Novel Potassium-Ion Hybrid Capacitor Based on an Anode of

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A Novel Potassium-Ion Hybrid Capacitor Based on an Anode of K2Ti6O13 Micro-Scaffolds Shengyang Dong, Zhifei Li, Zhenyu Xing, Xianyong Wu, Xiulei Ji, and Xiaogang Zhang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b15314 • Publication Date (Web): 23 Apr 2018 Downloaded from http://pubs.acs.org on April 24, 2018

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A Novel Potassium-Ion Hybrid Capacitor Based on an Anode of K2Ti6O13 Micro-Scaffolds Shengyang Dong,†,‡ Zhifei Li,‡ Zhenyu Xing,‡ Xianyong Wu,‡ Xiulei Ji*,‡ and Xiaogang Zhang*,† †

Jiangsu Key Laboratory of Electrochemical Energy Storage Technologies,

College of Material Science and Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing, 210016, P. R. China ‡

Department of Chemistry, Oregon State University, Corvallis, Oregon 97330, United

States

Abstract: To fill the gap between batteries and supercapacitors requires integration of the following features in a single system: energy density well above that of supercapacitors, cycle life much longer than Li-ion batteries, and low cost.

Along

this line, we report a novel non-aqueous potassium-ion hybrid capacitor (KIC) that employs an anode of K2Ti6O13 (KTO) micro-scaffolds constructed by nanorods and a cathode of N-doped nanoporous graphenic carbon (NGC).

K2Ti6O13 micro-scaffolds

are studied for potential applications as the anode material in potassium-ion storage for the first time. 1000 cycles.

This material exhibits a excellent capacity retention of 85% after

In addition, the NGC//KTO KIC delivers a high energy density of 58.2

Wh kg−1 based on the active mass in both electrodes, high power density of 7200 W kg−1, and outstanding cycling stability over 5000 cycles. The usage of K-ions as the anode charge carrier instead of Li-ions and the amenable performance of this device 1

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suggest that hybrid capacitor devices may welcome a new era of beyond lithium.

Keywords: Energy storage, Hybrid capacitor, Potassium-ion intercalation, K2Ti6O13, Nanoporous graphenic carbon

1. INTRODUCTION Recently, tremendous efforts have been focused on developing sustainable alternative energy storage technologies.1-9

Due to the rarity and high

extraction cost of lithium, batteries based on earth-abundant elements have attracted much attention, among which potassium-ion batteries (KIBs) is of great interest arising from the unique properties of K-ion storage.10,

11

Recently, KIBs have observed encouraging performance of carbon-based anodes,12-15 metal oxide cathodes,16, 17 as well as the Prussian blue analogues as cathodes.18-21

To maximize batteries’ cycle life, the anode side plays a pivotal

role, where parasitic reactions between the anode and the electrolyte should be mitigated.

One approach is to employ metal oxides as the anode, where

titanates and the associated high operation potentials are known responsible for their ultra-long cycling performance in Li-ion batteries (LIBs) and Na-ion batteries (NIBs).22-26

Along this line, two K-ion-based titanates, K2Ti8O17 and

K2Ti4O9 were reported for K-ion anodes; however, only very limited cycling performance was demonstrated.27, 28

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A recent technological innovation in energy storage is about hybrid cells, where it attempts to integrate the superiorities of high energy output of secondary batteries and high power delivery of electrochemical capacitors.29-32 So far, Li-based and Na-based hybrid cells have been extensively reported.33-37 As for K-based systems, only a few K-ion hybrid capacitors were reported.38-41 Here, we report a novel non-aqueous potassium-ion hybrid capacitor (KIC), which employs K2Ti6O13 (KTO) micro-scaffolds as an anode and a cathode of N-doped nanoporous graphenic carbon (NGC).

KTO micro-scaffolds are

successfully prepared using a simple hydrothermal method combined with a subsequent annealing process.

The unique KTO electrode exhibits high rate

performance and cycling property.

Additionally, the KIC delivers a high energy

density of 58.2 Wh kg−1, a high power density of 7200 W kg−1, and excellent energy retention of 75.5% over 5000 cycles. Via this full-cell device design, we hope to point out that K-ion hybrid devices are as competitive as devices based on Li-ions but potentially at a lower cost.

2. EXPERIMENTAL SECTION 2.1 Synthesis of K2Ti6O13 (KTO) Micro-Scaffolds K2Ti6O13 micro-scaffolds were prepared via a simple hydrothermal process using potassium hydroxide and tetrabutyltitanate (TBT) as the potassium and titanium sources, respectively.

