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Through a simple gelation-solvothermal method with graphene oxide as the additive, a Cu4SnS4-rich composite of nanoparticles and nanotubes is synthesized and applied for thin and flexible Li-metal batteries. Unlike the Cu2SnS3-rich electrode, the Cu4SnS4-rich electrode cycles stably with an enhanced conversion capacity of ∼416 mAh g-1 (∼52% of total capacity) after 200 cycles. The lithiation/delithiation mechanisms of Cu-Sn-S electrodes and the voltage ranges of conversion and alloying reactions are informed by in situ X-ray diffraction tests. The conversion process of three Cu-Sn-S compounds is compared by density functional theory (DFT) calculations based on three algorithms, elucidating the enhanced conversion stability and superior diffusion kinetics of Cu4SnS4 electrodes. The reaction pathway of Cu-Sn-S electrodes and the root cause for the unstable capacity are revealed by in situ/ex situ characterizations, DFT calculations, and various electrochemical tests. This work provides insight into developing energy materials and power devices based on multiple lithiation mechanisms.

By preventing electrical contact between anode and cathode electrodes while promoting ionic transport, separators are critical components in the safe operation of rechargeable battery technologies. However, traditional polymer-based separators have limited thermal stability, which has contributed to catastrophic thermal runaway failure modes that have conspicuously plagued lithium-ion batteries. Here, we describe the development of phase-inversion composite separators based on carbon-coated hexagonal boron nitride (hBN) nanosheets and poly(vinylidene fluoride) (PVDF) polymers that possess high porosity, electrolyte wettability, and thermal stability. The carbon-coated hBN nanosheets are obtained through a scalable liquid-phase shear exfoliation method using ethyl cellulose as a polymer stabilizer and source of the carbon coating following thermal pyrolysis. When incorporated within the PVDF matrix, the carbon-coated hBN nanosheets promote favorable interfacial interactions during the phase-inversion process, resulting in porous, flexible, free-standing composite separators. The unique chemical composition of these carbon-coated hBN separators implies high wettability for a wide range of liquid electrolytes. This combination of high porosity and electrolyte wettability enables enhanced ionic conductivity and lithium-ion battery electrochemical performance that exceeds incumbent polyolefin separators over a wide range of operating conditions. The hBN nanosheets also impart high thermal stability, providing safe lithium-ion battery operation up to 120 °C.

Solid-state electrolytes based on ionic liquids and a gelling matrix are promising for rechargeable lithium-ion batteries due to their safety under diverse operating conditions, favorable electrochemical and thermal properties, and wide processing compatibility. However, gel electrolytes also suffer from low mechanical moduli, which imply poor structural integrity and thus an enhanced probability of electrical shorting, particularly under conditions that are favorable for lithium dendrite growth. Here, we realize high-modulus, ion-conductive gel electrolytes based on imidazolium ionic liquids and exfoliated hexagonal boron nitride (hBN) nanoplatelets. Compared to conventional bulk hBN microparticles, exfoliated hBN nanoplatelets improve the mechanical properties of gel electrolytes by 2 orders of magnitude (shear storage modulus ∼5 MPa), while retaining high ionic conductivity at room temperature (1 mS cm

The power characteristics of lithium-ion batteries (LIBs) are crucial for the advent of commercialized, high-power applications, such as electric vehicles. Through both first-principles multiscale simulations and experiments, here, we present fundamental understanding on the power characteristics of the high-voltage spinel cathode correlated with its elastic softness and phase transformation in nanodomains for high-power LIBs. Atomic models of LiNi0.5Mn1.5O4 and LiNi0.5Mn1.5−xTixO4 are developed for multiscale phase field modeling based on structural information for the as-prepared nanopowders. The combined computational and experimental investigations suggest that the thermodynamic phase stability of LiNi0.5Mn1.5O4 can be effectively enhanced by the incorporation of Ti into the structure without any change to the redox mechanism. Ti incorporation provides a faster ionic mobility and the improved phase stability because of the reinforced Ti4+–O bonds. Based on the multiscale phase transformation kinetics, LiNi0.5Mn1.5−xTixO4 exhibits an enhanced elastic softness and slower phase separation than LiNi0.5Mn1.5O4 in the nanodomain during Li+ insertion and extraction. Such characteristics are mainly responsible for the improved electrochemical performance at higher current rates, as confirmed by electrochemical experiments. This fundamental understanding of the power characteristics with respect to the correlations with elastic softness and phase transformation will provide a guideline to develop and design advanced materials for high-power LIBs.

In lithium-ion batteries (LIBs) comprising spinel cathode materials, the dissolution of transition metals (TMs) in the cathodes causes severe cyclic degradation. We investigate the origin and mechanism of surface TM dissolution in high-voltage spinel oxide (LiNi0.5Mn1.5O4) nanoparticles to find a practical method for its mitigation. Atomic structures of the LiNi0.5Mn1.5O4 surfaces are developed, and the electronic structures are investigated by first-principles calculations. The results indicate that titanium is a promising dopant for forming a more stable surface structure by reinforcing metal–oxygen bonds in LiNi0.5Mn1.5O4. Experimentally synthesized LiNi0.5Mn1.5O4 with titanium surface doping exhibits improved electrochemical performance by suppressing undesirable TM dissolution during cycles. The theoretical prediction and experimental validation presented here suggest a viable method to suppress TM dissolution in LiNi0.5Mn1.5O4.

