Quantum‐Chemical Study of the FeNCN Conversion‐Reaction Mechanism in Lithium‐ and Sodium‐Ion Batteries

We report a computational study on 3d transition‐metal (Cr, Mn, Fe, and Co) carbodiimides in Li‐ and Na‐ion batteries. The obtained cell voltages semi‐quantitatively fit the experiments, highlighting the practicality of PBE+U as an approach for modeling the conversion‐reaction mechanism of the FeNCN archetype with lithium and sodium. Also, the calculated voltage profiles agree satisfactorily with experiment both for full (Li‐ion battery) and partial (Na‐ion battery) discharge, even though experimental atomistic knowledge is missing up to now. Moreover, we rationalize the structural preference of intermediate ternaries and their characteristic lowering in the voltage profile using chemical‐bonding and Mulliken‐charge analysis. The formation of such ternary intermediates for the lithiation of FeNCN and the contribution of at least one ternary intermediate is also confirmed experimentally. This theoretical approach, aided by experimental findings, supports the atomistic exploration of electrode materials governed by conversion reactions.     

电化学储钠材料的研究进展

大规模储能的二次电池不仅需要具有适宜的电化学性能,更需考虑资源、成本和环境效益等应用要求. 锂离子电池储能的大规模应用也将受到制约. 从资源与环境方面考虑,钠离子电池作为储能电池更具应用优势. 然而,从目前的技术现状来看,几类不同的嵌钠正极材料虽显现出可观的嵌钠容量与较好的循环性,但能量密度与功率密度尚待提高. 硬碳材料和合金负极最有希望用于钠离子电池,这类材料的初始充放电效率和循环稳定性仍有待改善. 本文简要分析了锂离子电池与钠离子电池在材料要求方面的差异,回顾了近年来钠离子电池材料探索中的突破性进展,并主要结合本课题组的研究工作讨论了钠离子电池及其关键材料的发展方向.     

Two-dimensional 1T-PS2 as a promising anode material for sodium-ion batteries with ultra-high capacity,low average voltage and appropriate mobility

As electrodes, two-dimensional materials show special advantages including the infinite planar lengths, broad electrochemical window, large surface–volume ratio, and much exposed active sites. In theory, the two-dimensional materials consist of the elements with high electronegativity may absorb more Na atoms, resulting in a high battery storage capacity. Based on the above idea, we selected the two dimensional metallic PS₂ with 1T-Type structure as an anode material, and explored its potential applications as an electrode material for Na-ion battery through first-principle calculations. As we expected, when two dimensional PS₂ is used as an anode in Na-ion battery, it can adsorb maximum three layers of sodium atoms on both sides of the monolayer, resulting in a maximum theoretical capacity of 1692 mAh/g. Furthermore, it also possesses a rather small sodium diffusion barrier of 0.17 eV, a low average open-circuit voltage of 0.18 V, and a relatively small lattice changes within 13% during the intercalation of Na. These results suggested that the two dimensional PS₂ is a potentially excellent Na-ion battery anode. Our idea of designing two-dimensional anode materials with high storage capacity may provide some references for designing the next generation anode materials of metal-ion batteries.     

Understanding the structural and electronic properties of the cathode material NaFeF3 in a Na-ion battery

Na-ion battery cathode material NaFeF₃ and the corresponding desodiated products were investigated by using first-principle density functional theory calculations within the generalized gradient approximation (GGA) + U framework. Our results show that Na_0.5FeF₃ is the only energetically stable intermediate phase among the cases considered in the present work (x?=?0.75, 0.5, 0.25), leading to theoretically two voltage plateaus, i.e., 2.63 V (1?≥?x?≥?0.5) and 2.82 V (0.5?≥?x?≥?0) in Na _x FeF₃, respectively. The mean charge voltage of the extraction of the first 0.5 Na ions agrees well with the experimental value, but the one of the extraction of the second 0.5 Na ions exhibits a relatively low value comparing to the experimental results, indicating that another end phase exists, which is consistent with the recent experiments. Furthermore, the electronic structures upon the desodiation are also discussed, and charge localization into distinct Fe²⁺ and Fe³⁺ is found in the intermediate-phase Na_0.5FeF₃.     

High capacity, reversible alloying reactions in SnSb/C nanocomposites for Na-ion battery applications

A new SnSb/C nanocomposite based on Na alloying reactions is demonstrated as anode for Na-ion battery applications. The electrode can achieve an exceptionally high capacity (544 mA h g(-1), almost double that of intercalation carbon materials), good rate capacity and cyclability (80% capacity retention over 50 cycles) for Na-ion storage.     

