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An_ultrafast_rechargeable_aluminium-ion_battery

An ultrafast rechargeable aluminium-ion battery

Meng-Chang Lin 1,2*,Ming Gong 1*,Bingan Lu 1,3*,Yingpeng Wu 1*,Di-Yan W ang 1,4,5,Mingyun Guan 1,Michael Angell 1,Changxin Chen 1,Jiang Yang 1,Bing-Joe Hwang 6&Hongjie Dai 1

The development of new rechargeable battery systems could fuel var-ious energy applications,from personal electronics to grid storage 1,2.Rechargeable aluminium-based batteries offer the possibilities of low cost and low flammability,together with three-electron-redox properties leading to high capacity 3.However,research efforts over the past 30years have encountered numerous problems,such as cathode material disintegration 4,low cell discharge voltage (about 0.55volts;ref.5),capacitive behaviour without discharge voltage plateaus (1.1–0.2volts 6or 1.8–0.8volts 7)and insufficient cycle life (less than 100cycles)with rapid capacity decay (by 26–85per cent over 100cycles)4–7.Here we present a rechargeable aluminium bat-tery with high-rate capability that uses an aluminium metal anode and a three-dimensional graphitic-foam cathode.The battery oper-ates through the electrochemical deposition and dissolution of alu-minium at the anode,and intercalation/de-intercalation of chloroaluminate anions in the graphite,using a non-flammable ionic liquid electrolyte.The cell exhibits well-defined discharge voltage plateaus near 2volts,a specific capacity of about 70mA h g –1and a Coulombic efficiency of approximately 98per cent.The cathode was found to enable fast anion diffusion and intercalation,affording charging times of around one minute with a current density

of 4,000mA g –1(equivalent to 3,000W kg –1),and to withstand more than 7,500cycles without capacity decay.Owing to the low-cost,low-flammability and three-electron redox properties of aluminium (Al),rechargeable Al-based batteries could in principle offer cost-effectiveness,high capacity and safety,which would

lead to a substantial advance in energy storage technology 3,8.However,research into rechargeable Al batteries over the past 30years has failed to compete with research in other battery systems.This has been due to problems such as cathode material disintegration 4,low cell discharge voltage (,0.55V;ref.5),capacitive behaviour without discharge voltage plateaus (1.1–0.2V,or 1.8–0.8V;refs 6and 7,respectively),and insuf-ficient cycle life (,100cycles)with rapid capacity decay (by 26–85%over 100cycles)4–7.Here we report novel graphitic cathode materials that afford unprecedented discharge voltage profiles,cycling stabilities and rate capabilities for Al batteries.

We constructed Al/graphite cells (see diagram in Fig.1a)in Swagelok or pouch cells,using an aluminium foil (thickness ,15–250m m)anode,a graphitic cathode,and an ionic liquid electrolyte made from vacuum dried AlCl 3/1-ethyl-3-methylimidazolium chloride ([EMIm]Cl;see Methods,residual water ,500p.p.m.).The cathode was made from either pyrolytic graphite (PG)foil (,17m m)or a three-dimensional graphitic foam 9,10.Both the PG foil and the graphitic-foam materials exhibited typical graphite structure,with a sharp (002)X-ray diffraction (XRD)

graphite peak at 2h <26.55u (d spacing,3.35A

?;Extended Data Fig.1).The cell was first optimized in a Swagelok cell operating at 25u C with a PG foil cathode.The optimal ratio of AlCl 3/[EMIm]Cl was found to be ,1.3–1.5(Extended Data Fig.2a),affording a specific discharging capacity of 60–66mA h g 21(based on graphitic cathode mass)with a Coulombic efficiency of 95–98%.Raman spectroscopy revealed that with an AlCl 3/[EMIm]Cl ratio of ,1.3,both AlCl 42and Al 2Cl 72anions were present (Extended Data Fig.2b)at a ratio [AlCl 42]/[Al 2Cl 72]<2.33

*These authors contributed equally to this work.

1Department of Chemistry,Stanford University,Stanford,California 94305,USA.2Green Energy and Environment Research Laboratories,Industrial Technology Research Institute,Hsinchu 31040,Taiwan.3

School of Physics and Electronics,Hunan University,Changsha 410082,China.4Department of Chemistry,National Taiwan Normal University,Taipei 11677,Taiwan.5Institute of Atomic and Molecular Sciences,Academia Sinica,Taipei 10617,Taiwan.6Department of Chemical Engineering,National Taiwan University of Science and Technology,Taipei 10607,Taiwan.

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e –4

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b c

(aluminium)

(graphite)

C n [AlCl 4] + e

C n + AlCl 4

EMI +

Al 2Cl 7

4Al 2Cl 7 + 3e

AlCl 3/[EMIm]Cl Ionic liquid

Al + 7AlCl 4

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V o l t a g e (V )

S p e c i fi c c a p a c i t y (m A h g –1)

Coulombic efficiency (%)

–

––

–

Figure 1|Rechargeable Al/graphite cell.a ,Schematic drawing of the Al/graphite cell during discharge,using the optimal composition of the AlCl 3/[EMIm]Cl ionic liquid electrolyte.On the anode side,metallic Al and AlCl 4–were transformed into Al 2Cl 7–during discharging,and the reverse reaction took place during charging.On the cathode side,predominantly AlCl 4–was

intercalated and de-intercalated between graphite layers during charge and discharge reactions,respectively.b ,Galvanostatic charge and discharge curves of an Al/pyrolytic graphite (PG)Swagelok cell at a current density of

66mA g 21.Inset,charge and discharge cycles.c ,Long-term stability test of an Al/PG cell at 66mA g 21.