Typically, 1.0 mL H2O2 (30 wt%) was dispersed in 2M KOH

(30 mL), followed by addition of 1.5 mM TBT. After stirring for 50 min, the 3

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transparent solution was transferred into an autoclave (50 mL), which was then held at 160 ℃ for 24 h.

After this hydrothermal process, the precipitate was collected by

centrifugation, washed with de-ionized (DI) water and absolute ethyl alcohol for several times, and then dried at 80 °C for 12 h.

Finally, the KTO precursor sample

was heat at 700 °C for 10 h in Ar gas. 2.2 Synthesis of N-doped Nano-porous Graphenic Carbon (NGC) The detailed synthesis process of NGC can be found in our previous work.42

2.3 Materials Characterization and Electrochemical Measurement Detailed information about the Materials characterization and electrochemical measurement are provided in the Supporting Information.

3. RESULTS AND DISCUSSION The K2Ti6O13 (KTO) anode was prepared via a novel hydrothermal process under alkaline conditions, using tetrabutyltitanate (TBT) and potassium hydroxide as precursors, followed by annealing at 700 °C. The crystallinity of KTO precursor is very low (Figure S1a, Supporting Information).

As shown in the TG plot (Figure

S1b), the as-prepared KTO precursor has a weight loss before 400 ℃, which is attributed to the adsorbed water and a little residual titanate.

As shown in the XRD

pattern (Figure 1a), after calcined at 700 °C, the primary peaks are indexed to the monoclinic K2Ti6O13 (space group: C2/m; JCPDS no. 40-0403).43

The tiny

diffraction peaks marked by stars correspond to a minor phase of K2TiO3.

Figure 1b

depicts the crystallographic arrangements of KTO, in which edge-shared TiO6 4

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octahedra are connected by corners to form a tunnel structure, where the potassium ions reside between the TiO6 slabs.43

This structure is similar to the A2Ti6O13 (A = H,

Li, Na) materials, containing vacant tunnels along the b-axis.44, 45

Figure 1. (a) XRD pattern KTO. (b) The crystallographic arrangement of KTO. Interestingly, KTO precursor and KTO exhibit unique micro-scaffold morphology, where as shown in the SEM images (Figure S2 and Figure 2a, b), KTO comprises micron-sized spheres that are constructed by tiny nanorods in an interwoven style. Notably, if the hydrothermal time is reduced to 9 h, the interwoven structure of KTO precursor has partially grown (Figure S3a). However, if the hydrothermal time is extended to 36 h, the micro-scaffolds structure has been broken to some extent (Figure S3b). The transmission electron microscopy (TEM) (Figure 2c) corroborates the nanostructure of KTO, where the nanorods are ~ 20 to 60 nm wide.

High resolution TEM

(HRTEM) reveal the (200) and (31-2) crystal planes of KTO with inter-planar distances of 0.770 and 0.265 nm, respectively (Figure 2d), where the large inter-layer may help accommodate the large K-ions.28 5

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electron diffraction (SAED) pattern in Figure 2d inset indicates that the KTO has a single crystal structure.

As shown in Figure S4 KTO also possesses a

high BET specific surface area of 279 m2 g−1 with the pore size distribution from 20 to 80 nm.

Figure 2. (a, b) SEM and (c, d) TEM images of KTO. b and d are the enlarged marked areas in a and c, respectively. The K-ion storage in KTO was evaluated in coin-type cells.

Figure 3a

and Figure S5 depict the GCD profiles of KTO at 50 mA g–1.

The initial

potassiation/depotassiation capacities, based on the mass of KTO, are about 267 and 91 mAh g–1, respectively, with a low initial Coulombic efficiency (CE) of 34% (Figure S5).

This low CE is at the same level as K2Ti4O9 and K2Ti8O17

reported in KIBs;27, 28 the cause of low initial CE may be due to the formation 6

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of solid electrolyte interphase (SEI) film or trapping of large K-ions in the KTO’s structure.

After the initial cycling, the reversible capacity of KTO is

stabilized at about 90 mAh g–1 (Figure 3a). Note that the specific capacity of the carbon additive, C-45, is less than 80 mAh g–1 (Figure S6).

Considering

10 wt.% of C-45 in the anode, its capacity contribution is less than 10 mAh g–1.

Figure 3. (a) GCD profiles of KTO electrode at 50 mA g−1. (b) The rate property of KTO. (c) The cycling from on the 6th cycle at 500 mA g−1. (d) EIS curves of KTO electrode before cycling and after 20 cycles. Figure 3b shows the rate capability of KTO, where KTO delivers capacities of 95, 89, 82, 72, and 64 mAh g−1 at the current densities of 20, 50, 100, 200, and 500 mA g−1, respectively.

