Li_4Ti_5O_(12)/(Ag+C)极材料的固相合成及电化学性能

以Li_2CO_3,TiO_2为原料,葡萄糖为碳源,采用固相煅烧工艺合成了亚微米级的Li_4Ti_5O_(12)/C复合负极材料.并将之与AgNO_3复合,采用固相方法制备出了Ag表面修饰的Li_4Ti_5O_(12)(AG+C)复合材料.采用XRD、SEM和TEM测试方法对材料的微结构进行了表征.结果表明,C的存在对Ag单质在Li_4Ti_5O_(12)/C颗粒表面的大量形成起到了积极的促进作用.从而很大程度地提高了Li_4Ti_5O_(12)/C的电导率,因此有效地改善了其电化学性能.在1C倍率下,Li_4Ti_5O_(12)/(Ag+C)复合材料的首次放电容量达到了164 mAh·g(-1).     

High Rate Performance of Aqueous Magnesium-iron-ion Batteries Based on Fe_2O_3@GH as the Anode

Aqueous Mg-ion batteries (MIBs) are safe,non-toxic and low-cost.Magnesium has a high theoretical specific capacity with its ion radius close to that of lithium.Therefore,aqueous magnesium ion batteries have great research advantages in green energy.To acquire the best electrode materials for aqueous magnesium ion batteries,it is necessary for the structural design in material.Fe_2O_3 is an anode material commonly used in Li-ion battery.However,the nano-cube Fe_2O_3 combined with graphene hydrogels (GH) can be successfully prepared and employed as an anode,which is seldom researched in the aqueous batteries system.The Fe_2O_3/GH is used as anode in the dual Mg SO_4+Fe SO_4 aqueous electrolyte,avoiding the irreversible deintercalation of magnesium ions.In addition,the Fe element in anode material can form the Fe~(3+)/Fe~(2+)and Fe~(2+)/Fe~(3+)redox pairs in the Mg SO_4+Fe SO_4 electrolyte.Thus,the reversible insertion/(de)insertion of magnesium and iron ions into/from the host anode material can be simultaneously achieved.After the initial charge,the anodic structure is changed to be more stable,avoiding the formation of Mg O.The Fe_2O_3/GH demonstrates high rate properties and reversible capacities of 198,151,121,80,75 and 27 m Ah g~(-1) at 50,100,200,300,500 and1000 m A g~(-1) correspondingly.     

Free-standing ternary metallic sulphides/Ni/C-nanofiber anodes for high-performance lithium-ion capacitors

As a promising energy-storage device,the hybrid lithium-ion capacitor coupling with both a large energy density battery-type anode and a high power density capacitor-type cathode is attracting great attention.For the sake of improving the energy density of hybrid lithium-ion capacitor,the free-standing anodes with good electrochemical performance are essential.Herein,we design an effective electrospinning strategy to prepare free-standing MnS/Co_4S_3/Ni_3S_2/Ni/C-nanofibers(TMSs/Ni/C-NFs)film and firstly use it as a binder-free anode for hybrid lithium-ion capacitor.We find that the carbon nanofibers can availably prevent MnS/Co_4S_3/Ni_3S_2/Ni nanoparticles from aggregation as well as significantly improve the electrochemical performance.Therefore,the binder-free TMSs/Ni/C-NFs membrane displays an ultrahigh reversible capacity of 1246.9 m Ah g~(-1)at 100 m A g~(-1),excellent rate capability(398 mAh g~(-1) at2000 mA g~(-1)),and long-term cyclic endurance.Besides,we further assemble the hybrid lithium-ion capacitor,which exhibits a high energy density of 182.0 Wh kg~(-1)at 121.1 W kg~(-1)(19.0 Wh kg~(-1) at 3512.5 W kg~(-1))and remarkable cycle life.     

All boron-based 2D material as anode material in Li-ion batteries

To design the high-energy-density Li-ion batteries, the anode materials with high specific capacity have attracted much attention. In this work, we adopt the first principles calculations to investigate the possibility of a new two dimensional boron material, named BG, as anode material for Li-ion batteries. The calculated results show that the maximum theoretical specific capacity of B_G is 1653 m Ah g~(-1)(LiB1.5).Additionally, the energy barriers of Li ion and Li vacancy diffusion are 330 meV and 110 meV, respectively, which imply fast charge and discharge ability for BGas an anode material. The theoretical findings reported in this work suggest that BGis a potential candidate as anode material of high-energy-density Li-ion batteries.     

