Room-Temperature Solid-State Polymer Electrolyte in Li-LiFePO4 , Li-S and Li-O2 Batteries.

A solid polymer electrolyte has been developed and employed in lithium-metal batteries of relevant interest. The material includes crystalline poly(ethylene glycol)dimethyl ether (PEGDME), LiTFSI and LiNO3 salts, and a SiO2 ceramic filler. The electrolyte shows ionic conductivity more than 10-4  S cm-1 at room temperature and approaching 10-3  S cm-1 at 60 °C, a Li+ -transference number exceeding 0.3, electrochemical stability from 0 to 4.4 V vs. Li+ /Li, lithium stripping/deposition overvoltage below 0.08 V, and electrode/electrolyte interphase resistance of 400 Ω. Thermogravimetry indicates that the electrolyte stands up to 200 °C without significant weight loss, while FTIR spectroscopy suggests that the LiTFSI conducting salt dissolves in the polymer. The electrolyte is used in solid-state cells with various cathodes, including LiFePO4 olivine exploiting the Li-insertion, sulfur-carbon composite operating through Li conversion, and an oxygen electrode in which reduction and evolution reactions (i. e., ORR/OER) evolve on a carbon-coated gas diffusion layer (GDL). The cells operate reversibly at room temperature with a capacity of 140 mA h g-1 at 3.4 V for LiFePO4 , 400 mA h g-1 at 2 V for sulfur electrode, and 500 mA h g-1 at 2.5 V for oxygen. The results suggest that the electrolyte could be applied in room-temperature solid polymer cells.

New Electrode and Electrolyte Configurations for Lithium-Oxygen Battery.

Cathode configurations reported herein are alternative to the most diffused ones for application in lithium-oxygen batteries, using an ionic liquid-based electrolyte. The electrodes employ high surface area conductive carbon as the reaction host, and polytetrafluoroethylene as the binding agent to enhance the oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) reversibility. Roll-pressed, self-standing electrodes (SSEs) and thinner, spray deposited electrodes (SDEs) are characterized in lithium-oxygen cells using an ionic liquid (IL) based electrolyte formed by mixing lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt and N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium bis(trifluoromethanesulfonyl)imide (DEMETFSI). The electrochemical results reveal reversible reactions for both electrode configurations, but improved electrochemical performance for the self-standing electrodes in lithium-oxygen cells. These electrodes show charge/discharge polarizations at 60 °C limited to 0.4 V, with capacity up to 1 mAh cm-2 and energy efficiency of about 88 %, while the spray deposited electrodes reveal, under the same conditions, a polarization of 0.6 V and energy efficiency of 80 %. The roll pressed electrode combined with the DEMETFSI-LiTFSI electrolyte and a composite Lix Sn-C alloy anode forms a full Li-ion oxygen cell showing extremely limited polarization, and remarkable energy efficiency.

A Long-Life Lithium Ion Battery with Enhanced Electrode/Electrolyte Interface by Using an Ionic Liquid Solution.

In this paper, we report an advanced long-life lithium ion battery, employing a Pyr14 TFSI-LiTFSI non-flammable ionic liquid (IL) electrolyte, a nanostructured tin carbon (Sn-C) nanocomposite anode, and a layered LiNi1/3 Co1/3 Mn1/3 O2 (NMC) cathode. The IL-based electrolyte is characterized in terms of conductivity and viscosity at various temperatures, revealing a Vogel-Tammann-Fulcher (VTF) trend. Lithium half-cells employing the Sn-C anode and NMC cathode in the Pyr14 TFSI-LiTFSI electrolyte are investigated by galvanostatic cycling at various temperatures, demonstrating the full compatibility of the electrolyte with the selected electrode materials. The NMC and Sn-C electrodes are combined into a cathode-limited full cell, which is subjected to prolonged cycling at 40 °C, revealing a very stable capacity of about 140 mAh g(-1) and retention above 99 % over 400 cycles. The electrode/electrolyte interface is further characterized through a combination of electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) investigations upon cell cycling. The remarkable performances reported here definitively indicate that IL-based lithium ion cells are suitable batteries for application in electric vehicles.

Highly Cyclable Lithium-Sulfur Batteries with a Dual-Type Sulfur Cathode and a Lithiated Si/SiOx Nanosphere Anode.