The capacity retains at 57 mAh g−1

even at 1000 mA g−1, 60% the capacity at 20 mA g−1, indicative of the excellent 7

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When the current density returns to 20 mA g−1, KTO’s

capacity returns back to 90 mAh g−1. 500 mA g−1 for 1000 times.

Subsequently, the half-cell was cycled at

At the 1000th cycle, the reversible capacity

remains at 59 mAh g−1 with only 16% loss (Figure 3c).

Note that the

structure and morphology did not vary after 1000 cycles (Figure S7). Figure 3d displays the Nyquist plot of KTO electrode before cycling and after 20 cycles under 50 mA g−1. All curves show semi-circle at high-frequency region and a sloping line at low frequency. Compared with before cycling plot, the KTO electrode shows slight higher resistance after 20 cycles. Notably, the first semi-circle in high-frequency region after 20 cycles is due to the SEI film. The potassium ion diffusion coefficient (DK, cm2 s−1) can be calculated from the Warburg region. As shown in Figure S8, the DK of KTO electrode is about 1.2 × 10−14 cm2 s−1 after 20 cycles. To reveal the impact of the K-ion storage on the structure of KTO, we collected ex situ XRD (Figure S9) patterns at selected state of charge (SOC) in the first two cycles at 50 mA g−1.

There are only minor peak shifts after potassiation (Figure

S9b), where the (200) peak shifts from 11.5° to 11.4° (Figure S9c).

During the

subsequent depotassiation process, the (200) peak shifts back to its original position. We also conducted XPS (Figure S10) at different SOCs to analyze the reaction mechanism.

The Ti2p binding energy of pristine KTO are located at 464.6 and 458.9

eV, confirming Ti (IV); when discharged to 0.1 V, the new two peaks at 463.5 and 457.7 eV are indexed to Ti (III).

Upon charging back to 2.5 V, the Ti2p peaks almost 8

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recovered back to the binding energy of Ti (IV). The tiny residual Ti (III) demonstrates that some K-ions are trapped in the KTO structure. The purpose of employing NGC is to provide a positive electrode that operates on electrical double layer capacitance (EDLC) for the K-ion hybrid capacitor.

The N-doped nanoporous graphenic carbon (NGC) was prepared

by reacting Mg with gaseous mixture of CO2 and N2.42 BET surface area of about 1800 m2 g−1.

42

NGC exhibits a large

Figure S11 depicts its XRD

pattern, where a sharp tip emerges from the broad (002) peak around 26°, indicating both amorphous regions as well as nanosized graphitic regions in NGC.42

NGC has an atomic ratio of C, O, and N in 94.1/4.8/1.1, where

N-doping may play a role in tuning the surface reactivity and wettability.42 The typical GCD profiles of the NGC cathode are shown in Figure 4a with a voltage window of 3.0 − 4.5 V vs K+/K.

Note that the potential of zero charge

(PZC) of NGC cathode in the electrolyte is 2.6 V vs K+/K, as measured by the dipping method.46

Thus, from 3.0 to 4.5 V, NGC is positively polarized.

The discharge capacity reaches 50 mAh g−1 at a current density of 20 mA g−1. The linear GCD profiles suggest the EDLC behaviour over the large surface of NGC.

Figure 4b shows the rate property of the NGC electrode; the discharge

capacity remains at 35 mAh g−1 even at 2000 mA g−1, equivalent to 70% the capacity at 50 mA g−1.

As shown in Figure 4c, the NGC electrode also shows

long cycle life with the capacity retention of about 85% after 1000 cycles at the current density of 500 mA g−1. 9

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Figure 4. (a) Typical GCD profiles of NGC electrode at 20 mA g−1. (b) The rate property of NGC. (c) The cycling of NGC from on the 6th cycle at 500 mA g−1. Based on the above results, we assemble a potassium-ion hybrid capacitor (KIC) with the KTO anode and NGC cathode in a non-aqueous system. Figure 5a shows the schematic of the proposed KIC, in which during charge, K+ are inserted into the KTO anode while PF6− ions are electrostatically adsorbed onto NGC’s surface; during discharge, the K+ and PF6− are released from KTO and NGC, respectively, into the electrolyte.