Insights on the mechanism of Na-ion storage in expanded graphite anode

Currently,Na-ion battery(NIB) has become one of the most potential alternatives for Li-ion batteries due to the safety and low cost.As a promising anode for Na-ion storage,expanded graphite has attracted considerable attention.However,the sodiation-desodiation process is still unclear.In our work,we obtain expanded graphite through slight modified Hummer's method and subsequent thermal treatment,which exhibits excellent cycling stability.Even at a high current density of 1 A g^-1,our expanded graphite still remains a high reversible capacity of 100 mA h g^-1 after 2600 cycles.Furthermore,we also investigate the electrochemical mechanism of our expanded graphite for Na-ion storage by operando Raman technique,which illuminate the electrochemical reaction during different sodiation-desodiation processes.     

DFT Investigation of the Potential of B<Subscript>21</Subscript>N<Subscript>21</Subscript> and Al<Subscript>21</Subscript>P<Subscript>21</Subscript> Nanocages as Anode Electrodes in Metal Ion Batteries

In present paper, the potential of B₂₁N₂₁ and Al₂₁P₂₁ nanocages as anode electrodes of Li-ion, Na-ion and K-ion batteries by using of density functional theory was investigated. The effects of adoption of B₂₁N₂₁ and Al₂₁P₂₁ nanocages with halogen atoms on potential of metal-ion batteries were examined. Results showed that Al₂₁P₂₁ as anode electrode in metal ion batteries has higher potential than B₂₁N₂₁. Results indicated that K-ion battery has higher cell voltage than Li-ion and Na-ion batteries. Results showed that adoption of B₂₁N₂₁ and Al₂₁P₂₁ with halogen atoms increased the cell voltage of metal-ion batteries. Results showed that F-doped metal-ion batteries have higher cell voltage than Cl- and Br-doped metal-ion batteries. It can be concluded that F–Al₂₀P₂₁ as anode electrode in metal-ion battery has higher potential than F–B₂₀N₂₁.     

Facile Synthesis of Amorphous Ge Supported by Ni Nanopyramid Arrays as an Anode Material for Sodium-Ion Batteries

In this work, we introduce Ni nanopyramid arrays (NPAs) supported amorphous Ge anode architecture and demonstrate its effective improvement in sodium storage properties. The Ni−Ge NPAs are prepared by facile electrodeposition and sputtering method, which eliminates the need for any binder or conductive additive when used as a Na-ion battery anode. The electrodes display stable cycling performance and enhanced rate capabilities in contrast with planar Ge electrodes, which can be owing to the rational design of the architectured electrodes and firm bonding between current collector and active material (i. e. Ni and Ge, respectively). To validate improvement of nanostructures on electrochemical performance, sodium insertion behavior of crystalline Ge derived from Mg₂Ge precursor has been investigated, in which limited but effective enhancement of sodium storage properties are realized by introducing porous nanostructure in crystalline Ge. These results show that elaborately designed configuration of Ge electrodes may be a promising anode for Na-ion battery applications.     

Nitrogen-doped porous carbon derived from bimetallic zeolitic imidazolate frameworks for electrochemical Li+/Na+ storage

Journal of Solid State Electrochemistry - Porous carbon is regarded as one of the most promising anode candidates for Li-ion battery and Na-ion battery, and the specific porous structure and...     

Surface-assembled highly flexible Na_3(VOPO_4)_2F nanocube cathode for high-rate binder-free Na-ion batteries

Flexible Na-ion storage cathodes are still very few due to the challenge in achieving both reliable mechanical flexibility and excellent electrochemical performances.Herein,a new type of flexible Na_3(VOPO_4)_2F cathode with nanocubes tightly assembled on carbon cloth is fabricated by a facile solvothe rmal method for the first time.The cathode is able to exhibit superior rate capability and stable cycling performa nce up to 1000 cycles,due to the surface-assembling of crystalline nanocubes on carbon fibers.In addition,it shows good mechanical flexibility,nearly no capacity decay is observed after continuous bending of 500 times.With this novel cathode and a directly-grown Na_2Ti_2O_5 anode,a fully binde r-free Na-ion battery is assembled.It can deliver a high wo rking voltage and increased gravimetric energy/power densities(maximum values:220.2 Wh/kg;5674,7 W/kg),and can power a LED indicator at bending angles fro m 0° to 180°.     

