Conductive 2D metal-organic framework for high-performance cathodes in aqueous rechargeable zinc batteries

Currently, there is considerable interest in developing advanced rechargeable batteries that boast efficient distribution of electricity and economic feasibility for use in large-scale energy storage systems. Rechargeable aqueous zinc batteries are promising alternatives to lithium-ion batteries in terms of rate performance, cost, and safety. In this investigation, we employ Cu3(HHTP)2, a two-dimensional (2D) conductive metal-organic framework (MOF) with large one-dimensional channels, as a zinc battery cathode. Owing to its unique structure, hydrated Zn2+ ions which are inserted directly into the host structure, Cu3(HHTP)2, allow high diffusion rate and low interfacial resistance which enable the Cu3(HHTP)2 cathode to follow the intercalation pseudocapacitance mechanism. Cu3(HHTP)2 exhibits a high reversible capacity of 228 mAh g−1 at 50 mA g−1. At a high current density of 4000 mA g−1 (~18 C), 75.0% of the initial capacity is maintained after 500 cycles. These results provide key insights into high-performance, 2D conductive MOF designs for battery electrodes.

S ocietal interest in energy storage systems (ESSs) has been increasing rapidly with the need to utilize and distribute effectively electricity generated using renewable energy sources [1][2][3] . Among the most suitable candidates for energy storage are lithium-ion batteries (LIBs) since they provide high performance in mobile devices, such as cellular phones and laptops. Their utilization, however, in large-scale applications, such as electric vehicles, is inhibited by high material costs and safety concerns 4,5 . In order to resolve the limitations of LIBs, numerous investigations [4][5][6][7] have been focused on greener electrode materials and aqueous electrolytes. From these perspectives, rechargeable aqueous zinc batteries (ZBs) have recently attracted [8][9][10][11][12][13] considerable attention for use in large-scale ESSs because of their high theoretical capacity (820 mAh g −1 ), their low toxicity, and the relatively low cost of zinc 14 . Furthermore, ZBs operate in aqueous electrolytes 4,5 , thereby gaining additional advantages related to safety, cost, and rate performance.
Despite all these advantages, rechargeable ZBs have several obstacles that need to be addressed before they can hope to replace LIBs in terms of electrochemical performance 15,16 . In particular, the development of a new high-performance cathode is crucial for the commercialization of ZBs. α-MnO 2 with a 2 × 2 tunnel structure has been used 14 as a rechargeable ZB cathode, in which the large tunnels facilitate Zn 2+ ion diffusion within the host structure, providing high capacity and rate performance. These materials, however, are associated with low cyclability that can be attributed 15,16 to an unstable phase transition from a tunneled to a layered structure with simultaneous Mn 2+ dissolution during the discharge-charge process. Vanadium-based cathodes 8,17 also provide high capacity and rate performance, although the costliness of vanadium prohibits large-scale energy storage applications. Recently, organic-based cathodes, such as quinone derivatives, have been investigated because they are low cost, ubiquitous, and lightweight compared with inorganic cathodes 13,18 . Dissolution issues, however, during battery cycling inhibit the use of quinone derivatives in ZBs. In an effort to improve the stability of the quinone-based materials, polymerization 19 , carbon composites 20 , and an extended analog 13 have all been explored: the dissolution issues, however, of organic cathodes remain a drawback. Reflecting on all these difficulties, the development of new materials for ZB cathodes is a necessity.
Conductive metal-organic frameworks (MOFs) provide excellent platforms for resolving dissolution issues, related to organicbased cathodes. In these MOFs, the active organic species are immobilized by metal-ligand coordinate covalent bonds. In addition, their porous structures and electrical conductivities are favorable to ion and electron transport in the framework, improving high rate capability and cyclability. The potential applications of these materials in batteries has been confirmed, with high performance being achieved in electrochemical doublelayer capacitors 21,22 and Na + storage 23 , as well as in reports of their use in various battery systems [24][25][26][27] .
