Patent Publication Number: US-2017373342-A1

Title: Battery with molybdenum sulfide electrode and methods

Description:
RELATED APPLICATION 
     This application claims priority to U.S. Provisional Patent Application No. 62/355,699, entitled “RECHARGEABLE BATTERY WITH ALUMINUM NEGATIVE ELECTRODE AND CHERVEL PHASE MOLYBDENUM SULFIDE POSITIVE ELECTRODE,” filed on Jun. 28, 2016, which is incorporated herein by reference in its entirety. 
    
    
     TECHNICAL FIELD 
     This invention relates to batteries. 
     BACKGROUND 
     Improved batteries are desired. One example of a battery structure that can be improved is an electrode and electrolyte structure and material choice. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIGS. 1A-1B  show SEM images and XRD data of a metal sulfide material according to an example of the invention. 
         FIGS. 2A-2D  show electrochemical data of a metal sulfide battery according to an example of the invention. 
         FIGS. 3A-3D  show characterization data of a metal sulfide material according to an example of the invention. 
         FIGS. 4A-4B  show additional characterization data of a metal sulfide material according to an example of the invention. 
         FIGS. 5A-5C  show electrochemical data of a metal sulfide battery according to an example of the invention. 
         FIG. 6  shows images of a metal sulfide material according to an example of the invention. 
         FIGS. 7A-7F  show electrochemical data of a metal sulfide battery according to an example of the invention. 
         FIG. 8  shows chemical analysis data of a metal sulfide material according to an example of the invention. 
         FIGS. 9A-9C  show a crystallographic model of a metal sulfide material according to an example of the invention. 
         FIGS. 10A-10B  show electrochemical data of a metal sulfide battery according to an example of the invention. 
         FIG. 11  shows surface area data of a metal sulfide material according to an example of the invention. 
         FIGS. 12A-12D  show characterization data of a metal sulfide material according to an example of the invention. 
         FIGS. 13A-13C  show additional characterization data of a metal sulfide material according to an example of the invention. 
         FIGS. 14A-14B  show electrochemical data of a metal sulfide battery according to an example of the invention. 
         FIGS. 15A-15D  show additional electrochemical data of a metal sulfide battery according to an example of the invention. 
         FIGS. 16A-16B  show additional electrochemical data of a metal sulfide battery according to an example of the invention. 
         FIGS. 17A-17D  show additional electrochemical data of a metal sulfide battery according to an example of the invention. 
         FIG. 18  shows a battery according to an example of the invention. 
     
    
    