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(ref.11).The cathode specific discharging capacity was found to be independent of graphite mass (Extended Data Fig.3),suggesting that the entirety of the graphite foil participated in the cathode reaction.The Al/PG cell exhibited clear discharge voltage plateaus in the ranges 2.25–2.0V and 1.9–1.5V (Fig.1b).The relatively high discharge voltage plateaus are unprecedented among all past Al-ion charge-storage sys-tems 4–7.Similar cell operation was observed with the amount of elec-trolyte lowered to ,0.02ml per mg of cathode material (Extended Data Fig.4).Charge–discharge cycling at a current density of 66mA g 21(1C charging rate)demonstrated the high stability of the Al/PG cell,which nearly perfectly maintained its specific capacity over .200cycles with a 98.160.4%Coulombic efficiency (Fig.1c).This was consistent with the high reversibility of Al dissolution/deposition,with Coulombic efficiencies of 98.6–99.8%in ionic liquid electrolytes 12–15.No dendrite formation was observed on the Al electrode after cycling (Extended Data Fig.5).To maintain a Coulombic efficiency .96%,the cut-off voltage of the Al/PG cell (that is,the voltage at which charging was stopped)was set at 2.45V,above which reduced efficiencies were observed (see Extended Data Fig.6a),probably due to side reactions (especially above ,2.6V)involving the electrolyte,as probed by cyclic voltamme-try with a glassy carbon electrode against Al (Extended Data Fig.6b).We observed lowered Coulombic efficiency and cycling stability of the Al/graphite cell when using electrolytes with higher water contents,up to ,7,500p.p.m.(Extended data Fig.6c,d),accompanied by obvious H 2gas evolution measured by gas chromatography (Extended Data Fig.6e).This suggested side reactions triggered by the presence of resi-dual water in the electrolyte,with H 2evolution under reducing poten-tial on the Al side during charging.Further lowering the water content

of the ionic liquid electrolyte could be important when maximizing the Coulombic efficiency of the Al/graphite cells.

The Al/PG cell showed limited rate capability with much lower specific capacity when charged and discharged at a rate higher than 1C (Extended Data Fig.7).It was determined that cathode reactions in the Al/PG cell involve intercalation and de-intercalation of relatively large chloroa-luminate (Al x Cl y 2)anions in the graphite (see below for XRD evidence of intercalation),and the rate capability is limited by slow diffusion of anions through the graphitic layers 16.When PG was replaced by nat-ural graphite,intercalation was evident during charging owing to dra-matic expansion (,50-fold)of the cathode into loosely stacked flakes visible to the naked eye (Extended Data Fig.8a).In contrast,expansion of PG foil upon charging the Al/PG cell was not observable by eye (Extended Data Fig.8b),despite the similar specific charging capacity of the two materials (Extended Data Fig.8c).This superior structural integrity of PG over natural graphite during charging was attributed to the existence of covalent bonding between adjacent graphene sheets in PG 17,which was not present in natural https://www.sodocs.net/doc/b610333623.html,ing PG,which has an open,three-dimensionally-bound graphitic structure,we prevented excessive electrode expansion that would lead to electrode disinteg-ration,while maintaining the efficient anion intercalation necessary for high performance.

Because high-rate and high-power batteries are highly desirable for applications such as electrical grid storage,the next step in the investi-gation was to develop a cathode material that would have reduced ener-getic barriers to intercalation during charging 16.We investigated a flexible graphitic foam (Fig.2a),which was made on a nickel foam template by chemical vapour deposition 9,10(see Methods),as a possible material for

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S p e c i fi c c a p a c i t y (m A h g –1)S p e c i fi c c a p a c i t y (m A h g –1)Figure 2|An ultrafast and stable rechargeable Al/graphite cell.a ,A

scanning electron microscopy image showing a graphitic foam with an open frame structure;scale bar,300m m.Inset,photograph of graphitic foam;scale bar,1cm.b ,Galvanostatic charge and discharge curves of an Al/graphitic-foam pouch cell at

a current density of 4,000mA g 21.c ,Long-term stability test of an Al/graphitic-foam pouch cell over 7,500charging and discharging cycles at a current density of 4,000mA g 21.d ,An Al/graphitic-foam pouch cell charging at 5,000mA g 21and discharging at current densities ranging from 100to 5,000mA g 21.

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ultrafast Al batteries.The graphite whiskers in the foam were 100m m in width (Fig.2a),with large spaces in between,which greatly decreased the diffusion length for the intercalating electrolyte anions and facili-tated more rapid battery operation.

Remarkably,the Al/graphitic-foam cell (in a pouch cell configuration)could be charged and discharged at a current density up to 5,000mA g 21,about 75times higher (that is,at a 75C rate,,1min charge/discharge time)than the Al/PG cell while maintaining a similar voltage profile and discharge capacity (,60mA h g 21)(Figs 1b and 2b).An impres-sive cycling stability with ,100%capacity retention was observed over 7,500cycles with a Coulombic efficiency of 9762.3%(Fig.2c).This is the first time an ultrafast Al-ion battery has been constructed with stability over thousands of cycles.The Al/graphitic-foam cell retained similar capacity and excellent cycling stability over a range of charge–discharge rates (1,000–6,000mA g 21)with 85299%Coulombic effi-ciency (Extended Data Fig.9a).It was also found that this cell could be rapidly charged (at 5,000mA g 21,in ,1min)and gradually discharged (down to 100mA g 21,Fig.2d and Extended Data Fig.9b)over ,34min while maintaining a high capacity (,60mA h g 21).Such a rapid char-ging/variable discharging rate could be appealing in many real-world applications.

We propose that simplified Al/graphite cell redox reactions during charging and discharging can be written as:

4Al 2Cl {7z 3e {

'Al z 7AlCl {4e1TC n z AlCl {4'C n AlCl 4? z e

{e2T

where n is the molar ratio of carbon atoms to intercalated anions in the

graphite.The balanced AlCl 4–and Al 2Cl 7–concentrations in the electro-lyte allowed for an optimal charging capacity at the cathode,with abun-dant AlCl 4–for charging/intercalation in graphite (equation (2)),and sufficient Al 2Cl 7–concentration for charging/electrodeposition at the anode (equation (1).

