Improvement of elevated-temperature performance of Li1.02Cr0.1Mn1.9O4 cathode material by silicious surface modification was studied. The Li1.02Cr0.1Mn1.9O4 cathode material was treated by silanes coupling agent and t...Improvement of elevated-temperature performance of Li1.02Cr0.1Mn1.9O4 cathode material by silicious surface modification was studied. The Li1.02Cr0.1Mn1.9O4 cathode material was treated by silanes coupling agent and then heated at 580 ℃ to remove organic material. The structures of the modified and unmodified Li1.02Cr0.1Mn1.9O4 were characterized by SpectraPlus, SEM and XRD. The results show that the surface layer of Li1.02Cr0.1Mn1.9O4 material is found to be rich in silicious compound. X-ray diffraction show that all the samples have perfect spinel structure. The electrochemical characterization of modified Li1.02Cr0.1Mn1.9O4 cathode material was tested. The cycle stability of charge/discharge at 55℃ is improved. The results of the charge/discharge curves show that the modified Li1.02Cr0.1Mn1.9O4 has better performance than those unmodified according to the inhibition of decline of reversible capacity of spinel Li1.02Cr0.1Mn1.9O4. Therefore, cycle performance is improved so obviously that 86.03% of the initial capacity is preserved after 100 cycles.展开更多
采用溶胶-凝胶的方法低温制备石榴石结构的固体电解质Li5La3Ta2O12,并用其包覆Li Mn2O4来改善材料的电化学性能。通过XRD,SEM和TEM等表征手段对材料的结构和形貌进行分析,并通过恒电流充放电、循环伏安、交流阻抗等测试分析材料的电化...采用溶胶-凝胶的方法低温制备石榴石结构的固体电解质Li5La3Ta2O12,并用其包覆Li Mn2O4来改善材料的电化学性能。通过XRD,SEM和TEM等表征手段对材料的结构和形貌进行分析,并通过恒电流充放电、循环伏安、交流阻抗等测试分析材料的电化学性能。研究结果表明:Li5La3Ta2O12包覆的Li Mn2O4材料与未包覆的材料相比,其电化学性能得到明显改善,经过150次循环后包覆材料的放电比容量保持率为92%,在高倍率10C(C为倍率)下包覆材料放电比容量为61.2 m A·h/g,而未包覆材料放电比容量仅为40.7 m A·h/g;包覆Li5La3Ta2O12后,Li Mn2O4的阻抗明显减小,大幅度提高了其循环性能和倍率性能。展开更多
The pure Cr2O3 coated Li4Ti5O12 microspheres were prepared by a facile and cheap solution- based method with basic chromium（III） nitrate solution （pH=ll.9）. And their Li-storage properties were investigated as ano...The pure Cr2O3 coated Li4Ti5O12 microspheres were prepared by a facile and cheap solution- based method with basic chromium（III） nitrate solution （pH=ll.9）. And their Li-storage properties were investigated as anode materials for lithium rechargeable batteries. The pure Cr2O3 works as an adhesive interface to strengthen the connections between Li4Ti5O12 par- ticles, providing more electric conduction channels, and reduce the inter-particle resistance. Moreover, Li2Cr2O3, formed by the lithiation of Cr2O3, can further stabilize LiTTi5O12 with high electric conductivity on the surface of particles. While in the acid chromium solution （pH=3.2） modification, besides Cr2O3, Li2CrO4 and TiO2 phases were also found in the final product. Li2CrO4 is toxic and the presence of TiO2 is not welcome to im- prove the electrochemical performance of Li4Ti5O12 microspheres. The reversible capacity of 1% Cr2O3-coated sample with the basic chromium solution modification was 180 mAh/g at 0.1 C, and 134 mAh/g at 10 C. Moreover, it was even as high as 127 mAh/g at 5 C after 600 cycles. At -20 ℃, its reversible specific capacity was still as high as 118 mAh/g.展开更多
Spinel lithium manganese oxide ion-sieves have been considered the most promising adsorbents to extract Li^+ from brines and sea water.Here,we report a lithium ion-sieve which was successfully loaded onto tubular α-A...Spinel lithium manganese oxide ion-sieves have been considered the most promising adsorbents to extract Li^+ from brines and sea water.Here,we report a lithium ion-sieve which was successfully loaded onto tubular α-Al2 O3 ceramic substrates by dipping crystallization and post-calcination method.The lithium manganese oxide Li4 Mn5 O(12)was first synthesized onto tubular α-Al2 O3 ceramic substrates as the ion-sieve precursor(i.e.L-AA),and the corresponding lithium ion-sieve(i.e.H-AA) was obtained after acid pickling.The chemical and morphological properties of the ion-sieve were confirmed by X-ray diffraction(XRD) and scanning electron microscopy(SEM).Both L-AA and H-AA showed characteristic peaks of α-Al2 O3 and cubic phase Li4 Mn5 O(12) and the peaks representing cubic phase could still exist after pickling.The lithium manganese oxide Li4 Mn5 O(12) could be uniformly loaded not only on the surface of α-Al2 O3 ubstrates but also inside the pores.Moreover,we found that the equilibrium adsorption capacity of H-AA was 22.9 mg·g^-1.After 12 h adsorption,the adsorption balance was reached.After 5 cycles of adsorption,the adsorption capacity of H-AA was 60.88% of the initial adsorption capacity.The process of H-AA adsorption for Li^+correlated with pseudo-second order kinetic model and Langmuir model.Adsorption thermodynamic parameters regarding enthalpy(△N), Gibbs free energy(△G) and entropy(AS) were calculated.For the dynamic adsorptiondesorption process of H-AA,the H-AA exhibited excellent adsorption performance to Li^+ with the Li^+ dynamic adsorption capacity of 9.74 mg·g^-1 and the Mn^2+dissolution loss rate of 0.99%.After 3 dynamic adsorption-desorption cycles,80% of the initial dynamic adsorption capacity was still kept.展开更多
文摘Improvement of elevated-temperature performance of Li1.02Cr0.1Mn1.9O4 cathode material by silicious surface modification was studied. The Li1.02Cr0.1Mn1.9O4 cathode material was treated by silanes coupling agent and then heated at 580 ℃ to remove organic material. The structures of the modified and unmodified Li1.02Cr0.1Mn1.9O4 were characterized by SpectraPlus, SEM and XRD. The results show that the surface layer of Li1.02Cr0.1Mn1.9O4 material is found to be rich in silicious compound. X-ray diffraction show that all the samples have perfect spinel structure. The electrochemical characterization of modified Li1.02Cr0.1Mn1.9O4 cathode material was tested. The cycle stability of charge/discharge at 55℃ is improved. The results of the charge/discharge curves show that the modified Li1.02Cr0.1Mn1.9O4 has better performance than those unmodified according to the inhibition of decline of reversible capacity of spinel Li1.02Cr0.1Mn1.9O4. Therefore, cycle performance is improved so obviously that 86.03% of the initial capacity is preserved after 100 cycles.