Electrochemical Performance of Li_4Ti_5O_(12) Prepared by Different Methods

A series of Li4Ti5O12 materials were prepared by three different methods： solvothermal, sol-gel, and solid-state reaction methods. Phase composition, morphology, and particle sizes of the samples were studied by powder X-ray diffraction （XRD） and scanning electron microscopy （SEM）. Electrochemical properties of the samples were investigated by charge-discharge tests. It is demonstrated that both sol-gel and solid-state reaction methods provided good control over the chemical composition and microstructure of the active material, in which sol-gel method yielded a fine Li4Ti5O12 spinel having an initial specific capacity of 146 mAh g-1 and low capacity fade during cycling. Comparatively, the solid-state method is simple and promising to prepare Li4Ti5O12 for commercial applications.     

3D porous V_2O_5 architectures for high-rate lithium storage

The discovery of novel electrode materials promises to unleash a number of technological advances in lithium-ion batteries. V_2O_5 is recognized as a high-performance cathode that capitalizes on the rich redox chemistry of vanadium to store lithium. To unlock the full potential of V_2O_5, nanotechnology solution and rational electrode design are used to imbue V_2O_5 with high energy and power density by addressing some of their intrinsic disadvantages in macroscopic crystal form. Here, we demonstrate a facile and environmental-friendly method to prepare nanorods-constructed 3D porous V_2O_5 architectures(3 D-V_2O_5)in large-scale. The 3D porous architecture is found to be responsible for the enhanced charge transfer kinetics and Li-ion diffusion rate of the 3D-V_2O_5 electrode. As the result, the 3D-V_2O_5 surpasses the conventional bulk V_2O_5 by showing enhanced discharge capacity and rate capability(delivering 154 and127 m Ah g~(-1) at 15 and 20 C, respectively).     

Porous nanostructured ZnCo_2O_4 derived from MOF-74:High-performance anode materials for lithium ion batteries

Nanostructured metal oxides derived from metal organic frameworks have been shown to be promising materials for application in high energy density lithium ion batteries. In this work, porous nanostructured ZnCo_2O_4 and Co_3O_4 were synthesized by a facile and cost-effective approach via the calcination of MOF-74 precursors and tested as anode materials for lithium ion batteries. Compared with Co_3O_4, the electrochemical properties of the obtained porous nanostructured ZnCo_2O_4 exhibit higher specific capacity, more excellent cycling stability and better rate capability. It demonstrates a reversible capacity of 1243.2 m Ah/g after 80 cycles at 100 m A/g and an excellent rate performance with high average discharge specific capacities of 1586.8, 994.6, 759.6 and 509.2 m Ah/g at 200, 400, 600 and 800 m A/g, respectively.The satisfactory electrochemical performances suggest that this porous nanostructured ZnCo_2O_4 is potentially promising for application as an efficient anode material for lithium ion batteries.     

Understanding the roles of Ti on the structure and electrochemical performances of Li_2Ru_(1-x)Ti_xO_3 cathode materials for Li-ion batteries

The lattice doping has been widely used to improve the electrochemical performances of Li-rich cathode materials but the roles of the introduced foreign atoms are still not very clear.Herein,a series of Li_2Ru_(1-x)Ti_xO_3 solid solutions have been synthesized and the roles of Ti doping on the structural and electrochemical properties of Li_2RuO_3 have been comprehensively investigated.The Rietveld refinement exhibits that the interlayer spacing gradually shortens with increasing Ti content.This shrinkage is favorable to the layered structure stability but increases the lithium diffusion barrier.Galvanostatic measurements show that Li_2Ru_(0.8)Ti_(0.2)O_3 possesses the best cyclability with 196.9 and 196.1 m Ah g~(-1)for charge and discharge capacity retaining after 90 cycles,respectively.Cyclic voltammetry scanning indicates that Ti dopant promotes the formation of more peroxo-or superoxo-like species but reduces the initial coulumbic efficiency.Results of electrochemical impedance spectroscopy display that Ti doping reduces the charge transfer impedance,which facilitates the lithium-ion diffusion across the electrolyteelectrode interface and improves the electronic conductivity.Li_2Ru_(0.8)Ti_(0.2)O_3exhibits the best electrochemical performance owing to the balance among all the factors discussed above.This study also offers some new insights into optimizing the electrochemical performances of Li-rich cathode materials through the lattice doping.     