Ex situ XRD measurement of graphite foil (Fig.3a)confirmed graphite intercalation/de-intercalation by chloroaluminate anions during charging/discharging.The sharp pristine graphite foil (002)peak at

2h 526.55u (d spacing 53.35A

?)(Fig.3a)vanished on charging to a specific capacity of ,30mA h g –1,while two new peaks appeared at

,28.25u (d <3.15A

?)and ,23.56u (d <3.77A ?)(Fig.3a),with peak intensities further increasing on fully charging to ,62mA h g –1.The doublet XRD peak suggested highly strained graphene stacks formed on anion intercalation 18.Analysis of the peak separation (see Methods)suggested a stage 4graphite intercalation compound with an interca-lant gallery height (spacing between adjacent graphitic host layers)of

,5.7A

?,indicating that the AlCl 4–anions (size ,5.28A ?;ref.19)were intercalated between graphene layers in a distorted state.Full dischar-ging led to the recovery of the graphite peak but with a broad shoulder (Fig.3a),probably caused by irreversible changes in the stacking between the graphene layers or a small amount of trapped species.In situ Raman spectroscopy was also performed to probe chloroalu-minate anion intercalation/de-intercalation from graphite during cell charge/discharge (Fig.3b).The graphite G band (,1,584cm –1)diminished and split into a doublet (1,587cm –1for the E 2g2(i)mode and ,1,608cm –1for the E 2g2(b)mode)upon anion intercalation (Fig.3b)20,and then evolved into a sharp new peak (,1,636cm –1,the G2band of the E 2g2(b)mode,spectrum 2.41V,Fig.3b)once fully charged.The spectral changes were then reversed upon discharging (Fig.3b),as the typical graphite Raman G band (1584cm –1)was recovered when fully discharged (spectrum 0.03V,Fig.3b).Similar Raman spectra and XRD data were obtained with a graphitic-foam cathode (Extended Data Fig.10a,b).Interestingly,calcination of a fully charged PG foil at 850u C in air (Fig.3c)yielded a white aluminium oxide foam (Extended Data Fig.10c),confirming the intercalation of chloroaluminate anions into the carbon network,which had been evi-dently removed oxidatively.

Lastly,X-ray photoelectron spectra (XPS)and Auger electron spec-troscopy (AES)were performed to probe the chemical nature of the intercalated species in our graphitic cathodes (see Methods for details).To minimize the amount of trapped electrolyte,graphitic foam was used and the electrode was thoroughly washed with anhydrous methanol.XPS revealed that upon charging pristine graphite,the 284.8eV C 1s peak developed a shoulder at higher energy (,285.9eV,Fig.4a),con-firming electrochemical oxidation of graphitic carbon by intercalation of AlCl 4–anions (equation (2)).Chloroaluminate intercalation was evi-dent from the appearance of Al 2p and Cl 2p peaks (Fig.4b,c).Upon

Fully charged PG

850°C in air

20253035

discharged charged

charged 30 mA h g –124 mA h g –1I n t e n s i t y (a .u .)

62 mA h g –1Pristine

discharged 60 mA h g –13.77 ?

3.35 ?

3.15 ?

Second cycle

I n t e n s i t y (a .u .)

Raman shift (cm –1)

2q (degrees)

Figure 3|Al/graphite cell reaction mechanisms.a ,Ex situ X-ray diffraction patterns of PG in various charging and discharging states through the second cycle.b ,In situ Raman spectra recorded for the PG cathode through a charge–discharge cycle,showing chloroaluminate anion intercalation/de-intercalation into graphite.c ,After calcination of a fully charged

(62mA h g 21)PG electrode at 850u C in air,the sample completely transformed into a white foam made of aluminium oxide.Scale bar,1cm.

I n t e n s i t y (a .u .)

Binding energy (eV)

400

8001,2001,6002,000

–2.0

–1.00.01.0

2.0C l O

C d N (E )/d E (×104)

d N (E )/d E (×104)

Kinetic energy (eV)

Discharged cathode

Charged cathode

C+Al+Cl

f e

Kinetic energy (eV)

Figure 4|Chemical probing of a graphitic cathode by XPS and AES.a ,XPS data of the C 1s peak of a graphitic-foam electrode:pristine,fully charged and fully discharged.b ,c ,XPS data of Al 2p and Cl 2p peaks observed with a graphitic-foam electrode:pristine,fully charged and fully discharged.d–g ,AES mapping images for C,Al and Cl (d ,f ),and the AES spectrum of the boxed regions (e ,g )obtained with a fully charged graphitic-foam sample (d ,e )and a fully discharged graphitic-foam sample (f ,g ).Scale bars:d ,25m m;f ,10m m.

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discharging,the C1s XPS spectrum of the cathode reverted to that of the pristine graphite due to anion de-intercalation and carbon reduc-tion(Fig.4a).Also,a substantial reduction in the Al2p and Cl2p signals was recorded over the graphite sample(see Fig.4b,c).The remaining Al and Cl signals observed were attributed to trapped/adsorbed species in the graphite sample,which was probed by XPS over a large area.Fur-thermore,high spatial resolution AES elemental mapping of a single graphite whisker in the fully charged graphitic foam clearly revealed Al and Cl Auger signals uniformly distributed over the whisker(Fig.4d,e), again confirming chloroaluminate anion intercalation.When fully dis-charged,AES mapping revealed anion de-intercalation from graphite with much lower Al and Cl Auger signals observed(Fig.4f,g).These spectroscopic results clearly revealed chloroaluminate ion intercala-tion/de-intercalation in the graphite redox reactions involved in our rechargeable Al cell.

The Al battery pouch cell is mechanically bendable and foldable(Sup-plementary Video1)owing to the flexibility of the electrode and sepa-rator materials.Further,we drilled through Al battery pouch cells during battery operation and observed no safety hazard,owing to the lack of flammability of the ionic liquid electrolyte in air(see Supplementary Video2).

