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 Page 1 of 21 Journal of Materials Chemistry A
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DOI: 10.1039/C6TA09829K

A long-life rechargeable Al ion battery based on molten salts

Yang Song1, Shuqiang Jiao1*, Jiguo Tu1, Junxiang Wang1, Yingjun Liu2*, Handong Jiao1, Xuhui Mao3*, Zhancheng Guo1

Journal of Materials Chemistry A Accepted Manuscript

and Derek J Fray2
1
State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083, PR
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China. *Corresponding author: sjiao@ustb.edu.cn (S Jiao)

2
Department of Materials Science and Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge, CB3

0FS, UK.*Corresponding author: yjl26@cam.ac.uk (Y Liu)

3
School of Resources and Environmental Science, Wuhan University, Wuhan 430072, PR China.*Corresponding author:

clab@whu.edu.cn (X Mao)

Affordable and scalable energy storage systems are necessary to mitigate the output fluctuation of an electrical

power grid integrating intermittent renewable energy sources. Conventional battery technologies are unable to meet the

demanding low-cost and long-life span requirements of a grid-scale application1, 2, although some of them demonstrated

impressive high energy density and capacity. More recently, the prototype of Al-ion battery has been developed using

cheap electrode materials (Al and graphite) in an organic room-temperature ionic liquid electrolyte. Here we implement a

different Al-ion battery in an inorganic molten salt electrolyte, which contains only an extremely low-cost and

nonflammable sodium chloroaluminate melt working at 120 oC. Due to the superior ionic conductivity of melt electrolyte

and the enhanced Al-ion interaction/deintercalation dynamics at an elevated temperature of 120 oC, the battery delivered

a discharge capacity of 190 mAhg-1 at a current density of 100 mAg-1 and showed an excellent cyclic performance even

at an extremely high current density of 4000 mAg-1: 60 mAhg-1 capacity after 5000 cycles and 43 mAhg-1 capacity after

9000 cycles, with a coulombic efficiency constantly higher than 99%. The low-cost and safe characteristics, as well as

the outstanding long-term cycling capability at high current densities allow the scale-up of this brand-new battery for

large-scale energy storage applications.

1. Introduction

Due to the roaring energy demand as well as the rising environmental problems worldwide, energy storage devices such

as rechargeable batteries have attracted great attention, especially regarding their prospect on large-scale use for

minimizing the output fluctuation of electrical grid.3-5 Among the existing commercialized energy storage systems, Li-ion

batteries have become a mainstay for electrical energy storage (EES)1, 2, 6, 7due to their high power density and high

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energy density. However, the implementation of a lithium-based technology for large-scale energy storage faces a major

challenge considering battery cost and lithium availability8-11. Therefore, alternative energy storage solutions to cope with

Journal of Materials Chemistry A Accepted Manuscript

the foreseen amazing energy storage demand in the coming decades, such as sodium-ion batteries12, 13, magnesium-ion

batteries14-17 and calcium ion batteries18, have received wide attentions in recent years. In comparison with these batteries,
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Al-ion rechargeable battery is a more up-to-date energy storage system. Theoretically, an Al-ion battery can deliver three

electrons in one redox couple (Al3+/Al), which enables larger gravimetric capacity and volumetric capacity than the

batteries based on the redox couples of Li+/Li and Na+/Na19, 20. The expected merits of Al3+/Al couple encourage the

research on exploring suitable hosting materials for Al-ion intercalation/deintercalation. A limited number of hosting

materials that have been reported in recent years included V2O521, 22, VO223, anatase TiO224, fluorinated natural graphite25,

polymers26, copper hexacyanoferrate27. However, the results demonstrated that these materials were restricted from

practical applications by various reasons, such as the disintegration of the hosting material28, low cell discharge voltage21,

capacitive behaviors without discharge voltage plateaus25, 26, insufficient cycle life (less than 100 cycles) and rapid

capacity decay (by 26–85 percent over 100 cycles)21, 28. These findings indicated that an exquisite design of electrolyte

chemistry as well as the hosting materials for Al-ion battery is needed prior to the application of the Al-ion rechargeable

batteries.

