All Carbon Dual Ion Batteries - ACS Applied Materials & Interfaces

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All Carbon Dual Ion Batteries Zhe Hu, Qiannan Liu, Kai Zhang, Limin Zhou, Lin Li, Mingzhe Chen, Zhanliang Tao, Yong-Mook Kang, Liqiang Mai, Jun Chen, Shulei Chou, and Shi Xue Dou ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b11824 • Publication Date (Web): 12 Sep 2018 Downloaded from http://pubs.acs.org on September 13, 2018

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ACS Applied Materials & Interfaces

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All Carbon Dual Ion Batteries

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Zhe Hu,†,‡ Qiannan Liu,‡ Kai Zhang,§ Limin Zhou,|| Lin Li,† Mingzhe Chen,‡ Zhanliang

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Tao,*,† Yong-Mook Kang,§ Liqiang Mai,*,|| Jun Chen,† Shu-Lei Chou,*,†,‡ and Shi-Xue

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Dou‡

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†

Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Collaborative

Innovation Center of Chemical Science and Engineering, College of Chemistry, Nankai University, Tianjin 300071, China ‡

Institute for Superconducting and Electronic Materials, University of Wollongong, Wollongong, New

South Wales 2522, Australia §

Department of Energy and Materials Engineering, Dongguk University-Seoul, Seoul 100-715,

Republic of Korea ||

State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan

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University of Technology, Wuhan 430070, China

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KEYWORDS: Graphite; Hard carbon; Dual ion batteries; Anion ion batteries, Pseudocapacitance

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ABSTRACT: Dual ion batteries based on Na+ and PF6− received considerable attention due to their

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high operating voltage and the abundant Na resources. Here, cheap and easily-obtained graphite that

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served as a cathode material for dual ion battery delivered a very high average discharge platform

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(4.52 V vs. Na+/Na) by using sodium hexafluorophosphate in propylene carbonate as electrolyte.

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Moreover, the all-carbon dual ion batteries with graphite as cathode and hard carbon as anode

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exhibited an ultra-high discharge voltage of 4.3 V, and a reversible capacity of 62 mAh·g−1 at 40

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mA·g−1 . Phase changes have been investigated in detail through in-situ X-ray diffraction and in-situ

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Raman characterizations. The stable structure provides long life cycling performance, and the ACS Paragon Plus Environment

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pseudocapacitance behavior also demonstrates its benefits to the rate capability. Thus dual ion

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batteries based on sodium chemistry are very promising to find their applications in future.

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1. INTRODUCTION

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Among all the techniques for renewable energy storage, secondary rechargeable batteries have

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demonstrated their capability and potential in terms of portable devices, electric vehicles, and even

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grid-scale energy storage stations.1 Sodium ion batteries (SIBs) have attracted much attention due to

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the low cost and high abundance of sodium during the last decade.2-3 Cathode materials of SIBs,

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however, often suffer from limited working voltage (always lower than 4.5 V vs. Na+/Na). For

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example, Na3V2(PO4)3 has been widely investigated as perfect sodium storage material, because of its

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stable cycling performance and low over-potential during charging and discharging.4-5 The output

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voltage is below 3.5V, however, and the low energy and power density will limit their application.

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Dual-ion batteries (DIBs) based on sodium chemistry are developed and investigated because of their

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advantages of wide voltage window, low cost, high safety and high energy density.6-8 The use of both

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cations and anions of electrolyte for charge transfer on discrete electrodes ensures them high power,

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and the storage of two types of ions inside the electrode materials endows them high energy density

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with increased capacity.9-10 For sodium based DIBs, the issue of low discharge potential, however, still

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needs to be further addressed. Cathode materials with a high working platform and proper electrolyte

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selection are highly demanded.

