Surface Reconstruction of High-Voltage LiNi0.5Mn1.5O4 Cathode via the Sculpture Method toward Enhanced Stability.

High-voltage LiNi0.5Mn1.5O4 (LNMO) cathodes suffer from severe capacity degradation during long-term cycling due the manganese dissolution and their high operating voltage (∼4.95 V), which pose serious challenges at the surface or interface. Moreover, both traditional ion-doping and passivation layer coating are difficult to apply consistently to LNMO cathode because of their complicated procedures, especially in large-scale production. To address these issues, a strategy employing HNO3/H2O2 leaching in synergy with a sintering process at a mid-temperature of 700 °C was used to achieve selective surface reconstruction. An optimal ratio of reactants was applied to balance the capacity and the cyclic stability of the LNMO cathode. The optimized valence composition of Mn on the material surface mitigates the occurrence of Jahn-Teller distortion, accompanied by a reasonable ratio of ordered and disordered phases and the concentration of oxygen vacancies after sintering, which improves the interface behavior between the electrode and electrolyte. This method delivers a high reversible capacity of 116.5 mAh g-1 after 200 cycles at 0.5 C (1 C = 147 mAh g-1) with a capacity retention of 91.30% and 110 mAh g-1 with a remarkably high capacity retention of 86.85% after 500 cycles at 2 C. This balanced approach, utilizing the protective effects of oxidation (O22-) and the erosive action of acid (H+), is proposed to achieve regional surface reconstruction of advanced LNMO cathode. This opens up a strategy for improving oxide-based cathode materials with low cost and mass production capability, especially favoring high consistency.

Failure of Lithium-Ion Batteries Accelerated by Gravity.

The safety concerns surrounding lithium-ion batteries (LIBs) have garnered increasing attention due to their potential to endanger lives and incur significant financial losses. However, the origins of battery failures are diverse, presenting significant challenges in developing safety measures to mitigate accidental catastrophes. In this study, the aging mechanism of LiNi0.5Co0.2Mn0.3O2||graphite-based cylindrical 18,650 LIBs stored at room temperature for two years was investigated. It was found that an uneven distribution of electrolytes can be caused by gravity, leading to temperature variations within the battery. Specifically, it was observed that the temperature at the top of the battery was approximately -0.89 °C higher than at the bottom, correlating with an increase in partial internal resistance. Additionally, upon disassembly and analysis of spent batteries, the most significant damage to electrode materials at the top of the battery was observed. These findings suggest that gravity-induced electrolyte insufficiency exacerbates side reactions, particularly at the top of the battery. This study offers a unique perspective on the safety concerns associated with high-energy-density batteries in long-term and large-scale applications.

Oriented Gradient Doping of Zirconium in Ni-Rich Cathode to Achieve Ultrahigh Stability and Rate Capability.

Ni-rich layered oxide materials exhibit great prospects for practical applications in lithium-ion batteries due to their high specific capacity. However, the poor cycling performance and suboptimal rate performance have caused obstacles for their widespread application. Herein, we developed a gradient Zr element doping method based on the bulk gradient concentration of Ni-rich layered oxide material to reinforce the cycle stability and rate performance of the cathode. In particular, the orientations of the gradient Zr doping were achieved via coprecipitation in a positive or negative correlation between the concentrations of Zr and Ni, and it was revealed that the material behaves better when the Zr content is abundant in the core. The gradient doping of Zr decreases the content of Ni2+ and mitigates the mixing degree of Li+ and Ni2+, implying the superior performance of doped cathode material. Compared with the bare sample (70.7%, 121.4 mAh g-1), the Zr-doped sample delivered a higher capacity retention of 85.6% after 300 cycles at 1C (1C = 180 mA g-1) and exhibited a considerable rate performance of 122.5 mAh g-1 at 20C. In particular, the Zr-doped cathodes performed dramatically on high rate cycling at 10C, with an initial capacity of 143.6 and 103.9 mAh g-1 after 300 cycles. Furthermore, the Zr-doped cathode delivered significant stability at a high potential of 4.5 V with a capacity retention of 72.1% after 300 cycles, while that of the bare sample was only 37.4%. The concept of gradient doping strategies during coprecipitation offers new insight into the design of advanced cathodes with excellent cycling stability and rate capability.

Garnet Li7La3Zr2O12-Based Solid-State Lithium Batteries Achieved by In Situ Thermally Polymerized Gel Polymer Electrolyte.

Garnet Li7La3Zr2O12 (LLZO) is a potential solid electrolyte for solid-state batteries (SSBs) because of its high ionic conductivity, electrochemical stability, and mechanical strength. However, large interface resistances arising from deserted cathodes and rigid garnet/electrode interfaces block its application. In order to deal with this issue, a gel polymer electrolyte (GPE) was introduced into the cathode and both sides of LLZO to achieve a solid-state battery. Especially, the provided GPE could be thermally polymerized and solidified in situ, which would integrate LLZO with both anode and cathode and dramatically simplify the battery manufacturing process. Since the interface from rigid LLZO is improved by the flexible GPE buffer, the inability of flexible GPE to inhibit lithium dendrites is compensated by the rigid LLZO in return. As a result, the interface resistances are reduced from 6880 to 473 Ω, the Li symmetric cell exhibits a flat galvanostatic charge/discharge for 400 h without lithium dendrites, and the solid-state Li|GPE@LLZO|LiCoO2 battery exerts a capacity retention of 82.6% after 100 cycles at 0.5 C at room temperature. Such an interfacial engineering approach represents a promising strategy to address solid-solid interface issues and provides a new design for SSBs with high performance.

Direct surface coating of high voltage LiCoO2 cathode with P(VDF-HFP) based gel polymer electrolyte.

For high-voltage cycling of lithium-ion batteries, a gel polymer Li-ion conductor layer, P(VDF-HFP)/LiTFSI (PHL) with high electrochemical stability has been coated on the surfaces of as-formed LiCoO2 (LCO) cathodes by a solution-casting technique at low temperature. An LCO cathode coated with around 3 µm thickness of the PHL ultrathin membrane, retains 88.4% of its original capacity (184.3 mA h g-1) after 200 cycles in the 3.0-4.6 V range with a standard carbonate electrolyte, while the non-coated one retains only 80.4% of its original capacity (171.5 mA h g-1). The reason for the better electrochemical behaviors and high-voltage cycling is related to the distinctive characteristics of the PHL coating layer that is compact, has highly-continuous surface coverage and penetrates the bulk of LCO, forming an integrated electrode. The PHL coating layer plays the role of an ion-conductive protection barrier to inhibit side reactions between the charged LCO surface and electrolyte, reduces the dissolution of cobalt ions and maintains the structural stability of LCO. Further, the PHL coated LCO cathode is well preserved, compared to the uncoated one which is severely cracked after 200 cycles at a charging cut-off voltage of 4.6 V.