More recently, it is inspiring that a prototype of a rechargeable aluminium battery with high-rate capability was

established by Dai’s group29. The battery consisted of an aluminium metal anode, a three-dimensional graphitic-foam

cathode and a non-flammable ionic liquid electrolyte29, exhibiting high discharge voltage profiles, excellent cycling

stability and rate capability. Almost at the same time, Jiao’s group also established an Al-ion battery with high average

voltage plateaus30. These two batteries, although demonstrating excellent performances at room temperature, are both

constructed with moisture-sensitive and high-cost ionic liquid electrolytes, being not mature for large-scale energy

storage applications.

In this study, we re-engineered the electrolyte chemistry of the Al-ion battery, and established a rechargeable

aluminum ion super battery with high-rate capability using a low temperature inorganic molten salt which is much

cheaper, safer and environmentally friendly. The Al-ion battery use affordable aluminium metal anode and graphitic

carbon paper cathode. Deposition and dissolution of aluminium occurs at the anode, and intercalation/deintercalation of

chloroaluminate anions into graphitic cathode corresponds to the charge/discharge of the battery. The low viscosity and

relative higher working temperature of the inorganic molten salt not only greatly improve the ionic conductivity of the

electrolyte, but also facilitates the kinetics of ion intercalation and deintercalation. As such, excellent high-rate and cyclic

performances are expected for the Al-ion battery. From a perspective of large-scale industrial application, the working
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temperature of the battery can be maintained by the jouleheat generated from the charge/discharge processes of itself, or

by the exhausted heat from industrial processes.

Journal of Materials Chemistry A Accepted Manuscript

2. Results and discussion
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2.1 The design of Al /graphite cell

Fig. 1a (left) schematically illustrates the assembly of the Al-ion battery, and the experimental Al/graphite cell used

in this study is presented in the right of Fig. 1a. An Al/graphite cell was established in a glassy reactor (also see Fig. S1a,

ESI), using a high-purity aluminum foil (50~150µm thickness) as the anode and a graphitic carbon paper wrapped by a

glassy fiber membrane as the cathode. The appearances of the electrodes can be seen from Fig. S1b. Fig.S2 (ESI) showed

the XRD pattern and SEM image of the pristine graphitic carbon paper before test. The molten salt electrolyte was

prepared by melting the mixture of AlCl3 and NaCl with a mole ratio of ~1.63. The reason for choosing this eutectic melt

at this mole ratio is that it owns the lowest melting temperature (close to the eutectic temperature of 108oC)31-33(see Fig.

S3, ESI). The ionic conductivity of molten salt electrolyte at different temperatures is shown in Fig. 1b. The results show

that the ionic conductivity increases quickly with the increasing temperature from 110 oC to 120 oC. Afterwards, the ionic

conductivity increases relatively slow when the temperature is higher than 120 oC. Considering that a much higher

temperature is unfavorable for operation, 120 oC was thereby selected as the temperature of electrolyte in this study. The

XRD pattern confirmed the presence of the NaAlCl4 in the eutectic melts of AlCl3 and NaCl (Fig. S4a, ESI), and the

Raman spectroscopy analysis further revealed that both AlCl4- and Al2Cl7- anions existed in the mixture of AlCl3 and

NaCl (Fig. S4b, ESI). The multi-coordination of Al ions results in a melting point as low as 120 oC for the electrolyte,

thereby the assembled cell can be easily operated in an oil-bath heater.

2.2 The performance of Al/Graphite battery

The charge and discharge profiles of the Al/graphite cell at current density of 500 mAg-1 (in terms of the mass of

graphitic carbon cathode) are shown in Fig. 1c (first cycle). The cut-off voltage of the Al/graphite cell (the voltage at

which charging was stopped) was set at 2.27 V vs. Al3+/Al. The theoretical decomposition potential of NaAlCl4 is 2.20V

vs. Al3+/Al at 120 oC, being 0.1V higher than that of AlCl3 (Fig. S5, ESI). Considering the overpotential in a real

charging/discharging process, a 2.27 V cut-off voltage, slightly higher than the theoretical decomposition potential of