For large-scale energy storage applications requiring high energy density, the development of Li-rich oxides with enhanced cyclic stabilities during high-voltage operations and large specific capacities is required. In this regard, high-Mn, Li-rich oxides (HMLOs; xLi2MnO3 (1 − x)LiNi1/3Co1/3Mn1/3O2 at x > 0.5) warrant an in-depth study because of their good cyclic performance at high operating voltages and potentially large specific capacities. Here, to understand the synergistic effects and enhanced cyclic stability of HMLOs, mechanically blended HMLO (m-HMLO) and chemically bonded HMLO (c-HMLO) were prepared and investigated. c-HMLO exhibits relatively high reaction voltages, large specific capacities, and enhanced cyclic stabilities (∼99%) at a high operating voltage (∼4.8 V vs. Li/Li+) compared with m-HMLO. First-principles calculations with electronic structure analysis were performed using an atomic model developed by Rietveld refinement using as-synthesised c-HMLO. The redox mechanisms of Ni, Co, and Mn ions were determined via the partial density of states of the ground states predicted using the cluster expansion method, which elucidates that LiNi1/3Co1/3Mn1/3O2 stabilises the transition metal (TM) layer of Li2MnO3 and separates Li delithiation potentials in Li2MnO3 in the HMLO. Kinetic analyses including electronic structures revealed that the interlayer migration of TMs from the TM layer to the Li layer depends on the crystal field stabilisation. Thus, TMs with reduced character in the tetrahedral sites than the octahedral sites owing to the effects of crystal field stabilisation, such as Ni ions, in HMLOs would face a higher interlayer migration barrier, impeding phase transformation into spinel phases. Furthermore, Cu ions could constitute a doping source for HMLOs to improve the material’s cyclic stability through this mechanism. These characteristics may be widely applied to explain experimental phenomena and improve the properties of cathode materials for Li-ion batteries.

Through first-principles calculations and experimental observations, we first present the correlation between the Ni and Mn ratio and the redox behaviors of the layered NCM cathodes. The equilibrium potentials based on redox reactions of Ni2+/Ni3+ are highly dependent on the Mn ratio (NCM523 and NCM721: ∼3.7 and 3.5 V) because of a donor electron, in the eg band, transferred from Mn to Ni owing to their crystal field splitting (CFS) with different electronegativities, leading to oxidation states of Ni2+-like and Mn4+. Considering the electronic donor (Mn) based on CFS with electronegativity of transition metals (TMs), we finally expect V as a promising doping source to provide donor electrons for Ni redox reactions in Ni-rich layered oxides, leading to be higher delithiation potentials (NCV523: 3.8 V). From our theoretical calculations in the NCV oxide, the oxidation states of Ni and V are stable Ni2+-like and V5+, respectively, and the fractional d-band fillings of Ni are the highest value as compared wi...

Lithium-rich oxide materials are promising candidates for high-energy lithium ion batteries, but currently have critical challenges of poor cycle performance and voltage drop induced by undesirable phase transformation. To resolve these problems, it is necessary to identify the origins and mechanism of phase transformation in Li2MnO3, a key component of Li-rich oxides. In this work, the phase transformation of bulk Li2MnO3 is investigated by thermodynamic and kinetic approaches based on first-principles calculations and validated by experiments. Using the calculated thermodynamic energies, the most stable structure is determined as a function of Li extraction for Li2−xMnO3: monoclinic (x = 0.0–0.75), layered-like (x = 1.0–1.25), and spinel-like (x = 1.5–2.0) structures. The phase transformation becomes kinetically possible for Li2−xMnO3 (x > 1.0). Atomic scale origins and the mechanism of phase transformation are elucidated by the thermodynamically stable and kinetically movable tetrahedral coordination of Mn4+ in the transition state. These theoretical observations are validated by ex situ X-ray photoelectron spectroscopy combined with electrochemical experiments for Li2−xMnO3 with various Li contents upon cycling. The mechanistic understanding from theoretical calculations and experimental observations is expected to provide a fundamental solution and guidelines for improving the electrochemical performance of Li-rich oxides and, by extension, the battery performance.

As a promising hybrid energy storage system, lithium ion capacitors (LICs) have been intensively investigated regarding their practical use in various applications, ranging from portable electronics to grid support. The asymmetric LIC offers high-energy and high-power densities compared with conventional energy storage systems such as electrochemical double-layer capacitors (EDLCs) and lithium ion batteries (LIBs). To enable suitable operation of the LIC, the negative electrode should be pre-lithiated prior to cell operation, which is regarded as a key technology for developing self-sustainable LICs. In this work, we have demonstrated the potential use of Li6CoO4 as an alternative lithium source to metallic lithium. A large amount of Li+ can be electrochemically extracted from the structure incorporated into the positive electrode via a highly irreversible process. Most of the extracted Li+ is available for pre-lithiation of the negative electrode during the first charge. This intriguing electrochemical behaviour of Li6CoO4 is suitable for providing sufficient Li+ to the negative electrode. To obtain a fundamental understanding of this system, the electrochemical behaviour and structural stability of Li6CoO4 is thoroughly investigated by means of electrochemical experiments and theoretical validation based on first principles calculations.

