The ion-exchanger LiMg0.5Mn1.5O4 of spinel type was prepared by the common precipitation/heated crystallization method, and was acid modified. Its properties of ion-exchange for alkali ions such as saturation capacity...The ion-exchanger LiMg0.5Mn1.5O4 of spinel type was prepared by the common precipitation/heated crystallization method, and was acid modified. Its properties of ion-exchange for alkali ions such as saturation capacity of exchange, distribution coefficient and the pH titration curve have been determined. LiMg0.5Mn1.5O4 was characterized by X-ray diffraction. These results show that this inorganic ion-exchanger has better remembering and selectivity of ion exchange, and higher capacity of exchange for Li+, the capacity of exchange reaches 32.39 mg·g-1 for Li+.展开更多
The high Li-ion conductivity of the Li7P3S11 sulfide-based solid electrolyte makes it a promising candidate for all-solid-state lithium batteries. The Li-ion transport over electrode-electrolyte and electrolyteelectro...The high Li-ion conductivity of the Li7P3S11 sulfide-based solid electrolyte makes it a promising candidate for all-solid-state lithium batteries. The Li-ion transport over electrode-electrolyte and electrolyteelectrolyte interfaces, vital for the performance of solid-state batteries, is investigated by impedance spectroscopy and solid-state NMR experiments. An all-solid-state Li-ion battery is assembled with the Li7P3S11 electrolyte, nano-Li2S cathode and Li-In foil anode, showing a relatively large initial discharge capacity of 1139.5 m Ah/g at a current density of 0.064 m A/cm^ 2 retaining 850.0 m Ah/g after 30 cycles. Electrochemical impedance spectroscopy suggests that the decrease in capacity over cycling is due to the increased interfacial resistance between the electrode and the electrolyte. 1D exchange ^7Li NMR quantifies the interfacial Li-ion transport between the uncycled electrode and the electrolyte, resulting in a diffusion coefficient of 1.70(3) ×10^-14cm^2/s at 333 K and an energy barrier of 0.132 e V for the Li-ion transport between Li2S cathode and Li7P3S11 electrolyte. This indicates that the barrier for Li-ion transport over the electrode-electrolyte interface is small. However, the small diffusion coefficient for Li-ion diffusion between the Li2S and the Li7P3S11 suggests that these contact interfaces between electrode and electrolyte are relatively scarce, challenging the performance of these solid-state batteries.展开更多
A new model of porous electrodes based on the Gibbs free energy is developed, in which lithium-ion(Liion) diffusion, diffusion-induced stress(DIS), Butler–Volmer(BV) reaction kinetics, and size polydispersity of elec...A new model of porous electrodes based on the Gibbs free energy is developed, in which lithium-ion(Liion) diffusion, diffusion-induced stress(DIS), Butler–Volmer(BV) reaction kinetics, and size polydispersity of electrode particles are considered. The influence of BV reaction kinetics and concentration-dependent exchange current density(ECD) on concentration profile and DIS evolution are numerically investigated. BV reaction kinetics leads to a decrease in Li-ion concentration and DIS. In addition, concentrationdependent ECD results in a decrease in Li-ion concentration and an increase in DIS. Size polydispersity of electrode particles significantly affects the concentration profile and DIS.Optimal macroscopic state of charge(SOC) should consider the influence of the microscopic SOC values and mass fractions of differently sized particles.展开更多
Li4SiO4 ceramic pebble is considered as a candidate tritium breeding material of Chinese Helium Cooled Solid Breeder Test Blanket Module （CH HCSB TBM） for the International Thermonuclear Experimental Reactor （ITER...Li4SiO4 ceramic pebble is considered as a candidate tritium breeding material of Chinese Helium Cooled Solid Breeder Test Blanket Module （CH HCSB TBM） for the International Thermonuclear Experimental Reactor （ITER）. In this paper, LiaSiO4 ceramic pebbles deposited with catalytic metals, including Pt, Pd, Ru and Ir, were prepared by wet impregnation method. The metal particles on Li4SiO4 pebble exhibit a good promotion of hydrogen isotope exchange reactions in H2-D20 gas system, with conversion equilibrium temperature reduction of 200-300 ~C. The out-of-pile tritium release experiments were performed using 1.0 wt% Pt/Li4SiO4 and Li4SiO4 pebbles irradiated in a thermal neutron reactor. The thermal desorption spectroscopy shows that Pt was effective to increase the tritium release rate at lower temperatures, and the ratio of tritium molecule （HT） to tritiated water （HTO） of 1.0 wt% Pt/LiaSiO4 was much more than that of Li4SiO4, which released mainly as HTO. Thus, catalytic metals deposited on LiaSiO4 pebble may help to accelerate the recovery of bred tritium particularly in low temperature region, and increase the tritium molecule form released from the tritium breedin~ materials.展开更多
