A Rhombic 2D Conjugated Metal-Organic Framework as Cathode for High-Performance Sodium-Ion Battery.

2D conjugated metal-organic frameworks (2D c-MOFs) have garnered significant attention as promising electroactive materials for energy storage. However, their further applications are hindered by low capacity, limited cycling life, and underutilization of the active sites. Herein, Cu-TBA (TBA = octahydroxyltetrabenzoanthracene) with large conjugation units (narrow energy gap) and a unique rhombus topology is introduced as the cathode material for sodium-ion batteries (SIBs). Notably, Cu-TBA with a rhombus topology exhibits a high specific surface area (613 m2 g-1) and metallic band structure. Additionally, Cu-TBA outperforms its hexagonal counterpart, Cu-HHTP (HHTP = 2,3,6,7,10,11-hexahydroxyltriphenylene), demonstrating superior reversible capacity (153.6 mAh g-1 at 50 mA g-1) and outstanding cyclability with minimal capacity decay even after 3000 cycles at 1 A g-1. This work elucidates a new strategy to enhance the electrochemical performance of 2D c-MOFs cathode materials by narrowing the energy gap of organic linkers, effectively expanding the utilization of 2D c-MOFs for SIBs.

2D Conjugated Metal-Organic Frameworks Bearing Large Pore Apertures and Multiple Active Sites for High-Performance Aqueous Dual-Ion Batteries.

2D conjugated metal-organic frameworks (2D c-MOFs) with large pore sizes and high surface areas are advantageous for adsorbing iodine species to enhance the electrochemical performance of aqueous dual-ion batteries (ADIBs). However, most of the reported 2D c-MOFs feature microporous structures, with few examples exhibiting mesoporous characteristics. Herein, we developed two mesoporous 2D c-MOFs, namely PA-TAPA-Cu-MOF and PA-PyTTA-Cu-MOF, using newly designed arylimide based multitopic catechol ligands (6OH-PA-TAPA and 8OH-PA-PyTTA). Notably, PA-TAPA-Cu-MOF exhibits the largest pore sizes (3.9 nm) among all reported 2D c-MOFs. Furthermore, we demonstrated that these 2D c-MOFs can serve as promising cathode host materials for polyiodides in ADIBs for the first time. The incorporation of triphenylamine moieties in PA-TAPA-Cu-MOF resulted in a higher specific capacity (423.4 mAh g-1 after 100 cycles at 1.0 A g-1) and superior cycling performance, retaining 96 % capacity over 1000 cycles at 10 A g-1 compared to PA-PyTTA-Cu-MOF. Our comparative analysis revealed that the increased number of N anchoring sites and larger pore size in PA-TAPA-Cu-MOF facilitate efficient anchoring and conversion of I3 -, as supported by spectroscopic electrochemistry and density functional theory calculations.

Tuning Electron Delocalization of Redox-Active Porous Aromatic Framework for Low-Temperature Aqueous Zn-K Hybrid Batteries with Air Self-Chargeability.

Air self-charging aqueous batteries promise to integrate energy harvesting technology and battery systems, potentially overcoming a heavy reliance on energy and the spatiotemporal environment. However, the exploitation of multifunctional air self-charging battery systems using promising cathode materials and suitable charge carriers remains challenging. Herein, for the first time, we developed low-temperature self-charging aqueous Zn-K hybrid ion batteries (AZKHBs) using a fully conjugated hexaazanonaphthalene (HATN)-based porous aromatic framework as the cathode material, exhibiting redox chemistry using K+ as charge carriers, and regulating Zn-ion solvation chemistry to guide uniform Zn plating/stripping. The unique AZKHBs exhibit the exceptional electrochemical properties in all-climate conditions. Most importantly, the large potential difference causes the AZKHBs discharged cathode to be oxidized using oxygen, thereby initiating a self-charging process in the absence of an external power source. Impressively, the air self-charging AZKHBs can achieve a maximum voltage of 1.15 V, an impressive discharge capacity (466.3 mAh g-1), and exceptional self-charging performance even at -40 °C. Therefore, the development of self-charging AZKHBs offers a solution to the limitations imposed by the absence of a power grid in harsh environments or remote areas.

Conjugation and Topology Engineering of 2D π-d Conjugated Metal-Organic Frameworks for Robust Potassium Organic Batteries.