Process-Structure-Formulation Interactions for Enhanced Sodium Ion Battery Development: A Review

Before the viability of a cell formulation can be assessed for implementation in commercial sodium ion batteries, processes applied in cell production should be validated and optimized. This review summarizes the steps performed in constructing sodium ion (Na-ion) cells at research scale, highlighting parameters and techniques that are likely to impact measured cycling performance. Consistent process-structure-performance links have been established for typical lithium-ion (Li-ion) cells, which can guide hypotheses to test in Na-ion cells. Liquid electrolyte viscosity, sequence of mixing electrode slurries, rate of drying electrodes and cycling characteristics of formation were found critical to the reported capacity of laboratory cells. Based on the observed importance of processing to battery performance outcomes, the current focus on novel materials in Na-ion research should be balanced with deeper investigation into mechanistic changes of cell components during and after production, to better inform future designs of these promising batteries.     

三元锂离子动力电池衰减机理

失效分析是通过剖析电池循环过程中复杂的物理和化学变化引起的失效现象,优化材料制备和电池制作工艺,提升电池性能的有效途径。 通过对3.0～4.2 V电压范围1C循环1000周镍钴锰酸锂(NCM,LiNi_0.5Co_0.2Mn_0.3O₂)三元锂离子动力电池拆解分析后发现,正极容量损失约为2.73%,负极容量损失约为2.4%。 对比正负极片循环前后X射线衍射和场发射扫描电子显微镜分析发现,正极容量损失主要由正极颗粒破碎和结构转变引起的,负极衰减主要由循环过程中Li⁺持续脱嵌导致石墨层状结构损伤引起的。 正极过渡金属阳离子溶解并沉积在负极,催化电解液/电极界面副反应,导致负极过度成膜,活性锂损失,影响电极过程动力学也是电池失效的原因之一。     

Size-controlled flow synthesis of metal-organic frameworks crystals monitored by in-situ ultraviolet-visible absorption spectroscopy

Size-controlled flow synthesis of nanoporous particles are of considerable interest for future industrial applications,however,is facing challenges due to lack of in-situ method for size-characterization in fluidic environment.We present that ultraviolet-visible(UV-vis) absorption spectroscopy can be integrated into a flow-synthesis system which was produced by femtosecond laser micro machining.The shift of the absorption peak position of the ex-situ and in-situ UV-vis spectra correlates to variation of size of porous metal-organic frameworks crystals.ZIF-67 crystals with a size in the range from 200 nm to1025 nm are fabricated with the assistance of tri-ethylamine under monitoring of in-situ UV-vis spectra.The ZIF-67 crystals are converted into nanoporous carbons particles with controlled sizes.These materials show size-dependent performance in Na-ion battery and size-independent performance in metal/H_2 O seawater battery.     

First‐Principles Study of Na‐Ion Battery Performance and Reaction Mechanism of Tin Sulfide as Negative Electrode

We study the Na‐ion battery characteristics of SnS as a negative electrode by first‐principles calculations. From energy analyses, we clarify the discharge reaction process of the Na/SnS half‐cell system. We show a phase diagram of Na?Sn?S ternary systems by constructing convex‐hull curves, and show a possible reaction route considering intermediate products in discharge reactions. Voltage‐capacity curves are calculated based on the Na?SnS reaction path that is obtained from the ternary phase diagram. It is found that the conversion reactions and subsequently the alloying reactions proceed in the SnS electrode, contributing to its high capacity compared with the metallic Sn electrode, in which only the alloying reactions progresses stepwise. To verify the calculated reaction process, x‐ray absorption spectra (XAS) are calculated and compared with experimental XAS at S K‐edge, showing meaningful XAS changes associated with Na₂S and SnS in discharged and charged states, respectively.     

A Hierarchically Ordered Mesoporous-Carbon-Supported Iron Sulfide Anode for High-Rate Na-Ion Storage

Sodium-ion batteries (SIBs) are promising alternatives to lithium-based energy storage devices for large-scale applications, but conventional lithium-ion battery anode materials do not provide adequate reversible Na-ion storage. In contrast, conversion-based transition metal sulfides have high theoretical capacities and are suitable anode materials for SIBs. Iron sulfide (FeS) is environmentally benign and inexpensive but suffers from low conductivity and sluggish Na-ion diffusion kinetics. In addition, significant volume changes during the sodiation of FeS destroy the electrode structure and shorten the cycle life. Herein, we report the rational design of the FeS/carbon composite, specifically FeS encapsulated within a hierarchically ordered mesoporous carbon prepared via nanocasting using a SBA-15 template with stable cycle life. We evaluated the Na-ion storage properties and found that the parallel 2D mesoporous channels in the resultant FeS/carbon composite enhanced the conductivity, buffered the volume changes, and prevented unwanted side reactions. Further, high-rate Na-ion storage (363.4 mAh g⁻¹ after 500 cycles at 2 A g⁻¹, 132.5 mAh g⁻¹ at 20 A g⁻¹) was achieved, better than that of the bare FeS electrode, indicating the benefit of structural confinement for rapid ion transfer, and demonstrating the excellent electrochemical performance of this anode material at high rates.     

