Fully sp2 Carbon-conjugated Covalent Organic Frameworks with Multiple Active Sites for Advanced Lithium-ion Battery Cathodes.

Covalent organic frameworks (COFs) hold great promise for rechargeable batteries. However, the synthesis of COFs with abundant active sites, excellent stability, and increased conductivity remains a challenge. Here, chemically stable fully sp2 carbon-conjugated COFs (sp2c-COFs) with multiple active sites are designed by the polymerization of benzo[1,2-b:3,4-b':5,6-b'']trithiophene-2,5,8-tricarbaldehyde) (BTT) and s-indacene-1,3,5,7(2H,6H)-tetrone (ICTO) (denoted as BTT-ICTO). The morphology and structure of the COF are precisely regulated from "butterfly-shaped" to "cable-like" through an in-situ controllable growth strategy, significantly promoting the exposure and utilization of active sites. When the unique "cable-like" BTT-ICTO@CNT is employed as lithium-ion batteries (LIBs) cathode, it exhibits exceptional capacity (396 mAh g-1 at 0.1 A g-1 with 97.9% active sites utilization rate), superb rate capacity (227 mAh g-1 at 5.0 A g-1), and excellent cycling performance (184 mAh g-1 over 8000 cycles at 2.0 A g-1 with 0.00365% decay rate per cycle). The lithium storage mechanism of BTT-ICTO is exhaustively revealed by in-situ Fourier transform infrared, in-situ Raman, and density functional theory calculations. This work provides in-depth insights into fully sp2c-COFs with multiple active sites for high-performance LIBs.

Design Principles of Quinone Redox Systems for Advanced Sulfide Solid-State Organic Lithium Metal Batteries.

The emergence of solid-state battery technology presents a potential solution to the dissolution challenges of high-capacity small molecule quinone redox systems. Nonetheless, the successful integration of argyrodite-type Li6PS5Cl, the most promising solid-state electrolyte system, and quinone redox systems remains elusive due to their inherent reactivity. Here, a library of quinone derivatives is selected as model electrode materials to ascertain the critical descriptors governing the (electro)chemical compatibility and subsequently the performances of Li6PS5Cl-based solid-state organic lithium metal batteries (LMBs). Compatibility is attained if the lowest unoccupied molecular orbital level of the quinone derivative is sufficiently higher than the highest occupied molecular orbital level of Li6PS5Cl. The energy difference is demonstrated to be critical in ensuring chemical compatibility during composite electrode preparation and enable high-efficiency operation of solid-state organic LMBs. Considering these findings, a general principle is proposed for the selection of quinone derivatives to be integrated with Li6PS5Cl, and two solid-state organic LMBs, based on 2,5-diamino-1,4-benzoquinone and 2,3,5,6-tetraamino-1,4-benzoquinone, are successfully developed and tested for the first time. Validating critical factors for the design of organic battery electrode materials is expected to pave the way for advancing the development of high-efficiency and long cycle life solid-state organic batteries based on sulfides electrolytes.

Dendritic sp Carbon-Conjugated Benzothiadiazole-Based Polymers with Synergistic Multi-Active Groups for High-Performance Lithium Organic Batteries.

Green organic materials composed of C, H, O, and N elements are receiving more and more attention worldwide. However, the high solubility, poor electrical conductivity, and long activation time limit the development of organic materials in practice. Herein, two stable covalent organic materials with alkynyl linkage between benzene rings and benzothiadiazole groups with different amounts of fluorine atoms modification (defined as BOP-0F and BOP-2F), are designed for lithium-ion batteries. Both BOP-0F and BOP-2F can achieve superior reversible capacities of ≈719.8 and 713.5 mAh g-1 over 100 cycles on account of the redox activity of alkynyl (two-electron involved) and benzothiadiazole units (five-electron involved) in these organic materials. While BOP-2F electrodes exhibit much more stable cycling performance than BOP-0F electrodes, especially without pronounced capacity ascending during initial cycling. It can be assigned to the synergy effect of alkynyl linkage and fluorine atom modification in BOP-2F. The lithium storage and activation mechanism of alkynyl, benzothiadiazole, and fluorine groups have also been deeply probed by a series of material characterizations and theoretical simulations. This work could be noteworthy in providing novel tactics for the molecular design and investigation of high-efficiency organic electrodes for energy storage.

Stable quasi-solid-state lithium-organic battery based on composite gel polymer electrolyte and compatible organic cathode material.

