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- 1. -足 油1 油-足 油 Two-足dimensional 油Transi/on 油Metal 油 Carbides 油Produced 油by 油Exfolia/on 油of 油 MAX 油Phases 油 Yury 油Gogotsi 油& 油Michel 油Barsoum 油 Students: 油 Michael 油Naguib, 油Olha 油Mashtalir, 油Murat 油Kurtoglu 油 油 Drexel 油University 油 AJ 油Drexel 油Nanotechnology 油Ins7tute 油 油 Materials 油Science 油and 油Engineering 油Department 油 Philadelphia, 油Pennsylvania 油 NSF/AFOSR 油Workshop 油on 油2D 油Materials 油Beyond 油Graphene, 油 油 May 油30-足31, 油2012 油
- 2. -足 油2 油-足 油 2 油 M X A M Composition of Mn+1AXn ; with n =1,2,3 Ternary metals carbides and/or nitrides Layered hexagonal structure (P63/mmc) Examples: Ti2AlC, Ti2AlN, Ti3AlC2,Ti4AlN3 Ta2AlC, Ta4AlC3 Cr2AlC, Cr3AlC2 V2AlC, V3AlC2 Nb2AlC, Nb4AlC3 (>60 phases) (Ti0.5Nb0.5)2AlC, Ti3Al(C0.5N0.5)2 (considering solid solution, there will be more) Barsoum, M.W. Progress in Solid State Chemistry 28 (2000) 201 281 211 312 413 MAX 油Phases 油 Strong but Ductile Ceramics - not van der Waals Solids
- 3. -足 油3 油-足 油 MAX 油phase 油 MAX 油phases 油are 油layered 油ternary 油 carbides, 油nitrides, 油and 油carbonitrides 油 consisJng 油of 油M, 油A, 油and 油X 油layers 油 油 SelecJve 油etching 油only 油of 油the 油A 油 layers 油from 油the 油MAX 油phase 油 MXene 油sheets 油 Physically 油separated 油2-足D 油MXene 油 sheets 油aOer 油sonicaJon 油 Summary 油 Schematic of Solution Synthesis
- 4. -足 油4 油-足 油 HF 油 T reatment 油 O 油 C 油 H 油 Al 油 Ti 油 Sonica/on 油 Michael Naguib, et al. Advanced Materials 23 (2011) 4248-4253 MAX MAX MXene The Solution Approach to Ti3AlC2 Exfoliation and Dispersion Ti3AlC2 in HF 50% for 2 hours at room temperature, then sonication
- 5. M. Naguib, et al. Advanced Materials 23 (2011) 4248-4253 Ti3AlC2 HF 50% for 2 hours at room temperature After HF treatment, the most intense peak of Ti3AlC2 vanished. XRD after HF treatment matches with DFT simulated Ti3C2(OH)2. Sonication results in weakening the intensity of the peaks (losing the crystalline ordering). XRD Analysis of MAX and MXene
- 6. Raman Spectra of MAX and MXene 100 200 300 400 500 600 700 800 Intensity (I) (II) (IV) (V) (III) (VI) Raman shift (cm-1) Ti3AlC2 HF etched 油 Ti3AlC2 etched in 50% HF for 2 hours at room temperature Raman spectroscopy: 514.5 nm excitation M. Naguib, et al. Advanced Materials 23 (2011) 4248-4253 V. Presser, M. Naguib, et al. J. Raman Spectroscopy 43 (2011) 168-172.
- 7. -足 油7 油-足 油 Ti3AlC2 etched in HF 50% for 2 hours at room temperature: 2 袖m M. Naguib, et al. Advanced Materials 23 (2011) 4248-4253 L. M. Viculis, et al., Journal of Materials Chemistry 15 (2005) 974-978. Exfoliated Graphite SEM 油Images 油of 油MXene 油
- 8. -足 油8 油-足 油 Science 2012 Vol. 335, pp 526-527 Peoples choice award for International Science & Engineering Visualization Challenge from NSF, 2012. MXene on the Cover
- 9. -足 油9 油-足 油 Ti3AlC2 treated in HF 50% for 2 hours at room temperature, then sonication Michael Naguib, et al. Advanced Materials 23 (2011) 4248-4253 TEM 油Analysis 油of 油Ti3C2 油
- 10. -足 油10 油-足 油 5 nm R<20nm 5 nm Michael Naguib, et al. Advanced Materials 23 (2011) 4248-4253 Ti3AlC2 in 50%-HF for 2 hours at room temperature, then sonication MXene Scrolls/Nanotubes MXene shows behavior typical of graphene or other 2-D materials
- 11. -足 油11 油-足 油 4 袖m 3 袖m 1 袖m 2 袖m 1 袖m 1 袖m As 油received 油 Ti3C2 油 Ti2C 油 (Ti0.5Nb0.5)2C 油 油 Ti3(C0.5N0.5 油)2 油 Ta4C3 油 油 Michael Naguib, et al. ACS Nano 6 (2012) 1322-1331 MXenes A Large Family of Transition Metal Carbides and/or Nitrides Several MAX phases have been exfoliated, producing MXenes