     DETAILED DESCRIPTION 
     In the following detailed description, reference is made to the accompanying drawings which form a part hereof, and in which is shown, by way of illustration, specific embodiments in which the invention may be practiced. In the drawings, like numerals describe substantially similar components throughout the several views. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention. Other embodiments may be utilized and structural, or logical changes, etc. may be made without departing from the scope of the present invention. 
     Among the rechargeable batteries beyond lithium chemistry, the ones based on aluminum (Al) are particularly promising: Al not only is the most abundant metal in the earth&#39;s crust but also has attractive capacity due to its trivalency. To date, there were only scarce investigations on rechargeable Al batteries in literature. The initial investigations, as summarized in the review article by Li and Bjerrum, were focused on identifying Al-ion electrolytes from organic solvents and demonstrating potential cathode materials. However, these early attempts had little success due to the sluggish electrochemical Al deposition-dissolution in organic solvents. On the other hand, reversible electrochemical Al deposition-dissolution can be facilely achieved in ionic liquid (ILs) electrolytes composed of aluminum chloride (AlCl 3 ) and organic salts such as 1-butylpyridinium chloride, 1-ethyl-3-methylimidazolium chloride, and 1-butyl-3-methylimidazolium chloride ([BMIm]Cl). Utilizing IL electrolytes, aluminum-chlorine (Al—Cl2) rechargeable batteries were demonstrated. Despite the high discharge voltage (&gt;1.5 V), good capacity, and cycle stability, the gaseous Cl 2  cathode was problematic. Furthermore, the Cl 2  cathode had to be first generated from the electrolysis of electrolyte through charging, which was also undesirable. More recently, vanadium oxide fluorinated graphite, chloroaluminate-doped conductive polymers, and graphitic carbons were also reported as cathode materials vs Al in the IL-based electrolytes. 
     Unlike lithium, electrochemical Al intercalation into a host crystal structure can be very difficult due to the strong Coulombic effect induced by the three positive charges carried by the Al cation. Therefore, transition metal oxides, i.e., oxide anionic frameworks, may not be the ideal hosts for Al because of their strong electrostatic attraction with Al cations. It can hinder the redistribution of the charge of Al cations in the crystal, thus preventing the Al intercalation. On the other hand, sulfur has lower electronegativity than oxygen and is more polarizable due to its larger atom radius. Therefore, the charge redistribution in the sulfide anionic frameworks should be superior to oxides. Based on this concept, we demonstrate in this study the reversible electrochemical Al intercalation in Chevrel phase molybdenum sulfide (Mo 6 S 8 ) for the first time. 
     Mo 6 S 8  has a unique crystal structure of stacked Mo 6 S 8  blocks composed of an octahedral cluster of Mo atoms inside a sulfur anion cubic cell. It is known to have two types of sites between the sulfur cubes that are capable to accommodate small cations such as Li+, Cu+, and Mg2+.14,15 Aurbach and co-workers first demonstrated Mo 6 S 8  as a cathode material for rechargeable magnesium-ion batteries.16 In this study, we synthesized Mo 6 S 8  particles through a precipitation method modified from the reported works by Kumta et al, and Liu et al. As shown in the scanning electron microscopy (SEM) image in  FIG. 1A , the particle shape is cubic and the typical particle size is within the range of 1-2 μm.  FIG. 1B  shows the X-ray powder diffraction (XRD) pattern, which is in excellent agreement with the pure Mo 6 S 8  standard without the typical impurity of MoS 2 . 
     The electrochemical Al intercalation in Mo 6 S 8  was analyzed in CR2016 coin cells with Al foil as the counter/reference electrode. An IL electrolyte composed of a mixture of AlCl 3  and [BMIm]Cl with a molar ratio of 1.5:1 was used, it has been demonstrated that reversible Al deposition-dissolution can only be achieved in a Lewis acidic electrolyte composed of AlCl 3  and an IL with molar ratio &gt;1, and the electroactive species in the electrolyte is [Al 2 Cl 7 ]-anion. Indeed, facile Al deposition-dissolution was enabled by the prepared AlCl3-[BMIm]Cl electrolyte as shown in  FIGS. 4A-4B . 
     The results of the electrochemical characterizations of Mo 6 S 8  vs Al are presented in  FIGS. 2A-2D . Cyclic voltammetry (CV, scan rate=0.1 mV s−1) were first performed at both room temperature ( FIGS. 5A-5C ) and 50° C. The electrochemical characteristics at these two temperatures are essentially the same; however, the elevated temperature apparently improved the electrochemical reaction kinetics indicated by the distinct shape of the current peaks and the narrowed redox peak separation as shown in  FIG. 2A . Therefore, the presented electrochemical studies were all performed at 50° C. The room temperature electrochemical characterizations are shown as a comparison in the Supporting Information. It is worth noting that the ionic conductivity of the AlCl 3 -[BMIm]Cl electrolyte is 2.21×10 −2  S cm  −1  at room temperature and 3.29×10−2 S cm−1 at 50° C., both of which are sufficient for facile ion conducting. Therefore, the sluggish kinetics at room temperature may not be due to the low conductivity of the electrolyte but to the large particle size of Mo 6 S 8 , i.e., long solid-state diffusion pathway of Al. 
     As shown in  FIG. 2A , the stabilized CV scans of Mo 6 S 8  vs Al demonstrate two cathodic peaks at 0.50 and 0.36 V and two corresponding anodic peaks at 0.40 and 0.75 V, indicating a two-step electrochemical reaction between Mo 6 S 8  and Al. We speculate that these two pairs of CV peaks represent the Al intercalation/extraction in/from the two different sites in Mo 6 S 8 , which is verified by the crystallographic study described in the later section. A small additional cathodic peak at 0.20 V in the first scan and 0.26 V in the following scans, respectively, is also observed. This peak may be due to certain irreversible decomposition of the electrolyte, which is under investigation. 
       FIG. 2B  depicts the representative galvanostatic charge-discharge (GCD) curves of the Al—Mo 6 S 8  coin cell with a current density of 12 mA g−1 at 50° C. at the 1st, 2nd, and 20 th  cycles. The first discharge curve demonstrates two distinct plateaus at 0.55 and 0.37 V, which are consistent with the two cathodic peaks in the CV. These two discharge plateaus also indicate two phase-transition processes induced by the Al intercalation. The Al intercalation capacity in the first discharge is 148 mA h g −1  (based on the chemical formula weight of Mo 6 S 8 ). However, the first charging capacity is only 85 mA h g −1 . By comparing the length of the discharge plateaus with the corresponding charged ones, it is clear that the intercalated Al atoms are partially trapped in the Mo 6 S 8  crystal lattice. Furthermore, the voltage slope from 0.75 to 0.55 V in the first discharge curve, which may be due to the solid-solution Al intercalation prior to phase-transition, is significantly reduced in the subsequent discharges, which also contributes to the irreversible capacity. 
     We attribute the irreversible capacity to the electrostatic attraction between Al cations and the sulfide anionic framework. Nevertheless, the Mo 6 S 8  electrode exhibits promising cycle stability: as shown in  FIG. 2C , the discharge capacity of Mo 6 S 8  is quickly stabilized after the first cycle and retains a capacity of 70 mA h g−1 after 50 cycles. After cycling, the morphology of the Mo 6 S 8  particles was analyzed with SEM. As shown in  FIG. 6 , cracks on the cycled Mo 6 S 8  particles are visible, which suggests the large mechanical stress imposed by the Al intercalation. Therefore, the physical degradation of the Mo 6 S 8  particles during cycling may be one of the reasons for the slow capacity fading. Another reason may still be the gradual Al trapping in Mo 6 S 8  crystal, which is suggested by the &gt;100% Coulombic efficiency (intercalation/extraction &gt;1). The Al—Mo 6 S 8  coin cells were also discharged/charged at different current densities from 6 mA g −1  to 120 mA g −1 . As shown in  FIG. 2Dd , the Mo 6 S 8  electrode can deliver a discharge capacity of 40 mA h g −1  and 25 mA h g −1  at current densities of 60 mA g −1  and 120 mA g −1 , respectively. In addition, the discharge capacity can be recovered to 70 mA h g −1  after changing the current density from 120 mA g −1  back to 6 mA g −1 . The Al—Mo 6 S 8  intercalation behaviors in electrolytes with different AlCl 3 /[BMIm]Cl ratio (acidity) are shown in  FIGS. 7A-7F . 
     To further analyze the composition and the crystal structure of the Al intercalated Mo 6 S 8  (Al x Mo 6 S 8 ), discharge-charge chronopotentiometry was performed using a small current density of 2.4 mA g −1 . As shown in  FIG. 3A , the electrochemically achievable Al interaction capacity is 167 mA h g −1 , which is equivalent to a formula of Al 1.73 Mo 6 S 8 . The Al intercalated Mo 6 S 8  sample was subsequently analyzed with the inductively coupled plasma optical emission spectrometry (ICP-OES) to verify the Al content. The ICP-OES result ( FIG. 8 ) demonstrates that the chemical composition of the Al intercalated Mo 6 S 8  is Al 1.67 Mo 6 S 8 , which is in great agreement with the composition obtained from the chronopotentiometry experiment. Meanwhile, the charge curve in  FIG. 3A  confirms that part of the Al atoms is trapped resulting in a chemical formula of Al 0.69 Mo 6 S 8  after Al extraction. The XRD pattern of the Al intercalated Mo 6 S 8  from the chronopotentiometry described above is shown in  FIG. 3B , which is distinctly different from that of the pristine Mo 6 S 8 . Rietveld refinement (TOPAS program) was performed to obtain the crystal structure parameters of the Al intercalated Mo 6 S 8 . Chevrel phase Ga 2 Mo 6 S 8  was used as the starting structural model. As shown in  FIG. 3C , the refinement XRD pattern (simulation) is in excellent agreement with the experimental data (Experiment). The Rietveld refinement results including various agreement factors are listed in Table 1. 
     
       
         
           
               
             
               
                 TABLE 1 
               
               
                   
               
               
                 Lattice Parameters of Al 2 Mo 6 S 8   
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                   
                 space group: R3H 
                 R exp : 2.37 
               
               
                   
                 a (Å): 9.6356 
                 R wp : 4.58 
               
               
                   
                 c (Å): 9.9942 
                 R p : 3.40 
               
               
                   
                 cell volume (Å 3 ): 803.5904 
                 R-Bragg: 3.312 
               
               
                   
                 crystallite size (nm): 145.2 
                 GOF: 1.93 
               
               
                   
               
            
           
         
       
     
     The refinement result supports the hypothesis that Al atoms are intercalated into two different sites in the Mo 6 S 8  lattice with a theoretical formula of Al 2 Mo 6 S 8  at full Al intercalation (theoretical capacity of 193 mA h g −1 ). The crystal structure of Al 2 Mo 6 S 8  is illustrated in  FIG. 3D , showing the packing of Mo 6 S 8  units and Al atoms intercalated in two different sites. The larger site (Al 1 ) can be seen as a cubic center of a hexahedron with eight Mo 6 S 8  units as the vertices, while the smaller site (Al 2 ) can be seen as face centered. Crystallographic views of Al 2 Mo 6 S 8  from more directions are shown in  FIGS. 9A-9C . Al can be more easily intercalated into the Al 1  sites leading to a stoichiometric formula of AlMo 6 S 8  (corresponding to the first discharge plateau). 
     As for the Al 2  sites, although we can identify six available sites on the faces of the hexahedron mentioned above, the strong electrostatic force from the Al cation with three positive charges can only allow filling in two of the six sites, which also gives a stoichiometric formula of AlMo 6 S 8  (corresponding to the second discharge plateau). Therefore, the fully Al intercalated formula is Al 2 Mo 6 S 8 , which is consistent with the refinement result. The discharge and charge reactions are proposed as follows: 
       Al+7[AlCl 4 ] −    4[Al 2 Cl 7 ] − +3e −  (anode)
 
       8[Al 2 Cl 7 ] − +6e − +Mo 6 S 8  ⇄ Al 2 Mo 6 S 8 +14[AlCl 4 ] −  (cathode)
 