We have developed a new Al-ion battery using novel graphitic cath-ode materials with a stable cycling life up to7,500charge/discharge cycles without decay at ultrahigh current densities.The present Al/graphite battery can afford an energy density of,40W h kg–1(comparable to lead–acid and Ni–MH batteries,with room for improvement by opti-mizing the graphitic electrodes and by developing other novel cathode materials)and a high power density,up to3,000W kg–1(similar to super-capacitors).We note that the energy/power densities were calculated on the basis of the measured,65mA h g–1cathode capacity and the mass of active materials in electrodes and electrolyte.Such recharge-able Al ion batteries have the potential to be cost effective and safe,and to have high power density.

Online Content Methods,along with any additional Extended Data display items and Source Data,are available in the online version of the paper;references unique to these sections appear only in the online paper.

Received12March2014;accepted6February2015.

Published online6April2015.

1.Yang,Z.et al.Electrochemical energy storage for green grid.Chem.Rev.111,

3577–3613(2011).

2.Huskinson,B.et al.A metal-free organic-inorganic aqueous flow battery.Nature

505,195–198(2014).

3.Li,Q.&Bjerrum,N.J.Aluminum as anode for energy storage and conversion:a

review.J.Power Sources110,1–10(2002).

4.Gifford,P.R.&Palmisano,J.B.An aluminum/chlorine rechargeable cell

employing a room temperature molten salt electrolyte.J.Electrochem.Soc.135, 650–654(1988).

5.Jayaprakash,N.,Das,S.K.&Archer,L.A.The rechargeable aluminum-ion battery.

https://www.sodocs.net/doc/b610333623.html,mun.47,12610–12612(2011).

6.Rani,J.V.,Kanakaiah,V.,Dadmal,T.,Rao,M.S.&Bhavanarushi,S.Fluorinated

natural graphite cathode for rechargeable ionic liquid based aluminum-ion

battery.J.Electrochem.Soc.160,A1781–A1784(2013).7.Hudak,N.S.Chloroaluminate-doped conducting polymers as positive electrodes

in rechargeable aluminum batteries.J.Phys.Chem.C118,5203–5215(2014).

8.Armand,M.&Tarascon,J.M.Building better batteries.Nature451,652–657

(2008).

9.Yu,X.,Lu,B.&Xu,Z.Super long-life supercapacitors based on the construction of

nanohoneycomb-like strongly coupled CoMoO4–3D graphene hybrid electrodes.

Adv.Mater.26,1044–1051(2014).

10.Chen,Z.et al.Three-dimensional flexible and conductive interconnected graphene

networks grown by chemical vapour deposition.Nature Mater.10,424–428

(2011).

11.Wasserscheid,P.&Keim,W.Ionic liquids—new‘‘solutions’’for transition metal

catalysis.Angew.Chem.Int.Edn39,3772–3789(2000).

12.Auborn,J.J.&Barberio,Y.L.An ambient temperature secondary aluminum

electrode:its cycling rates and its cycling efficiencies.J.Electrochem.Soc.132, 598–601(1985).

13.Wilkes,J.S.,Levisky,J.A.,Wilson,R.A.&Hussey,C.L.Dialkylimidazolium

chloroaluminate melts:a new class of room-temperature ionic liquids for

electrochemistry,spectroscopy and synthesis.Inorg.Chem.21,1263–1264(1982).

https://www.sodocs.net/doc/b610333623.html,i,P.K.&Skyllas-Kazacos,M.Electrodeposition of aluminium in aluminium

chloride/1-methyl-3-ethylimidazolium chloride.J.Electroanal.Chem.Interfacial Electrochem.248,431–440(1988).

15.Jiang,T.,Chollier Brym,M.J.,Dube′,G.,Lasia,A.&Brisard,G.M.Electrodeposition of

aluminium from ionic liquids:Part I—electrodeposition and surface morphology of aluminium from aluminium chloride(AlCl3)–1-ethyl-3-methylimidazolium chloride([EMIm]Cl)ionic liquids.Surf.Coat.Tech.201,1–9(2006).

16.Borg,R.J.&Dienes,G.J.An Introduction to Solid State Diffusion(Academic,1988).

17.Zhu,Y.-J.,Hansen,T.A.,Ammermann,S.,McBride,J.D.&Beebe,T.P.Nanometer-

size monolayer and multilayer molecule corrals on HOPG:a depth-resolved

mechanistic study by STM.J.Phys.Chem.B105,7632–7638(2001).

18.Schmuelling,G.et al.X-ray diffraction studies of the electrochemical intercalation

of bis(trifluoromethanesulfonyl)imide anions into graphite for dual-ion cells.

J.Power Sources239,563–571(2013).

19.Takahashi,S.,Koura,N.,Kohara,S.,Saboungi,M.L.&Curtiss,L.A.Technological

and scientific issues of room-temperature molten salts.Plasmas Ions2,91–105 (1999).

20.Hardwick,L.J.et al.An in situ Raman study of the intercalation of supercapacitor-

type electrolyte into microcrystalline graphite.Electrochim.Acta52,675–680 (2006).

Supplementary Information is available in the online version of the paper. Acknowledgements We thank M.D.Fayer for discussions.We also thank Y.Cui’s group for use of an argon-filled glove box and a vacuum oven.M.-C.L thanks the Bureau of Energy,Ministry of Economic Affairs,Taiwan,for supporting international cooperation between Stanford University and ITRI.B.L.acknowledges support from the National Natural Science Foundation of China(grant no.21303046),the China Scholarship Council(no.201308430178),and the Hunan University Fund for Multidisciplinary Developing(no.531107040762).We also acknowledge support from the US Department of Energy for novel carbon materials development and electrical characterization work(DOE DE-SC0008684),Stanford GCEP,the Precourt Institute of Energy,and the Global Networking Talent3.0plan(NTUST104DI005)from the Ministry of Education of Taiwan.