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Graphite has been extensively regarded as a suitable anode material for rechargeable lithium ion

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batteries. Due to co-intercalation of sodium ions and solvent, graphite can also be used as anode

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materials, but exhibits limited electrochemical performance in sodium ion batteries.11 Its stable layered ACS Paragon Plus Environment

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structure however, can serve as a matrix for anion groups, such as PF6−.5, 12-14 At very high charging

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voltage (above 4 V vs. Na+/Na), the PF6− anions can be inserted into graphite interlayers to form a

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stable structure. Thus DIBs based on Na+ and PF6− may introduce a new route for low-cost

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rechargeable battery system. Zhang et al. applied 4 M LiPF6 in ethyl methyl carbonate with 2 wt.%

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vinylene carbonate additive as the electrolyte in lithium ion based dual ion batteries.7 The high

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concentration of the electrolyte increased the viscosity and hindered the ionic transfer. Recent

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investigations on graphite as cathode dual ion batteries have also provided strong evidence that

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sodium based dual ion batteries will be very promising for next generation energy storage devices.15-19

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Those full cells displayed high operating voltage around 4 V (vs. Na+/Na) and good cycling

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performances.

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In our research, graphite as a cathode material for dual ion battery was investigated. Graphite

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demonstrated attractive performance with common electrolyte consisting of NaPF6 in propylene

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carbonate (PC). During the charging process, PF6− intercalates into the graphite interlayer, and sodium

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ions participate in the reaction at the counter electrode, which means both Na+ and PF6− have been

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involved in the electrochemical reaction (Figure 1). From the results of electrochemical testing, the

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specific discharge capacity was 72 mAh·g−1, and the average discharge voltage can reach 4.52 V at 0.4

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C (1 C = 93 mA·g−1). A stable reversible intercalation reaction guarantees the high capacity retention

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of 92.4% after 200 cycles at 2 C. In-situ Raman and in-situ X-ray diffraction (XRD) characterizations

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demonstrated the changes in the C-C bonds and the phase conversion. For anode materials, hard

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carbon and other carbon nanomaterials have shown their potential in high performance sodium storage

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devices.20-21 Thus all-carbon dual ion batteries including graphite and hard carbon were fabricated and

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showed an ultra-high discharge platform of 4.3 V at 40 mA·g−1 (based on the mass of graphite) which ACS Paragon Plus Environment


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can significantly restrain the generation of dendrites. Thus, this research is expected to show the

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potential of graphite to act as a cathode material in all-carbon dual ion battery for the next-generation

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low-cost and environmentally friendly rechargeable battery.

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Figure 1. Schematic illustration of graphite/Na dual ion battery when charging.

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2. EXPERIMENTAL SECTION

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Material characterization. Graphite powder was purchased from the MTI Shenyang KJ group.

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The hard carbon powder was purchased from Imerys Graphite & Carbon. The crystal structure was

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investigated by X-ray diffraction (XRD, Cu Kα radiation) by using a D8 Advance X-ray

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diffractometer. Raman spectroscopy was conducted on a confocal Raman microscope (DXR,

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Thermo-Fisher Scientic) with an Ar-ion laser (λ = 532 nm) in ambient air. The morphology and

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microstructure were examined by scanning electron microscopy (SEM, JEOL JSM7500F).

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Electrochemical characterization. CR2032 coin cells were used as the device to test the

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electrochemical performance. Natural graphite powder and poly(vinylidene fluoride) (PVDF) in a ACS Paragon Plus Environment

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mass ratio of 9:1 were used as the cathode material, and N-methyl-2-pyrrolidone (NMP) was used as

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the solvent to make a homogeneous mixture. Then, the slurry was pasted onto the aluminium current

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collector and dried at 110°C for 10 h in vacuum. Glass fiber membrane and sodium foil were used as

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the separator and anode, respectively. Five kinds of electrolytes were prepared: (1) 0.8 M NaPF6 in PC,

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(2) 0.8 M NaPF6 in ethylene carbonate (EC) and PC (v:v, 1:1), (3) 0.8 M NaPF6 in EC and diethyl

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carbonate (DEC) (v:v, 1:1), (4) 0.8 M NaCF3SO3 in PC, and (5) 1 M NaClO4 in PC. Coin cell

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fabrication was conducted in a Mbraun glove box under argon atomosphere. Charge and discharge

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profiles were collected with a Land battery test system, and the voltage range was set to 3.0−5.0 V (vs.

