All-Climate Aqueous Dual-Ion Hybrid Battery with Ultrahigh Rate and

May 28, 2019 - (17,18) Recently, some lithium-free (involving Na, K, Ca, Zn, and Al) DIBs ... Herein, we demonstrated a ultrahigh-rate and ultralong-l...
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Article Cite This: ACS Appl. Energy Mater. 2019, 2, 4370−4378

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All-Climate Aqueous Dual-Ion Hybrid Battery with Ultrahigh Rate and Ultralong Life Performance Qingshun Nian,† Shuang Liu,† Jian Liu,† Qiu Zhang,† Jinqiang Shi,† Chang Liu,† Rui Wang,† Zhanliang Tao,*,† and Jun Chen† †

Key Laboratory of Advanced Energy Materials Chemistry, College of Chemistry, Nankai University, Tianjin 300071, P. R. China

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S Supporting Information *

ABSTRACT: Aqueous sodium ion batteries (ASIBs) with the characteristics of long cycling life, all-climate compatibility, and low cost need to be developed urgently. Herein, a novel dual-ion battery baesd on Na+ and ClO4− electrochemistry is proposed, consisting of an nano/microstructured Ni(OH)2 (NNH) cathode, a carbon-coated NaTi2(PO4)3 (NTP@C) anode, and 2 M NaClO4 aqueous (aq.) electrolyte. In a charging process, sodium ions are inserted into NaTi2(PO4)3 to form Na3Ti2(PO4)3, and ClO4− is stored in the electric double layers of the NNH cathode; in a reverse process, the Na+ is extracted from Na3Ti2(PO4)3 to form NaTi2(PO4)3, and the adsorption ClO4− is released into the electrolyte. Because of the mechanism of the dual-ion reaction, the aqueous sodium-ion-based dual-ion hybrid battery (ASDHB) displays excellent rate performance, with a capacity of 82.3 mA h g−1anode even at the ultrahigh rate of 50 C. Moreover, the ASDHB displays an ultralong cycling life at a wide temperature range (i.e., from −20 to 50 °C), even at a low temperature of −20 °C, the capacity retention is still as high as 85% after 10 000 cycles at the rate of 10 C. At the same time, it shows a high energy density of 40.1 Wh kg−1total and power density of 257.7 W kg−1total, indicating the potential application on electrial energy storage. KEYWORDS: ultrahigh rate, ultralong life, all climate, aqueous sodium ion batteries, dual-ion hybrid battery

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resources, this has hindered their long-term development.17,18 Recently, some lithium-free (involving Na, K, Ca, Zn, and Al) DIBs have been reported.16,19−21 Because of the advantages of low cost and high abundance and the similar chemical properties of sodium to lithium, sodium-based dual-ion batteries (SDIBs) have been recently studied by some groups.29−31 Despite the use of organic electrolytes, batteries have higher voltage and more material options, and environmental and safety issues are caused by flammable and toxic organic electrolytes.22−28 In addition, the much higher cost and lower ionic conductivity of organic solvents may impose additional restrictions on the large scale application of batteries compared to aqueous electrolytes. The development of aqueous sodium-ion-based dual-ion hybrid batteries (ASDHBs) represents a promising methode for long cycling stability, high rate and large-scale store electricity. However, some cathode materials of SDIBs cannot be used in ASDHBs, for the following reasons: Some cathode materials of SDIBs need more than 4.0 V voltage to make the anion intercalation reaction occurs. Such a high voltage will damage the electrochemical stability window of aqueous elelctrolyte. Thus, the selection of suitable cathode host materials for

INTRODUCTION As renewable solar and wind energy blend into the smart grid, electrical energy storage (EES) devices with the characteristics of long cycling life, all-climate compatibility, high energy densit,y and low cost urgently need to be developed. Although lithium-ion batteries (LIBs) made great achievements in electric vehicles and portable electronics in recent years, limited lithium resources have prompted us to find low-cost alternatives to LIBs.1−7 Nonaqueous and aqueous sodium-ion batteries (SIBs) are widely studied, which have been considered as the most promising candidate for LIBs, because of the rich sodium resources and the similar chemical properties of sodium to lithium.5,6,8−12 Furthermore, because of the high security, high ionic conductivity, and low cost, aqueous sodium-ion batteries (ASIBs) represent a promising direction. However, the two advantages of long cycling stability and high rate performance of aqueous-based battery are not well reflected in the ASIBs. It is necessary to explore novel ASIBs systems with the long cycling stability and high rate performance. Multi-ion reaction, such as dual-ion batteries (DIBs) is a viable way to improve ASIBs performance. The working mechanism of DIBs is both cations and anions are participated in the electrode reaction.13−16 However, most of the reports on DIBs are mainly based on organic Li-ion electrolyte. Considering the limited and uneven distribution of lithium © 2019 American Chemical Society

