Considering the ever‐growing climatic degeneration, sustainable and renewable energy sources are needed to be effectively integrated into the grid through large‐scale electrochemical energy storage ...and conversion (EESC) technologies. With regard to their competent benefit in cost and sustainable supply of resource, room‐temperature sodium‐ion batteries (SIBs) have shown great promise in EESC, triumphing over other battery systems on the market. As one of the most fascinating cathode materials due to the simple synthesis process, large specific capacity, and high ionic conductivity, Na‐based layered transition metal oxide cathodes commonly suffer from the sluggish kinetics, multiphase evolution, poor air stability, and insufficient comprehensive performance, restricting their commercialization application. Here, this review summarizes the recent advances in layered oxide cathode materials for SIBs through different optimal structure modulation technologies, with an emphasis placed on strategies to boost Na+ kinetics and reduce the irreversible phase transition as well as enhance the store stability. Meanwhile, a thorough and in‐depth systematical investigation of the structure–function–property relationship is also discussed, and the challenges as well as opportunities for practical application electrode materials are sketched. The insights brought forward in this review can be considered as a guide for SIBs in next‐generation EESC.
The recent research progress of structure modulation technology on layered transition metal oxide cathodes for sodium‐ion batteries is summarized, concentrating especially on morphology design, coating technology, phase transition, ordering‐disordering, air stability, and composite structure to boost Na+ kinetics, suppress the irreversible phase transition, enhance the storage stability, improve the overall performance, and further realize sodium‐ion battery commercialization for market applications.
As one of the most promising cathodes for rechargeable sodium‐ion batteries (SIBs), O3‐type layered transition metal oxides commonly suffer from inevitably complicated phase transitions and sluggish ...kinetics. Here, a NaLi0.05Ni0.3Mn0.5Cu0.1Mg0.05O2 cathode material with the exposed {010} active facets by multiple‐layer oriented stacking nanosheets is presented. Owing to reasonable geometrical structure design and chemical substitution, the electrode delivers outstanding rate performance (71.8 mAh g−1 and 16.9 kW kg−1 at 50C), remarkable cycling stability (91.9% capacity retention after 600 cycles at 5C), and excellent compatibility with hard carbon anode. Based on the combined analyses of cyclic voltammograms, ex situ X‐ray absorption spectroscopy, and operando X‐ray diffraction, the reaction mechanisms behind the superior electrochemical performance are clearly articulated. Surprisingly, Ni2+/Ni3+ and Cu2+/Cu3+ redox couples are simultaneously involved in the charge compensation with a highly reversible O3–P3 phase transition during charge/discharge process and the Na+ storage is governed by a capacitive mechanism via quantitative kinetics analysis. This optimal bifunctional regulation strategy may offer new insights into the rational design of high‐performance cathode materials for SIBs.
An O3‐type NaLi0.05Ni0.3Mn0.5Cu0.1Mg0.05O2 cathode material with exposed {010} active facets by multiple‐layer oriented stacking nanosheets is successfully constructed via reasonable structure design and chemical substitution. An optimal bifunctional regulation is demonstrated to be an efficient strategy to restrain the unfavorable multiphase transformation and greatly improve Na+ transport kinetics resulting in excellent performance for sodium‐ion batteries.
Demands for large‐scale energy storage systems have driven the development of layered transition‐metal oxide cathodes for room‐temperature rechargeable sodium ion batteries (SIBs). Now, an abnormal ...layered‐tunnel heterostructure Na0.44Co0.1Mn0.9O2 cathode material induced by chemical element substitution is reported. By virtue of beneficial synergistic effects, this layered‐tunnel electrode shows outstanding electrochemical performance in sodium half‐cell system and excellent compatibility with hard carbon anode in sodium full‐cell system. The underlying formation process, charge compensation mechanism, phase transition, and sodium‐ion storage electrochemistry are clearly articulated and confirmed through combined analyses of in situ high‐energy X‐ray diffraction and ex situ X‐ray absorption spectroscopy as well as operando X‐ray diffraction. This crystal structure engineering regulation strategy offers a future outlook into advanced cathode materials for SIBs.
An abnormal layered‐tunnel heterostructure Na0.44Co0.1Mn0.9O2 cathode material induced by chemical element substitution is described. The crystal‐structure engineering strategy that was used gives an outlook into high‐performance sodium ion batteries.