Ni/Li exchange is a detrimental effect on electrochemical performances for high-Ni cathode materials(LiNi_(x)Co_(y)Mn_(z)O_(2),x≥0.6).Adjusting Li-excess degree has been proved to be an effective way to optimize Ni/L...Ni/Li exchange is a detrimental effect on electrochemical performances for high-Ni cathode materials(LiNi_(x)Co_(y)Mn_(z)O_(2),x≥0.6).Adjusting Li-excess degree has been proved to be an effective way to optimize Ni/Li exchange in the materials.However,until now,how the Ni/Li exchange and thus the structural properties is affected by the Li-excess has not been understood and clearly elucidated in the literature.Herein,a feasible strategy is utilized to optimize Ni/Li exchange and the amount of anti-Li^(+)in LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) by mixing Ni_(0.8)Co_(0.1)Mn_(0.1)(OH)_(2) precursor with different amounts of lithium sources during lithiation.It was found that morphology and phase stability of the material can be tuned with moderate excessive lithium.With 10%Li-excess,LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) exhibits an initial discharge capacity of 211.5 mAh·g^(–1) at 0.1 C and maintains 93.3%of its initial capacity after 100 cycles at 1 C.Different technologies were used to characterize the materials and it shows that the formation of broader Li slab space,decreased anti-Ni^(2+)in Li layer,and gradient distribution of Ni3+in the surface is contributed to moderate Li-excess in the materials.Broader Li slab space facilitates diffusion of Li^(+),decreased antisite-Ni^(2+)and gradient distribution of Ni3+in materials surfaces optimizes the Ni/Li exchange.Based on these results,we thus believe that it is the moderate Li-excess in material that optimized the electrochemical performance of high-Ni cathode materials.展开更多
文摘The ion-exchanger LiMg0.5Mn1.5O4 of spinel type was prepared by the common precipitation/heated crystallization method, and was acid modified. Its properties of ion-exchange for alkali ions such as saturation capacity of exchange, distribution coefficient and the pH titration curve have been determined. LiMg0.5Mn1.5O4 was characterized by X-ray diffraction. These results show that this inorganic ion-exchanger has better remembering and selectivity of ion exchange, and higher capacity of exchange for Li+, the capacity of exchange reaches 32.39 mg·g-1 for Li+.
基金funding from the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013)/ERC Grant Agreement no.[307161] of M.W.
文摘The high Li-ion conductivity of the Li7P3S11 sulfide-based solid electrolyte makes it a promising candidate for all-solid-state lithium batteries. The Li-ion transport over electrode-electrolyte and electrolyteelectrolyte interfaces, vital for the performance of solid-state batteries, is investigated by impedance spectroscopy and solid-state NMR experiments. An all-solid-state Li-ion battery is assembled with the Li7P3S11 electrolyte, nano-Li2S cathode and Li-In foil anode, showing a relatively large initial discharge capacity of 1139.5 m Ah/g at a current density of 0.064 m A/cm^ 2 retaining 850.0 m Ah/g after 30 cycles. Electrochemical impedance spectroscopy suggests that the decrease in capacity over cycling is due to the increased interfacial resistance between the electrode and the electrolyte. 1D exchange ^7Li NMR quantifies the interfacial Li-ion transport between the uncycled electrode and the electrolyte, resulting in a diffusion coefficient of 1.70(3) ×10^-14cm^2/s at 333 K and an energy barrier of 0.132 e V for the Li-ion transport between Li2S cathode and Li7P3S11 electrolyte. This indicates that the barrier for Li-ion transport over the electrode-electrolyte interface is small. However, the small diffusion coefficient for Li-ion diffusion between the Li2S and the Li7P3S11 suggests that these contact interfaces between electrode and electrolyte are relatively scarce, challenging the performance of these solid-state batteries.