Received: March 15, 2019 Accepted: May 28, 2019 Published: May 28, 2019 4370

DOI: 10.1021/acsaem.9b00566 ACS Appl. Energy Mater. 2019, 2, 4370−4378

Article

ACS Applied Energy Materials

Figure 1. (a) Schematic diagram of preparing NNH from Ni/MH batteries for aqueous sodium-ion based duai-ion hybrid battery; (b-d) SEM images of the NNH; (e) EDS pattern and elemental mapping images of the NNH; (f) XRD patterns of the NNH.

ASDHBs should meet the requirement of reacting with anions under a stable electrochemical stability window of aqueous elelctrolyte. The Ni(OH)2 has stable electrochemical stability window and ultralong cycling stability in aqueous battery systems, including Ni/MH and Cd/Ni.32−34 In this regard, it may be a candidate cathode material for ASDHBs. Compared with oxygen evolution reaction of the Ni(OH)2 electrode in an alkaline electrolyte (OER, 4OH− → 2H2O + O2 + 4e−), the OER potential in neutral electrolyte has a large reaction overpotential. Therefore, Ni(OH)2 cathode has the possibility of further increasing the oxidation potential before oxygen would evolve. The sodium superionic conductor (NASICON) structured NaTi2(PO4)3 (NTP) has received extensive attention as an anode material for ASIBs due to its large ionic channels, abundant sodium insertion sites, high capacity (133 mA h g−1), and stable structure.35−37 Like other phosphates, the NTP faces the inherent problems of low electronic conductivity. Coating conductive carbon layer on the NTP surface is an effective approach to solve this problem.38 The NTP applications are limited by the dissolution of NTP in alkaline electrolytes, but excellent electrochemical performance have been demonstrated in neutral electrolytes.39 NASICON-type NTP can transport Na+ rapidly and has a stable structure, which makes it a candidate anode material for high-rate and ultralong cycling SIBs. Herein, we demonstrated a ultrahigh-rate and ultralong-life performance ASDHB operated in a wide temperature range with nano/microstructured Ni(OH)2 (NNH) as cathode, carbon-coated NaTi2(PO4)3 (NTP@C) as the anode, and 2 M NaClO4 aqueous as electrolyte. Upon charging, Na+ is inserted into NaTi2(PO4)3 to form Na3Ti2(PO4)3, and the ClO4−

anions in the electrolyte are adsorbed into the NNH cathode. When discharging, the Na3Ti2(PO4)3 is desodiated to NaTi2(PO4)3, and the adsorbed ClO4− is released into the electrolyte. The NTP@C // NNH system can deliver ultralong cycling stability, with 83% capacity maintenance after 10 000 cycles at −20 °C and good rate performance, with 82.3 mA h g−1anode at 50 C, 25 °C. What’s more, in the range of the wide temperature this system shows excellent performance (i.e., from −20 to 50 °C). The sluggish kinetics of the ASIB system is successfully overcome by developing a stable, highperforming ASDHB system, which opens up a new development path for low-cost and high-performance energy storage devices and gives it potential as a new EES device under all climates.

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RESULTS AND DISCUSSION Figure 1a schematically illustrates the NNH obtained from commercialized Ni/MH batteries and application for ASDHB and the device structure of ASDHB (the specific process is in the experimental part). Scanning electron microscopy (SEM) images of the NNH are shown in Figure 1b, c. Most of the particles are found to be spherical, with a diameter of about 10 μm. It can be observed from Figure 1d that these spheres are composed of nanosheets. Energy-dispersive spectrometry (EDS) (Figure 1e) reveals the homogeneous distribution of Ni, O, and Co in the Ni(OH)2 sample. The molar ratio of Ni:O:Co is 30.97:65.68:3.35, and the ratio of Ni:O is close to 1:2, consistent with the Ni(OH)2 composition. The reason for containing a small amount of Co is that Co acts as a conductor in the commercial Ni/MH batteries. The crystalline phase of NNH sample is obtained by X-ray diffraction (XRD). In a good match with the characteristic peaks of Ni(OH)2 (JCPDS 4371