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Na+/Na). Cyclic voltammograms (CV) and electrochemical impedance spectra (EIS) were collected on

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a Parstat 2273 electrochemical workstation (AMETEK). The frequency ranged from 100 mHz to 100

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kHz.

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Fabrication of all-carbon full cell. Hard carbon was mixed with PVDF in a mass ratio of 9:1 by

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using NMP as solvent. The slurry was pasted onto copper foil and was then dried at 110 °C for 10 h in

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vacuum. The coin cell fabrication was the same as for the graphite/Na half-cell, except for using

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pre-activated hard carbon as the anode material. The capacity ratio between graphite and hard carbon

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was 1: (1.2−1.4). The charge and discharge voltage range was 4.8−1.5 V.

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3. RESULTS AND DISCUSSION

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The graphite powders show typical XRD diffraction peaks, as shown in Figure 2a. The (002) peak

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appears at 26.4°, and the corresponding d-spacing is 0.335 nm. The average particle size of the

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graphite powders is about 10 µm from the SEM image in Figure 2b.

ACS Paragon Plus Environment


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Figure 2. (a) X-ray diffraction pattern and (b) scanning electronic microscopy image of graphite.

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Figure 3a shows the charge profiles of graphite/Na cells in five kinds of electrolyte containing

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different salts and solvents. From the solvent testing, EC and DEC based electrolytes experience side

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reaction at around 3.8 V, which blocks the intercalation of PF6− into the graphite layers.22 The cell with

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PC based electrolyte can be charged up to 5.0 V and finally obtains a charge capacity of 73 mAh·g−1.

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When it comes to salt contribution, according to the charging profiles, NaCF3SO3 is not able to insert

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into the graphite layers and NaClO4 is not stable when charging close to 5V. Then, further

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electrochemical investigations on graphite/Na cells using NaPF6/PC as electrolyte were conducted,

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and the results are shown in Figure 3b−d. Figure 3b displays the charge and discharge plots at 0.4, 1,

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2, 3, 5, and 6 C, and the specific discharge capacities are 72, 58, 57, 55, 50, and 46 mAh·g−1,

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respectively. This excellent rate capability is attributed to the good electronic conductivity of graphite.

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The specific power density and specific energy density can reach 2550 W·kg−1 and 325 Wh·kg−1,

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respectively. The average discharge voltage is 4.52 V at 0.4 C and the small over potential of 0.14 V

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(0.4 C) also makes it very competitive in practical use. The cycling performance was also tested and is

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shown in Figure 3c. The capacity retention at 1 C and 2 C is 92.5% and 92.4%, respectively. The

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initial coulombic efficiency (CE) of the cell cycled at 1 C is 78.3%. After few cycles’ activation, the

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CE is close to 100%. The cyclic voltammetry (CV) curves at different sweep rates are summarized in ACS Paragon Plus Environment

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Figure S1 and Figure 3d. According to previous reports, pseudocapacitance has always been found in

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layered structure materials and nanostructures during cycling, and is beneficial for the cycling and rate

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properties.23-26 Then, the capacitance-type contribution was calculated using Equations S1−S3. It was

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found that that half of the capacity came from fast intercalation process. Electrochemical impedance

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spectroscopy (EIS) was conducted when the cell was at 4.5 V (state of discharge) at the 1st and 2nd

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cycles (Figure S2). The results demonstrate that, after the initial cycle activation, the charge transfer

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resistance (Rct) decreases and the slope of the linear part in the low frequency region is close to 90°,

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which means that the reaction consists of not only the redox reaction, but also a supercapacitance

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contribution. This is in accordance with the CV analysis.

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Figure 3. Electrochemical performances of graphite/Na dual ion batteries. (a) Charge profiles with

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different electrolytes at 1C, (b) galvanostatic profiles at different current densities, (c) cycling



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performance, and (d) CV curve with marked pseudocapacitance contribution. CE: Coulombic

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efficiency.