Synthesis and performance of Li_4Ti_5O_(12) anode materials using the PVP-assisted combustion method

Li_4Ti_5O_(12) was synthesized by a facile gel-combustion method(GCM) with polyvinylpyrrolidone(PVP) as the polymer chelating agent and fuel.The structural and electrochemical properties of the sample were compared with the one prepared by the conventional solid-state reaction(SSR) through X-ray diffraction(XRD),scanning electron microscopy(SEM),cyclic voltammetry(CV),charge-discharge measurements,and electrochemical impedance spectroscopy(EIS),respectively.The sub-microscale Li_4Ti_5O_(12) oxides,with a high phase purity and good stoichiometry,can be obtained by annealing at 800 C.The grain size is smaller than that of the samples that were power prepared by SSR.Lithium-ion batteries with a GCM Li_4Ti_5O_(12) anode exhibit excellent reversible capacities of 167.6,160.7,152.9,and 144.2 mAh/g,at the current densities of 0.5 C,1 C,3 C and 5 C,respectively.The excellent cycling and rate performance can be attributed to the smaller particle size,lower charge-transfer resistance and larger lithium ion diffusion coefficient.It is therefore concluded that GCM Li_4Ti_5O_(12) is a promising candidate for applications in highrate lithium ion batteries.     

FeP nanoparticles derived from metal-organic frameworks/GO as high-performance anode material for lithium ion batteries

Double carbon coated Fe P composite(Fe P@NC@r GO)was in situ fabricated via the phosphorization process of the as-prepared Prussian blue@graphene oxide(PB@GO)precursor.The Fe P nanocrystals were successfully embedded in the nitrogen-doped porous carbon matrix.When used as the anode for lithium ion batteries(LIBs),the Fe P@NC@r GO anode shows superior lithium storage properties,delivering a high specific capacity of 830 m A h g~(-1)after 100 cycles at 100 m A g~(-1)and excellent rate capability of 359 m A h g~(-1)at 5 A g~(-1).The outstanding performance mainly ascribes to the synergistic effect of the double carbon coating and porous structure design.The introduction of porous carbon and graphene coating on Fe P nanoparticles greatly enhance the electronic conductivity of the active material and well accommodates the large volume variation of Fe P during the cycling process.     

Highly stable aqueous rechargeable Zn-ion battery: The synergistic effect between NaV_6O_(15) and V_2O_5 in skin-core heterostructured nanowires cathode

The aqueous rechargeable Zn-ion batteries based on the safe,low cost and environmental benignity aqueous electrolytes are one of the most compelling candidates for large scale energy storage applications.However,pursuing suitable insertion materials may be a great challenge due to the strong electrostatic interaction between Zn^{^(2+})and cathode materials.Hence,a novel NaV₆O₁₅/V₂O₅ skin-core heterostructure nanowire is reported via a one-step hydrothermal method and subsequent calcination for high-stable aqueous Zn-ion batteries(ZIBs).The NaV₆O₁₅/V₂O₅ cathode delivers high specific capacity of 390 m Ah/g at 0.3 A/g and outstanding cycling stability of 267 m Ah/g at 5 A/g with high capacity retention over 92.3%after 3000 cycles.The superior electrochemical performances are attributed to the synergistic effect of skin-core heterostructured NaV₆O₁₅/V₂O₅,in which the sheath of NaV₆O₁₅ possesses high stability and conductivity,and the V₂O₅ endows high specific capacity.Besides,the heterojunction structure not only accelerates intercalation kinetics of Zn²⁺transport but also further consolidates the stability of the layers of V₂O₅ during the cyclic process.This work provides a new perspective in developing feasible insertion materials for rechargeable aqueous ZIBs.     

Yolk-shell Si/C composites with multiple Si nanoparticles encapsulated into double carbon shells as lithium-ion battery anodes

The conceptual design of yolk-shell structured Si/C composites is considered to be an effective way to improve the recyclability and conductivity of Si-based anode materials. Herein, a new type of yolk-shell structured Si/C composite(denoted as TSC-PDA-B) has been intelligently designed by rational engineering and precise control. In the novel structure, the multiple Si nanoparticles with small size are successfully encapsulated into the porous carbon shells with double layers benefiting from the strong etching effect of HF. The TSC-PDA-B product prepared is evaluated as anode materials for lithium-ion batteries(LIBs).The TSC-PDA-B product exhibits an excellent lithium storage performance with a high initial capacity of 2108 mAh g~(-1) at a current density of 100 mA g~(-1) and superior cycling performance of 1113 mAh g~(-1) over 200 cycles. The enhancement of lithium storage performance may be attributed to the construction of hybrid structure including small Si nanoparticles, high surface area, and double carbon shells, which can not only increase electrical conductivity and intimate electrical contact with Si nanoparticles, but also provide built-in buffer voids for Si nanoparticles to expand freely without damaging the carbon layer.The present findings can provide some scientific insights into the design and the application of advanced Si-based anode materials in energy storage fields.     

