石墨相關材料可分別當成鋁電池和鋰離子電池中的正極和陰極，其主要優點包括穩定的組成與在化學插層/去插層中易於合成，以及成本相當低廉。
AlCl4-離子和AlCl4分子石墨插層化合物表現出多樣化的準粒子現象，主要由於尺寸較大的插層離子/分子和明顯的電荷轉移現象；根據精細的VASP模擬和理論分析，以stage1之情況對晶體結構、晶體對稱性、碳、氯和鋁原子於能譜中主導的特定能量範圍、插層前和插層之後的電荷分佈與電荷密度差異、各原子之軌域投影其van Hove singularities出現之能量範圍進行分析，活躍的化學鍵包含層內/層間碳-碳、層間碳-插層劑與插層劑內部原子之軌域混成。
與A-B堆疊石墨相比，AlCl4離子/AlCl4分子插層的過程，層距發生了明顯的擴大，並於插層後於能帶結構中看出其高對稱點的變化、子能帶的建立、費米能階佔用與不佔用的不對稱、自由載子密度的變化、於費米面附近各向同性與遠離費米面附近的各向異性、頻繁的交叉與反交叉行為、碳，鋁和氯主導能帶結構中不同能量範圍。於分子、離子插層化合物中展現了許多不同之性質，例如碳層層距、半導體、半金屬、金屬性質展現，主要由於分子插層、離子插層之電子組態之差異性。
在C-C/C-Cl/Al-Cl/Cl-Cl鍵中，特定的軌域混成是[2s, 2px, 2py]-[2s, 2px, 2py] & 2pz-2pz/[2s, 2px, 2py, 2pz]-[3s, 3px, 3py, 3pz]/[3s, 3px, 3py, 3pz]-[3s, 3px, 3py, 3pz]/[3s, 3px, 3py, 3pz]-[3s, 3px, 3py, 3pz]. 。然而C-Al、Al-Al之間之交互作用並無法由數據觀察而得。

關鍵字：石墨、四氯化鋁、鋁離子電池、VASP、第一原理計算

It is well know that graphite-related materials could serve as anode and cathode in aluminum- and lithium-ion-based batteries, respectively. Their main merits cover the most stable configuration,an easy synthesis in chemical intercalation/de-intercalation,and a quite low cost.
〖AlCl_4〗^--ion and AlCl4-molecule graphite intercalation compounds exhibit the diversified quasiparticle phenomena, mainly owing to large intercalants and distinct charge cases . Based on the delicate VASP simulations and theoretical analyses, all the active chemical bonds are covered in the intralayer/interlayer C-C orbital hybridizations, the interlayer C-intercalant interactions, and intra- & intercalant ones. They have been thoroughly examined from the stage-1 crystal symmetries, C-, Al-, & Cl-dominated energy spectra at specific energy ranges, charge distributions before & after intercalations/de-intercalations, and atom- & orbital-projected van Hove singularities, as well as their emergences. Very interesting, the greatly diversified fundamental properties reveal as follows: the periodical arrangements along the longitudinal and transverse directions simultaneously, the absence of stage-1 & stage-2 cases, the Moire superlattices, the generation of many valence & conduction energy subbands, the changes of initial high-symmetry valleys, the strengthened asymmetry of hole and electron spectra about EF=0, the obvious reduce or enhancement of band overlaps [the diversified free carrier densities], the almost isotropic/highly anisotropic features near/away from EF=0, the diverse energy dispersions at the distinct critical points, the frequent band crossings & anti-crossings, the undefined behaviors of the whole π & σ valence bands, the carbon-, aluminum- & chloride -dominated band structures within the different energy ranges. The specific orbital hybridizations in significant C-C/C-Cl/Al-Cl/Cl-Cl bonds are [2s, 2px, 2py]-[2s, 2px, 2py] & 2pz-2pz/[2s, 2px, 2py, 2pz]-[3s, 3px, 3py, 3pz]/[3s, 3px, 3py, 3pz]-[3s, 3px, 3py, 3pz]/[3s, 3px, 3py, 3pz]-[3s, 3px, 3py, 3pz]. However, the obvious evidences are absent for C-Al and Al-Al bonds.

