Gaining a thorough understanding of the reactions on the electrode surfaces of lithium batteries is critical for designing new electrode materials suitable for high-power, long-life operation. A technique for directly observing surface structural changes has been developed that employs an epitaxial LiMn(2)O(4) thin-film model electrode and surface X-ray diffraction (SXRD). Epitaxial LiMn(2)O(4) thin films with restricted lattice planes (111) and (110) are grown on SrTiO(3) substrates by pulsed laser deposition. In situ SXRD studies have revealed dynamic structural changes that reduce the atomic symmetry at the electrode surface during the initial electrochemical reaction. The surface structural changes commence with the formation of an electric double layer, which is followed by surface reconstruction when a voltage is applied in the first charge process. Transmission electron microscopy images after 10 cycles confirm the formation of a solid electrolyte interface (SEI) layer on both the (111) and (110) surfaces and Mn dissolution from the (110) surface. The (111) surface is more stable than the (110) surface. The electrode stability of LiMn(2)O(4) depends on the reaction rate of SEI formation and the stability of the reconstructed surface structure.
Considering the promising electrochemical performance of the recently reported pyrophosphate family in lithium ion batteries as well as the increasing importance of sodium ion batteries (SIBs) for emerging large‐scale applications, here, the crystal structure, electrochemical properties, and thermal stability of Na2FeP2O7, the first example ever reported in the pyrophosphate family for SIBs, are investigated. Na2FeP2O7 maintains well‐defined channel structures (triclinic framework under the P1 space group) and exhibits a reversible capacity of ≈90 mAh g−1 with good cycling performance. Both quasi‐equilibrium measurements and first‐principles calculations consistently indicate that Na2FeP2O7 undergoes two kinds of reactions over the entire voltage range of 2.0–4.5 V (vs Na/Na+): a single‐phase reaction around 2.5 V and a series of two‐phase reactions in the voltage range of 3.0–3.25 V. Na2FeP2O7 shows excellent thermal stability up to 500 °C, even in the partially desodiated state (NaFeP2O7), which suggests its safe character, a property that is very critical for large‐scale battery applications.
In order to confirm reasons that deteriorate cathode performances, Ni-rich Li[Ni0.7Mn0.3]O2 is modified by lithium isopropoxide to artificially provide lithium excess environment by forming Li2O on the surface of active materials. X-ray diffraction patterns indicate that the lithium oxide coating does not affect structural change comparing to the bare material. Scanning electron microscopy and transmission electron microscopy data show the presence of coating layers on the surface of Li[Ni0.7Mn0.3]O2. Electrochemical tests demonstrate that the Li2O-coated Li[Ni0.7Mn0.3]O2 exhibits a greater irreversible capacity with a small capacity because of the presence of insulating layers composed of lithium compounds on the active materials since these layers delay facile Li+ diffusion. Also, the Li2O layer forms byproducts such as Li2CO3, LiOH, and LiF, as are proved by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry. The presence of residual lithium tends to bond with hydrocarbons induced from decomposition of electrolytic salt during electrochemical reactions. And the reaction, accelerated by the decomposition of electrolytic salt that produces the byproducts, causes the formation of passive layers on the surface of active material. As a result, the new layers consequently impede diffusion of lithium ions that deteriorate electrochemical properties.
Spinel-structured lithium manganese oxide (LiMn(2)O(4)) cathodes have been successfully commercialized for various lithium battery applications and are among the strongest candidates for emerging large-scale applications. Despite its various advantages including high power capability, however, LiMn(2)O(4) chronically suffers from limited cycle life, originating from well-known Mn dissolution. An ironical feature with the Mn dissolution is that the surface orientations supporting Li diffusion and thus the power performance are especially vulnerable to the Mn dissolution, making both high power and long lifetime very difficult to achieve simultaneously. In this investigation, we address this contradictory issue of LiMn(2)O(4) by developing a truncated octahedral structure in which most surfaces are aligned to the crystalline orientations with minimal Mn dissolution, while a small portion of the structure is truncated along the orientations to support Li diffusion and thus facilitate high discharge rate capabilities. When compared to control structures with much smaller dimensions, the truncated octahedral structure as large as 500 nm exhibits better performance in both discharge rate performance and cycle life, thus resolving the previously conflicting aspects of LiMn(2)O(4).
All-solid-state batteries (ASSBs) are gaining prominence for their ability to overcome the intrinsic drawbacks of conventional liquid-based counterparts, such as electrolyte leakage, flammability, and limited voltage window. Nevertheless, ASSBs have so far been mainly investigated using lab-scale dry mixing processes and therefore suffer from limitation of scalability and agglomeration of active particles in the composite electrodes. Here, we report a systematic investigation on ASSBs fabricated by a solution-based casting process. By screening a wide range of binders and solvents, acrylonitrile butadiene rubber and para-xylene were a suitable binder and solvent, respectively, compatible with sulfide glass-ceramic solid electrolyte. This binder-solvent combination facilitates homogeneous dispersion of the solid electrolyte in the slurry and electrolyte layer, offering high adhesion between electrode materials and comparable lithium ionic conductivity to that of the dry mixing-based counterpart. When solution-based casting processes were adopted for both electrolyte and composite cathode (containing LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) layers, the solution-processed cell exhibits decent performance in rate capability and cyclability due to higher homogeneity of the electrode components, originating from the appropriate combination of solvent and binder.
Lithium ion batteries are encountering ever-growing demand for further increases in energy density. Li-rich layered oxides are considered a feasible solution to meet this demand because their specific capacities often surpass 200 mAh g−1 due to the additional lithium occupation in the transition metal layers. However, this lithium arrangement, in turn, triggers cation mixing with the transition metals, causing phase transitions during cycling and loss of reversible capacity. Here we report a Li-rich layered surface bearing a consistent framework with the host, in which nickel is regularly arranged between the transition metal layers. This surface structure mitigates unwanted phase transitions, improving the cycling stability. This surface modification enables a reversible capacity of 218.3 mAh g−1 at 1C (250 mA g−1) with improved cycle retention (94.1% after 100 cycles). The present surface design can be applied to various battery electrodes that suffer from structural degradations propagating from the surface.
The phase transition of layered manganese oxides to spinel phases is a well-known phenomenon in rechargeable batteries and is the main origin of the capacity fading in these materials. This spontaneous phase transition is associated with the intrinsic properties of manganese, such as its size, preferred crystal positions, and reaction characteristics, and it is therefore very difficult to avoid. The introduction of crystal water by an electrochemical process enables the inverse phase transition from spinel to a layered Birnessite structure. Scanning transmission electron microscopy can be used to directly visualize the rearrangement of lattice atoms, the simultaneous insertion of crystal water, the formation of a transient structure at the phase boundary, and layer-by-layer progression of the phase transition from the edge. This research indicates that crystal water intercalation can reverse phase transformation with thermodynamically favored directionality.
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