The evolution of two-dimensional conjugated metal-organic frameworks (2D c-MOFs) provides a significant prospect for researching the next generation of green and advanced energy storage systems (ESSs). Especially, conjugation and topology engineering serve as an irreplaceable character in adjusting the electrochemical properties of ESSs. Herein, we proposed a novel strategy using conjugation and topology engineering to demonstrate the application of 2D c-MOFs in robust potassium-ion batteries (PIBs) for the first time. By comparing 2D c-MOFs with the rhombus/kagome structure as well as three/four-arm core, the rhombus structure (sql-Cu-TBA-MOF) cathode for PIBs can display the impressive electrochemical performance, including a high specific discharge capacity of 178.4 mAh g-1 (at 0.2 A g-1) and a well long-term cycle stability of more than 9,000 (at 10.0 A g-1). Moreover, full PIBs (FPIBs) are constructed by pairing sql-Cu-TBA-MOF cathode with dipotassium terephthalate (KTP) anode, which delivers a high reversible discharge specific capacity of 146.6 mAh g-1 (at 0.1 A g-1) and great practical application prospect. These findings provide reasonable implications for the design of 2D c-MOFs from the perspective of conjugation and topology engineering for advanced energy storage systems.

A bipolar organic molecule towards the anion/cation-hosting cathode compatible with polymer electrolytes for quasi-solid-state dual-ion batteries.

Ion concentration and mobility are tightly associated with the ionic conductance of polymer electrolytes in solid-state lithium batteries. However, the anions involved in the movement are irrelevant to energy generation and cause uncontrolled dendritic growth and concentration polarization. In the current study, we proposed the strategy of using a bipolar organic molecule as the anion/cation-hosting cathode to expand the active charge carriers of polymer electrolytes. As a proof-of-concept demonstration of the novel strategy, a bipolar phthalocyanine derivative (2,3,9,10,16,17,23,24-octamethoxyphthalocyaninato) Ni(II) (NiPc-(OH)8) that could successively store anions and cations was used as the cathode hosting material in quasi-solid-state dual-ion batteries (QSSDIBs). Interestingly, peripheral polyhydroxyl substituents could build a compatible interface with poly(vinylidene fluoride-hexafluoro propylene-based gel polymer electrolytes (PVDF-HFP). As expected, NiPc-(OH)8 displays a high specific capacity of 248.2 mAh/g (at 50 mA g-1) and improved cyclic stability compared with that in liquid electrolyte. This study provides a solution to the issue of anion migration and could open another way to build high-performance QSSDIBs.

.Boosting lithium storage in covalent triazine framework for symmetric all-organic lithium-ion batteries by regulating the degree of spatial distortion.

Covalent triazine frameworks (CTFs) with tunable structure, fine molecular design and low cost have been regarded as a class of ideal electrode materials for lithium-ion batteries (LIBs). However, the tightly layered structure possessed by the CTFs leads to partial hiding of the redox active site, resulting in their unsatisfactory electrochemical performance. Herein, two CTFs (BDMI-CTF and TCNQ-CTF) with higher degree of structural distortion, more active sites exposed, and large lattice pores were prepared by dynamic trimerization reaction of cyano. As a result, BDMI-CTF as a cathode material for LIBs exhibits high initial capacity of 186.5 mAh/g at 50 mA g-1 and superior cycling stability without capacity loss after 2000 cycles at 1000 mA g-1 compared with TCNQ-CTF counterparts. Furthermore, based on their bipolar functionality, BDMI-CTF can be used as both cathode and anode materials for symmetric all-organic batteries (SAOBs), and this work will open a new window for the rational design of high performance CTF-based LIBs.

Anchoring π-d Conjugated Metal-Organic Frameworks with Dual-Active Centers on Carbon Nanotubes for Advanced Potassium-Ion Batteries.

Potassium-ion batteries (PIBs) are gradually gaining attention owing to their natural abundance, excellent security, and high energy density. However, developing excellent organic cathode materials for PIBs to overcome the poor cycling stability and slow kinetics caused by the large radii of K+ ions is challenging. This study demonstrates for the first time the application of a hexaazanonaphthalene (HATN)-based 2D π-d conjugated metal-organic framework (2D c-MOF) with dual-active centers (Cu-HATNH) and integrates Cu-HATNH with carbon nanotubes (Cu-HATNH@CNT) as the cathode material for PIBs. Owing to this systematic module integration and more exposed active sites with high utilization, Cu-HATNH@CNT exhibits a high initial capacity (317.5 mA h g-1 at 0.1 A g-1 ), excellent long-term cycling stability (capacity retention of 96.8% at 5 A g-1 after 2200 cycles), and outstanding rate capacity (147.1 mA h g-1 at 10 A g-1 ). The reaction mechanism and performance are determined by combining experimental characterization and density functional theory calculations. This contribution provides new opportunities for designing high-performance 2D c-MOF cathodes with multiple active sites for PIBs.

Boosting H+ Storage in Aqueous Zinc Ion Batteries via Integrating Redox-Active Sites into Hydrogen-Bonded Organic Frameworks with Strong π-π Stacking.

In the emerging aqueous zinc ion batteries (AZIBs), proton (H+ ) with the smallest molar mass and fast (de)coordination kinetics is considered as the most ideal charge carrier compared with Zn2+ counterpart, however, searching for new hosting materials for H+ storage is still at its infancy. Herein, redox-active hydrogen-bonded organic frameworks (HOFs) assembled from diaminotriazine moiety decorated hexaazatrinnphthalene (HOF-HATN) are for the first time developed as the stable cathode hosting material for boosting H+ storage in AZIBs. The unique integration of hydrogen-bonding networks and strong π-π stacking endow it rapid Grotthuss proton conduction, stable supramolecular structure and inclined H+ storage. As a consequence, HOF-HATN displays a high capacity (320 mAh g-1 at 0.05 A g-1 ) and robust cyclability of (>10000 cycles at 5 A g-1 ) based on three-step cation coordination storage. These findings get insight into the proton transport and storage behavior in HOFs and provide the molecular engineering strategy for constructing well-defined cathode hosting materials for rechargeable aqueous batteries.

Ion Pre-Embedding Engineering of δ-MnO2 for Chemically Self-Charging Aqueous Zinc Ions Batteries.

Aqueous zinc ion batteries (ZIBs), especially those with self-charging properties, have been promisingly developed in recent years. Yet, most inorganic materials feature high redox potential, which limit their development in the self-charging field. To achieve this target, by pre-embedding potassium ions into δ-MnO2 to reduce the energy barrier in oxygen adsorption, the first application of MnO2 in self-charging ZIBs is realized. The design features a facile two-electrode configuration with no excessively complex component to allow for energy storage and conversion. Due to the voltage difference between the oxygen in the air and the discharge products, a redox reaction can be carried out spontaneously to realize the self-charging process. After the chemical self-charging process, the Zn-K0.37 MnO2 ·0.54H2 O/C cell achieves an open circuit voltage of around 1.42 V and a discharge capacity of 201 mAh g-1 , reflecting the promising self-charging capability. Besides, the chemically self-charging ZIBs operate well in multiple modes of constant current charge/discharge/chemical charging. And decent cycling capability can also be achieved at extreme temperatures and high mass loading. This work promotes the development of ZIBs and further broadens the application of inorganic metal oxides in the self-charging systems.

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.

Immobilizing Quinone-Fused Aza-Phenazine into π-d Conjugated Coordination Polymers with Multiple-Active Sites for Sodium-Ion Batteries.

The development of coordination polymers with π-d conjugation (CCPs) provides ide prospects for exploring the next generation of environmental-friendliness energy storage systems. Herein, the synthesis, experimental characterizations, and Na-ion storage mechanism of π-d CCPs with multiple-active sites are reported, which use quinone-fused aza-phenazine (AP) and aza-phenazin (AP) as the organic ligands coordinated with the metal center (Ni2+ ). Among them, NiQAP as the cathode material exhibits impressive electrochemical properties applied in sodium-ion batteries (SIBs), including the high initial/stable discharge specific capacities (180.0/225.6 mAh g-1 ) at 0.05 A g-1 , a long-term cycle stability up to 10,000 cycles at 1.0 A g-1 with a high reversible capacity of 100.1 mAh g-1 , and good rate capability of 99.6 mAh g-1 even at 5.0 A g-1 . Moreover, the Na-ion storage mechanism of NiQAP is also performed by the density functional theory (DFT) calculation, showing multiple-active sites of C≐O and C≐N (in the quinone and phenazine structure) and NiO4 (in the coordination unit) for Na-ion storage. These results highlight the importance of organic electrode material with the coordination units and provide a foundation for further studying the CCPs with multiple active sites for energy storage systems.

Cobalt Nanoparticles Embedded into Nitrogen-doped Graphene with Abundant Macropores as a Bifunctional Electrocatalyst for Rechargeable Zinc-air Batteries.

Nitrogen doped carbon materials containing transition metal nanoparticles have attracted much attention as bifunctional oxygen electrocatalysts. In this paper, the template etching method is used to obtain the nitrogen-doped graphene with abundant macropores embedded with cobalt nanoparticles (Co@N-C). The prepared Co@NC-800 catalyst has a half-wave potential (E1/2= 0.835 V) close to Pt/C and good stability in excess of Pt/C for oxygen reduction reaction (ORR). At the same time, the catalyst has good oxygen evolution reaction (OER) performance. In addition, zinc-air batteries (ZABs) based on the Co@NC-800 catalyst show good cycle stability of up to 200000 s and high power density of 73.5 mW cm-2 . The synergistic effect of the integrated component between nitrogen-doped graphene and cobalt nanoparticles as well as the macroporous structure endow Co@NC-800 with abundant exposed active sites and mass/electron transfer capacity, thus leading to the high electrocatalytic activity. This work shows potential for practical applications in electrochemistry.

A redox-active metal-organic compound for lithium/sodium-based dual-ion batteries.

Currently, there is considerable interest in developing new electrode materials to construct the new-generation dual-ion batteries (DIBs) with the potential advantages of higher working voltage, good safety, low cost, and environmental friendliness. Herein, a well-known charge-transfer metal-organic compound, copper-tetracyanoquinodimethane (CuTCNQ), is synthesized and then used as an anode material, which can reversibly store Li+/Na+ ions under the lower working voltage. Consequently, the lithium/sodium-based DIBs (LDIBs/SDIBs) are constructed by coupling CuTCNQ anode with graphite cathode and their working mechanisms are also understood in detail. As expected, LDIBs exhibit a high average potential of 4.26 V, a high initial discharge capacity of 195.4 mAh g-1 at 0.1 A g-1, long cycling performance after 200 cycles with good capacity retention and excellent rate capability of 106.2 mAh g-1 at 5 A g-1. Especially, high average potential of 4.23 V and good rate capability of 34.5 mAh g-1 at 5 A g-1 could be maintained in SDIBs. These results may open a new avenue for using metal-organic compound in the field of high-performance energy-storage devices.

Conjugated microporous polyarylimides immobilization on carbon nanotubes with improved utilization of carbonyls as cathode materials for lithium/sodium-ion batteries.

Aromatic polyimide (PI)-based compounds have been widely studied for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) due to their higher specific energy density, economical, environmentally friendly and adjustable redox potential window. However, their solubility in aprotic electrolytes, inherently poor conductivity and low active site utilization limit their application in large-scale energy storage system (ESS). Here, we synthesized two aromatic PI-based conjugated microporous polymers (CMPs) and integrated them with multi-walled carbon nanotubes (CNT) (TAPT-NTCDA@CNT and TAPT-PMDA@CNT) for using as cathode materials for LIBs and SIBs. The aromatic PI-based CMP can effectively utilize the redox activity site due to its abundant π-conjugated redox active units, stable imide bond, high specific surface area and clear pore structure. As expected, the optimum TAPT-NTCDA@CNT exhibits good rate performance (89.7 mAh g-1 at 2000 mA g-1) and long cycle stability (87.3% capacity retention after 500 cycles) in LIBs. Also, TAPT-NTCDA@CNT can provide a higher initial capacity of 91.1 mAh g-1 in SIBs at 30 mA g-1. This work provides key insights for the further development of other new organic electrodes for other advanced rechargeable batteries.

Carbonyl-rich Poly(pyrene-4,5,9,10-tetraone Sulfide) as Anode Materials for High-Performance Li and Na-Ion Batteries.

Organic carbonyl electrode materials are widely employed for alkali metal-ion secondary batteries in terms of their sustainability, structure designability and abundant resources. As a typical redox-active organic electrode materials, pyrene-4, 5, 9, 10-tetraone (PT) shows high theoretical capacity due to the rich carbonyl active sites. But its electrochemical behavior in secondary batteries still needs further exploration. Herein, PT-based linear polymers (PPTS) is synthesized with thioether bond as bridging group and then employed as an anode material for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). As expected, PPTS shows improved conductivity and insolubility in the non-aqueous electrolyte. When used as an anode material for LIBs, PPTS delivers a high reversible specific capacity of 697.1 mAh g-1 at 0.1 A g-1 and good rate performance (335.4 mAh g-1 at 1 A g-1 ). Moreover, a reversible specific capacity of 205.2 mAh g-1 at 0.05 A g-1 could be obtained as an anode material for SIBs.

Metal Phthalocyanine-Porphyrin-based Conjugated Microporous Polymer-derived Bifunctional Electrocatalysts for Zn-Air Batteries.

