Effect of crystal morphology of ultrahigh-nickel cathode materials on high temperature electrochemical stability of lithium ion batteries

Higher nickel content endows Ni-rich cathode materials LiNi_(x)Co_yMn_(1-x-y)O_(2)(x>0.6)with higher specific capacity and high energy density,which is regarded as the most promising cathode materials for Li-ion batteries.However,the deterioration of structural stability hinders its practical application,especially under harsh working conditions such as high-temperature cycling.Given these circumstances,it becomes particularly critical to clarify the impact of the crystal morphology on the structure and high-temperature performance as for the ultrahigh-nickel cathodes.Herein,we conducted a comprehensive comparison in terms of microstructure,high-temperature long-cycle phase evolution,and high-temperature electrochemical stability,revealing the differences and the working mechanisms among polycrystalline(PC),single-crystalline(SC)and Al doped SC ultrahigh-nickel materials.The results show that the PC sample suffers a severe irreversible phase transition along with the appearance of microcracks,resulting a serious decay of both average voltage and the energy density.While the Al doped SC sample exhibits superior cycling stability with intact layered structure.In-situ XRD and intraparticle structural evolution characterization reveal that Al doping can significantly alleviate the irreversible phase transition,thus inhibiting microcracks generation and enabling enhanced structure.Specifically,it exhibits excellent cycling performance in pouch-type full-cell with a high capacity retention of 91.8%after 500 cycles at 55℃.This work promotes the fundamental understanding on the correlation between the crystalline morphology and high-temperature electrochemical stability and provides a guide for optimization the Ni-rich cathode materials.

Boosting High-Voltage and Ultralong-Cycling Performance of Single-Crystal LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) Cathode Materials via Three-in-One Modification

LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) is extensively researched as one of the most widely used commercially materials for Li-ion batteries at present.However,the poor high-voltage performance(≥4.3 V)with low reversible capacity limits its replacement for LiCoO_(2) in high-end digital field.Herein,three-in-one modification,Na-doping and Al_(2)O_(3)@Li_(3)BO_(3) dual-coating simultaneously,is explored for single-crystalline LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(N-NCM@AB),which exhibits excellent high-voltage performance.N-NCM@AB displays a discharge-specific capacity of 201.8 mAh g^(−1) at 0.2 C with a high upper voltage of 4.6 V and maintains 158.9 mAh g^(−1) discharge capacity at 1 C over 200 cycles with the corresponding capacity retention of 87.8%.Remarkably,the N-NCM@AB||graphite pouch-type full cell retains 81.2% of its initial capacity with high working voltage of 4.4 V over 1600 cycles.More importantly,the fundamental understandings of three-in-one modification on surface morphology,crystal structure,and phase transformation of N-NCM@AB are clearly revealed.The Na+doped into the Li–O slab can enhance the bond energy,stabilize the crystal structure,and facilitate Li+transport.Additionally,the interior surface layer of Li^(+)-ions conductor Li_(3)BO_(3) relieves the charge transfer resistance with surface coating,whereas the outer surface Al_(2)O_(3) coating layer is beneficial for reducing the active materials loss and alleviating the electrode/electrolyte parasite reaction.This three-in-one strategy provides a reference for the further research on the performance attenuation mechanism of NCM,paving a new avenue to boost the high-voltage performance of NCM cathode in Li-ion batteries.

Vinyltrimethylsilane as a novel electrolyte additive for improving interfacial stability of Li-rich cathode working in high voltage

Boosting the interfacial stability between electrolyte and Li-rich cathode material at high operating voltage is vital important to enhance the cycling stability of Li-rich cathode materials for high-performance Li-ion batteries.In this work,vinyltrimethylsilane as a new type of organic silicon electrolyte additive is studied to address the interfacial instability of Li-rich cathode material at high operating voltage.The cells using vinyltrimethylsilane additive shows the high capacity retention of 73.9%after 300 cycles at 1 C,whereas the cells without this kind of additive only have the capacity retention of 58.9%.The improvement of stability is mainly attributed to the additive helping to form a more stable surface film for Li-rich cathode material,thus avoiding direct contact between the electrolyte and the cathode material,slowing down the dissolution of metal ions and the decomposition of the electrolyte under high operating voltage.Our findings in this work shed some light on the design of stable cycling performance of Li-rich cathode toward advanced Li-ion batteries.

LiPO_(2)F_(2) electrolyte additive for high-performance Li-rich cathode material

Li-rich layered oxide cathodes have received considerable attention because of the high operating potential and specific capacity. However, the structural instability and parasitic reactions at high potential cause severe degradation of the electrochemical performance. In our studies, the cycling stability of Li_(1.14)Ni_(0.133)Co_(0.133)Mn_(0.544)O_(2) cathode is improved with LiPO_(2)F_(2) electrolyte additive. After 500 cycles, the capacity retention is increased from 53.6% to 85% at 3 C by LiPO_(2)F_(2) modification. This performance is mainly attributed to the enhanced interfacial stability of the Li-rich cathode. Based on systematic characterization, LiPO_(2)F_(2) additive was found to promote a stable interface film on the cathode surface during the cycling and mitigates the interfacial side reactions. This study provides new insights for improving high-potential Li-rich layered oxide batteries.

Van der Waals heterostructure engineering by 2D space-confinement for advanced potassium-ion storage

Molybdenum disulfide (MoS_(2)) has received enormous attentions in the electrochemical energy storage due to its unique two-dimensional layered structure and relatively high reversible capacity. However, the application of MoS_(2) in potassium-ion batteries (PIBs) is restricted by poor rate capability and cyclability, which are associated with the sluggish reaction kinetics and the huge volume expansion during K+ intercalation. Herein, we propose a two-dimensional (2D) space confined strategy to construct van der Waals heterostructure for superior PIB anode, in which the MoS_(2) nanosheets can be well dispersed on reduced graphene oxide nanosheets by leveraging the confinement effect within the graphene layers and amorphous carbon. The strong synergistic effects in 2D van der Waals heterostructure can extremely promote the electron transportation and ions diffusion during K+ insertion/extraction. More significantly, the 2D space-confinement effect and van der Waals force inhibit polysulfide conversion product dissolution into the electrolyte, which significantly strengthens the structural durability during the long-term cycling process. As anticipated, the as-synthesized the “face-to-face” C/MoS_(2)/G anode delivers remarkable K-storage performance, especially for high reversible capacity (362.5 mAh·g^(-1) at 0.1 A·g^(-1)), excellent rate capability (195.4 mAh·g^(-1) at 10 Ag^(-1)) and superior ultrahigh-rate long-cycling stability (126.4 mAh·g^(-1) after 4000 cycles at high rate of 5 A·g^(-1)). This work presents a promise strategy of structure designing and composition optimization for 2D layered materials in advanced energy storage application.