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A high capacity small molecule quinone cathode for rechargeable aqueous zinc-organic batteries

A high capacity small molecule quinone cathode for rechargeable aqueous zinc-organic batteries ARTICLE https://doi.org/10.1038/s41467-021-24701-9 OPEN A high capacity small molecule quinone cathode for rechargeable aqueous zinc-organic batteries 1 1 1 1 1 1 Zirui Lin , Hua-Yu Shi , Lu Lin , Xianpeng Yang , Wanlong Wu & Xiaoqi Sun Rechargeable aqueous zinc-organic batteries are promising energy storage systems with low- cost aqueous electrolyte and zinc metal anode. The electrochemical properties can be sys- tematically adjusted with molecular design on organic cathode materials. Herein, we use a symmetric small molecule quinone cathode, tetraamino-p-benzoquinone (TABQ), with desirable functional groups to protonate and accomplish dominated proton insertion from weakly acidic zinc electrolyte. The hydrogen bonding network formed with carbonyl and amino groups on the TABQ molecules allows facile proton conduction through the Grotthuss- type mechanism. It guarantees activation energies below 300 meV for charge transfer and −1 −1 proton diffusion. The TABQ cathode delivers a high capacity of 303 mAh g at 0.1 A g in a −1 −1 zinc-organic battery. With the increase of current density to 5 A g , 213 mAh g capacity is still preserved with stable cycling for 1000 times. Our work proposes an effective approach towards high performance organic electrode materials. 1 ✉ Department of Chemistry, Northeastern University, Shenyang, China. email: [email protected] NATURE COMMUNICATIONS | (2021) 12:4424 | https://doi.org/10.1038/s41467-021-24701-9 | www.nature.com/naturecommunications 1 1234567890():,; ARTICLE NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-021-24701-9 echargeable lithium-ion batteries have been widely used in aqueous zinc-organic batteries. The four amino groups are 1–5 portable electronics and electric vehicles . However, cost available for protonation in weakly acidic zinc electrolytes, which Rand potential safety issues restrict their application areas would create a proton active environment and initiate proton 6–10 and scales . Rechargeable aqueous batteries using aqueous insertion. At the same time, hydrogen bonds are formed among electrolytes largely reduce those concerns and experience rapid amino and carbonyl groups, so that the compound does not development in the past few years. The zinc metal is a desirable sublimate even at elevated temperatures. More importantly, the anode for aqueous systems and delivers high theoretical specific hydrogen bonding network allows facile proton conduction −1 capacity (820 mAh g ), low redox potential (-0.76 V vs. S.H.E.) through the breaking and reforming of hydrogen bonds. The 11–13 as well as good compatibility with water . The research on TABQ electrode thus functions with dominated proton de/ suitable cathode materials to couple with the zinc anode mainly intercalation and experiences low activation energies for charge focuses on inorganic compounds such as metal oxides, Prussian transfer and diffusion. Excellent electrochemical performance is 14–17 blue salts and polyanion compounds . Among them, man- achieved. 18–21 ganese oxides and vanadium oxides deliver high capacities; however, problems such as active material dissolution are important challenges for their further applications . Results In comparison to inorganic materials, organic compounds are The TABQ active material is soluble in N-Methyl-2-pyrrolidone less explored as cathode materials for aqueous batteries . (NMP), and it undergoes a dissolution-reprecipitation process Nevertheless, organic compounds are more flexible with mole- during electrode manufacturing. Figure 1a shows the Fourier cular design, which allows the systematic adjustment of voltage, transform infrared (FT-IR) spectrum of the TABQ active material capacity, conductivity, redox kinetics and other properties for after drying out from NMP (no carbon and binder). The multiple 23–25 −1 electrode materials . For example, Koshika et al. attached the absorption peaks between 3469 and 3262 cm (purple part) electrochemically active 2,2,6,6-tetramethylpiperidine-1-oxyl to belong to the N-H stretching vibrations with different symmetry the poly(vinyl ether) chain in order to avoid dissolution. The modes from the four amino groups in TABQ. Notably, a broad −1 obtained electrode delivers 131 mAh g capacity and excellent band shows up on the right side as highlighted in cyan. It suggests rate capability with the facile radical-involved redox process . the redshift of part of the N-H stretching vibration peak, which is 38,39 Our group showed that sulfo group can be introduced to the six- a typical behavior upon the formation of hydrogen bonds . membered carbon ring of polyaniline to function as an internal Another site available for forming hydrogen bonds with amino is proton reservoir and retain a locally high acidic environment. The oxygen on carbonyl in the case of TABQ. Correspondingly, the −1 electrochemical activity of polyaniline is therefore maintained in carbonyl stretching vibration at 1547 cm in TABQ (pink part) 27 −1 the weakly acidic Zn electrolyte . experiences more than 100 cm of redshift in comparison to −1 Among organic materials, quinone compounds show good 1661 cm in benzoquinone (spectral database for organic com- environmental friendliness. They widely exist in nature, and the pounds SDBS). Although the electron-donor property of amino redox process between quinone and hydroquinone is an impor- also causes the redshift of carbonyl, such a significant shift results 28 37,40 tant physiological progress in living organisms . The excellent from additional effects, i.e., the hydrogen bonding . Finally, −1 redox activity of quinones also makes them desirable cathode the peaks in the range of 1700–1270 cm shown in green belong materials for aqueous zinc batteries. Zhao et al. reported a calix[4] to the vibrations of the six-membered carbon ring containing quinone (C4Q) molecule, where each benzoquinone unit is carbon–carbon single bonds, double bonds and their synergistic connected by C-C single bond to form a bowl-like structure. The effects. −1 −1 28 cathode displays a high capacity of 335 mAh g at 20 mA g . The above analysis on FT-IR demonstrates the formation of Nam and co-workers designed a medium molecular weight qui- hydrogen bonds with the amino and carbonyl functional groups none compound, triangular macrocyclic phenanthrenequinone in TABQ molecules. It results in strong interactions between 2+ (PQ-Δ), which allows the co-insertion of Zn and water and adjacent molecules and furthermore affects the physical and −1 −1 29 delivers a specific capacity of 225 mAh g at 30 mA g . Guo chemical properties. We studied the sublimation behavior of et al. proposed a pyrene-4,5,9,10-tetraone (PTO) cathode, TABQ using the setup shown in Supplementary Fig. 1, and −1 −1 30 achieving 336 mAh g capacity at 40 mA g . benzoquinone was applied as the comparing standard. When the 2+ Zn de/intercalation is demonstrated for most quinone benzoquinone powder was heated at 90 °C for 3 h in the oven, no materials in zinc cells; however, the diffusion of multivalent original powder is left and yellow crystals are condensed all over cation could be sluggish . On the other hand, the facile insertion the flask which stayed at room temperature (Fig. 1b). It of proton into cathode materials from weakly acidic zinc elec- demonstrates the sublimation of benzoquinone. With TABQ, on 2+ trolytes is possible with the hydrolysis of Zn to continuously the contrary, the original powder remains on the aluminum cover 31–33 generate proton , and proton could take part in the redox which stayed in the oven and the flask is completely clear 34–36 process of quinones . Besides, most of the previously studied (Fig. 1c). The same phenomenon is observed even with more quinone-based compounds are relatively complex in molecular elevated temperature of 150 °C (Fig. 1d). In addition, thermo- structures and require multi-step synthesis procedures. In com- gravimetric analysis (TGA) with constant temperature hold at 90 parison, small molecule quinones provide the advantage of simple °C shows continuous weight loss of benzoquinone as a result of synthesis, corresponding to a reduced cost. However, many small sublimation, whereas a stable weight evolution is obtained with quinone molecules, such as benzoquinone, are prone to sub- TABQ (Fig. 1e). The above analysis confirms the introduction of limation. It leads to difficulties in electrode manufacturing, hydrogen bonds effectively suppresses the sublimation of small handling and storage. Another important concern of small molecule quinone. It would provide convenience for various molecules is their relatively high solubility, resulting in the electrode treatments. shuttling of active material in electrolytes and capacity decay. The solubility of TABQ in 1 M ZnSO , which is a conventional Nevertheless, previous studies have shown that molecules with electrolyte for zinc batteries, was quantified by UV–vis analysis high symmetry possess low dipole moments and thus low solu- (Fig. 1f) . The saturated concentration was determined to be 37 −1 bilities in aqueous solutions . Considering the above factors, we 1.7 mmol L . This low solubility would ensure stable cycling in herein specifically apply a symmetric small molecule of aqueous zinc cells. The relationship between molecular structure tetraamino-p-benzoquinone (TABQ) as the cathode material for and solubility is further studied by comparing with related 2 NATURE COMMUNICATIONS | (2021) 12:4424 | https://doi.org/10.1038/s41467-021-24701-9 | www.nature.com/naturecommunications NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-021-24701-9 ARTICLE Fig. 1 Characterizations of TABQ. a FT-IR spectrum of TABQ. b, c, d Sublimation test of benzoquinone and TABQ at 90 °C and 150 °C. e TGA curves of benzoquinone and TABQ with constant temperature hold at 90 °C. f UV-vis calibration curve of TABQ in 1 M ZnSO together with the calculation of the 100 times diluted saturated solution. g SEM image of the TABQ electrode. compounds of tetrahydroxy-p-benzoquinone (THBQ), tetrachloro- is majorly contributed by the TABQ active material. With the −1 o-benzoquinone (o-TCBQ) and tetrachloro-p-benzoquinone (p- increase of current density to 5 A g , the TABQ cathode still −1 −1 TCBQ). UV–vis analysis results in the solubilities of 3.4 mmol L maintains 213 mAh g capacity. It suggests the excellent electro- −1 and 2.3 mmol L for THBQ and o-TCBQ, respectively (Supple- chemical activity of both carbonyl groups on TABQ. Figure 2c −1 mentary Fig. 2), and very trace dissolution of p-TCBQ is noticed. shows the differential capacity curve at 0.1 A g .Two pairsofredox Literature also demonstrated the insoluble nature of p-TCBQ . peaks are observed at 0.90 V/1.02 V and 0.77 V/0.83 V, respectively. Comparing among the p-quinones, the higher solubilities of TABQ The small overpotential demonstrates the good cation de/insertion and THBQ than p-TCBQ should be attributed to the more kinetics into TABQ. The electrochemical performance of TABQ is hydrophilic amino or hydroxyl functional groups. Nevertheless, the compared with previously reported quinone cathode materials in 28 29 30 41 solubilities are still quite low thanks to their highly symmetric zinc-organic batteries, including C4Q ,PQ-Δ ,PTO ,TCBQ , 37 42 43 molecular structures and thus low dipole moments . For example, HqTp , poly(benzoquinonyl sulfide) (PBQS) and dibenzo[b,i] the p-TCBQ molecule is more symmetric than o-TCBQ and pre- thianthrene-5,7,12,14-tetraone (DTT) .Asshown in Fig. 2d, TABQ −1 sents lower solubility. delivers the highest capacity at 0.1 A g and presents the best rate Figure 1g shows the scanning electron microscopy (SEM) capability. Figure 2e and Supplementary Fig. 5 show the long-term −1 image of the TABQ electrode. The TABQ active material forms as cycling behavior. At the current density of 5 A g ,the TABQ thin layer and is homogeneously distributed over Ketjen Black cathode exhibits stable capacity retention for over 1000 cycles after (KB) spherical particles, resulting in a conductive network with slight capacity decay during the first few cycles. The coulombic porous structure. The effective interaction between TABQ and efficiencies are close to 100%. FT-IR and SEM analysis on the carbon would ensure good electrical conductivity in electrodes. electrode after 1000 cycles verifies the excellent compositional and Comparing with the high crystallinity of as-prepared TABQ, the morphological stabilities of TABQ (Supplementary Fig. 6), which X-ray diffraction (XRD) pattern of TABQ electrode shows broad ensures the superior cycling performance. peaks due to short coherent lengths in the thin layer (Supple- The stability of TABQ in zinc cells was further confirmed by a mentary Fig. 3). The diffractions can be attributed to the parallel rest test, where the cell was cycled and rested for 10 h after dis- stacking of six-membered carbon rings in the quinone charged to half capacity, fully discharged, charged to half capacity structure . and fully charged, respectively (Supplementary Fig. 7a). It cor- The electrochemical performance of the TABQ cathode was responds to a total of 40 h rest period, allowing any possible tested in zinc-organic cells with zinc foil anode and 1 M ZnSO dissolution to take place. Supplementary Fig. 7b–d shows the aqueous electrolyte. The two most commonly used salts in zinc capacity retention, charge-discharge and differential capacity electrolytes are ZnSO and Zn(CF SO ) . They provide similar curves during the test. They are well preserved before, during and 4 3 3 2 performance for TABQ (discussed later), and ZnSO was selected after the rest cycle, verifying the excellent stability of TABQ at considering the lower price. Figure 2a, b shows the voltage profiles various states. Another Zn-TABQ cell was assembled with the and capacity evolution at various current densities. The cathode electrolyte of 1 M ZnSO containing saturated TABQ and cycled −1 −1 −1 delivers 303 mAh g capacity at the current density of 0.1 A g . at 0.1 A g . The anode does not show any nitrogen signal by X- The Ketjen Black (KB) conductive agent provides less than 25 ray photoelectron spectroscopy (XPS) after 10 cycles (Supple- −1 mAh g capacity without any redox peaks in the differential mentary Fig. 8). It demonstrates that the small amount of TABQ capacity curve (Supplementary Fig. 4), demonstrating the capacity dissolved in electrolyte does not react with Zn and there is no NATURE COMMUNICATIONS | (2021) 12:4424 | https://doi.org/10.1038/s41467-021-24701-9 | www.nature.com/naturecommunications 3 ARTICLE NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-021-24701-9 ab c 1.4 2.0 1.02 V -1 1.3 Current density unit (A g ) 1.5 1.2 0.1 1.1 1.0 -1 0.2 0.1 A g 0.5 0.83 V 1.0 -1 1.0 0.2 A g 2.0 0.5 -1 0.9 0.5 A g 5.0 -1 1.0 A g 0.8 -1 0.0 2.0 A g 150 -1 0.7 5.0 A g -0.5 0.6 100 Charge 0.77 V 0.5 Discharge -1.0 0.4 0.90 V 0.3 0 -1.5 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 0 50 100 150 200 250 300 350 0 5 10 15 20 25 30 35 -1 Cycle number Capacity (mAh g ) Voltage (V) de 400 300 110 250 100 This work 200 90 200 150 80 100 70 Charge Discharge TABQ C4Q 50 60 CE% TCBQ PQ-Δ DTT PBQS PTO HqTp 0 0 50 0.01 0.1 1 10 0 100 200 300 400 500 600 700 800 900 1000 -1 Current density (A g ) Cycle number Fig. 2 Electrochemical performance of the TABQ cathode in aqueous zinc-organic batteries. a Charge/discharge curves and b capacity evolution under −1 various current densities. c Differential capacity curve at 0.1 A g . d Comparison with previously reported quinone materials. e Capacity and coulombic −1 efficiency evolution at 5 A g for 1000 cycles. ab Pristine Discharged Charged 4000 3500 3000 2500 2000 1500 1000 500 0.4 0.6 0.8 1.0 1.2 1650 1500 -1 -1 Wavenumber (cm ) Voltage (V) Wavenumber (cm ) Fig. 3 Ex-situ FT-IR characterizations of TABQ. a FT-IR spectra of the TABQ electrode at the pristine, discharged and charged states. b Detailed FT-IR peak evolution along discharge and charge. shuttling of TABQ. Overall, the excellent cycling stability of Zn- In addition, a periodic peak shape change is observed in the −1 TABQ cells is confirmed. range of 3000–4000 cm (Fig. 3a). At the end of discharge, a The evolution of TABQ during charge and discharge was studied broad band appears and overlaps the original peaks of amino by ex-situ FT-IR (Fig. 3a). Upon discharge, the carbonyl peak at groups. The band disappears and the amino vibrations are −1 1547 cm disappears, and the stretching vibration of carbon-carbon revealed upon charge. The broad band is the characteristic −1 double bond at 1627 cm shows much reduced intensity. The absorption of water. The electrode was further studied to track its disappearance of carbonyl vibration is a result of its reduction during origin. Figure 4a shows the XRD of the electrode at different the discharge process. More specifically, -C=O accepts electron and states. The change on the TABQ diffractions results from the transforms into -C-O anion. Simultaneously, cations insert to transformation between conjugated quinone rings and π- 34–36,45 compensate the negative charge . This reduction process also conjugated benzene rings which exhibit different stacking converts the conjugated quinone ring to the π-conjugated benzene distances . The narrower peaks in the charged electrode suggest ring. Since the quinone structure exhibits symmetric double bonds in an enhanced long-range ordering. More significantly, the dif- the six-membered carbon ring while the benzene ring does not, the fraction peak of Zn SO (OH) ·4H O shows up in the discharged 4 4 6 2 former provides larger dipole moment change of anti-symmetric electrode, and it disappears upon charge. The same change is also stretching vibration and therefore shows stronger IR absorption. noted in an in-situ XRD cell (Supplementary Fig. 9), suggesting Upon charge, the FT-IR spectrum resembles the one for the pristine the reversible formation of Zn SO (OH) ·4H O at the cathode 4 4 6 2 electrode, confirming the reversible redox of carbonyl group and during the electrochemical processes. The SEM image of the transition between conjugated structures. Figure 3bshows the more electrode shows the reversible appearance and disappearance of detailed peak evolution with measurements taken at various states platelets over the pristine nano-particles upon discharge and along discharge and charge. charge (Fig. 4b), which is the typical morphology of zinc sulfate 4 NATURE COMMUNICATIONS | (2021) 12:4424 | https://doi.org/10.1038/s41467-021-24701-9 | www.nature.com/naturecommunications Voltage (V) -1 Capacity (mAh g ) Transmittance (arb. units) -1 Capacity (mAh g ) -1 Capacity (mAh g ) -1 Capacity (mAh g ) -1 -1 dQ/dV (Ah g V ) Transmittance (arb. units) Coulombic efficiency (%) NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-021-24701-9 ARTICLE Discharged Charged SEM Carbon Nitrogen Oxygen Zinc 2 μm 2 μm 2 μm 2 μm 2 μm 10 20 30 40 50 2 theta (degree) 0.2 2 μm 2 μm 2 μm 2 μm 2 μm 0.0 -0.2 -0.4 -0.6 2 μm 2 μm 2 μm 2 μm 2 μm -5 1MZnSO 1MZn(CF SO ) 5×10 MH SO 4 3 3 2 2 4 -0.8 1MZnSO +0.5MH SO 0.5 M H SO 4 2 4 2 4 0 50 100 