Oleic acid-treated synthesis of MnO@C with superior electrochemical properties

MnO@C nanocomposites are synthesized by annealing MnO microspheres treated with oleic acid as carbon source. The obtained MnO@C nanocomposites exhibit a discharge capacity of 1075 m Ah/g for the initial cycle, and show the excellent cycling performance with a discharge capacity of 421 mAh/g after100 cycles at a current density of 100 mA/g. The total specific capacity of MnO@C nanocomposites is higher than those of pure MnO microspheres in our experiments. Owing to the superior electrochemical behavior, the as-obtained MnO@C nanocomposites are potentially applied as next-generation anode material for lithium-ion batteries.     

Leaf-inspired design of mesoporous Sb_2S_3/N-doped Ti_3C_2T_x composite towards fast sodium storage

Owing to excellent conductivity and abundant surface terminals,MXene-based heterostructures have been intensively investigated as energy storage materials.However,elaborate design of the structure and composition of MXene-based hybrids towards superior electrochemical performance is still challenging.Herein,we present an ingenious leaf-inspired design for preparing a unique Sb_2S_3/nitrogen-doped Ti_3C_2T_x MXene (L-Sb_2S_3/Ti_3C_2) hybrid.In-situ TEM observations reveal that the leaflike Sb_2S_3 nanoparticles with numerous mesopores can well relieve the large volume changes via an inward pore filling mechanism with only 20%outward expansion,whereas highly conductive N-doped Ti_3C_2T_x nanosheets can serve as the robust mechanical support to reinforce the structural integrity of the hybrid.Benefiting from the structural and constituent merits,the L-Sb_2S_3/Ti_3C_2anode fabricated exhibits a fast sodium storage behavior in terms of outstanding rate capability (339.5 mA h g~(-1)at 2,000 mA g~(-1)) and high reversible capacity at high current density (358.2 mA h g~(-1)at 1,000 mA g~(-1)after 100 cycles).Electrochemical kinetic tests and theoretical simulation further manifest that the boosted electrochemical performance mainly arises from such a unique leaf-like Sb_2S_3 mesoporous nanostructure with abundant active sites,and enhanced Na~+ adsorption energy on the heterojunction formed between Sb_2S_3 nanoparticles and Ti_3C_2 matrix.     

Confining Li_2O_2 in tortuous pores of mesoporous cathodes to facilitate low charge overpotentials for Li-O_2 batteries

Achieving low charge overpotentials represents one of the most critical challenges for pursuing highperformance lithium-oxygen(Li-O₂)batteries.Herein,we propose a strategy to realize low charge overpotentials by confining the growth of lithium peroxide(Li₂O₂)inside mesoporous channels of cathodes(CMK-8).The CMK-8 cathode with tortuous pore structures can extend the diffusion distance of lithium superoxide(LiO₂)in the mesoporous channels,facilitating the further reduction of LiO₂ to lithium peroxide(Li₂O₂)inside the pores and preventing them to be diffused out of the pores.Therefore,Li₂O₂ is trapped in the mesoporous channels of CMK-8 cathodes,ensuring a good Li₂O₂/CMK-8 contact interface.The CMK-8 electrode exhibits a low charge overpotential of 0.43 V and a good cycle life for 72 cycles with a fixed capacity of 500 m Ah g^-1 at 0.1 A g^-1.This study proposes a strategy to achieve a low charge overpotential by confining Li₂O₂ growth in the mesoporous channels of cathodes.     

Niobium oxyphosphate nanosheet assembled two-dimensional anode material for enhanced lithium storage

The development of high-capacity and high-rate anodes has become an attractive endeavor for achieving high energy and power densities in lithium-ion batteries(LIBs).Herein,a new-type anode material of reduced graphene oxide(rGO) supported niobium oxyphosphate(NbOPO_4) nanosheet assembled twodimensional composite material(NbOPO_4/rGO) is firstly fabricated and presented as a promising highperformance LIB anode material.In-depth electrochemical analyses and in/ex situ characterizations reveal that the intercalation-conversion reaction takes place during the first discharge process,followed by the reversible redox process between amorphous NbPO_4 and Nb which contributes to the reversible capacity in the subsequent cycles.Meanwhile,the lithiation-generated Li3 PO_4,behaving as a good lithium ion conductor,facilitates ion transport.The rGO support further regulates the structural and electron/ion transfer properties of NbOPO_4/rGO composite compared to neat NbOPO_4, resulting in greatly enhanced electrochemical performances.As a result,NbOPO_4/rGO as a new-type LIB anode material achieves a high capacity of 502.5 mAh g^-1 after 800 cycles and outstanding rate capability of 308.4 mAh g^-1 at 8 A g^-1.This work paves the way for the deep understanding and exploration of phosphate-ba sed high-efficiency anode materials for LIBs.     

