Methylene blue intercalated vanadium oxide with synergistic energy storage mechanism for highly efficient aqueous zinc ion batteries

With the rise of aqueous multivalent rechargeable batteries,inorganic-organic hybrid cathodes have attracted more and more attention due to the complement of each other’s advantages.Herein,a strategy of designing hybrid cathode is adopted for high efficient aqueous zinc-ion batteries(AZIBs).Methylene blue(MB)intercalated vanadium oxide(HVO-MB)was synthesized through sol-gel and ion exchange method.Compared with other organic-inorganic intercalation cathode,not only can the MB intercalation enlarge the HVO interlayer spacing to improve ion mobility,but also provide coordination reactions with the Zn^(2+)to enhance the intrinsic electrochemical reaction kinetics of the hybrid electrode.As a key component for the cathode of AZIBs,HVO-MB contributes a specific capacity of 418 mA h g^(-1) at 0.1 A g^(-1),high rate capability(243 mA h g^(-1) at 5 A g^(-1))and extraordinary stability(88%of capacity retention after 2000cycles at a high current density of 5 A g^(-1))in 3 M Zn(CF_(3)SO_(3))_(2) aqueous electrolyte.The electrochemical kinetics reveals HVO-MB characterized with large pseudocapacitance charge storage behavior due to the fast ion migration provided by the coordination reaction and expanded interlayer distance.Furthermore,a mixed energy storage mechanism involving Zn^(2+)insertion and coordination reaction is confirmed by various ex-situ characterization.Thus,this work opens up a new path for constructing the high performance cathode of AZIBs through organic-inorganic hybridization.

Carbon materials toward efficient potassium storage:Rational design,performance evaluation and potassium storage mechanism

Potassium-ion batteries(PIBs)are potential“Beyond Li-ion Batteries”candidates for their resource advantage and low standard electrode potential.To date,the research on PIBs is in its early stages,the most urgent task is to develop high-performance electrode materials and reveal their potassium storage mechanism.For PIBs anode materials,carbon with tunable microstructure,excellent electrochemical activity,nontoxicity and low price is considered as one of the most promising anode materials for commercialization.Although some breakthrough works have emerged,the overall electrochemical performance of the reported carbon anode is still far away from practical application.Herein,we carry out a comprehensive overview of PIBs carbon anode in terms of three aspects of rational design of structure,performance evaluation criteria and characterization of potassium storage mechanism.First,the regulation mechanism of key structural features of carbon anode on its potassium storage performance and the representative structural regulation strategies are introduced.Then,in view of the undefined performance evaluation criteria of PIBs carbon anode,a reference principle for evaluating the potassium storage performance of carbon anode is proposed.Finally,the advanced characterization techniques for the potassium storage mechanism of carbon anode are summarize.This review aims to provide guidance for the development of practical PIBs anode.

Understanding of the charge storage mechanism of MnO_(2)-based aqueous zinc-ion batteries:Reaction processes and regulation strategies

Though secondary aqueous Zn ion batteries(AZIBs)have been received broad concern in recent years,the development of suitable cathode materials of AZIBs is still a big challenge.The MnO_(2) has been deemed as one of most hopeful cathode materials of AZIBs on account of some extraordinary merits,such as richly natural resources,low toxicity,high discharge potential,and large theoretical capacity.However,the crystal structure diversity of MnO_(2) results in an obvious various of charge storage mechanisms,which can cause great differences in electrochemical performance.Furthermore,several challenges,including intrinsic poor conductivity,dissolution of manganese and sluggish ion transport dynamics should be conquered before real practice.This work focuses on the reaction mechanisms and recent progress of MnO_(2)-based materials of AZIBs.In this review,a detailed review of the reaction mechanisms and optimal ways for enhancing electrochemical performance for MnO_(2)-based materials is proposed.At last,a number of viewpoints on challenges,future development direction,and foreground of MnO_(2)-based materials of aqueous zinc ions batteries are put forward.This review clarifies reaction mechanism of MnO_(2)-based materials of AZIBs,and offers a new perspective for the future invention in MnO_(2)-based cathode materials,thus accelerate the extensive development and commercialization practice of aqueous zinc ions batteries.