     In conclusion, Mo 6 S 8  shows unambiguous electrochemical activity for reversible Al intercalation and extraction with good cycle stability. In addition to the electrochemical analysis, XRD investigations provide the crystallographic information on the Al intercalated Mo 6 S 8 . We conclude that the theoretical formula of fully Al intercalated Mo 6 S 8  is Al 2 Mo 6 S 8  with Al occupying two different sites in the Mo 6 S 8  crystal lattice. From the practical aspect, the theoretical material-level specific energy of a battery with Al anode and Mo 6 S 8  cathode is approximately 90 W h kg −1  (assuming 0.5 V nominal voltage), which can he an attractive alternative for large-scale energy storage technologies. Further investigation is under way to understand the Al trapping mechanism and to address the large irreversible capacity in the first cycle. 
     EXPERIMENTAL 
     Synthesis of Chevrel Phase Mo 6 S 8    
     All reagents were used after purchase without further purification unless otherwise noted. In a typical synthesis of Mo 6 S 8 , stoichiometric amounts of anhydrous copper(II) chloride (CuCl 2 , 0.3442 g, 2.56 mmol, Sigma Aldrich 99.995%) and ammonium tetrathiomolybdate ((NH 4 ) 2 MoS 4 , 2.000 g, 7.68 mmol; Fisher Scientific 99.99%) were dissolved in 65 mL N,N-Dimethylformamide (DMF, Sigma Aldrich 99.8%) and the mixture was stirred for 30 min at room temperature. The resultant solution was then heated at 90° C. for 6 hours under continuous argon bubbling. After the reaction was completed, the solution was filtered, and then 325 mL THF (1:5 by volume) was added immediately to the filtrate to initiate precipitation. The precipitate was collected by centrifuge, washed with THF and dried in the vacuum oven at 150° C. overnight. The dried solid agglomerate was then ground and heated in a tube furnace at 1000° C. for 7 hour under reducing environment (95 vol. % argon and 5 vol. % H 2 ) to yield Chevrel phase Cu 2 Mo 6 S 8 . The obtained Cu 2 Mo 6 S 8  was then added into 20 mL 6M HCl solution. Oxygen was bubbled into the solution for 8 hours while stirring to leach out Cu to yield Mo 6 S 8 . After the reaction, the obtained Mo 6 S 8  was centrifuged, washed with adequate amount of deionized water, and dried in vacuum oven at 50° C. overnight. 
     Electrochemical Analysis. 
     For battery preparation, Al foil with 0.2 mm thickness (Alfa Aesar 99.9999%) was used as the anode. Cathode was fabricated by coating Mo 6 S 8  slurry onto carbon paper current collector (Fuel Cell Earth). The carbon paper current collector was demonstrated to be electrochemically inert in the applied potential window as shown in  FIGS. 10A-10B . The slurry was made by mixing 80 wt. % Mo 6 S 8 , 10 wt. % carbon black, and 10 wt. % polyvinylidene fluoride in N-Methyl-2-pyrrolidone solution via a mechanical mixer for 5 min in an argon-filled glovebox. 
     A single Whitman® glass fiber filter was used as the separator. The electrolyte was synthesized by slowly adding anhydrous AlCl 3  (Sigma Aldrich 99.99%) into [BMIm]Cl (Sigma Aldrich 99.0%) with a molar ratio of 1.5:1 while stirring. Both AlCl 3  and [BMIm]Cl were further dried in vacuum oven at 150° C. overnight prior mixing. CR2016 coin cells were assembled in the argon filled glovebox. To prevent potential corrosion from the acidic electrolyte, titanium foil was used as lining at both electrodes inside the stainless steel coin cell case. 
     The cyclic voltammetry (CV) of Al deposition-dissolution and the galvanostatic Al deposition were performed in three-electrode cells with a Gamry potentiostat/galvanostat/ZRA (Interface 3000) using Nickel (0.025 mm thick, Alfa Aesar 99.5%) working electrode and two Al wires (2.0 mm diameter, Alfa Aesar 99.9995%) as the counter and the reference electrodes, respectively. The CV scan rate for Al deposition-dissolution experiment was 100 mV s−1 from −1.0 V to 2.0 V vs. Al. A constant current density of −5 mA cm −2  was applied in electrochemical Al deposition experiment. The ionic conductivity of the AlCl 3 -[BMIm]Cl electrolyte at room temperature and 50° C. was obtained from the resistance measurement in a cell with two parallel Pt electrodes. 
     The cell constant was obtained through calibration using standard aqueous KCl solutions. The resistance was measured with a Gamry potentiostat/galvanostat/ZRA (Interface 1000). The GCD experiments of Al—Mo 6 S 8  batteries were performed on an Arbin battery test station, and the CV analysis of Al—Mo 6 S 8  was conducted on a Gamry Interface 1000 with a scan rate of 0.1 mV s −1 . 
     Materials Characterization. 
     The surface area of the synthesized Mo 6 S 8  was measured with nitrogen adsorption-desorption method, and the isotherms are shown in  FIG. 11 . The BET surface area of the Mo 6 S 8  is 6.9 m2 g −1 . The X-ray diffraction (XRD) was conducted using PAN alytical EMPYREAN instrument (45 kV/40 mA) with a Cu—Kα source. The inductively coupled plasma optical emission spectrometry (ICP-OES) of Al intercalated Mo 6 S 8  was performed by Elemental Analysis, Inc. (Lexington, Ky.). Prior to the ICP-OES analysis, the Al—Mo 6 S 8  coin cell was dissembled in the argon-filled glovebox. The electrode containing Mo 6 S 8  particles was first soaked in 3 ml NMP and sonicated for 5 minutes. The NMP dissolved the PVDF polymer binder and suspended the powder (Mo 6 S 8  and carbon black) in the solution. The suspension was centrifuged and the collected powder was further washed three times with NMP followed by adequate THF for three times to remove the electrolyte residue. Finally, the powder was vacuum dried at 60° C. overnight. The Rietveld refinement was performed using the TOPAS program. Scanning electron microscopy (SEM) was performed with a FEI XL30-FEG (10 kV/192 μA). 
       FIGS. 4A-4B  show (a) The CV scan of Al deposition-dissolution on Ni working electrode in the AlCl 3 -[BMIm]Cl electrolyte (AlCl 3 :[BMIm]Cl=1.5:1). The CV curves demonstrate facile Al deposition-dissolution with small deposition overpotential of 200 mV; (b) the SEM image of the deposited Al on Ni, inset shows the XRD of the deposited Al. 
       FIGS. 5A-5C  show electrochemical characterization of the Al—Mo 6 S 8  cells at room temperature: (a) The 1 st , 2 nd  and 5 th  CV curves of Mo 6 S 8  vs. Al with a scan rate of 01 mV s −1  in the range of 0.1 V to 1.2 V. (b) First two GCD curves of Al—Mo 6 S 8  cell with a current density of 12 mA g −1  in the voltage window of 0.3 V to 1.0 V. (c) Cycle stability of first 24 cycles at room temperature with discharge/charge rate of 12 mA g −1    
       FIG. 6  shows SENT images of the Chevrel phase Mo 6 S 8  after 50 cycles of galvanostatic charge-discharge with a current density of 12 mA g −1    
