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Yifei Li
Materials Science and Engineering Program
Department of Electrical and Computer Engineering
University of Houston...
Contents
1. Introduction
1.1. Introduction of LIB
1.2. Beyond LIB
2. 2D materials for LIB and beyond
2.1. 2D layered graph...
3
1. Introduction
1.1Introduction of LIB (Lithium Ion Battery)
Figure 1. (a) Movement of Li+ in an electrolyte and inserti...
Annu. Rev. Chem. Biomol. Eng. 2012. 3:445–71
Figure 2. (a) Cylindrical lithium secondary batteries. (b) A comparison of th...
1.2 Motivation for Beyond LIB
1.2.1 Low-cost, Earth Abundant Cations
5
Lithium Sodium Magnesium
Gravimetric Capacity (mAh ...
2. 2D materials for LIB and beyond
2.1 2D layered graphite as anode
Figure 3. (a) Schematic drawing of the crystal structu...
2.2. 2D layered dichalcogenides
Figure 4. (a) The two-dimensional crystal structures of TiS2, MoS2, and NbS2. (b) Discharg...
Staging Effect
S. M. Whittingha. Intercalation chemistry. Elsevier, 2012.
Staging Effect in TiS2
J. Electrochem. Soc. 127 (1980) 2097-2099Electrochim. Acta 50 (2005) 2927-2932
Na-TiS2
Figure 5. (a...
2.3. 2D layered AxMOy oxide materials
LiCoO2:
First successful commercialized LIB using
LiCoO2 as cathode and carbon as an...
Figure 6 . Crystal structures of various NaxMOy : (a) P2-NaxCoO2, (b) O3-
NaxCoO2, (c) P3-NaxCoO2.
Electrochemistry Communications 12 (2010) 355–358
NaCrO2
P2-Na2/3Co2/3Mn1/3O2
Dalton Trans., 2011, 40, 9306–9312
P2-Nax[Fe1/2Mn1/2]O2 O3-Nax[Fe1/2Mn1/2]O2
Figure 7. a,b, Galvanostatic charge/discharge
(oxidation/reduction) curves for N...
2.4. Other 2D oxide electrode materials
ACS Nano, 2012, 6 (1), pp 530–538
Bilayered V2O5
V2O5·nH2O for Na ion battery
Figure 8. SIB performance of the V2O5·nH2O cathode. CV curves (a) and discharge–charge
curves...
J. Electrochem. Soc. 1993, 140, 140.
V2O5 used in Mg ion battery
V2O5
Shielding Effect
Mo6S8
Mo6S8 is the most successful ...
Graphene based hybrid electrode materials
Adv. Mater. 2012, 24, 4097–4111
Figure 9. (a) Growth of self-Assembled (rutile a...
Table 2. Capacities and rate performance of high-capacity oxide/graphene hybrids. Adv. Mater. 2012, 24, 4097–4111
Challenges for NIB (Na Ion Battery) and MIB (Mg Ion Battery)
Inorganic Chemistry, Vol. 46, No. 8, 2007
Na0.44MnO2
NIB:
• C...
Electrode Design for NIB and MIB
Figure 10. With the increase of interlayer distance of MoS2, the interaction between
cati...
3.1 MoS2-PEO Nanocomposites
3.1.1 Materials Consideration
MoS2
 A layered transition-metal dichalcogenide.
 MoS2 layers ...
Figure 11. (a) Synthesis of interlayer expanded MoS2 composites. (a) (b,c,d,e) TEM images of com-
MoS2, res-MoS2, peo1- Mo...
3.3.2 Materials Characterization for MoS2
Figure 12. (a) XRD spectra and (b) TGA analysis of com-MoS2, restacked-exfoliate...
3.3. Mg-Ion Battery of MoS2
Figure 13. Performance of Li and Mg cells with the MoS2 samples as working electrode. (a) Disc...
Conclusions
1. Due to the high cost, difficult for large scale application
and dendrite formation on Li anode, new candida...
