Review and prospects on the low-voltage Na_(2)Ti_(3)O_(7) anode materials for sodium-ion batteries

Due to its low cost and natural abundance of sodium,Na-ion batteries(NIBs)are promising candidates for large-scale energy storage systems.The development of ultralow voltage anode materials is of great significance in improving the energy density of NIBs.Low-voltage anode materials,however,are severely lacking in NIBs.Of all the reported insertion oxides anodes,the Na_(2)Ti_(3)O_(7) has the lowest operating voltage(an average potential of 0.3 V vs.Na^(+)/Na)and is less likely to deposit sodium,which has excellent potential for achieving NIBs with high energy densities and high safety.Although significant progress has been made,achieving Na_(2)Ti_(3)O_(7) electrodes with excellent performance remains a severe challenge.This paper systematically summarizes and discusses the physicochemical properties and synthesis methods of Na_(2)Ti_(3)O_(7).Then,the sodium storage mechanisms,key issues and challenges,and the optimization strategies for the electrochemical performance of Na_(2)Ti_(3)O_(7) are classified and further elaborated.Finally,remaining challenges and future research directions on the Na_(2)Ti_(3)O_(7) anode are highlighted.This review offers insights into the design of high-energy and high-safety NIBs.

High‑Energy and High‑Power Pseudocapacitor–Battery Hybrid Sodium‑Ion Capacitor with Na^(+) Intercalation Pseudocapacitance Anode

High-performance and low-cost sodium-ion capacitors(SICs)show tremendous potential applications in public transport and grid energy storage.However,conventional SICs are limited by the low specific capacity,poor rate capability,and low initial coulombic efficiency(ICE)of anode materials.Herein,we report layered iron vanadate(Fe5V15O39(OH)9·9H2O)ultrathin nanosheets with a thickness of~2.2 nm(FeVO UNSs)as a novel anode for rapid and reversible sodium-ion storage.According to in situ synchrotron X-ray diffractions and electrochemical analysis,the storage mechanism of FeVO UNSs anode is Na+intercalation pseudocapacitance under a safe potential window.The FeVO UNSs anode delivers high ICE(93.86%),high reversible capacity(292 mAh g^−1),excellent cycling stability,and remarkable rate capability.Furthermore,a pseudocapacitor–battery hybrid SIC(PBH-SIC)consisting of pseudocapacitor-type FeVO UNSs anode and battery-type Na3(VO)2(PO4)2F cathode is assembled with the elimination of presodiation treatments.The PBH-SIC involves faradaic reaction on both cathode and anode materials,delivering a high energy density of 126 Wh kg^−1 at 91 W kg^−1,a high power density of 7.6 kW kg^−1 with an energy density of 43 Wh kg−1,and 9000 stable cycles.The tunable vanadate materials with high-performance Na+intercalation pseudocapacitance provide a direction for developing next-generation highenergy capacitors.

Surface pseudocapacitance of mesoporous Mo_(3)N_(2) nanowire anode toward reversible high-rate sodium-ion storage

Sodium-ion storage devices are highly desirable for large-scale energy storage applications owing to the wide availability of sodium resources and low cost.Transition metal nitrides(TMNs)are promising anode materials for sodium-ion storage,while their detailed reaction mechanism remains unexplored.Herein,we synthesize the mesoporous Mo3N2 nanowires(Meso-Mo_(3)N_(2)-NWs).The sodium-ion storage mechanism of Mo3N2 is systematically investigated through in-situ XRD,ex-situ experimental characterizations and detailed kinetics analysis.Briefly,the Mo_(3)N_(2) undergoes a surface pseudocapacitive redox charge storage process.Benefiting from the rapid surface redox reaction,the Meso-Mo_(3)N_(2)-NWs anode delivers high specific capacity(282 m Ah g^(-1) at 0.1 A g^(-1)),excellent rate capability(87 m Ah g^(-1) at 16 A g^(-1))and long cycling stability(a capacity retention of 78.6%after 800 cycles at 1 A g^(-1)).The present work highlights that the surface pseudocapacitive sodium-ion storage mechanism enables to overcome the sluggish sodium-ion diffusion process,which opens a new direction to design and synthesize high-rate sodiumion storage materials.