DOI: 10.1021/acsaem.9b00566 ACS Appl. Energy Mater. 2019, 2, 4370−4378

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ACS Applied Energy Materials

Figure 2. (a) CV curves of NTP@C aqueous half-cell at a scan rate of 0.5 mV s−1 and NNH aqueous half-cell at a scan rate of 1 mV s−1; working mechanism of the (b−e) NNH and (f, g) NTP@C. (b) CV curves of NNH electrodes at different scanning rates in half-cell; (c) plot of log i and log v are used to calculate the b value; (d) Cl 2pand (e) Ni 2p3/2 XPS spectra at the pristine, charged, and discharged states of the NNH electrode in the second cycle;(f) ex situ FT-IR spectra of NNH electrode (the NNH electrodes are taken out from full-cell); (g) ex situ XRD of NTP@C electrode; (h) partially enlarged view of the e-picture.

charge/discharge voltage platform, which has good correspondence with the position of the redox peak in the CV curves. It is found that NNH electrochemical behavior changes in aqueous 2 M NaClO4 compared with that in alkaline electrolyte.41−43 It is known that Ni(OH)2 has a pair of redox peaks in alkaline electrolyte. However, it behaves as a highly electrochemical capacitor in aqueous 2 M NaClO4 solution. Figure S2b exhibits the first, second. and fifth cycle charge/ discharge profiles of NNH, showing a tilt voltage curve from 0 to 0.6 V. The charge storage mechanism of the NNH electrode is discussed and characterized via analyzing the cyclic voltammetry data at various sweep rates(Figure 2b) according to the following equations:

No. 73−1520) (Figure 1f). The morphologies of NTP@C are investigated via SEM and transmission electron microscopy (TEM). Figure S1a, b clearly show that the hierarchical microflower morphology of NTP@C and the microflowers have an average diameter ca. 5 μm. This structure can offer a large specific surface area to provide more Na+ transport paths, shortening the transmission path and enabling NTP@C to have a good rate performance. Figure S1c, d displays the lattice fringes of 0.37 nm, which can be assigned to the (110) crystal plane of NTP@C and show that the thickness of carbon layer coated on the surface is 2−5 nm. The crystal structure of NTP@C is characterized by XRD, as shown in Figure S1e. All the diffraction peaks are accurately indexed to the NASICON structured NTP with R-3c space group (JCPDS No. 084− 2011), and the sharp peaks, showing good crystallinity. Thermal gravimetric analysis (TGA) curve for the NTP@C recorded in air is shown in Figure S 1f. The amount of carbon coated on the NTP@C is calculated to be 12.6 wt % based on the curve of the TGA weight loss. Figure 2a displays the cyclic voltammetry (CV) measurement of NTP@C at a scan rate of 0.5 mV s−1 and NNH at a scan rate of 1 mV s−1, in three electrodes system (work electrode: NTP@C, reference electrode: Ag/AgCl (1 M KCl, 0.2224 V vs. NHE), counter electrode: platinum sheet). NTP@C shows a pair of redox peaks in good symmetry at −0.81 V and −0.75 V (vs. Ag/AgCl) and remained unchanged during continuous scanning, indicating that the NTP @ C material has excellent reversibility and cycle stability in 2 M NaClO4 aqueous solution. Figure S2 a displays the NTP@C

i = avb

(1)

which can be rewritten as log(i) = b log(v) + log(a)

(2)

where i is the current density, v is the sweep rate, and both a and b are constants.44,45 When the b value is 1, it is a capacitive reaction, and when the b value is close 0.5, it is the reaction that represents the diffusion limitation.46 On the basis of the slope of the corresponding log(i)−log(v) plots shown in Figure 2c, the b value is 0.92, which is close to 1, it is shown that the storage charge mainly displays capacitance behavior. To furtuer distinguish the capacitance behavior of the NNH electrode, we performed ex situ X-ray photoelectron spectroscopy (XPS), XRD ,and Fourier transform infrared spectroscopy (FT-IR). Figure 2d, e displays the ex situ XPS spectrum of 4372