Through a gelation–solvothermal method without heteroadditives, Cu–Sn–S composites self-assemble to form nanotubes, sub-nanotubes, and nanoparticles. The nanotubes with a Cu3–4SnS4 core and Cu2SnS3 shell can tolerate long cycles of expansion/contraction upon lithiation/delithiation, retaining a charge capacity of 774 mAh g–1 after 200 cycles with a high initial Coulombic efficiency of 82.5%. The importance of the Cu component for mitigation of the volume expansion and structural evolution upon lithiation is informed by density functional theory calculations. The self-generated template and calculated results can inspire the design of analogous Cu–M–S (M = metal) nanotubes for lithium batteries or other energy storage systems.

A fundamental understanding of anomalous redox mechanisms in hexacyanometallate compounds, compared with conventional NaMO2 systems (M: transition metals), is presented based on first-principles calculations and experimental validations. From theoretical calculations, we identified low-spin and high-spin states of Fe ions coordinated by the cyanide group (-CN) with the same oxidation state (Fe2+) in Na2Fe2(CN)6. Considering the site dependency of d electronic spin configurations based on the crystal field theory (CFT) of transition metals (TMs), we calculated the thermodynamic mixing energy using Na2Fe2(CN)6 and Na2Mn2(CN)6 for obtaining a thermodynamically stable phase of Na2FeMn(CN)6. The phase stabilities of Na2Fe2-xMnx(CN)6 among many atomic configurations and lattice parameters originating from octahedral structures (i.e., Fe(CN)6 and Mn(NC)6) are highly dependent on the electronic structures of TMs with spin states. From partial density of states (PDOS) and spatial electron distributions, it was observed that Fe2+ in the low-spin state (t) and Mn2+ in the high-spin states (t and e) in the stable phase lead to higher redox potentials (∼3.55 V vs. Na/Na+) with the removal of Na+ as compared to that of Na2Fe2(CN)6. In addition, lattice parameters from x = 0 to x = 1 in Na2Fe2-xMnx(CN)6 are increased due to the larger ionic radius of Mn2+ in the high-spin states. On the other hand, Fe2+ in the high-spin states (t and e) and Mn2+ in the low-spin state (t) in the most unstable phase of Na2FeMn(CN)6 would have lower redox potentials. Based on the fundamental correlation between redox potentials and CFT with spin configurations of TMs, we suggest a material design concept for intercalation compounds with higher energy densities for rechargeable battery systems.

2D materials have shown great promise to advance next-generation lithium-ion battery technology. Specifically, tin-based chalcogenides have attracted widespread attention because lithium insertion can introduce phase transformations via three types of reactions-intercalation, conversion, and alloying-but the corresponding structural changes throughout these processes, and whether they are reversible, are not fully understood. Here, the first real-time and atomic-scale observation of reversible phase transformations is reported during the lithiation and delithiation of SnSe2 single crystals, using in situ high-resolution transmission electron microscopy complemented by first-principles calculations. Lithiation proceeds sequentially through intercalation, conversion, and alloying reactions (SnSe2 → Lix SnSe2 → Li2 Se + Sn → Li2 Se + Li17 Sn4 ) in a manner that maintains structural and crystallographic integrity, whereas delithiation forms numerous well-aligned SnSe2 nanodomains via a homogeneous deconversion process, but gradually loses the coherent orientation in subsequent cycling. Furthermore, alloying and dealloying reactions cause dramatic structural reorganization and thereby consequently reduce structural stability and electrochemical cyclability, which implies that deep discharge for Sn chalcogenide electrodes should be avoided. Overall, the findings elucidate atomistic lithiation and delithiation mechanisms in SnSe2 with potential implications for the broader class of 2D metal chalcogenides.

Critical degradation mechanism of many cathode materials for Li-ion batteries is closely related to phase transformations at the surface/interface. Li2MnO3 in x Li2MnO3 ⋅(1-x) LiMO2 (M=Ni, Co, Mn) provides high capacity, but the Li2MnO3 phase is known to degrade during cycling through phase transformation and O2 evolution. To resolve such degradation problems, it is critical to develop a fundamental understanding of the underlying mechanism. Using first-principles calculations, we identified the surface delithiation potential (4.5 V vs. Li/Li(+) ) of Li2MnO3, which is significantly lower than the bulk redox potential. A lower Mn oxidation state at the surface would reduce the delithiation potential compared with the fully oxidized Mn(4+) in the bulk. As a result, the delithiation would be initiated from the surface, which induces a phase transformation of Li2MnO3 into a spinel-like structure from the surface. These theoretical findings have been confirmed by experimental analyses. Based on these detailed mechanistic understanding, it would be possible to develop rational approaches to modify and coat the surface to suppress degradation mechanisms.