150 200 250 300 350 -1 Capacity (mAh g ) Fig. 4 Proof of proton insertion in TABQ. a XRD of TABQ at the end of discharge and charge (the asterisk shows the characteristic diffraction peak of Zn SO (OH) ·4H O). b SEM images and EDS mappings of TABQ at different states. c Charge/discharge curves of TABQ in three electrode cells with SCE 4 4 6 2 reference electrode and different electrolytes. hydroxide . Energy dispersive X-ray spectroscopy (EDS) analysis demonstrates proton involved reaction, and the potential differ- gives a Zn:S ratio around 4 in the discharged electrode (Supple- ence obeys the Nernst equation (please find detailed calculations mentary Fig. 10), in agreement with the Zn SO (OH) ·4H O in Supplementary Discussions). The electrode presents high 4 4 6 2 −5 composition. The elemental mappings further suggest that the overpotential in the 5 × 10 MH SO electrolyte due to the low 2 4 platelets formed at the discharged state are Zn-rich. The above ion activity, but the average potential is close to the other pH~4 results demonstrate that Zn SO (OH) ·4H O is formed upon electrolytes. In 1 M ZnSO and Zn(CF SO ) , on the other hand, 4 4 6 2 4 3 3 2 2+ discharge and its crystal water gives rise to the broad band in FT- continuous Zn hydrolysis provides enough proton for cathode IR. Since Zn SO (OH) ·4H O precipitation takes place in solu- reactions. The results confirm that proton is the dominated active 4 4 6 2 46,47 tions with pH above 5.5 , its formation in ZnSO electrolyte is cation associated with the redox of TABQ. due to proton insertion into cathode which leaves OH behind Importantly, the performance of zinc anode is not influenced 19,48,49 and causes local pH increase . It suggests reversible proton by the proton de/insertion at the cathode, thanks to the reversible de/insertion into TABQ during charge/discharge. Despite the formation of Zn (OH) SO·4H O as pH buffer. Supplementary 4 6 2 insulating nature of Zn SO (OH) ·4H O, it forms as individual Fig. 12 shows the potential curves of zinc electrode in a three- 4 4 6 2 platelets rather than uniform film over active material. Therefore, electrode cell with SCE reference and TABQ counter electrode. the electrical conductivity of the electrode is not hindered as The flat and stable curves at different cycles demonstrate the confirmed by electrochemical impedance spectroscopy (EIS, excellent stability of Zn plating/stripping reaction in the system. It Supplementary Fig. 11). Its reversible formation also functions as allows the coupling of zinc metal anode with a proton inserted a pH buffer for the system. cathode in the zinc-organic battery. 2+ Since Zn would also function as the charge carrier in the The unique proton insertion manner in TABQ should be 2+ ZnSO electrolyte, the amount of proton vs. Zn storage in attributed to its amino groups, which are available to protonate in TABQ was quantified by inductively coupled plasma optical the weakly acidic electrolyte of ZnSO . It allows continuous emission spectroscopy (ICP-OES) and ion chromatography (IC). proton exchange with electrolyte to create a proton active They result in the Zn and sulfate weight percentages of 17.34% environment, which initiates proton insertion and helps with and 5.76% in the discharged electrode, respectively, and the desolvation. The protonation of TABQ was confirmed by UV–vis 2+ inserted proton is calculated to be 13.5 times of Zn (please find analysis. In the non-protonated TABQ, the lone pair electrons on detailed calculations in Supplementary Discussions). It suggests the amino groups would form extended conjugation with the π 50,51 the domination of proton storage in TABQ during the redox electrons on quinone rings . Such interaction is disturbed processes. upon the protonation of amino groups. Therefore, the K-band in The dominated proton insertion in TABQ was further verified protonated TABQ possesses similar energy with benzoquinone by the investigation of pH influence on cathode behaviors. The and is blue-shifted in comparison to non-protonated TABQ due TABQ electrode was tested in three electrode cells with saturated to the absence of extended conjugation. Figure 5a shows the UV- calomel electrode (SCE) as the reference and a series of electro- vis spectra of TABQ in water and 1 M ZnSO . A clear blueshift of lytes: group A of pH~4 solutions, including 1 M ZnSO ,1MZn K-band from 268 nm in water to 201 nm in 1 M ZnSO is noted, 4 4 −5 (CF SO ) and 5 × 10 MH SO ; group B of pH~0 solutions, confirming the protonation in the latter. 3 3 2 2 4 including 0.5 M H SO and 1 M ZnSO + 0.5 M H SO . The The effect of protonation on proton insertion is further 2 4 4 2 4 average charge/discharge potentials of TABQ in the pH~0 elec- extended to the compounds of 2,5-diamino-1,4-benzoquinone trolytes (group B) are around 0.13 V vs. SCE, while the ones with (DABQ) , THBQ and 2,5-dihydroxy-1,4-benzenediacetate the pH~4 electrolytes (group A) are around −0.12 V vs. SCE (DOBDA) . Supplementary Fig. 13a shows their charge- (Fig. 4c). Such pH dependent redox potential of TABQ discharge curves, and the discharged electrodes were NATURE COMMUNICATIONS | (2021) 12:4424 | https://doi.org/10.1038/s41467-021-24701-9 | www.nature.com/naturecommunications 5 Potential (V vs. SCE) Intensity (arb. units) Charged Discharged Pristine ARTICLE NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-021-24701-9 ab c -3.0 -18.9 0.5 -3.1 -19.0 TABQ in 1 M ZnSO TABQ in H O 0.4 -3.2 -19.1 -3.3 -19.2 0.3 -3.4 -19.3 0.2 -3.5 -19.4 0.1 -3.6 -19.5 E =288 meV E '=181 meV a a -3.7 -19.6 0.0 -3.8 -19.7 200 300 400 500 600 3.05 3.10 3.15 3.20 3.25 3.30 3.05 3.10 3.15 3.20 3.25 3.30 -1 -1 1000/T (K ) Wavelength (nm) 1000/T (K ) Carbon Hydrogen Oxygen Nitrogen Fig. 5 Proton insertion behavior into TABQ. a UV–vis absorption spectra of TABQ in 1 M ZnSO and water. The Arrhenius plots of b ln(R ) vs. 1000/T 4 ct and c ln(D) vs. 1000/T for TABQ. d Schematic illustration for the proton conduction manner in the hydrogen bonding network in TABQ. characterized by XRD (Supplementary Fig. 13b). The allows much more facile ion conduction in comparison to the Zn SO (OH) ·4H O diffraction peak is shown in the discharged conventional diffusion mode. The charge/discharge kinetics of 4 4 6 2 DABQ and DOBDA, which indicates proton insertion. It is TABQ were studied by the method proposed by Dunn et al. . attributed to the active protonation/deprotonation of amino or The relationship of the peak current i and scan rate v from cyclic carboxyl groups. On the other hand, the proton activity on voltammetry (CV) obeys the equation of i = av . The b values of hydroxyl groups is low in 1 M ZnSO , and the protonation of the two pairs of TABQ redox peaks are close to 1 (Supplementary 55–57 carbonyl groups on quinones is negligible . Proton insertion Fig. 16), suggesting the domination of non-diffusion-controlled 62,63 is thus less favored in THBQ. Previously reported quinone process and indicating facile reaction kinetics . It guarantees materials undergoing Zn storage, such as TCBQ, PTO and the excellent electrochemical performance of the Zn-TABQ 28,30,41 C4Q , would not protonate in the weakly acidic zinc elec- battery. trolytes, either. The charge transfer behavior in TABQ was studied by EIS with measurements taken at various temperatures. A typical equivalent Discussion circuit was applied to calculate charge transfer resistance (R ) ct In this work, specific functional groups are chosen for the small from the Nyquist plots (Supplementary Fig. 14 and Supplemen- molecule quinone cathode of TABQ for aqueous zinc-organic −1 tary Table 1). A linear correlation was obtained between ln(R ) ct batteries. The hydrogen bonds suppress the sublimation and −1 and T (Fig. 5b), suggesting the applicability of Arrhenius provides convenience for various electrode treatments. The high −1 58,59 equation of ln(R ) = −E /RT + C . The activation energy ct a molecular symmetry results in low solubility in aqueous electro- E for charge transfer processes was calculated to be 288 meV. a lytes. More importantly, the redox of carbonyl group is associated The low value suggests facile ion desolvation thanks to the help of with dominated proton de/insertion thanks to the amino groups amino groups. which undergoes protonation in the weakly acidic zinc electrolyte. The proton conduction in TABQ was studied by galvanostatic Facile proton conduction in TABQ is furthermore achieved with intermittent titration technique (GITT) at various temperatures. a Grotthuss-type mechanism through the hydrogen bonding The obtained diffusion coefficient (D) values were used to cal- network formed with the amino and carbonyl groups. Therefore, culate the activation energy for ion diffusion according to the proton insertion in TABQ experiences much enhanced kinetics Arrhenius equation of ln(D) = -E ’/RT + C’ (Fig. 5c and Sup- a and is favored for energy storage. Despite the low concentration 2+ plementary Fig. 15) . It results in a low E ’ value of 181 meV. a of proton in the electrolyte, the continuous hydrolysis of Zn Considering the hydrogen bonding network formed among generates sufficient proton for insertion. The unique proton TABQ molecules as discussed earlier, the result demonstrates a conduction manner results in activation energies below 300 meV unique proton conduction manner via the Grotthuss-type for charge transfer and proton diffusion, which guarantees a high 61,62 −1 mechanism (E < 400 meV) , where proton transfer takes capacity of 303 mAh g with excellent rate capability for the place by forming/breaking of hydrogen bonds between adjacent TABQ electrode. Stable cycling is also achieved for 1000 cycles. carbonyl/hydroxyl