Engineering the microstructures of manganese dioxide coupled with oxygen vacancies for boosting aqueous ammonium-ion storage in hybrid capacitors

The aqueous ammonium ion(NH_(4)^(+))is a promising charge carrier in virtue of its safety,environmental friendliness,abundant resources and small hydrated ionic size.The exploration of NH_(4)^(+)host electrodes with good reversibility and large storage capacity to construct high-performance ammonium-ion hybrid capacitors(AIHCs),however,is still in its infancy.Herein,a facile etching technique is put forward to produce oxygen-deficient MnO_(2)(O_(d)-MnO_(2))as the electrode material for NH_(4)^(+)storage.According to the experimental and theoretical calculation results,the etching process not only creates more porosity,offering abundant active sites,but also generates abundant oxygen vacancies,which modify the structure of pristine MnO_(2),enhance charge storage capacity and boost ion diffusion kinetics.Consequently,Od-MnO_(2)can deliver a specific capacity of 155 mAh·g^(-1)at 0.5 A·g^(-1)and a good long-term cycling stability with86.8%capacity maintained after 10,000 cycles at5.0 A·g^(-1).Additionally,the NH_(4)^(+)storage mechanism was evidenced by several ex-situ characterization analyses.To examine the actual implementation of O_d-MnO_(2)as a positive electrode for NH_(4)^(+)full device,AIHCs are assembled with activated carbon functionalized with Fe_3O_(4)nanoparticles(Fe_(3)O_(4)@AC)as a negative electrode.A high specific capacitance of 184 F·g^(-1)at 0.5 A·g^(-1),satisfactory energy density of 102 Wh·kg^(-1)at 500 W·kg^(-1),a low self-discharge rate and good cycling durability after 10,000 cycles are attained.The electrochemical performance of these AIHCs is comparable to or surpass those of traditional supercapacitors with metal ions as charge carriers,highlighting the advantages of structural modification in enhancing the NH_(4)^(+)storage performance.