High-Current Capable and Non-Flammable Protic Organic Electrolyte for Rechargeable Zn Batteries

Rechargeable Zinc batteries (RZBs) are considered a potent competitor for next-generation electrochemical devices, due to their multiple advantages. Nevertheless, traditional aqueous electrolytes may cause serious hazards to long-term battery cycling through fast capacity fading and poor Coulombic efficiency (CE), which happens due to complex reaction kinetics in aqueous systems. Herein, we proposed the novel adoption of the protic amide solvent, N-methyl formamide (NMF) as a Zinc battery electrolyte, which possesses a high dielectric constant and high flash point to promote fast kinetics and battery safety simultaneously. Dendrite-free and granular Zn deposition in Zn-NMF electrolyte assures ultra-long lifespan of 2000 h at 2.0 mA cm⁻²/2.0 mAh cm⁻², high CE of 99.57 %, wide electrochemical window (≈3.43 V vs. Zn²⁺/Zn), and outstanding durability up to 10.0 mAh cm⁻². This work sheds light on the efficient performance of the protic non-aqueous electrolyte, which will open new opportunities to promote safe and energy-dense RZBs.     

An aqueous rechargeable lithium battery based on doping and intercalation mechanisms

An aqueous rechargeable lithium battery (ARLB) using an electroactive polymer, polypyrrole (PPy), as a negative electrode; a lithium ion intercalation compound LiCoO₂ as a positive electrode; and Li₂SO₄ aqueous solution as an electrolyte and its working mechanism are described. The charge/discharge process is associated with the doping/un-doping of anions at the negative electrode and intercalation/deintercalation of lithium ions at the positive electrode. The average output voltage of the PPy//LiCoO₂ battery is about 0.85 V. This battery exhibits excellent cycling performance. This new technology solves the major problem of poor cycling life of ARLBs and will provide a new strategy to explore advanced energy storage and conversion systems.     

垂直自支撑式金属有机框架多级结构单晶用于锂定向沉积

金属有机框架材料(MOF)是由金属离子或簇和有机配体通过配位键自组装形成的多孔晶体材料.MOF及其衍生物具有开放金属位点和极大的比表面积,广泛地应用在催化领域.然而,MOF材料由于存在暴露活性位点较少,传质受限或易发生不可控制的聚集等问题,会导致活性位点的损失,极大地限制了其在催化领域的应用.多级结构不仅提供更多的暴露...     

Structural and electronic properties of lithium ion battery anode material LiMN (M = Ni, Co, Cu)

The structural and electronic properties of anode materials LiMN (M = Ni, Co, Cu) for lithium ion batteries have been studied by the first-principles method. The calculations reveal different bonding characteristics for LiMN (M = Ni, Co, Cu). The Li–N bond on the LiN planes shows covalent mixed with ionic characters, with the covalent interaction strengthened and ionic one weakened gradually from LiNiN to LiCoN and then to LiCuN. In the direction of N–M chains, the bonding characteristics are analogous on the whole. The N–M bonding shows both ionic and covalent characters again, while the covalent interaction slightly weakened in sequence. Electronic structure calculations suggest that LiMN (M = Ni, Co, Cu) are all metallic, where the LiNiN is of anisotropic conductivity along the directions of N–Ni chains, while for LiCoN and LiCuN, electrons can also be feebly conductive on the LiN planes besides along the linear N–Co and N–Cu chains.     

Kinetics of the electrochemical reduction of trivalent neptunium ion in the /Li-K/Cl eutectic at 450 °C

We report voltammetric and chronoamperometric investigations on the reduction of Np/III/ in the /Li–K/Cl melt. The electrode reaction is nearly reversible and a nucleation phenomenon appears in the early deposition of neptunium metal. The Tafel equation corresponding to that deposition indicates that the charge transfer is the rate-determining step of the overall electrode process.     

Understanding the electrochemistry of “water-in-salt” electrolytes: basal plane highly ordered pyrolytic graphite as a model system