NaAlCl4, was adopted for the Al/graphite cell. Preliminary experiments showed that this cut-off voltage can promise the

chemical stability of the electrolyte and coulombic efficiency of the battery. In Fig. 1c, the discharge voltage plateaus can
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be clearly observed in the ranges of 1.95-1.8 V, 1.6-1.5 V and 1.2-1.0 V vs. Al3+/Al. The selected charge–discharge

curves from the 5th to 100th cycles at a current density of 500 mA g-1 are also shown in Fig. 1c. As can be seen, in the

Journal of Materials Chemistry A Accepted Manuscript

initial five cycles, the capacity increased from 122 mAh g-1 (in terms of the mass of graphite cathode) at the first cycle to

the maximum value 136 mAh g-1 in the fifth cycle. Afterwards, the capacity gradually decreased and tended to stabilize at

~115mAhg-1(see the 100th cycle). The increasing capacity of the cell in the first five cycles reflected the better utilization
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of the interlayer space of graphitic carbon for chloroaluminate ions intercalation/deintercalation. At this current density,

five cycles are needed to achieve a maximum exploitation of the capacity of the graphitic carbon. It’s uplifting that the

Al/graphite cell shows impressive stability and cycling capability in the followed cycles. As shown in Fig. 1d, its specific

capacity was perfectly maintained over 100 cycles with an average coulombic efficiency of 97.1±2.4% and the capacity

remained up to 115 mAh g-1 even after 100 cycles.

Fig. 2a shows the capacity retention capability of the cell under different current densities from 1000 mAg-1 to 3000

mAg-1. Even at a very high current density of 3000 mA g-1, 85.5 mAh g-1 discharge capacity still remained over the last

100 cycles. It is noted that the capacity of the cell gradually increased in the initial 100 cycles, which is indicative of the

progressive utilization of the interlayer space inside the graphitic carbon. For different charging current density, the

battery needs charge/discharge for different cycles to achieve the stability of the battery performance. When the charge

current density is low, the charge and discharge process is slow. Only 5 cycles are needed to achieve stable performance

of the battery. However, when the charging current density is higher, the charge and discharge process is very fast, so

more cycles are needed to achieve the stability of the battery. At the second stage running at 1000~3000 mAg-1, the

capacity became quite stable over the rest cycles, and the coulombic efficiencies were constantly very close to 100%. The

average discharge capacity and coulombic efficiency of the battery under different current densities from 100mAg-1 to

4000mAg-1 are shown in Fig. 2b. In comparison to the charge/discharge processes at lower current densities (< 500

mAg-1) (Fig. S6, ESI), the high current density cases showed lower cell capacities. Relative to the 190 mAhg-1 capacity at

100 mAg-1 current density, the capacities faded by 52.6%, 50.0%, 40.5 and 31.6% at the current densities of 1500 mAg-1,

2000 mAg-1, 3000 mAg-1 and 4000 mAg-1, respectively. Meanwhile, slightly decreased coulombic efficiencies (e.g.,

down to 94.5% for 100 mAg-1) were observed for the cycles at low rates. This observation can be explained by the

oxidation of chloroaluminate anions on graphitic carbon during the charge process. At a low rate, the current density is

low, and thereby a lower voltage loss associated with the ohmic resistance across the electrolyte. As a result, the

real charging potential on the graphitic cathode at low rate is supposed to be closer to the theoretical decomposing

potential of NaAlCl4 electrolyte (2.2 V vs. Al3+/Al).

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2.3 The long-term cycling performance of Al/Graphite battery

Journal of Materials Chemistry A Accepted Manuscript

The long-term cycling performance of the cell was further evaluated at an extremely high current density of 4000

mAg-1 (~ 1min for a cycle). From Fig. 2c, an encouraging cycling performance was observed over 9000 cycles with a

coulombic efficiency of 97.7±2.2%. Meanwhile, the discharge capacity did not show obvious fade after 5000 cycles, and
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43 mAhg-1 capacity remained after 9000 cycles, which mean that the capacity retention was more than 66.4% relative to

the initial capacity of 64.9 mAhg-1 (Fig. S7a, ESI). Subsequently, the cell was tested at the current density of the 2000

mAg-1 for extra 1000 cycles. The results showed that the discharge capacity went back to 75.5 mAh g-1 and the average

coulombic efficiency was 98.9%±1.0% in the additional 1000 cycles, indicating that both electrodes and electrolytes

worked effectively even after a high current density operation. It was also found that this cell could be rapidly charged (at