Lithium-sulfur batteries could become an excellent alternative to replace the currently used lithium-ion batteries due to their higher energy density and lower production cost; however, commercialization of lithium-sulfur batteries has so far been limited due to the cyclability problems associated with both the sulfur cathode and the lithium-metal anode. Herein, we demonstrate a highly reliable lithium-sulfur battery showing cycle performance comparable to that of lithium-ion batteries; our design uses a highly reversible dual-type sulfur cathode (solid sulfur electrode and polysulfide catholyte) and a lithiated Si/SiOx nanosphere anode. Our lithium-sulfur cell shows superior battery performance in terms of high specific capacity, excellent charge-discharge efficiency, and remarkable cycle life, delivering a specific capacity of ∼750 mAh g(-1) over 500 cycles (85% of the initial capacity). These promising behaviors may arise from a synergistic effect of the enhanced electrochemical performance of the newly designed anode and the optimized layout of the cathode.

Advanced Na[Ni0.25Fe0.5Mn0.25]O2/C-Fe3O4 sodium-ion batteries using EMS electrolyte for energy storage.

While much research effort has been devoted to the development of advanced lithium-ion batteries for renewal energy storage applications, the sodium-ion battery is also of considerable interest because sodium is one of the most abundant elements in the Earth's crust. In this work, we report a sodium-ion battery based on a carbon-coated Fe3O4 anode, Na[Ni0.25Fe0.5Mn0.25]O2 layered cathode, and NaClO4 in fluoroethylene carbonate and ethyl methanesulfonate electrolyte. This unique battery system combines an intercalation cathode and a conversion anode, resulting in high capacity, high rate capability, thermal stability, and much improved cycle life. This performance suggests that our sodium-ion system is potentially promising power sources for promoting the substantial use of low-cost energy storage systems in the near future.

An advanced lithium-ion battery based on a graphene anode and a lithium iron phosphate cathode.

We report an advanced lithium-ion battery based on a graphene ink anode and a lithium iron phosphate cathode. By carefully balancing the cell composition and suppressing the initial irreversible capacity of the anode in the round of few cycles, we demonstrate an optimal battery performance in terms of specific capacity, that is, 165 mAhg(-1), of an estimated energy density of about 190 Wh kg(-1) and a stable operation for over 80 charge-discharge cycles. The components of the battery are low cost and potentially scalable. To the best of our knowledge, complete, graphene-based, lithium ion batteries having performances comparable with those offered by the present technology are rarely reported; hence, we believe that the results disclosed in this work may open up new opportunities for exploiting graphene in the lithium-ion battery science and development.

Sodium-ion battery based on an electrochemically converted NaFePO4 cathode and nanostructured tin-carbon anode.

We report a new sodium-ion battery formed by coupling a NaFePO(4) cathode and a nanocomposite tin-carbon (Sn-C) sodium-alloying anode. The NaFePO(4) cathode is obtained by Li-Na conversion of a LiFePO(4) cathode directly in the full cell employing the Sn-C anode and a sodium-ion electrolyte. The results show that the unique approach adopted here is capable of successfully and efficiently converting LiFePO(4) into NaFePO(4) in a sodium-ion battery operating at a voltage of 3 V, with a maximum reversible capacity of 150 mAh g(-1), high reversibility, and high rate capability.

Influence of temperature on lithium-oxygen battery behavior.

In this Letter we report an electrochemical and morphological study of the response of lithium-oxygen cells cycled at various temperatures, that is, ranging from -10 to 70 °C. The results show that the electrochemical process of the cells is thermally influenced in an opposite way, that is, by a rate decrease, due to a reduced diffusion of the lithium ions from the electrolyte to the electrode interface, at low temperature and a rate enhancement, due to the decreased electrolyte viscosity and consequent increased oxygen mobility, at high temperature. In addition, we show that the temperature also influences the crystallinity of lithium peroxide, namely of the product formed during cell discharge.

Electrochemical performance of a graphene nanosheets anode in a high voltage lithium-ion cell.

We demonstrate the feasibility of a lithium ion battery (LIB) using graphene nanosheets (GNS) as the anode in combination with a LiNi(0.5)Mn(1.5)O4 (LNMO) high voltage, spinel-structure cathode. The GNS anode is characterized by a reversible capacity of the order of 600 mA h g(-1) and a working voltage of around 0.9 V, while the 4.8-V cathode has a theoretical capacity of 146.7 mA h g(-1). The full GNS/LiNi(0.5)Mn(1.5)O4 cell has an average working voltage of about 3.75 V and a capacity of the order of 100 mA h g(-1). The findings of this paper suggest that the graphene may be proposed as a suitable anode for application in lithium ion batteries.