Here, on account of these properties, we have tested the electrochemical performance of the Cu 3 (HHTP) 2 cathode. Cu 3 (HHTP) 2 shows redox switching at 1.06 V and 0.88 V vs. Zn/ Zn 2+ with the highest reversible capacity of 228 mAh g −1 at 50 mA g −1 to the best of our knowledge. These reversible capacities in rechargeable aqueous ZBs are the first example in MOFs and one of the highest reported values for cathodes with open-framework structures, including Prussian Blue analogs [31][32][33] that have exhibited substantially smaller values of <70 mAh g −1 at similar current densities. In addition, the high diffusion rate of Zn 2 + ions and low interfacial resistance by the insertion of hydrated Zn 2+ ions allows Cu 3 (HHTP) 2 to follow the intercalation pseudocapacitance mechanism. As a consequence, Cu 3 (HHTP) 2 achieves a high rate performance and cyclability, indicating that 75.0% of the initial capacity (124.4 mAh g −1 ) is maintained after 500 cycles at an extremely high current density of 4000 mA g −1 (~18 C). This work reveals the reason for the observed high rate performance and charge-storage mechanism of the Cu 3 (HHTP) 2 , which is poised to facilitate the development of 2D conductive MOFs for energy storage.
A transmission electron microscopy (TEM) image also reveals ( Supplementary Fig. 2a) the one-dimensional (1D) nanorod structure of Cu 3 (HHTP) 2 . The length of the Cu 3 (HHTP) 2 nanorods extends ( Fig. 2b and Supplementary Fig. 1a (Fig. 2f) from the selected area ( Fig. 2e) indicates clearly that the Cu 3 (HHTP) 2 nanorods have well developed (100) and (200) planes. These planes indicate 28 that the as-synthesized Cu 3 (HHTP) 2 is highly crystalline in nature with the [100] axis being the preferred orientation for the 1D nanorods. The unique structure of Cu 3 (HHTP) 2 , along with the shape of the 1D nanorods and the large pores, facilitate the diffusion of Zn 2+ ions during the discharge-charge process. In addition, scanning electron microscopy-energy-dispersive Xray spectroscopy (SEM-EDX) was used to verify ( Supplementary  Fig. 1c, d) Fig. 3) that the Zn 2+ insertion and extraction reaction is reversible. The reaction of Zn 2+ ions with Cu 3 (HHTP) 2 occurs reversibly at approximately 0.65/1.10 V and 0.90/1.21 V (vs. Zn/ Zn 2+ ), respectively. Galvanostatic tests revealed that this reversibility is reflected (Fig. 3a) in the voltage profiles, with plateaus at the corresponding voltages. The first discharge plateau at~0.90 V (vs. Zn/Zn 2+ ) originates from the redox process between Cu 2+ and Cu + . Furthermore, the second discharge plateau at 0.65 V (vs. Zn/Zn 2+ ) may be attributed to a two-electron uptake associated with the HHTP linkers. A detailed redox reaction mechanism is discussed in the upcoming sections. The initial reversible capacity is 228 mAh g −1 at a rate of 50 mA g −1 , followed by a capacity of 215 mAh g −1 in the second cycle, and the voltage profiles and capacity are retained ( Fig. 3a  In order to verify the influence of the Cu 3 (HHTP) 2 2D structure with large pores on the electrochemical performance, we conducted rate-capability tests. In these electrochemical tests, Cu 3 (HHTP) 2 demonstrated excellent rate capability (Fig. 3b). The Cu 3 (HHTP) 2 electrode exhibited capacities of 191.4, 189.2, 152.4, and 124.5 mAh g −1 when the current density was increased, respectively, by 2, 4, 10, and 80 times (100, 200, 500, and 4000 mA g −1 ) from 50 mA g −1 . These results correspond to capacity retentions of 89.0%, 88.0%, 70.9%, and 57.9%, respectively, with respect to the initial capacity of 215.0 mAh g −1 . Moreover, the Cu 3 (HHTP) 2 electrodes show promising cycling stability. At a current density of 500 mA g −1 (~2 C), 75.0% of the initial capacity (152.5 mAh g −1 ) was maintained (Fig. 3c) after 100 cycles. In addition, by increasing the mass loading of active materials from 60 to 90%, although the initial capacity decreased slightly to 125 mAh g −1 at 500 mA g −1 ( Supplementary Fig. 5a), the retention of capacity after 100 cycles was 76% of the initial capacity ( Supplementary Fig. 5b). This capacity retention for a 90% active materials loading electrode is almost identical to that of a 60% active materials loading electrode. Furthermore, at an extremely high current density of 4000 mA g −1 (~18 C), 75.0% of the initial capacity (124.4 mAh g −1 ) was maintained (Fig. 3d) after 500 cycles. This cyclability reflects the structural stability of Cu 3 (HHTP) 2 during repeated (de)intercalation of the Zn 2+ ions.