DOI: 10.1021/acsaem.9b00566 ACS Appl. Energy Mater. 2019, 2, 4370−4378

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Figure 3. Electrochemical performance of full-cell at 25 °C: (a) charge/discharge curves at different rate of 5, 10, 20, 30, and 50 C, respectively; (b) rate performance of full-cell; (c) long cycling performance of the full-cell at 10 C; (d) Ragone plots of performance compared to other ASIBs in previous works. (e) Photograph of a small LED panel powered by three full cells connected in series.

capacitance behavior with adsorption/desorption of ClO4− during charge/discharge in aqueous 2 M NaClO4 electrolyte. Density functional theory (DFT) calculations are conducted to reveal the combination of Ni(OH)2 and ClO4− when Ni(OH)2 adsorbs ClO4−. Conclusion can be drawn from Figure S4 that the Ni(OH)2 adsorbs ClO4− and consequently form Ni(OH)2[ClO4−]2 with minimum energy. The working mechanism of NTP@C in the new system is also explored. Figure 2g, h display the ex situ XRD of the NTP@C electrode is in the selected charging/discharging state, where the peaks at 24 and 32.5° (corresponding to the (113) and (116) reflection of NTP@C) gradually shift to lower degree during the charge process. However, impressively, the two peaks finally recover to the initial state during the discharge process. All above results indicate the continuous and reversible insertion/extraction of Na+ in NTP@C crystal during cycling. To clarify this point, ex situ XPS is applied to the determine the valence state change of Ti at the pristine state, the end of charging state, and the end of discharging state. Figure S5 shows the transformation of Ti4+ and Ti3+ occurring in the charging/discharging. The valence state of Ti

Cl 2p and Ni 2p3/2 of the NNH electrode (NNH electrodes are taken out from full-cell in an argon-filled glovebox, then washed with anaerobic deionized water to remove residual electrolytes). There is no Cl signal in the pristine electrode sheet. After charging, in the spectra of Cl 2p, new peaks present at 208.5 eV that can be assigned to the Cl 2p of ClO4−,47 indicating the capacitive adsorption of ClO4− on the NNH cathode. Upon discharging, the new peak decreases apparently because of the release of ClO4− into the electrolyte. It can be seen from the Ni 2p3/2 spectrum that the valence of Ni2+ does not change, it shows that Ni(OH)2 is not oxidized to NiOOH via the reaction Ni(OH)2 + OH− → NiOOH + H2O + e−. Ex situ FT-IR is employed to provide further evidence for the reversible adsorption/desorption process of ClO4− in NNH electrode. In the ex situ FT-IR spectra of the NNH electrode (Figure 2f), the peak at 1100 cm−1 belonging to ClO4− gradually enhances in the charge process.48 During the discharge process, it changes weaker gradually. Simultaneously, the ex situ XRD of the NNH electrode (Figure S3) shows that the crystal structure of NNH does not change. Therefore, it can be concluded that the electrochemical activity of NNH is 4373

DOI: 10.1021/acsaem.9b00566 ACS Appl. Energy Mater. 2019, 2, 4370−4378

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ACS Applied Energy Materials

Figure 4. Electrochemical performance of full battery in all climates; (a) 500-cycle performance of the full cell at different temperature of 50 °C, room-T, and −20 °C with a rate of 10 C; (b) cycle test at different temperatures; (c) 10 000 cycles of the battery at −20 °C with a rate of 10 C.

cycles process. This ultralong cycling life and excellent rate performance are impressive and superior to most ASIBs.49−53 The ultralong cycling life due to the stability of the NTP@C structure and the excellent rate performance are notthe only benefit from the capacitive behavior of the cathode; the NASICON structure anode of NTP@C with mesoporous micron-flower provides a large specific surface area for the ions and electrons transfer quickly. Figure 3d displays the Ragone plots of performance compared to other ASIBs in previous works. The ASDHB system shows a high energy density of 40.1 W h kg−1total and power density of 257.7 W kg−1total (detailed calculations are presented in methods). Figure 3e displays the “ASDHB”shaped LED panel, which can be lightened by connecting three full cellsin series , illustrating the practical application potential of our NTP@C // NNH batteries. To demonstrate the suitability of the full cell in all climates for stable electricity supply application, we measured the full cell in all climates. Figure 4a shows the cycle performance of the full cell at 10 C for 500 cycles at 50 °C, room-T, and −20 °C. It can deliver ca. 83, 87, and 100% of the initial capacity, respectively. Figure 4b displays the charge/discharge capacity under varying temperature conditions (the initial temperate is controlled at 25 °C, then down to 0, −10, and −20 °C and back to 25 °C). When the temperature from low-T return 25 °C, the specific capacity of 94.8 mA h g−1anode is recovered, indicating the battery’s highly adaptable to temperature. Furthermore, Figure 4c shows the full cell also has remarkable stability at low-T with a retention of 85% at 10 C after 10 000 cycles at −20 °C (the full cell is placed in a low-temperature test chamber for the low-T test, which is shown in Figure S6). That is equivalent to a fading rate of ca. 0.0015% for each cycle. It can be collectively concluded that the full cell can offer an outstandingly stable electrochemical performance at low-T. To comprehensively compare the performance of the NTP@C // NNH novel battery systems with other ASIBs,