A simple wet chemical process followed by high temperature calcination has been successfully used to coat Li-ion conductive Li4Ti5O12 on the surface of Ni-rich LiNi0.8Co0.1Mn0.1O2. Physicochemical ...characterization results indicate that a Li4Ti5O12 with a thickness of about 2–3 nm was uniformly distributed on the surface of microspheres, without inducing significant change of the structure and morphology. Electrochemical test results show that proper content of Li4Ti5O12 coating layer can greatly improve the cycling performance and rate capability of Ni-rich LiNi0.8Co0.1Mn0.1O2 for the improved Li+ ions diffusion rate and suppressed side reactions between electrode and electrolyte. Notably, the 1 wt% Li4Ti5O12 coated sample exhibits excellent cycling stability with the capacity retention of 75.86% at 1 C after 170 cycles when cycled between 2.7 and 4.3 V at 25 °C, while that is only 39.40% for bare LiNi0.8Co0.1Mn0.1O2.
Due to the highest theoretical specific capacity of 4200 mA h g−1 for Li4.4Si, silicon(Si)-based materials could fulfill the increasing demands of high-energy lithium-ion batteries (LIBs). However, ...the intrinsic huge volume expansion during the lithiation/delithiation process results in rapid capacity decay and short cycle life and restricts the satisfactory electrical performance of Si-based anodes. Binder plays an important role of maintaining the contact integrity between active material, conductive additive and the current collector, thereby reducing the pulverization of the Si particles during charge/discharge. Here, the review systematically summarizes the synthesis methods, design principles and working mechanisms, including chemical composition, superstructure, and various interactions between different functional moieties of synthetic binders and natural biomass binders, to reveal the structure-composition-performance relationship, offer practical solutions to challenging problems associated with defects of Si-based electrode materials in LIBs and aim at exploiting new family of binders that could be used in industrial level as well as providing design principles for other electrode binders in rechargeable batteries.
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•Working mechanisms and design principles of Si-based anodes binders are presented.•Synergistic strategy of combining binders with anode structure design is discussed.•Synthesis methods, applied anodes, ICE and cycling performance are listed.
Structural instability and inferior storage property are bottlenecks of the Ni-rich cathodes. Herein, a coating and doping co-modified Ni-rich cathode, in which La and Al is homogeneously doped in ...the inner and an epitaxial layer is distributed in the outer surface region of secondary particle, is constructed. The outer surface layer tightly integrates a La2O3 coating layer, an epitaxial grown LaAl doped atomic structure and a Ni concentration gradient into the bulk phase. The La and Al act as a pillar ion enlarging c axis spacing and a positively charged center, enhancing Li+ transportation and suppressing the phase transition. The outer surface region with La-enriched layer and decreased Ni concentration suppresses the side reactions between organic electrolyte and oxidizing Ni4+ and improves the storage stability in air. During cycling, the modified material exhibits enhanced rate capability and cycling stability with capacity retention of 80.0% after 480 cycles at 10C in the cell potential range of 2.7–4.3 V.
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•Ni-rich cathode is modified with synergy of coating and doping by La and Al.•Lower lattice expansion and higher Li+ transportation due to La doping.•The coating layer suppresses erosion of electrolyte and improve storage stability.
Metal sulfides have been intensively investigated for efficient sodium‐ion storage due to their high capacity. However, the mechanisms behind the reaction pathways and phase transformation are still ...unclear. Moreover, the effects of designed nanostructure on the electrochemical behaviors are rarely reported. Herein, a hydrangea‐like CuS microsphere is prepared via a facile synthetic method and displays significantly enhanced rate and cycle performance. Unlike the traditional intercalation and conversion reactions, an irreversible amorphization process is evidenced and elucidated with the help of in situ high‐resolution synchrotron radiation diffraction analyses, and transmission electron microscopy. The oriented (006) crystal plane growth of the primary CuS nanosheets provide more channels and adsorption sites for Na ions intercalation and the resultant low overpotential is beneficial for the amorphous Cu‐S cluster, which is consistent with the density functional theory calculation. This study can offer new insights into the correlation between the atomic‐scale phase transformation and macro‐scale nanostructure design and open a new principle for the electrode materials' design.