An advanced sodium-ion rechargeable battery based on a tin-carbon anode and a layered oxide framework cathode.

In this work we report the characteristics and performance of a sodium-ion battery based on a Sn-C anode and a Na(Ni(0.5)Mn(0.5))O(2) cathode. We show that both electrodes behave satisfactorily in terms of capacity delivery and cycle life when tested in sodium semicells. By coupling these electrodes in an electrolyte solution of sodium perchlorate in a mixture of propylene carbonate and 2 %vol of fluoroethylene carbonate, a sodium-ion battery showing promising electrochemical performance is obtained. This sodium ion battery in fact operates at an average voltage of 2.8 V, with a specific capacity of 120 mA h g(-1) and with a life extending to 50 cycles with minor capacity decays.

A metal-free, lithium-ion oxygen battery: a step forward to safety in lithium-air batteries.

A preliminary study of the behavior of lithium-ion-air battery where the common, unsafe lithium metal anode is replaced by a lithiated silicon-carbon composite, is reported. The results, based on X-ray diffraction and galvanostatic charge-discharge analyses, demonstrate the basic reversibility of the electrochemical process of the battery that can be promisingly cycled with a rather high specific capacity.

A transmission electron microscopy study of the electrochemical process of lithium-oxygen cells.

The electrochemical reaction of a lithium-oxygen cell using a tetraethylene glycol dimethyl ether-lithium triflate, TEGDME-LiCF(3)SO(3) electrolyte, is investigated by a detailed transmission electron microscopy analysis. The results confirm the reversibility of the process by showing the formation-dissolution of lithium peroxide, Li(2)O(2), upon repeating cell charge and discharge cycles.

Diffusional Features of a Lithium-Sulfur Battery Exploiting Highly Microporous Activated Carbon.

Diffusion processes at the electrode/electrolyte interphase drives the performance of lithium-sulfur batteries, and activated carbon (AC) can remarkably vehicle ions and polysulfide species throughout the two-side liquid/solid region of the interphase. We reveal original findings such as the values of the diffusion coefficient at various states of charge of a Li-S battery using a highly porous AC, its notable dependence on the adopted techniques, and the correlation of the diffusion trend with the reaction mechanism. X-ray photoelectron spectroscopy (XPS) and X-ray energy dispersive spectroscopy (EDS) are used to identify in the carbon derived from bioresidues heteroatoms such as N, S, O and P, which can increase the polarity of the C framework. The transport properties are measured by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic intermittent titration technique (GITT). The study reveals Li+ -diffusion coefficient (DLi + ) depending on the technique, and values correlated with the cell state of charge. EIS, CV, and GITT yield a DLi + within 10-7 -10-8  cm2 s-1 , 10-8 -10-9  cm2 s-1 , and 10-6 -10-12  cm2 s-1 , respectively, dropping down at the fully discharged state and increasing upon charge. GITT allows the evaluation of DLi + during the process and evidences the formation of low-conducting media upon discharge. The sulfur composite delivers in a Li-cell a specific capacity ranging from 1300 mAh g-1 at 0.1 C to 700 mAh g-1 at 2C with a S loading of 2 mg cm-2 , and from 1000 to 800 mAh g-1 at 0.2C when the S loading is raised to 6 mg cm-2 .

Influence of Ion Diffusion on the Lithium-Oxygen Electrochemical Process and Battery Application Using Carbon Nanotubes-Graphene Substrate.

