Recent Progress and Challenges of Micro‐/Nanostructured Transition Metal Carbonate Anodes for Lithium Ion Batteries

Abstract

Lithium ion batteries (LIBs) have attracted tremendous interest in electric vehicles and smart grids, due to their inherent advantages of being powerful and environmentally benign. However, their performance is presently far from meeting the continually increasing demands for long-durance mileage and long lifespan. High-performance anodes with high specific capacity and long cyclability are of great significance to high-energy/high-power lithium ion batteries; however, there are still great challenges in advancing new materials beyond commercial graphite, whose capacity is low and limited by the theoretical values (372 mAh g -1 ). That is why scientists are continually searching for satisfying anode alternatives to graphite. [a] 4515 Figure 13. SEM and TEM images of (a) Mn 0.2 Fe 0.8 CO 3 /r-GO composites, (b, c) Co 0.2 Mn 0.8 CO 3 /graphene composites, and (d) Zn 0.12 Co 0.88 CO 3 /CNT composites. Reprinted with permission from ref. [62] Copyright 2017 Elsevier. The superiority of graphene (e, f and g) or CNT hybrid composites (h) indicated by the enhanced electrochemical behaviors. Reprinted with permission from ref. [67,68]

Utilizing Cyclic Voltammetry to Understand the Energy Storage Mechanisms for Copper Oxide and its Graphene Oxide Hybrids as Lithium‐Ion Battery Anodes

“…Although undesirable, this material is expected to show similar chemistry to CuO, with respect to lithiation. We note that previous literature has described the use of transition metal carbonates an anode material . The absence of the GO peak at 2 θ ≈11° in Cu‐3, Cu‐4, and Cu‐5 indicates that the graphene is present as mono/few layers in the graphene hybrid materials.…”

Crystal Water‐Assisted Additional Capacity for Nickel Hydroxide Anode Materials

“…However, previous reports have shown that CoCO 3 delivers a higher capacity than its theoretical value, as the conversion reaction product, Li 2 CO 3 , participates reversibly in the electrochemical reaction via the redox reaction of C 4+ to low valence C. [ 10,11 ] Owing to the reversible redox reaction of carbon in Li 2 CO 3 , transition metal carbonates exhibit higher practical capacities than transition metal oxides with the same metal oxidation state, despite their lower theoretical capacities. [ 12,13 ]…”

“…However, previous reports have shown that CoCO 3 delivers a higher capacity than its theoretical value, as the conversion reaction product, Li 2 CO 3 , participates reversibly in the electrochemical reaction via the redox reaction of C 4+ to low valence C. [10,11] Owing to the reversible redox reaction of carbon in Li 2 CO 3 , transition metal carbonates exhibit higher practical capacities than transition metal oxides with the same metal oxidation state, despite their lower theoretical capacities. [12,13] Similarly, it was also reported that the LiOH formed by the conversion reaction of Co(OH) 2 contributes to extra reversible capacity in the presence of nanosized Co metal. [14] Hu et al demonstrated that some -OH groups at the surface of RuO 2 lead to LiOH formation, which then reacts with lithium to form Li 2 O and LiH phases, thereby providing unexpected additional capacity.…”

Formation of Li2CO3 Nanostructures for Lithium-Ion Battery Anode Application by Nanotransfer Printing

“…These reports assume that not only the crystal structure but also the physical shape (or morphology) of the anode materials, such as Si, hematite (Fe 2 O 3 ), and LMO (Li M O 2 , M = Co, Ni, Mn) can significantly affect the performance of LIBs, implying that control of anode nanostructures is necessary. As one of the strategies, nanoscale pattern formation of lithium carbonate (Li 2 CO 3 ) on the LIB anode such as graphite can provide good passivation and may also promote rich solid electrolyte interphase (SEI) at interface of anode and electrolyte [ 22 , 23 , 24 , 25 ].…”