Stable Lithium Storage at Subzero Temperatures for High‐capacity Co₃O₄@graphene Composite Anodes

Abstract

Achieving high energy density and long‐term stability at subzero temperatures remains one of the main challenges for the development of lithium‐ion batteries. Shortcomings in energy density and stability mainly highlight on the increase in internal resistance and electrode polarization at subzero temperatures, which greatly affect the reversible capacities of lithium‐ion batteries. In this work, a conversion type Co3O4@graphene (Co3O4@G) composite is prepared via a simple hydrothermal method and first evaluated at subzero temperatures. Benefitting from the especially suitable lithiation/delithiation potentials of Co3O4, ingenious nanostructure and high conductivity of graphene, the Co3O4@G anode exhibits much higher capacity retentions than intercalation‐ and alloying‐type anodes at subzero temperatures, with 58.4% of room‐temperature capacity retention at −30 °C for initial cycle and a highly stable reversible capacity of 605.0 mAh g−1 (0.5 A g−1) for 600 cycles at −10 °C. Furthermore, very high capacities of ∼920.4 mAh g−1 (0.2 A g−1) can be maintained at 30 °C, and ∼450.2 mAh g−1 (0.5 A g−1) can be remained at −20 °C during alternating cycling. This work demonstrates that conversion‐type Co3O4@G composites have superior extreme temperature lithium storage capabilities and can be viable Li‐ion anode materials with fast and highly efficient ion/electron transport capacity at subzero operating temperatures.

LiF‐Induced Stable Solid Electrolyte Interphase for a Wide Temperature SnO2‐Based Anode Extensible to −50 °C

“…For the Li 1s spectrum, the binding energy of around 55.8 and 55.1 eV are corresponding to the Li-F and Li-O/Li-C, [40,42] respectively. And for the C1s spectrum, the binding energy of around 284.8, 286.5, 288.1, and 289.7 eV represent the CC, CO, CO, and CCO, [11] respectively. Besides, the Sn 3d, F 1s, and O 1s spectra were shown in Figure S13, Supporting Information.…”

“…Recently, extensive efforts have been committed to promote the low‐temperature Li storage capability of the anode materials, including alloying‐type Sn–Cu and Sn–C, [ 9 ] conversion‐type metal oxides, such as V 2 O 5 , [ 10 ] Co 3 O 4 , [ 11 ] CoFe 2 O 4 , [ 12 ] MnO, [ 13 ] and metal sulfide MnS. [ 14 ] It has been shown that all these anode materials can discharge the LIBs successfully from subzero temperature to −25 °C, however, they cannot maintain cycle stability at high temperatures.…”

“…[8] For the latter, the awkward cycling ability of the anode at elevated temperature is mainly due to the increased instability of the electrolyte, in which the in situ-formed SEI is unable to avoid the oxidative decomposition of the electrolyte at a high potential, resulting in unstable electrode cycling and abnormal consumption of electrolyte. Therefore, to achieve a superior operation at a wide temperature, the electrode material in LIBs needs to have decent Li + conductivity at sub-zero temperature and have stable SEI with fast Li + transport at elevated temperature.Recently, extensive efforts have been committed to promote the low-temperature Li storage capability of the anode materials, including alloying-type Sn-Cu and Sn-C, [9] conversion-type metal oxides, such as V 2 O 5 , [10] Co 3 O 4 , [11] CoFe 2 O 4 , [12] MnO, [13] and metal sulfide MnS. [14] It has been shown that all these anode materials can discharge the LIBs successfully from subzero temperature to −25 °C, however, they cannot maintain cycle stability at high temperatures.…”

Carbon-based materials and their composites as anodes: A review on lithium-ion batteries

“…At the current density of 100 mA/g, the initial discharge capacity of the composite was 1974 mAh/g [217]. Tan et al [218] employed a simple hydrother-mal method to synthesize the conversion Co 3 O 4 /Graphene composite. Outstanding extreme-temperature Li storage capacity was provided by this composite.…”

Engineering hierarchical Sb2S3/N–C from natural minerals with stable phase-change towards all-climate energy storage

“…From previous reports, it could be found that the relative working potential (0.2 V below) would further deteriorate this unexpected behavior. 46 Thus, despite the effect on energy density, exploring promising electrodes with high working voltage was very signicant for ESSs. Surprisingly, owing to the relatively high operation potential, metal suldes have been considered suitable candidates.…”