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Figure 5. (a) Schematic of the NGC//KTO KIC configuration. (b) Typical GCD profiles at various current densities from 0.1 to 5.0 A g−1. (c) Long-term cycling stability at the current density of 1 A g−1. (d) Ragone plot obtained by the total active mass in both cathode and anode. Added for comparison are the values from representative Li-based, Na-based and K-based hybrid devices. In order to fully reveal the cycling stability of the KIC full cell without being masked by the irreversibility effect, both KTO and NGC electrodes were pre-conditioned in half-cells at 20 mA g−1 for three cycles.

The

electrochemical properties of the KTO//NGC full cells were investigated by GCD tests at room temperature with the voltage window of 0-3.5 V.

As

shown is Figure S12a, the KIC full cell shows a relatively quasi-rectangular shape, which indicates the capacity is mainly ascribed to capacitive behavior. 11

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In addition, the EIS spectra of the KIC (Figure S12b) are almost vertical in the low frequency region even after 500 cycles, further indicating that the electrochemical process is mainly capacitive and the device possesses super cycling stability.

Figure 5b illustrates the typical GCD profiles at various

current densities.

Furthermore, as shown in Figure 5c, the KIC shows

impressive cycle stability over 5000 cycles with a capacity retention of 75.5% at 1 A g−1. lithium-based

This capacity retention outperforms most conventional and

nanobelts//graphene

sodium-based hydrogels

hybrid

(73%

after

capacitors, only

600

such

as

cycles),47

TiO2 3D

graphene//Fe3O4 (70% after 1000 cycles),48 Na2Fe2(SO4)3//Ti2CTx (83% after only100 cycles),49 and AC//V2O5/CNT (80% of after 900 cycles).50 This KIC delivers a large energy density of 58.2 Wh kg−1 and a maximum power density of 7200 W kg−1. The specific energy density (E, Wh kg−1) and power density (P, W kg−1) of the KIC can be obtained as follows:51 E = ∫UIdt

(1)

P = E/Δt

(2)

Δt = t2 – t1

(3)

where I is the current density normalized by the total active mass in both cathode and anode (A g−1), and t1 and t2 are the start and end time during the discharge process (h), U is the voltage (V).

For the sake of evaluating the novel KIC configuration in the

context, a Ragone plot is constructed (Figure 5d), which demonstrates that NGC//KTO KIC provides a high energy density and power density comparable to the 12

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state-of-the-art Li-based, Na-based and K-based hybrid energy storage devices, such as, AC//LTO (Li),52 AC/CNT//CNT threaded TiO2 (Li),53 AC//Na-TNT (Na),54 AC//V2O5/CNT (Na),50 GF//NTO/CT (Na),55 and AC//graphite (K).41 The high energy and power features of the NGC//KTO KIC can be ascribed to the following factors.

The unique cross-linked porous structure

consisting of KTO nanorods ensures that most nanorod participate in the ultrafast

electrochemical

reaction.

The hierarchical

micro-nanometric

structure facilitates the full exposure of active mass to the electrolyte, which promotes rate capability.

Regarding the NGC cathode, its capacitance is

suitable for amenable full-cell performance.

The large surface area secures

the high electrical-double-layer capacitance, and the high degree of graphitization enhances the conductivity.

All these features ensure excellent

performance of this new KIC in terms of rate capability, energy density, and cycling stability.

4. Conclusions In summary, a novel non-aqueous potassium-ion hybrid capacitor has been developed, based on the anode of K2Ti6O13 micro-scaffolds and the cathode of N-doped nanoporous graphenic carbon with potassium-based electrolyte. Such a potassium-ion hybrid capacitor can exhibit battery-like high-energy characteristics, i.e., energy density of 58.2 Wh kg−1 and supercapacitor-like high-power characteristics, i.e., power density of 7200 W kg−1. 13

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The device

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can exhibit an outstanding cycling stability with approximately 75.5% capacity retention after 5000 cycles.

These findings provide an opportunity for the

further development of hybrid ion capacitors that are beyond lithium for a wide range of high energy and high power required by storage applications.

ASSOCIATED CONTENT Supporting information The Supporting information is available free of charge on the ACS Publications website. Materials characterization and electrochemical measurement. Additional XRD, TGA, and SEM images of KTO precursor, BET analysis of the prepared samples, ex situ XRD and XPS patterns of the KTO electrode. SEM images of KTO precursor with different hydrothermal time and KTO electrode after 1000 cycles. Charge−discharge test of C-45 electrode. XRD pattern of NGC. CV and EIS of KIC.

AUTHOR INFORMATION Corresponding Authors. *E-mail: [email protected] (X. G. Zhang). *E-mail: [email protected] (X. L. Ji).