Author Contributions M.-C.L.,M.G.,B.L.and Y.W.contributed equally to this work. M.-C.L.and H.D.conceived the idea for the project.B.L.prepared the graphitic foam. M.-C.L.,M.G.,B.L.,Y.W.,D.-Y.W.,M.A.and M.Guan performed electrochemical experiments.M.-C.L.,C.C.and J.Y conducted in situ Raman spectroscopy measurements.M.-C.L.,M.G.,B.L.and Y.W.performed ex situ X-ray diffraction measurements.M.G.,M.-C.L.,B.L.and Y.W.performed X-ray photoelectron spectroscopy and Auger electron spectroscopy measurements.M.-C.L.,M.G.,B.L.,Y.W., D.-Y.W.,M.A.,B.-J.H.and H.D.discussed the results,analysed the data and drafted the manuscript.

Author Information Reprints and permissions information is available at

https://www.sodocs.net/doc/b610333623.html,/reprints.The authors declare no competing financial interests. Readers are welcome to comment on the online version of the paper.Correspondence and requests for materials should be addressed to H.D.(hdai@https://www.sodocs.net/doc/b610333623.html,).

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METHODS

Preparation of ionic liquid electrolytes.A room temperature ionic liquid electro-lyte was made by mixing1-ethyl-3-methylimidazolium chloride([EMIm]Cl,97%, Acros Chemicals)and anhydrous aluminium chloride(AlCl3,99.999%,Sigma Aldrich).[EMIm]Cl was baked at130u C under vacuum for16–32h to remove residual water.([EMIm]Al x Cl y)ionic liquid electrolytes were prepared in an argon-atmosphere glove box(both[EMIm]Cl and AlCl3are highly hygroscopic)by mix-ing anhydrous AlCl3with[EMIm]Cl,and the resulting light-yellow,transparent liquid was stirred at room temperature for10min.The mole ratio of AlCl3to[EMIm]Cl was varied from1.1to1.8.The water content of the ionic liquid was determined (500–700p.p.m.)using a coulometric Karl Fischer titrator,DL39(Mettler Toledo). The predominant anions in basic melts(AlCl3/[EMIm]Cl mole ratio,1)are Cl2 and AlCl42,while in acidic melts(AlCl3/[EMIm]Cl mole ratio.1)chloroalumi-nate anions such as Al2Cl72,Al3Cl102,and Al4Cl132are formed11.The ratio of anions to cations in the AlCl3/[EMIm]Cl electrolyte was determined using a glass fibre filter paper(Whatman GF/D)loaded with a4–8m m Au-coated SiO2beads21in a cuvette cell(0.35ml,Starna Cells)with random orientation quartz windows.Then,in the glove box,the cuvette cell was filled with AlCl3/[EMIm]Cl51.3(by mole).Raman spectra(200–650cm-1)were obtained using a785-nm laser with2cm–1resolution. Raman data were collected from the surface of the Au-coated SiO2bead so as to benefit from surface enhanced Raman21,22(Extended Data Fig.2b). Preparation of graphitic foam.Nickel(Ni)foams(Alantum Advanced Technology Materials,Shenyang,China),were used as3D scaffold templates for the CVD growth of graphitic foam,following the process reported previously9,10. The Ni foams were heated to1,000u C in a horizontal tube furnace(Lindberg Blue M,TF55030C)under Ar(500standard cubic centimetres per minute or s.c.c.m.)and H2(200s.c.c.m.)and annealed for10min to clean their surfaces and to eliminate a thin surface oxide layer.Then,methane(CH4)was introduced into the reaction tube at ambient pressure at a flow rate of10s.c.c.m.,corresponding to a concen-tration of1.4vol.%in the total gas flow.After10min of reaction gas mixture flow, the samples were rapidly cooled to room temperature at a rate of300u C min21 under Ar(500s.c.c.m.)and H2(200s.c.c.m.).The Ni foams covered with graphite were drop-coated with a poly(methyl methacrylate)(PMMA)solution(4.5%in ethyl acetate),and then baked at110u C for0.5h.The PMMA/graphene/Ni foam structure was obtained after solidification.Afterwards,these samples were put into a3M HCl solution for3h to completely dissolve the Ni foam to obtain the PMMA/graphite at80u C.Finally,the pure graphitic foam was obtained by removing PMMA in hot acetone at55u C and annealing in NH3(80s.c.c.m.)at 600u C for2h,and then annealing in air at450u C for2h.The microstructure of the graphitic foam was examined by SEM analysis using a FEI XL30Sirion scanning electron microscope(Fig.2a in the main text).

Preparation of glassy carbon.Glassy carbon(GC)was used as the current collector in the Swagelok-type cell.72g phenol(Sigma-Aldrich)and4.5ml ammonium hydroxide(30%,Fisher Scientific)were dissolved in100ml formaldehyde solution (37%,Fisher Scientific)under reflux while stirring rapidly.The solution was stirred at90u C until the solution turned a milk-white colour.Rotary evaporation was used to remove the water and get the phenolic resin.The phenolic resin was solidified at 100u C in a mould(1/2-inch glass tube),and then carbonized at850u C under an Ar atmosphere for four hours to obtain the GC rod.The resulting GC rod contributed negligible capacity to the cathode(Extended Data Fig.6b).

Electrochemical measurements.Prior to assembling the Al/graphite cell in the glove box,all components were heated under vacuum at60u C for more than12h to remove residual water.All electrochemical tests were performed at2561u C.