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During the intercalation process, there exists a stage evolution mechanism and the products are

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named as stage-n graphite intercalation compounds (GICs), where n equals the number of graphite

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layers between two adjacent intercalate planes (Figure 4a). The in-situ Raman characterization was

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conducted to measure the effects of PF6− on the bounded layers and to find the n value of the final

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charge product as shown in Figure 4b. Hexagonal graphite consists of a unique layered structure, and

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the Raman-active vibration mode E2g corresponds to the peak at around 1580 cm−1.27 The E2g vibration

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mode is derived from the strong C-C stretch vibration called G band, which indicates the degree of

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graphitization. During the charging process, with the continuous intercalation, the G band peak is split,

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and a new shoulder peak appears at ~1602 cm−1 (E2gʹ), indicating that the intercalated PF6− ions have

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changed the chemical environment of the adjacent graphite layers.28 As the intensity of E2g peak drops,

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the E2gʹ peak forms increasing intensity. In the fully charged state, however, the E2g peak still exists,

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but the intensity is lower than that of E2gʹ, which means that the final charge product is not a stage-1

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GIC. That is also the reason why the capacity of a graphite/Na cell is ~70 mAh·g−1. Then, during the

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discharge process, the E2gʹ peak gradually weakens and finally disappears, indicating the reversible

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nature of the electrochemical reaction. In-situ Raman spectroscopy can prove the intercalation of PF6−

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into the graphite layers and the change in the C-C bonds, but in order to know the details of the PF6−

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stable sites in the GICs, in-situ XRD characterization was applied to the graphite/Na cell.

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As expected, the in-situ XRD patterns obviously exhibit the stage conversion and changes in the

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interlayer distance during cycling, as shown in Figure 4c and 4d. During the charging process, the


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main (002) peak of graphite gradually moves left, and new peaks at around 20° and 30° appear.

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According to Bragg’s law:

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d(00n)=Ic/l

(1)

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d=λ/(2sinθ)

(2)

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l=1/((sinθ(00(n+1))/sinθ00n) −1) ds=Ic−0.335×(n−1)

(3) (4)

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where d is the d-spacing value, Ic is the identity period along the c-axis, θ is the measured Bragg angle,

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and ds is the d-spacing of the expanded intercalate layers. The Ic, n, and ds for stage 4−7 can be

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calculated, and the results are summarized in Figure S3. The different stage-n GICs have been indexed

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in Figure 4c. At the beginning of the charging process, the stage changes very rapidly, and the indexed

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n value is higher than 8. From the XRD data, only one phase at a time is discovered, except for the

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marked region in Figure 4c. At very close to 5 V, a platform corresponding to the transformation

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between stage-4 and stage-5 is found, which means that the final charge products are a mixture of two

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stage GICs. During the discharging process, the phase change is opposite to that in the charging

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process, but no obvious coexistence of stages is found at ~4.3 V. Finally, the GICs are transformed to

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graphite, and the typical peak of the (002) crystal planes reappears, indicating the good reversibility of

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the graphite/Na cell even at such high working voltage.

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Figure 4. Electrochemical reaction mechanism of graphite/Na dual ion battery. (a) Schematic

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illustration of stage-n GICs, (b) in-situ Raman data, with corresponding (c) charge-discharge profile and

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(d) in-situ XRD characterization.

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The electrochemical performances of all-carbon full cell based on graphite cathode and hard carbon

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anode using NaPF6/PC electrolyte are summarized in Figure 5. Figure S4 shows the typical charge and

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discharge curves of the hard carbon half-cell. Both the charge and the discharge platforms are in the

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low voltage region, which makes it a good choice for fabricating high voltage full cells. The capacity

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of the hard carbon half-cell is about 200 mAh·g−1 at 40 mA·g−1. From Figure 5, the average charge

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and discharge voltage is 4.55 V and 4.3 V at 40 mA·g−1, respectively. The specific energy density is

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252 Wh·kg−1 based on the cathode materials, and the energy density of a real battery device can be

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estimated to reach 63 Wh·kg−1. The high output voltage contributes to the high energy density and

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makes it very competitive for renewable energy storage.


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Figure 5. (a) The charge and discharge curves and (b) cycling performances of Graphite/hard carbon

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dual ion battery at 40 mA·g−1 and 100 mA·g−1.

