Tuning electronic structure ofδ-MnO_(2) by the alkali-ion(K,Na,Li)associated manganese vacancies for high-rate supercapacitors

Cation vacancies can bring numerous surprising characters due to its multifarious electron and orbit distribution.In this work,d-MnO_(2) with alkali-ion(K,Na,Li)associated manganese(Mn)vacancies is fabricated by a simple hydrothermal reaction,and the correlation between their electronic structure and pseudocapacitance are systematically investigated.FESEM/TEM images have shown that the morphology of MnO_(2) is obviously changed after the introducing of cation vacancies.The position of alkali-ion in MnO_(2) structure can be controlled by adjusting the ion concentration.XRD patterns and Raman spectra demonstrate that the alkali-ion is embedded in Mn vacancies at low concentration,while entered the interlayer of MnO_(2) at high concentration.The existence of Mn vacancies will resulting in the distortion of neighboring atoms,leading to the electronic delocalization,and thus enhancing the conductivity,pseudocapacitance and rate capability of MnO_(2).Accordingly,the specific capacitances of optimized 0.4 KMO,0.4 NaMO and 0.4 LiMO samples are enhanced about 1.9,1.6 and 1.6 times compared to pure MnO_(2).Meanwhile,the rate performance has also been improved about 76%,46%and 42%,respectively.Theoretical calculations further confirm that the Mn vacancies can generate additional occupancy states and cause an increase in carrier concentration,which will improve the conductivity and further boost the pseudocapacitance of MnO_(2).This result open up a promising approach to explore active and durable electrode materials.

水系锌电池中自组装电极-电解质界面相实现高可逆的锌金属负极

由于缺乏先进的固体电解质界面相,水系锌电池的循环寿命受到锌金属负极副反应和枝晶等问题的严重制约.本文介绍了一种由两性分子(APMs)电解液添加剂构建而成的自组装电极-电解质界面相(AEEI).作为一个示范,这里选取聚乙烯吡咯烷酮(PVP)用做APMs,因为它的羰基氧原子与芳香性的吡咯环共轭,从而具有较强的电子给体性质.X射线光电子能谱和傅里叶变换红外光谱分析表明,AEEI的形成和稳定是由APMs的羰基氧原子同时与锌金属和锌离子相互作用推动的.所形成的AEEI主要由富含锌离子的APMs致密层状胶束构成.在电解质中保持APMs的含量在临界聚集浓度(~0.1%)以上,可以保证AEEI的固有稳定性,避免裂纹形成或脱落等问题.得益于其抑制水分解副反应和不利的二维锌扩散的能力,在AEEI的作用下实现了无枝晶的锌沉积.在1 M Zn(OTf)_(2)添加1%PVP的电解液中,形成的AEEI保证了锌对称电池具有超过2000小时的长循环寿命,Zn||Ti电池500个循环后库仑效率高于99.2%,以及V_(2)O_(5)||Zn全电池500个循环后容量的高保持率(达76%).