Recent advances and perspectives on vanadium-and manganese-based cathode materials for aqueous zinc ion batteries

The growing demand for energy storage has inspired researchers’exploration of advanced batteries.Aqueous zinc ion batteries(ZIBs)are promising secondary chemical battery system that can be selected and pursued.Rechargeable ZIBs possess merits of high security,low cost,environmental friendliness,and competitive performance,and they are received a lot of attention.However,the development of suitable zinc ion intercalation-type cathode materials is still a big challenge,resulting in failing to meet the commercial needs of ZIBs.Both vanadium-based and manganese-based compounds are representative of the most advanced and most widely used rechargeable ZIBs electrodes.The valence state of vanadium is+2~+5,which can realize multi-electron transfer in the redox reaction and has a high specific capacity.Most of the manganese-based compounds have tunnel structure or three-dimensional space frame,with enough space to accommodate zinc ions.In order to understand the energy storage mechanism and electrochemical performance of these two materials,a specialized review focusing on state-of-the-art developments is needed.This review offers access for researchers to keep abreast of the research progress of cathode materials for ZIBs.The latest advanced researches in vanadium-based and manganese-based cathode materials applied in aqueous ZIBs are highlighted.This article will provide useful guidance for future studies on cathode materials and aqueous ZIBs.

Distinctive electrochemical performance of novel Fe-based Li-rich cathode material prepared by molten salt method for lithium-ion batteries

For constructing next-generation lithium-ion batteries with advanced performances,pursuit of highcapacity Li-rich cathodes has caused considerable attention.So far,the low discharge specific capacity and serious capacity fading are strangling the development of Fe-based Li-rich materials.To activate the extra-capacity of Fe-based Li-rich cathode materials,a facile molten salt method is exploited using an alkaline mixture of LiOH–LiNO3–Li2O2 in this work.The prepared Li1.09(Fe0.2Ni0.3Mn0.5)0.91O2 material yields high discharge specific capacity and good cycling stability.The discharge specific capacity shows an upward tendency at 0.1 C.After 60 cycles,a high reversible specific capacity of ~250 m Ah g-1is delivered.The redox of Fe3+/Fe4+and Mn3+/Mn4+are gradually activated during cycling.Notably,the redox reaction of Fe2+/Fe3+can be observed reversibly below 2 V,which is quite different from the material prepared by a traditional co-precipitation method.The stable morphology of fine nanoparticles(100–300 nm)is considered benefiting for the distinctive electrochemical performances of Li1.09(Fe0.2Ni0.3Mn0.5)0.91O2.This study demonstrates that molten salt method is an inexpensive and effective approach to activate the extra capacity of Fe-based Li-rich cathode material for high-performance lithium-ion batteries.

Restraining migration and dissolution of transition-metal-ions via functionalized separator for Li-rich Mn-based cathode with high-energy-density

Lithium-rich manganese-based materials(LRMs) are promising cathode for high-energy-density lithiumion batteries due to their high capacity,low toxicity,and low cost.However,LRMs suffer from serious voltage decay and capacity fade due to continual migration and dissolution of transition metal ions(TMs) during cycling process.Herein,a novel strategy is proposed to inhibit the TMs migration of LRMs through a modified separator by means of functionalized carbon coating layer,which depends on the chemical constraint of the abundant functional groups in the modified super P.In addition,it has been found that the dissolution of TMs can be restrained based on the Le Chatelier's principle.Moreover,the modified separator owns good wettability toward the electrolyte.As a result,the LRMs cathode with the modified separator delivers a high discharge capacity of 329.93 mA h g-1 at 0.1 C,and achieves good cyclic performance,the enhanced reaction kinetics and low voltage decay.Therefore,this work provides a new idea to promote the comprehensive electrochemical performances of Li-ion batteries with LRMs cathode through a strategy of separator modification.

The Multiple Modification Road of Li-Rich Manganese-Based Cathode Materials

Li-rich manganese-based cathode materials(LR) are considered as excellent cathode materials for a new generation of lithium-ion batteries causes their outstanding electrochemical performance, friendly price, and environmental friendliness. But defects such as rapid voltage decay and loss of lattice oxygen limit their applications. The electrochemical performance of LR has to be improved by means of modification. The previous single modification methods like element doping, surface coating, structure design, etc. can only optimize the electrochemical performance of LR from one aspect. Recently, multiple modifications,which can combine the advantages of multiple modifications, have been favored by researchers. Here, we comprehensively review the recent progress of multiple modification of LR based on the combination of different modification means. The review and summary of the multiple modification of LR will play a guiding role in its development in the future.