High-performance organic small-molecule electrode materials are troubled with their high solubility in liquid electrolytes. The construction of quasi-solid-state lithium organic batteries (LOBs) using gel polymer electrolytes with high mechanical properties, compromised ionic conductivity, high safety, and eco-friendly is an effective way to inhibit the dissolution of active materials. Herein, two hexaazatriphenylene (HATN)-based organic cathode materials (HATNA-6OCH3 and HATNA-6OH) are synthesized and then matched with polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP)-based gel polymer electrolytes to construct quasi-solid-state LOBs. Thanks to the enhanced interfacial compatibility between organic cathode material and gel polymer electrolyte, HATNA-6OH with compatible hydroxyl group shows the enhanced electrochemical properties compared with HATNA-6OCH3. Further, the electrochemical performance is improved when HATNA-6OH is combined with a gel polymer electrolyte modified with a succinonitrile (SN) plasticizer (GPE-0.4SN), including a high specific capacity of 153.3 mAh g-1 at 50 mA g-1 and a good reversible capacity of 88 mAh g-1 after 100 cycles at 200 mA g-1. In addition, the good electrochemical properties and lithium-ion storage mechanism of HATNA-6OH have been elucidated using density functional theory (DFT) and spectral characterizations.

Conjugated and Non-conjugated Polymers Containing Two-Electron Redox Dihydrophenazines for Lithium-Organic Batteries.

Organic p-type cathode materials have recently attracted increasing attention due to their higher redox potentials and rate capabilities in comparison to n-type cathodes. However, most of the p-type cathodes based on one-electron redox still suffer from limited stability and low specific capacity (<150 mAh g-1 ). Herein, two polymers, conjugated poly(diethyldihydrophenazine vinylene) (CPP) and non-conjugated poly(diethyldihydrophenazine ethylidene) (NCPP) containing two-electron redox dihydrophenazine, have been developed as p-type cathode materials. It is experimentally and theoretically found that the conjugated linkage among the redox centers in polymer CPP is more favorable for the effective charge delocalization on the conjugated polymer backbone and the sufficient oxidation in the higher potential region (3.3-4.2 V vs. Li/Li+ ). Consequently, the CPP cathode displays a higher reversible specific capacity of 184 mAh g-1 with excellent cycling stability.

In Situ Growth of Covalent Organic Framework Nanosheets on Graphene as the Cathode for Long-Life High-Capacity Lithium-Ion Batteries.

The poor electronic and ionic conductivities of covalent organic frameworks (COFs) severely restrict the development of COF-based electrodes for practical rechargeable batteries, therefore inspiring more research interest from the direction of both material synthesis and technology. Herein, a dual-porous COF, USTB-6, with good crystallinity and rich redox-active sites is conceived and fabricated by the polymerization of 2,3,8,9,14,15-hexa(4-formylphenyl)diquinoxalino [2,3-a:2',3'-c]phenazine and 2,7-diaminopyrene-4,5,9,10-tetraone. In particular, the heterogeneous polymerization of the same starting materials in the presence of graphene affords uniformly dispersed COF nanosheets with a thickness of 8.3 nm on a conductive carbon substrate, effectively enhancing the electronic conductivity of the COF-based electrode. Such a graphene-supported USTB-6 nanosheets cathode when used in a lithium-ion battery exhibits a specific capacity of 285 mA h g-1 at a current density of 0.2 C and excellent rate performance with a prominent capacity of 188 mA h g-1 at 10 C. More importantly, a capacity of 170 mA h g-1 is retained by using the USTB-6 nanosheets cathode after 6000 cycles charge and discharge measurement at 5 C.

Cross-Linked PVA/HNT Composite Separator Enables Stable Lithium-Organic Batteries under Elevated Temperature.

Li-organic batteries (LOBs) are promising advanced battery systems because of their unique advantages in capacity, cost, and sustainability. However, the shuttling effect of soluble organic redox intermediates and the intrinsic dissolution of small-molecular electrodes have hindered the practical application of these cells, especially under high operating temperatures. Herein, a cross-linked membrane with abundant negative charge for high-temperature LOBs is prepared via electrospinning of poly(vinyl alcohol) containing halloysite nanotubes (HNTs). The translocation of negatively charged organic intermediates can be suppressed by the electronic repulsion and the cross-linked network while the positively charged Li+ are maintained, which is attributed to the intrinsic electronegativity of HNTs and their well-organized and homogeneous distribution in the PVA matrix. A battery using a PVA/HNT composite separator (EPH-10) and an anthraquinone (AQ) cathode exhibits a high initial discharge capacity of 231.6 mAh g-1 and an excellent cycling performance (91.4% capacity retention, 300 cycles) at 25 °C. Even at high temperatures (60 and 80 °C), its capacity retention is more than 89.2 and 80.4% after 100 cycles, respectively. Our approach demonstrates the potential of the EPH-10 composite membrane as a separator for high-temperature LOB applications.

Soluble Organic Cathodes Enable Long Cycle Life, High Rate, and Wide-Temperature Lithium-Ion Batteries.