4000 mAg-1, within 1 min) and gradually discharged (down to100 mAg-1, Fig. S7b in the ESI) with a discharge capacity

of 60 mAh g-1 was constantly maintained. Such a rapid charging/variable discharging rate is appealing in many practical

applications. The long-term cycling performance of the cell was also investigated at a high charge current density (3000

mAg-1) and low discharge current density (200mA g-1), as shown in Fig. S7c in the ESI. A favorable cycling performance

was observed over 1000 cycles with a coulombic efficiency of 95.7±2.2%. Meanwhile, the discharge capacity did not

show a significant fade, and 70 mAhg-1 was achieved after 1000 cycles. In addition to the excellent long-term cycling

performance, the Al|NaAlCl4|graphite battery also demonstrated a good shelf-life at a charged state; the electrical charge

loss was around 20% after 3 months of resting relative to a normal discharge procedure without resting.

The Al anode (0.243 g) after 10000 cycles was inspected by SEM. It can be seen that no dendrite formed on the Al

electrode after thousands of cycles (Fig. S8, ESI). The recovery rate of Al anode after 10000 cycles is 90%. Even when a

quite small Al anode with the mass of 0.0304g was used the recovery rate of Al anode can be as high as 85%. More

importantly, we did use Al anodes with different weights to test the performances of the cells. As shown in Fig. S9 (ESI),

the mass of the aluminum anode has a very small effect on the specific capacity of the battery. This observation was due

to the high reversibility of Al dissolution/deposition, as reported in the room-temperature ionic liquid electrolyte34.

Meanwhile, the graphite cathode after 10000 cycles was characterized by SEM and TEM; the graphite cathode suffered a

slight damage after 10000 cycles due to the intercalation/deintercalation of AlCl4- /Al2Cl7- ions (Fig. S10, ESI). In order

to compare the electrochemical performance of aluminum ion batteries with the molten salts and ionic liquids as

electrolyte at 120℃, we have carried out a series of test by elevated temperature of the ionic liquid, and the results

are shown in (Fig. S11, ESI). It can be seen from the figure that the electrochemical properties is still not so good by

raising the temperature of the ionic liquid. The results proved that the inorganic molten salt electrolyte showed

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more advantages over ionic liquid.

Journal of Materials Chemistry A Accepted Manuscript

2.4 The mechanism of Al/Graphite battery

The cyclic voltammetry (CV) curves of the graphitic carbon in the assembled cell are shown in Fig. 3a. The cell was
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rested overnight prior to the CV test. The initial cycle of CV curve is different from the other curves, which could be

attributed to the volume adjustment of the graphite in the initial cycle. The curves exactly coincide with each other from

the second to fifth cycle, demonstrating a highly reversible electrochemical reaction. For the first cycle, there are three

oxidation peaks displaying at 2.14V vs. Al3+/Al (peak a), 1.98V vs. Al3+/Al (peak b) and 1.80V vs. Al3+/Al (peak c). The

corresponding reduction peaks are found at ca. 1.81V vs. Al3+/Al (peak a’), 1.58Vvs.Al3+/Al (peak b’) and 1.25V vs.

Al3+/Al (peak c’), respectively. The CV measurement is in good agreement with charge/discharge behaviors shown in Fig.

1C. The formation of (c and c’) peaks may be due to the adsorption and desorption of chloroaluminate ions onto the

electrode. The formation of (a and a’) and (b and b’) peaks are ascribed to the intercalation and deintercalationof AlCl4-

and Al2Cl7- ions. The sodium anions (Na+) present in the electrolyte, however, the potential for their intercalation into the

graphite was extremely low (~0.3V vs. Na+/Na)35-37; therefore, the intercalation of Na+ ions cannot happen in the range

from 0.5~2.2V vs. Al3+/Al. At a larger scan rate, the three pairs of redox peaks united into a pair of wide peaks (Fig. S12,

ESI). To exclude the influence of the Mo current collector, the CV curve of Mo current collector is also shown in Fig. 3a.