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4. CONCLUSION

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The above results indicate the potential of graphite to be a high voltage cathode material for dual

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ion batteries, and the fabricated full cell coupled with hard carbon also demonstrates its advantages in

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high output voltage. By optimizing the electrolyte, the NaPF6/PC electrolyte has proved to be the best

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electrolyte for this battery system. The in-situ characterization proves the intercalation process and a

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good reversibility for graphite/Na dual ion batteries. Graphite can also adopt Na+ as anode materials,

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but during the reaction the Na always couples with the electrolyte molecule and co-intercalate into the

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carbon matrix, which will damage the graphite structure and shorten the cycling life.11, 29-30 The PF6−

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anion group intercalation, however, only induces small lattice changes of the GICs compared to that of

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graphite indicating the good cycling behavior. The only issue is the decomposition of electrolyte, but it

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is likely to be solved by further investigation on the electrolyte optimization. In addition, graphite is

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far more outstanding than any other organic compounds which also possess the anion intercalation

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mechanism, in terms of conductivity, working voltage, and raw material cost.31-33



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In conclusion, graphite used as a cathode material for dual ion batteries has demonstrated good

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cycling stability and high power density. The proper selection of NaPF6/PC electrolyte makes the

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battery function good and safe. The pseudocapacitance also facilitates ion absorption, leading to high

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rate capability. The in-situ Raman and in-situ XRD characterizations demonstrate the phase changes

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from graphite to a mixture of stage-4 GICs and stage-5 GICs at 5.0 V, which also can be reversed in

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the fully discharged state. The all-carbon dual ion battery shows ultra-high voltage, which is suitable

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for the demands of electric and hybrid electric vehicles. Thus, we hope that this research can shed

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light on graphite as a high voltage cathode material in dual ion batteries for future investigations.

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ASSOCIATED CONTENT

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Supporting Information

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Pseudocapacitance contribution. CVs at different sweep rates and EIS data of graphite/Na cell. The

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values of d(00n), ds, and Ic for stage-n GICs. Charge and discharge curves of hard carbon/Na cell.

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AUTHOR INFORMATION

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Corresponding Author

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*Email addresses: [email protected] (Shu-Lei Chou), [email protected] (Liqiang Mai),

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[email protected] (Zhanliang Tao)

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Acknowledgements

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The research is supported by Australian Research Council through a Linkage Project (LP120200432),

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the Commonwealth of Australia through the Automotive Australia 2020 Cooperative Research Centre

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(Auto CRC) and the National key R&D Program (2016YFB0901502) NFSC (51771094). K. Zhang

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would like to thank the Korea Research Fellowship Program of the NRF, which was funded by the ACS Paragon Plus Environment

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Ministry of Science and ICT; the number for this grant is 2016H1D3A1906790. The authors would

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like to thank Dr. Tania Silver for critical reading of the manuscript.

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References

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Figure 1. Schematic illustration of graphite/Na dual ion battery when charging. 198x126mm (300 x 300 DPI)


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Figure 2. (a) X-ray diffraction pattern and (b) SEM image of graphite. 196x92mm (300 x 300 DPI)



Figure 3. Electrochemical performances of graphite/Na dual ion batteries. (a) Charge profiles with different electrolytes at 1C, (b) galvanostatic profiles at different current densities, (c) cycling performance, and (d) CV curve with marked pseudocapacitance contribution. CE: Coulombic efficiency. 160x99mm (300 x 300 DPI)


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Figure 4. Electrochemical reaction mechanism of graphite/Na dual ion battery. (a) Schematic illustration of stage-n GICs, (b) in-situ Raman data, with corresponding (c) charge-discharge profile and (d) in-situ XRD characterization. 91x46mm (300 x 300 DPI)



Figure 5. (a) The charge and discharge curves and (b) cycling performances of Graphite/hard carbon dual ion battery at 40 mA·g−1 and 100 mA·g−1. 160x49mm (300 x 300 DPI)


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All Carbon Dual Ion Batteries - ACS Applied Materials & Interfaces

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