Recent Advancements in Two-Dimensional Materials for Li-Air Battery

Pedram Abbasi

LAS 493-Fall 2017

Agenda

 Motivation of research on Li-air batteries

 How two dimensional materials can contribute?

 Carbon based materials

Graphene
Doped-graphene
reduced-Graphene oxide

 Carbon Free Materials

TMDCs
h-Bn
Transition metal oxides

 Conclusion and Remarks

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Current states of Li Batteries

 Production of Electric Drive Vehicle (EDV) batteries has been ~ doubling globally
every year since 2010.
 Economies of scale continue to push costs towards $200/kWh.
 New material chemistries and lower-cost manufacturing, cost parity with (Internal
Combustion Engines (ICEs)) should be reached in the next ten years.

Tesla’s battery pack in the floorpan of the Model S (Image: First Reporter)

Low Price High Energy density doi:10.1038/nmat3191

Advantages

 Very high energy density compared to the Li-Ion

 Cost Effective
 Environmentally friendly

Energy density comparison among different Metal-Air batteries

𝐷𝑖𝑠𝑐ℎ𝑎𝑟𝑔𝑖𝑛𝑔 𝑂𝑅𝑅 2𝐿𝑖 + + 2𝑒 − + 𝑂2 → 𝐿𝑖2 𝑂2 1

𝐶ℎ𝑎𝑟𝑔𝑖𝑛𝑔 (𝑂𝐸𝑅) 𝐿𝑖2 𝑂2 → 2𝐿𝑖 + + 2𝑒 − + 𝑂2 2
2D Materials in metal air battery applications:
“Two-dimensional (2D) materials are showing promise for many
energy-related applications and particularly for energy storage,
because of the efficient ion transport between the layers and the large
surface areas available for improved ion adsorption and faster surface
redox reactions.”

Five common 2D materials reported for charge storage application. Different synthetic approaches for the preparation of 2D materials.

 High Surface to volume ratio  Scalable synthesis methods

 Tunable electronic property  Cheap and cost effective

DOI: 10.1039/c6cc05357b DOI: 10.1039/c6cc05357b

Evolution of Carbon based 2D materials for Metal-Air batteries:

a b Figure1. (a) A schematic

representation of the Li/02 plastic
battery(b)The cycling data for a
li/PAN-based polymer electrolyte/
oxygen cell at room temperature in an
atmosphere of oxygen.
The cathode contained 20 w/o
catalyzed Chevron carbon
black and 80 w/o polymer electrolyte.
The cell was discharged at
Kuzhikalail M. 0.1 mA/cm2 and charged at 0.05
Abraham mA/cm2
10.1149/1.1836378

Figure2. a) Schematic illustration of a rechargeable Li-air cell based on a GNSs electrode. b) Discharge profiles
of the 20 wt% Pt/CB, GNS, and acetylene black electrodes at a current density of 0.5 mA cm-2 for 24 hours,
respectively. c) Correlation between cycle numbers and capacity of Li-air cells based on GNS electrodes.
Reproduced with permission.
10.1021/nn200084u
Carbon based doped materials for Li-Air Batteries Nitrogen Doped Graphene

Introducing dopant into the

structure of graphene to tune the
electronic property and morphology
Sulfur Doped Graphene

Figure4. a) Scheme of the formation for nitrogen-doped graphene sheets

Figure3. a images of (a) sulfur-doped and (b) pristine graphene discharged electrodes and the
discharge/charge curves for (c) sulfur-doped and (d) pristine graphene.
derived from polyaniline and Co precursors using MWNTs as templates. (b
and c) HR-TEM images of the graphene-rich nanocomposites observed in
Co–N–MWNT catalysts. (d) RDE testing results for the ORR at 25 1C in
oxygen-saturated 0.1 M LiPF6 in 1,2-dimethoxyethane (e) Initial discharge
performance for various catalysts at a current density of 50 mA/gcat
1 in Li– O2 battery tests

10.1039/C2JM34718K 10.1021/nn303275d
r-GO with LiI for high cycle life lithium air Reduced Graphene Oxide

Introducing dopant into

the structure of graphene
to tune the electronic
property and morphology

Figure5. a) SEM image of pristine rG-O electrodes used in the Li-O 2 battery. b) Discharge/charge curves for Li-O
2 battery using mesoporous SP and TiC, and macroporous rG-O electrodes, with capacities limited to 500 mAh g
−1 . Discharge/charge curves for Li-O 2 batteries using rG-O electrodes with capacity limits of: c) 1000 mAh g c −1
, d) 5000 mAh g c −1 , and e) 8000 mAh g c −1 , and f) as a function of rate. DOI: 10.1126/science.aac7730.

10.1126/science.aac7730
Ir-rGO for lithium superoxide battery
Iridium- Reduced Graphene oxide

This unique battery can cycle the Li-

oxygen system through a one-
electron process. This process can
significantly increase the energy
efficiency of the system by forming
lithium super oxide instead of
lithium per oxide.