Compared with the graphitic carbon, the current of Mo can be neglected. The polarization curve of a Mo sheet in the

NaAlCl4 electrolyte further confirmed that the Mo current collector did not cause the significant decomposition of

electrolyte until 2.4 V vs. Al3+/Al. (Fig. S13a, ESI). Meanwhile, the charge–discharge curves of Mo current collector

also indicated that its contribution on capacity was negligible (Fig. S13b, ESI). The CV curves of Al anode and graphite

cathode shown in Fig. 3b further depict the redox reactions in an Al|NaAlCl4|graphite battery. With an Al foil reference

electrode, the Al foil anode displays a reversible deposition/dissolution of aluminum metal in the potential range of

-0.5~0.6V vs Al3+/Al. When the graphite carbon was used as working electrode, three pairs of redox peaks can be

observed in the potential range of 1.25~2.2V vs. Al3+/Al; and the NaAlCl4 electrolyte decomposed on the graphite

electrode when the potential was higher than 2.4V vs. Al3+/Al.

To further illustrate the reaction of Al-ion battery at each potential peak, the Al-ion battery was charged to different

cut-off voltages at a constant current density of 100 mAg-1, and the X-ray diffraction (XRD) patterns of the charged

graphitic carbon (Fig. 3c) show that the peak shifted from 26.5° to 25.5° when the cut-off voltage changed from 1.8V to

2.14V vs. Al3+/Al. The peak shift along with the charge process indicates the increasing space between the interlayers of

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the graphitic carbon caused by the intercalation of chloroaluminate anions. When discharged to 0.5V vs. Al3+/Al, the peak

centered at 25.5° remained unchanged, which meant that the increased interlayer space was preserved after a cycle of

Journal of Materials Chemistry A Accepted Manuscript

intercalation/deintercalation. The Raman spectra of the original, charged and discharged carbon paper are shown in Fig.

3d. The peak at ~1352 cm-1 (D band) is associated with the presence of structural defects and disorders in a carbon

material, while the peak at ~1580 cm-1 (G band) comes from the first-order scattering of E2g symmetry, being related to
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the vibration of sp2 bonded carbon atoms in a two-dimensional hexagonal lattice38-40. It can be found that the D-band was

diminished with the increasing charging potential, suggesting that the intercalation of chloroaluminate ions decreased the

structural defects and disorders on both edges and basal planes of graphite. Moreover, after discharged to 0.5V vs.

Al3+/Al, the disappeared D-band did not come back. This observation reveals that the ordered structure of graphitic

carbon after the first intercalation/deintercalation cycle was well retained. The observations in the Raman spectra are in a

good accordance with the previously reported work, in which the intercalation of TFSI- anions also caused a

diminishing D-band for a microcrystalline graphite electrode.41

The self-discharge test was carried out to investigate the reaction mechanism. The results are shown in Fig. 3e, in

which the voltage drop (∆E) decreased with the cut-off voltage value (Table S1, ESI). This suggests the formation of (c

and c’) peak is owing to the adsorption and desorption of chloroaluminate ions onto the electrode. The formation of peak

(a and a’) and (b and b’) are due to the intercalation and deintercalation of chloroaluminate ions of AlCl4- and Al2Cl7- ions.

In addition, in order to further evidence the above results, the TGA tests were applied to investigate the intercalation and

deintercalation process of chloroaluminate ions. For the charge process, with the increase of cut-off potential, the mass

loss of graphitic carbon anode also increased (Fig. 3f). This phenomenon implies that more chloroaluminate ions were

intercalated into carbon paper as the potential increased. For the discharge process, when discharge to 0.5Vvs. Al3+/Al,

the weight loss was very small, which means that the ions have substantively been deintercalated from the graphitic

carbon. The schematic illustration of the intercalation and deintercalation processes of chloroaluminate ions is shown in

Fig. 3g. When the charge of the cut-off potential was 1.8V vs. Al3+/Al(Fig. 3g(1)), the main reaction was the adsorption

of chloroaluminate ion. When the cut-off potential increased to 1.98V vs. Al3+/Al(Fig. 3g(2)), the main reaction was the

intercalation of AlCl4- ions, and the interlayer space of the graphitic carbon paper increased. When the cut-off potential

reached 2.14V vs. Al3+/Al(Fig. 3g(3)) Al2Cl7- was intercalated into the graphite interlayer, and the interlayer space of

carbon paper further increased. In the following cycles (Fig. 3g(4)), the interlayer space of carbon paper remained

unchanged, the intercalation/deintercalation of AlCl4- and Al2Cl7- occurred in a stable interlayer space.