A Swagelok-type cell(1/2inch diameter)was constructed using a,4mg PG foil

(0.017mm,Suzhou Dasen Electronics Materials)cathode and a90mg Al foil (0.25mm,Alfa Aesar)anode.A1/2inch GC rod(10mm)was used as the current collector for the PG cathode,and a1/2inch graphite rod(10mm)was used for the Al anode.Six layers of1/2inch glass fibre filter paper(Whatman934-AH)were placed between the anode and cathode.Then,,1.0ml of ionic liquid electrolyte (prepared with AlCl3/[EMIm]Cl mole ratios of1.1,1.3,1.5and1.8)was injected and the cell sealed.The Al/PG cell was then charged(to2.45V)and discharged(to 0.01V)at a current density of66mA g–1with a MTI battery analyser(BST8-WA) to identify the ideal AlCl3/[EMIm]Cl mole ratio(Extended Data Fig.2a).To investigate the Coulombic efficiency of the Al/PG cell in AlCl3/[EMIm]Cl<1.3 (by mole)electrolyte,the cell was charged to2.45,2.50,2.55and2.60V,respectively, and discharged to0.4V at a current density of66mA g–1(Extended Data Fig.6a). For long-term cycling stability tests,an Al/PG cell using electrolyte AlCl3/ [EMIm]Cl<1.3by mole was charged/discharged at a current density of 66mA g21(Fig.1b,c in the main text).To study the rate capability of the Al/ PG cell,the current densities were varied from66to264mA g21(Extended Data Fig.7).Note that we lowered the electrolyte amount to,0.02ml per mg of cathode material and observed similar cell operation(Extended Data Fig.4). Further decrease in the electrolyte ratio is possible through battery engineering.

PG foil was synthesized by pyrolysis of polyimide at high temperature,in which some covalent bonding is inevitably generated due to imperfections.Natural graphite foil was produced by compressing expanded graphite flakes,leading to stacking of natural graphite flakes by Van der Waals bonding between them.Similar battery characteristics were observed with PG and graphite foil electrodes,indicating that the battery behaviour was derived from the graphitic property of the electrodes (Extended Data Fig.8c).However,since the natural graphite foils are synthesized by compressing expanded natural graphite powders without the covalent linkage between them,these foils suffered from drastic electrode expansion obvious to the naked eye,whereas pyrolytic graphite foils showed no obvious electrode expan-sion due to covalency(Extended Data Fig.8a,b).

Pouch cells were assembled in the glove box using a graphitic-foam(,3mg) cathode and an Al foil(,70mg)anode,which were separated by two layers of glass fibre filter paper to prevent shorting.Polymer(0.1mm34mm35mm)coated Ni foils(0.09mm33mm360mm in size;MTI corporation)were used as current collectors for both anode and cathode.The electrolyte(,2ml prepared using AlCl3/[EMIm]Cl51.3by mole)was injected and the cell was closed using a heat sealer.The cell was removed from the glove box for long-term cycling stability tests,in which the cell was charged/discharged at a current density of4,000mA g21 (Fig.2b,c).To determine the rate capability and fast-charge/slow-discharge beha-viours of the Al/graphitic-foam cell,various current densities from100to 5,000mA g21were used(Extended Data Fig.9and Fig.2d).The pouch cell was charged to2.42V and discharged to a cut-off voltage of0.5V to prevent the dissolution reaction of Ni foil in the ionic liquid electrolyte.

Cyclic voltammetry measurements were performed using a potentiostat/galva-nostat model CHI760D(CH Instruments)in either three-electrode or two-electrode mode.The working electrode was an Al foil or a PG foil,the auxiliary electrode consisted of an Al foil,and an Al foil was used as the reference electrode.Copper tape(3M)was attached to these electrodes as the current collector.The copper tape was covered by poly-tetrafluoroethylene(PTFE)tape to prevent contact with the ionic liquid electrolyte and the part of the copper tape covered by PTFE was not immersed in the ionic liquid electrolyte.This prevented corrosion of the copper tape during cyclic voltammetry measurements.All three electrodes were placed in a plastic(1.5ml)cuvette cell(containing electrolyte AlCl3/ [EMIm]Cl51.3by mole)in the glove box,and then sealed with a rubber cap using a clamp.The scanning voltage range was set from–1.0to1.0V(versus Al) for Al foil and0to2.5V(versus Al)for graphitic material,and the scan rate was 10mV s–1(Extended Data Fig.10d).To investigate the working voltage range of the electrolyte without involving cathode intercalation,two-electrode measurement was performed by using a GC rod cathode against an Al anode in a Swagelok cell in AlCl3/[EMIm]Cl(,1.3by mole)electrolyte.The scanning voltage range was set from0to2.9V at a scan rate of10mV s–1(Extended Data Fig.6b).

We investigated the Al ion cell operation mechanism and electrode reactions in the ionic liquid electrolyte,using the optimal mole ratio of AlCl3/[EMIm]Cl51.3. Using CV(Extended Data Fig.10d),a reduction wave from–1.0to–0.08V(versus Al)and an oxidation wave from20.08to0.80V(versus Al)for the anode were observed(Extended Data Fig.10d,left plot),corresponding to Al reduction/elec-trodeposition and oxidation/dissolution13,15,23–25during charging and discharging, respectively.This was consistent with Al redox electrochemistry in chloroalumi-nate ionic liquids13,15,23–25via equation(1)in the main text,and consistent with our Raman measurements,which showed both AlCl42and Al2Cl72in the electrolyte (Extended Data Fig.2b).On the graphitic cathode side,an oxidation wave of1.83 to2.50V(versus Al)and a reduction wave of1.16to2.36V(versus Al)were observed (Extended Data Fig.10d,right plot)and attributed to graphite oxidation and reduc-tion through intercalation and de-intercalation of anions(predominantly AlCl42 due to its smaller size),respectively.The oxidation voltage range of1.83to2.50V (versus Al,Extended Data Fig.10d,right plot)was close to the anodic voltage range (1.8to2.2V versus Al)of a previously reported dual-graphite cell26attributed to AlCl42intercalation in graphite.The reduction wave range of1.16to2.36V(versus Al)was assigned to the AlCl42de-intercalation26.The nature of the shoulder in the reduction curve of graphite ranging from2.36to1.9V(Extended Data Fig.10d, right plot)and a higher discharge plateau(2.25to2.0V)of an Al/PG cell upon charging(Fig.1b in the main text)remained unclear,but could be due to different stages of anion–graphite intercalation27.