High-Resolution Mass Spectroscopy for Revealing the Charge Storage Mechanism in Batteries: Oxamide Materials as an Example

The pursuit of high-performance electrode materials is highly desired to meet the demand of batteries with high energy and power density.However,a deep understanding of the charge storage mechanism is always challenging,which limits the development of advanced electrode materials.Herein,high-resolution mass spectroscopy(HR-MS)is employed to detect the evolution of organic electrode materials during the redox process and reveal the charge storage mechanism,by using small molecular oxamides as an example,which have ortho-carbonyls and are therefore potential electrochemical active materials for batteries.The HR-MS results adequately proved that the oxamides could reversibly store lithium ions in the voltage window of 1.5–3.8 V.Upon deeper reduction,the oxamides would decompose due to the cleavage of the C–N bonds in oxamide structures,which could be proved by the fragments detected by HR-MS,^(1)H NMR,and the generation of NH_(3)after the reduction of oxamide by Li.This work provides a strategy to deeply understand the charge storage mechanism of organic electrode materials and will stimulate the further development of characterization techniques to reveal the charge storage mechanism for developing high-performance electrode materials.

Recent advances in energy storage mechanism of aqueous zinc-ion batteries

Aqueous rechargeable zinc-ion batteries(ZIBs)have recently attracted increasing research interest due to their unparalleled safety,fantastic cost competitiveness and promising capacity advantages compared with the commercial lithium ion batteries.However,the disputed energy storage mechanism has been a confusing issue restraining the development of ZIBs.Although a lot of efforts have been dedicated to the exploration in battery chemistry,a comprehensive review that focuses on summarizing the energy storage mechanisms of ZIBs is needed.Herein,the energy storage mechanisms of aqueous rechargeable ZIBs are systematically reviewed in detail and summarized as four types,which are traditional Zn^(2+)insertion chemistry,dual ions co-insertion,chemical conversion reaction and coordination reaction of Zn^(2+)with organic cathodes.Furthermore,the promising exploration directions and rational prospects are also proposed in this review.

Charge storage mechanism of MOF-derived Mn2O3 as high performance cathode of aqueous zinc-ion batteries

Aqueous Zinc-ion batteries(ZIB) are attracting immense attention because of their merits of excellent safety and quite cheap properties compared with lithium-ion batteries(LIB).Manganese oxide is one of the most important cathode materials of ZIB.In this paper,α-Mn2O3 used as cathode of ZIB is synthesized via Metal-Organic Framework(MOF)-derived method,which delivers a high specific capacity of225 mAh g^(-1) at 0.05 A g^(-1) and 92.7 mAh g^(-1) after 1700 cycles at 2 A g^(-1).The charge storage mechanism of α-Mn2O3 cathode is found to greatly depend on the discharge current density.At lower current density discharging,the H+ and Zn2+ are successively intercalated into the α-Mn2O3 before and after the "turning point" of discharge voltage and their discharging products present obviously different morphologies changing from flower-like to large plate-like products.At a higher current density,the low-voltage plateau after the turning point disappears due to the decrease of amount of Zn2+ intercalation and the H+intercalation is dominated in α-Mn2 O3.This study provides significant understanding for future design and research of high-performance Mn-based cathodes of ZIB.

Understanding of the sodium storage mechanism in hard carbon anodes

Hard carbon has been regarded as the most promising anode material for sodiumion batteries(SIBs)due to its low cost,high reversible capacity,and low working potential.However,the uncertain sodium storage mechanism hinders the rational design and synthesis of high-performance hard carbon anode materials for practical SIBs.During the past decades,tremendous efforts have been put to stimulate the development of hard carbon materials.In this review,we discuss the recent progress of the study on the sodium storage mechanism of hard carbon anodes,and the effective strategies to improve their sodium storage performance have been summarized.It is anticipated that hard carbon anodes with high electrochemical properties will be inspired and fabricated for large-scale energy storage applications.