Hydrated ammonium manganese phosphates by electrochemically induced manganese-defect as cathode material for aqueous zinc ion batteries

Aqueous zinc ion batteries(AZIBs) with the merits of low cost, low toxicity, high safety, environmental benignity as well as multi-valence properties as the large-scale energy storage devices demonstrate tremendous application prospect. However, the explorations for the most competitive manganese-based cathode materials of AZIBs have been mainly limited to some known manganese oxides. Herein, we report a new type of cathode material NH_(4)MnPO_(4)·H_(2)O(abbreviated as AMPH) for rechargeable AZIBs synthesized through a simple hydrothermal method. An in-situ electrochemical strategy inducing Mn-defect has been used to unlock the electrochemical activity of AMPH through the initial charge process, which can convert poor electrochemical characteristic of AMPH towards Zn^(2+)and NH_(4)+into great electrochemically active cathode for AZIBs. It still delivers a reversible discharge capacity up to 90.0 m Ah/g at 0.5 A/g even after 1000thcycles, which indicates a considerable capacity and an impressive cycle stability. Furthermore, this cathode reveals an(de)insertion mechanism of Zn^(2+)and NH_(4)+without structural collapse during the charge/discharge process. The work not only supplements a new member for the family of manganese-based compound for AZIBs, but also provides a potential direction for developing novel cathode material for AZIBs by introducing defect chemistry.

Simultaneous surface modification method for 0.4Li2MnO3-0.6LiNi1/3Co1/3Mn1/3O2 cathode material for lithium ion batteries： Acid treatment and LiCoPO4 coating

Li-rich layered cathode materials have been considered the most promising candidates for large-scale Li-ion batteries due to their low cost and high reversible capacity. However, these materials have many drawbacks that hinder commercialization, such as low initial efficiency and cyclability at elevated temperatures. To overcome these barriers, we propose an efficient and effective surface modification method, in which chemical activation （acid treatment） and LiCoPO4 coating were carried out simultaneously. During the synthesis, the lithium ions were extracted from the lattice, leading to improved Columbic efficiency, and these ions were used for the formation of LiCoPO4. The Ni and Co doped spinel phase was formed at the surface of the host material, which gives rise to the facile pathway for lithium ions. The LiCoPO4 and highly doped spinel on the surface acted as double protection layers that effectively prevented side reactions on the surface at 60℃. Moreover, the transition metal migration of the modified cathode was weakened, due to the presence of the spinel structure at the surface. Consequently, the newly developed Li-rich cathode material exhibited a high 1st efficiency of 94%, improved capacity retention of 82% during 100 cycles at 60℃, and superior rate capability of 62% at 12C （1C = 200 mA/g） rate at 24℃. In addition, the thermal stability of the modified cathode was significantly improved as compared to that of a bare counterpart at 4.6 V, showing a 60% decrease in the total heat generation.

Dual-modification of manganese oxide by heterostructure and cation pre-intercalation for high-rate and stable zinc-ion storage

Zinc-ion batteries(ZIBs)possess great advantages in terms of high safety and low cost,and are regarded as promising alternatives to lithium-ion batteries(LIBs).However,limited by the electrochemical kinetics and structural stability of the typical cathode materials,it is still difficult to simultaneously achieve high rates and high cycling stability for ZIBs.Herein,we present a manganese oxide(Sn_(x)Mn O_(2)/Sn O_(2))material that is dual-modified by Sn O_(2)/Mn O_(2)heterostructures and pre-intercalated Sn;cations as the cathode material for ZIBs.Such modification provides sufficient hetero-interfaces and expanded interlayer spacing in the material,which greatly facilitates the insertion/extraction of Zn^(2+).Meanwhile,the“structural pillars”of Sn^(4+) cations and the“pinning effect”of SnO_(2)also structurally stabilizes the Mn O_(2)species during the repeated Zn^(2+) insertion/extraction,leading to ultra-high cycling stability.Due to these merits,the Sn_(x)MnO_(2)/SnO_(2)cathode exhibits a high reversible capacity of 316.1 m Ah g^(-1) at 0.3 A g^(-1),superior rate capability of 179.4 m Ah g^(-1) at 2 A g^(-1),and 92.4%capacity retention after 2000 cycles.Consequently,this work would provide a promising yet efficient strategy by combining heterostructures and cations preintercalation to obtain high-performance cathodes for ZIBs.

