Crystalline and amorphous metal sulfide composite electrode materials with long cycle life:Preparation and performance of hybrid capacitors

Crystalline@amorphous NiCo_(2)S_(4)@MoS_(2)(v-NCS@MS)nanostructures were designed and constructed via an ethylene glycol-induced strategy with hydrothermal synthesis and solvothermal method,which simultaneously realized the defect regulation of crystal NiCo_(2)S_(4) in the core.Taking advantage of the flexible protection of an amor-phous shell and the high capacity of a conductive core with defects,the v-NCS@MS electrode exhibited high specif-ic capacity(1034 mAh·g^(-1) at 1 A·g^(-1))and outstanding rate capability.Moreover,a hybrid supercapacitor was assembled with v-NCS@MS as cathode and activated carbon(AC)as anode,which can achieve remarkably high specific energy of 111 Wh·kg^(-1) at a specific power of 219 W·kg^(-1) and outstanding capacity retention of 80.5%after 15000 cycling at different current densities.

Amorphous phosphorus chalcogenide as an anode material for lithiumion batteries with high capacity and long cycle life

The ever-increasing demands for modern energy storage applications drive the search for novel anode materials of lithium(Li)-ion batteries(LIBs) with high storage capacity and long cycle life, to outperform the conventional LIBs anode materials. Hence, we report amorphous ternary phosphorus chalcogenide(aP_(4)SSe_(2)) as an anode material with high performance for LIBs. Synthesized via the mechanochemistry method, the a-P_(4)SSe_(2) compound is endowed with amorphous feature and offers excellent cycling stability(over 1500 mA h g^(-1) capacity after 425 cycles at 0.3 A g^(-1)), owing to the advantages of isotropic nature and synergistic effect of multielement forming Li-ion conductors during battery operation. Furthermore,as confirmed by ex situ X-ray diffraction(XRD) and transmission electron microscope(TEM), the a-P_(4)SSe_(2)anode material has a reversible and multistage Li-storage mechanism, which is extremely beneficial to long cycle life for batteries. Moreover, the autogenous intermediate electrochemical products with fast ionic conductivity can facilitate Li-ion diffusion effectively. Thus, the a-P_(4)SSe_(2)electrode delivers excellent rate capability(730 mA h g^(-1)capacity at 3 A g^(-1)). Through in situ electrochemical impedance spectra(EIS) measurements, it can be revealed that the resistances of charge transfer(R_(SEI)) and solid electrolyte interphase(R_(Ct)) decrease along with the formation of Li-ion conductors whilst the ohmic resistance(R_(Ω)) remains unchanged during the whole electrochemical process, thus resulting in rapid reaction kinetics and stable electrode to obtain excellent rate performance and cycling ability for LIBs. Moreover, the formation mechanism and electrochemical superiority of the a-P_(4)SSe_(2)phase, and its expansion to P_(4)S_(3-x)Se_(x)(x = 0, 1, 2, 3) family can prove its significance for LIBs.

Mesoporous Mn-Sn bimetallic oxide nanocubes as long cycle life anodes for Li-ion half/full cells and sulfur hosts for Li-S batteries

Mesoporous Mn-Sn bimetallic oxide （BO） nanocubes with sizes of 15-30 run show outstanding stable and reversible capacities in lithium ion batteries CLIBs）, reaching 856.8 mAh.g-1 after 400 cycles at 500 mA·g^-1 and 506 mAh·g^-1 after 850 cycles at 1,000 mA·g^-1. The prelimLnary investigation of the reaction mechanism, based on X-ray diffraction measurements, indicates the occurrence of both conversion and alloying-dealloying reactions in the Mn-Sn bimetallic oxide electrode. Moreover, Mn-Sn BO//LiCoO2 Li-ion full cells were successfully assembled for the first time, and found to deliver a relatively high energy density of 176.25 Wh·kg^-1 at 16.35 W·kg^-1 （based on the total weight of anode and cathode materials）. The superior long-term stability of these materials might be attributed to their nanoscale size and unique mesoporous nanocubic structure, which provide short Li^＋ diffusion pathways and a high contact area between electrolyte and active material. In addition, the Mn-Sn BOs could be used as advanced sulfur hosts for lithium-sulfur batteries, owing to their adequate mesoporous structure and relatively strong chemisorption of lithium polysulfide. The present results thus highlight the promising potential of mesoporous Mn-Sn bimetallic oxides for application in Li-ion and Li-S batteries.