Organic electrode materials free of rare transition metal elements are promising for sustainable, cost-effective, and environmentally benign battery chemistries. However, severe shuttling effect caused by the dissolution of active materials in liquid electrolytes results in fast capacity decay, limiting their practical applications. Here, using a gel polymer electrolyte (GPE) that is in situ formed on Nafion-coated separators, the shuttle reaction of organic electrodes is eliminated while maintaining the electrochemical performance. The synergy of physical confinement by GPE with tunable polymer structure and charge repulsion of the Nafion-coated separator substantially prevents the soluble organic electrode materials with different molecular sizes from shuttling. A soluble small-molecule organic electrode material of 1,3,5-tri(9,10-anthraquinonyl)benzene demonstrates exceptional electrochemical performance with an ultra-long cycle life of 10 000 cycles, excellent rate capability of 203 mAh g-1 at 100 C, and a wide working temperature range from -70 to 100 °C based on the solid-liquid conversion chemistry, which outperforms all previously reported organic cathode materials. The shielding capability of GPE can be designed and tailored toward organic electrodes with different molecular sizes, thus providing a universal resolution to the shuttling effect that all soluble electrode materials suffer.

Few-Layered Fluorinated Triazine-Based Covalent Organic Nanosheets for High-Performance Alkali Organic Batteries.

In order to fulfill the increasing demand for renewable energy, besides the lithium-ion batteries, other alkali (Na, K)-ion batteries are extensively investigated. However, the difficulty to find universal and environmentally benign electrodes for these alkali (Na, K)-ion batteries still severely restricts their development. Promising characteristics, including molecular diversity, low cost, and operation safety, endow the organic electrodes more advantages for applications in alkali-ion batteries. However, organic electrodes usually deliver a reversible capacity smaller than that of their inorganic counterparts due to sluggish ion/electron diffusion and possible dissolution in organic electrolytes. This work introduces fluorine atoms into the covalent triazine frameworks (CTF) to obtain two-dimensional layered fluorinated CTF (FCTF) and its exfoliated few-layered product (E-FCTF) and uses them as anodes of Li, Na, and K organic batteries. Exfoliated E-FCTF electrode delivers high reversible capacities, as well as excellent cycle life for alkali organic batteries (1035 mAh g-1 at 100 mA g-1 after 300 cycles and 581 mAh g-1 at 2 A g-1 after 1000 cycles for lithium organic batteries). In view of the experimental probing and the theoretical calculation, the Li storage mechanism for the E-FCTF can be determined to be an intriguing multielectronic redox reaction originated from lithium storage on the benzene ring and triazine ring units.

Conjugated Carbonyl Polymer-Based Flexible Cathode for Superior Lithium-Organic Batteries.

Conjugated carbonyl compounds are deemed as high theoretical capacity and green electrode materials for lithium-ion batteries (LIBs) but are limited by their high dissolution and poor electronic conductivity. In this paper, we have successfully synthesized a series of multicarbonyl conjugated polymers using the coupling polymerization reaction and then constructed carbonyl-conjugated polymer/carbon nanotube hybrid films by a vacuum-filtration method. Importantly, the hybrid films could serve as a flexible, binder-free, and free-standing organic cathode for LIBs, which could deliver a high reversible discharge capacity of 142.3 mAh g-1 at 50 mA g-1, good cycling stability with a capacity retention of 74.6% at 500 mA g-1 after 300 cycles, and excellent rate capability of 120.6 mAh g-1 at 1000 mA g-1. In addition, the theoretical calculation has proved that the symmetrical conjugated structure can well accommodate four Li+ ions during the electrochemical reaction. Interestingly, the assembled full cell and flexible battery can power the small devices, suggesting its potential to use in bendable or wearable energy-storages devices.

High-Lithium-Affinity Chemically Exfoliated 2D Covalent Organic Frameworks.

Covalent organic frameworks (COFs) with reversible redox behaviors are potential electrode materials for lithium-ion batteries (LIBs). However, the sluggish lithium diffusion kinetics, poor electronic conductivity, low reversible capacities, and poor rate performance for most reported COF materials limit their further application. Herein, a new 2D COF (TFPB-COF) with six unsaturated benzene rings per repeating unit and ordered mesoporous pores (≈2.1 nm) is designed. A chemical stripping strategy is developed to obtain exfoliated few-layered COF nanosheets (E-TFPB-COF), whose restacking is prevented by the in situ formed MnO2 nanoparticles. Compared with the bulk TFPB-COF, the exfoliated TFPB-COF exhibits new active Li-storage sites associated with conjugated aromatic π electrons by facilitating faster ion/electron kinetics. The E-TFPB-COF/MnO2 and E-TFPB-COF electrodes exhibit large reversible capacities of 1359 and 968 mAh g-1 after 300 cycles with good high-rate capability.

High-Power-Density Organic Radical Batteries.

Batteries that are based on organic radical compounds possess superior charging times and discharging power capability in comparison to established electrochemical energy-storage technologies. They do not rely on metals and, hence, feature a favorable environmental impact. They furthermore offer the possibility of roll-to-roll processing through the use of different printing techniques, which enables the cost-efficient fabrication of mechanically flexible devices. In this review, organic radical batteries are presented with the focus on the hitherto developed materials and the key properties thereof, e.g., voltage, capacity, and cycle life. Furthermore, basic information, such as significant characteristics, housing approaches, and applied additives, are presented and discussed in the context of organic radical batteries.