In order to better understand the electrochemical performance of the as-prepared cell, the cell was analyzed by

electrochemical impedance spectroscopy (EIS) at different voltages bias from 0.0 V to 1.0 V with a frequency range of
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105Hz to 1 Hz, as shown in Fig. S14a(ESI). In the high frequency region, obvious depressed semicircle was observed,

which was attributed to the charge transfer impedance (Rct). In the low frequency region, the slope line (about 45°) was

Journal of Materials Chemistry A Accepted Manuscript

Warburg impedance, which corresponded to the semi-infinite diffusion of AlCl4- or Al2Cl7- into the electrode electrolyte

interface. Obviously, the charge transfer impedance(Rct=0.80Ω) was essentially low, representing a fast rate of

intercalation and deintercalation of AlCl4- or Al2Cl7-. Even at a high bias voltage (1.0V vs. Open circuit potential), the
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charge-transfer impedance (Rct=0.72Ω) was essentially low. The diffusion coefficient of the AlCl4- or Al2Cl7- ions (DAl)

can be estimated from the low-frequency region of the plots using the following equation42-45:

DAl= 0.5R2T2/A2n4F4C2σ2 (1)

In this equation, R is the gas constant (8.314J·mol-1·K-1); T is the absolute temperature(393K); A is the active

surface area of the carbon paper cathode(2.25cm2); n is the number of transferred electrons(n=1); F is the Faraday

constant (96500Cmol-1); C is the concentration of chloroaluminate in the cathode electrode (which was approximately

1.65×10-2 molcm-3); σ is the Warburg coefficient, which was determined as the slope of Z’ vs. the square root of the

frequency (ω1/2) in the low-frequency region. Fig. S14b (ESI) shows the linear relationship between Z’ and ω1/2 in the

low-frequency region, the slope σ was calculated to be 1.07Ωs1/2. Therefore, the DAl value of the electrode was calculated

to be 3.86×10-11cm2s-1. This value confirms the perfect rate of intercalation and deintercalation of AlCl4-/Al2Cl7-, which is

equivalent to the diffusion coefficient of lithium ion44, 46.Fig. S14c (ESI) shows the Nyquist plots of the battery after

10000 cycles. It can be found that the charge-transfer impedance increases from 0.80Ω (1 cycle) to 1.2Ω (10000 cycles),

indicating that the charge-transfer impedance increased with the cycle number47.

X-ray photoelectron spectra (XPS) and energy dispersive spectrometer (EDS) were engaged to probe the chemical

nature of the intercalated species in our graphitic cathodes. To minimize the amount of trapped electrolyte, graphitic

cathode was thoroughly washed with deionized water and anhydrous ethanol. The XPS spectra of the original, charged

and discharged graphitic carbon paper are shown in Fig. 4a-c. The C 1s XPS peaks of the original and cycled carbon

remain unchanged, and no essential information regarding the intercalation/deintercalation can be observed (Fig. 4a). For

the fully charged state, the intercalation of chloroaluminate ions was evidenced by the increased Al 2p and Cl 2p peaks

(Fig. 4b, c) relative to the discharged state. The EDS mapping of fully charged graphitic carbon sample also revealed

stronger Al and Cl signals (Fig. 4d-g). These spectroscopic results confirmed the intercalation/de-intercalation of

chloroaluminate ions into the graphitic carbon.

Based on the above results, the Al/graphite cell redox reactions during charging and discharging can be proposed, as

schematically illustrated in Fig. 5. During the discharge process, zero-valent Al was dissolved into Al3+ (equation (2)).