Origin of high rate performance of Cu 3 (HHTP) 2 . In order to investigate more detailed reasons for the high rate performance of Cu 3 (HHTP) 2 , diffusion coefficient and interfacial resistance studies were carried out. The Zn 2+ ion diffusion coefficient of Cu 3 (HHTP) 2 was obtained by applying galvanostatic intermittent titration technique (GITT) measurements; See the Supplementary Note 1 for details. The overall diffusion coefficient of Zn 2+ ions in Cu 3 (HHTP) 2 over the whole potential range was 3.9 × 10 −10 cm 2 s −1 ( Supplementary Fig. 6), which is similar to that of single crystalline Zn 0.25 V 2 O 5 ·nH 2 O nanobelts 8 . Specifically, by excluding the loss of diffusion coefficient from the high overpotential of the copper redox region, attributed to the self-discharge, and calculating the diffusion coefficient only with the main redox region of the quinoid, the diffusion coefficient of Zn 2+ ions in Cu 3 (HHTP) 2 showed 1.2 × 10 −9 cm 2 s −1 ( Supplementary Fig. 6), indicating fast redox reactions.
Furthermore, an interfacial resistance between the electrode and the electrolyte was studied in order to determine the rate performance of electrode materials. In order to investigate the interfacial resistance of the Cu 3 (HHTP) 2 electrode, an electrochemical impedance spectroscopy (EIS) investigation was conducted with symmetric cells of the Cu 3 (HHTP) 2 electrodes in aqueous or organic electrolytes. Notably, the interfacial resistance of Cu 3 (HHTP) 2 showed 150 and 16,000 Ω cm 2 ( Supplementary  Fig. 7), and obtained conductivities from these interfacial resistances of Zn 2+ ions are 0.7 × 10 −2 and 0.6 × 10 −5 S cm −1 ( Supplementary Fig. 7 2 was studied in an organic electrolyte. On account of the high interfacial resistance caused by the organic electrolyte, the initial discharge capacity of Cu 3 (HHTP) 2 decreased to 144 mAh g −1 at a rate of 50 mA g −1 , and the subsequent charging reaction almost did not occur because of the high overpotential ( Supplementary Fig. 9a). This phenomenon which is also evident [35][36][37] in the case of Mg 2+ ions in organic electrolytes, is caused by the strong interaction of divalent ions with the cathode, i.e., extracting of divalent ions from the host electrode is unfavorable [35][36][37] . As a result of this phenomenon, the capacity retention of Cu 3 (HHTP) 2 in the organic electrolyte was almost zero (Supplementary Fig. 9b). In total, the origin of the high rate properties of Cu 3 (HHTP) 2 is thought to be a consequence of the high diffusion rate of Zn 2+ ions in the cathode and low interfacial resistance by the hydrated Zn 2+ ion insertion.