and amino groups (Fig. 5d). Such process The unique proton conduction manner presented in our work 6 NATURE COMMUNICATIONS | (2021) 12:4424 | https://doi.org/10.1038/s41467-021-24701-9 | www.nature.com/naturecommunications Absorbance -1 -1 ln[R (Ω )] ct 2 -1 ln[D (cm s )] NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-021-24701-9 ARTICLE O O N K O O O 80% Hydrazine hydrate, N N Cl Cl H N NH 2 2 65 ˚C, 2 h O O O O Acetonitrile, 80 ˚C, 12 h Cl Cl H N NH N N 2 2 O O O O O Step 1 Step 2 TCBQ TABQ TPQ Fig. 6 Synthetic routes of TABQ. TABQ was obtained by a two-step synthesis with low-cost reactants. proposes a promising direction for the design of high- mm, and dried at 60 °C under vacuum overnight followed by 90 °C overnight. The −2 mass loading of TABQ was around 1.3 mg cm . Galvanostatic charge/discharge performance organic electrode materials for aqueous batteries. measurements were carried out in PFA Swagelok type cells with titanium rods as the current collectors. Rest test was performed with the following process: regular −1 Methods discharge and charge for 20 cycles at 1 A g , rest for 10 h after discharged to half Materials. Graphite foil was purchased from the SGL group (Germany). TCBQ, capacity, fully discharged, charged to half capacity and fully charged, respectively (a THBQ, o-TCBQ, DABQ, DOBDA, benzoquinone and potassium phthalimide were total of 40 h rest period), and return to regular cycles. The study of electrolyte pH purchased from Aladdin Bio-Chem Technology (China). KB conductive additive influence was carried out in T-shaped PFA Swagelok type cells with TABQ was purchased from Lion Specialty Chemicals (Japan). Poly(vinylidene fluoride) working electrode, graphite foil counter electrode, SCE reference electrode and the −5 (PVDF) was purchased from Kejing Materials Technology (China). The other aqueous electrolytes of 1 M ZnSO , 1 M Zn(CF SO ) ,5×10 MH SO , 0.5 M 4 3 3 2 2 4 reagents were obtained from Sinopharm Chemical Reagent (China). H SO , or 1 M ZnSO + 0.5 M H SO . EIS measurements were carried out in a T- 2 4 4 2 4 shaped PFA Swagelok type cell with TABQ working electrode, Zn counter elec- trode, SCE reference electrode and 1 M ZnSO aqueous electrolyte. GITT was Synthesis of TABQ. The TABQ was prepared according to a previously reported carried out in a T-shaped PFA Swagelok type cell with TABQ working electrode, method as summarized in Fig. 6 and described below. Zn counter electrode, Zn reference electrode and 1 M ZnSO aqueous electrolyte. Step 1: 20.0 g (0.081 mol) of TCBQ, 60.0 g (0.32 mol) of potassium phthalimide The cells for EIS and GITT measurements were placed in an oven which was set to and 200.0 mL of acetonitrile were added into a 500 mL round bottom flask. The the desired temperatures of 35, 40, 45, and 50 °C. All electrochemical experiments mixture was kept at 80 °C for 12 h under stirring. After cooling down to room were carried out on a Bio-Logic VMP3. temperature, the solid was separated by filtration and washed with 2 L boiled water. The product was dried at 60 °C overnight, and brown-yellow powder of tetra (phthalimido)-benzoquinone (TPQ) was obtained (45.0 g, yield = 80.7%). In-situ XRD analysis. The test was carried out with a home-made in-situ XRD cell. Step 2: 9.41 g (0.014 mol) of TPQ was dispersed in 200 mL of 80% hydrazine The TABQ slurry was drop casted on a carbon cloth substrate. The cell was hydrate in a 500 mL round bottom flask. The mixture was stirred at room discharged and charged to the desired voltages and XRD measurements were taken. temperature for 2 h, followed by heating at 65 °C for 2 h. The system was cooled down to room temperature, filtered, washed with water and ethanol, and the dark purple Activation energy calculation. The Nyquist plots from EIS were fitted with a product of TABQ was obtained (1.3 g, yield= 56.6%). H NMR, (500 MHz, [D ] typical equivalent circuit shown in Supplementary Fig. 14b, and the obtained R ct DMSO): δ 4.55 (s, 8H) (Supplementary Fig. 17); elemental analysis (calcd., found for values were summarized in Supplementary Table 1. The low errors confirmed the C H N O ): C (42.86, 42.09), H (4.80, 4.03), N (33.32, 33.27), O (19.03, 21.41). 6 8 4 2 −1 applicability of the circuit for calculating R . The ln(R ) values were plotted vs. ct ct 1000/T and linear fit was carried out according to the Arrhenius equation of ln −1 Characterizations. FT-IR was performed on VERTEX70 (Bruker, Germany). XRD (R ) = −E /RT + C, where C is constant under a stable experimental condition, ct a was carried out on an Empyrean diffractometer with Cu-Kα radiation (PANalytical R is gas constant and T is temperature . The E represents the activation energy B.V., Holland). H NMR was measured on Bruker 500 M (Bruker, Germany) with for charge transfer and was calculated from the slope of the fitted line. Similarly, (methyl sulfoxide)-d as the solvent and tetramethylsilane (TMS) as the internal the activation energy E ’ for diffusion was calculated from the Arrhenius equation 6 a standard. Elemental analysis was determined by an Elementar Vario EL III (Ele- with diffusion coefficient (D) of ln(D) = −E ’/RT + C’. D was calculated from mentar, Germany). TGA was carried out on a TGA/DSC3+ thermal analysis GITT based on the following equation: system (Mettler toledo, Switzerland). The morphology was obtained by a SU8010 4L ΔE SEM equipped with an EDS detector (HITACHI, Japan). UV–vis absorption s ð1Þ D ¼ πτ ΔE spectra were recorded on a U-3900 spectrophotometer (HITACHI, Japan). XPS was carried out on a K-Alpha+ X-ray Photoelectron Spectroscopy (Thermo fisher where τ is the relaxation time, ΔE is the steady-state potential change after a single Scientific, America). ICP-OES analysis was carried out on ICP-OES 730 (Agilent, pulse, and ΔE is the potential change during a pulse after eliminating iR drop. The America). IC analysis was carried out on ICS-1100 (DIONEX, America). diffusion length L was measured by the geometric thickness of cathode. Since L was a constant, the value would not affect the activation energy obtained from slope of 1/2 the Arrhenius equation. The linearity between cell voltage and t during titration Sublimation behavior study. The benzoquinone or TABQ powder was placed on the aluminum foil cover of a long-neck round-bottom flask. It was placed upside was checked to confirm the applicability of the equation (Supplementary Fig. 18) . down with the powder and neck sticking into the oven which was set at 90 °C or 150 °C and the round part staying outside at room temperature. Sublimation was Kinetics studies. The charge/discharge kinetics of TABQ in aqueous zinc cells evidenced by the disappearance of powder on the aluminum cover and con- were studied by CV tests at various scan rates (Supplementary Fig. 16a). The CV densation of crystals on the round part. curves showed two pairs of redox peaks. The peak current i and scan rate v obeys the relationship of i = av , where a and b are coefficients. In the limiting cases, a b value of 0.5 suggests diffusion-controlled process whereas 1 indicates non- UV–vis analysis. Standard solutions were prepared by dissolving known com- 62,63 pound concentrations in 1 M ZnSO . Saturated solutions were obtained by mixing diffusion-controlled process . The peak current at different scan rates was extracted, and the ln of peak current was plotted vs. ln of scan rate. By carrying out an excess of compounds in 1 M ZnSO and filtered. Saturated solutions were diluted by the factors of 100, 200 and 100 with 1 M ZnSO for TABQ, THBQ and linear fit, the b values were obtained from the slopes of the lines (Supplementary Fig. 16b). o-TCBQ, respectively. UV–vis absorbance was measured in the range of 190–600 nm. Calibration curves were obtained by the linear fit of the absorbance at 365 nm, 363 nm and 335 nm for TABQ, THBQ and o-TCBQ, respectively, with respect to Data availability the compound concentrations of standard solutions using the Beer-Lambert law: A The data that support the findings of this study are available from the corresponding = εlc (A: absorbance; ε: molar extinction coefficient; l: length of the cell; c: com- author upon reasonable request. pound concentration). 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Supplementary information The online version contains supplementary material 63. Wang, J., Polleux, J., Lim, J. & Dunn, B. Pseudocapacitive contributions to available at https://doi.org/10.1038/s41467-021-24701-9. electrochemical energy storage in TiO (anatase) nanoparticles. J. Phys. Chem. C. 111, 14925–14931 (2007). Correspondence and requests for materials should be addressed to X.S. 64. Luo, Z. Q. et al. A microporous covalent-organic framework with abundant Peer review information Nature Communications thanks the anonymous reviewer(s) for accessible carbonyl groups for lithium-ion batteries. Angew. Chem. Int. Ed. 57, their contribution to the peer review of this work. Peer reviewer reports are available. 9443–9446 (2018). 65. Weppner, W. & Huggins, R. A. Determination of the kinetic parameters of Reprints and permission information is available at http://www.nature.com/reprints mixed-conducting electrodes and application to the system Li Sb. J. Electrochem. 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A high capacity small molecule quinone cathode for rechargeable aqueous zinc-organic batteries