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Notes The authors declare no competing financial interest. ACKNOWLEDGMENTS X. Z. acknowledges financially support by the National Key Basic Research Program of China Award Number 2014CB239701 (973 Program), National Natural Science Foundation of China (No. 21773118, 51504139, 51672128). X. J. is grateful to United States National Science Foundation Award Number 1551693 for the financial supports. S. D. is grateful to the Funding for Outstanding Doctoral Dissertation in NUAA (BCXJ16-07), Funding

of

Jiangsu

Innovation

Program

for

Graduate

Education

(KYLX16_0341), and the Priority Academic Program Development of Jiangsu Higher Education (PAPD).

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(37) Wang, P.; Wang, R.; Lang, J.; Zhang, X.; Chen, Z.; Yan, X. Porous Niobium Nitride as a Capacitive Anode Material for Advanced Li-Ion Hybrid Capacitors With Superior Cycling Stability. J. Mater. Chem. A 2016, 4, 9760-9766. (38) Zhou, L.; Zhang, M.; Wang, Y.; Zhu, Y.; Fu, L.; Liu, X.; Wu, Y.; Huang, W. Cubic Prussian Blue Crystals From a Facile One-Step Synthesis as Positive Electrode Material for Superior Potassium-Ion Capacitors. Electrochim. Acta 2017, 232, 106-113. (39) Zhang, B.; Liu, Y.; Chang, Z.; Yang, Y.; Wen, Z.; Wu, Y. Nanowire K0. 19MnO2 from Hydrothermal Method as Cathode Material for Aqueous Supercapacitors of High Energy Density. Electrochim. Acta 2014, 130, 693-698. (40) Wang, H.; Yoshio, M. KPF6 Dissolved in Propylene Carbonate as an Electrolyte for Activated Carbon/Graphite Capacitors. J. Power Sources 2010, 195, 1263-1265. (41) Le Comte, A.; Reynier, Y.; Vincens, C.; Leys, C.; Azaïs, P. First prototypes of hybrid potassium-ion capacitor (KIC): An Innovative, Cost-Effective Energy Storage Technology for Transportation Applications. J. Power Sources 2017, 363, 34-43. (42) Xing, Z.; Luo, X.; Qi, Y.; Stickle, W. F.; Amine, K.; Lu, J.; Ji, X. Nitrogen‐ Doped Nanoporous Graphenic Carbon: An Efficient Conducting Support for O2 Cathode. ChemNanoMat 2016, 2, 692-697. (43) Zhang, Q.; Guo, Y.; Guo, K.; Zhai, T.; Li, H. Ultrafine Potassium Titanate Nanowires: A New Ti-based Anode for Sodium Ion Batteries. Chem. Commun. 2016, 52, 6229-6232.

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(44) Pérez-Flores, J. C.; García-Alvarado, F.; Hoelzel, M.; Sobrados, I.; Sanz, J.; Kuhn, A. Insight into The Channel Ion Distribution and Influence on The Lithium Insertion Properties of Hexatitanates A2Ti6O13 (A= Na, Li, H) as Candidates for Anode Materials in Lithium-Ion Batteries. Dalton Transactions 2012, 41, 14633-14642. (45) Rudola, A.; Saravanan, K.; Devaraj, S.; Gong, H.; Balaya, P. Na2Ti6O13: A Potential Anode for Grid-Storage Sodium-Ion Batteries. Chem Commun 2013, 49, 7451-7453. (46) Wang, X.; Chandrabose, R. S.; Jian, Z.; Xing, Z.; Ji, X. A 1.8 V Aqueous Supercapacitor with a Bipolar Assembly of Ion-Exchange Membranes as the Separator. J. Electrochem. Soc. 2016, 163, A1853-A1858. (47) Wang, H. W.; Guan, C.; Wang, X. F.; Fan, H. J. A High Energy and Power Li‐Ion Capacitor Based on a TiO2 Nanobelt Array Anode and a Graphene Hydrogel Cathode. Small 2015, 11, 1470-1477. (48) Zhang, F.; Zhang, T.; Yang, X.; Zhang, L.; Leng, K.; Huang, Y.; Chen, Y. A High-Performance Supercapacitor-Battery Hybrid Energy Storage Device Based on Graphene-Enhanced Electrode Materials with Ultrahigh Energy Density. Energy Environ. Sci. 2013, 6, 1623-1632. (49) Wang, X.; Kajiyama, S.; Iinuma, H.; Hosono, E.; Oro, S.; Moriguchi, I.; Okubo, M.; Yamada, A. Pseudocapacitance of MXene Nanosheets for High-Power Sodium-Ion Hybrid Capacitors. Nat. Commun. 2015, 6, 6544-6549.

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