       FIGS. 7A-7F  show electrochemical behaviors of Al—Mo 6 S 8  in electrolytes with different AlCl 3 /[BMIm]Cl ratio at 50° C.: AlCl 3 :[BMIm]Cl=1.1:1 (top), AlCl 3 :[BMIm]Cl=1:1 (middle) and AlCl 3 :[BMIm]Cl=0.9:1 (bottom). The CV scan rate is 0.1 mV s −1  and the GCD current density is 12 mA g −1 . Comparing with the electrolyte (AlCl 3 :[BMIm]Cl=1.5:1) used in the study, the electrolyte with AlCl 3 :[BMIm]Cl=1.1:1 is still Lewis acidic containing active species [Al 2 Cl 7 ] − . This acidic electrolyte is still able to enable the reversible Al intercalation-extraction as indicated by the CV and GCD curves. It is also noticed that the CV peak separation and charge-discharge hysteresis become larger, which can be attributed to the lower acidity (i.e. lower concentration of [Al 2 Cl 7 ] − ). The electrolyte with AlCl 3 :[BMIm]Cl=1:1 is neutral without [Al 2 Cl 7 ] −  (species in the electrolyte are [AlCl 4 ] −  and [BMIm] + ). It does not enable any electrochemical activity between Al and Mo 6 S 8 , noticing the current of the CV and the capacity demonstrated in the GCD are extremely low. The similar non-active behavior is also demonstrated by the Lewis base electrolyte (AlCl 3 :[BMIm]Cl=0.9:1). 
       FIG. 8  shows a report of Al and Mo contents via ICP-OES from Elemental Analysis, Inc. The rest content in the sample includes sulfur, carbon black, and polymer binder residue. 
       FIGS. 9A-9C  show (a) Crystal structure of the pristine Chevrel phase Mo 6 S 8 . (b) Schematic of Chevrel phase Mo 6 S 8  and possible Al intercalation sites. (c) Schematic of the smaller Al intercalation site (inner site) which can be interpreted as in the center of the square with four Mo 6 S 8  clusters as vertices. 
       FIGS. 10A-10B  show (a) Electrochemical stability test of the carbon paper current collector via CV (0.1 mV s −1 , Al RE and Al CE) at room temperature. The scan rate and experiment set up are the same as when using Mo 6 S 8  cathode. (b) Comparison between CV curves of Mo 6 S 8  on carbon paper vs. Al and blank carbon paper vs. Al at room temperature. These plots clearly demonstrated the electrochemical stability of the carbon paper current collector. 
       FIG. 11  shows N 2  adsorption-desorption isotherms of the synthesized Mo 6 S 8  powder. 
     Although Lithium-ion batteries have made significant positive impact on portable electronics and electric vehicle industries, the feasibility of wide deployment of lithium-based batteries for land-based renewable energy storage and grid applications may be questionable due to the limited lithium resource, the resource geographic distribution, and the cost of lithium mining and recycling. Therefore, alternative rechargeable battery technologies based on abundant elements need to be developed for sustainable energy storage. Among the potential candidates, aluminum (Al) may be the ultimate choice as the anode material: Al is not only the most abundant metal in earth&#39;s crust, but also has attractive capacity due to its trivalency. Al has the second highest specific capacity of 2980 mA h g− 1  (Li has 4634 mA h g− 1 ) and the highest capacity density of 8046 mA h cm −3  (Li has 2456 mA h cm− 3 ) among all metal anodes. 
     The most developed Al battery at current stage is the Al-air technology, which is essentially a fuel cell utilizing Al metal as the fuel, concentrated aqueous alkaline (KOH) solution as the electrolyte, and air (O 2 ) as the oxidant. The Al-air battery is non-rechargeable due to the high irreversibility of Al(III) reduction in the aqueous electrolyte: The electrolysis of water is inevitable due to its preferential potential comparing to Al(III) reduction. Besides Al-air, there are a number of other Al batteries using aqueous electrolyte with different cathode materials including manganese oxide (MnO 2 ), solver oxide, hydrogen peroxide, sulfur, ferricyanide and nickel oxide hydroxide, which are all primary batteries. 
     To date, there were only scarce investigations on rechargeable Al batteries with little success. Matsuda and coworkers studied the anodic dissolution activity of Al in a number of aluminum chloride (AlCl 3 ) solutions in organic solvents. Their results indicated that AlCl 3  saturated in formamide (FA) had the lowest Al dissolution overpotential followed by 1 M AlCl 3  in propylene carbonate (PC) and 1 M AlCl 3  in tetrahydrofuran (THF). However the conductivity of FA-based electrolyte was too low for sufficient current delivery. A number of combinations of salts and organic solvents have been investigated including AlCl 3  and tetraethylammonium chloride ((C 2 H 5 ) 4 NCl) inγ-butyrolactone (γ-BL) and acetonitrile (ACN), respectively. Their results demonstrated that the electrolyte composed of 0.3 M (C 2 H 5 ) 4 NCl in ACN with 10 mM mercury(II) acetate had the lowest Al dissolution overpotential. Based on this electrolyte, a number of potential cathode materials were tested including MnO 2 , titanium disulfide (TiS 2 ), molybdenum disulfide (MoS 2 ), vanadium(V) oxide (V 2 O 5 ) and fluorinated graphite (FG) with Al metal anode. Among these materials, both V 2 O 5  and FG demonstrated slender electrochemical activity toward Al (presumably Al intercalation) indicated by short discharge plateaus in their galvanostatic charge-discharge (GCD) curves, although there was no direct evidence of Al intercalation in either V 2 O 5  or FG. Furthermore, the discharge reaction of neither V 2 O 5  nor FG with Al was reversible. 
     One of the decisive disadvantages of Al electrolytes based on organic solvents is the sluggish electrochemical Al deposition-dissolution. On the other hand, facile Al deposition-dissolution can be achieved in high-temperature molten salt electrolytes, which are used in today&#39;s production of Al (electrowinning). With electrolytes based on molten salts, various metal sulfides including TiS 2 , iron disulfide (FeS 2 ), iron(II) sulfide (FeS), chromium sulfide (Cr 2 S 3 ), ternary sodium iron sulfide (NaFeS 2 ), nickel sulfide (NiS 2 ) and amorphous molybdenum(VI) sulfide (MoS 3 ) were investigated as cathode materials with Al anode representative study was reported, in which a FeS 2  cathode was investigated in high-temperature molten salt electrolytes composed of AlCl 3 —NaCl-1-butylpyridinium and AlCl 3 —LiCl-1-butylpyridinium. The Al—FeS 2  pair demonstrated somewhat reversible discharge-charge reaction at high temperature above 100° C., indicating the potential of metal sulfides as cathode materials in rechargeable Al batteries. In the past two decades, electrolytes based on ionic liquids (ILs) have been demonstrated for reversible Al deposition-dissolution at room temperature, particularly for systems based on AlCl 3  and organic salts such as 1-butylpyridinium chloride ([BP]Cl), 1-ethyl-3-methyllimidazolium chloride ([EMIm]Cl), and I-butyl-3-methyllimidazolium chloride ([BMIm]Cl). With IL-based electrolytes, V 2 O 5 , FG and chloroaluminate-doped conductive polymers were attempted as cathode materials against Al anode. Most recently, an Al rechargeable battery with graphitic carbons cathode in IL-based electrolytes was reported. 