Energy Storage Mechanism of Vanadium Nitride via Intercalating Different Atomic Radius for Expanding Interplanar Spacing

As a promising anode material in supercapacitors,vanadium nitride has been widely concerned due to its ultra-high theoretical specific capacitance.However,its routine test capacitance value is still far from the theoretical value and its energy storage mechanism is controversial.In order to solve these two key problems,here we prepare interplanar spacing expanded vanadium nitride materials with different impurity atoms intercalation from two anionic precursors of vanadium-based metal organic frameworks with different functional groups.The obtained vanadium nitride reaches a higher specific capacitance;and further,through ex situ X-Ray diffraction and in situ Raman,the charge storage of vanadium nitride is contributed by two processes:the first benefit is from the K^(+) de/intercalation in the interplanar spacing,and the other one is derived from the redox reaction with OH−by adsorption on surface.Furthermore,both of the first principle calculation and extended experiments support this idea.We believe that such detailed research on the energy storage mechanism can provide a clear idea for the application of metal nitrides in supercapacitors and other energy storage devices.

Data Secure Storage Mechanism of Sensor Networks Based on Blockchain

As the number of sensor network application scenarios continues to grow,the security problems inherent in this approach have become obstacles that hinder its wide application.However,it has attracted increasing attention from industry and academia.The blockchain is based on a distributed network and has the characteristics of non-tampering and traceability of block data.It is thus naturally able to solve the security problems of the sensor networks.Accordingly,this paper first analyzes the security risks associated with data storage in the sensor networks,then proposes using blockchain technology to ensure that data storage in the sensor networks is secure.In the traditional blockchain,the data layer uses a Merkle hash tree to store data;however,the Merkle hash tree cannot provide non-member proof,which makes it unable to resist the attacks of malicious nodes in networks.To solve this problem,this paper utilizes a cryptographic accumulator rather than a Merkle hash tree to provide both member proof and non-member proof.Moreover,the number of elements in the existing accumulator is limited and unable to meet the blockchain’s expansion requirements.This paper therefore proposes a new type of unbounded accumulator and provides its definition and security model.Finally,this paper constructs an unbounded accumulator scheme using bilinear pairs and analyzes its performance.

Computational Insights into Charge Storage Mechanisms of Supercapacitors

Computational modeling methods,including molecular dynamics(MD)and Monte Carlo(MC)simulations,and density functional theory(DFT),are receiving booming interests for exploring charge storage mechanisms of electrochemical energy storage devices.These methods can effectively be used to obtain molecular scale local information or provide clear explanations for novel experimental findings that cannot be directly interpreted through experimental investigations.This short review is dedicated to emphasizing recent advances in computational simulation methods for exploring the charge storage mechanisms in typical nanoscale materials,such as nanoporous carbon materials,2 D MXene materials,and metal-organic framework electrodes.Beyond a better understanding of charge storage mechanisms and experimental observations,fast and accurate enough models would be helpful to provide theoretical guidance and experimental basis for the design of new high-performance electrochemical energy storage devices.

Non-desolvation Zn^(2+)storage mechanism enables MoS_(2)anode with enhanced interfacial charge-transfer kinetics for low temperature zinc-ion batteries

The emerging rocking-chair aqueous zinc-ion battery(AZIB)configuration provides a promising approach for realizing their practical applications by avoiding the critical drawbacks of Zn metal anodes including unsatisfactory Coulombic efficiency and low Zn utilization.Therefore,exploiting appropriate insertion-type anodes with fast charge-transfer kinetics is of great importance,and many modifications focusing on the improvement of electron transport and bulk Zn^(2+)diffusion have been proposed.However,the interfacial Zn^(2+)transfer determined by the desolvation process actually dominates the kinetics of overall battery reactions,which is mainly overlooked.Herein,the interlayer structure of Mo S_(2)is rationally co-intercalated with water and ethylene glycol(EG)molecules(Mo S2@EG),giving rise to a fast non-desolvation Zn^(2+)storage mechanism,which is verified by the extraordinarily smaller activation energy of interfacial Zn^(2+)transfer(4.66 k J mol^(-1))compared with that of pristine Mo S_(2)(56.78 k J mol^(-1)).Furthermore,the results of theoretical calculations,in-situ Raman and ex-situ characterizations also indicate the enhanced structural integrity of Mo S2@EG during cycling due to the enlarged interlayer spacing and charge screening effect induced by interlaminar EG molecules.Consequently,the Mo S_(2)@EG anode enables excellent cycling stability of both high-energy-density Mo_S2@EG||PVO(polyaniline intercalated V_(2)O_(5))and high-voltage Mo S2@EG||Na_(3)V_(2)(PO_(4))_2O_(2)F(NVPF)full batteries with neglectable capacity decay at-20℃.