基金financial support by the National Natural Science Foundation of China (Grants 11472165, 11332005)
文摘A new model of porous electrodes based on the Gibbs free energy is developed, in which lithium-ion(Liion) diffusion, diffusion-induced stress(DIS), Butler–Volmer(BV) reaction kinetics, and size polydispersity of electrode particles are considered. The influence of BV reaction kinetics and concentration-dependent exchange current density(ECD) on concentration profile and DIS evolution are numerically investigated. BV reaction kinetics leads to a decrease in Li-ion concentration and DIS. In addition, concentrationdependent ECD results in a decrease in Li-ion concentration and an increase in DIS. Size polydispersity of electrode particles significantly affects the concentration profile and DIS.Optimal macroscopic state of charge(SOC) should consider the influence of the microscopic SOC values and mass fractions of differently sized particles.
基金supported by the Development Fund of China Academy of Engineering Physics (No.2010B0301035)the National Magnetic Confinement Fusion Science Program (No. 2010GB112004)
文摘Li4SiO4 ceramic pebble is considered as a candidate tritium breeding material of Chinese Helium Cooled Solid Breeder Test Blanket Module （CH HCSB TBM） for the International Thermonuclear Experimental Reactor （ITER）. In this paper, LiaSiO4 ceramic pebbles deposited with catalytic metals, including Pt, Pd, Ru and Ir, were prepared by wet impregnation method. The metal particles on Li4SiO4 pebble exhibit a good promotion of hydrogen isotope exchange reactions in H2-D20 gas system, with conversion equilibrium temperature reduction of 200-300 ~C. The out-of-pile tritium release experiments were performed using 1.0 wt% Pt/Li4SiO4 and Li4SiO4 pebbles irradiated in a thermal neutron reactor. The thermal desorption spectroscopy shows that Pt was effective to increase the tritium release rate at lower temperatures, and the ratio of tritium molecule （HT） to tritiated water （HTO） of 1.0 wt% Pt/LiaSiO4 was much more than that of Li4SiO4, which released mainly as HTO. Thus, catalytic metals deposited on LiaSiO4 pebble may help to accelerate the recovery of bred tritium particularly in low temperature region, and increase the tritium molecule form released from the tritium breedin~ materials.
基金the National Natural Science Foundation of China(No.21271145)the Natural Science Foundation of Hubei Province(No.2015CFB537)for the financial support for this investigation.
文摘Ni/Li exchange is a detrimental effect on electrochemical performances for high-Ni cathode materials(LiNi_(x)Co_(y)Mn_(z)O_(2),x≥0.6).Adjusting Li-excess degree has been proved to be an effective way to optimize Ni/Li exchange in the materials.However,until now,how the Ni/Li exchange and thus the structural properties is affected by the Li-excess has not been understood and clearly elucidated in the literature.Herein,a feasible strategy is utilized to optimize Ni/Li exchange and the amount of anti-Li^(+)in LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) by mixing Ni_(0.8)Co_(0.1)Mn_(0.1)(OH)_(2) precursor with different amounts of lithium sources during lithiation.It was found that morphology and phase stability of the material can be tuned with moderate excessive lithium.With 10%Li-excess,LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) exhibits an initial discharge capacity of 211.5 mAh·g^(–1) at 0.1 C and maintains 93.3%of its initial capacity after 100 cycles at 1 C.Different technologies were used to characterize the materials and it shows that the formation of broader Li slab space,decreased anti-Ni^(2+)in Li layer,and gradient distribution of Ni3+in the surface is contributed to moderate Li-excess in the materials.Broader Li slab space facilitates diffusion of Li^(+),decreased antisite-Ni^(2+)and gradient distribution of Ni3+in materials surfaces optimizes the Ni/Li exchange.Based on these results,we thus believe that it is the moderate Li-excess in material that optimized the electrochemical performance of high-Ni cathode materials.