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ARTICLE https://doi.org/10.1038/s41467-021-24701-9 OPEN A high capacity small molecule quinone cathode for rechargeable aqueous zinc-organic batteries 1 1 1 1 1 1 Zirui Lin , Hua-Yu Shi , Lu Lin , Xianpeng Yang , Wanlong Wu & Xiaoqi Sun Rechargeable aqueous zinc-organic batteries are promising energy storage systems with low- cost aqueous electrolyte and zinc metal anode. The electrochemical properties can be sys- tematically adjusted with molecular design on organic cathode materials. Herein, we use a symmetric small molecule quinone cathode, tetraamino-p-benzoquinone (TABQ), with desirable functional groups to protonate and accomplish dominated proton insertion from weakly acidic zinc electrolyte. The hydrogen bonding network formed with carbonyl and amino groups on the TABQ molecules allows facile proton conduction through the Grotthuss- type mechanism. It guarantees activation energies below 300 meV for charge transfer and −1 −1 proton diffusion. The TABQ cathode delivers a high capacity of 303 mAh g at 0.1 A g in a −1 −1 zinc-organic battery. With the increase of current density to 5 A g , 213 mAh g capacity is still preserved with stable cycling for 1000 times. Our work proposes an effective approach towards high performance organic electrode materials. 1 ✉ Department of Chemistry, Northeastern University, Shenyang, China. email: [email protected] NATURE COMMUNICATIONS | (2021) 12:4424 | https://doi.org/10.1038/s41467-021-24701-9 | www.nature.com/naturecommunications 1 1234567890():,; ARTICLE NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-021-24701-9 echargeable lithium-ion batteries have been widely used in aqueous zinc-organic batteries. The four amino groups are 1–5 portable electronics and electric vehicles . However, cost available for protonation in weakly acidic zinc electrolytes, which Rand potential safety issues restrict their application areas would create a proton active environment and initiate proton 6–10 and scales . Rechargeable aqueous batteries using aqueous insertion. At the same time, hydrogen bonds are formed among electrolytes largely reduce those concerns and experience rapid amino and carbonyl groups, so that the compound does not development in the past few years. The zinc metal is a desirable sublimate even at elevated temperatures. More importantly, the anode for aqueous systems and delivers high theoretical specific hydrogen bonding network allows facile proton conduction −1 capacity (820 mAh g ), low redox potential (-0.76 V vs. S.H.E.) through the breaking and reforming of hydrogen bonds. The 11–13 as well as good compatibility with water . The research on TABQ electrode thus functions with dominated proton de/ suitable cathode materials to couple with the zinc anode mainly intercalation and experiences low activation energies for charge focuses on inorganic compounds such as metal oxides, Prussian transfer and diffusion. Excellent electrochemical performance is 14–17 blue salts and polyanion compounds . Among them, man- achieved. 18–21 ganese oxides and vanadium oxides deliver high capacities; however, problems such as active material dissolution are important challenges for their further applications . Results In comparison to inorganic materials, organic compounds are The TABQ active material is soluble in N-Methyl-2-pyrrolidone less explored as cathode materials for aqueous batteries . (NMP), and it undergoes a dissolution-reprecipitation process Nevertheless, organic compounds are more flexible with mole- during electrode manufacturing. Figure 1a shows the Fourier cular design, which allows the systematic adjustment of voltage, transform infrared (FT-IR) spectrum of the TABQ active material capacity, conductivity, redox kinetics and other properties for after drying out from NMP (no carbon and binder). The multiple 23–25 −1 electrode materials . For example, Koshika et al. attached the absorption peaks between 3469 and 3262 cm (purple part) electrochemically active 2,2,6,6-tetramethylpiperidine-1-oxyl to belong to the N-H stretching vibrations with different symmetry the poly(vinyl ether) chain in order to avoid dissolution. The modes from the four amino groups in TABQ. Notably, a broad −1 obtained electrode delivers 131 mAh g capacity and excellent band shows up on the right side as highlighted in cyan. It suggests rate capability with the facile radical-involved redox process . the redshift of part of the N-H stretching vibration peak, which is 38,39 Our group showed that sulfo group can be introduced to the six- a typical behavior upon the formation of hydrogen bonds . membered carbon ring of polyaniline to function as an internal Another site available for forming hydrogen bonds with amino is proton reservoir and retain a locally high acidic environment. The oxygen on carbonyl in the case of TABQ. Correspondingly, the −1 electrochemical activity of polyaniline is therefore maintained in carbonyl stretching vibration at 1547 cm in TABQ (pink part) 27 −1 the weakly acidic Zn electrolyte . experiences more than 100 cm of redshift in comparison to −1 Among organic materials, quinone compounds show good 1661 cm in benzoquinone (spectral database for organic com- environmental friendliness. They widely exist in nature, and the pounds SDBS). Although the electron-donor property of amino redox process between quinone and hydroquinone is an impor- also causes the redshift of carbonyl, such a significant shift results 28 37,40 tant physiological progress in living organisms . The excellent from additional effects, i.e., the hydrogen bonding . Finally, −1 redox activity of quinones also makes them desirable cathode the peaks in the range of 1700–1270 cm shown in green belong materials for aqueous zinc batteries. Zhao et al. reported a calix[4] to the vibrations of the six-membered carbon ring containing quinone (C4Q) molecule, where each benzoquinone unit is carbon–carbon single bonds, double bonds and their synergistic connected by C-C single bond to form a bowl-like structure. The effects. −1 −1 28 cathode displays a high capacity of 335 mAh g at 20 mA g . The above analysis on FT-IR demonstrates the formation of Nam and co-workers designed a medium molecular weight qui- hydrogen bonds with the amino and carbonyl functional groups none compound, triangular macrocyclic phenanthrenequinone in TABQ molecules. It results in strong interactions between 2+ (PQ-Δ), which allows the co-insertion of Zn and water and adjacent molecules and furthermore affects the physical and −1 −1 29 delivers a specific capacity of 225 mAh g at 30 mA g . Guo chemical properties. We studied the sublimation behavior of et al. proposed a pyrene-4,5,9,10-tetraone (PTO) cathode, TABQ using the setup shown in Supplementary Fig. 1, and −1 −1 30 achieving 336 mAh g capacity at 40 mA g . benzoquinone was applied as the comparing standard. When the 2+ Zn de/intercalation is demonstrated for most quinone benzoquinone powder was heated at 90 °C for 3 h in the oven, no materials in zinc cells; however, the diffusion of multivalent original powder is left and yellow crystals are condensed all over cation could be sluggish . On the other hand, the facile insertion the flask which stayed at room temperature (Fig. 1b). It of proton into cathode materials from weakly acidic zinc elec- demonstrates the sublimation of benzoquinone. With TABQ, on 2+ trolytes is possible with the hydrolysis of Zn to continuously the contrary, the original powder remains on the aluminum cover 31–33 generate proton , and proton could take part in the redox which stayed in the oven and the flask is completely clear 34–36 process of quinones . Besides, most of the previously studied (Fig. 1c). The same phenomenon is observed even with more quinone-based compounds are relatively complex in molecular elevated temperature of 150 °C (Fig. 1d). In addition, thermo- structures and require multi-step synthesis procedures. In com- gravimetric analysis (TGA) with constant temperature hold at 90 parison, small molecule quinones provide the advantage of simple °C shows continuous weight loss of benzoquinone as a result of synthesis, corresponding to a reduced cost. However, many small sublimation, whereas a stable weight evolution is obtained with quinone molecules, such as benzoquinone, are prone to sub- TABQ (Fig. 1e). The above analysis confirms the introduction of limation. It leads to difficulties in electrode manufacturing, hydrogen bonds effectively suppresses the sublimation of small handling and storage. Another important concern of small molecule quinone. It would provide convenience for various molecules is their relatively high solubility, resulting in the electrode treatments. shuttling of active material in electrolytes and capacity decay. The solubility of TABQ in 1 M ZnSO , which is a conventional Nevertheless, previous studies have shown that molecules with electrolyte for zinc batteries, was quantified by UV–vis analysis high symmetry possess low dipole moments and thus low solu- (Fig. 1f) . The saturated concentration was determined to be 37 −1 bilities in aqueous solutions . Considering the above factors, we 1.7 mmol L . This low solubility would ensure stable cycling in herein specifically apply a symmetric small molecule of aqueous zinc cells. The relationship between molecular structure tetraamino-p-benzoquinone (TABQ) as the cathode material for and solubility is further studied by comparing with related 2 NATURE COMMUNICATIONS | (2021) 12:4424 | https://doi.org/10.1038/s41467-021-24701-9 | www.nature.com/naturecommunications NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-021-24701-9 ARTICLE Fig. 1 Characterizations of TABQ. a FT-IR spectrum of TABQ. b, c, d Sublimation test of benzoquinone and TABQ at 90 °C and 150 °C. e TGA curves of benzoquinone and TABQ with constant temperature hold at 90 °C. f UV-vis calibration curve of TABQ in 1 M ZnSO together with the calculation of the 100 times diluted saturated