Dual-ion carrier storage through Mg^(2+) addition for high-energy and long-life zinc-ion hybrid capacitor

Cation additives can efficiently enhance the total electrochemical capabilities of zinc-ion hybrid capacitors (ZHCs).However their energy storage mechanisms in zinc-based systems are still under debate.Herein,we modulate the electrolyte and achieve dual-ion storage by adding magnesium ions.And we assemble several Zn//activated carbon devices with different electrolyte concentrations and investigate their electrochemical reaction dynamic behaviors.The zinc-ion capacitor with Mg^(2+)mixed solution delivers 82 mAh·g^(-1)capacity at 1 A·g^(-1) and maintains 91%of the original capacitance after 10000 cycling.It is superior to the other assembled zinc-ion devices in single-component electrolytes.The finding demonstrates that the double-ion storage mechanism enables the superior rate performance and long cycle lifetime of ZHCs.

Covalency competition induced selective bond breakage and surface reconstruction in manganese cobaltite towards enhanced electrochemical charge storage

Manganese cobaltite(MnCo_(2)_(4))is a promising electrode material because of its attractive redox chemistry and excellent charge storage capability.Our previous work demonstrated that the octahedrally-coordinated Mn are prone to react with the hydroxyl ions in alkaline electrolyte upon electrochemical cycling and separates on the surface of spinel to reconstruct into d-MnO_(2) nanosheets irreversibly,thus results in a change of the reaction mechanism with Kþion intercalation.However,the low capacity has greatly limited its practical application.Herein,we found that the tetrahedrally-coordinated Co_(2) þions were leached when MnCo_(2)_(4) was equilibrated in 1 mol L^(-1) HCl solution,leading to the formation of layered CoOOH on MnCo_(2)_(4) surface which is originated from the covalency competition induced selective breakage of the CoT–O bond in CoT–O–CoO and subsequent rearrangement of free Co_(6) octahedra.The as-formed CoOOH is stable upon cycling in alkaline electrolyte,exhibits conversion reaction mechanism with facile proton diffusion and is free of massive structural evolution,thus enables utilization of the bulk electrode material and realizes enhanced specific capacity as well as facilitated charge transfer and ion diffusion.In general,our work not only offers a feasible approach to deliberate modification of MnCo_(2)_(4)'s surface structure,but also provides an in-depth understanding of its charge storage mechanism,which enables rational design of the spinel oxides with promising charge storage properties.

Revisiting lithium-storage mechanisms of molybdenum disulfide

Molybdenum disulfide(MoS_(2)),a typical two-dimensional transition metallic layered material,attracts tremendous attentions in the electrochemical energy storage due to its excellent physicochemical properties.However,with the deepening of the research and exploration of the lithium storage mechanism of these advanced MoS_(2)-based anode materials,the complex reaction process influenced by internal and external factors hinders the exhaustive understanding of the lithium storage process.To design stable anode material with high performance,it is urgent to review the mechanisms of reported anode materials and summarize the related factors that influence the reaction processes.This review aims to dissect all possible side reactions during charging and discharging process,uncover internal and external factors inducing various anode reactions and finally put forward strategies of controlling high cycling capacity and super-stable lithium storage capability of MoS_(2).This review will be helpful to the design of MoS_(2)-based lithium-ion batteries(LIBs) with excellent cycle performance to enlarge the application fields of these advanced electrochemical energy storage devices.

