Voltage Hysteresis Research Articles

State of charge estimation with hysteresis-prone open circuit voltage in lithium-ion batteries using the trajectory correction hysteresis (TCH) model

State-of-the-art lithium-ion cell chemistries with pronounced open-circuit voltage hysteresis (OCV), characterised by asymmetry and directional dependence, present a challenge for estimating the state of charge (SOC). Without understanding the hysteresis behaviour, OCV measurement points that lie within the hysteresis window cannot be used for SOC correction. After obtaining the data efficiency of the trajectory correction hysteresis (TCH) model with the introduction of the transfer fit (TF) method, this work applies the TF TCH for OCV-based SOC correction. The TF method plays a key role as it enables the cell-specific adaptation of an existing TCH model - ageing update is achieved with solely 12 (SOC/OCV) measurement points. With the precise hysteresis model, the developed framework successfully corrects the faulty SOC history, which could originate from a vehicle data logger. Given that two OCV measurement points are available that arbitrarily lie within the SOC history, the SOC correction is achieved by minimising the voltage deviation between the measurement points and the TCH model’s simulation. Identifying the two SOC parameters shift and scale enables subsequent SOC estimation until an additional OCV measurement is available for a further update. The functionality of the presented SOC correction framework is demonstrated using two validation profiles.

Surface engineering of Li3V2(PO4)3-based cathode materials with enhanced performance for lithium-ion batteries working in a wide temperature range

Operating at extreme temperatures is the biggest challenge for lithium-ion batteries (LIBs) in practical applications, as both the capacity and cycling stability of LIBs are largely decreased due to the sluggish reaction kinetics of the cathodes. Therefore, developing suitable cathode materials is the key point to tackling this challenge. Lithium vanadium phosphate [Li3V2(PO4)3, LVP] is a promising cathode with good features of a high working voltage, high intrinsic ionic diffusion coefficiency, and stable olivine structure in a wide temperature range, although it is perplexed by the low electronic conductivity. To tackle this issue, a series of nitrogen-doped carbon network (NC) coated LVP composites were synthesized using a hydrothermal-assisted sol-gel method. Among them, the LVP@NC-0.8 sample exhibited a remarkable tolerance at a high charging cutoff voltage of 4.8 V in a wide temperature range. Full cells of LVP@NC-0.8||graphite exhibited superior performance at different current rates. Moreover, the reaction mechanism of the LVP@NC-0.8 electrode was proved by in-situ X-ray diffraction technique, demonstrating that temperature was a critical factor that contributed to the sluggish phase transformation with high voltage hysteresis at low temperature and severe crystal structure distortion at high temperature. Theoretical calculations further demonstrated the superiority of the NC for high electronic conductivity and reduced lithium transportation barriers. The enhanced electrochemical performances of LVP-based cathode materials have provided the possible application of LIBs in a wide temperature range.

State of health as a function of voltage hysteresis in Li-ion battery half-cells

State of health as a function of voltage hysteresis in Li-ion battery half-cells

A physically motivated voltage hysteresis model for lithium-ion batteries using a probability distributed equivalent circuit

The open circuit voltage hysteresis of lithium-ion batteries is a phenomenon that, despite intensive research, is still not fully understood. However, it must be taken into account for accurate state-of-charge estimation in battery management systems. Mechanistic models of the open circuit voltage hysteresis previously published are not suitable for deployment in a battery management system. Phenomenological models on the other hand can only superficially represent the processes taking place. To address this limitation, we propose a probability distributed equivalent circuit model motivated by the physical insights into hysteresis. The model incorporates hysteresis effects that are often disregarded for state estimation, while keeping the computational cost low. Although the parameterization is more demanding, the model has the advantage of providing insight into the internal state of the battery and intrinsically incorporating the effect of path-dependent rate capability.