solution. g SEM image of the TABQ electrode. compounds of tetrahydroxy-p-benzoquinone (THBQ), tetrachloro- is majorly contributed by the TABQ active material. With the −1 o-benzoquinone (o-TCBQ) and tetrachloro-p-benzoquinone (p- increase of current density to 5 A g , the TABQ cathode still −1 −1 TCBQ). UV–vis analysis results in the solubilities of 3.4 mmol L maintains 213 mAh g capacity. It suggests the excellent electro- −1 and 2.3 mmol L for THBQ and o-TCBQ, respectively (Supple- chemical activity of both carbonyl groups on TABQ. Figure 2c −1 mentary Fig. 2), and very trace dissolution of p-TCBQ is noticed. shows the differential capacity curve at 0.1 A g .Two pairsofredox Literature also demonstrated the insoluble nature of p-TCBQ . peaks are observed at 0.90 V/1.02 V and 0.77 V/0.83 V, respectively. Comparing among the p-quinones, the higher solubilities of TABQ The small overpotential demonstrates the good cation de/insertion and THBQ than p-TCBQ should be attributed to the more kinetics into TABQ. The electrochemical performance of TABQ is hydrophilic amino or hydroxyl functional groups. Nevertheless, the compared with previously reported quinone cathode materials in 28 29 30 41 solubilities are still quite low thanks to their highly symmetric zinc-organic batteries, including C4Q ,PQ-Δ ,PTO ,TCBQ , 37 42 43 molecular structures and thus low dipole moments . For example, HqTp , poly(benzoquinonyl sulfide) (PBQS) and dibenzo[b,i] the p-TCBQ molecule is more symmetric than o-TCBQ and pre- thianthrene-5,7,12,14-tetraone (DTT) .Asshown in Fig. 2d, TABQ −1 sents lower solubility. delivers the highest capacity at 0.1 A g and presents the best rate Figure 1g shows the scanning electron microscopy (SEM) capability. Figure 2e and Supplementary Fig. 5 show the long-term −1 image of the TABQ electrode. The TABQ active material forms as cycling behavior. At the current density of 5 A g ,the TABQ thin layer and is homogeneously distributed over Ketjen Black cathode exhibits stable capacity retention for over 1000 cycles after (KB) spherical particles, resulting in a conductive network with slight capacity decay during the first few cycles. The coulombic porous structure. The effective interaction between TABQ and efficiencies are close to 100%. FT-IR and SEM analysis on the carbon would ensure good electrical conductivity in electrodes. electrode after 1000 cycles verifies the excellent compositional and Comparing with the high crystallinity of as-prepared TABQ, the morphological stabilities of TABQ (Supplementary Fig. 6), which X-ray diffraction (XRD) pattern of TABQ electrode shows broad ensures the superior cycling performance. peaks due to short coherent lengths in the thin layer (Supple- The stability of TABQ in zinc cells was further confirmed by a mentary Fig. 3). The diffractions can be attributed to the parallel rest test, where the cell was cycled and rested for 10 h after dis- stacking of six-membered carbon rings in the quinone charged to half capacity, fully discharged, charged to half capacity structure . and fully charged, respectively (Supplementary Fig. 7a). It cor- The electrochemical performance of the TABQ cathode was responds to a total of 40 h rest period, allowing any possible tested in zinc-organic cells with zinc foil anode and 1 M ZnSO dissolution to take place. Supplementary Fig. 7b–d shows the aqueous electrolyte. The two most commonly used salts in zinc capacity retention, charge-discharge and differential capacity electrolytes are ZnSO and Zn(CF SO ) . They provide similar curves during the test. They are well preserved before, during and 4 3 3 2 performance for TABQ (discussed later), and ZnSO was selected after the rest cycle, verifying the excellent stability of TABQ at considering the lower price. Figure 2a, b shows the voltage profiles various states. Another Zn-TABQ cell was assembled with the and capacity evolution at various current densities. The cathode electrolyte of 1 M ZnSO containing saturated TABQ and cycled −1 −1 −1 delivers 303 mAh g capacity at the current density of 0.1 A g . at 0.1 A g . The anode does not show any nitrogen signal by X- The Ketjen Black (KB) conductive agent provides less than 25 ray photoelectron spectroscopy (XPS) after 10 cycles (Supple- −1 mAh g capacity without any redox peaks in the differential mentary Fig. 8). It demonstrates that the small amount of TABQ capacity curve (Supplementary Fig. 4), demonstrating the capacity dissolved in electrolyte does not react with Zn and there is no NATURE COMMUNICATIONS | (2021) 12:4424 | https://doi.org/10.1038/s41467-021-24701-9 | www.nature.com/naturecommunications 3 ARTICLE NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-021-24701-9 ab c 1.4 2.0 1.02 V -1 1.3 Current density unit (A g ) 1.5 1.2 0.1 1.1 1.0 -1 0.2 0.1 A g 0.5 0.83 V 1.0 -1 1.0 0.2 A g 2.0 0.5 -1 0.9 0.5 A g 5.0 -1 1.0 A g 0.8 -1 0.0 2.0 A g 150 -1 0.7 5.0 A g -0.5 0.6 100 Charge 0.77 V 0.5 Discharge -1.0 0.4 0.90 V 0.3 0 -1.5 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 0 50 100 150 200 250 300 350 0 5 10 15 20 25 30 35 -1 Cycle number Capacity (mAh g ) Voltage (V) de 400 300 110 250 100 This work 200 90 200 150 80 100 70 Charge Discharge TABQ C4Q 50 60 CE% TCBQ PQ-Δ DTT PBQS PTO HqTp 0 0 50 0.01 0.1 1 10 0 100 200 300 400 500 600 700 800 900 1000 -1 Current density (A g ) Cycle number Fig. 2 Electrochemical performance of the TABQ cathode in aqueous zinc-organic batteries. a Charge/discharge curves and b capacity evolution under −1 various current densities. c Differential capacity curve at 0.1 A g . d Comparison with previously reported quinone materials. e Capacity and coulombic −1 efficiency evolution at 5 A g for 1000 cycles. ab Pristine Discharged Charged 4000 3500 3000 2500 2000 1500 1000 500 0.4 0.6 0.8 1.0 1.2 1650 1500 -1 -1 Wavenumber (cm ) Voltage (V) Wavenumber (cm ) Fig. 3 Ex-situ FT-IR characterizations of TABQ. a FT-IR spectra of the TABQ electrode at the pristine, discharged and charged states. b Detailed FT-IR peak evolution along discharge and charge. shuttling of TABQ. Overall, the excellent cycling stability of Zn- In addition, a periodic peak shape change is observed in the −1 TABQ cells is confirmed. range of 3000–4000 cm (Fig. 3a). At the end of discharge, a The evolution of TABQ during charge and discharge was studied broad band appears and overlaps the original peaks of amino by ex-situ FT-IR (Fig. 3a). Upon discharge, the carbonyl peak at groups. The band disappears and the amino vibrations are −1 1547 cm disappears, and the stretching vibration of carbon-carbon revealed upon charge. The broad band is the characteristic −1 double bond at 1627 cm shows much reduced intensity. The absorption of water. The electrode was further studied to track its disappearance of carbonyl vibration is a result of its reduction during origin. Figure 4a shows the XRD of the electrode at different the discharge process. More specifically, -C=O accepts electron and states. The change on the TABQ diffractions results from the transforms into -C-O anion. Simultaneously, cations insert to transformation between conjugated quinone rings and π- 34–36,45 compensate the negative charge . This reduction process also conjugated benzene rings which exhibit different stacking converts the conjugated quinone ring to the π-conjugated benzene distances . The narrower peaks in the charged electrode suggest ring. Since the quinone structure exhibits symmetric double bonds in an enhanced long-range ordering. More significantly, the dif- the six-membered carbon ring while the benzene ring does not, the fraction peak of Zn SO (OH) ·4H O shows up in the discharged 4 4 6 2 former provides larger dipole moment change of anti-symmetric electrode, and it disappears upon charge. The same change is also stretching vibration and therefore shows stronger IR absorption. noted in an in-situ XRD cell (Supplementary Fig. 9), suggesting Upon charge, the FT-IR spectrum resembles the one for the pristine the reversible formation of Zn SO (OH) ·4H O at the cathode 4 4 6 2 electrode, confirming the reversible redox of carbonyl group and during the electrochemical processes. The SEM image of the transition between conjugated structures. Figure 3bshows the more electrode shows the reversible appearance and disappearance of detailed peak evolution with measurements taken at various states platelets over the pristine nano-particles upon discharge and along discharge and charge. charge (Fig. 4b), which is the typical morphology of zinc sulfate 4 NATURE COMMUNICATIONS | (2021) 12:4424 | https://doi.org/10.1038/s41467-021-24701-9 | www.nature.com/naturecommunications Voltage (V) -1 Capacity (mAh g ) Transmittance (arb. units) -1 Capacity (mAh g ) -1 Capacity (mAh g ) -1 Capacity (mAh g ) -1 -1 dQ/dV (Ah g V ) Transmittance (arb. units) Coulombic efficiency (%) NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-021-24701-9 ARTICLE Discharged Charged SEM Carbon Nitrogen Oxygen Zinc 2 μm 2 μm 2 μm 2 μm 2 μm 10 20 30 40 50 2 theta (degree) 0.2 2 μm 2 μm 2 μm 2 μm 2 μm 0.0 -0.2 -0.4 -0.6 2 μm 2 μm 2 μm 2 μm 2 μm -5 1MZnSO 1MZn(CF SO ) 5×10 MH SO 4 3 3 2 2 4 -0.8 1MZnSO +0.5MH SO 0.5 M H SO 4 2 4 2 4 0 50 100 150 200 250 300 350 -1 Capacity (mAh g ) Fig. 4 Proof of proton insertion in TABQ. a XRD of TABQ at the end of discharge and charge (the asterisk shows the characteristic diffraction peak of Zn SO (OH) ·4H O). b SEM images and EDS mappings of TABQ at different states. c Charge/discharge curves of TABQ in three electrode cells with SCE 4 4 6 2 reference electrode and different electrolytes. hydroxide . Energy dispersive X-ray spectroscopy (EDS) analysis demonstrates proton involved reaction, and the