transforms in order to balance the charge, when inserting/ extracting Na+ in NTP @ C The working mechanism of ASDHB energy storage device is summarized as follows: During charging, nonfaradiac reaction occurs on the cathode, the ClO4− adsorbs on NNH surface. At the same time, Faraday reaction also occurred on the anode, whereas Na+ insertion occurs in the NTP@C crystal. On the contrary, in the process of discharge, ClO4− desorbs from the NNH surface and Na+ is extracted from the NTP@C. Hence, the electrochemical reactions equation of the NTP@C // NNH system can be summarized as follows: Cathode: Ni(OH)2 + 2ClO4 − ↔ Ni(OH)2 [ClO4 −]2 + 2e−

(3)

Anode: NaTi 2(PO4 )3 + 2Na + +2e − ↔ Na3Ti 2(PO4 )3

(4)

Overall Ni(OH)2 + 2NaClO4 + NaTi 2(PO4 )3 ↔ Ni(OH)2 [ClO4 −]2 + Na3Ti 2(PO4 )3

(5)

The electrochemical performance of the full cell is measured. Figure 3presents the full-cell charge/discharge curves at different rate of 5, 10, 20, 30, and 50 C (for the battery test, 1 C = 133 mA g−1, based on anode mass). The discharge plateau is at 1.25 V and the charge plateau is a slightly higher without significant voltage hysteresis. The rate capability of the ful cell is also assessed on different rate from 5 to 50 C (Figure 3b). The reversible capacity of the full-cell is 95.2 mA h g−1anode at 5 C, and 82.3 mA h g−1anode even at a high rate of 50 C. Although the rate return to 5 C, the capacity of 94.8 mA h g−1anode is restored, demonstrating an superior rate capability of the battery. Importantly, ∼ 87% of its initial capacity can be maintained after 500 cycles at a rate of 10 C and room-T (25 °C) (Figure 3c), with the coulombic efficiency ∼99.8% in the 4374

DOI: 10.1021/acsaem.9b00566 ACS Appl. Energy Mater. 2019, 2, 4370−4378

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Figure 5. (a) Fitting map of the Nyquist plots and equivalent circuit of full battery at different temperature; (b) ln σ as a function of temperature; (c) SEM image, EDS elemental mappings, and TEM image of NTP@C electrode at pristine, 500th cycle, and 10 000th cycle.

the slope of the corresponding ln(σ) − 1000/T plots show in Figure 5b, and the Arrhenius equation:

the electrochemical performance of various ASIBs show in Table S1. The novel battery systems give an operating voltage of 1.25 V, which is higher than most ASIBs. At all climates, the NTP@C // NNH full cell exhibits the best rate performance and cyclic stability among the reported ASIBs. Figure S7 shows that the “ASDHB”-shaped LED panel can be lightened under the temperature of −20 °C by connecting in series three full cells (the LED panel is placed in a low temperature test chamber), illustrating the practical application potential of our NTP@C//NNH batteries under low-T. To further illustrate the sensitivity of the full cell to temperature, the activation energy of the battery reaction is calculated by Arrhenius equation. Because the cathode NNH undergoes adsorption/desorption reaction, and the anode NTP@C occurs redox reaction, in the process of charging and discharging. Therefore, the redox reaction of the anode can be regarded as the full-cell reaction. Figure S8 displays the Nyquist diagram of the full battery at different temperatures. The equivalent circuit models fitted from the Nyquist are shown in Figure 5a (green lines are experimental results, orange lines are fitting results), the diffusion resistance (Rct) of the battery can be derived from fitting Nyquist. At the same time the ionic conductivity (σ) is obtained by Rct. According to