Engineering Sb/Zn4(OH)6SO4·5H2O interfacial layer by in situ chemically reacting for stable Zn anode

Rechargeable aqueous zinc ion batteries with abundant resources and high safety have gained extensive attention in energy storage technology. However, the cycle stability is largely limited by notorious Zn dendrite growth and water-induced interfacial side reactions. Here, a uniform and robust protection layer consisting of metal antimony (Sb) nanoparticles and micrometer-size sheets Zn4(OH)6SO4·5H2O (ZHS) is purposely designed to stabilize Zn anode via an in situ chemical reaction strategy. The two-phase protection layers (Sb/ZHS) induce a reinforcement effect on the Zn anode (Zn@Sb/ZHS). Specifically, Sb nanoparticles play the part of nucleation sites to facilitate uniform Zn plating and homogenize the electric field around the Zn surface. ZHS micrometer-size sheets possess sufficient electrolyte wettability, fast ion transfer kinetics, and anti-corrosion, thus guaranteeing uniform ion flux and inhibiting H2O decomposition. As expected, the symmetric Zn@Sb/ZHS//Zn@Sb/ZHS cells achieve a minimal voltage hysteresis and a reversible cycle of over 2000 h at 1 mA cm−2. By pairing with the MnO2 cathode, the full cell exhibits a significantly improved stability (∼94.17 % initial capacity after 1500 cycles). This study provides a new strategy to design artificial protection layers.

Tautomeric pillars in vanadyl phosphate cathode to screen the divalent charge on Zn2+ for aqueous Zn batteries

Cathode materials with high redox potential are important for constructing high-energy-density aqueous zinc batteries. The polyanion compound of layered hydrate vanadyl phosphate (H2O-VOP) provides high potential thanks to the inductive effect. However, the sluggish Zn2+ diffusion in the lattice results in large voltage hysteresis, obstructing the capacity release at high voltage. Herein, tautomeric pillars are inserted in the VOPO4 layers (Tau-VOP) by the desulfhydryl reaction of l-cysteine, aiming to suppress voltage hysteresis with their charge screening effect. Specifically, the Lewis alkaline sites on the tautomers capture inserted Zn2+, and the divalent charge is further delocalized over the conjugated structure of pillars. This reduction of effective charge on cations ensures much weakened electrostatic interactions with the lattice and reduced diffusion barrier. As a result, the Tau-VOP cathode achieves 193 mAh g−1 capacity with 1.47 V/1.6 V redox voltage in zinc cells, which are superior to 110 mAh g−1 capacity and 1.1 V average discharge voltage with large voltage hysteresis obtained with H2O-VOP. The rate performance and energy efficiency are also significantly improved with the help of tautomer pillars. This work presents an effective charge screening strategy by suitable pillars to facilitate multivalent cation transport in cathode structures and enhance electrochemical performance.

Investigation of negative differential resistance on negative capacitance Germanium source vertical TFET

In this article, a systematic investigation of negative differential resistance (NDR) on a negative capacitance Germanium source vertical TFET (NC-Ge-vTFET) is presented. The implementation and increased ferroelectric (FE) film thickness (t FE) offers a significantly high current ratio, improved subthreshold slope, high transconductance with a very low hysteresis voltage. However, NDR is exhibited and is increasingly prominent at lower gate voltage and higher t FE due to the coupling of the internal gate and drain voltages. NDR is an undesired effect in analog circuits that has to be mitigated. To suppress the impacts of NDR on the device, different approaches are carried out: varying the overlap channel thickness, gate length, drain doping and gate-drain underlap. Circuit analysis is carried out with the implementation of NC-Ge-vTFET as digital inverter. When the gate-drain underlap length is increased from 0 nm to 15 nm, the propagation delay is significantly reduced by 30.98%. Benchmarking of the proposed device has also been carried out. This renders the gate-drain underlapped NC-Ge-vTFET to be a viable candidate for high performance, nanoscale, low power digital applications.

Bimetallic MOFs-Derived NiFe2O4/Fe2O3 Enabled Dendrite-free Lithium Metal Anodes with Ultra-High Area Capacity Based on An Intermittent Lithium Deposition Model.

In practical operating conditions, the lithium deposition behavior is often influenced by multiple coupled factors and there is also a lack of comprehensive and long-term validation for dendrite suppression strategies. Our group previously proposed an intermittent lithiophilic model for high-performance three-dimensional (3D) composite lithium metal anode (LMA), however, the electrodeposition behavior was not discussed. To verify this model, this paper presents a modified 3D carbon cloth (CC) backbone by incorporating NiFe2O4/Fe2O3 (NFFO) nanoparticles derived from bimetallic NiFe-MOFs. Enhanced Li adsorption capacity and lithiophilic modulation were achieved by bimetallic MOFs-derivatives which prompted faster and more homogeneous Li deposition. The intermittent model was further verified in conjunction with the density functional theory (DFT) calculations and electrodeposition behaviors. As a result, the obtained Li-CC@NFFO||Li-CC@NFFO symmetric batteries exhibit prolonged lifespan and low hysteresis voltage even under ultra-high current and capacity conditions (5 mA cm-2, 10 mAh cm-2), what's more, the full battery coupled with a high mass loading (9 mg cm-2) of LiFePO4 cathode can be cycled at a high rate of 5 C, the capacity retention is up to 95.2 % before 700 cycles. This work is of great significance to understand the evolution of lithium dendrites on the 3D intermittent lithiophilic frameworks.