XRD and Raman studies of graphite cathodes during charge and discharge. For ex situ X-ray diffraction(XRD)study,an Al/PG cell(in a Swagelok configu-ration)was charged and discharged at a constant current density of66mA g–1.The reactions were stopped after30mA h g–1charged,fully charged(62mA h g–1)and 40mA h g–1discharged after charge/discharge capacities were in a stable state.Fully charged(62mA h g–1)graphitic foam was also prepared.After either the charge or the discharge reaction,the graphitic cathode was removed from the cell in the glove box.To avoid reaction between the cathode and air/moisture in the ambient atmo-sphere,the cathode was placed onto a glass slide and then wrapped in a Scotch tape.

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The wrapped samples were immediately removed from the glove box for ex situ XRD measurements,which were performed on a PANalytical X’Pert instrument (Fig.3a in the main text and Extended Data Fig.10b).

The periodic repeat distance (I C ),the intercalant gallery height (d i )and the gallery expansion (D d )28,29can be calculated using

I C ~d i z 3:35A 0àá|n {1eT~(D d z 3:35A 0

)|n ~l |d obs e3Twhere l is the index of (00l )planes oriented in the stacking direction and d obs is the

observed value of the spacing between two adjacent planes 18,28,29.The d spacing of

graphite is 3.35A

?.During the charging/anion-intercalation process,the graphite (002)peak completely vanished and two new peaks arose.The intensity pattern is commonly found for a stage n graphite intercalation compound (GIC),where the most dominant peak is the (00n 11)and the second most dominant peak is the (00n 12)18,28,29.Based on our experimental data,by increasing the charging state from 48–60%charged (30mA h g –1)to the fully charged state (62mA h g –1),the distance between the (00n 11)and (00n 12)peaks gradually increased,as more Al x Cl y –anions intercalated.The d spacing values of (00n 11)and (00n 12)peaks (that is,d (n 11)and d (n 12),respectively)were calculated from XRD data (for example,Fig.3a).By determining the ratio of the d (n 12)/d (n 11)peak position and correlating these to the ratios of stage pure GICs (that is,ideal cases),the most dominant stage phase of the observed GIC can be assigned 28,29.After assigning the (00l )indices,we calculated the intercalant gallery height (d i )through equation (3).

For simultaneous in situ Raman and galvanostatic charge/discharge reaction measurements,a cuvette cell (0.35ml,Starna Cells)with random orientation quartz windows was used.An aluminium foil and a graphitic material (PG or graphitic foam)were used as the anode and cathode,respectively.The electrolyte was mixed AlCl 3/[EMIm]Cl 51.3(by mole).The electrochemical cell was assembled in the glove box following the process mentioned above.Raman spectra were obtained (1,500–1,700cm -1)using a HeNe laser (633nm)with 2cm 21resolution.The spectral data were collected after a few successive charge/discharge scans between 2.45and 0.01V at a current density of 66mA g –1(PG)(Fig.3b in the main text)or 1,000mA g –1(graphitic foam)(Extended Data Fig.10a).

XPS and AES measurements.Al/graphitic-foam cells were fully charged/discharged at a current density of 4,000mA g 21.Then,the Al/graphitic-foam cells were trans-ferred to the glove box for preparation for XPS and AES analysis.Fully charged/

discharged graphitic foams were collected from the pouch cell and washed with anhydrous methanol to remove the residual AlCl 3/EMIC ionic liquid electrolyte.The as-rinsed graphitic foams were attached to a Si wafer and baked at 90u C for 10min to remove residual methanol.The samples were sealed in a plastic pouch to avoid contamination by reaction with moisture and oxygen before XPS and AES characterization.Auger electron spectra were taken by a PHI 700Scanning Auger Nanoprobe operating at 10kV and 10nA.XPS spectra were collected on a PHI VersaProbe Scanning XPS Microprobe (Fig.4in the main text).

TGA measurements.Fully charged PG cathodes were washed with methanol for 24h to remove the residual AlCl 3/EMIC ionic liquid electrolyte.The as-washed PG samples were calcined at 850u C for 3h in air.The as-calcined samples (white foam)were collected,weighed,and analysed by SEM-EDX to study the chemical com-position (Extended Data Fig.10c).SEM and SEM-EDX analyses were performed using an FEI XL30Sirion scanning electron microscope.

Sample size.No statistical methods were used to predetermine sample size.

21.Zhang,B.et al.Plasmonic micro-beads for fluorescence enhanced,multiplexed protein detection with flow cytometry.Chem.Sci.5,4070–4075(2014).

22.Tabakman,S.M.,Chen,Z.,Casalongue,H.S.,Wang,H.&Dai,H.A new approach to solution-phase gold seeding for SERS substrates.Small 7,499–505(2011).23.

Lee,J.J.,Bae,I.T.,Scherson,D.A.,Miller,B.&Wheeler,K.A.Underpotential deposition of aluminum and alloy formation on polycrystalline gold electrodes from AlCl 3/EMIC room-temperature molten salts.J.Electrochem.Soc.147,562–566(2000).

24.Pan,S.-J.,Tsai,W.-T.,Chang,J.-K.&Sun,I.W.Co-deposition of Al–Zn on AZ91D magnesium alloy in AlCl 3–1-ethyl-3-methylimidazolium chloride ionic liquid.Electrochim.Acta 55,2158–2162(2010).

25.Endres,F.,MacFarlane,D.&Abbott,A.Electrodeposition from Ionic Liquids (Wiley &Sons,2008).

26.Carlin,R.T.,De Long,H.C.,Fuller,J.&Trulove,P.C.Dual intercalating molten electrolyte batteries.J.Electrochem.Soc.141,L73–L76(1994).