Pore-scale mechanisms and characterization of light oil storage in shale nanopores:New method and insights

A new method is proposed to analyze the pore-scale mechanisms and characterization of light oil storage in shale nanopores,which is based on the Hydrocarbon Vapor Adsorption(HVA)and Pore Calculation Model(PCM).First,the basic principle of the HVA-PCM method is introduced,and the experimental/mathematical analysis processes are given.Then,the HVA-PCM method is applied to shale samples to analyze the mechanisms and characterization of light oil storage in shale nanopores.The results provide insights into the pore-scale oil storage mechanisms,oil storage structure,oil film thickness,oil distribution within different sized pores,and the oil storage state.Finally,the advantages and limitations of the HVA-PCM method are discussed,and suggestions for further improvement are proposed.Overall,the HVA-PCM method is a powerful tool for extracting quantitative information on the light oil storage in shale nanopores.

Tungsten diselenide nanoplates as advanced lithium/ sodium ion electrode materials with different storage mechanisms

Transition-metal dichalcogenides （TMDs） exhibit immense potential as lithium/ sodium-ion electrode materials owing to their sandwich-like layered structures. To optimize their lithium/sodium-storage performance, two issues should be addressed： fundamentally understanding the chemical reaction occurring in TMD electrodes and developing novel TMDs. In this study, WSe2 hexagonal nanoplates were synthesized as lithium/sodium-ion battery （LIB/SIB） electrode materials. For LIBs, the WSe2-nanoplate electrodes achieved a stable reversible capacity and a high rate capability, as well as an ultralong cycle life of up to 1,500 cycles at 1,000 mA·g^-1. Most importantly, in situ Raman spectroscopy, ex situ X-ray diffraction （XRD）, transmission electron microscopy, and electrochemical impedance spectroscopy measurements performed during the discharge-charge process clearly verified the reversible conversion mechanism, which can be summarized as follows： WSe2 ＋ 4Li^＋ ＋ 4e^- ←→ W ＋ 2Li2Se. The WSe2 nanoplates also exhibited excellent cycling performance and a high rate capability as SIB electrodes. Ex situ XRD and Raman spectroscopy results demonstrate that WSe2 reacted with Na^＋ more easily and thoroughly than with Li^＋ and converted to Na2Se and tungsten in the Ist sodiated state. The subsequent charging reaction can be expressed as Na2Se → Se ＋ 2Na^＋＋ 2e^-, which differs from the traditional conversion mechanism for LIBs. To our knowledge, this is the first systematic exploration of the lithium/sodium-storage performance of WSe2 and the mechanism involved.

Charge storage mechanisms of cathode materials in rechargeable aluminum batteries

Rechargeable aluminum batteries(RABs)have attracted great interest as one of the most promising candidates for large-scale energy storage because of their high volumetric capacity,low cost,high safety and the abundance of aluminum.However,compared with the aluminum anodes,the cathode materials face more problems including low specific capacity,relatively sluggish kinetics in most host structures and/or limited cycle lifespan,which pose the major challenge for RABs in further practical applications.During the past years,intensive efforts have been devoted to developing new cathode materials and/or designing engineered nanostructures to greatly improve RABs’electrochemical performances.In addition to nanotechnologybased electrode structure designs,the intrinsic chemical structures and charge storage mechanisms of cathode materials play an equally crucial role,if not more,in revolutionizing the battery performances.This review,here,focuses on current understandings into the charge storage mechanisms of cathode materials in RABs from a chemical reaction point of view.First,the fundamental chemistry,charge storage mechanisms and design principles of RAB cathode materials are highlighted.Based on different ion charge carriers,the current cathode materials are classified into four groups,including Al^(3+)-hosting,Al Cl_(4)^(-)-hosting,Al Cl_(2)^(+)/Al Cl_(2)^(+)-hosting,and Cl^(-)-hosting cathode materials.Next,the respective typical electrode structures,optimization strategies,electrochemical performances and charge storage mechanisms are discussed in detail to establish their chemistry-structure-property relationships.This review on current understandings of the cathode charge storage mechanisms will lay the ground and hopefully set new directions into the rational design of high-performance cathode materials in RABs,and open up new opportunities for designing new electrolyte systems with respect to the targeted cathode systems.