Electrochemical and structural performances of Li[Ni_(0.133)Li_(0.2)Co_(0.133)Mn_(0.533)]O_(2)material during different cycle potential windows

The effects of cycle potential window on electrochemical behaviors,structural characteristics,and surface changes in Li[Ni_(0.133)Li_(0.2)Co_(0.133)Mn_(0.533)]O_(2)(or 0.5 Li_(2)MnO_(3)·0.5 Li(Co_(0.333)Ni_(0.333)Mn_(0.333))O2)in lithium-ion battery were investigated.Two flat charge potential plateaus,~3.9 and~4.5 V,are observed in the initial charge curves of the cells.Sharp changes in specific capacity and columbic efficiency are presented at~4.5 V during the first cycle.XRD specific peaks show an obvious shift with the increase in charge cutoff potential.When the charge cutoff potential is above4.4 V,the cycle performance decreases with the increase in charge cutoff potentials.A film with the composition of C and O elements is observed on the cycled composite particle.

Surface modification with oxygen vacancy in Li-rich layered oxide Li1.2Mn0.54Ni0.13Co0.13O2 for lithium-ion batteries

A couple of layered Li-rich cathode materials Li1.2Mn0.54Ni0.13Co0.13O2 without any carbon modification are successfully synthesized by solvothermal and hydrothermal methods followed by a calcination process. The sample synthesized by the solvothermal method(S-NCM) possesses more homogenous microstructure, lower cation mixing degree and more oxygen vacancies on the surface, compared to the sample prepared by the hydrothermal method(H-NCM). The S-NCM sample exhibits much better cycling performance, higher discharge capacity and more excellent rate performance than H-NCM. At 0.2 C rate,the S-NCM sample delivers a much higher initial discharge capacity of 292.3 mAh g^-1 and the capacity maintains 235 m Ah g^-1 after 150 cycles(80.4% retention), whereas the corresponding capacity values are only 269.2 and 108.5 m Ah g^-1(40.3% retention) for the H-NCM sample. The S-NCM sample also shows the higher rate performance with discharge capacity of 118.3 mAh g^-1 even at a high rate of 10 C, superior to that(46.5 m Ah g^-1) of the H-NCM sample. The superior electrochemical performance of the S-NCM sample can be ascribed to its well-ordered structure, much larger specific surface area and much more oxygen vacancies located on the surface.

Surface yttrium-doping induced by element segregation to suppress oxygen release in Li-rich layered oxide cathodes

Doping electrochemically inert elements in Li-rich layered oxide cathodes usually stabilizes the structure to improve electrochemical performance at the expense of available capacity.Here,we use an element segregation principle to realize a uniform surface doping without capacity sacrifice.On the basis of Hume-Rothery rule,element yttrium is chosen as a candidate dopant to spontaneously segregate at particle surface due to mismatched ionic size.Combined with X-ray photoelectron spectroscopy and electron energy loss spectroscopy mapping,yttrium is demonstrated uniformly distributed on particle surface.More importantly,a significant alleviation of oxygen release after surface doping is detected by operando differential electrochemical mass spectrometry.As a result,the modified sample exhibits improved reversibility of oxygen redox with 82.1%coulombic efficiency and excellent cycle performances with 84.15%capacity retention after 140 cycles.Postmortem analysis by transmission electron microscopy,Raman spectroscopy and X-ray diffraction reveal that the modified sample maintains the layered structure without a significant structure transformation after long cycles.This work provides an effective strategy with a series of elements to meet the industrial application.

An analysis of F-doping in Li-rich cathodes

Li-rich materials,due to their high capacity(>250 mAh·g^(-1)),have recently been considered as an alternative to the current generation of cathode materials for Li-ion batteries(LIBs).However,their inferior cycling stability limits their practical applicability.Doping is a common technique to solve this problem.However,anion doping remains relatively underexplored.Fluorine(F)is one of the most effective anion dopants owning to the improved capacity,cycling stability,and rate performance in batteries.The explanations and experimental results,however,vary significantly from study to study.Herein,we find that bulk F-doping significantly improves both rate performance and cycling stability,likely driven by charge compensation and greater electronegativity.Additionally,bulk F-doping occasionally improves capacity via enhanced activation and occasionally decreases capacity by preventing activation from occurring.Surface F-doping has similar effects to bulk F-doping on capacity and stability,while significantly hindering the rate performance.Furthermore,the improvements in surface-doped materials do not appear to be a result of specific surface modification,and instead can be ascribed to the effect of fluorine on the near-surface bulk material.Greater understanding of fluo-rine's influence on activation,in particular,is required to unlock the full potential of synergistic cation/anion co-doping.