20 nm-ultra-thin fluorosiloxane interphase layer enables dendrite-free, fast-charging, and flexible aqueous zinc metal batteries

Dendrite growth of zinc (Zn) anode at high current density severely affects the fast-charging performance of aqueous zinc metal batteries (AZMBs). While interfacial modification strategies can optimize Zn performance, challenges such as complicated preparation processes, excessive layer thicknesses, and high voltage hysteresis should be addressed. Herein, we utilize a cost-effective liquid fluorosiloxane, (3,3,3-trifluoropropyl)trimethoxysilane, for scalable modification of Zn foil via drop-casting at room temperature, resulting in an ultra-thin interphase layer of only 20 nm. The Si-O-Zn bonds formed between fluorosiloxane and Zn ensure interfacial stability, and the Si-O-Si bonds between fluorosiloxane molecules help to homogenize the electric field distribution. Additionally, the abundant highly electronegative fluorine atoms on the anode surface act as zincophilic sites, promoting the uniform deposition of Zn2+. Thus, the modified Zn foil (SiFO-Zn) exhibits excellent dendrite suppression, reduced voltage hysteresis, and prolonged cycle life at ultra-high current density (40 mA/cm2), achieving a cumulative areal capacity of 12.9 Ah/cm2. Further, the full cell assembled with 10 μm-thick SiFO-Zn anode and MnO2 cathode achieves 2600 cycles at 5 A/g with minimal capacity degradation, and a large-size (22.5 cm−2) pouch cell powers the light-emitting diode even after reverse bending, demonstrating the potential of AZMBs for fast-charging flexible devices.

Regulating "Tip Effect" and Zn2+-Deposition Kinetics by In Situ Constructing Interphase for Low Voltage Hysteresis and Dendrite-Free Zn Anode.

Metal zinc (Zn) is being explored as a possible anode for aqueous zinc ion batteries (AZIBs). However, unrestrained Zn dendrite caused by "tip effect" and chemical corrosion continue to plague the Zn deposition process, limiting the functionality of AZIBs and prohibiting their use at high current densities. This work presents an in situ approach for introducing homogeneous ZnO nanoarrays onto the surface of Zn foil (Zn@ZnO NAs) as a functional protective interphase. On the one hand, well-distributed ZnO NAs protection layer can regulate the "tip effect" and confine the growth of Zn dendrite. On the other hand, the ZnO NAs layer can enhance the desolvation and diffusion process of Zn2+ on the surface of anode, attributing to low voltage hysteresis and exceptional electrochemical performance at high current densities. As a result, the Zn@ZnO NAs exhibits a low voltage hysteresis of 50.8mV with a superb lifespan of 1200h at a current density of 5mA cm-2. Moreover, Zn@ZnO NAs||α-MnO2 full-cell shows a superior cycling performance after 500 cycles at 0.5 A g-1 with a capacity of 216.69 mAh g-1. This work is expected to provide ideas for designing other reversible zinc anode chemical systems, especially under a high current density.

Reducing Voltage Hysteresis in Li-Rich Sulfide Cathodes by Incorporation of Mn.

Conventional intercalation-based cathode materials in Li-ion batteries are based on charge compensation of the redox-active cation and can only intercalate one mole of electron per formula unit. Anion redox, which employs the anion sublattice to compensate charge, is a promising way to achieve multielectron cathode materials. Most anion redox materials still face the problems of slow kinetics and large voltage hysteresis. One potential solution to reduce voltage hysteresis is to increase the covalency of the metal-ligand bonds. By substituting Mn into the electrochemically inert Li1.33Ti0.67S2 (Li2TiS3), anion redox can be activated in the Li1.33-2y/3Ti0.67-y/3Mn y S2 (y = 0-0.5) series. Not only do we observe substantial anion redox, but the voltage hysteresis is significantly reduced, and the rate capability is dramatically enhanced. The y = 0.3 phase exhibits excellent rate and cycling performance, maintaining 90% of the C/10 capacity at 1C, which indicates fast kinetics for anion redox. X-ray absorption spectroscopy (XAS) shows that both the cation and anion redox processes contribute to the charge compensation. We attribute the drop in hysteresis and increase in rate performance to the increased covalency between the metal and the anion. Electrochemical signatures suggest the anion redox mechanism resembles holes on the anion, but the S K-edge XAS data confirm persulfide formation. The mechanism of anion redox shows that forming persulfides can be a low hysteresis, high rate capability mechanism enabled by the appropriate metal-ligand covalency. This work provides insights into how to design cathode materials with anion redox to achieve fast kinetics and low voltage hysteresis.