Electronic states analysis during discharge-charge. With a view to investigating changes in the electronic states of Cu 3 (HHTP) 2 during discharge-charge, X-ray photoelectron spectroscopy (XPS) was conducted on the Zn, O, and Cu elements. After inserting Zn 2+ ions into the Cu 3 (HHTP) 2 , the Zn 2p peaks appear and disappear ( Fig. 4a and Supplementary Fig. 10) at the discharged and charged states, respectively; this behavior is a consequence of the reversible insertion/extraction of Zn 2+ into/from the Cu 3 (HHTP) 2 cathodes. The quinoid peak at 532 eV shifts (Fig. 4b) to a benzoid peak at 533 eV in the O 1s spectrum, while discharging from 0.8 V (point b in Fig. 3a) to a fully discharged state (point c in Fig. 3a). The peaks which had shifted returned to their original positions, while charging from the fully discharged state (point c in Fig. 3a) to 1.15 V (point d in Fig. 3a). This shift reveals that the second plateau (Fig. 3a), which exists during the discharge process, originates from the quinoid structure acting as a redox center. Based on these XPS results, we infer that the  quinoid structure is involved in the redox reaction; a similar redox mechanism was reported 26 for Cu(2,7-AQDC) MOF (2,7-H 2 AQDC = 2,7-anthraquinonedicarboxylic acid), where oxygen and copper are the redox centers for LIBs. Similarly, the presence of transition metals involved in the redox reaction in our system causes the peaks of Cu 2+ satellites in the pristine state to disappear (Fig. 4c). The Cu 2p peaks then separate into lower binding-energy peaks between the pristine state (point a in Fig. 3a) and 0.8 V (point b in Fig. 3a) in the Cu 2p spectrum (Fig. 4c). There is then no further shift in the Cu 2p peaks that lie between 0.8 V (point b in Fig. 3a) and 1.15 V (point d in Fig. 3a). As expected, the initial Cu 2p spectrum was reinstated, including its original profiles, between 1.15 V (point d in Fig. 3a) and the fully charged state (point e in Fig. 3a). From these changes in the Cu 2p peaks, the first plateau (Fig. 3a) that appears during the discharge process can be attributed to a partial redox reaction from Cu 2+ to Cu + . Consequently, these XPS analyses suggest that both the quinoid component and the copper in Cu 3 (HHTP) 2 participate as redox centers during the discharge-charge process. The theoretical capacity of Cu 3 (HHTP) 2 should be 197 mAh g −1 , when using the quinoid structure as the redox center and inserting Zn 2+ ions with two electrons. The initial capacity determined (Fig. 3a), however, for Cu 3 (HHTP) 2 is 228 mAh g −1 , revealing that these Cu 3 (HHTP) 2 cathodes can obtain 2.3 electrons (Fig. 1c). In light of these XPS results, the additional discharge capacity of Cu 3 (HHTP) 2 , equivalent to 0.3 electrons, can be derived from the redox events of Cu 2+ . In order to identify the redox center of Cu 3 (HHTP) 2 , density functional theory (DFT) calculations were performed. When supplying 6.9 extra electrons to Cu 3 (HHTP) 2 , Cu atom, as well as to the linker, takes of the additional electron (Fig. 4d), indicating that Cu atoms participate in the reduction reaction; See the Supplementary Note 2 for details. In the density of states (DOS) analysis ( Supplementary  Fig. 11), the electronic states just above the Fermi level consist of O, C, and Cu. This result supports the observed redox events occurring at these atoms. Furthermore, both peaks of O 1s and Cu 2p of the charged electrode after 500 cycles at a rate of 4000 mA g −1 (Fig. 4b, c) are more or less similar to those of the pristine electrode, indicating that the redox reaction of Cu 3 (HHTP) 2 is highly reversible.
