Lithium Organic Batteries Research Articles

A Porphyrin-Phenylalkynyl-Based Conjugated Organic Polymer as a High-Performance Cathode for Rechargeable Organic Batteries.

Organic electrode materials (OEMs) have attracted much attention for rechargeable batteries due to their low cost, environment friendliness, flexibility, and structural versatility. Despite the above advantages, high solubility in electrolyte and low electronic conductivity remain critical limitations for the application of OEMs. In this work, the conjugated organic polymer (COP) poly([5,10,15,20-tetrakis(4-phenylalkynyl)porphyrin]Cu(II)) (PCuTPEP) is proposed as a cathode for high performance in organic lithium batteries. The polymerization inhibits the dissolution of the organic electrodes in the electrolyte, and the porphyrin and ethynyl-phenyl groups greatly expand the conjugated system and result in a high average discharge plateau at 4.0 V (vs Li+/Li). The PCuTPEP cathode exhibits a reversible discharge capacity of 119 mAh g-1 at a current of 50 mA g-1. Even at a high current density of 2.0 A g-1, excellent cycling stability up to 1000 cycles is achieved with capacity retentions of 88.5 and 90.4% at operating temperatures of 25 and 50 °C in organic lithium batteries, respectively. This study provides the approach for the development of organic cathodes for electrochemical energy storage.

Two‐Electron Phenothiazine Based Cathode Achieved by Raising HOMO Energy Level for High Performance Lithium Organic Battery

AbstractRedox‐active p‐type phenothiazine based organic cathodes have captured increasing attention for lithium‐organic batteries due to their high voltage output and rich chemical modification. However, their capacities are generally limited to one redox event per molecule; while the di‐cation states are subject to rapid decomposition and cannot be effectively utilized. Herein, a scalable synthesis of phenothiazine‐based polymer (MPT‐CC) is reported, that can fully utilize the two‐electron storage by raising its highest occupied molecular orbital (HOMO). Lithium‐organic batteries using this polymer as cathode displayed a high specific capacity of 178 mAh g−1 at 0.2 A g−1. This polymer also displays excellent cycling stability. After 1000 cycles at 0.2 A g−1, a stable capacity of 194 mAh g−1 with ≈100% capacity retention can be obtained. Even at 2 A g−1 after 10,000 cycles, 98 mAh g−1 can be reversibly achieved. Its practical applicability has been successfully demonstrated in MPT‐CC//graphite full cell, also displaying good performance. This work contributes to a major advancement of phenothiazine‐based polymer design for high performance energy storage devices.

A Solvent-Free Covalent Organic Framework Single-Ion Conductor Based on Ion–Dipole Interaction for All-Solid-State Lithium Organic Batteries

HighlightsA class of solvent-free covalent organic framework (COF) single-ion conductors (Li-COF@P) has been designed via ion–dipole interaction as opposed to traditional ion–ion interaction, promoting ion dissociation and Li+ migration through directional ionic channels.The Li-COF@P enabled long cycle life (88.3% after 2000 cycles) in all-solid-state Li organic batteries (ASSLOBs) under ambient operating conditions, which outperformed those of previously reported ASSOLBs.This Li-COF@P strategy holds promise as a viable alternative to the currently prevalent inorganic solid electrolytes.

Cross-linking enhances the performance of four-electron carbonylpyridinium based polymers for lithium organic batteries.

Design and integration of multiple redox-active organic scaffolds into tailored polymer structures to enhance the specific capacity and cycling life is a long-term research goal. Inspired by nature, we designed and incorporated a 4-electron accepting dicarbonylpyridinium redox motif into linear (DBMP) and cross-linked polymer (TBMP) structures. Benefiting from the suppressed solubility and higher electronic conductivity, the cross-linked TBMP based electrode exhibits improved cycling stability and higher specific capacity than the linear counterpart. After 4000 cycles at 1 A g-1, TBMP can maintain a high capacity of 252 mA h g-1, surpassing the performance of many reported organic cathodes. The structural evolution and reaction kinetics during charge and discharge have been investigated in detail. This study demonstrates that cross-linking is an effective strategy to push the bio-derived carbonylpyridinium materials for high performance LOBs.