     For the first time, we demonstrate a new prototype rechargeable Al battery comprised of Chevrel phase molybdenum sulfide (Mo 6 S 8  as the intercalation-type cathode, Al metal as the anode, and a mixture of AlCl 3  and 1-butyl-3-methyin1idazolium chloride (AlCl 3 -[BMIm]Cl) as the electrolyte. Mo 6 S 8  has a unique crystal structure of stacked Mo 6 S 8  blocks composed of an octahedral cluster of Mo atoms inside a sulfur anion cubic cell. Aurbach and coworkers first demonstrated Mo 6 S 8  as a cathode material for rechargeable magnesium-ion batteries. ll 6 1 
       FIG. 12A  shows the scanning electron microscopy (SEM) image of the Mo 6 S 8  particles synthesized through a precipitation method modified from the reported works, particle shape is cubic and the typical particle size is within the range of 1 to 2 μm.  FIG. 12B  shows the X-ray diffraction (XRD) pattern which is in excellent agreement with pure Mo 6 S 8  without the typical impurity of MoS 2 . The IL electrolyte was prepared by mixing AlCl 3  with [BMIm]Cl with a molar ratio of 1.5:1. It was known that reversible Al deposition-dissolution could only be achieved in a Lewis acidic electrolyte composed of AlCl 3  and an IL with molar ratio higher than 1, and the electroactive species is [AlCl 3 ]″ anion.  FIG. 12E  shows the cyclic voltammetry (CV) of Al deposition-dissolution on a nickel (Ni) working electrode in the prepared AlCl 3 -[BMIm]Cl electrolyte with an Al counter electrode and an Al reference electrode. The CV curves demonstrate facile Al deposition-dissolution with small deposition overpotential of 200 mV. The SEM image of the deposited Al on Ni is shown in  FIG. 12D , and the inset shows the XRD of the deposited Al. 
     The electrochemical properties of the Al—Mo 6 S 8  batteries were evaluated as 2016 type coin cells and the results are presented in  FIGS. 2A-2D . CV (scan rate=0.1 mV s −1  were first performed at both room temperature ( FIGS. 5A-5C ) and 50° C. as shown in  FIG. 2A . The electrochemical characteristics at these two temperatures are essentially the same, however, the elevated temperature apparently improved the charge transfer kinetics indicated by the distinct shape of the current peaks and narrowed redox peak separation. Therefore, the presented electrochemical characterizations in this study were all performed at 50° C. The room temperature electrochemical characterizations were also conducted and shown as comparison in the supporting information. As shown in  FIG. 2A , the CV characteristic of Mo 6 S 8  vs. Al is stabilized after the first cycle. The stabilized CV curves demonstrate two cathodic peaks at 0.50 V and 0.36 V and two corresponding anodic peaks at 0.40 V and 0.75 V, indicating a two-step electrochemical reaction between Mo 6 S 8  and Al. It is known that there are two types of sites available to accommodate small cations such as Li+, Cu+, and Mg 2+  in the Mo 6 S 8  lattice.  [ 2.0 211  We speculate that the observed two pairs of CV peaks represent the Al intercalation/extraction in/from these two sites at different potential, which is verified by the crystallographic study described in the later section. 
       FIG. 2B  depicts the representative GCD curves of the Al—Mo 6 S 8  coin cell with a current density of 12 mA g″ 1  at 50° C. at the 1″, 2″d and 20 cycles. The first discharge curve demonstrates two distinct plateaus at 0.55 V and 0.37 V, which are consistent with the two cathodic peaks in the CV. These two chronopotentiometric plateaus also indicate two phase-transition processes induced by the Al intercalation into the two types of sites. The Al intercalation capacity in the first discharge is 148 mA h g −1 , however, the first charging capacity is only 85 mA h g −1 . The large irreversible capacity may be partly due to the strong electrostatic attraction between Al cations and the sulfide anionic framework: certain Al population can be trapped in the host sites after the first intercalation. If assuming the length of the discharge and charge plateaus represents the relative extent of Al intercalation in and extraction from the two-phase regions, it can be concluded that Al ions in both sites are partially trapped. Furthermore, the voltage slope from 0.75 V to 0.55 V in the first discharge curve, which may be due to the solid-solution Al intercalation prior to phase-transition, is significantly reduced in the subsequent discharges, which also contributes to the irreversible capacity. Nevertheless, this prototype rechargeable Al battery exhibits promising cycle stability: as shown in  FIG. 2C , the discharge capacity of Mo 6 S 8  is quickly stabilized after the first cycle, and retaining a capacity of 70 mA h g −1  after 50 cycles. The Al—Mo 6 S 8  coin cells were also discharged/charged at different current densities from 6 mA g″ 1  to 120 mA g −1 . As shown in  FIG. 2D , the Mo 6 S 8  cathode can deliver a discharge capacity of 40 mA h g −1  and 25 mA h g −1  at current densities of 60 mA g −1  and 120 mA g −1 , respectively. In addition, the discharge capacity can be recovered to 70 mA h g −1  after changing the current density from 120 mA g −1  back to 6 mA g −1 . 
     To further analyze the composition and the crystal structure of the Al intercalated Mo 6 S 8 (Al x Mo 6 S 8 ), discharge-charge chronopotentiometry was performed using a small constant current density of 2.4 mA g −1  at 50° C. As shown in  FIGS. 14A-14B , the electrochemically achievable Al interaction capacity is 167 mA h g −1  (based on the chemical formula weight of Mo 6 S 8 ), which is equivalent to Al 1.73 Mo 6 S 8 . The Al intercalated Mo 6 S 8  sample was subsequently analyzed with inductively coupled plasma optical emission spectrometry (ICP-OES) to verify the Al content. The ICP-OES result ( FIG. 8 ) demonstrates that the chemical composition of the Al intercalated Mo 6 S 8  is Al 1.61 Mo 6 S 8 , which is in great agreement with the composition obtained from the chronopotentiometry experiment. Meanwhile, the charge curve in  FIG. 3A  confirms that part of the Al atoms is trapped resulting in a chemical formula of Al 0.69 Mo 6 S 8  after Al extraction. 
     The XRD pattern of the Al intercalated Mo 6 S 8  from the chronopotentiometly described above is shown in  FIG. 3B . It is clear that the XRD pattern of Al intercalated Mo 6 S 8  is distinctly different from that of the pristine Mo 6 S 8 . Rietveld refinement was used to obtain the crystal structure parameters of the Al intercalated Mo 6 S 8 . As shown in  FIG. 3C , the refinement XRD pattern (simulation) is in excellent agreement with the experimental data (Experiment). The Rietveld refinement results including various agreement factors are listed in Table 1. 
     