A new approach to expand the accessible voltage window of electrochemical energy storage systems, based on so-called “water-in-salt” electrolytes, has been expounded recently. Although studies of transport in concentrated electrolytes date back over several decades, the recent demonstration that concentrated aqueous electrolyte systems can be used in the lithium ion battery context has rekindled interest in the electrochemical properties of highly concentrated aqueous electrolytes. The original aqueous lithium ion battery conception was based on the use of concentrated solutions of lithium bis(trifluoromethanesulfonyl)imide, although these electrolytes still possess some drawbacks including cost, toxicity, and safety. In this work we describe the electrochemical behavior of a simple 1 : 1 electrolyte based on highly concentrated aqueous solutions of potassium fluoride (KF). Highly ordered pyrolytic graphite (HOPG) is used as well-defined model carbon to study the electrochemical properties of the electrolyte, as well as its basal plane capacitance, from a microscopic perspective: the KF electrolyte exhibits an unusually wide potential window (up to 2.6 V). The faradaic response on HOPG is also reported using K₃Fe(CN)₆ as a model redox probe: the highly concentrated electrolyte provides good electrochemical reversibility and protects the HOPG surface from adsorption of contaminants. Moreover, this electrolyte was applied to symmetrical supercapacitors (using graphene and activated carbon as active materials) in order to quantify its performance in energy storage applications. It is found that the activated carbon and graphene supercapacitors demonstrate high gravimetric capacitance (221 F g⁻¹ for activated carbon, and 56 F g⁻¹ for graphene), a stable working voltage window of 2.0 V, which is significantly higher than the usual range of water-based capacitors, and excellent stability over 10 000 cycles. These results provide fundamental insight into the wider applicability of highly concentrated electrolytes, which should enable their application in future of energy storage technologies.

The stability of water-in-salt electrolyte systems is investigated using highly concentrated solutions of KF(aq) with graphite as a model system.     

锂电池电极过程的原位电化学原子力显微镜研究进展

随着人类对能源的使用与存储需求不断增加,高能量密度和高安全性能的二次锂电池体系正在被不断地开发与完善.深入理解充放电过程中锂电池内部电极/电解质界面的电化学过程以及微观反应机理,有利于指导电池材料的优化设计.原位电化学原子力显微镜将原子力显微镜的高分辨表界面分析优势与电化学反应装置相结合,能够在电池运行条件下实现对电极/电解质界面的原位可视化研究,并进一步从纳米尺度上揭示界面结构的演化规律与动力学过程.本文总结了原位电化学原子力显微镜在锂电池电极过程中的最新研究进展,主要包括基于转化型反应的正极过程、固体电解质中间相的动态演化以及固态电池界面演化与失效分析.     

锂离子电池电解液除酸除水添加剂的研究进展

商用锂离子电池电解液在应用过程中存在电解质锂盐六氟磷酸锂（LiPF₆）易在痕量水环境中发生水解反应，进而导致锂离子电池体系的综合电化学性能受损。因此，亟需控制电解液本体中痕量水的引入以及减小锂盐与痕量水反应产物对电池体系影响的措施。本文主要综述了含有不同官能团的添加剂在除去电解液中痕量水和酸时所具有的特性，并重点分析介绍了其除酸除水的作用机理。 最后，对除酸、除水型添加剂未来的研究方向和应用前景进行了展望。     

Reversing the dendrite growth direction and eliminating the concentration polarization via an internal electric field for stable lithium metal anodes

Lithium (Li) dendrite growth is a long-standing challenge leading to short cycle life and safety issues in Li metal batteries. Li dendrite growth is kinetically controlled by ion transport, the concentration gradient, and the local electric field. In this study, an internal electric field is generated between the anode and Au-modified separator to eliminate the concentration gradient of Li⁺. The Li–Au alloy is formed during the first cycle of Li plating/stripping, which causes Li⁺ deposition on the Au-modified side and lithium anode electrode, reversing the lithium dendrite growth direction. The electrically coupled Li metal electrode and Au-modified film create a uniform electric potential and Li⁺ concentration distribution, resulting in reduced concentration polarization and stable Li deposition. As a result, the Au-modified separator improves the lifespan of Li‖Li batteries; the Li‖LiFePO₄ cells show excellent capacity retention (>97.8% after 350 cycles), and Li‖LiNi_0.8Co_0.1Mn_0.1O₂ cells deliver 75.1% capacity retention for more than 300 cycles at 1C rate. This strategy offers an efficient approach for commercial application in advanced metallic Li batteries.

An internal electric field is built between the anode and the Au-modified separator to eliminate the concentration gradient of Li⁺ and reverse the dendrite growth direction.     

Influence of sol–gel derived lithium cobalt phosphate in alkaline rechargeable battery

A lithium cobalt phosphate (LiCoPO₄) cathode was synthesised by citric acid assisted sol?Cgel method and its electrochemical behaviour in alkaline secondary battery (using novel lithium hydroxide as the electrolyte) is reported. The sol?Cgel method using metal acetate precursors with citric acid as a chelating agent influenced the particle size and the homogeneity while yielding a single phase LiCoPO₄ at a considerably lower temperature and shortened heating time, compared to that of the conventional solid state reaction. The cyclic voltammogram of LiCoPO₄ showed a reversible redox process implying that de-intercalation and intercalation of lithium can occur in aqueous electrolyte. This was supported by X-ray diffraction (XRD) and Infra-red (IR) studies. The charge?Cdischarge performance of the Zn/LiCoPO₄ battery showed good capacity retention (after 25 cycles it delivered 90?% of its initial capacity). This enhanced capacity retention was attributed to the synergistic effect of particle homogeneity, reduced Li⁺ diffusion path and stability of the non-reactive aqueous electrolyte between the electrode and the electrolyte interface.     