High-performance lithium metal anode enhanced by multifunctional film of PAN@AgNWs with antimicrobial activity

Lithium metal is expected to be the perfect anode material for the next generation of rechargeable batteries owing to its ultra-high theoretical specific capacity, low density and the lowest redox potential. However, the practical application of lithium metal batteries faces serious challenges, including uneven lithium deposition, negative electrode volume expansion, and short circuits brought by dendritic protrusions. Although the 3D structure of silver nanowires is effective in inhibiting lithium dendrite growth and lithium metal volume expansion, it still suffers from lithium inhomogeneity caused by uneven distribution of silver nanowires and complicated preparation. Therefore, PAN@AgNWs collector was prepared by a simple suction filtration method, and uniform dispersion of silver nanowires and uniform deposition of lithium were achieved. Lithium nucleation overpotential and lithium dendrite formation can be effectively reduced by PAN@AgNWs hosts due to the reduction of local current density by 3D collectors and the improved lithiophilicity of silver nanowires. With low voltage hysteresis, the symmetric battery constructed with its composite anode may cycle steadily for 4500 h at 1 mA cm−2 and 1 mAh cm−2. At the same time, the Li-PAN@AgNWs||LFP full cell still possesses a reversible of 144.18 mAh g−1 after 500 cycles at 1C. Moreover, due to large specific surface area and high surface energy of 3D silver nanowires, it exhibits excellent antimicrobial properties, with an inactivation efficiency of 96.3 % after contacting with E. coli for 2.5 h. This work shows the possibility of using PAN@AgNWs in a large scale for LMBs, and paves the way for development of high-performance antimicrobial materials.

Regulation of fiber surface nucleation kinetics via ordered nitrogen-rich carbon dots

Three dimensional (3D) carbon-based current collectors have attracted much attentions as host for Li metal anodes (LMAs) owing to their lightweight, flexible, and wide sources etc. However, the lithiophobic nature of carbon makes it difficult to achieve low nucleation overpotential and dendrite-free Li deposition. Herein, carbon dots (CDs) with nitrogen (N)-rich were introduced to modify carbonized cotton fiber (CCF) coated by reduced graphene oxide (CD@RGCCF). Coating graphene oxide (GO) increases the active site of cotton fiber (CF), which facilitates the growth of CDs on the surface of CF fiber. The introduction of ordered structure CDs drives fast migration of Li+ in the “highway-like” channels and induces the uniform nucleation of Li in the initial stage. As a result, the obtained CD@RGCCF decreases the nucleation overpotential of Li, and achieves dendrite-free Li deposition. the CD@RGCCF|Li half cells exhibit extending cycling life over 5000 h with a voltage hysteresis of 10.5 mV at 2 mA cm−2. As coupled with the LiFePO4 (LFP), the Li@CD@RGCCF||LFP composite anode enables a high reversible specific capacity and improved cycle stability. This work provides a low-cost modification method for carbon substrate to realize dendritic-free LMAs.

Towards reusable 3D-printed graphite framework for zinc anode in aqueous zinc battery

Aqueous zinc ion batteries (AZIBs) are an increasingly popular high-safety and eco-friendly energy storage solution. However, the development of high-performance zinc (Zn) anodes remains a formidable challenge, primarily due to dendrite formation and poor reversibility. To address these challenges, this study harnesses the potential of digital light process (DLP) 3D printing technology to fabricate reduced graphite oxide-based 3D gyroid structure (3DP-rGG) as zinc anode frameworks for aqueous zinc batteries. The 3D-printed structure effectively regulates local current density distribution, offering ample nucleation sites and free space for inducing uniform zinc deposition and accommodating diminutive zinc nodules. Consequently, the 3D-printed graphite framework demonstrates remarkable reversibility in zinc plating and stripping processes, resulting in commendable coulombic efficiency and low voltage hysteresis. The full battery with a 3D-printed zinc anode, incorporating a polyaniline-intercalated vanadium oxide cathode (PVO), exhibits high specific capacity and superior long-term cycling stability. Remarkably, the robust 3DP-rGG structure can be reused over ten times without any discernible impact on its electrochemical performance, thereby underscoring the potential of this controllable and efficient fabrication of 3D graphite current collectors as a promising solution to develop reusable 3D frameworks for high-performance metal batteries.