Synthesis of Co-Ni oxide microflowers as a superior anode for hybrid supercapacitors with ultralong cycle life

Li-ion hybrid capacitors（LIHCs）,composing of a lithium-ion battery（LIB） type anode and a supercapacitor（SC） type cathode,gained worldwide popularity due to harmonious integrating the virtues of high energy density of LIBs with high power density of SCs.Herein,nanoflakes composed microflower-like Co-Ni oxide（CoNiO） was successfully synthesized by a simple co-precipitation method.The atomic ratio of as-synthesized CoNiO is determined to be 1：3 through XRD and XPS analytical method.As a typical battery-type material,CoNiO and capacitor-type activated polyanilinederived carbon（APDC） were used to assemble LIHCs as the anode and cathode materials,respectively.As a result,when an optimized mass ratio of CoNiO and APDC was 1：2,CoNiO//APDC LIHC could deliver a maximum energy density of 143 Wh kg^-1 at a working voltage of 1-4 V.It is worth mentioning that the LIHC also exhibits excellent cycle stability with the capacitance retention of -78.2%after 15,000 cycles at a current density of 0.5 A g^-1.

Universal organic anodes enable safe low-cost aqueous rechargeable batteries with long cycle life,high capacity, and fast kinetics

Future battery advances and economies of scale will help scrub CO2emissions from transportation and the grid.Economical energy storage lets battery-powered electric vehicles replace internal combustion engines in the transportation sector,which now accounts for the plurality of CO2emissions.For grid-scale applications,the benefits of adding storage are many and well documented[1–2].Beyond increased penetration of intermittent renewable energy generated from such as solar panels

Electrolyte design strategies towards long-term Zn metal anode for rechargeable batteries

Rechargeable Zinc(Zn)batteries exhibit great potentials as alternative energy storage devices due to their high safety,low cost,and environmental friendliness.However,the long-standing issues of low Coulombic efficiency(CE)and poor cycle stability of Zn anode,derived from dendrite,H_(2)evolution,and passivation are directly related to their thermodynamic instability in aqueous electrolyte,severely shorten the battery's cycle life.Recently reported electrolyte design strategies,which have made great progress to address Zn metal anode problems,are summarized into two categories,that is,aqueous electrolytes about cation-water interaction controlling and interface adjusting,and novel types of electrolytes towards less water,non-aqueous solvents,even no solvents.The final section shows the brief comparisons,including failure mechanisms of electrolyte exhaustion and short circuit for aqueous and nonaqueous electrolyte based full cells respectively,and possible perspectives for future research.

Functionally gradient materials for sustainable and high-energy rechargeable lithium batteries:Design principles,progress,and perspectives

Rechargeable lithium batteries with high-capacity cathodes/anodes promise high energy densities for nextgeneration electrochemical energy storage.However,the associated limitations at various scales greatly hinder their practical applications.Functional gradient material(FGM)design endows the electrode materials with property gradient,thus providing great opportunities to address the kinetics and stability obstacles.To date,still no review or perspective has covered recent advancements in gradient design at multiple scales for boosting lithium battery performances.To fill this void,this work provides a timely and comprehensive overview of this exciting and sustainable research field.We begin by overviewing the fundamental features of FGM and the rationales of gradient design for improved electrochemical performance.Then,we comprehensively review FGM design for rechargeable lithium batteries at various scales,including natural or artificial solid electrolyte interphase(SEI)at the nanoscale,micrometer-scale electrode particles,and macroscale electrode films.The link between gradient structure design and improved electrochemical performance is particularly highlighted.The most recent research into constructing novel functional gradients,such as valence and temperature gradients,has also been explored.Finally,we discussed the current constraints and future scope of FGM in rechargeable lithium batteries,aiming to inspire the development of novel FGM for next-generation high-performance lithium batteries.