Unsuspected Organometallic Fibers Used As Potential Separators for Supercapacitors Device

Since the last decade, the interest of organic frameworks for electrochemical application the been more studied.1 In general, very few works have been found in the literature. We can mainly mention the use of these derivatives in the presence of inorganic materials both to form solid electrolytes or to protect electrodes. For example, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (H4DOTA) has been used to functionalize PVA to coat the surface of the negative electrode in order to suppress its degradation.2 This resulted in the improvement of the electrochemical properties of the LMNO/graphite cell. Recently, Kim et al. reported the addition of 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane to a carbonate-based electrolyte intended to stabilize the Li metal-electrolyte interface by improving the solid electrolyte interphase.3 More recently, Liu et al. reported a novel carbonyl network polymer NP4 used as a cathode material for organic lithium batteries.4 Very few examples of fully organic frameworks used as separators have been reported.Therefore, our investigation to develop new supramolecular metal-based objects via a self-assembly process of molecular bricks will be presented. The work on cyclen derivatives allows to obtain metal complexes very stable able to pack in a well oriented dimension. Cyclen derivatives, in the presence of metal salts such as copper or zinc chlorides and polar solvents such as aliphatic alcohols, have a strong affinity for metals and spontaneously assemble in some conditions.5 In terms of applications, these self-assembled "organometallic" fibers represent an original and relatively easy to access substrate for fabricating 1D organic objects. Moreover, taking advantage of the properties and potentialities of these materials, we format an adequate shape to handle it as a potential separator for application in Energy Storage Systems (ESS).After a presentation of their synthesis and their formatting as potential separators for supercapacitors, preliminary electrochemical studies will be discussed. 1. J. Mater.Chem. A 2016, 4, 16812; ACS Energy let., 2022, 7, 885.2. ACS Appl. Energy Mater., 2021, 4, 128.3. ACS Appl. Matter. Interface, 2022, 14, 35645.4. J. Electoanalytical. Chem. 2023, 117251.5. Chem. Commun. 2010, 46, 1464. Figure 1

Tailoring the Periphery Aliphatic Group of Cathode Organosulfide for Rechargeable High‐Performance All‐Solid‐State Lithium Battery

Organic cathode materials exhibit higher energy storage capacity, their poor cyclability due to dissolution in liquid organic electrolytes remains a challenge. However, recently, the electrochemical behavior of organopolysulfides incorporating N‐heterocycles unveils promising cathode materials with stable cycling performance. Herein, the integration of organosulfides salt as cathodes with solid electrolytes, exemplified by sodium allyl(methyl)carbamodithioate and sodium diethylcarbamodithioate with a polymer solid electrolyte of polyethylene oxide and LiTFSI, addresses the poor electrochemical stability of organic electrodes. Comparative analysis highlights sodium allyl(methyl)carbamodithioate's superior electrochemical performance and stability compared with sodium diethylcarbamodithioate, emphasizing the efficacy of periphery aliphatic modification in enhancing electrode capacity, rate performance, and electrochemical stability for organosulfide materials within all‐solid‐state lithium organic batteries. We also explore the origin of periphery aliphatic modification in these enhancing electrochemical performances by kinetic analysis and thermodynamic analysis. Furthermore, employing density functional theory calculations and ex situ FTIR experiments elucidates the critical role of the N–C=S structure in the energy storage mechanism. This research advances organic cathode design within organosulfide materials, unlocking the potential of all‐solid‐state lithium organic batteries with enhanced cyclability, propelling the development of next‐generation energy storage systems.

Engineering the Interfacial Compatibility of a Small-Molecule Quinone Cathode toward Stable Quasi-Solid-State Lithium-Organic Batteries

Engineering the Interfacial Compatibility of a Small-Molecule Quinone Cathode toward Stable Quasi-Solid-State Lithium-Organic Batteries

Reviving Cost-Effective Organic Cathodes in Halide-Based All-Solid-State Lithium Batteries.

The evolution of inorganic solid electrolytes has revolutionized the field of sustainable organic cathode materials, particularly by addressing the dissolution problems in traditional liquid electrolytes. However, current sulfide-based all-solid-state lithium-organic batteries still face challenges such as high working temperatures, high costs, and low voltages. Here, we design an all-solid-state lithium battery based on a cost-effective organic cathode material phenanthrenequinone (PQ) and a halide solid electrolyte Li2ZrCl6. Thanks to the good compatibility between PQ and Li2ZrCl6, the PQ cathode achieved a high specific capacity of 248 mAh g-1 (96 % of the theoretical capacity), a high average discharge voltage of 2.74 V (vs. Li+/Li), and a good capacity retention of 95 % after 100 cycles at room temperature (25 °C). Furthermore, the interactions between the high-voltage carbonyl PQ cathode and both sulfide and halide solid electrolytes, as well as the redox mechanism of the PQ cathode in all-solid-state batteries, were carefully studied by a variety of advanced characterizations. We believe such a design and the corresponding investigations into the underlying chemistry give insights for the further development of practical all-solid-state lithium-organic batteries.