Key words: Graphite, AlCl4, Aluminium-ion battery,VASP, First Principles Computational

[1] Sutter P,Sadowski JT and Sutter EA 2010 Chemistry under Cover : Tuning Metal-Graphene Interaction by Reactive Intercalation. Journal of the American Chemical Society .132, 8175-8179.
[2] Dale A ,C Brownson and Craig E Banks 2010 Graphene electrochemistry: an overview of potential applications. Analyst 135,2768-2778.
[3] CY Lin, JY Wu, YJ Ou, YH Chiu and MF Lin 2015 Magneto-electronic properties of multilayer graphenes. Physical Chemistry Chemical Physics, 17(39),26008.
[4] RozpLlocha F, Patyk J and Stankowski J 2007 Graphenes Bonding Forces in Graphite. Institute of Physics, Nicolaus Copernicus UniversityGrudzi 5/7, 87-100.
[5] Brownson DAC and Banks CE 2010 Graphene electrochemistry: an overview of potential applications . Analyst 135,2768-2778.
[6] Hu M ,Dong X , Wu YJ , Liu LY and Zhao ZS 2018 Low-energy 3D sp(2) carbons with versatileproperties beyond graphite and graphene. Dalton Transactions 47,6233-6239.
[7] Konschuh S , Gmitra M and Fabian J 2010 Tight-binding theory of the spin-orbit coupling in graphene. Physical Review B 82, 245412.
[8] Huang JR,Lin JY ,Chen BH and Tsai MH 2008 Structural and electronic properties of few-layer graphenes from first-principles. Physica Status Solid B-Basic Solid State Physics 245,136-141.
[9] de Andres PL,Ramirez R and Verges JA 2008 Strong covalent bonding between two graphene layers. Physical Review B 77,045403.
[10]Abergel DSL,Apalkov V,Berashevich J,Ziegler K and Chakraborty T 2010 Properties of graphene: a theoretical perspective. Advances In Physics 59 ,261-482.
[11] Lee SH , Chiu CW and Lin MF 2010 Deformation effects on electronic structures of bilayer graphenes.Physica E-low-Dimensional Systems &Nanost- Ructures 42,732-735.
[12] Briggs N,Gebeyehu ZM ,Vera A ,Zhao T ,Wang K ,Duran AD ,Bersch B ,Bowen T,Knappenberger KL and Robinson JA.2019 Epitaxial graphene/silicon carbide intercalation: a minireview on graphene modulation and unique 2D materials. Nanoscale 11,15440-15447.
[13] Silva CC,Cai JQ , Jolie W,Dombrowski D ,zum Hagen FHF ,Martinez-Galera AJ ,Schlueter C,Lee TL and Busse C 2019 Lifting Epitaxial Graphene by Intercalation of Alkali Metals.Journal of Physical Chemistry C 123 ,3712-13719.
[14] Yoo H,Engelke R,Carr S ,Fang SA ,Zhang K ,Cazeaux P ,Sung SH ,Hoyden R ,Tsen AW and Taniguchi T 2019 Atomic and electronic reconstruction at the van der Waals interface in twisted bilayer graphene. Nature Materlals 18,448.
[15] Kaneko T and Saito R 2017 First-principles study on interlayer state in alkali and alkaline earth metal atoms intercalated bilayer graphene. Surface Science 665 1-9.
[16] Silva CC,Cai JQ , Jolie W , Dombrowski D ,zum Hagen FHF ,Martinez-Galera, AJ,Schlueter C,Lee Tl and Busse C 2019 Lifting Epitaxial Graphene by Intercalation of Alkali Metals. Journal Of Physical Chemistry C 123,13712-13719.
[17] J. H. Ho, C. L. Lu, C. C. Hwang, C. P. Chang, and M. F. Lin 2006 Coulomb excitations in AA- and AB-stacked bilayer graphites. Physical Review B, 74(8),085406.
[18] Chun-Jern Pana ,Chunze Yuana ,Guanzhou Zhua,Qian Zhangc,Chen-Jui Huangb,Meng-Chang,LindMichaelAngella,Bing-JoeHwangb,Payam Kaghazchic and Hongjie Daia 2018 An operando X-ray diffraction study of chloroaluminate anion-graphite intercalation in aluminum batteries. Pnas 115 , 22.
[19] Preeti Bhauriyal , Arup Mahata and Biswarup Pathak 2017 The staging mechanism of AlCl4 inter & calation in a graphite electrode for an aluminium-ion battery. Phys.Chem.Chem.Phys 19 , 7980.