Intrinsic lithiophilic carbon host derived from bacterial cellulose nanofiber for dendrite-free and long-life lithium metal anode

Although lithium metal is considered a promising anode for advanced Li-S and Li-air batteries,the uncontrolled dendrite growth and infinite volume change impede its practical application.Herein,we report an ideal framework composed of carbonized bacterial cellulose(CBC)nanofibers,which shows intrinsic lithiophilicity to molten lithium without any lithiophilic surface modification.The wetting behavior of molten lithium can be significantly improved because its surface functional groups provide thermodynamical driving force,and the high surface roughness derived from nanocracks leads to rapid infusion in kinetics.The hybrid anode exhibits long cycle life up to 2000 h and excellent deep stripping-platting capacity up to 20 mAh·cm^(-2).When the anode is assembled with LiFePO_(4) cathode,the full cell delivers a good cycling stability up to 700 cycles.This is attributed to the intrinsic lithiophilic scaffold,which can not only lower the nucleation barrier of Li and provide uniform nucleation sites for stable Li stripping/plating,but also offer interspace to accommodate volume fluctuation of lithium during long cycling.This work provides a new manner to achieve a series of intrinsic lithiophilic carbon skeletons based on the large family of biomass materials and organic materials.

Pseudocapacitive Heteroatom-Doped Carbon Cathode for Aluminum-Ion Batteries with Ultrahigh Reversible Stability

Aluminum(Al)-ion batteries have emerged as a potential alternative to conventional ion batteries that rely on less abundant and costly materials like lithium.Nonetheless,given the nascent stage of advancement in Al-ion batteries(AIBs),attaining electrode materials that can leverage both intercalation capacity and structural stability remains challenging.Herein,we demonstrate a C3N4-derived layered N,S heteroatom-doped carbon,obtained at different pyrolysis temperatures,as a cathode material for AIBs,encompassing the diffusion-controlled intercalation and surface-induced capacity with ultrahigh reversibility.The developed layered N,S-doped corbon(N,S-C)cathode,synthesized at 900℃,delivers a specific capacity of 330 mAhg^(-1)with a relatively high coulombic efficiency of~85%after 500 cycles under a current density of 0.5 A g^(-1).Owing to its reinforced adsorption capability and enlarged interlayer spacing by doping N and S heteroatoms,the N,S-C900 cathode demonstrates outstanding energy storage capacity with excellent rate performance(61 mAhg^(-1)at 20 A g^(-1))and ultrahigh reversibility(90 mAhg^(-1)at 5Ag^(-1)after 10000cycles).

Boron heteroatom-doped silicon-carbon peanut-like composites enables long life lithium-ion batteries

Carbon coated Si core–shell structures have been proposed to solve the adverse effects of Si-based anode.However,designing ideal core–shell architecture with excellent surface and interface properties is still a significant challenge.Herein,a novel peanut-like structure of B-doped silicon/carbon nanoparticle(Si@B-C)synthe-sized by sol–gel process and subsequent thermal reduction is reported.The peanut-like Si@B-C electrode demon-strates a superior cyclability of 534 mAh·g^(-1)after 1000 cycles at high current density of 1000 mA·g^(-1).The exceptional electrochemical performance is attributed to the boric acid-induced highly interconnected peanut-like structure and boron heteroatom framework could provide a continuous electron pathway to reduce the irreversible lithium ion loss during rapid cycling.This work provides insight into the development of the heteroatom-doped Si-based anodes with stable cycling performance for LIBs.