Structure analysis during discharge-charge. The PXRD patterns of Cu 3 (HHTP) 2 in the discharged (inserting Zn 2+ ions into Cu 3 (HHTP) 2 ) electrode demonstrate that the (100) peak has a slight right-side shift from 4.70°to 4.85°, revealing (Fig. 5a) that the pore size in Cu 3 (HHTP) 2 decreases from 19.3 to 18.7 Å. This change indicates that inserting Zn 2+ ions into Cu 3 (HHTP) 2 decreases the pore size of Cu 3 (HHTP) 2 as a result of the electrostatic interaction between divalent Zn 2+ cations and the oxygen anion of the host structure. With the exception of peak shifts following Zn 2+ insertion, no changes (appearance or disappearance of peaks) are observed, indicating that the discharge process does not include H + insertion accompanied by the formation of the Zn(OH) 2 analog 39 . After the charge process (extracting Zn 2+ ions from Cu 3 (HHTP) 2 ), the PXRD peaks in the charged electrode return fully (Fig. 5a) to the position of the original pristine state. In addition, after 500 cycles at a rate of 4000 mA g −1 , the PXRD patterns of Cu 3 (HHTP) 2 are identical (Fig. 5a) Fig. 12b, d), is almost the same (Supplementary Fig. 12a, c) as that of Cu 3 (HHTP) 2 in a pristine state. In addition, ion-exchange from Cu 2+ to Zn 2+ ions is endothermic by 0.8 eV per ion, according to DFT calculations ( Supplementary Fig. 13), indicating the high stability of Cu 3 (HHTP) 2 against Zn 2+ substitution. Consequently, the PXRD results lead us to infer that the Zn 2+ ions are accommodated in the large pores of Cu 3 (HHTP) 2 , thus enabling high long-term stability while cycling at a high rate.
Confirmation of inserting Zn 2+ ions into the pore structure of Cu 3 (HHTP) 2 . The uniform presence of Zn 2+ ions in Cu 3 (HHTP) 2 nanorods was confirmed (Fig. 5b) by EDX chemical mapping which shows uniform distribution of Zn ions over the entire electrode area at the fully discharged state. In order to elucidate the consequences of the insertion of Zn 2+ ions into the pores of Cu 3 (HHTP) 2 , the lattice parameter changes were analyzed (Fig. 5c) with LD-HRTEM in the discharged state. Significantly, after inserting Zn 2+ ions into Cu 3 (HHTP) 2 nanorods, the lattice distance of the (100) plane (inset of Fig. 5c, d) decreases slightly to 1.87 nm, demonstrating the same tendency observed (Fig. 5a) in the PXRD patterns. In addition, selected-area diffraction patterns from pristine and discharged samples (Fig. 5e, f) demonstrate that the (100) lattice distance decreases from 2.01(±0.01) nm to 1.90(±0.01) nm, in the consequent interaction of divalent cations inserted into the pores of the framework. This result verifies the fact that Zn 2+ ions are inserted into the pores in MOFs in a battery system.
Charge-storage mechanism of Cu 3 (HHTP) 2 . In order to understand the charge-storage mechanism of Cu 3 (HHTP) 2 , CV measurements were carried out using various scan rates (Fig. 6a). Currents depending on the scan rates study enables determining bvalues from the equation of a power law [40][41][42][43][44][45] : i = aν b where i is the current (A), v is the potential scan rate (V s −1 ), a and b are arbitrary coefficients. Generally, battery electrode materials are characterized by b = 0.5, indicating a semi-infinite diffusion process [40][41][42][43][44][45] , whereas the closer the b-values are to 1, the closer to the capacitive contribution. The b-values are the slope obtained by plotting the peak currents (i) and scan rates (ν) in a log plot ( Supplementary Fig. 14a) with an assumption that the current obeys the power-law relationship. The b-values of Cu 3 (HHTP) 2 are above 0.85 within all operating voltage ranges (Fig. 6b), indicating the operating mechanism is not dominated by diffusion. Furthermore, for quantitative analysis of capacitance, the scan rate dependence of the current was plotted ( Supplementary  Fig. 14b). The capacitive effect (k 1 ν) and diffusion-controlled insertion (k 2 ν 1/2 ) could be calculated with the plot, see the Supplementary Note 3 for details. The capacitive contribution was 83% (Fig. 6c) out of the total current, at a scan rate of 0.5 mV s −1 , indicating the total energy storage in Cu 3 (HHTP) 2 arises from a capacitive process rather than the solid-state diffusion of Zn 2+ in Cu 3 (HHTP) 2 . Unlike a non-Faradaic surface adsorption present in the typical responses of a capacitor, reversible redox peaks on CV profiles (Fig. 6a, c) and the reversible shifts of (100) peaks in PXRD (Fig. 5a) during the discharge-charge process were observed, indicating that the Cu 3 (HHTP) 2 follows an intercalation pseudocapacitance charge-storage mechanism [41][42][43][44][45] . In this mechanism, charge-storage occurs by intercalation/deintercalation of cations in the bulk active materials, and its kinetics are not limited by the diffusion of the cations. As a consequence, the advantage of batteries (high capacitance) and supercapacitors (high rate) are integrated into one system. In addition, a self-discharge test 46 was carried out to confirm the ability of charge-storage, and Cu 3 (HHTP) 2 showed (Fig. 6d) remarkably low self-discharge rate of 0.003 V h −1 . The loss of the capacity during self-discharge mainly occurs near the Cu redox region above 0.9 V, agreeing well with the GITT study ( Supplementary Fig. 6). Furthermore, after 5 days of storage, 83% of the initial capacity was still maintained (inset of Fig. 6d) and therefore proving its outstanding stability in the fully charged state.