[20] MS Wua ,B Xua ,LQ Chenb and CY Ouyanga. 2016 Geometry and fast diffusion of AlCl4 cluster intercalated in graphite. Electrochimica Acta 195,158–165.
[21]Do.TN, Chang.CP, Shih.PH, Wu.JY and Lin.MF 2017 Stacking enrichedmagneto transport properties of few-layer graphenes. Physical Chemistry Chemical Physics, 19, 29525-29533.
[22] Leon A and Pacheco M 2011 Electronic and dynamics properties of a molecular wire of graphane nanoclusters. Physics Letters A 375, 4190-4197.
[23] Mounet N and Marzari N 2005 First-principles determination of the structural, vibrational and thermodynamic properties of diamond, graphite, and derivatives. Physical Review B 71 ,205214.
[24] Yurui Gao ,Chongqin Zhu , Zheng Zheng Chen and Gang Lu 2017 Understanding Ultrafast Rechargeable Aluminum-Ion Battery from First-Principles. J. Phys. Chem. C 121 7131–7138.
[25] M. F. Lin, C. S. Huang, and D. S. Chuu 1997 Plasmons in graphite and stage-1 graphite intercalation compounds. Phys. Rev. B 55, 13961.
[26] Alder BJ and Wainwright TE 1959 Studies In Molecular Dynamics .1. General Method . Ournal Of Chemical Phtsics 31, 459-466.
[27] Di-Yan Wang , Shao-Ku Huang ,Hsiang-Ju Liao ,Yu-Mei Chen , ShengWen Wang ,Yu-Ting Kao , Ji-Yao An ,Yi-Cheng Lee , Cheng-Hao Chuang ,Yu-Cheng Huang ,Ying-Rui Lu ,Hong-Ji Lin ,Hung-Lung Chou ,Chun-Wei Chen,Ying-Huang Lai and Chung-LiDong 2019 Insights into dynamic molecular intercalation mechanism for Al-C battery by operando synchrotron X-ray techniques.Carbon 146 ,528-534.
[28] C. Y. Lin, R. B. Chen, Y. H. Ho and M. F. Lin.2018 Electronic and optical properties of graphite-related systems. CRC Press, Boca Raton, Florida.
[29] Malko D,Neiss C,Vines F and Gorling A 2012 Competition for Graphene: Graphynes with Direction-Dependent Dirac Cones. Physical Revier Letters 108, 086804.
[30] Castro Neto AH,Guinea F, Peres NMR,Novoselov KS and Geim AK 2009 The electronic properties of graphene. Reviews Of Modern Physica 81,109-162.
[31] Abergel D,Apalkov V ,Berashevich J,Ziegler K andChakraborty T 2010 Properties of graphene: a theoretical perspective.Advances In Physics 59,261-482.
[32] Wu CJ and DasSarma S 2008 px,y-orbital counterpart of graphene: Cold atoms in the honeycomb optical lattice . Physical Review B .77,23.
[33] Sprinkle M ,Siegel D ,Hu Y ,Hicks J , Tejeda A ,Taleb-Ibrahimi , Le Fevre, P ,Bertran F ,Vizzini S and Enriquez H 2009 First Direct Observation of a Nearly Ideal Graphene Band Structure. Physical Review Letters .103,226803.
[34] Dresselhaus Ms and Dresselhaus G 2002 Intercalation compounds of graphite. Advances In Physica 51,1-186.
[35] C. Y. , J. Y. Wu, Y. H. Chiu, and M. F. Lin 2014 Stacking-dependent magneto-electronic properties in multilayer graphenes. Physical Review B 90(20),205434.
[36] J. Y. Wu, S. C. Chen, Oleksiy Roslyak, Godfrey Gumbs, and M. F. Lin.2011 Plasma Excitations in Graphene: Their Spectral Intensity and Temperature Dependence in Magnetic Field. ACS NANO 5(2), 1026.
[37] Goerbig MO 2011 Electronic properties of graphene in a strong magnetic field. Reviews Of Modern Physics 83,1193-1243.
[38] Shih-Yang Lin, Shen-Lin Chang, Feng-Lin Shyu, Jian-Ming Lu, and Ming-Fa Lin 2015 Feature-rich electronic properties in graphene ripples. Carbon 86,207-216.