Nb_2O_5-carbon core-shell nanocomposite as anode material for lithium ion battery

Nb2O5-carbon nanocomposite is synthesized through a facile one-step hydrothermal reaction from sucrose as the carbon source, and stuclled as an anode material for high-performance lithium ion battery. The structural characterizations reveal that the nanocomposite possesses a core-shell structure with a thin layer of carbon shell homogeneously coated on the Nb2O5 nanocrystals. Such a unique structure enables the composite electrode with a long cycle life by preventing the Nb2O5 from volume change and pulverization during the charge-discharge process. In addition, the carbon shell efficiently improves the rate capability. Even at a current density of 500 mA.g-1, the composite electrode still exhibits a specific capacity of ~100 mAh.g-1. These results suggest the possibility to utilize the Nb2O5-carbon core-shell composite as a high performance anode material in the practical application of lithium ion battery.

Freestanding strontium vanadate/carbon nanotube films for long-life aqueous zinc-ion batteries

Aqueous rechargeable zinc-ion battery(ZIB)is considered to be a potential energy storage system for large-scale applications due to its environmental friendliness,high safety,and low cost.However,it remains challenging to develop suitable cathode materials with high specific capacity and long-term cyclic stability.Herein,we have fabricated freestanding Sr0.19V2O51.3H2O/carbon nanotubes(SrVO/CNTs)composite films with different mass ratios by incorporating SrVO into CNTs network.The synthesized SrVO possesses a large interlayer spacing of 1.31 nm,which facilitates Zn(2+)diffusion.Furthermore,the SrVO/CNTs composite film with conductive network structure promotes electron transfer and ensures good contact between SrVO and CNTs during the long-term cycling process.As a result,the battery based on the SrVO/CNTs composite cathode with a mass ratio of 7:3 delivers a specific capacity of 326 mAh·g^(-1)at 0.1 A·g^(-1)and 145 mAh·g^(-1)at 5 A·g^(-1),demonstrating a high capacity and excellent rate capability.Remarkably,the assembled ZIB shows good capacity retention of 91%even after ultra-long cycling for 7500 cycles at a high current rate of 5 Ag^(-1).More importantly,the battery also delivers a high energy density and power density,as 290 Wh·kg^(-1)at 125 W·kg^(-1)(0.1 A·g^(-1)),or 115 Wh·kg^(-1)at 6078 W·kg^(-1)(5 Ag^(-1)).The results demonstrate that the SrVO/CNTs composite is a promising cathode toward large-scale energy storage applications.

Nitrogen-doped carbon stabilized Li Fe0.5Mn0.5PO4/rGO cathode materials for high-power Li-ion batteries

Exploring high ion/electron conductive olivine-type transition metal phosphates is of vital significance to broaden their applicability in rapid-charging devices.Herein,we report an interface engineered Li Fe0.5Mn0.5PO4/rGO@C cathode material by the synergistic effects of r GO and polydopamine-derived N-doped carbon.The well-distributed Li Fe0.5Mn0.5PO4nanoparticles are tightly anchored on r GO nanosheet benefited by the coating of N-doped carbon layer.The design of such an architecture can effectively suppress the agglomeration of nanoparticles with a shortened Li+transfer path.Meantime,the high-speed conducting network has been constructed by r GO and N-doped carbon,which exhibits the face-to-face contact with Li Fe0.5Mn0.5PO4nanoparticles,guaranteeing the rapid electron transfer.These profits endow the Li Fe0.5Mn0.5PO4/rGO@C hybrids with a fast charge-discharge ability,e.g.a high reversible capacity of 105 m Ah·g^-1at 10 C,much higher than that of the Li Fe0.5Mn0.5PO4@C nanoparticles(46 mA·h·g^-1).Furthermore,a 90.8%capacity retention can be obtained even after cycling 500 times at 2 C.This work gives a new avenue to fabricate transition metal phosphate with superior electrochemical performance for high-power Li-ion batteries.