       
         
           
               
             
               
                 TABLE 1 
               
               
                   
               
               
                 Lattice parameters of Al 2 Mo 6 S 8   
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                   
                 Space group: R-3H 
                 R exp : 2.37 
               
               
                   
                 a (Å): 9.6356 
                 R wp : 4.58 
               
               
                   
                 c (Å): 9.9942 
                 R p : 3.40 
               
               
                   
                 Cell volume (Å 3 ): 803.5904 
                 R-Bragg: 3.312 
               
               
                   
                 Crystallite size (nm): 145.2 
                 GOF: 1.93 
               
               
                   
               
            
           
         
       
     
     More importantly, the refinement result support the hypothesis that Al atoms are intercalated into two different sites in the Mo 6 S 8  lattice with a theoretical formula of AL 2 Mo 6 S 8  at full Al intercalation (theoretical capacity of 193 mA h g −1 ). The crystal structure of AL 2 Mo 6 S 8  is illustrated in  FIG. 3D , showing the packing of Mo 6 S 8  units and Al atoms intercalated in two different sites. The larger site (Al1) can be seen as a cubic center of a hexahedron with eight Mo 6 S 8  unites as the vertices, while the smaller site (Al2) can be seen as face centered. 
     Crystallographic views of AL 2 Mo 6 S 8  from more directions are shown in  FIGS. 9A-9C . Al can be more easily intercalated into the Al, sites leading to a stoichiometric formula of AL 2 Mo 6 S 8  (corresponding to the first discharge plateau). As for the Al 2  sites, although we can identify six available sites on the faces of the hexahedron mentioned above, in the case of Al ion with three positive charges we hypothesize the strong electrostatic force can only allow filling in two of the six sites,1 231  which also gives a stoichiometric formula of ALMo 6 S 8  (corresponding to the second discharge plateau). Therefore the fully Al intercalated formula is AL 2 Mo 6 S 8 , which is consistent with the refinement result. Furthermore, the stronger electrostatic interaction in Ah sites may be the reason of the incomplete Al intercalation and extraction. 
     In conclusion, we present in this study a new prototype rechargeable Al battery with Al metal anode, Chevrel phase Mo 6 S 8  cathode, and AlCl 3 -[BMIm]Cl ionic liquid based electrolyte. The Mo 6 S 8  cathode shows unambiguous electrochemical activity for reversible Al intercalation and extraction and good cycle stability. The chronopotentiometric plateaus in Al—Mo 6 S 8  charge-discharge curves indicate phase-transition type of electrochemical reaction, which is proposed as follows. 
       Discharge: Al+7[AlCl 4 ] − →4[Al 2 Cl 7 ] − +3e −  (at Al anode)
 
       8[Al 2 Cl 7 ] − +6e − +Mo 6 S 8 →Al 2 Mo 6 S 8 +14[AlCl 4 ] −  (at Mo 6 S 8  cathode)
 
       Charge: 4[Al 2 Cl 7 ] − +3e − →Al+7[AlCl 4 ] −  (at Al anode)
 
       Al 2 Mo 6 S 8 +14[AlCl 4 ] − →8[Al 2 Cl 7 ] − +6e − +Mo 6 S 8  (at Mo 6 S 8  cathode)
 