文摘采用溶胶-凝胶的方法低温制备石榴石结构的固体电解质Li5La3Ta2O12,并用其包覆Li Mn2O4来改善材料的电化学性能。通过XRD,SEM和TEM等表征手段对材料的结构和形貌进行分析,并通过恒电流充放电、循环伏安、交流阻抗等测试分析材料的电化学性能。研究结果表明:Li5La3Ta2O12包覆的Li Mn2O4材料与未包覆的材料相比,其电化学性能得到明显改善,经过150次循环后包覆材料的放电比容量保持率为92%,在高倍率10C(C为倍率)下包覆材料放电比容量为61.2 m A·h/g,而未包覆材料放电比容量仅为40.7 m A·h/g;包覆Li5La3Ta2O12后,Li Mn2O4的阻抗明显减小,大幅度提高了其循环性能和倍率性能。
基金This work was supported by the National Natural Science Foundation of China （No.51372060 and No.31501576）.
文摘The pure Cr2O3 coated Li4Ti5O12 microspheres were prepared by a facile and cheap solution- based method with basic chromium（III） nitrate solution （pH=ll.9）. And their Li-storage properties were investigated as anode materials for lithium rechargeable batteries. The pure Cr2O3 works as an adhesive interface to strengthen the connections between Li4Ti5O12 par- ticles, providing more electric conduction channels, and reduce the inter-particle resistance. Moreover, Li2Cr2O3, formed by the lithiation of Cr2O3, can further stabilize LiTTi5O12 with high electric conductivity on the surface of particles. While in the acid chromium solution （pH=3.2） modification, besides Cr2O3, Li2CrO4 and TiO2 phases were also found in the final product. Li2CrO4 is toxic and the presence of TiO2 is not welcome to im- prove the electrochemical performance of Li4Ti5O12 microspheres. The reversible capacity of 1% Cr2O3-coated sample with the basic chromium solution modification was 180 mAh/g at 0.1 C, and 134 mAh/g at 10 C. Moreover, it was even as high as 127 mAh/g at 5 C after 600 cycles. At -20 ℃, its reversible specific capacity was still as high as 118 mAh/g.
基金This work was financially supported by National Key Research and Development Program(2018YFE0203502),ChinaPrimary Research and Development Plan ofJiangsu Province(BE2019117),China and National Students'Platform for Innovation and Entrepreneurship Training(201910291051Z),China.
文摘Spinel lithium manganese oxide ion-sieves have been considered the most promising adsorbents to extract Li^+ from brines and sea water.Here,we report a lithium ion-sieve which was successfully loaded onto tubular α-Al2 O3 ceramic substrates by dipping crystallization and post-calcination method.The lithium manganese oxide Li4 Mn5 O(12)was first synthesized onto tubular α-Al2 O3 ceramic substrates as the ion-sieve precursor(i.e.L-AA),and the corresponding lithium ion-sieve(i.e.H-AA) was obtained after acid pickling.The chemical and morphological properties of the ion-sieve were confirmed by X-ray diffraction(XRD) and scanning electron microscopy(SEM).Both L-AA and H-AA showed characteristic peaks of α-Al2 O3 and cubic phase Li4 Mn5 O(12) and the peaks representing cubic phase could still exist after pickling.The lithium manganese oxide Li4 Mn5 O(12) could be uniformly loaded not only on the surface of α-Al2 O3 ubstrates but also inside the pores.Moreover,we found that the equilibrium adsorption capacity of H-AA was 22.9 mg·g^-1.After 12 h adsorption,the adsorption balance was reached.After 5 cycles of adsorption,the adsorption capacity of H-AA was 60.88% of the initial adsorption capacity.The process of H-AA adsorption for Li^+correlated with pseudo-second order kinetic model and Langmuir model.Adsorption thermodynamic parameters regarding enthalpy(△N), Gibbs free energy(△G) and entropy(AS) were calculated.For the dynamic adsorptiondesorption process of H-AA,the H-AA exhibited excellent adsorption performance to Li^+ with the Li^+ dynamic adsorption capacity of 9.74 mg·g^-1 and the Mn^2+dissolution loss rate of 0.99%.After 3 dynamic adsorption-desorption cycles,80% of the initial dynamic adsorption capacity was still kept.