Surface-engineering enhanced sodium storage performance of Na_3V_2(PO_4)_3 cathode via in-situ self-decorated conducting polymer route

The key to the development of sodium ion battery is materials with a high rate capacity and cycle stability. Conducting coating is an efficient approach to improve electrochemical performance. As a case study, the Na_3V_2(PO_4)_3@PEDOT composite was prepared through an in-situ self-decorated conducting polymer route without further calcination. The Na_3V_2(PO_4)_3 electrode with a 7%poly(3,4-ethylenedioxythiophene)(PEDOT) coating can deliver an initial reversible capacity of 100 mA h g~(-1) at 1 cycle, and 82%capacity retention over 200 cycles. The results also show that the Na_3V_2(PO_4)_3 electrode without and with a thick PEDOT coating exhibits poor electrochemical performance, indicating that an appropriate coating layer is important for improving electronic conductivity and regulating Na-ion insertion. Therefore, this work offers possibility to promote the electrochemical performance of poor-conducting materials in sodium-ion batteries using an in-situ self-decorated conducting polymer.     

Prussian blue: a new framework of electrode materials for sodium batteries

Prussian blue and its analogues consisting of different transition-metal ions (Fe, Mn, Ni, Cu, Co and Zn) have been synthesized at room temperature. Insertion of Na into KFe(2)(CN)(6) in a carbonate electrolyte exhibited a reversible capacity near 100 mA h g(-1) with no capacity fade in 30 cycles. The data indicate that a Na-ion battery with a Prussian blue framework as a cathode will be feasible.     

全钒液流单电池充放电行为及特性研究

建立具有外置双饱和甘汞参比电极及双液流电池的实验装置系统.使用该装置可在同一时刻同时测定小型液流单电池充放电时的电池电压、电池正负极电位及正负极开路电位,进而计算充放电过程电池的欧姆内阻降(iR)及其正负极过电位.以石墨毡为电极、Nafion 117作隔膜的全钒液流单电池,在60 mA.cm-2电流密度下,每一充放电循环的平均iR降约占总电压损耗的74%,表明该电池的电压效率受制于电池的欧姆内阻.充放电曲线显示,电池放电终点之所以出现主要是由于电池负极电位在放电末期的快速上升而引起的.本文设计的全钒单电池于60 mA.cm-2下工作时,其电压及能量效率分别达89%和85%,表明该电池结构合理,且石墨毡是钒电池合适的电极材料.     

三元锂离子电池容量衰减机理研究进展

三元锂离子电池主要是指使用镍钴锰酸锂(NCM)或镍钴铝酸锂(NCA)作为正极材料的锂离子电池,三元锂离子电池广泛应用于电动汽车、3C电子产品、储能等领域。然而,三元锂离子电池的循环寿命已成为其进一步发展的最大障碍,因此了解三元锂离子电池的容量衰退机理具有重要意义。三元锂离子电池的衰退机理主要包括五个方面:晶体结构的改变和相变、活性材料的损失、电解质的分解和消耗、可脱嵌锂离子的损耗以及固体电解质界面的形成。本文总结了近年来相关方面的研究进展,以期更全面地总结三元锂离子电池的容量衰减机理,并对三元锂离子电池的应用前景进行了展望。     

Electronic and magnetic structure of transition-metal carbodiimides by means of GGA+U theory

The electronic structures and magnetic properties of MNCN (M = Fe, Co, and Ni) have been investigated by density-functional theory including explicit electronic correlation through an ad hoc Coulomb potential (GGA+U). The results evidence CoNCN and NiNCN as type-II anti-ferromagnetic semiconductors (that is, intralayer ferromagnetic and interlayer anti-ferromagnetic), in accordance with experimental observations. Just like the prototype MnNCN, the MNCN phases, with M = Ni and Co, thus resemble the corresponding MO monoxides with respect to their magnetic and transport properties. By contrast, FeNCN remains (semi)metallic even upon applying a strong Coulomb correlation potential. This, most probably, is in contradiction with its observed optical transparency and expected insulating behavior and points toward a serious density-functional theory problem.