Two-Dimensional Layered Materials for Battery Application--Yifei Li
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Two-Dimensional Layered Materials for Battery Application--Yifei Li

  1. 1. Yifei Li Materials Science and Engineering Program Department of Electrical and Computer Engineering University of Houston To those who may concern
  2. 2. Contents 1. Introduction 1.1. Introduction of LIB 1.2. Beyond LIB 2. 2D materials for LIB and beyond 2.1. 2D layered graphite as anode 2.2. 2D layered dichalcogenides 2.3. 2D layered AxMOy oxide materials 2.4. Other 2D oxide electrode materials 3. Novel electrode design for enhanced battery performance 3.1. MoS2-PEO nanocomposites
  3. 3. 3 1. Introduction 1.1Introduction of LIB (Lithium Ion Battery) Figure 1. (a) Movement of Li+ in an electrolyte and insertion-extraction of Li+ within electrodes in a lithium secondary battery. (b) Illustrative voltage curves as a function of state of charge of a battery for charging and discharging cycles at constant current. a b
  4. 4. Annu. Rev. Chem. Biomol. Eng. 2012. 3:445–71 Figure 2. (a) Cylindrical lithium secondary batteries. (b) A comparison of the energy and power densities of common rechargeable batteries. Li-ion batteries are superior to the others. a b
  5. 5. 1.2 Motivation for Beyond LIB 1.2.1 Low-cost, Earth Abundant Cations 5 Lithium Sodium Magnesium Gravimetric Capacity (mAh g-1 ) 3861 1166 2205 Volumetric Capacity (mAh cm-3 ) 2066 1128 3833 Potential (V vs NHE) −3.04 −2.71 −2.372 Global Production (kg yr-1 ) 2.5×107 (very low) 1010 (high) 6.3×109 (high) Price (carbonate; $ ton-1 ) 5000 200 600 Mn+ Radius (Å) 0.68 0.95 0.65 Polarization Strength (105 /pm-2 ) 21.6 11.1 47.3
  6. 6. 2. 2D materials for LIB and beyond 2.1 2D layered graphite as anode Figure 3. (a) Schematic drawing of the crystal structure of hexagonal graphite, showing the AB layer stacking sequence and the unit cell. (b) Constant current charge/discharge curves (1st and 2nd cycle) of the graphite. Adv. Mater. 1998, 10, No. 10 a b 𝐴𝐴 = 𝜋𝜋𝑟𝑟2
  7. 7. 2.2. 2D layered dichalcogenides Figure 4. (a) The two-dimensional crystal structures of TiS2, MoS2, and NbS2. (b) Discharge/charge curve of Li/TiS2 at 10 mA/cm2. (c) Electrochemical insertion of lithium into VSe2. Chemical Reviews, 2004, Vol. 104, No. 10 TiS2 Adv. Mater. 1998, 10, No. 10 a b c
  8. 8. Staging Effect S. M. Whittingha. Intercalation chemistry. Elsevier, 2012.
  9. 9. Staging Effect in TiS2 J. Electrochem. Soc. 127 (1980) 2097-2099Electrochim. Acta 50 (2005) 2927-2932 Na-TiS2 Figure 5. (a) Alkali metal intercalation compounds of TiS2. (b) Cell emf during primary discharge and first recharge.
  10. 10. 2.3. 2D layered AxMOy oxide materials LiCoO2: First successful commercialized LIB using LiCoO2 as cathode and carbon as anode, by SONY in 1990. It dominated the lithium battery Market for about 20 years. Sony Corporation, Battery Group, Solid State Ionics 69 (1994) 212-221
  11. 11. Figure 6 . Crystal structures of various NaxMOy : (a) P2-NaxCoO2, (b) O3- NaxCoO2, (c) P3-NaxCoO2.
  12. 12. Electrochemistry Communications 12 (2010) 355–358 NaCrO2 P2-Na2/3Co2/3Mn1/3O2 Dalton Trans., 2011, 40, 9306–9312
  13. 13. P2-Nax[Fe1/2Mn1/2]O2 O3-Nax[Fe1/2Mn1/2]O2 Figure 7. a,b, Galvanostatic charge/discharge (oxidation/reduction) curves for Na/NaFe1/2Mn1/2O2 (a) and Na-Na2/3TFe1/2Mn1/2O2 (b) cells at a rate of 12mAg-1 in the voltage range of 1.5 and 4.3V. (c) Comparison of the discharge capacity retention of the sodium cells. Nature Materials, 11, 512–517 (2012)
  14. 14. 2.4. Other 2D oxide electrode materials ACS Nano, 2012, 6 (1), pp 530–538 Bilayered V2O5
  15. 15. V2O5·nH2O for Na ion battery Figure 8. SIB performance of the V2O5·nH2O cathode. CV curves (a) and discharge–charge curves at current density of 0.1 A g1 (b). Cycling performance at the current density of 0.1 A g1 (c) and the rate performance (d). J. Mater. Chem. A, 2015,3, 8070-8075
  16. 16. J. Electrochem. Soc. 1993, 140, 140. V2O5 used in Mg ion battery V2O5 Shielding Effect Mo6S8 Mo6S8 is the most successful MIB cathode material, which has plateau and moderate capacity.