Discussion
In summary, we have demonstrated a Cu 3 (HHTP) 2 2D conductive MOF that may be utilized as a ZB cathode. The solid-state structure of Cu 3 (HHTP) 2 , with a high diffusion rate of Zn 2+ ions, and low interfacial resistance caused by the insertion of hydrated Zn 2+ ions, as a result of the large open channel structures, provides an increased rate performance and cyclability compared with those of conventional organic-based materials. In addition, the kinetic analyses of the electrochemical behavior of Cu 3 (HHTP) 2 obtained by CV suggest that the charge-storage mechanism of Cu 3 (HTTP) 2 is intercalation pseudocapacitance, indicating that the mechanism is not determined by diffusion. Furthermore, XPS measurements and DFT calculations suggest that Cu 3 (HHTP) 2 utilizes both copper and the quinoid structure as redox-active sites, increasing the specific capacity of the material. In addition, the PXRD and LD-HRTEM data indicate that inserted Zn 2+ ions are stored in the Cu 3 (HHTP) 2 pores. These findings point to the potential of these cathodes for use in large-scale applications. This investigation paves the way for the further exploration of 2D conductive MOFs with other transition metals that could increase their redox potential, thus improving the performance of 2D conductive MOF-based ZB cathodes.

Methods
Materials. All commercially available reagents and solvents were purchased from Sigma-Aldrich and used as received without further purification. Zn and SUS films were purchased from Goodfellow. All the parts for making coin cells were obtained from Pred Materials International. Cu 3 (HHTP) 2 was prepared according to a previously reported procedure 28 , washed with deionized H 2 O and Me 2 CO, respectively, and dried in air.
Characterization. The morphology of powder and elementary analysis was obtained by field-emission scanning electron microscopy (FE-SEM, Hitachi S-4800) with implemented energy-dispersive X-ray spectroscopy (EDX, Oxford Aztec X-max 80 SDD EDX detector). Images were acquired at a working distance of 7 mm with an electron beam energy of 20 kV and emission current of 20 µA. In order to investigate the H 2 O content after the discharge process, thermogravimetric analysis (TGA, Netzsch Jupiter) was performed by raising the temperature from room temperature to 300°C at a ramp rate of 5°C min −1 under an Ar flow. Powder X-ray diffraction (PXRD, STOE STADI-P) with Cu-Kα1 radiation was measured through transmission geometry for crystal structure analysis by scanning in the 2θ range of 2°-90°with scan steps of 0.015°with accelerating voltage and current of 40 kV and 40 mA. For the characterization of Cu 3 (HHTP) 2 at different charge and discharge states, the cells were opened and rinsed with deionized H 2 O inside a glove-box. The oxidation states of electrodes were analyzed by X-ray photoelectron spectroscopy (XPS, Thermo scientific ESCALAB 250Xi). Each sample was dried under vacuum for 1 h prior to XPS measurements. For the ex situ XPS characterization of Cu 3 (HHTP) 2 at different charge and discharge states, the cells were opened and rinsed with deionized H 2 O inside a glove-box. The electrical conductivity of Cu 3 (HHTP) 2 was measured by the two-point probe method at 25°C. A pellet was placed on a home-built in situ pellet press 47 and connected to an electrometer (Keithley 4200-SCS). The current-voltage (I-V) measurements were performed at 25°C by sweeping the voltage.