     Although Chloride ionic liquids are shown as an example, the invention is not so limited. Other ionic liquids include, but are not limited to AlBr 3 . Corresponding electrolytes may include organic salts such as 1-butylpyridinium bromide, 1-ethyl-3-methylimidazolium bromide, and 1-butyl-3-methylimidazolium bromide. Other chemical systems apart from chloride and bromide systems are also within the scope of the invention. 
     In addition to the electrochemical analysis, XRD investigations provide the crystallographic information of the Al intercalated Mo 6 S 8 . We conclude that the theoretical chemical formula of fully Al intercalated Mo 6 S 8  is Al 2 Mo 6 S 8  with Al occupying two different sites in the Mo 6 S 8  crystal lattice. The theoretical material-level specific energy of the Al—Mo 6 S 8  battery is approximately 90 Wh kg −1  (assuming 0.5 V nominal voltage), which makes this new rechargeable battery technology an attractive alternative for large-scale sustainable energy storage. 
     Experimental Section: 
     Synthesis of Chevrel Phase Mo6S8: All reagents were used after purchase without further purification. Stoichiometric amounts of anhydrous copper(II) chloride (CuCl 2 , 0.3442 g, 2.56 mmol, Sigma Aldrich 99.995%) and ammonium tetrathiomolybdate ((NHi) 2 MoS 4 , 2.000 g, 7.68 mmol; Fisher Scientific 99.99%) were dissolved in N,N-Dimethylfonnamide (DMF, 65 mL, Sigma Aldrich 99.8%) and the mixture was stirred for 30 min at room temperature. The resultant solution was then heated at 90° C. for 6 hours under continuous argon bubbling. After the reaction was completed, the solution was filtered, and tetrahydrofuran (THF, 1:5 by volume) was added immediately to the filtrate to initiate precipitation. The precipitate was collected by centrifuge, washed with THF and dried in the vacuum oven at 150° C. overnight. The dried solid agglomerate was then ground and heated in a tube furnace at 1000° C. for 7 hour under reducing environment (95 vol. % Ar and 5 vol. % H2) to yield Cu 2 Mo 6 S 8 . The obtained Cu 2 Mo 6 S 8  was then added into 20 mL 6M HCl solution. Oxygen was bubbled into the solution for 8 hours to leach copper out of Cu 2 Mo 6 S 8  to yield Mo 6 S 8 . After the reaction, the obtained Mo 6 S 8  was centrifuged, washed with deionized water three times and dried in vacuum oven at 50° C. overnight. 
     Electrochemical Measurement: CR2016 type coin cells were assembled in an argon-filled glovebox. To prevent the potential corrosion from the acidic electrolyte, titanium foil was used as lining at both electrodes inside the stainless steel coin cell casing. Al foil with 0.2 nun thickness (Alfa Aesar 99.9999%) was used as the anode. Cathode was fabricated by coating. 
     Mo 6 S 8  slurry onto carbon paper current collector (Toray Paper, Fuel Cell Earth). The electrochemical stability of the carbon paper current collector is shown in  FIGS. 10A-10B . The slurry was made by mixing 80 wt. % Mo 6 S 8 , 10 wt. % carbon black, and 10 wt. % polyvinylidene fluoride in N-Methyl-2-pyrrolidone solution via a mechanical mixer for 5 min in the argon-filled glovebox. A single Whitman® glass fiber filter was used as the separator in each coin cell. The electrolyte was synthesized by slowly adding anhydrous AlCl 3  (Sigma Aldrich 99.99%) into [BMIm]Cl (Sigma Aldrich 99.0%) with a molar ratio of 1.5:1 while stirring. The CV of Al deposition-dissolution, the constant current Al deposition and the electrochemical stability test of the carbon paper current collector were performed in three-electrode cells with a potentiostat (Gamry Interface 3000) using two Al wires (2.0 mm diameter, Alfa Aesar 99.9995%) as the counter and the reference electrodes, respectively. The CV scan rate for Al deposition-dissolution experiment was 100 mV s −1 . A constant current density of −5 mA cm −2  was applied on Ni working electrode in electrochemical Al deposition experiment. The GCD experiments of Al—Mo 6 S 8  were performed with an Arbin battery test station, and the CV analysis of Al—Mo 6 S 8  was conducted on a Gamry potentiostat (Interface 1000) with a scan rate of 0.1 mV s −1 . 
     Materials Characterization: The X-ray diffraction was conducted using PANalytical EMPYREAN instrument (45 kV/40 mA) with a Cu-Ku source. The inductively coupled plasma optical emission spectometry of Al intercalated Mo 6 S 8  was performed by Elemental Analysis, Inc. (Lexington, Ky.). The Rietveld refinement was performed using the TOPAS program. Scanning electron microscopy was performed with a PEI XL30-FEG (10 kV/192 (μA) 
       FIGS. 12A-12D  shows a) SEM image and b) XRD pattern of the synthesized Mo 6 S 8 . c) CV curves of Al deposition-dissolution. d) SEM image and the XRD pattern (inset) of the deposited Al on Ni. 
     Rechargeable batteries based on aluminum (Al) anode have attracted great attention recently. Despite a few cathode materials that have been proposed, cathode materials with potentially higher energy density need to be explored. Herein, we investigate the layered TiS 2  and cubic Ti 2 S 4  as intercalation-type cathodes at both room temperature and 50° C. We confirm the Al intercalation in the TiS 2  and Ti 2 S 4  crystal structure using ex-situ XRD and XPS. The proposed titanium sulfide cathodes showed promising reversible capacity and a higher working potential than previously demonstrated Chevrel phase molybdenum sulfide cathode. More importantly, it further validates the generalization of transition metal sulfides as feasible cathodes for rechargeable Al batteries. 
     Rechargeable aluminum (Al) battery system is very intriguing due to the following reasons: First of all, aluminum has high capacity due to its trivalency. Al is the most abundant metal element in earth&#39;s crust. However, not too many investigations have been made on developing rechargeable aluminum battery in the past decades. One of the main reasons is the lack of electrolyte that can enable facile deposition and dissolution of aluminum on the anode side. To date, facile electrochemical deposition and dissolution of Al at room temperature can be only achieved in Lewis Acidic room temperature ionic liquid (RTIL) electrolytes synthesized by mixing aluminum chloride (AlCl 3 ) with organic salts such as 1-butylpyridinium chloride, 1-ethyl-3-methylimidazolium chloride, etc. 
     Our group proposed Chevrel phase Mo 6 S 8  as the first conventional intercalation type cathode material. The logic of choosing transition metal sulfide instead of transition metal oxide as cathode material for aluminum ion battery is very important. Due to the strong coulombic effect, the energy barrier of multivalent ions transportation in the crystal structure is very high. Thus, a softer anionic framework is needed. Sulfide has a much lower electronegativity than oxide, which makes transition metal sulfides very promising cathode candidates for rechargeable aluminum ion battery. Herein, we report the synthesis of cubic Ti 2 S 4  and layered TiS 2  and investigation on their electrochemical and structural properties as cathode materials for rechargeable aluminum ion batteries. 
     The reason we picked cubic Ti 2 S 4  as cathode candidate for rechargeable aluminum ion battery is the similarities between it and the Chevrel Phase Mo 6 S 8 . The synthesis route of both the materials are very alike: first, copper based materials (Cu 2 Mo 6 S 8 , CuTi 2 S 4 ) can be synthesized using solid state method. Then copper is chemically leached out to produce the desired materials. More importantly, we believe the void space in the crystal structure created by leaching copper out will make it easier for the intercalation of aluminum ion. Titanium sulfide has a higher working potential than molybdenum sulfide. Titanium sulfide also has a higher electrochemical capacity than molybdenum sulfide. 
     As for layered TiS 2 , it has the same chemical composition with cubic Ti 2 S 4  while the crystal structure is totally different. It would make a very interesting comparison between their electrochemical activities towards aluminum ion. Both cubic Ti 2 S 4  and layered TiS 2  were synthesized via solid state reaction by heating of stoichiometric mixture of elements in vacuum sealed quartz tube. Then we generated the nano sized particles by ball milling. The detailed synthesis information is in the method session. 
       FIG. 13A  shows the x-ray diffraction pattern of as synthesized nano Ti 2 S 4  and TiS 2  which are in very good agreement with standard. Moreover, we can easily notice the peak widening after the ball milling treatment of the particle that indicates the decrease of the particle size.  FIG. 13B  shows the SEM image of layered TiS 2  with the typical layered structure featuring of a pellet shape. The particle size is mostly around 1 μm while the thickness of the pellets is much smaller.  FIG. 13C  depicts the typical particle morphology of ball milled cubic Ti 2 S 4 . The particle size is mostly sub 1 μm. 
     All the electrochemical analysis of the cathode materials is undertaken in the 2016 type coin cells. Pure aluminum metal foil serves as the anode. Titanium sulfide pasted on the carbon paper current collector serves as cathode. The AlCl 3 /EMImCl ionic liquid with molar ratio of 1.5:1 is the electrolyte. Titanium foil lining was applied at both ends of the battery case to prevent the corrosion effect on stainless steel from the ionic liquid electrolyte containing chloride ions. Based on the assumption that the energy barrier of aluminum ion transportation in the crystal structure will be very high, so besides analyzing the electrochemical properties at room temperature, we also operated all the tests at elevated temperature of 50° C. in order to accelerate the reaction transportation and kinetics. 
       FIGS. 14A and 14B  are the second cycle of cyclic voltammetry (CV) of layered TiS 2  and cubic Ti 2 S 4  at room temperature and 50° C. respectively. From the 14a we can see that there are clearly two reduction peaks at around 0.9V and 0.3V for layered TiS 2 . We can notice that the reduction peak at higher potential is more pronounced at elevated temperature than itself at room temperature. As for the oxidation peaks, the situation is more complicated. At room temperature, two corresponding oxidation peaks can be easily observed locating at about 1.1V and 0.7V accordingly. While at 50° C., the oxidation peaks shifted to the left making the redox peak separation smaller, indicating a better kinetics. In addition, we started to observe corrosion effect starting around 1.2V. We believe the later part of the oxidation peak is overlapping with the corrosion reaction peak before 1.4V, which thereafter the corrosion reaction takes complete charge. 