A hydrangea‐like CuS microsphere with high geometrical symmetry and oriented (006) crystal plane growth is successfully constructed through a facile synthetic route. The oriented (006) crystal plane growth of the primary CuS nanosheets provide more channels and adsorption sites for Na ions intercalation, and the resultant low overpotential is beneficial for the amorphous Cu‐S cluster.
This study reports on the solid-state synthesis and characterization of novel quaternary P/O intergrown biphasic Na
0.8
Mn
y
Ni
0.8−
y
Fe
0.1
Ti
0.1
O
2
(
y
= 0.6, 0.55, 0.5, 0.45) cathode materials. ...Electrochemical tests reveal superior performance of the P/O biphasic materials in a sodium ion battery compared to the single P2 or O3 phases, proving the beneficial effect of the intergrowth of P2 and O3 materials. The nature of the P/O interface was studied by transmission electron microscopy. The analysis shows a semi-coherent interface grown along the
a
/
b
and
c
axes with local differences in the transition metal concentration along the interface between the two phases. EDX and EELS characterization revealed a charge compensation mechanism across the phase boundary based on variation of the transition element distribution, balancing the different sodium contents in the P and O phases. The results reported in this study provide a better understanding of P/O biphasic materials.
P/O intergrown biphasic sodium cathode materials with improved electrochem. properties were prepared. TEM revealed a semi-coherent interface with uniform oxidation state but different metal concentrations balancing sodium concentration differences.
LiNi0.8Co0.1Mn0.1O2 cathode materials with high energy density, low cost possesses the potential to meet the development of next-generation lithium ion batteries for electrical vehicles. ...Nevertheless, the practical applications of LiNi0.8Co0.1Mn0.1O2 were severely hindered by poor cycling stability, limited storage properties and insufficient safety due to the unstable structure with high nickel content. Though surface coating could effectively protect the cathode from electrolyte attack，it usually suffers deteriorative electronic and ion conductivity. In this report, LaAlO3 coating, which possesses high ion conductivity and stable structure, was firstly implemented via a simple solid method and extensively investigated with various techniques to clarify the coating effect. The sample with optimized LaAlO3 coating content (3.0 wt%) showed significantly improved cycle stability with a high capacity retention of 84.5% after 200 cycles at 1.0 C，which is about two times higher than that of the pristine (40.6%). And some further investigations also demonstrated the enhanced structural stability, suppressed side reactions and facilitated lithium ion diffusion kinetics.
•LaAlO3 coated on nickel-rich LiNi0.8Co0.1Mn0.1O2 cathodes is firstly reported.•The Li2CO3 impurity could be consumed by LaAlO3 coating.•The dissolution behavior of Mn is restrained by LaAlO3 coating.•The cycling stability of LaAlO3 coated LiNi0.8Co0.1Mn0.1O2 is greatly improved.
The small tyrosine kinase inhibitors (TKIs) subversively altered the lung cancer treatments, but patients will inevitably face the therapy resistance and disease recurrence. We aim to explore the ...potential roles of non-coding RNAs in sensitizing the TKIs effects.
Multiple cellular and molecular detections were applied to confirm the mechanistic regulations and intracellular connections.
We explored the specific gene features of candidates in association with resistance, and found that m6A controlled the stemness of EMT features through METTL3 and YTHDF2. The miR-146a/Notch signaling was sustained highly activated in a m6A dependent manner, and the m6A regulator of YTHDF2 suppressed TUSC7, both of which contributed to the resistant features. Functionally, the sponge type of TUSC7 regulation of miR-146a inhibited Notch signaling functions, and affected the cancer progression and stem cells' renewal in Erlotinib resistant PC9 cells (PC9ER) and Erlotinib resistant HCC827 cells (HCC827ER) cells. The Notch signaling functions manipulated the cMYC and DICER inner cytoplasm, and the absence of either cMYC or DICER1 lead to TUSC7 and miR-146a decreasing respectively, formed the closed circle to maintain the balance.
PC9ER and HCC827ER cells harbored much more stem-like cells, and the resistance could be reversed by Notch signaling inactivation. The intrinsic miR-146 and TUSC7 levels are monitored by m6A effectors, the alternation of either miR-146 or TUSC7 expression could lead to the circling loop to sustain the new homeostasis. Further in clinics, the combined delivery of TKIs and Notch specific inhibitory non-coding RNAs will pave the way for yielding the susceptibility to targeted therapy in lung cancer.
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