Constructing 3D Zincophilic Skeleton in Nitrogen-Doped Carbon Hybrid Fibers for Dendrite-Free Zn Anodes.

The Zn dendrite growth and side reactions are two major issues for the practical use of Zn metal anodes (ZMAs). Herein, an N-doped carbon-based hybrid fiber with the 3D porous skeleton and the zincophilic Cu nanoparticles (denoted as Cu@HLCF) is developed for stable ZMAs. The zincophilic Cu particles in the skeleton work as the active sites to facilitate uniform Zn nucleation. Meanwhile, the abundant pores in the framework of the hybrid fibers provide a large space to relieve the structural stress and suppress the dendrite growth. Moreover, the good mechanical characteristics of the hybrid fiber ensure its high potential applications for flexible electronics. Theoretical analysis results disclose the strong interaction between Zn and Cu sites, and experimental results demonstrate the low voltage hysteresis, high reversibility, and dendrite-free behavior of the Cu@HLCF host for Zn plating/stripping. Moreover, the solid-state Zn-ion battery (ZIB) assembled with a Cu@HLCF/Zn anode shows the prominent flexibility, impressively reliability, and outstanding cycling capability. Therefore, this work not only provides a novel design for the efficient and stable Zn metal anode but also promotes the development of flexible power sources for flexible electronics.

Lithiophilic 3D scaffold orienteering induced Li uniform deposition for highly stable lithium metal batteries

With the restrict of dendrites growth and endless volume expansion, the practical application of lithium metal batteries is stagnant. Constructing 3D scaffold is an effective strategy, which is not only inhibiting the dendrites growth by redistribute the local current density, but also accommodating large volume fluctuate during Li metal plating/striping. Whereas, the “top-growth” mode of lithium deposit on current collector limited the utilization of 3D structure. Hence, Cu foam scaffold modified with ZnO coating is prepare through magnetron sputtering. The lithiophilic ZnO coating can adjusting electrons and Li+ distribution on the anode surface simultaneously, which can orienteering induce Li deposit on the bottom surface firstly, achieving “bottom-up” growth mode. Furthermore, benefiting from the reversible Li plating-striping behavior, the half-cell with CF-ZnO scaffold endows a longer lifespan at various current density, the symmetrical cell can stable cycle for more than 1100 h with steadily voltage hysteresis of 12 mV (1 mA cm−2, 1 mA h cm−2). For the practical application measurement, the LiFePO4 full cell has a lifespan for more than 1000 cycles with capacity retention of 79.19 % at 2 A g−1.

Reduced Order Electrochemical-Thermal Modeling of Cylindrical Cells Containing Graphite-Silicon Anodes Considering Thermal Gradients and Hysteresis

Electrochemical thermal modeling of cylindrical cells presents unique challenges compared to other cell formats due to the effect of internal temperature gradients, which typically requires time-consuming simulations due to the number of mesh elements solved numerically. Adding to the difficulty, the emergence of silicon anodes induces voltage hysteresis that affects the cell behavior. In this paper, a reduced-order electrochemical-thermal model is developed for a 21700 cell, which is highlighted by three microcells considering the effects of internal temperature gradients, and an anodic stress model capturing the hysteresis effects caused by the silicon content. The electrochemical, thermal, and mechanical behaviors are investigated. During operations, a temperature gradient arises in the radial direction, resulting in a decrease in local resistance and an increase in reaction rate at the high-temperature core location. The presence of silicon causes a voltage hysteresis that is dominant in the low SOC range, which affects not only the irreversible but also the entropic heat generation. The proposed method achieves an 85% calculation time reduction compared with the existing literature method and a 95% reduction compared with the full order method, while maintaining the accuracy of the terminal voltage and heat generation rate predictions that are validated by experiments.

Enhancing Zinc Electrode Stability Through Pre-Desolvation and Accelerated Charge Transfer via a Polyimide Interface for Zinc-Ion Batteries.