Disclosure of charge storage mechanisms in molybdenum oxide nanobelts with enhanced supercapacitive performance induced by oxygen deficiency

Molybdenum oxide(MoO_(3)), with superior features of multi-electrochemical states, high theoretical capacitance, and low cost, is a desirable supercapacitor electrode material but suffers from low conductivity and insufficient active sites. The MoO_(3) capacitance can be largely amplified by introducing oxygen(O) vacancies, but the mechanisms at the atomic scale are still ambiguous.Herein, O vacancies are created at the O2 and O3 sites in the MoO_(3) nanobelts by carbonization to maximize the supercapacitance in the MoO_(2.39). The supercapacitive storage is mainly ascribed to the proton adsorption at the O1 sites to create Mo–OH, leading to an expansion of the interlayer spacing along the lattice B-axis. Roughly 98% of the initial supercapacitance is retained after 1000 cycles,due to the reversible change in the interlayer spacing. Our results provide an insight into the oxygen deficiency-related mechanisms of the supercapacitive performance at the atomic scale and devise a facile method to enhance the supercapacitance for energy storage and conversion.

Sulfur-containing polymer cathode materials: From energy storage mechanism to energy density

Besides lithium-ion batteries, it is imperative to develop new battery energystorage system with high energy density. In conjunction with the developmentof Li-S batteries, emerging sulfur-containing polymers with tunable sulfur-chain length and organic groups gradually attract much attention as cathodematerials. This can avoid the problems that are impeding the development ofthe typical Li-S batteries, such as volume expansion, active material dissolu-tion, shuttle effect, and so on. This review aims to generalize the type ofsulfur-containing polymers and the working principles in Li-S batteries. Thesulfur-containing polymers (R-Sn-R) with different sulfur-chain length (n > 6,n ≤ 2, and 3 ≤ n ≤ 6) are summarized. It also discusses several organic groupssuch as phenyl rings, N-heterocycles, and unique structure with cross-linkednetworks and multi-micropores skeleton. This review also explores other strat-egies of sulfur-containing polymers in the rest of Li-S batteries, providing asummary of the advantages of sulfur-containing polymers, recent develop-ment, in-depth discussion of the mechanism in Li-S batteries, and organicgroup-structure-performance relationship. This review would have guidelinesfor future development of sulfur-containing polymers in Li-S batteries.

Progress and prospect of carbon dioxide capture, utilization and storage in CNPC oilfields

The development history of carbon capture,utilization and storage for enhanced oil recovery(CCUS-EOR)in China is comprehensively reviewed,which consists of three stages:research and exploration,field test and industrial application.The breakthrough understanding of CO_(2) flooding mechanism and field practice in recent years and the corresponding supporting technical achievements of CCUS-EOR project are systematically described.The future development prospects are also pointed out.After nearly 60 years of exploration,the theory of CO_(2) flooding and storage suitable for continental sedimentary reservoirs in China has been innovatively developed.It is suggested that C7–C15 are also important components affecting miscibility of CO_(2) and crude oil.The mechanism of rapid recovery of formation energy by CO_(2) and significant improvement of block productivity and recovery factor has been verified in field tests.The CCUS-EOR reservoir engineering design technology for continental sedimentary reservoir is established.The technology of reservoir engineering parameter design and well spacing optimization has been developed,which focuses on maintaining miscibility to improve oil displacement efficiency and uniform displacement to improve sweep efficiency.The technology of CO_(2) capture,injection and production process,whole-system anticorrosion,storage monitoring and other whole-process supporting technologies have been initially formed.In order to realize the efficient utilization and permanent storage of CO_(2),it is necessary to take the oil reservoir in the oil-water transition zone into consideration,realize the large-scale CO_(2) flooding and storage in the area from single reservoir to the overall structural control system.The oil reservoir in the oil-water transition zone is developed by stable gravity flooding of injecting CO_(2) from structural highs.The research on the storage technology such as the conversion of residual oil and CO_(2) into methane needs to be carried out.