Layered barium vanadate nanobelts for high-performance aqueous zinc-ion batteries

Aqueous zinc-ion batteries(ZIBs)are deemed as the idea option for large-scale energy storage systems owing to many alluring merits including low manufacture cost,environmental friendliness,and high operations safety.However,to develop high-performance cathode is still significant for practical application of ZIBs.Herein,Ba_(0.23)V_(2)O_(5)·1.1H_(2)O(BaVO)nanobelts were fabricated as cathode materials of ZIBs by a typical hydrothermal synthesis method.Benefiting from the increased interlayer distance of 1.31 nm by Ba2+ and H2O pre-intercalated,the obtained BaVO nanobelts showed an excellent initial discharge capacity of 378 mAh·g^(-1) at 0.1 A·g^(-1),a great rate performance(e.g.,172 mAh·g^(-1) at 5 A·g^(-1)),and a superior capacity retention(93% after 2000 cycles at 5 A·g^(-1)).

Defect-engineered Mn_(3)O_(4)/CNTs composites enhancing reaction kinetics for zinc-ions storage performance

The designing of reasonable nanocomposite materials and proper introduction of defect engineering are of great significance for the improvement of the poor electronic conductivity and slow reaction kinetics of manganese-based compounds. Herein, we report manganese-deficient Mn_(3)O_(4) nanoparticles which grow in-situ on highly conductive carbon nanotubes(CNTs)(denoted as DMOC) as an advanced cathode material for aqueous rechargeable zinc-ion batteries(RAZIBs). According to experimental and calculation results, the DMOC cathode integrates the advantages of enriched Mn defects and small particle size. These features not only enhance electronic conductivity but also create more active site and contribute to fast reaction kinetics. Moreover, the structure of DMOC is maintained during the charging and discharging process, thus benefiting for excellent cycle stability. As a result, the DMOC electrode delivers a high specific capacity of 420.6 m A h g^(-1) at 0.1 A g^(-1) and an excellent cycle life of 2800 cycles at 2.0 A g^(-1) with a high-capacity retention of 84.1%. In addition, the soft-packaged battery assembled with DMOC cathode exhibits long cycle life and high energy density of 146.3 Wh kg^(-1) at 1.0 A g^(-1) . The results are beneficial for the development of Zn/Mn_(3)O_(4) battery for practical energy storage.

Novel fusiform core-shell-MOF derived in tact metal@carb on composite:An efficient cathode catalyst for aqueous and solid-state Zn-air batteries

Owing to the varied mechanisms of ORR/OER,exploiting cost-effective bifunctional catalysts with robust ORR/OER activities and excellent performances in Zn-air batteries is still a challenge.In this work,the Co/CoO@NSC bifunctional catalyst is obtained by using Zn-MOF@Co-MOF as self-template.The Co/CoO@NSC composite has interconnected porous architecture with in tact metal@carb on structure,exhibiting superior electrocatalytic activities toward ORR and OER that can be comparable with the Pt/C and RuO_(2) catalysts,respectively.The Co/CoO@NSC-based aqueous Zn-air battery achieves a high specific capacity(759.7 mAh/g)and energy density(990.5 Wh/kg),and ultra-long rechargeable property(more than 400 h/1200 cycles).The Co/CoO@NSC-based solid-state Zn-air battery also delivers an excellent performance with a long cycle life(more than 143 h/858 cycles).Most importantly,the newly synthesized and recharged Co/CoO@NSC-based solid-state Zn-air battery can be used to light up a 2 V LED lamp for more than 28 h,demonstrating the superior practicability as rechargeable power source.

Carbon coated ultrasmall anatase TiO_2 nanocrystal anchored on N,S-RGO as high-performance anode for sodium ion batteries

Anatase TiO_2 has been investigated as one of the most promising anode materials for sodium ion batteries(SIBs)with low cost and high theoretical capacity.Herein,a composite material of TiO_2 /N,S-RGO@C with carbon coated ultrasmall anatase TiO_2 anchored on nitrogen and sulfur co-doped RGO matrix was successfully prepared by a rational designed process.The composite structure exhibited ultrasmall crystal size,rich porous structure,homogeneous heteroatoms doping and thin carbon coating,which synergistically resulted in elevated electron and ion transfer.The anode exhibited high rate capacities with good reversibility under high rate cycling.The carbon coating was investigated to be effective to prevent active material falling and lead to long term cycling performance with a high capacity retention of 181 m Ah g^(à1)after 2000cycles at 2 C.Kinetic studies were carried out and the results revealed that the superior performance of the composite material were derived from the decreased charge transfer resistance and elevated ion diffusion.Results suggested that the TiO_2 /N,S-RGO@C composite is a promising anode material for sodium ion batteries.