Meanwhile, Al and AlCl4- can be transformed into Al2Cl7-, as illustrated by equation (3). The reverse reactions take place
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during charging (equation (6-7)).The unique dynamic equilibrium between Al3+, AlCl4-and Al2Cl7- in the NaAlCl4 melt

allows the intercalation and deintercalation processes in the cell. In case of the cathode, the AlCl4- and Al2Cl7- ions are

Journal of Materials Chemistry A Accepted Manuscript

deintercalated from the interlayers of graphite during discharge processes(equation(4-5)); and the reverse reactions take

place during charging (equation(8-9)). The electrode reactions for both anode and cathode are described as follows:
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In the discharge process,

Anode: Al - 3e-→Al3+ (2)

Al+7AlCl4--3e-→ 4Al2Cl7- (3)

Cathode: Cn[AlCl4] + e-→Cn + AlCl4- (4)

Cn[Al2Cl7] + e-→Cn + Al2Cl7- (5)

In the charge process,

Anode: Al3++3e-→Al (6)

4Al2Cl7- + 3e-→+Al+7AlCl4- (7)

Cathode: Cn + AlCl4- - e-→Cn[AlCl4] (8)

Cn + Al2Cl7- -e-→Cn[Al2Cl7] (9)

3. Conclusions

In this study, a novel Al-ion battery based on low temperature inorganic molten electrolyte was established. The

battery exhibited with an extremely long cycling life up to 9000 charge/discharge cycles even at a ultrahigh current

density of 4000mAg-1. Based on the ~60 mAhg-1 cathode capacity measured at 4000 mAg-1 current density, the present

battery was calculated to afford a high power density equivalent to ~ 3000Wkg–1 and an energy density of 50Whkg–1.

Due to the low cost and abundance of raw materials (aluminium ~ 1520$/t, graphite ~ 654$/t, NaCl ~ 152$/t and AlCl3

~1521$/t), the battery is cost-competitive and shows good prospect in commercial applications. The Al-ion batteries

as-designed cell has marked advantages of an extremely low-cost and nonflammable sodium chloroaluminate melt. In

addition, the working temperature of the battery is 120℃, which will increase of ionic conductivity and the enhance the

Al-ion interaction/deintercalation dynamics compared to the aluminum ion battery using ionic liquid as the electrolyte.

The most important thing is that the capacity of think type of Al-ion battery is about 2~3 times of the ionic liquid Al-ion

battery at lower current density. All of the advantages allow the scale-up of this battery for large-scale energy

storage.The only disadvantages of the as-designed cell is the battery needs to maintain a temperature of 120 ℃, which

brings some difficulties for the miniaturization of the battery, because the battery needs a number of heating equipment.

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However, the working temperature of the battery can also be maintained by the jouleheat generated from the

charge/discharge processes of itself, or by the exhausted heat from industrial processes.

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4. Experimental section

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4.1 Materials

All materials and chemicals were purchased commercially and used as received. A sealed electrolytic tank (Ai Da in
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Tian Jin corporation) (Fig. S1a, ESI) was used for the Al-ion battery. A and 15×15 mm graphitic carbon paper (Hua Tai

Graphite, China, > 99.9% purity, mass18.7mg) was fixed by a molybdenum sheet (Fig. S1b, ESI) to form the cathode.

Fig. S2 showed the XRD pattern and SEM image of the pristine graphitic carbon paper before test. The cathode was

further wrapped by a piece of glass fiber membrane (GF/D, Whatman) prior to cell assembly. The specific capacity (mAh

g-1) of the battery was calculated in terms of the mass of the graphite cathode. An aluminium foil (General Research

Institute for Nonferrous Metals,> 99.95% purity) (12 mm × 50 mm, 150µm thickness, mass 0.243g) was used as anode

(Fig. S1B, ESI). Before testing, the aluminium foil was washed in an ultrasonic cleaner for 15 min. The electrolyte was

prepared by heating the mixture of vacuum dried sodium chloride (Sinopharm, 99.9%) and sublimed aluminium chloride

(Sinopharm, 99.9%). The Al-ion full battery comprised of cathode, anode, electrolyte and a Teflon-sealed electrolytic

tank, as shown in Fig. S1b(ESI).

4.2 Electrochemical measurements

The charge/discharge of cell was performed using a Solartron electrochemical work station (Solatron 1287/1255B).