σ(T ) = A exp( −Ea /RT )

(6)

which can be reformulated as ln(σ ) = −Ea /RT + ln(A)

(7)

where σ is the ionic conductivity, T is the thermodynamic temperature, Ea is the activation energy, and A is the preexponential factor,54,55 the battery reaction activation energyis as low as 8.21 kJ mol−1 (compared to the 39 kJ mol−1 of the anode MmH of a commercial NiMH battery),56 indicating that the battery system is insensitive to temperature, which enables the battery to have a good performance under all climates. The cycle stability of full-cell at low-T (−20 °C) is explored. Figure 5c displays the SEM images of NTP@C electrode, after 500 cycles, 10 000 cycles, and at pristine, respectively (NTP@ C electrodes are taken out from full-cell in an argon-filled glovebox, then washed with anaerobic deionized water to remove residual electrolytes). As can be seen from the SEM images that there is no pulverization and agglomeration on the surface of the electrode after 500 cycles and 10 000 cycles. The EDS elemental mappings and line scan of the selected NTP@ C particle show that Na, Ti, P, and O are uniformly distributed 4375

DOI: 10.1021/acsaem.9b00566 ACS Appl. Energy Mater. 2019, 2, 4370−4378

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carried out on a NETZSCH STA 449 F3 Jupiter analyzer from 30 to 600 °C at a heating rate of 10 °C min−1 under an air atmosphere. XPS results are recorded by Kratos AXIS 165 equipment. FT-IR measurements are measured by a BRUKER TENSOR II (FTS6000) equipment. Electrochemical Measurement. The electrochemical properties of NTP@C and NNH half-cell in aqueous 2 M NaClO4 electrolyte are investigated in three-electrode system using a platinum and an Ag/AgCl electrode (1 M KCl, 0.2224 V vs. SHE) as counter and reference electrode, respectively. The slurry of the anode is prepared by dissolving 80 wt % NTP@C, 10 wt % super P and 10 wt % polyvinylidene fluoride (PVDF) in an appropriate amount of Nmethyl-2-pyrrolidone (NMP). The slurry is spread onto 1 cm2 titanium foil and dried in a vacuum oven at 100 °C for 12 h, and the loading mass of the NTP@C anode is 1.0−3.0 mg cm−2. The full cell is assembled in a CR2032-type coin cell in an argon-filled glovebox, using NNH as cathode, NTP@C as anode, filter paper as the separator, and 2 M NaClO4 aq. as electrolyte. The galvanostatic charging/discharging tests are performed on a cell testing system (Land CT2001A, WuHan). The CVs are obtained on an electrochemical workstation (CHI660D, Chenhua ShangHai). Electrochemical impedance spectroscopy (EIS) is also tested on the CHI660D. High- and low-temperature battery tests are obtained on a high- and low-temperature test chamber (Suoyate WuXi). Calculation of Energy Density of the NTP@C // NNH System. The system based on NNH cathode and NTP@C anode is a dual-ion battery, and the salt in the electrolyte is spent during the charging process (i.e., the cations and anions separation). Thus, the active materials of the system should contain both the electrode active materials (NNH + NTP@C) and the spent salts (NaClO4). The theoretical energy density of NTP@C // NNH rechargeable battery can thus be evaluated according to eq 8 as follows:

in the whole particle, further implying that there is no pulverization and agglomeration on the electrode after cycle. The HR-TEM image of NTP@C demonstrates the clear lattice fringes and the high crystallization with d-spacing of 0.37 nm, allocate to the (113) planes of NTP@C after 500 cycles and 10 000 cycles, which implies that the crystal structure of NTP@C is well-maintained after repeated extraction/insertion of Na+ ions under neutral electrolyte. The NTP@C is still homogeneously implanted in the carbon matrix and the carbon layer remains intact. M. R. Palaciń Group’s reported that after Na+ inserting into NaTi2(PO4)3 the unit cell volume only increases 8.1%, which is negligible.40 The stability of crystal structure is also a factor in why the full cell can achieve long cycling performance at low temperature.