Aqueous zinc-based energy storage devices possess superior safety, cost-effectiveness, and high energy density; however, dendritic growth and side reactions on the zinc electrode curtail their widespread applications. In this study, these issues are mitigated by introducing a polyimide (PI) nanofabric interfacial layer onto the zinc substrate. Simulations reveal that the PI nanofabric promotes a pre-desolvation process, effectively desolvating hydrated zinc ions from Zn(H2O)6 2+ to Zn(H2O)4 2+ before approaching the zinc surface. The exposed zinc ion in Zn(H2O)4 2+ provides an accelerated charge transfer process and reduces the activation energy for zinc deposition from 40 to 21kJ mol-1. The PI nanofabric also acts as a protective barrier, reducing side reactions at the electrode. As a result, the PI-Zn symmetric cell exhibits remarkable cycling stability over 1200h, maintaining a dendrite-free morphology and minimal byproduct formation. Moreover, the cell exhibits high stability and low voltage hysteresis even under high current densities (20mA cm-2, 10 mAh cm-2) thanks to the 3D porous structure of PI nanofabric. When integrated into full cells, the PI-Zn||AC hybrid zinc-ion capacitor and PI-Zn||MnVOH@SWCNT zinc-ion battery achieve impressive lifespans of 15000 and 600 cycles with outstanding capacitance retention. This approach paves a novel avenue for high-performance zinc metal electrodes.

A simple and highly sensitive flexible sensor with extended-gate field-effect transistor for epinephrine detection utilizing InZnSnO sensing films

This study introduces a straightforward method for depositing InZnSnO films onto flexible polyimide substrates at room temperature, enabling their application in electrochemical pH sensing and the detection of epinephrine. A comprehensive analysis of these sensing films, spanning structural, morphological, compositional, and profiling characteristics, was conducted using diverse techniques, including X-ray diffraction, atomic force microscopy, X-ray photoelectron spectroscopy, and secondary ion mass spectroscopy. The investigation into the influence of oxygen flow rates on the performance of InZnSnO sensitive films revealed a significant correlation between their structural properties and sensing capabilities. Notably, exposure to an oxygen flow rate of 30/2 (Ar/O2) the ratio of resulted in the InZnSnO sensitive film demonstrating outstanding pH sensitivity at 59.58 mV/pH within a broad pH range of 2–12, surpassing the performance observed with other oxygen flow rates. Moreover, under this specific condition, the film exhibited excellent stability, with a minimal drift rate of 0.14 mV/h at pH 7 and a low hysteresis voltage of 1.8 mV during a pH cycle of 7 → 4→7 → 10→7. Given the critical role of epinephrine in mammalian central nervous and hormone systems, monitoring its levels is essential for assessing human health. To facilitate the detection of epinephrine, we utilized the carboxyl group of 4-formylphenylboronic acid to enable a reaction with the amino group of the 3-aminopropyltriethoxysilane-coated InZnSnO film. Through optimization, the resulting InZnSnO-based flexible sensor displayed a broad and well-defined linear relationship within the concentration range of 10−7 to 0.1 μM. In practical applications, this sensor proved effective in analyzing epinephrine in human serum, showcasing notable selectivity, stability, and reproducibility. The promising outcomes of this study underscore the potential for future applications, leveraging the advantages of electrochemical sensors, including affordability, rapid response, and user-friendly operation.

Redox Molecular Junction Metal-Covalent Organic Frameworks for Light-assisted CO2 Energy Storage.

Visible-light sensitive and bi-functionally favored CO2 reduction (CRR)/evolution (CER) photocathode catalysts that can get rid of the utilization of ultraviolet light and improve sluggish kinetics is demanded to conquer the current technique-barrier of traditional Li-CO2 battery. Here, a kind of redox molecular junction sp2c metal-covalent organic framework (i.e. Cu3-BTDE-COF) has been prepared through the connection between Cu3 and BTDE and can serve as efficient photocathode catalyst in light-assisted Li-CO2 battery. Cu3-BTDE-COF with redox-ability, visible-light-adsorption region, electron-hole separation ability and endows the photocathode with excellent round-trip efficiency (95.2 %) and an ultralow voltage hysteresis (0.18 V), outperforming the Schiff base COFs (i.e. Cu3-BTDA-COF and Cu3-DT-COF) and majority of the reported photocathode catalysts. Combined theoretical calculations with characterizations, Cu3-BTDE-COF with the integration of Cu3 centers, thiazole and cyano groups possess strong CO2 adsorption/activation and Li+ interaction/diffusion ability to boost the CRR/CER kinetics and related battery property.