Figure 6. Electrochemical tests and discharge products. a, Voltage profiles of the Ir–
rGO cathode. Inset shows capacity as a function of cycle number. b, Voltage profiles
of the rGO cathode. Inset shows capacity as a function of cycle number. c, Main
panel, SEM image of discharge product on Ir–rGO (scale bar, 1 µm d, DEMS profile
showing O2, H2 and CO2 gases released (n′ is the number of moles per second) from
the cell during the charging

doi:10.1038/nature16484
Carbon-Free Materials - TMDCs

 Layered materials with strong in-plane bonding and weak

out-of-plane interactions.
 One transition-metal atom for every two chalcogen atoms.
 For example; MoS2, TaTe2, WSe2, NbSe2, VS2.

DOI:10.1038/nnano.2012.193
Carbon-Free Materials - TMDCs

The cell with MoS2/AuNP nanohybrids exhibits discharge

and charge overpotentials of 0.21 and 1.28 V, respectively,
which resulted in the highest round-trip efficiency and a
specific capacity of about 4336 mA.h.g-1.
A synergistic catalytic effect between MoS2 and gold
nanoparticles (AuNPs) has been achieved for a highly
efficient ORR.
Figure7.(a) discharge/charge profiles of the Li–O2 battery with the pristine Super P, MoS2
nanoflowers, and MoS2/AuNP nanohybrids at a current density of 70 mA.g-1. (b) The first
discharge/charge profiles of the Li–O2 battery with Super P, MoS2 nanoflowers, and MoS2/AuNP
nanohybrids at current densities of 200 and 500 mA.g-1. (c) Curtailing capacity at a current density of
300 mA.g-1. (d) Terminal discharge voltage.

Zhang, Panpan, et al. "MoS2 nanosheets decorated with gold nanoparticles for
rechargeable Li–O2 batteries." Journal of Materials Chemistry A 3.28 (2015).
 in Lithium-Air Battery
Carbon-Free Materials – TMDCs

(c)
(d)

Figure 8.
(a) SEM images of MoS2 NFs deposited on the gas diffusion layer.
(b) (b) Dynamic light scattering and Raman spectroscopy of MoS2 NFs.
(c) Charging and discharging voltage profiles of a battery using
(e) (f) carbon-free MoS2 NFs and an ionic liquid electrolyte saturated with
0.1M LiTFSI as a Li salt. (d) Differential electrochemical mass
spectroscopy (DEMS) profiles of the cell after the 1st, 20th, and
50th cycles.

(e) An optical image of a crytalline structure of MoS2 grown by chemical vapor transport method.
(f) Synthesized TMDC NFs after 20 hours of sonication and 1 hour of centrifugation at 2000 rpm. Asadi, Mohammad, et al. "Cathode Based on Molybdenum Disulfide
Nanoflakes for Lithium–Oxygen Batteries." ACS nano 10.2 (2016).
Carbon-Free Materials - h–BN

 From the family of “Boron Nitrates”.

 Layered structure which boron and nitrogen atoms are
bound by strong covalent bonds and layers are bound
by weak van der Waals forces.
 Wide bandgap semiconductor.
 Very high thermal and chemical stability.
 High thermal conductivity.
 Called as “White Graphene”.

DOI:10.1038/nphoton.2015.277
Carbon-Free Materials - h–BN Hexagonal boron nitride as SEI Layer in Lithium-Air Battery

The problems of dendritic and mossy Li formation

and its highly reactive nature cause poor safety and
low cycling efficiency during charge and discharge.

Morphology studies of Li metal deposition.

Used the method of chemical vapor deposition

(CVD): Copper foil was heated up to 1000°C in Ar
and H2 at low pressure followed by ammonia
borane (NH3−BH3) vapor.

stable cycling over 50 cycles

with Coulombic efficiency ∼97%. Figure9. Cycling performance of Li metal anode with and
Schematic diagrams of lithium deposition.
without h-BN protection at various current rates.

Yan, Kai, et al. "Ultrathin two-dimensional atomic crystals as stable interfacial layer for improvement of lithium metal anode." Nano letters 14.10 (2014): 6016-6022.
Transition metal oxides:

RuO2 based catalyst

Figure10. SEM images of pre-prepared layered precursor (a-b) and

as-prepared RuO2 nanosheets; and (c) their corresponding XRD
patterns (d).HRTEM image of the asprepared RuO2 nanosheet. The
left inset shows the corresponding TEM image, and the right inset is
a photo of the as-prepared RuO2 sample suspended by a thin hair. Figure11. Electrochemical impedance spectra of the Li-O2 cell with RuO2 nanosheet cathode at different states.

DOI: 10.1039/C5EE01451D
Conclusion

 Carbon based two dimensional materials such as graphene and reduced graphene oxides
have been widely utilized as air cathode and catalyst for Li-air batteries, there are still lot of
room for discoveries in this field.

 Other two dimensional families such as TMDCs or TMOs have shown promising
performance to be used as the air cathode and also SEI layer for anode protection

 More in-depth modeling and predictive tools are needed to be able to find the right two-
dimensional structures that can address not only the cathode interphase issues but also
electrolyte and anode limitations as well.

 Practical implementation of Li-air as an alternative for current Li-ion systems requires some
techno economical assessments such as designing the battery pack, power densities at
different charge-discharge rates etc. that are as important as catalysis development.