[39] Shallcross S ,Sharma S ,Kandelaki E and Pankratov OA 2010 Electronic structure of turbostratic graphene. Physical Review B 81,165105.
[40] Reich S ,Maultzsch J ,Thomsen C and Ordejon P 2002 Tight-binding description of graphene. Physical Review B 66,035412.
[41] Lin Y ,Chen G,Sadowski JT ,Li YZ ,Tenney SA ,Dadap JI ,Hybertsen MS and Osgood RM 2019 Observation of intercalation-driven zone folding in quasi-free-standing graphene energy bands Physical Review B 99,035428.
[42] Loh KP,Bao QL,Ang PK and Yang JX 2010 The chemistry of graphene. Journal Of Materlals Chemistry 20,2277-2289.
[43] Jung SC,Kang YJ ,Yoo DJ ,Choi Jw and Han YK 2016 Flexible Few-Layered Graphene for the Ultrafast Rechargeable Aluminum-Ion Battery. Journal Of Physical Chemistry C 120,13384-13389.
[44] Qianpeng Wang,Daye Zheng,Lixin He and Xinguo Ren 2019 Cooperative Effect in a Graphite Intercalation Compound: Enhanced Mobility of AlCl4 in the Graphite Cathode of Aluminum-Ion Batteries. Physical Review Applied 12 , 044060.
[45] T Kiss1 ,Shimojima1 K ,Ishizaka1 A , Chainani T,Togashi T,Kanai1 X,Y Wang C,T Chen,S Watanabe and S Shin 2008 A versatile system for ultrahigh resolution, low temperature, and polarization dependent Laser-angle-resolved photoemission spectroscopy. Review of Scientific Instruments 79 ,023106.
[46] C. Y. Lin, C. H. Yang, C. W. Chiu, H. C. Chung, S. Y. Lin, and M. F. Lin. 2021 Many-particle interactions in carbon nanotubes. IOP Concise Physics, San Raefel, CA, USA: Morgan & Claypool Publishers, in print.
[47] Hwang EH and Das Sarma S 2008 Quasiparticle spectral function in doped graphene: Electron-electron interaction effects in Arpes Physical Review B 77,081412.
[48] C. Y. Lin, M. H. Lee, and M. F. Lin. 2018 Coulomb excitations in trilayer ABC-stacked graphene. Physical Review B Rapid communication, 98(4),041408.
[49] Tasaki K 2014 Density Functional Theory Study on Structural and Energetic Characteristics of Graphite Intercalation Compounds. Journal Of Physical Chemistry C 118,1443-1450.
[50] Li. WB, Lin SY, Tran NTT, Lin MF, and Lin KI. 2020 Essential geometric and electronic properties in stage-n graphite alkali-metal-intercalation compounds. RSC Advances,10,23573-23581.
[51] Geim AK and Mac Donald AH 2007 Graphene: Exploring carbon flatland. Physics Today 60,35-41.
[52] Duong DLF,Yun Sj and Lee YH. 2017 van der Waals Layered Materials: Opportunities and Challenges. Acs Nano 11,11803-11830.
[53] Hiroshi Shioyama, and Rokuro Fujii 1987 Electrochemical reactions of stage 1 sulfuric acid—Graphite intercalation compound. Carbon 25,771-774.
[54] NE Sorokina, NV Maksimova, AV Nikitin, ON Shornikova , and VV Avdeev 2001 Synthesis of Intercalation Compounds in the Graphite–HNO3–H3PO4 System. Inorganic Materials,37, 584–590.
[55] Da Zhan, Li Sun, Zhen Hua Ni, Lei Liu, Xiao Feng Fan, Ying ying Wang, Ting Yu, Yeng Ming Lam, Wei Huang, Ze Xiang Shen 2010 FeCl3‐Based Few‐Layer Graphene Intercalation Compounds: Single Linear Dispersion Electronic Band Structure and Strong Charge Transfer Doping. Advanced Functionnal Materials.
[56] Ro senzweig P, Karakachian H, Marchenko D, Kuster K, and Starke U. 2020 Overdoping Graphene Beyond the van Hove Singularity. Physical Review Letters,125 ,176403.
[57] Bostwick A,Ohta T,Seyller T,Horn K and Rotenberg E 2007 Quasiparticle dynamics in graphene. Nature Physics 3,36-40.