Electropolymerization of 3-methylthiophene at liquid 3-methylthiophene | aqueous solution | graphite three-phase junction

Droplets of 3-methylthiophene are mechanically attached to the surface of paraffin-impregnated graphite electrode (PIGE) and immersed into aqueous solution of LiClO₄. It is demonstrated that the oxidative electropolymerization (observed in non-aqueous solutions) can be accomplished by potential cycling between −0.3 and 1.4 V vs. saturated calomel electrode (SCE). Since the droplets do not contain a dissolved electrolyte, the electrochemical reaction starts at the very edge of the three-phase junction organic droplet | graphite | aqueous electrolyte.     

Non-aqueous lithium bromine battery of high energy density with carbon coated membrane

Flow batteries with high energy density and long cycle life have been pursued to advance the progress of energy storage and grid application. Non-aqueous batteries with wide voltage windows represent a promising technology without the limitation of water electrolysis, but they suffer from low electrolyte concentration and unsatisfactory battery performance. Here, a non-aqueous lithium bromine rechargeable battery is proposed, which is based on Br_2/Br~-and Li~+/Li as active redox pairs, with fast redox kinetics and good stability. The Li/Br battery combines the advantages of high output voltage(~3.1 V),electrolyte concentration(3.0 mol/L), maximum power density(29.1 m W/cm~2) and practical energy density(232.6 Wh/kg). Additionally, the battery displays a columbic efficiency(CE) of 90.0%, a voltage efficiency(VE) of 88.0% and an energy efficiency(EE) of 80.0% at 1.0 m A/cm~2 after continuously running for more than 1000 cycles, which is by far the longest cycle life reported for non-aqueous flow batteries.     

Synthesis and electrochemical study of Li-Mn-Ni-O cathodes for lithium battery applications

Cathode powders of the Li–Mn–Ni–O system have been prepared at a Mn/(Mn+Ni) ratio varying from 0 to 1. The solid state reaction method was used to obtain the cathode materials by mixing MnO₂, LiCO₃ and NiO. A 20% excess of lithium was used in the precursors. The materials produced were examined by X-rays to identify their structure. Batteries were assembled by using these materials as cathode with a liquid electrolyte consisting of EC/DC 1:1, 1 LiPF₆ and Li anode. Their capacity, cycle fading and charge-discharge conditions were evaluated.Presented at the 3rd International Meeting "Advanced Batteries and Accumulators", June 16th–June 20th 2002, Brno, Czech Republic     

Ga和Cu/In衬底上电沉积金属Ga

在酸性水溶液中,分别在金属Ga和Cu/In衬底上进行了Ga电沉积的研究。用循环伏安法研究了导电盐、pH值对电沉积Ga的影响。系统研究了Ga的沉积过程,发现Ga会逐渐向薄膜内部扩散,在Cu/In界面上与CuIn合金反应生成CuGa₂合金。针对Cu/In薄膜和Ga薄膜是活泼金属的特点,在溶液中加入三乙醇胺有效地保护了Cu/In薄膜和Ga金属薄膜不被氧化,并且提高了Ga沉积的电流效率。在Cu/In薄膜上制备出了均匀光亮的金属Ga薄膜。对电沉积出Cu-In-Ga预置层进行了硒化处理,得到了质量较好的Cu(In_1-xGa_x)Se₂(CIGS)薄膜,并制备了太阳电池。电池效率达到了9.42%。     

锂电池Li／KIBr2—非水体系的研究

本非水电池体系由Ｌｉ负极、多孔石墨电极和电解质溶液组成；电解质溶液由无机溶剂ＰＯＣｌ＿３（或有机溶剂硝基苯）和溶解在该溶剂中的活性物质（ＫＩＢｒ＿２）及支持电解质构成。该电池体系的开路电压为８．５０伏左右，放电性能良好，可望在实际中得到应用。此外，对电池体系的反应机理也作了初步的探讨。     