Lithium-oxygen (Li-O2) batteries are nowadays among the most appealing next-generation energy storage systems in view of a high theoretical capacity and the use of transition-metal-free cathodes. Nevertheless, the practical application of these batteries is still hindered by limited understanding of the relationships between cell components and performances. In this work, we investigate a Li-O2 battery by originally screening different gas diffusion layers (GDLs) characterized by low specific surface area (<40 m2 g-1) with relatively large pores (absence of micropores), graphitic character, and the presence of a fraction of the hydrophobic PTFE polymer on their surface (<20 wt %). The electrochemical characterization of Li-O2 cells using bare GDLs as the support indicates that the oxygen reduction reaction (ORR) occurs at potentials below 2.8 V vs Li+/Li, while the oxygen evolution reaction (OER) takes place at potentials higher than 3.6 V vs Li+/Li. Furthermore, the relatively high impedance of the Li-O2 cells at the pristine state remarkably decreases upon electrochemical activation achieved by voltammetry. The Li-O2 cells deliver high reversible capacities, ranging from ∼6 to ∼8 mA h cm-2 (referred to the geometric area of the GDLs). The Li-O2 battery performances are rationalized by the investigation of a practical Li+ diffusion coefficient (D) within the cell configuration adopted herein. The study reveals that D is higher during ORR than during OER, with values depending on the characteristics of the GDL and on the cell state of charge. Overall, D values range from ∼10-10 to ∼10-8 cm2 s-1 during the ORR and ∼10-17 to ∼10-11 cm2 s-1 during the OER. The most performing GDL is used as the support for the deposition of a substrate formed by few-layer graphene and multiwalled carbon nanotubes to improve the reaction in a Li-O2 cell operating with a maximum specific capacity of 1250 mA h g-1 (1 mA h cm-2) at a current density of 0.33 mA cm-2. XPS on the electrode tested in our Li-O2 cell setup suggests the formation of a stable solid electrolyte interphase at the surface which extends the cycle life.

Toward Sustainable Li-S Battery Using Scalable Cathode and Safe Glyme-Based Electrolyte.

The search for safe electrolytes to promote the application of lithium-sulfur (Li-S) batteries may be supported by the investigation of viscous glyme solvents. Hence, electrolytes using nonflammable tetraethylene glycol dimethyl ether added by lowly viscous 1,3-dioxolane (DOL) are herein thoroughly investigated for sustainable Li-S cells. The electrolytes are characterized by low flammability, a thermal stability of ∼200 °C, ionic conductivity exceeding 10-3 S cm-1 at 25 °C, a Li+ transference number of ∼0.5, electrochemical stability window from 0 to ∼4.4 V vs Li+/Li, and a Li stripping-deposition overpotential of ∼0.02 V. The progressive increase of the DOL content from 5 to 15 wt % raises the activation energy for Li+ motion, lowers the transference number, slightly limits the anodic stability, and decreases the Li/electrolyte resistance. The electrolytes are used in Li-S cells with a composite consisting of sulfur and multiwalled carbon nanotubes mixed in the 90:10 weight ratio, exploiting an optimized current collector. The cathode is preliminarily studied in terms of structure, thermal behavior, and morphology and exploited in a cell using standard electrolyte. This cell performs over 200 cycles, with sulfur loading increased to 5.2 mg cm-2 and the electrolyte/sulfur (E/S) ratio decreased to 6 µL mg-1. The above sulfur cathode and the glyme-based electrolytes are subsequently combined in safe Li-S batteries, which exhibit cycle life and delivered capacity relevantly influenced by the DOL content within the studied concentration range.

A Lithium-Sulfur Battery Using Binder-Free Graphene-Coated Aluminum Current Collector.

Lithium-sulfur battery of practical interest requires thin-layer support to achieve acceptable volumetric energy density. However, the typical aluminum current collector of Li-ion battery cannot be efficiently used in the Li/S system due to the insulating nature of sulfur and a reaction mechanism involving electrodeposition of dissolved polysulfides. We study the electrochemical behavior of a Li/S battery using a carbon-coated Al current collector in which the low thickness, the high electronic conductivity, and, at the same time, the host ability for the reaction products are allowed by a binder-free few-layer graphene (FLG) substrate. The FLG enables a sulfur electrode having a thickness below 100 µm, fast kinetics, low impedance, and an initial capacity of 1000 mAh gS -1 with over 70% retention after 300 cycles. The Li/S cell using FLG shows volumetric and gravimetric energy densities of 300 Wh L-1 and 500 Wh kg-1, respectively, which are values well competing with commercially available Li-ion batteries.

An advanced lithium ion battery based on high performance electrode materials.

In this paper we report the study of a high capacity Sn-C nanostructured anode and of a high rate, high voltage Li[Ni(0.45)Co(0.1)Mn(1.45)]O(4) spinel cathode. We have combined these anode and cathode materials in an advanced lithium ion battery that, by exploiting this new chemistry, offers excellent performances in terms of cycling life, i.e., ca. 100 high rate cycles, of rate capability, operating at 5C and still keeping more than 85% of the initial capacity, and of energy density, expected to be of the order of 170 Wh kg(-1). These unique features make the battery a very promising energy storage for powering low or zero emission HEV or EV vehicles.