  17. 17. Graphene based hybrid electrode materials Adv. Mater. 2012, 24, 4097–4111 Figure 9. (a) Growth of self-Assembled (rutile and anatase TiO2 − FGS nanostructured hybrids stabilized by Anionic Sulfate Surfactant; (b) Specific capacity of control rutile TiO2 and the rutile TiO2 − FGS hybrids at different charge/discharge rates; (c) Specific capacity of control anatase TiO2 and the anatase TiO2 − FGS hybrids at different charge/discharge rates.
  18. 18. Table 2. Capacities and rate performance of high-capacity oxide/graphene hybrids. Adv. Mater. 2012, 24, 4097–4111
  19. 19. Challenges for NIB (Na Ion Battery) and MIB (Mg Ion Battery) Inorganic Chemistry, Vol. 46, No. 8, 2007 Na0.44MnO2 NIB: • Capacity decay due to large Na+ • Many phases transitions MIB: • Sluggish diffusion due to high polarization • Mg2+ passivation film on Mg anode • Very few suitable electrolytes 3. Novel electrode design for enhanced battery performance
  20. 20. Electrode Design for NIB and MIB Figure 10. With the increase of interlayer distance of MoS2, the interaction between cations and the negatively charged S atoms host weakens, and the spacing to afford larger Na+ and polarized Mg2+ is enlarged. So the intercalation and diffusion for both Na+ and Mg2+ will be facilitated.
  21. 21. 3.1 MoS2-PEO Nanocomposites 3.1.1 Materials Consideration MoS2  A layered transition-metal dichalcogenide.  MoS2 layers are held by van der Walls interactions. So guest molecules may have chance to get intercalated.  A range of MoS2−PEO intercalate composites have already been documented, allowing for a precise tuning of the interlayer distance. Pillar Molecule: Polyethylene oxide (PEO)  PEO is a solid-state Li+, Na+ and Mg2+ conductor.  PEO is flexible and water dissolved, so PEO can be intercalated into the host in aqueous solution.  MoS2-PEO and MoO3-PEO composites have been documented. MoS2
  22. 22. Figure 11. (a) Synthesis of interlayer expanded MoS2 composites. (a) (b,c,d,e) TEM images of com- MoS2, res-MoS2, peo1- MoS2, and peo2-MoS2, respectively. Yanliang Liang, Hyun Deog Yoo, Yifei Li and Yan Yao, Nano Lett. 2015, 15, 2194−2202
  23. 23. 3.3.2 Materials Characterization for MoS2 Figure 12. (a) XRD spectra and (b) TGA analysis of com-MoS2, restacked-exfoliated (re)-MoS2, PEO1L-MoS2 and PEO2L-MoS2. a b
  24. 24. 3.3. Mg-Ion Battery of MoS2 Figure 13. Performance of Li and Mg cells with the MoS2 samples as working electrode. (a) Discharge−charge profile of Li cells. (b) Discharge−charge profile of Mg cells with 0.25 M all-phenyl complex (APC) electrolyte and Mg metal as counter and reference electrodes. (c) Cycling stability at higher current densities. (d) Normalization and comparison of the capacity retention at different current densities.
  25. 25. Conclusions 1. Due to the high cost, difficult for large scale application and dendrite formation on Li anode, new candidates are needed to compete with Li ion battery. Na and Mg ion batteries thus have their potential application. 2. Two dimensional materials have been employed all the time with the development of LIB, from graphite, TiS2 to LiCoO2. 3. 2D layered materials are even more beneficial in NIB and MIB. 4. Interlayer distance expansion strategy is a novel way to address the issue of Na and Mg in 2D materials. MoS2- PEO composite is introduced as a model material.

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