High-power and long-life supercapacitive performance of hierarchical, 3-D urchin-like W18049 nanostructure electrodes

We report the facile, one-pot synthesis of 3-D urchin-like W18O49 nanostructures （U-WO） via a simple solvothermal approach. An excellent supercapacitive performance was achieved by the U-WO because of its large Brunauer-Emmett- Teller （BET） specific surface area （ca. 123 m2.g-1） and unique morphological and structural features. The U-WO electrodes not only exhibit a high rate-capability with a specific capacitance （Csp） of -235 F·g-1 at a current density of 20 A.g-1, but also superior long-life performance for 1,000 cycles, and even up to 7,000 cycles, showing -176 F·g-1 at a high current density of 40 A.g-1.

A double-layer covered architecture with spinel phase induced by LiPP for Co-free Li-rich cathode with high-rate performance and long lifespan

Co-free Li-rich Mn-based layered oxides are promising candidates for next-generation lithium-ion batteries(LIBs)due to their high specific capacity,high voltage,low cost.However,their commercialization is hindered by limited cycle life and poor rate performance.Herein,an in-situ simple and low-cost strategy with a nanoscale double-layer architecture of lithium polyphosphate(LiPP)and spinel phase covered on top of the bulk layered phase,is developed for Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2)(LMNO)using Li^(+)-conductor LiPP(denoted as LMNO@S-LiPP).With such a double-layer covered architecture,the half-cell of LMNO@S-LiPP delivers an extremely high capacity of 202.5 mAh·g^(−1)at 1 A·g^(−1)and retains 85.3%of the initial capacity after 300 cycles,so far,the best highrate electrochemical performance of all the previously reported LMNOs.The energy density of the full-cell assembled with commercial graphite reaches 620.9 Wh·kg^(−1)(based on total weight of active materials in cathode and anode).Mechanism studies indicate that the superior electrochemical performance of LMNO@S-LiPP is originated from such a nanoscale double-layer covered architecture,which accelerates Li-ion diffusion,restrains oxygen release,inhibits interfacial side reactions,suppresses structural degradation during cycling.Moreover,this strategy is applicable for other high-energy-density cathodes,such as LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2),Li_(1.2)Ni_(0.13)Co_(0.13)Mn_(0.54)O_(2),LiCoO_(2).Hence,this work presents a simple,cost-effective,scalable strategy for the development of high-performance cathode materials.

Uniform zinc deposition on O,N-dual functionalized carbon cloth current collector

The society’s urgent demand for environmentally friendly, safe and low-cost energy storage devices has promoted the research of aqueous zinc-ion batteries. However, the uneven deposition of Zn ions on anodes will lead to the growth of the dendrite and reduce the Coulombic efficiency as well as the lifespan of the devices. Herein, we construct an O,N-dual functionalized carbon cloth current collector via a simple hydrothermal strategy, in which the oxygen-containing functional groups and the N heteroatoms can regulate the transmission and deposition of Zn ions, respectively. The proposed synergistic strategy ensures the uniform distribution of Zn ions on the surface of the Zn anode and inhibits the formation of dendrites. The symmetric cell based on the O,N-dual doped carbon cloth presents superior cycling stability(318 h) with a low voltage hysteresis(11.2 mV) at an areal capacity of 1 m Ah cm^(-2)(20% depth of diacharge). Meanwhile, the appreciably low overpotential(16 m V) and high Columbic efficiency(98.2%)also demonstrate that the O,N-dual functionalized carbon cloth can be worked as a promising host for Zn ions deposition.