The specific capacity and current density of the Al-ion battery were calculated based on the mass of the graphitic carbon

paper. An AC Impedance Analyser (Solartron 1287/1255B) is used for the measurements of the cell impedance. The ac

amplitude was 10 mV, the frequency was varied from 1 to 100 kHz, A personal computer was used for controlling the

Solartron 1287/1255B, and for collection of the data. The value of the electrolyte resistance obtained was used for the

evaluation of the electrical conductivity of the melt, using Eq. (10),

k =C/Rel (10)

where k is the electrical conductivity of the melt (Scm-1), C is the cell constant (0.4cm-1), and Rel is the true electrolyte

resistance (Ω).

4.3 Characterization

The crystal structure of the samples was determined by an X-ray diffractmeter (XRD, Rigaku, D/max-RB), Raman

spectrum and X-ray photoelectron spectroscopy (XPS, Kratos AXIS Ultra DLD). The morphology was characterized by

transmission electron microscopy (TEM, JEOL, JEM-2010) and field emission scanning electron microscope (FESEM,

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JEOL, JSM-6701F). Thermogravimetry analysis (TGA, NETZSCH, STA409C) was performed in the temperature range

of 200 oC to 450 oC at a heating rate of 10 oC min-1.

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Acknowledgements

This work was supported by the Fundamental Research Funds for the Central Universities (FRF-TP-15-002C1).
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Figure caption

Fig. 1(a)Illustration of the construction rechargeable Al/graphite cell (left) and the assembled cell for experiment (right).

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(b)The ionic conductivity of NaAlCl4 electrolyte at different temperatures. The insets present the solid state(left) and

liquid state(right) of NaAlCl4 electrolyte. (c)The 1st, 5th, 10th, 50th and 100th charge–discharge curves at 500mAg-1.

(d)The cycling performance and coulombic efficiency at a current density of 500mA g-1.
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Fig. 2 (a)The capacity retention capabilities of an Al-ion full battery at the larger current densities range from 1000 to

3000mAg-1. (b)The discharge capacity and coulombic efficiency at different current densities ranging from 100 to

4000mAg-1. (c)Long-term cycling performance of an Al/graphitic cell over 9000 charging and discharging cycles at a

current density of 4000mAg-1 and the extra 1000 cycles at a current density of 2000mA g-1

Fig. 3 (a)Cyclic voltammetry curves of the graphitic carbon in an Al-ion full battery (2mVs-1 scan rate).(b)Cyclic

voltammetry curves of Al foil and graphite electrode against an Al reference electrode (5 mVs-1 scan rate). (c)X-ray

diffraction patterns of the graphite electrodes in the Al/Graphite cells that had been charged to different cut-off voltages

(1.80V, 1.98V, 2.14V vs. Al3+/Al) and discharged to 0.5 V vs. Al3+/Al. (d) The Raman spectra of the graphite electrodes in

Al/Graphite cells that had been charged to different cut-off voltages (1.80V, 1.98V and 2.14V vs. Al3+/Al) and discharged

to 0.5V vs. Al3+/Al. (e) The voltage drop (∆E) of the Al/Graphite cells that had been charged to different cut-off voltages

(1.80V, 1.98V, 2.14V vs. Al3+/Al). (f)TGA diagram of the graphite electrodes that had been charged/discharged to

different voltages. (g)The schematic representation of the intercalation and deintercalation processes of chloroaluminate

ions.

Fig. 4 XPS and EDS analysis on the graphitic carbon cathode.(a)C 1s peak of the graphitic carbon cathodes: pristine,

fully charged and fully discharged. (b, c) Al 2p and Cl 2p peaks of the graphitic carbon cathode: original, fully charged

and fully discharged. (d, f)EDS mapping images for the C, Al and Cl elements of graphitic carbon cathodes. (e, g)The

EDS spectra of the boxed regions.

Fig. 5 Schematic representation of an aluminium-based full-battery system. During the discharge process, two reactions

occurred on the anode: ① Al was transformed into metallic Al3+; ②metallic Al and AlCl4- were transformed into

Al2Cl7-, and the reverse reactions took place during charging. Two reactions occurred on the cathode: ③

predominantly AlCl4- was deintercalated into graphite interlayers during discharge processes; ④ Al2Cl7- was

deintercalated from graphite interlayers during discharge processes and the reverse reactions took place during charging.

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Fig. 1

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Fig. 2

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Fig. 3

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Fig. 4

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Fig. 5

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TOC
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