ABSTRACT
As an emerging green energy storage and conversion system, rechargeable Li-CO2 batteries have undergone extensive research due to their ultra-high energy density and their significant role in greenhouse gas CO2 conversion. However, current Li-CO2 batteries have some shortcomings that severely limit their large-scale application. The most critical problems involve the insulation of the discharge product Li2CO3 and the slow decomposition kinetics, meaning that the battery generates a large overpotential and has a low cycle life, so the rational design of an efficient cathode catalyst is imperative. Here, we prepared a composite material via the magnetron sputtering of Pt onto nitrogen-doped polypyrrole carbon nanotubes (NPPy-CNTs) as a high-efficiency cathode catalyst for Li-CO2 batteries. The three-dimensional hollow tubular NPPy-CNTs can provide efficient channels for CO2 diffusion and enough space for the uniform deposition and decomposition of Li2CO3. Benefiting from the doping of nitrogen, more defects and active sites are introduced into the polypyrrole carbon nanotubes. Furthermore, the introduction of a small amount of the precious metal Pt effectively improves the catalytic activity of the CO2 reduction reaction (CO2RR) and the CO2 release reaction (CO2ER), greatly improving the cycle life of the battery. The Pt-NPPy-CNT-based battery shows a much improved electrochemical performance. The overpotential of the battery is reduced to 0.75 V, and the battery shows a specific discharge capacity of up to 29 614 mA h g-1.
ABSTRACT
Nowadays, Li-CO2 batteries have attracted enormous interests due to their high energy density for integrated energy storage and conversion devices, superiorities of capturing and converting CO2. Nevertheless, the actual application of Li-CO2 batteries is hindered attributed to excessive overpotential and poor lifespan. In the past decades, catalysts have been employed in the Li-CO2 batteries and been demonstrated to reduce the decomposition potential of the as-formed Li2CO3 during charge process with high efficiency. However, as a representative of promising catalysts, the high costs of noble metals limit the further development, which gives rise to the exploration of catalysts with high efficiency and low cost. In this work, we prepared a K+ doped MnO2 nanowires networks with three-dimensional interconnections (3D KMO NWs) catalyst through a simple hydrothermal method. The interconnected 3D nanowires network catalysts could accelerate the Li ions diffusion, CO2 transfer and the decomposition of discharge products Li2CO3. It is found that high content of K+ doping can promote the diffusion of ions, electrons and CO2 in the MnO2 air cathode, and promote the octahedral effect of MnO6, stabilize the structure of MnO2 hosts, and improve the catalytic activity of CO2. Therefore, it shows a high total discharge capacity of 9,043 mAh g-1, a low overpotential of 1.25 V, and a longer cycle performance.
ABSTRACT
Lithium-rich layered oxide is one of the most promising candidates for the next-generation cathode materials of high-energy-density lithium ion batteries because of its high discharge capacity. However, it has the disadvantages of uneven composition, voltage decay, and poor rate capacity, which are closely related to the preparation method. Here, 0.5Li2MnO3·0.5LiMn0.8Ni0.1Co0.1O2 was successfully prepared by sol-gel and oxalate co-precipitation methods. A systematic analysis of the materials shows that the 0.5Li2MnO3·0.5LiMn0.8Ni0.1Co0.1O2 prepared by the oxalic acid co-precipitation method had the most stable layered structure and the best electrochemical performance. The initial discharge specific capacity was 261.6 mAh·g-1 at 0.05 C, and the discharge specific capacity was 138 mAh·g-1 at 5 C. The voltage decay was only 210 mV, and the capacity retention was 94.2% after 100 cycles at 1 C. The suppression of voltage decay can be attributed to the high nickel content and uniform element distribution. In addition, tightly packed porous spheres help to reduce lithium ion diffusion energy and improve the stability of the layered structure, thereby improving cycle stability and rate capacity. This conclusion provides a reference for designing high-energy-density lithium-ion batteries.