Transmission electron microscopy. Pristine and discharged Cu 3 (HHTP) 2 MOF samples were dispersed in EtOH and drop-cast on lacey carbon Mo-based TEM grids. LD-HRTEM was performed using a JEOL Grand ARM instrument operated at 300 kV. Data were collected using a Gatan K3-IS direct electron detector. In order to avoid MOF structure degradation under electron beams, images were collected at dose rates below 20 e − /pixel/s and the cumulative dose in the range of 15-20 e − /A [2 48 . For selected-area diffraction (SAD), the electron beam was spread out and with data acquired at low magnification to avoid sample damage. SAD Patterns were collected using a Gatan OneView camera. EDX data were collected using an SDD EDX detector.
Electrochemical tests. In order to investigate the electrochemical performance of Cu 3 (HHTP) 2 as a cathode in zinc batteries, coin cells with a two-electrode configuration-which comprise a Cu 3 (HHTP) 2 cathode and a Zn-film anode (100 μm in thickness)-were assembled. The Cu 3 (HHTP) 2 electrode was first of all prepared by making a slurry containing Cu 3 (HHTP) 2 :acetylene black:poly(vinylidene difluoride) (PVDF) in the ratio of 60:20:20 or 90:5:5 in 1-methyl-2-pyrrolidinone (NMP), respectively. The slurry was then cast onto stainless steel (SUS 304) foil, followed by drying at 70°C in a vacuum oven. The mass loading of the active material in each electrode was 2 mg cm −2 . The electrolyte solution was 3 M and 0.25 M zinc trifluoromethanesulfonate (Zn(CF 3 SO 3 ) 2 ) in deionized H 2 O and acetonitrile (MeCN), respectively. All cells were aged for 1 h prior to initiating electrochemical processes to ensure good soaking of the electrolyte solution into the electrodes. The cells were cycled in the voltage range of 0.5-1.3 V (vs. Zn/ Zn 2+ ). All measurements were made at 25°C using a battery tester (BST8-300-CST, MTI, USA). All galvanostatic measurements were recorded in the constant current mode (no constant voltage steps). CV was carried out using coin cells with a two-electrode configuration, which comprise the Cu 3 (HHTP) 2 cathode and the Zn-film anode (Reference 600 potentiostat, Gamry Instruments, USA). EIS measurements were performed on symmetric cells over the frequency range of 0.01 Hz-1 MHz with an input voltage amplitude of 10 mV (Reference 600 potentiostat, Gamry Instruments, USA).
DFT calculations. These calculations were performed using the Perdew-Burke-Ernzhof (PBE) exchange-correlation functional 49 and the projector-augmented wave (PAW) method 50 as implemented in the VASP 51 . An energy cutoff of 520 eV was used and the gamma centered single k-point was sampled for integration because of the large cell size. A Grimme's dispersion correction (D3) with a zero damping was also applied 52 . The convergence criteria were 10 −6 eV and 0.02 eV Å −1 for the electronic and ionic cycles, respectively. The monolayer of Cu 3 (HHTP) 2 was assumed because the long-range order of Cu 3 (HHTP) 2 has not yet been identified. In order to avoid a fictitious interaction between layers, the vacuum layer along the z-direction was set to be~20 Å so that the lattice size was 21 × 21 × 20 Å. In order to represent the reduction of Cu 3 (HHTP) 2 , we supplied extra electrons to the pristine state and the chargedensity difference between the reduced and pristine states was illustrated using the VESTA software 53 . In order to estimate the ion-substitution energy, we employed the hydrated Zn 2+ and Cu 2+ states as the reference. To this end, an implicit solvent model 54 was applied and a higher energy cutoff (650 eV) was used.
Data availability