potential differ- gives a Zn:S ratio around 4 in the discharged electrode (Supple- ence obeys the Nernst equation (please find detailed calculations mentary Fig. 10), in agreement with the Zn SO (OH) ·4H O in Supplementary Discussions). The electrode presents high 4 4 6 2 −5 composition. The elemental mappings further suggest that the overpotential in the 5 × 10 MH SO electrolyte due to the low 2 4 platelets formed at the discharged state are Zn-rich. The above ion activity, but the average potential is close to the other pH~4 results demonstrate that Zn SO (OH) ·4H O is formed upon electrolytes. In 1 M ZnSO and Zn(CF SO ) , on the other hand, 4 4 6 2 4 3 3 2 2+ discharge and its crystal water gives rise to the broad band in FT- continuous Zn hydrolysis provides enough proton for cathode IR. Since Zn SO (OH) ·4H O precipitation takes place in solu- reactions. The results confirm that proton is the dominated active 4 4 6 2 46,47 tions with pH above 5.5 , its formation in ZnSO electrolyte is cation associated with the redox of TABQ. due to proton insertion into cathode which leaves OH behind Importantly, the performance of zinc anode is not influenced 19,48,49 and causes local pH increase . It suggests reversible proton by the proton de/insertion at the cathode, thanks to the reversible de/insertion into TABQ during charge/discharge. Despite the formation of Zn (OH) SO·4H O as pH buffer. Supplementary 4 6 2 insulating nature of Zn SO (OH) ·4H O, it forms as individual Fig. 12 shows the potential curves of zinc electrode in a three- 4 4 6 2 platelets rather than uniform film over active material. Therefore, electrode cell with SCE reference and TABQ counter electrode. the electrical conductivity of the electrode is not hindered as The flat and stable curves at different cycles demonstrate the confirmed by electrochemical impedance spectroscopy (EIS, excellent stability of Zn plating/stripping reaction in the system. It Supplementary Fig. 11). Its reversible formation also functions as allows the coupling of zinc metal anode with a proton inserted a pH buffer for the system. cathode in the zinc-organic battery. 2+ Since Zn would also function as the charge carrier in the The unique proton insertion manner in TABQ should be 2+ ZnSO electrolyte, the amount of proton vs. Zn storage in attributed to its amino groups, which are available to protonate in TABQ was quantified by inductively coupled plasma optical the weakly acidic electrolyte of ZnSO . It allows continuous emission spectroscopy (ICP-OES) and ion chromatography (IC). proton exchange with electrolyte to create a proton active They result in the Zn and sulfate weight percentages of 17.34% environment, which initiates proton insertion and helps with and 5.76% in the discharged electrode, respectively, and the desolvation. The protonation of TABQ was confirmed by UV–vis 2+ inserted proton is calculated to be 13.5 times of Zn (please find analysis. In the non-protonated TABQ, the lone pair electrons on detailed calculations in Supplementary Discussions). It suggests the amino groups would form extended conjugation with the π 50,51 the domination of proton storage in TABQ during the redox electrons on quinone rings . Such interaction is disturbed processes. upon the protonation of amino groups. Therefore, the K-band in The dominated proton insertion in TABQ was further verified protonated TABQ possesses similar energy with benzoquinone by the investigation of pH influence on cathode behaviors. The and is blue-shifted in comparison to non-protonated TABQ due TABQ electrode was tested in three electrode cells with saturated to the absence of extended conjugation. Figure 5a shows the UV- calomel electrode (SCE) as the reference and a series of electro- vis spectra of TABQ in water and 1 M ZnSO . A clear blueshift of lytes: group A of pH~4 solutions, including 1 M ZnSO ,1MZn K-band from 268 nm in water to 201 nm in 1 M ZnSO is noted, 4 4 −5 (CF SO ) and 5 × 10 MH SO ; group B of pH~0 solutions, confirming the protonation in the latter. 3 3 2 2 4 including 0.5 M H SO and 1 M ZnSO + 0.5 M H SO . The The effect of protonation on proton insertion is further 2 4 4 2 4 average charge/discharge potentials of TABQ in the pH~0 elec- extended to the compounds of 2,5-diamino-1,4-benzoquinone trolytes (group B) are around 0.13 V vs. SCE, while the ones with (DABQ) , THBQ and 2,5-dihydroxy-1,4-benzenediacetate the pH~4 electrolytes (group A) are around −0.12 V vs. SCE (DOBDA) . Supplementary Fig. 13a shows their charge- (Fig. 4c). Such pH dependent redox potential of TABQ discharge curves, and the discharged electrodes were NATURE COMMUNICATIONS | (2021) 12:4424 | https://doi.org/10.1038/s41467-021-24701-9 | www.nature.com/naturecommunications 5 Potential (V vs. SCE) Intensity (arb. units) Charged Discharged Pristine ARTICLE NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-021-24701-9 ab c -3.0 -18.9 0.5 -3.1 -19.0 TABQ in 1 M ZnSO TABQ in H O 0.4 -3.2 -19.1 -3.3 -19.2 0.3 -3.4 -19.3 0.2 -3.5 -19.4 0.1 -3.6 -19.5 E =288 meV E '=181 meV a a -3.7 -19.6 0.0 -3.8 -19.7 200 300 400 500 600 3.05 3.10 3.15 3.20 3.25 3.30 3.05 3.10 3.15 3.20 3.25 3.30 -1 -1 1000/T (K ) Wavelength (nm) 1000/T (K ) Carbon Hydrogen Oxygen Nitrogen Fig. 5 Proton insertion behavior into TABQ. a UV–vis absorption spectra of TABQ in 1 M ZnSO and water. The Arrhenius plots of b ln(R ) vs. 1000/T 4 ct and c ln(D) vs. 1000/T for TABQ. d Schematic illustration for the proton conduction manner in the hydrogen bonding network in TABQ. characterized by XRD (Supplementary Fig. 13b). The allows much more facile ion conduction in comparison to the Zn SO (OH) ·4H O diffraction peak is shown in the discharged conventional diffusion mode. The charge/discharge kinetics of 4 4 6 2 DABQ and DOBDA, which indicates proton insertion. It is TABQ were studied by the method proposed by Dunn et al. . attributed to the active protonation/deprotonation of amino or The relationship of the peak current i and scan rate v from cyclic carboxyl groups. On the other hand, the proton activity on voltammetry (CV) obeys the equation of i = av . The b values of hydroxyl groups is low in 1 M ZnSO , and the protonation of the two pairs of TABQ redox peaks are close to 1 (Supplementary 55–57 carbonyl groups on quinones is negligible . Proton insertion Fig. 16), suggesting the domination of non-diffusion-controlled 62,63 is thus less favored in THBQ. Previously reported quinone process and indicating facile reaction kinetics . It guarantees materials undergoing Zn storage, such as TCBQ, PTO and the excellent electrochemical performance of the Zn-TABQ 28,30,41 C4Q , would not protonate in the weakly acidic zinc elec- battery. trolytes, either. The charge transfer behavior in TABQ was studied by EIS with measurements taken at various temperatures. A typical equivalent Discussion circuit was applied to calculate charge transfer resistance (R ) ct In this work, specific functional groups are chosen for the small from the Nyquist plots (Supplementary Fig. 14 and Supplemen- molecule quinone cathode of TABQ for aqueous zinc-organic −1 tary Table 1). A linear correlation was obtained between ln(R ) ct batteries. The hydrogen bonds suppress the sublimation and −1 and T (Fig. 5b), suggesting the applicability of Arrhenius provides convenience for various electrode treatments. The high −1 58,59 equation of ln(R ) = −E /RT + C . The activation energy ct a molecular symmetry results in low solubility in aqueous electro- E for charge transfer processes was calculated to be 288 meV. a lytes. More importantly, the redox of carbonyl group is associated The low value suggests facile ion desolvation thanks to the help of with dominated proton de/insertion thanks to the amino groups amino groups. which undergoes protonation in the weakly acidic zinc electrolyte. The proton conduction in TABQ was studied by galvanostatic Facile proton conduction in TABQ is furthermore achieved with intermittent titration technique (GITT) at various temperatures. a Grotthuss-type mechanism through the hydrogen bonding The obtained diffusion coefficient (D) values were used to cal- network formed with the amino and carbonyl groups. Therefore, culate the activation energy for ion diffusion according to the proton insertion in TABQ experiences much enhanced kinetics Arrhenius equation of ln(D) = -E ’/RT + C’ (Fig. 5c and Sup- a and is favored for energy storage. Despite the low concentration 2+ plementary Fig. 15) . It results in a low E ’ value of 181 meV. a of proton in the electrolyte, the continuous hydrolysis of Zn Considering the hydrogen bonding network formed among generates sufficient proton for insertion. The unique proton TABQ molecules as discussed earlier, the result demonstrates a conduction manner results in activation energies below 300 meV unique proton conduction manner via the Grotthuss-type for charge transfer and proton diffusion, which guarantees a high 61,62 −1 mechanism (E < 400 meV) , where proton transfer takes capacity of 303 mAh g with excellent rate capability for the place by forming/breaking of hydrogen bonds between adjacent TABQ electrode. Stable cycling is also achieved for 1000 cycles. carbonyl/hydroxyl and amino groups (Fig. 5d). Such process The unique proton conduction manner presented in our work 6 NATURE COMMUNICATIONS | (2021) 12:4424 | https://doi.org/10.1038/s41467-021-24701-9 | www.nature.com/naturecommunications Absorbance -1 -1 ln[R (Ω )] ct 2 -1 ln[D (cm s )] NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-021-24701-9 ARTICLE O O N K O O O 80% Hydrazine hydrate, N N Cl Cl H N NH 2 2 65 ˚C, 2 h O O O O Acetonitrile, 80 ˚C, 12 h Cl Cl H N NH N N 2 2 O O O O O Step 1 Step 2 