A bithiophene-substituted porphyrin displaying multi-electron redox processes as a cathode for lithium organic batteries

A non-metallated porphyrin, 5,15-di([2,2′-bithiophen]-5-yl)-10,20-diphenylporphyrin (BTPP) has been synthesized and utilized as an electrode material for lithium organic batteries (LOBs). Benefiting from the bipolar characteristics of the porphyrin core and extended [Formula: see text]-conjugation with bithiophene units, BTPP displayed as cathode material a discharge capacity of 128 mAh. g[Formula: see text] at a current density of 0.2 A. g[Formula: see text], with an average discharge voltage of 3.2 V and showed a good rate capability. At a high current density of 10 A. g[Formula: see text], it delivered a discharge capacity of 32 mAh. g[Formula: see text].

Ultra‐Long Lifespan Ni Based Porphyrin Complex Cathode for Organic Alkali Metal Batteries

AbstractThe high solubility and low intrinsic electronic conductivity are the key challenges for application of organic materials in electrochemical energy storage. Herein, a functionalized porphyrin complex of [5,15‐Bis(ethynyl)‐10,20‐diphenylporphinato]nickel(II) (NiDEPP) is proposed as new cathode material for alkali metal ion batteries. Owing to the in‐situ electropolymerization, NiDEPP became extremely stable after initial cycling. Therefore, the NiDEPP electrode delivers remarkable reversible capacity of 153 mAh g−1 at 1 A g−1, a high specific energy density of 459 Wh kg−1 and extremely stable cyclability for 4000 cycles with negligible capacity decay in organic lithium batteries. It can further be cycled upto 10000 cycles. Due to the bipolar capability of porphyrin ring, this cathode can also be extended in both sodium and potassium based organic cells. Similar charge storage mechanism enables highly reversible capacity and long‐term cycling stability. This study would open a pathway toward new organic electrodes with long cycling life and high energy densities for renewable charge storage devices.

Porphyrin-Thiophene Based Conjugated Polymer Cathode with High Capacity for Lithium-Organic Batteries.

Organic electrode materials are promising for next-generation energy storage materials due to their environmental friendliness and sustainable renewability. However, problems such as their high solubility in electrolytes and low intrinsic conductivity have always plagued their further application. Polymerization to form conjugated organic polymers can not only inhibit the dissolution of organic electrodes in the electrolyte, but also enhance the intrinsic conductivity of organic molecules. Herein, we synthesized a new conjugated organic polymer (COPs) COP500-CuT2TP (poly [5,10,15,20-tetra(2,2'-bithiophen-5-yl) porphyrinato] copper (II)) by electrochemical polymerization method. Due to the self-exfoliation behavior, the porphyrin cathode exhibited a reversible discharge capacity of 420 mAh g-1, and a high specific energy of 900 Wh Kg-1 with a first coulombic efficiency of 96 % at 100 mA g-1. Excellent cycling stability up to 8000 cycles without capacity loss was achieved even at a high current density of 5 A g-1. This highly conjugated structure promotes COP500-CuT2TP combined high energy density, high power density, and good cycling stability, which would open new opportunity for the designable and versatile organic electrodes for electrochemical energy storage.

Structure Characterizations and Electrode Performance of Poly(ethylene diaminoquinone) in Lithium–Organic Batteries

Structure Characterizations and Electrode Performance of Poly(ethylene diaminoquinone) in Lithium–Organic Batteries

Structural effects of conductive additives on the molecular shuttles in lithium–organic batteries

Structural effects of conductive additives on the molecular shuttles in lithium–organic batteries

A Nile red dye cathode with an asymmetric redox unit for lithium organic batteries.

A Nile red (NR) dye cathode with an asymmetric redox structure of para CN and CO bonds was developed for use in an efficient lithium organic battery with a good capacity of 125 mA h g-1 and two visible discharge/charge voltage plateaus (≈2.0 V and ≈1.7 V). The NR cathode demonstrated the advantages of employing cost-effective dyes to achieve multigradient voltage platform regulation.

Triphenylamine-containing dihydrophenazine copolymers with adjustable multi-electron redox characteristics and their application as cathodes in lithium-organic batteries

Arylamine p-type cathode materials have high redox potentials and rate capabilities, which have attracted increasing attention recently.

An electrospun three-layer nanofibrous membrane-based in situ gel separator for efficient lithium-organic batteries.