[58] Dresselhaus MS, and Dresselhaus G 2002 Intercalation compounds of graphite. Advances in Physics 51,1-186.
[59] Ro senzweig P,Karakachian H ,Marchenko D , Kuster K and Starke U 2020 Overdoping Graphene Beyond the van Hove Singularity. Physical Review Letters 125,176403.
[60] Dresselhaus MS and Dresselhaus G 2002 Intercalation compounds of graphite. Advances In Physics 51,1-186.
[61] Tasaki k 2014 Density Functional Theory Study on Structural and Energetic Characteristics of Graphite Intercalation Compounds Journal Of Physical Chemistry C 118,1443-1450.
[62] Liu HT,Liu YQ and Zhu DB 2011 Chemical doping of graphene . Journal Of Materlals Chemistry 21,3335-3345.
[63] Li GH,Luican A ,dos Santos JMBL ,Castro Neto, Reina, A ,Kong J and Andrei EY 2010 Observation of Van Hove singularities in twisted graphene layers. Nature Physics 6,109-113.
[64] Garcia N 1986 Theory of scanning tunneling microscopy and spectroscopy - resolution, image and field states, and thin oxide layers. Ibm Journal Of Research And Development 30,533-542.
[65]Bando H,Tokumoto H ,Mizutani W ,Endo K,Wakiyama S, Watanabe K and Kajimura K 1987 Measurement Of Local Density Of States By Scanning Tunneling Spectroscopy At Low-Temperature. Apanese Journal Of Applied Physics Part 1-Regular Papers Short Notes & Review Papers 26,627-628.
[66] Luican A,Li GH,Reina A,Kong J ,Nair, RR ,Novoselov KS,Geim AK and Andrei EY 2011 Single-Layer Behavior and Its Breakdown in Twisted Graphene Layers . Physical Review Letters 106,126802.
[67]Brihuega I,Mallet P,Gonzalez-Herrero H,de Laissardiere GT,Ugeda MM Magaud L,Gomez-Rodriguez JM ,Yndurain F and Veuillen JY 2012 Unraveling the Intrinsic and Robust Nature of van Hove Singularities in Twisted Bilayer Graphene by Scanning Tunneling Microscopy and Theoretical Analysis. Physical Review Letters 109,196802.
[68] Kravets VG,Grigorenko AN ,Nair RR ,Blake P ,Anissimova S ,Novoselov KS and Geim AK 2010 Spectroscopic ellipsometry of graphene and an exciton-shifted van Hove peak in absorption. Physical Review B 81,155413.
[69] Nozieres P and Pines D 1959 Electron Interaction IN Solids – Characteristic Energy Loss Spectrum. Physical Review 113,1254-1267.
[70] Csanyi G,Littlewood PB,Nevidomskyy AH ,Pickard CJ and Simons BD2005 The role of the interlayer state in the electronic structure of superconducting graphite intercalated compounds. Nature Physics 1,42-45.
[71] C. Y. Lin, R. B. Chen, Y. H. Ho and M. F. Lin.2018 Electronic and optical properties of graphite-related systems. CRC Press, Boca Raton, Florida.
[72]Tassin P,Koschny T , Kafesaki M and Soukoulis CM 2012 A comparison of graphene, superconductors and metals as conductors for metamaterials and plasmonics. Nature Photonics 6,259-264.
[73] JC. Charlier, JP. and Michenaud and X.Gonze. 1991 Tight-binding model for the electronic properties of simple hexagonal graphite. Physical Review B,44,13237.
[74] Wang DY , Huang SK , Liao HJ , Chen YM ,Wang SW ,Kao YT ,An JY ,Lee YC Chuang CH and Huang YC 2019 Insights into dynamic molecular intercalation mechanism for Al-C battery by operando synchrotron X-ray techniques Carbon 146,528-534.
[75] Childress AS,Parajuli P , Zhu JY , Podila R and Rao AM 2017 A Raman spectroscopic study of graphene cathodes in high-performance aluminum ion batteries. Biotechnology Advances 29,189-198.
[76] Childress AS, Parajuli P, Zhu JY, Podila R, and Rao AM 2017 A Raman spectroscopic study of graphene cathodes in high-performance aluminum ion batteries. Biotechnology Advances, 29 ,189-198.