- 12. -足 油12 油-足 油 Michael Naguib, et al. ACS Nano 6 (2012) 1322-1331 40nm 1 2 3 20nm 50nm 50nm Ti3C2 油 Ti3(C0.5N0.5 油)2 油 (Ti0.5Nb0.5)2C 油 油 Ta4C3 油 油 MXenes A Large Family of Transition Metal Carbides and/or Nitrides
- 13. -足 油13 油-足 油 M. Naguib, et al. ACS Nano 6 (2012) 1322-1331 HR TEM and SAD of Ta4C3 1100 油 0110 油 1010 油 1120 油 1210 油 2110 油 5 油1/nm 油 20 油nm 油 1.325 油nm 油 13 油 2 油nm 油 0.269 油nm 油 (0110) 油 0.155 油nm 油 (2110) 油 60属 油 Crystalline structure is maintained within the layer MXene layers are in registry in multilayer structures
- 14. -足 油14 油-足 油 10袖m 10袖m Ta4C3 flakes Ti3CN Individual (multi)layers are optically transparent under visible light Michael Naguib, et al. ACS Nano 6 (2012) 1322-1331 Light Microscopy of MXenes
- 15. -足 油15 油-足 油 Ti3C2(OH)2: 油OH 油terminated 油 油 Ti3C2 油nanosheets 油 Ti3C2: 油Bare 油layers, 油 油 no 油termina/ons 油 油 Ti3C2F2: 油F-足terminated 油 油 Ti3C2 油nanosheets 油 Semiconductor 油 (0.05 油eV 油bandgap) 油 Semiconductor 油 (0.1 油eV 油bandgap) 油 Metal 油 M. Naguib, et al. Advanced Materials 23 (2011) 4248-4253 Electronic Structure of MXenes DFT implemented in the CASTEP code in Material Studio software (Version 4.5)
- 16. -足 油16 油-足 油 Ti2C Ta4C3 (Ti0.5Nb0.5)2C Ti3(C0.5N0.5)2 R: 330 立/ 104 立/ 171 立/ 125 立/ CA: 32属 41属 31属 27属 Michael Naguib, et al. ACS Nano 6 (2012) 1322-1331 MXene can be cold pressed in the form of thin (300 袖m) free- standing discs. Resistivity is comparable to multi-layer graphene. Contact angle measurements of water showed hydrophilic behavior. 25mm Wetting and Conductivity
- 17. -足 油17 油-足 油 0 0.5 1 1.5 2 2.5 0 100 200 300 400 500 Q disch Cycle 1 Q ch Cycle 1 Q disch Cycle 2 Q ch Cycle 2 Q disch Cycle 20 Q ch Cycle 20 Q disch Cycle 25 Q ch Cycle 25 0 0.5 1 1.5 2 Potential (V vs. Li/Li + ) Specific Capacity (mAh揃g -1 ) Number of Inserted Li in the Structure (y) 1st 2nd 20-25 0 100 200 300 400 500 600 0 20 40 60 80 100 120 Data 31 4:08:31 PM 11/30/2011 Q discharg (C/25) Q charg (C/25) Qdischarge (C/6) Qcharge (C/6) Qdischarge (1C) Qcharge (1C/) Qdischarge (3C) Qcharge (3C) Qdischarge (10C) Qcharge (10C) Specific Capacity (mAh揃g -1 ) Cycle Number 0 100 200 300 400 500 600 0 5 10 15 20 Data 31 8:36:44 PM 11/3/2011 Q discharg (C/25) Q charg (C/25) Qdischarge (C/6) Qcharge (C/6) Qdischarge (1C) Qcharge (1C/) Qdischarge (3C) Qcharge (3C) Qdischarge (10C) Qcharge (10C) 3C 1C C/6 C/25 C/6 C/25 1C 3C & 10C 10C Ti2COx based anode properties similar to lithium titanate anodes M. Naguib, et al. Electrochemistry Communications 16 (2012) 61-64 MXene 油as 油a 油Li-足ion 油Ba[ery 油Anode 油
- 18. -足 油18 油-足 油 SelecJve 油etching 油of 油A 油layer 油from 油MAX 油phases 油results 油in 油the 油 formaJon 油of 油2-足D 油transiJon 油metals 油carbides 油and/or 油nitrides 油called 油 MXenes 油 油 Band 油gap 油of 油MXene 油predicted 油to 油change 油with 油the 油surface 油chemistry 油 油 Excellent 油mechanical 油properJes 油predicted 油(DFT) 油 Su鍖ciently 油ducJle 油for 油cold 油pressing 油 油 ConducJvity 油comparable 油to 油mulJ-足layer 油graphene 油 Hydrophilic 油(contact 油angle 油30-足40属) 油 油 Li 油inserJon 油allows 油use 油in 油Li-足ion 油ba[ery 油anodes 油 油 Summary of the Data to Date
- 19. -足 油19 油-足 油 Electrical 油energy 油storage 油 Pseudocapacitors, 油Lithium 油ion 油ba[eries, 油Hybrid 油devices 油 Composite 油materials 油 ConducJve, 油high-足strength, 油low-足permeability 油polymers, 油high 油 strength 油and 油high 油toughness 油ceramic-足metal 油composites 油 油 Sensors 油 2-足D 油and 油鍖exible 油electronics 油 油 Potential Applications M2X 油 M3X2 油 M4X3 油
- 20. -足 油20 油-足 油 Acknowledgments J辿r辿my Come & Patrice Simon, Universit辿 Paul Sabatier, Toulouse, France Jun Lu & Lars Hultman, Linkoping University, Sweden Gogotsi Nanomaterials Group Barsoum MAX Phase Group BATT Program