27.Bao,W.et al.Approaching the limits of transparency and conductivity in graphitic materials through lithium intercalation.Nature Commun.5,4224(2014).28.Zhang,X.,Sukpirom,N.&Lerner,M.M.Graphite intercalation of bis(trifluoromethanesulfonyl)imide and other anions with

perfluoroalkanesulfonyl substituents.Mater.Res.Bull.34,363–372(1999).29.

¨zmen-Monkul,B.&Lerner,M.M.The first graphite intercalation compounds containing tris(pentafluoroethyl)trifluorophosphate.Carbon 48,3205–3210(2010).

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Extended Data Figure1|X-ray diffraction patterns of graphitic cathode

materials.The natural graphite,pyrolytic graphite(PG)and graphitic foam

exhibited typical graphite structure,with a sharp(002)X-ray diffraction(XRD)

graphite peak at2h<26.55u(d spacing53.35A?).

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Extended Data Figure2|Determination of the optimal mole ratio of AlCl3/[EMIm]Cl ionic liquid electrolyte.a,Galvanostatic charge and discharge curves of Al/PG cells at a current density of66mA g21in various mole ratios(1.1,1.3,1.5and1.8)of AlCl3/[EMIm]Cl ionic liquid electrolytes in a Swagelok-type cell.The Coulombic efficiencies of the cells are shown in parentheses.b,Raman spectrum of the ionic liquid electrolyte with a mole ratio of AlCl3/[EMIm]Cl51.3.

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Extended Data Figure3|Calculated discharging capacities of Al/graphite cells with different masses of graphitic materials.a,Natural graphite foils of 50m m and130m m thickness;b,PG and graphitic foam.These data suggest that the entire graphitic material(natural graphite,PG and graphitic foam) participated in the cell cathode reaction.

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Extended Data Figure4|Galvanostatic charge and discharge curves of an

Al/PG cell.The cell was constructed with one layer of glass fibre separator and

0.08ml of ionic liquid electrolyte,suggesting that the minimum amount of

electrolyte could be0.02ml per mg of PG.This electrochemical study was

performed in an ionic liquid electrolyte of composition AlCl3/[EMIm]Cl51.3

(by mole)at a current density of66mA g21in a Swagelok-type cell.

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Extended Data Figure5|Surface observations of an Al anode.a,b,SEM images of the Al anode obtained from two Al/PG cells after20(a)and100(b)cycles, respectively,and indicate no dendrite formation over these cycles.Scale bars,10m m.

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Extended Data Figure6|Electrochemical stability of the AlCl3/[EMIm]Cl ionic liquid electrolyte.a,Galvanostatic curves of Al/PG cells with different cut-off charge voltages obtained at66mA g21in a Swagelok-type cell. b,Cyclic voltammetry curve of a Al/glassy carbon(GC)cell at10mV s21in a Swagelok-type cell.c,d,Stability test of Al/natural graphite pouch cell at

66mA g21in electrolytes containing water at7,500–10,000p.p.m.(c)and 500–700p.p.m.(d).The Coulombic efficiencies are respectively95.2%and 98.6%,and the discharge capacities are respectively54.9and61.8mA h g21 at the15cycle.e,Gas chromatography spectrum of gaseous samples withdrawn from Al/graphite cells after30cycles using electrolyte with7,500–10,000p.p.m. H2O content.The peak found in the retention time at,0.5min corresponds to hydrogen gas and matches the retention time of pure hydrogen gas used for calibration.

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Extended Data Figure7|Rate capability of an Al/PG cell.a,Capacity retention of an Al/PG cell cycled at various current densities,showing good cycling stability at different charge–discharge current densities.b,Coulombic efficiency versus current density data of Al/PG cells,indicating the Coulombic efficiency is,95–97%at current densities of66–132mA g21.Error bars, standard deviation from the Coulombic efficiency for each current density. All electrochemical studies were performed in an ionic liquid electrolyte of composition AlCl3/[EMIm]Cl51.3(by mole)in a Swagelok-type cell.

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Extended Data Figure8|Advantages of PG as the cathode for an

Al/graphite cell.a,b,Right:photographs of natural graphite(a)and pyrolytic graphite(PG;b)before and after being fully charged in an

AlCl3/[EMIm]Cl51.3(by mole)ionic liquid electrolyte.Scale bars,1cm. Left:the schematic plots indicate the chemical bonds between the graphene sheets of natural graphite(Vander Waals bonding)and of PG(covalent bonding).c,Galvanostatic charge and discharge curves of an Al/PG cell (at66mA g21)and an Al/natural graphite cell(at33mA g21)in an ionic liquid electrolyte of composition AlCl3/[EMIm]Cl51.3(by mole)in a Swagelok-type cell.

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Extended Data Figure9|Rate capability of an Al/graphitic-foam cell. a,Capacity retention of an Al/graphitic-foam cell cycled at various current densities,showing cycling stability at different charge–discharge current densities.All electrochemical studies were performed in an AlCl3/[EMIm]Cl51.3(by mole)ionic liquid electrolyte in a pouch cell.

b,Galvanostatic charge and discharge curves of Al/graphitic-foam cells charging at5,000mA g21and discharging at various current densities ranging from100to5,000mA g21.Same electrolyte and cell type as a.

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Extended Data Figure10|Reaction mechanism of graphitic cathodes. a,In situ Raman spectra recorded for the graphitic-foam cathode through a charge/discharge cycle showing chloroaluminate anion intercalation/de-intercalation into graphite.b,Ex situ XRD patterns of the pristine and fully charged(62mA h g21)graphitic foam.c,EDS spectrum of as-calcined fully charged(62mA h g21)PG at850u C in air.d,Cyclic voltammetry curves of Al foil and PG at a scan rate of10mV s21against an Al reference electrode.

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An_ultrafast_rechargeable_aluminium-ion_battery

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