed better cycling performance. This phenomenon is caused by the structural stress and peeling off of the Si layer by the high volume change of Si during the charge/discharge process.
Lithium intercalated carbon (LIC) are basically employed as an anode for currently commercialized lithium secondary batteries. However, there are still strong interests in modifying carbon surface of active materials of the anode because the amount of irreversible capacity, charge-discharge capacity and high rate capability are largely determined by the surface conditions of the carbon. In this study, the carbonaceous materials were coated with tin oxide and copper by fluidized-bed chemical vapor deposition (CVD) method and their coating effects on electrochemical characteristics were investigated. The electrode which coated with tin oxides gave the higher capacity than that of raw material. Their capacity decreased with the progress of cycling possibly due to severe volume changes. However, the cyclability was improved by coating with copper on the surface of the tin oxides coated carbonaceous materials, which plays an important role as an inactive matrix buffering volume changes. An impedance on passivation film was decreased as tin oxides contents and it resulted in the higher capacity.