Li_(3.22)Na_(0.569)Mn_(5.78)O_(12.0)的电化学性能

以L iOH.H2O和Mn(CH3COO)2.2H2O作原料,应用微波-固相两段烧结法合成具有L i4Mn5O12结构特征,组成为L i3.22Na0.569Mn5.78O12.0的锂离子电池正极材料.XRD分析表明,在380℃的后处理温度下,微波烧结前处理有利于生成纯L i4Mn5O12尖晶石相.充放电实验表明,在4.5~2.5V电压区间,新制样品的初始放电容量为132 mAh.g-1,100循环的容量衰减率为6.8%;4个月存放样的初始放电容量为122 mAh.g-1,100循环的容量衰减率为17.4%.表现出较好的充放电性能和循环寿命.微波烧结使样品的Mn-O键被加强.     

Improving cycling stability of Bi-encapsulated carbon fibers for lithium/sodium-ion batteries by Fe_2O_3 pinning

Bi draws increasing attention as anode materials for lithium-ion batteries and sodium-ion batteries due to its unique layered crystal structure,which is in favor of achieving fast ionic diffusion kinetics during cycling.However,the dramatic volume expansion upon lithiation/sodiation and an insufficient theoretical capacity of Bi greatly hinder its practical application.Herein,we report the Fe_2 O_3 nanoparticle-pinning Bi-encapsulated carbon fiber composites through the electrospinning technique.The introduction of Fe_2 O_3 nanoparticles can prevent the growth and aggregation of Bi nanoparticles during synthetic and cycling processes,re s pectively.Fe_2 O_3 with high specific capacity also contributes to the specific capacity of the composites.Consequently,the as-prepared Bi-Fe_2 O_3/carbon fiber composite exhibits outstanding long-term stability,which delivers reversible capacities 504 and 175 mAh/g after1000 cycles at 1 A/g for lithium-ion and sodium-ion batteries,respectively.     

Construction of CoS_2 nanoparticles embedded in well-structured carbon nanocubes for high-performance potassium-ion half/full batteries

Metal sulfides have been widely investigated as promising electrode materials for potassium-ion batteries(PIBs) due to their high theoretical capacities.However,the practical application of metal sulfides in PIBs is still hindered by their intrinsic shortcomings of low conductivity and severe volume changes during the potassiation/depotassiation process.Herein,a simple template-based two-step annealing strategy is proposed to impregnate CoS_2 nanoparticles in the well-structured carbon nanocubes(denoted CoS_2/CNCs) as an advanced anode material for PIBs.The ex-situ XRD measurements reveal the K storage mechanism in CoS_2/CNCs.Benefiting from the unique structures,including abundant active interfacial sites,high electronic conductivity,and significantly alleviated volume variation,CoS_2/CNCs present a high specific capacity(537.3 mAh g~(-1) at0.1 A g~(-1)),good cycling stability(322.4 mAh g~(-1) at 0.5 A g~(-1) after 300 cycles),and excellent rate capability(153.1 mAh g~(-1) at5 A g~(-1)).Moreover,the obtained nanocomposite shows superior potassium storage properties in K-ion full cells when it is coupled with a KVP04 F cathode.     

Fabrication of nanoreactors based on polyoxoperoxometalates and enhancement of their catalytic activity

The nanoreactors were fabricated by reacting amphiphilic quaternary ammoniums and polyoxoperoxometalates K_n[PW_12-xTi_x- O_40-x（O₂）_x]（x=1,2 and 3;n = 5,7 and 9）(K₅[PW₁₁TiO₃₉（O₂）],K₇[PW₁₀Ti₂O₃₈（O₂）₂]and K₉[PW₉Ti₃O₃₇（O₂）₃]).Fourier transform infrared spectroscopy（FT-IR）,transmission electron microscopy（TEM） were used to characterize the resulting samples. This kind of nanocatalysts could promote NH₄SCN’ degradation into simple inorganic compounds such as SO₄^2-,HCO₃^- and NO₃^- only using oxygen as an oxidant under room conditions.