An in situ gel separator based on an electrospun three-layer nanofibrous membrane (PSE11-Gel) is developed for high-performance lithium-organic batteries (LOBs). The highly efficient shuttle effect inhibition of organic cathode molecules or lithiated intermediates has been demonstrated for PSE11-Gel to realize high-capacity stable LOBs.

Tetrathiafulvalene-based covalent organic frameworks as high-voltage organic cathodes for lithium batteries

We report a series of 2D tetrathiafulvalene (TTF)-based COFs incorporating different organic linkers between the electroactive moieties that were investigated as p-type organic cathode materials for lithium-organic batteries.

Integrated High Voltage, Large Capacity, and Long‐Time Cyclic Stability of Lithium Organic Battery Based on a Bipolar‐Type Cathode of Triphenylamine‐Hydrazone COF Material

AbstractCovalent organic frameworks (COFs) are a promising class of electrode materials for lithium‐ion batteries. However, the reported cathodes of COFs typically exhibit low potential and voltage plateaus, which limits their further applications. In this work, a new hydrazone three‐dimensional (3D) COF material with bipolar characteristics, PTB‐DHZ‐COF, is constructed by Schiff base condensation of monomeric PTB with DHZ. The cell with PTB‐DHZ‐COF as the cathode exhibits a wide potential range of 1.2–4.2 V and a discharge voltage plateau of over 3.6 V. PTB‐DHZ‐COFX composites are successfully prepared by compounding PTB‐DHZ‐COF with carbon nanotubes. PTB‐DHZ‐COF40 cells show high specific capacity (114.24 mAh·g−1 at 1000 mA·g−1), excellent cycling capability (86.3% capacity retention after 5000 cycles), and ultra‐high energy density (489 Wh·kg−1 at 50 mA·g−1). This work provides a new strategy for the design of new COF materials and the development of high‐performance organic energy storage electrodes.

Regulating Electrostatic Interaction between Hydrofluoroethers and Carbonyl Cathodes toward Highly Stable Lithium-Organic Batteries.

Organic carbonyl electrode materials have shown great promise for high-performance lithium batteries due to their high capacity, renewability, and environmental friendliness. However, their practical application is hindered by the high solubility of these materials in traditional electrolytes, leading to poor cycling stability and serious shuttle effects. Here, we develop a series of hydrofluoroethers (HFEs) with weak electrostatic interaction toward organic carbonyl cathode materials, aiming to address the dissolution issue and achieve high cycling stability in lithium batteries. Theoretical calculations reveal that the electrostatic interactions between HFEs and pyrene-4,5,9,10-tetraone (PTO) are significantly weaker compared with common solvents such as 1,2-dimethoxyethane. Consequently, the dissolution of PTO in the HFE-based electrolyte is remarkably reduced, as observed by in situ ultraviolet-visible spectra. Notably, when using the electrolyte based on 1,1,1,3,3,3-hexafluoro-2-methoxypropane with a certain coordination ability, PTO exhibits excellent cycling stability with a high capacity retention of 78% after 1000 cycles. This work proposes the regulation of electrostatic interactions to inhibit the dissolution of organic carbonyl cathode materials and significantly enhance their cycle life.

Towards high performance polyimide cathode materials for lithium–organic batteries by regulating active-site density, accessibility, and reactivity

Organic carbonyl electrode materials offer promising prospects for future energy storage systems due to their high theoretical capacity, resource sustainability, and structural diversity. Although much progress has been made in the research of high-performance carbonyl electrode materials, systematic and in-depth studies on the underlying factors affecting their electrochemical properties are rather limited. Herein, five polyimides containing different types of diamine linkers are designed and synthesized as cathode materials for Li-ion batteries. First, the incorporation of carbonyl groups increases the active-site density in both conjugated and non-conjugated systems. Second, increased molecular rigidity can improve the accessibility of the active sites. Third, the introduction of the conjugated structure between two carbonyl groups can increase the reactivity of the active sites. Consequently, the incorporation of carbonyl structures and conjugated structures increases the capacity of polyimides. PTN, PAN, PMN, PSN, and PBN exhibit 212, 198, 199, 151, and 115 ​mAh ​g−1 ​at 50 ​mA ​g−1, respectively. In addition, the introduction of a carbonyl structure and a conjugated structure is also beneficial for improving cycling stability and rate performance. This work can deepen the understanding of the structure–function relationship for the rational design of polyimide electrode materials and can be extended to the molecular design of other organic cathode materials.