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CONCLUSIONS In summary, a high-rate and ultralong cycling full ASDHB with NNH cathode, NTP@C anode, and 2 M NaClO4 aqueous (aq.) electrolyte is successfully constructed to operate at a wide temperature range. The full ASDHB exhibits excellent rate performance with a capacity of 82.3 mA h g−1anode even at a high current density of 50 C with negligible capacity decay, and excellent cycling stability at a wide temperature range (i.e., from −20 to 50 °C), even at a low temperature of −20 °C, the capacity retention is still up to 85% after 10 000 cycles at 10 C, and it shows a high energy density of 40.1 Wh kg−1total and power density of 257.7 W kg−1total. The excellent performance of ASDHB is attributed to its hybrid energy storage mechanism. In general, these significant ultrahigh-rate characteristics are clearly owe to the anion absorption-type nano/microstructured Ni(OH)2 and fast Na+ transport in NASICON-type NTP@C enable ASDHB to have fast reaction kinetics. The ultralong cycle performance is attributed to the stable structure of NTP@C during charging and discharging. The improved performance makes this an aqueous sodiumion-based energy-storage device for next-generation energystorage technology.

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E=

QmanodeV melectrodes + mNaClO4

(8)

where E is the theoretical energy density of the electrodes (based on the total mass) and consumed salts (NNH cathode + NTP@C anode + NaClO4), Q is the discharge capacity based on the anode mass (88 mAh ganode−1 at 10 C, Figure 3c), V is the average voltage of the rechargeable battery (1.25 V, Figure 3a), manode is the mass of anode material (NTP@C), and melectrodes+NaClO4 is the total mass of electrodes and consumed salts (NNH cathode + NTP@C anode + NaClO4). It should be noted that equal molar NaClO4 is consumed with NTP@C during the charge process. Taking the mass ratio of 1:1.2 for NTP@C: NNH into consideration, the calculated theoretical energy density of the rechargeable battery can reach 40.1 Wh kg−1.

METHODS

Preparation of the Cathode and Anode Materials. The cathode material NNH is directly obtained from the commercialized Ni/MH battery (Pin sheng No. 5 battery, the specific disassembly procedure seeing Figure S9). The Ni/MH battery is first fully discharged and then disassembled in a glovebox filled with argon. After washing the NNH with a large amount of deionized water to remove the original electrolyte, the NNH drying for 12 h at 80 °C to get the final materials. The NTP@C are synthesized by solvothermal method:38 All the reagents used are of analytical grade. Tetrabutyl titanate (TBOT) (2 mmol) is slowly added dropwise to ethylene glycol (EG) (20 mL) and stirred for 30 min, get clear white solution, then 0.1 M NaH2PO4· 2H2O (10 mL), H3PO4 (2 mmol), 0.1 M glucose (10 mL) are added to the above solution sequentially. The above mixed solution is stirred for more than 1 h to get a uniformly transparent solution, then transferred into 50 mL Teflon-lined stainless-steel autoclave and reacted at 180 °C for 12 h. After the system is cooled to room temperature, dried at 120 °C to get the brown precursor. The following, the brown precursor precalcining at 350 °C for 2 h in a flowing argon atmosphere, and sintered at 700 °C for 4 h in a flowing argon atmosphere with the heating rate is 2 °C min−1. Material Characterization. TEM images and SEM images measurements are performed on Philips Tecnai F20 and JEOL JSM7500F microscopes equipped with EDS for performing elemental analysis. XRD patterns are getted via the Rigaku MiniFlex600, and the electrode characterization is obtained by ex situ XRD. TG analysis is

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsaem.9b00566.

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Material characterization, electrochemical measurement data, free energy profiles, discussion about the cost of the aqueous electrolyte, and electrochemical performance comparison (PDF)

AUTHOR INFORMATION

Corresponding Author

*Email: [email protected]. ORCID

Zhanliang Tao: 0000-0001-9401-1998 Jun Chen: 0000-0001-8604-9689 Notes

The authors declare no competing financial interest. 4376

DOI: 10.1021/acsaem.9b00566 ACS Appl. Energy Mater. 2019, 2, 4370−4378

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ACKNOWLEDGMENTS This study was was supported by the National Key R&D Program of China (2016YFB0901500, 2016YFB0101201), the National Natural Science Foundation of China (51771094), Ministry of Education of China (B12015 and IRT13R30), and Tianjin High-Tech (18JCZDJC31500).

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