Electrochemical construction of three-dimensional porous Mn₃O₄ nanosheet arrays as an anode for the lithium ion battery

Abstract

Three-dimensional (3D) porous Mn3O4 nanosheet arrays were constructed via an electrodeposition followed by high temperature annealing using 3D porous Cu, prepared by a facile electroless plating method, as the substrate. The 3D pores and voids between the nanosheet arrays were able to provide rapid ion transfer channels, as well as accommodating the volumetric changes of Mn3O4 during the electrochemical cycling. Electrons can directly exchange between the substrate and the nanosheet units, avoiding curving and the long transfer distance in conventional electrodes constructed using casting technology. Furthermore, the nanosheets were transformed into the architecture with smaller sub-nanosheets on the pristine nanosheets after 1 cycle, facilitating ion transferring, and were thoroughly transformed into smaller sub-nanosheets after 1000 cycles but without obvious exfoliation, assuring good electrical contact between the active particles and substrate. Based on the above unique characteristics, the 3D porous Mn3O4 nanosheet arrays could be directly used as a binder-free and conductive-agent-free electrode to deliver ultrahigh electrochemical performance that is much better than achieved in previous reports. The first reversible capacity was 1166.3 mA h g(-1) and remained 667.9 mA h g(-1) after 1000 cycles at 1.0 A g(-1). Also, the reversible capacities at high current densities of 10.0 A g(-1) and 20.0 A g(-1) remained high at 416.1 and 216.7 mA h g(-1), respectively.

Co(OH)2@MnO2 nanosheet arrays as hybrid binder-free electrodes for high-performance lithium-ion batteries and supercapacitors

“…Furthermore, by direct growth on current-collector, the electrical resistance of the binder can be avoided, and promote fast electron transport to current collector which improves the supercapacitive properties of the electrode. For example, Fan et al [21] deposited porous Mn3O4 nanosheet arrays on porous Cu and used as binder free anode for LIB. These electrodes exhibited a reversible capacity of 667.9 mA h g -1 even after 1000 cycles at 1.0 A g -1 .…”

Study on the Synthesis of Mn3O4 Nanooctahedrons and Their Performance for Lithium Ion Batteries

“…In the third cycle, the reduction/oxidation peaks are identical to those appeared in the second cycle, which indicate the good reversibility of Mn 3 O 4 nano-octahedrons electrode [7,70,75]. So the electrochemical reaction that occurs in the first discharge/charge cycle will be summarized as the following equations [14,76,77]:…”

“…The intensive peak emerging at 0.12 V may be related to the reduction of Mn 3 O 4 to MnO [71], the second peak locating at 0.88 V corresponds to the formation of the SEI layer on the electrode surface [69]. The third peak appearing at 1.06 V can be attributed to the reaction between Mn 3 O 4 and Li during the process of the SEI layer formation [14]. The latter two weak peaks disappeared in the following cycles because they were annihilated in the next cycles [74].…”

“…However, the low electrical conductivity and large volume change during charge/discharge processes decrease its specific capacity, render rapid capacity loss, and then restrict its applications in the energy conversion and energy storage [5,7]. Now, Mn 3 O 4 materials with micro/nanosizes have been synthesized by a variety of methods, such as the hydrothermal method [8,9], solvothermal method [10], precipitation method [11], chemical decomposition [12], sputtering [13], electrodeposition [14], thermal decomposition [15], and so on. Mn 3 O 4 nanoparticles with different morphologies have been successfully prepared.…”

Rice Husk‐Based 3D Porous Silicon/Carbon Nanocomposites as Anode for Lithium‐Ion Batteries

“…A lithium‐ion battery (LIB), due to its high energy density and long cycling life, is recognized as one of the most attractive energy storage devices . Silicon (Si) is abundant in crust and has been widely investigated as a promising anode for LIB to substitute the commercial graphite carbon (C) because of its better safety, where its higher electrode potential (≈0.5 V vs Li/Li + ) preventing the lithium metal deposition during battery overcharge and much higher theoretical capacity of 3579 mAh g −1 based on the formation of Li 15 Si 4 at room temperature .…”