     As for the CV of cubic Ti 2 S 4  in  FIG. 14B , we can also observe mainly two redox pairs similarly to layered Ti 2 . At room temperature, the first reduction is more like a slope at 1.0V. The second reduction peak is much more pronounced at around 0.35V. The corresponding oxidation peaks are very distinctive at around 1.1V and 0.65V. While at 50° C., two reduction peaks can be easily observed at 1.0V and 0.5V. And the corresponding oxidation peaks are located at 1.2V and 0.6V respectively. We can see that the peak separation at higher temperature is smaller due to the better kinetics. Similarly, corrosion effect is also seen when approach the end of the charging process. 
     Galvanostatic charge discharge tests were also undertaken at both room temperature and 50° C. for layered TiS 2  and cubic Ti 2 S 4  as can be depicted in  FIGS. 15A-15D . A current density of 5 mAg −1  was used in the tests. The charge discharge curves at room temperature and 50° C. are basically the same, Unsurprisingly, the capacity is higher and the charge discharge plateaus are more distinctive at 50° C. since the charge transfer kinetics is better due to the higher temperature. Therefore, only the charge discharge performance at 50° C. is going to be analyzed here. 
       FIG. 15B  shows the 1 st , 2 nd  and 20 th  galvanostatic charge discharge curves of layered TiS 2  at 50° C. In the first cycle, we can see that there is a discharge plateau at 0.75V, and then followed by a slope at around 0.4V, which correspond the two reduction peaks in the CV. A capacity of 100 mAhg −1  can he achieved in the first discharge. The first charge is also comprised with two stages which is also in good agreement with the CV. It is worth noting that the first charge is only 75 mAhg −1  indicating there is a big reversibility. Starting from the second cycle, two discharge stages can still be observed in the discharge process. However, the first discharge plateau voltage increased to around 0.9V instead of 0.75V in the first cycle. The second discharge process is still a slope at around 0.4V. 
     We hypothesize that the Al intercalation process in the first cycle expands the lattice parameter of TiS 2  that can enable the subsequent intercalation at a higher potential. Moreover, the capacity of the second discharge is only about 65 mAhg −1  which is only two thirds of the discharge capacity in the first cycle. But the discharge capacity stabilized from second cycle and slowly decreased to around 60 mAhg −1  in the 20 th  cycle.  FIG. 15D  shows the 1 st , 2 nd , 20 th  and 50 th  galvanostatic charge discharge curves of cubic Ti 2 S 4  at 50° C. From the 1 st  discharge curve, two slope-shape discharge processes can be observed at about 0.95V and 0.45V, which are in very good agreement with the two broad CV peaks in  FIG. 14B . The first discharge capacity of Ti 2 S 4  at 50° C. is often around 80 mAhg −1 . As for the first charge, two corresponding charging plateaus can be easily identified while the first charging capacity is only about 65 mAhg −1 . However, the following second discharge could only achieve a capacity of about 40 mAhg −1 , half the capacity in the first cycle. Then the discharge capacity quickly stabilized and a capacity of 30 mAhg −1  can be achieved after 50 cycles. 
     Cycle stability performance of both TiS 2  and Ti 2 S 4  is given in  FIGS. 16A-16B .  FIG. 16A  shows the cycle stability of layered TiS 2  at room temperature and 50° C. with a current density of 5 mAg −1 . At room temperature, the first discharge capacity of TiS 2  is as high as 185 mAg −1 . However, due to the large irreversibility, the capacity after stabilization dropped to about 35 mAhg −1 . While at 50° C., the irreversibility between the first and second cycle becomes smaller, with a discharge capacity of 100 mAhg −1  in the first cycle and 65 mAhg −1  in the second cycle. However, the stability is worse at 50° C. The discharge capacity dropped from 65 mAhg −1  in the second cycle to about 55 mAhg −1  in the 30 th  cycle. Also it is worth noting that the coulombic efficiency at 50° C. fluctuated fiercely while being higher than 100%. 
     We believe it is the corrosion effect that caused the deterioration of the cycle stability and coulombic efficiency of TiS 2  at 50° C.  FIG. 16B  shows the cycle performance of cubic Ti 2 S 4 . Similarly, the Ti 2 S 4  can also achieve a very high discharge capacity of 170 mAhg −1  in the first discharge at room temperature. However, the discharge capacity after stabilization is only around 25 mAhg−1. While at 50° C., cubic Ti 2 S 4  can achieve a first discharge capacity of 80 mAhg −1  and the capacity after stabilization is about 30 mAhg −1 . 
     By comparing the cycling performance of layered TiS 2  and cubic Ti 2 S 4 , we can speculate that TiS 2  will give higher electrochemical capacity than Ti 2 S 4 . On the other hand, cubic Ti 2 S 4  has a better cycle stability then layered TiS 2 . The reason is that spinel structure is more stable than layered structure especially in a harsh environment of acidic ionic liquid and high temperature. 
     Although aluminum ion has an even smaller ionic radius than lithium ion, the diffusion energy barrier of aluminum ion in the cathode material particle is significant higher mainly due to the 3 positive charges. As a result, it is very meaningful to know the diffusion coefficient of aluminum ion in layered TiS 2  and Ti 2 S 4  in order to shed some light on the aforementioned electrochemical behaviors. Galvanostatic intermittent titration techniques (GITT) along with equilibrium potential and calculated diffusion coefficients are presented in  FIGS. 17A-17D . 
     All the GITT experiments were conducted in such a way: imposing intermittent pulse with a current density of 10 mAg −1  for 15 minutes followed by a rest time of 2 hours.  FIGS. 17A and 17B  show the GITT of layered TiS 2  at room temperature and 50° C. We believe that the GITT curve of TiS 2  started with a solid state solution process followed by a charge transfer stage indicating by the equilibrium potential plateau, then followed by another solid state diffusion stage. This hypothesis is also supported by the changing trend of the diffusion coefficient. 
     In  FIG. 17A , the diffusion coefficient during the charge transfer stage at around 0.7V is in the range of 10 −14  cm 2  s −1 , which is more than 1 order of magnitude lower than that in the solid state diffusion stage. As for the GITT curve of TiS 2  at 50° C., it is very obvious that the capacity is doubled compared to the capacity of room temperature GITT. Moreover, the change transfer plateau is much longer. We can see that the diffusion coefficient during the charge transfer stage at 50° C. is in the range of 10 −14 -10 −15  cm 2  s −1 , which is even lower than that at room temperature. 
     We speculate that the higher temperature can enable aluminum ion transport much deeper to the core of the particle where the diffusion energy barrier is higher than that at the surface of the particle.  FIGS. 17C and 17D  show the GITT of cubic Ti 2 S 4  at RT and 50° C. respectively. With similar analysis, we can get a conclusion that the aluminum diffusion happened mostly superficially for cubic Ti 2 S 4  at room temperature because of the low capacity and high diffusion coefficient. While at 50° C. as can be seen in  FIG. 17D , the diffusion coefficient decreased to 10 −15 -10 −16  cm 2  s −1  as the diffusion approach deeper into the core of the Ti 2 S 4  particle. 
       FIG. 18  shows an example of a battery  1800  according to an embodiment of the invention. The battery  1800  is shown including an anode  1810  and a cathode  1812 . An electrolyte  1814  is shown between the anode  1810  and the cathode  1812 . In one example, the battery  1800  utilizes an ionic fluid electrolyte containing aluminum as described in examples above. In one example, the anode  1810  is formed from aluminum as described in examples above. In one example, the cathode  1812  is formed from a metal sulfide as described in examples above. In one example, although the invention is not so limited, the battery  1800  is formed to comply with a 2032 coin type form factor. In one example, although the invention is not so limited, the battery  1800  is formed to comply with a 2016 coin type form factor. 
     To better illustrate the method and apparatuses disclosed herein, a non-limiting list of embodiments is provided here. 
     Example 1 includes a battery. The battery includes a first electrode, including titanium sulfide, a second electrode, and an ionic liquid electrolyte in contact with both the first electrode and the second electrode, wherein the ionic liquid electrolyte includes aluminum. 
     Example 2 includes the battery of example 1, wherein the ionic liquid electrolyte includes an organic salt. 
     Example 3 includes the battery of any one of examples 1-2, wherein the ionic liquid electrolyte includes AlCl 3 . 
     Example 4 includes the battery of any one of examples 1-3, wherein the ionic liquid electrolyte includes 1-butylpyridinium chloride. 
     Example 5 includes the battery of any one of examples 1-4, wherein the ionic liquid electrolyte includes 1-ethyl-3-methylimidazolium chloride. 
     Example 6 includes the battery of any one of examples 1-5, wherein the ionic liquid electrolyte includes 1-butyl-3-methylimidazolium chloride. 
     Example 7 includes the battery of any one of examples 1-6, wherein the first electrode includes Ti 2 S 4.    
     Example 8 includes the battery of any one of examples 1-7, wherein the second electrode includes aluminum. 
     Example 9 includes the battery of any one of examples 1-8, wherein a molar ratio of AlCl 3  to organic salt is greater than 1. 
     Example 10 includes the battery of example 9, wherein the molar ratio of AlCl 3  to organic salt is equal to 1.5:1. 
     These and other examples and features of the present electronic device, and related methods will be set forth in part in the above detailed description. This overview is intended to provide non-limiting examples of the present subject matter—it is not intended to provide an exclusive or exhaustive explanation. 
     While a number of advantages of embodiments described herein are listed above, the list is not exhaustive. Other advantages of embodiments described above will be apparent to one of ordinary skill in the art, having read the present disclosure. Although specific embodiments have been illustrated and described herein, it will be appreciated by those of ordinary skill in the art that any arrangement which is calculated to achieve the same purpose may be substituted for the specific embodiment shown. This application is intended to cover any adaptations or variations of the present invention. It is to be understood that the above description is intended to be illustrative, and not restrictive. Combinations of the above embodiments, and other embodiments will be apparent to those of skill in the art upon reviewing the above description. The scope of the invention includes any other applications in which the above structures and fabrication methods are used. The scope of the invention should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled.