Weiwei Huang

Primary batteries are crucial for aerospace and medical implants; however, traditional inorganic systems (like Li‐MnO ₂ and Li‐CF _x ) face strict energy limits and high costs. Tunable, eco‐friendly organic cathodes offer a promising alternative. In this review, we categorize organic primary batteries into two main groups: carbonyl‐ and nitro‐based systems. Their massive energy density is unlocked when fluoroethylene carbonate (FEC) is added to the electrolyte. FEC triggers an irreversible four‐electron reduction for carbonyls and a six‐electron reduction for nitro groups. Despite better than inorganic systems in capacity and safety, organics still struggle with low discharge voltages, spontaneous dissolution during storage, capacity drops at high FEC levels, and difficulties in making high‐loading electrodes. To overcome these hurdles, future work could focus on targeted molecular redesign, modification of electrolytes and separators, and improvement of electrode processing techniques. Currently, organic primary batteries are still in early‐stage research but have already demonstrated comprehensive advantages, offering a new pathway toward safe, high‐energy, and green primary batteries.

The development of sodium‐carbon dioxide (Na‐CO ₂ ) batteries is crucial for renewable energy utilization and CO ₂ fixation. However, their practical application is severely hindered by Na dendrite formation coupled with aggressive CO ₂ electro‐/chemical corrosion, and extremely low Na anode utilization rates. This study addresses these interconnected challenges by employing a multifunctional covalent organic framework (COF) coating. Specifically, the C ₆ O ₆ ‐TAPT COF features a fully conjugated skeleton for rapid electron cloud response, abundantly distributed sodiophilic chelation sites (C═O and C═N) for Na ⁺ capture, and ordered AB stacked structure for homogenizing Na ⁺ flux. The COMSOL simulations further demonstrate the stress‐regulating strategy in mitigate solid electrolyte interphase (SEI) cracking and separator puncturing risks. Consequently, Na‐CO ₂ batteries using the designed industrial‐scale anode achieve low polarization (1.4 V) and sustain stable cycling for over 1100 h at 100 mA g ⁻¹ across 0–60 °C. Remarkably, it maintained over 100 cycles at reduced N/P of 10 and delivered a high discharge capacity of 11552 mAh g ⁻¹ under lean electrolyte conditions (8.7 µL mAh ⁻¹ ). This study validates stable and functionalized COF substrates with dendrite suppression capability in Na‐CO ₂ batteries, proposing a scalable pathway with implications for next‐generation energy storage.

The development of sodium‐carbon dioxide (Na‐CO ₂ ) batteries is crucial for renewable energy utilization and CO ₂ fixation. However, their practical application is severely hindered by Na dendrite formation coupled with aggressive CO ₂ electro‐/chemical corrosion, and extremely low Na anode utilization rates. This study addresses these interconnected challenges by employing a multifunctional covalent organic framework (COF) coating. Specifically, the C ₆ O ₆ ‐TAPT COF features a fully conjugated skeleton for rapid electron cloud response, abundantly distributed sodiophilic chelation sites (C═O and C═N) for Na ⁺ capture, and ordered AB stacked structure for homogenizing Na ⁺ flux. The COMSOL simulations further demonstrate the stress‐regulating strategy in mitigate solid electrolyte interphase (SEI) cracking and separator puncturing risks. Consequently, Na‐CO ₂ batteries using the designed industrial‐scale anode achieve low polarization (1.4 V) and sustain stable cycling for over 1100 h at 100 mA g ⁻¹ across 0–60 °C. Remarkably, it maintained over 100 cycles at reduced N/P of 10 and delivered a high discharge capacity of 11552 mAh g ⁻¹ under lean electrolyte conditions (8.7 µL mAh ⁻¹ ). This study validates stable and functionalized COF substrates with dendrite suppression capability in Na‐CO ₂ batteries, proposing a scalable pathway with implications for next‐generation energy storage.

Proton tautomerism, a ubiquitous phenomenon involving the dynamic interconversion of structural isomers through proton migration, has seldom been utilized in electrode design. One known example of this untapped potential is the imine‐enamine (─NH─/═N─) equilibrium in conjugated heterocycles. Herein, this reversible process is harnessed to regulate charge transport in covalent organic frameworks (COFs). Two π‐conjugated COFs, HATBQ and HATPT, were constructed via nucleophilic aromatic substitution (SNAr), which integrate dense C═N/C═O redox‐active sites into chemically stable skeletons. The conjugated imine bonds, formed via nucleophilic aromatic substitution, enable the formation of an extensive network of intramolecular hydrogen bonds. This network enhances the crystallinity of the COFs without compromising the reversible proton tautomerism. These combined characteristics endow the COFs, particularly HATPT, with exceptional long‐term cycling stability and rate performance. As a result, HATPT delivers outstanding durability in Sodium‐ ion batteries (SIBs), retaining 225 mAh g ⁻¹ after 5000 cycles at 10 A g ⁻¹ , and exhibits strong compatibility in full‐cell configurations with Na ₃ V ₂ (PO ₄ ) ₃ (NVP). This tautomerism‐driven electronic modulation significantly lowers the activation energy for redox reactions, thereby facilitating efficient Na ⁺ storage kinetics.

Proton tautomerism, a ubiquitous phenomenon involving the dynamic interconversion of structural isomers through proton migration, has seldom been utilized in electrode design. One known example of this untapped potential is the imine‐enamine (─NH─/═N─) equilibrium in conjugated heterocycles. Herein, this reversible process is harnessed to regulate charge transport in covalent organic frameworks (COFs). Two π‐conjugated COFs, HATBQ and HATPT, were constructed via nucleophilic aromatic substitution (SNAr), which integrate dense C═N/C═O redox‐active sites into chemically stable skeletons. The conjugated imine bonds, formed via nucleophilic aromatic substitution, enable the formation of an extensive network of intramolecular hydrogen bonds. This network enhances the crystallinity of the COFs without compromising the reversible proton tautomerism. These combined characteristics endow the COFs, particularly HATPT, with exceptional long‐term cycling stability and rate performance. As a result, HATPT delivers outstanding durability in Sodium‐ ion batteries (SIBs), retaining 225 mAh g ⁻¹ after 5000 cycles at 10 A g ⁻¹ , and exhibits strong compatibility in full‐cell configurations with Na ₃ V ₂ (PO ₄ ) ₃ (NVP). This tautomerism‐driven electronic modulation significantly lowers the activation energy for redox reactions, thereby facilitating efficient Na ⁺ storage kinetics.

Quinone compounds have been widely demonstrated as highly promising electrode materials for rechargeable batteries due to their cost‐effectiveness, eco‐friendliness, and multifunctionality. Among them, tetraamino‐benzoquinone (TABQ) has garnered significant attention as a common building block owing to its potential for large‐scale production and unique molecular design flexibility. The amino (–NH ₂ ) group in TABQ not only confers its multifunctionality in batteries but also enables the construction of one‐ to three‐dimensional electrode materials. These structural advantages give TABQ‐based electrode materials significant application potential in various rechargeable batteries. This minireview first outlines the design strategies and operating principles of TABQ‐based building bloks, then delves into their significance in battery technology, and finally discusses the potential challenges of TABQ‐based materials in rechargeable batteries.

As one type of promising material, porous organic polymers (POPs) have been widely used in sodium-ion battery (SIB) electrodes on account of their environmental friendliness and adjustable pore diameter. However, their capacity and rate performance require further improvement. Herein, a conjugated porous polymer (PQ-POP), containing an azaacene-deficient electron-deficient system, was synthesized by a simple condensation reaction. The conjugated and N-containing heteroaromatic structure improves the conductivity, charge-transfer efficiency, and physicochemical stability. Also, the porous polymeric framework shows a large specific surface area and high porosity, providing a large contact area with electrolytes and reducing the diffusion distance. Therefore, PQ-POP exhibits very good electrochemical properties. Besides its superior reversible specific capacity of 245 mAh g^-1, PQ-POP also shows remarkable cycling stability, maintaining almost 100% after 1000 cycles at 4 A g^-1. At 10 A g^-1, its capacity holds steady at 202 mAh g^-1, outperforming many similar materials. The sodium ion storage mechanism of PQ-POP was confirmed by in situ FTIR and XPS experiments. In order to broaden the application of PQ-POP in SIBs, the electrochemical performance of PQ-POP as the negative electrode and Na₃V₂(PO₄)₃ as the positive electrode were employed to assemble a full cell, where, even at 3 A g^-1, the full cell based on PQ-POP//Na₃V₂(PO₄)₃ maintained 101 mAh g^-1 of the capacity with nearly 100% coulomb efficiency, highlighting its potential in energy storage applications and providing perspectives into designing advanced POP electrodes for SIBs.

Sacrificial sodium dimethylglyoxime (Na ₂ DMGO) delivers 330 mAh g ⁻¹ via gas-free decomposition, boosting full-cell capacity retention from 62% to 85% and enhancing energy density by 12.4% (from 117 to 131.5 Wh kg ⁻¹ ).

Organic electrode materials (OEMs) hold significant development potential in the field of batteries and are regarded as excellent complementary materials to resource‐limited inorganic electrode materials, which have recently been the subject of extensive research. As research deepens, an increasing number of scholars recognize the influence of weak bond interactions on the properties of OEMs. Generally, weak bond interactions have more pronounced effects on organic materials compared to inorganic ones. Among various weak interactions, hydrogen bonds are particularly noteworthy, having been proven to play crucial roles in adjusting electrode charge distribution, stabilizing crystal structures, and inhibiting cyclic dissolution. The studies of hydrogen bonds in OEMs are therefore of paramount importance for guiding their future development. In this review, we primarily summarize the research progress in hydrogen bond science within OEMs and discuss future research directions and development prospects in this area. Hoping to provide valuable references for the advancement of OEMs.