TCBQ TABQ TPQ Fig. 6 Synthetic routes of TABQ. TABQ was obtained by a two-step synthesis with low-cost reactants. proposes a promising direction for the design of high- mm, and dried at 60 °C under vacuum overnight followed by 90 °C overnight. The −2 mass loading of TABQ was around 1.3 mg cm . Galvanostatic charge/discharge performance organic electrode materials for aqueous batteries. measurements were carried out in PFA Swagelok type cells with titanium rods as the current collectors. Rest test was performed with the following process: regular −1 Methods discharge and charge for 20 cycles at 1 A g , rest for 10 h after discharged to half Materials. Graphite foil was purchased from the SGL group (Germany). TCBQ, capacity, fully discharged, charged to half capacity and fully charged, respectively (a THBQ, o-TCBQ, DABQ, DOBDA, benzoquinone and potassium phthalimide were total of 40 h rest period), and return to regular cycles. The study of electrolyte pH purchased from Aladdin Bio-Chem Technology (China). KB conductive additive influence was carried out in T-shaped PFA Swagelok type cells with TABQ was purchased from Lion Specialty Chemicals (Japan). Poly(vinylidene fluoride) working electrode, graphite foil counter electrode, SCE reference electrode and the −5 (PVDF) was purchased from Kejing Materials Technology (China). The other aqueous electrolytes of 1 M ZnSO , 1 M Zn(CF SO ) ,5×10 MH SO , 0.5 M 4 3 3 2 2 4 reagents were obtained from Sinopharm Chemical Reagent (China). H SO , or 1 M ZnSO + 0.5 M H SO . EIS measurements were carried out in a T- 2 4 4 2 4 shaped PFA Swagelok type cell with TABQ working electrode, Zn counter elec- trode, SCE reference electrode and 1 M ZnSO aqueous electrolyte. GITT was Synthesis of TABQ. The TABQ was prepared according to a previously reported carried out in a T-shaped PFA Swagelok type cell with TABQ working electrode, method as summarized in Fig. 6 and described below. Zn counter electrode, Zn reference electrode and 1 M ZnSO aqueous electrolyte. Step 1: 20.0 g (0.081 mol) of TCBQ, 60.0 g (0.32 mol) of potassium phthalimide The cells for EIS and GITT measurements were placed in an oven which was set to and 200.0 mL of acetonitrile were added into a 500 mL round bottom flask. The the desired temperatures of 35, 40, 45, and 50 °C. All electrochemical experiments mixture was kept at 80 °C for 12 h under stirring. After cooling down to room were carried out on a Bio-Logic VMP3. temperature, the solid was separated by filtration and washed with 2 L boiled water. The product was dried at 60 °C overnight, and brown-yellow powder of tetra (phthalimido)-benzoquinone (TPQ) was obtained (45.0 g, yield = 80.7%). In-situ XRD analysis. The test was carried out with a home-made in-situ XRD cell. Step 2: 9.41 g (0.014 mol) of TPQ was dispersed in 200 mL of 80% hydrazine The TABQ slurry was drop casted on a carbon cloth substrate. The cell was hydrate in a 500 mL round bottom flask. The mixture was stirred at room discharged and charged to the desired voltages and XRD measurements were taken. temperature for 2 h, followed by heating at 65 °C for 2 h. The system was cooled down to room temperature, filtered, washed with water and ethanol, and the dark purple Activation energy calculation. The Nyquist plots from EIS were fitted with a product of TABQ was obtained (1.3 g, yield= 56.6%). H NMR, (500 MHz, [D ] typical equivalent circuit shown in Supplementary Fig. 14b, and the obtained R ct DMSO): δ 4.55 (s, 8H) (Supplementary Fig. 17); elemental analysis (calcd., found for values were summarized in Supplementary Table 1. The low errors confirmed the C H N O ): C (42.86, 42.09), H (4.80, 4.03), N (33.32, 33.27), O (19.03, 21.41). 6 8 4 2 −1 applicability of the circuit for calculating R . The ln(R ) values were plotted vs. ct ct 1000/T and linear fit was carried out according to the Arrhenius equation of ln −1 Characterizations. FT-IR was performed on VERTEX70 (Bruker, Germany). XRD (R ) = −E /RT + C, where C is constant under a stable experimental condition, ct a was carried out on an Empyrean diffractometer with Cu-Kα radiation (PANalytical R is gas constant and T is temperature . The E represents the activation energy B.V., Holland). H NMR was measured on Bruker 500 M (Bruker, Germany) with for charge transfer and was calculated from the slope of the fitted line. Similarly, (methyl sulfoxide)-d as the solvent and tetramethylsilane (TMS) as the internal the activation energy E ’ for diffusion was calculated from the Arrhenius equation 6 a standard. Elemental analysis was determined by an Elementar Vario EL III (Ele- with diffusion coefficient (D) of ln(D) = −E ’/RT + C’. D was calculated from mentar, Germany). TGA was carried out on a TGA/DSC3+ thermal analysis GITT based on the following equation: system (Mettler toledo, Switzerland). The morphology was obtained by a SU8010 4L ΔE SEM equipped with an EDS detector (HITACHI, Japan). UV–vis absorption s ð1Þ D ¼ πτ ΔE spectra were recorded on a U-3900 spectrophotometer (HITACHI, Japan). XPS was carried out on a K-Alpha+ X-ray Photoelectron Spectroscopy (Thermo fisher where τ is the relaxation time, ΔE is the steady-state potential change after a single Scientific, America). ICP-OES analysis was carried out on ICP-OES 730 (Agilent, pulse, and ΔE is the potential change during a pulse after eliminating iR drop. The America). IC analysis was carried out on ICS-1100 (DIONEX, America). diffusion length L was measured by the geometric thickness of cathode. Since L was a constant, the value would not affect the activation energy obtained from slope of 1/2 the Arrhenius equation. The linearity between cell voltage and t during titration Sublimation behavior study. The benzoquinone or TABQ powder was placed on the aluminum foil cover of a long-neck round-bottom flask. It was placed upside was checked to confirm the applicability of the equation (Supplementary Fig. 18) . down with the powder and neck sticking into the oven which was set at 90 °C or 150 °C and the round part staying outside at room temperature. Sublimation was Kinetics studies. The charge/discharge kinetics of TABQ in aqueous zinc cells evidenced by the disappearance of powder on the aluminum cover and con- were studied by CV tests at various scan rates (Supplementary Fig. 16a). The CV densation of crystals on the round part. curves showed two pairs of redox peaks. The peak current i and scan rate v obeys the relationship of i = av , where a and b are coefficients. In the limiting cases, a b value of 0.5 suggests diffusion-controlled process whereas 1 indicates non- UV–vis analysis. Standard solutions were prepared by dissolving known com- 62,63 pound concentrations in 1 M ZnSO . Saturated solutions were obtained by mixing diffusion-controlled process . The peak current at different scan rates was extracted, and the ln of peak current was plotted vs. ln of scan rate. By carrying out an excess of compounds in 1 M ZnSO and filtered. Saturated solutions were diluted by the factors of 100, 200 and 100 with 1 M ZnSO for TABQ, THBQ and linear fit, the b values were obtained from the slopes of the lines (Supplementary Fig. 16b). o-TCBQ, respectively. UV–vis absorbance was measured in the range of 190–600 nm. Calibration curves were obtained by the linear fit of the absorbance at 365 nm, 363 nm and 335 nm for TABQ, THBQ and o-TCBQ, respectively, with respect to Data availability the compound concentrations of standard solutions using the Beer-Lambert law: A The data that support the findings of this study are available from the corresponding = εlc (A: absorbance; ε: molar extinction coefficient; l: length of the cell; c: com- author upon reasonable request. pound concentration). 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Supplementary information The online version contains supplementary material 63. Wang, J., Polleux, J., Lim, J. & Dunn, B. Pseudocapacitive contributions to available at https://doi.org/10.1038/s41467-021-24701-9. electrochemical energy storage in TiO (anatase) nanoparticles. J. Phys. Chem. C. 111, 14925–14931 (2007). Correspondence and requests for materials should be addressed to X.S. 64. Luo, Z. Q. et al. A microporous covalent-organic framework with abundant Peer review information Nature Communications thanks the anonymous reviewer(s) for accessible carbonyl groups for lithium-ion batteries. Angew. Chem. Int. Ed. 57, their contribution to the peer review of this work. Peer reviewer reports are available. 9443–9446 (2018). 65. Weppner, W. & Huggins, R. A. Determination of the kinetic parameters of Reprints and permission information is available at http://www.nature.com/reprints mixed-conducting electrodes and application to the system Li Sb. J. Electrochem. Soc. 124, 1569–1578 (1977). Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. Acknowledgements This work was supported by the National Natural Science Foundation of China (51974070), the LiaoNing Revitalization Talents Program (XLYC1907069), and the Open Access This article is licensed under a Creative Commons Fundamental Research Funds for the Central Universities (N2105001). Special thanks are Attribution 4.0 International License, which permits use, sharing, due to the instrumental analysis from Analytical and Testing Center, Northeastern adaptation, distribution and reproduction in any medium or format, as long as you give University and SDBSWeb: https://sdbs.db.aist.go.jp (National Institute of Advanced appropriate credit to the original author(s) and the source, provide a link to the Creative Industrial Science and Technology, 2020-09-01). Commons license, and indicate if changes were made. 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