Carbon decorated Li_(3)V_(2)(PO_(4))_(3) for high-rate lithium-ion batteries:Electrochemical performance and charge compensation mechanism

Fast charging and high-power delivering batteries are highly demanded in mobile electronics,electric vehicles and grid energy storage,but there are full of challenges.The star-material Li_(3)V_(2)(PO_(4))_(3) is demonstrated as a promising high-rate cathode material meeting the above requirements.Herein,we report the carbon decorated Li_(3)V_(2)(PO_(4))_(3) (LVP/C) cathode prepared via a facile method,which displays a remarkable high-rate capability and long-term cycling performance.Briefly,the prepared LVP/C delivers a high discharge capacity of 122 mAh g^(-1)(-93% of the theoretical capacity) at a high rate up to 20 C and a superior capacity retention of 87.1% after 1000 cycles.Importantly,by applying a combination of X-ray absorption spectroscopy and full-range mapping of resonant inelastic X-ray scattering,we clearly elucidate the structural and chemical evolutions of LVP upon various potentials and cycle numbers.We show unambiguous spectroscopic evidences that the evolution of the hybridization strength between V and O in LVP/C as a consequence of lithiation/delithiation is highly reversible both in the bulk and on the surface during the discharge-charge processes even over extended cycles,which should be responsible for the remarkable electrochemical performance of LVP/C.Our present study provides not only an effective synthesis strategy but also deeper insights into the surface and bulk electrochemical reaction mechanism of LVP,which should be beneficial for the further design of high-performance LVP electrode materials.

Pseudocapacitive Vanadium-based Materials toward High-Rate Sodium-Ion Storage

Sodium-ion battery materials and devices are promising candidates for largescale applications,owing to the abundance and low cost of sodium sources.Emerging sodium-ion pseudocapacitive materials provide one approach for achieving high capacity at high rates,but are currently not well understood.Herein,a comprehensive overview of the fundamentals and electrochemical behaviors of vanadium-based pseudocapacitive materials for sodium-ion storage is presented.The insight of sodium-ion storage mechanisms for various vanadium-based materials,including vanadium oxides,vanadates,vanadium sulfides,nitrides,and carbides are systematically discussed and summarized.In particular,areas for further development to improve fundamental understanding of electrochemical and structural properties of materials are identified.Finally,we provide a perspective on the application of pseudocapacitive materials in high-power and high-energy sodium-ion storage devices(e.g.,sodium-ion capacitors).

High-rate sodium-ion storage of vanadium nitride via surface-redox pseudocapacitance

Vanadium nitride(VN)electrode displays high-rate,pseudocapacitive responses in aqueous electrolytes,however,it remains largely unclear in nonaqueous,Na+-based electrolytes.The traditional view supposes a conversion-type mechanism for Na+storage in VN anodes but does not explain the phenomena of their size-dependent specific capacities and underlying causes of pseudocapacitive charge storage behaviors.Herein,we insightfully reveal the VN anode exhibits a surface-redox pseudocapacitive mechanism in nonaqueous,Na+-based electrolytes,as demonstrated by kinetics analysis,experimental observations,and first-principles calculations.Through ex situ X-ray photoelectron spectroscopy and semiquantitative analyses,the Na+storage is characterized by redox reactions occurring with the V5+/V4+to V3+at the surface of VN particles,which is different from the well-known conversion reaction mechanism.The pseudocapacitive performance is enhanced through nanoarchitecture design via oxidized vanadium states at the surface.The optimized VN-10 nm anode delivers a sodium-ion storage capability of 106 mAh g−1 at the high specific current of 20 A g−1,and excellent cycling performance of 5000 cycles with negligible capacity losses.This work demonstrates the emerging opportunities of utilizing pseudocapacitive charge storage for realizing high-rate sodium-ion storage applications.