Conjugated microporous polymers (CMPs) as emerging porous materials with diverse structures and tunable building-units have attracted much attention in the electrochemical field. Herein, we designed phthalocyanine-porphyrin-based conjugated microporous polymers as precursors for fabrication of Co, Fe, N tri-doped graphene composites towards oxygen reduction and evolution reaction (ORR/OER). As expected, the elements cobalt and iron are well dispersed in graphene carbon and interact with the nitrogen sites, thereby providing extra electrocatalytic active sites and enhancing its overall conductivity. Benefiting from its unique design and structure, the obtained catalyst affords a superior bifunctional catalytic activity with a positive onset potential of 0.957 V for ORR, and a low overpotential of 0.36 V for OER. More attractively, the CoFeNG is employed as an air cathode catalyst in Zn-air batteries, showing a maximum current density of 215 mA cm-2 and good cycle stability for 20000 s. The rational design of phthalocyanine-porphyrin-based derivatives provides a feasible route for the construction of high-performance ORR/OER catalysts.

Multi-heteroatom-doped dual carbon-confined Fe3O4 nanospheres as high-capacity and long-life anode materials for lithium/sodium ion batteries.

The lithium/sodium-ion storage properties of transition metal oxides often undergo startling volume variation and poor electrical conductivity. Herein, N, P and S doped dual carbon-confined Fe3O4 nanospheres (Fe3O4@C@G) are prepared by the multi-heteroatom-doped dual carbon-confined strategy. The first carbon layer results from multi-heteroatom-containing polymer derived N, P and S doped carbon to form Fe3O4@doped carbon core-shell nanostructure. And the second carbon layer results from the further encapsulated reduced graphene oxide (rGO) to form Fe3O4@doped carbon@graphene 3D architecture (Fe3O4@C@G). As expected, the resulting Fe3O4@C@G can be served as the universal anode materials towards lithium/sodium-ion batteries (LIBs/SIBs). Interestingly, Fe3O4@C@G delivers higher reversible capacity of 919 mAh g-1 at 0.1 A g-1 for LIBs. As for SIBs, Fe3O4@C@G also shows a high reversible capacity of 180 mAh g-1 after 600 cycles at 0.1 A g-1. Furthermore, the electrochemical reaction kinetics in LIBs/SIBs are investigated and Li+ full cells are also assembled to demonstrate its practical application.

A Self-Polymerized Nitro-Substituted Conjugated Carbonyl Compound as High-Performance Cathode for Lithium-Organic Batteries.

Conjugated carbonyl compounds have received much attention as cathode materials for developing green lithium-ion batteries (LIBs). However, their high dissolution and poor electronic conductivity in organic electrolyte restrict their further application. Herein, a self-polymerized nitro-substituted conjugated carbonyl compound (2,7-dinitropyrene-4,5,9,10-tetraone, PT-2 NO2 ) is applied as a high-performance cathode material for LIBs. PT-2 NO2 exhibits a high reversible capacity of 153.9 mAh g-1 at 50 mA g-1 after 120 cycles, which is higher than that of other substituted compounds. Detailed characterization and theoretical calculations have testified that PT-2 NO2 is transformed into an azo polymer through an irreversible reductive coupling reaction in the first discharge process, and then carbonyl and azo groups reversibly react with Li ions in subsequent cycles. In addition, this azo polymer is also synthesized and applied as the electrode material, which shows similar electrochemical performance to PT-2 NO2 but with higher initial coulombic efficiency. Thus, this work provides a simple but effectively way to construct organic cathode materials with multiple redox sites for green and high-performance LIBs.

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.

A Bipolar and Self-Polymerized Phthalocyanine Complex for Fast and Tunable Energy Storage in Dual-Ion Batteries.

Bipolar redox organics have attracted interest as electrode materials for energy storage owing to their flexibility, sustainability and environmental friendliness. However, an understanding of their application in all-organic batteries, let alone dual-ion batteries (DIBs), is in its infancy. Herein, we propose a strategy to screen a variety of phthalocyanine-based bipolar organics. The self-polymerizable bipolar Cu tetraaminephthalocyanine (CuTAPc) shows multifunctional applications in various energy storage systems, including lithium-based DIBs using CuTAPc as the cathode material, graphite-based DIBs using CuTAPc as the anode material and symmetric DIBs using CuTAPc as both the cathode and anode materials. Notably, in lithium-based DIBs, the use of CuTAPc as the cathode material results in a high discharge capacity of 236 mAh g-1 at 50 mA g-1 and a high reversible capacity of 74.3 mAh g-1 after 4000 cycles at 4 A g-1 . Most importantly, a high energy density of 239 Wh kg-1 and power density of 11.5 kW kg-1 can be obtained in all-organic symmetric DIBs.