Microdistributions of Electrolytic Alloys and Their Components

Microdistributions of Cu–Ni and Cu–Co alloys electrodeposited from pyrophosphate; Ni–Cu, from sulfate–chloride and pyrophosphate–ammonium; Cu–Zn, from pyrophosphate and cyanide; Cu–Cd, from sulfate and pyrophosphate; and Ni–Cd, Ni–Co–Cd, and Zn–Cd, from sulfate, sulfate–chloride, pyrophosphate, chloride–ammonium, and acetate electrolytes are studied. The coatings' microprofile depends on the kinetics of reduction of each component and mutual influence of electrochemical processes at the cathode. Copper accelerates and cadmium inhibits the reduction of the second component of alloys, no matter the electrolyte type, reduction kinetics, and metal nature. In antileveling conditions, the diffusion-controlled Cu reduction accelerates the reduction of the second component of alloys and ensures deposition of coatings whose microprofiles are more uniform than expected from diffusion limitations only. Depolarizing action of Cu during the Cu–Zn deposition from a cyanide electrolyte can completely neutralize differences in the rates of supply of reduced metal ions; hence a constant chemical composition of the coating over its microprofile. Inhibiting action of the diffusion-controlled Cd deposition provides for leveling properties of electrolytes from which Ni–Cd, Ni–Co–Cd, and Zn–Cd alloys are deposited; the chemical composition of these deposits is nonuniform over their microprofiles.     

Electronic structure calculations on lithium battery electrolyte salts

New lithium salts for non-aqueous liquid, gel and polymeric electrolytes are crucial due to the limiting role of the electrolyte in modern lithium batteries. The solvation of any lithium salt to form an electrolyte solution ultimately depends on the strength of the cation-solvent vs. the cation-anion interaction. Here, the latter is probed via HF, B3LYP and G3 theory gas-phase calculations for the dissociation reaction: LiX <--> Li(+) + X(-). Furthermore, a continuum solvation method (C-PCM) has been applied to mimic solvent effects. Anion volumes were also calculated to facilitate a discussion on ion conductivities and cation transport numbers. Judging from the present results, synthesis efforts should target heterocyclic anions with a size of ca. 150 A(3) molecule(-1) to render new highly dissociative lithium salts that result in electrolytes with high cation transport numbers.     

Enabling High-Voltage Lithium Metal Batteries by Manipulating Solvation Structure in Ester Electrolyte

Lithium metal is an ideal electrode material for future rechargeable lithium metal batteries. However, the widespread deployment of metallic lithium anode is significantly hindered by its dendritic growth and low Coulombic efficiency, especially in ester solvents. Herein, by rationally manipulating the electrolyte solvation structure with a high donor number solvent, enhancement of the solubility of lithium nitrate in an ester-based electrolyte is successfully demonstrated, which enables high-voltage lithium metal batteries. Remarkably, the electrolyte with a high concentration of LiNO₃ additive presents an excellent Coulombic efficiency up to 98.8 % during stable galvanostatic lithium plating/stripping cycles. A full-cell lithium metal battery with a lithium nickel manganese cobalt oxide cathode exhibits a stable cycling performance showing limited capacity decay. This approach provides an effective electrolyte manipulation strategy to develop high-voltage lithium metal batteries.     

Enabling High‐Voltage Lithium Metal Batteries by Manipulating Solvation Structure in Ester Electrolyte

Lithium metal is an ideal electrode material for future rechargeable lithium metal batteries. However, the widespread deployment of metallic lithium anode is significantly hindered by its dendritic growth and low Coulombic efficiency, especially in ester solvents. Herein, by rationally manipulating the electrolyte solvation structure with a high donor number solvent, enhancement of the solubility of lithium nitrate in an ester‐based electrolyte is successfully demonstrated, which enables high‐voltage lithium metal batteries. Remarkably, the electrolyte with a high concentration of LiNO₃ additive presents an excellent Coulombic efficiency up to 98.8 % during stable galvanostatic lithium plating/stripping cycles. A full‐cell lithium metal battery with a lithium nickel manganese cobalt oxide cathode exhibits a stable cycling performance showing limited capacity decay. This approach provides an effective electrolyte manipulation strategy to develop high‐voltage lithium metal batteries.     

Full Dissolution of the Whole Lithium Sulfide Family (Li2S8 to Li2S) in a Safe Eutectic Solvent for Rechargeable Lithium–Sulfur Batteries

The lithium–sulfur battery is an attractive option for next‐generation energy storage owing to its much higher theoretical energy density than state‐of‐the‐art lithium‐ion batteries. However, the massive volume changes of the sulfur cathode and the uncontrollable deposition of Li₂S₂/Li₂S significantly deteriorate cycling life and increase voltage polarization. To address these challenges, we develop an ?‐caprolactam/acetamide based eutectic‐solvent electrolyte, which can dissolve all lithium polysulfides and lithium sulfide (Li₂S₈–Li₂S). With this new electrolyte, high specific capacity (1360 mAh g^?1) and reasonable cycling stability are achieved. Moreover, in contrast to conventional ether electrolyte with a low flash point (ca. 2 °C), such low‐cost eutectic‐solvent‐based electrolyte is difficult to ignite, and thus can dramatically enhance battery safety. This research provides a new approach to improving lithium–sulfur batteries in aspects of both safety and performance.