Synthesis of a High-Capacity α-Fe2O3@C Conversion Anode and a High-Voltage LiNi0.5Mn1.5O4 Spinel Cathode and Their Combination in a Li-Ion Battery.

A Li-conversion α-Fe2O3@C nanocomposite anode and a high-voltage LiNi0.5Mn1.5O4 cathode are synthesized in parallel, characterized, and combined in a Li-ion battery. α-Fe2O3@C is prepared via annealing of maghemite iron oxide and sucrose under an argon atmosphere and subsequent oxidation in air. The nanocomposite exhibits a satisfactory electrochemical response in a lithium half-cell, delivering almost 900 mA h g-1, as well as a significantly longer cycle life and higher rate capability compared to the bare iron oxide precursor. The LiNi0.5Mn1.5O4 cathode, achieved using a modified co-precipitation approach, reveals a well-defined spinel structure without impurities, a sub-micrometrical morphology, and a reversible capacity of ca. 120 mA h g-1 in a lithium half-cell with an operating voltage of 4.8 V. Hence, a lithium-ion battery is assembled by coupling the α-Fe2O3@C anode with the LiNi0.5Mn1.5O4 cathode. This cell operates at about 3.2 V, delivering a stable capacity of 110 mA h g-1 (referred to the cathode mass) with a Coulombic efficiency exceeding 97%. Therefore, this cell is suggested as a promising energy storage system with expected low economic and environmental impacts.

Lithium-Metal Batteries Using Sustainable Electrolyte Media and Various Cathode Chemistries.

Lithium-metal batteries employing concentrated glyme-based electrolytes and two different cathode chemistries are herein evaluated in view of a safe use of the highly energetic alkali-metal anode. Indeed, diethylene-glycol dimethyl-ether (DEGDME) and triethylene-glycol dimethyl-ether (TREGDME) dissolving lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium nitrate (LiNO3) in concentration approaching the solvents saturation limit are used in lithium batteries employing either a conversion sulfur-tin composite (S:Sn 80:20 w/w) or a Li+ (de)insertion LiFePO4 cathode. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) clearly show the suitability of the concentrated electrolytes in terms of process reversibility and low interphase resistance, particularly upon a favorable activation. Galvanostatic measurements performed on lithium-sulfur (Li/S) batteries reveal promising capacities at room temperature (25 °C) and a value as high as 1300 mAh gS -1 for the cell exploiting the DEGDME-based electrolyte at 35 °C. On the other hand, the lithium-LiFePO4 (Li/LFP) cells exhibit satisfactory cycling behavior, in particular when employing an additional reduction step at low voltage cutoff (i.e., 1.2 V) during the first discharge to consolidate the solid electrolyte interphase (SEI). This procedure allows a Coulombic efficiency near 100%, a capacity approaching 160 mAh g-1, and relevant retention particularly for the cell using the TREGDME-based electrolyte. Therefore, this work suggests the use of concentrated glyme-based electrolytes, the fine-tuning of the operative conditions, and the careful selection of active materials chemistry as significant steps to achieve practical and safe lithium-metal batteries.

Degradation of Layered Oxide Cathode in a Sodium Battery: A Detailed Investigation by X-Ray Tomography at the Nanoscale.

The degradation mechanism in a sodium cell of a layered Na0.48 Al0.03 Co0.18 Ni0.18 Mn0.47 O2 (NCAM) cathode with P3/P2 structure is investigated by revealing the changes in microstructure and composition upon cycling. The work aims to rationalize the gradual performance decay and the alteration of the electrochemical response in terms of polarization, voltage signature, and capacity loss. Spatial reconstructions of the electrode by X-ray computed tomography at the nanoscale supported by quantitative and qualitative analyses show fractures and deformations in the cycled layered metal-oxide particles, as well as inorganic side compounds deposited on the material. These irreversible morphological modifications reflect structural heterogeneities across the cathode particles due to formation of various domains with different Na+ intercalation degrees. Besides, X-ray photoelectron spectroscopy data suggest that the latter inorganic species in the cycled electrode are mainly composed of NaF, Na2 O, and NaCO3 formed by parasitic electrolyte decomposition. The precipitation of these insulating compounds at the electrode/electrolyte interphase and the related structural stresses induced in the material lead to a decrease in cathode particle size and partial loss of electrochemical activity. The retention of the NCAM phase after cycling suggests that electrolyte upgrade may improve the performance of the cathode to achieve practical application for sustainable energy storage.