Compacted mesoporous titania nanosheets anode for pseudocapacitance-dominated,high-rate,and high-volumetric sodium-ion storage

Surface-redox pseudocapacitive nanomaterials show promise for fast-charging energy storage.However,their high surface area usually leads to low density,which is not conducive to achieving both high volumetric capacity and high-rate capability.Herein,we demonstrate that TiO_(2)nanosheets(meso-TiO_(2)-NSs)with densely packed mesoporous are capable of fast pseudocapacitance-dominated sodium-ion storage,as well as high volumetric and gravimetric capacities.Through compressing treatment,the compaction density of meso-TiO_(2)-NSs is up to~1.6g/cm^(2),combined with high surface area and high porosity with mesopore channels for rapid Na+diffusion.The compacted meso-TiO_(2)-NSs electrodes achieve high pseudocapacitance(93.6%of total charge at 1mV/s),high-rate capability(up to 10 A/g),and long-term cycling stability(10,000 cycles).More importantly,the space-efficiently packed structure enables high volumetric capacity.The thick-film meso-TiO_(2)-NSs anode with the mass loading of 10mg/cm^(2)delivers a gravimetric capacity of 165 mAh/g and a volumetric capacity of 223 mAh/cm^(3)at 5 mA/cm^(2),much higher than those of commercial hard carbon anode(80mAh/g and 86mAh/cm^(3)).This work highlights a pathway for designing a dense nanostructure that enables fast charge kinetics for high-density sodium-ion storage.

Improved conductivity and capacitance of interdigital carbon microelectrodes through integration with carbon nanotubes for micro-supercapacitors

In the last decade, pyrolyzed-carbon-based composites have attracted much attention for their applications in micro-supercapacitors. Although various methods have been investigated to improve the performance of pyrolyzed carbons, such as conductivity, energy storage density and cycling performance, effective methods for the integration and mass-production of pyrolyzed-carbon- based composites on a large scale are lacking. Here, we report the development of an optimized photolithographic technique for the fine micropatterning of photoresist/chitosan-coated carbon nanotube （CHIT-CNT） composite. After subsequent pyrolysis, the fabricated carbon/CHIT-CNT microelectrode-based micro-supercapacitor has a high capacitance （6.09 mF.cm-2） and energy density （4.5 mWh.cm-3） at a scan rate of 10 mV.s-L Additionally, the micro-supercapacitor has a remarkable long-term cyclability, with 99.9% capacitance retention after 10,000 cyclic voltammetry cycles. This design and microfabrication process allow the application of carbon microelectromechanical system （C-MEMS）-based micro-supercapacitors due to their high potential for enhancing the mechanical and electrochemical performance of micro-supercapacitors.

Vertically stacked holey graphene/polyaniline heterostructures with enhanced energy storage for on-chip micro-supercapacitors

Planar micro-supercapacitors （MSCs） have drawn extensive research attention owing to their unique structural design and size compatibility for microelectronic devices. Graphene has been widely used to improve the performance of microscale electrochemical capacitors. However, investigations of an intrinsic electrochemical mechanism for graphene-based microscale devices are still not sufficient. Here, micro-supercapacitors with various typical architectures are fabricated as models to study the graphene effect, and their electrochemical performance is also evaluated. The results show that ionic accessibility and adsorption are greatly improved after the introduction of the holey graphene intermediate layer. This study provides a new route to understand intrinsic electrochemical behaviors and possesses exciting potential for highly efficient on-chip micro-energy storage.

Activated carbon clothes for wide-voltage high-energy-density aqueous symmetric supercapacitors

Commercial carbon clothes have the potential to be utilized as supercapacitor electrodes due to their low cost and high conductivity.However,the negligible surface area of the carbon clothes serves as a serious impediment to their utilization.Herein,we report a facile calcination activation method for carbon cloths to realize remarkable comprehensive electrochemical performance.The activated carbon cloths deliver a high areal capacitance(1700 mF/cm^2),good rate capability,and stable cycling performance up to 20,000 cycles.Owing to the stability in the wide potential window,a designed symmetric capacitor can function in a cell voltage of 2.0 V and delivers high volumetric and gravimetric energy densities of 7.62 mWh/cm^3 and 18.2 Wh/kg,respectively.The remarkable electrochemical performance is attributed to rich microporosity with high surface area,superior electrolyte wettability,and stability in wide potential window.