Graphene and Graphene-like Composites for anode materials

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Graphene and Graphene-like Composites for anode
materials in Li-ion battery Applications
Proposal Presentation PHYS-570X
Presented by Suprem R. Das
Department of Physcs, and Birck Nanotechnology
CenterPurdue UniversityWest Lafayette, IN
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Graphene and Graphene-like Composites for anode
materials in Li-ion battery Applications Seed
research proposal submitted by Suprem Ranjan
Das The Birck Nanotechnology Center and
Department of Physics, Purdue University, West
Lafayette, IN Single layer graphene and few
layer graphene, are recently shown to have
numerous scientific and technological
break-throughs having novel nanodevice
applications, the most important ones being
potential candidate for electronics and sensor
applications. However, in order to drive these
complex and tiny devices and circuits one needs
the compatible power supply systems that must fit
into the same circuits. Due to its very high
electronic conductivity, this material could be
thought of as fabricating the anode electrode in
the Li-ion battery. In this proposal, we discuss
the various approaches to make different types of
graphene powders (both elemental and composite)
and later use these materials to fabricate the
anode for Li-ion battery. Prior to using it
inside an electrochemical cell, various
structural techniques such as IR spectroscopy,
X-ray photoelectron spectroscopy and Raman
spectroscopy could be used to identify the
correct phase of the material. A prototype device
using LiMn1.5Ni0.5O4 cathode and both liquid
electrolyte (ECDMCLiPF6) and poly ethylene
oxide (PEO) solid electrolyte is discussed .
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Trends in battery technologies
Li-ion batteries are the key source of power
supply for wide applications High energy
density, design flexibility, and safest in
use However, technological advancement is not
as aggressive as semiconductor industry because
of the complexity in the device
Ref Tarascon et al., Nature 414, 359, 2001
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Charging and Discharging a Li-Ion battery
Current Li-Ion batteries use both cathode and
anode as intercalated compounds High energy
density nature of a cell is a function of cell
potential (V) and capacity (Ah/kg), both of which
related to material chemistry
lt DFT calculations
Ref1 Tarascon et al., Electrochimica Acta 38,
1221, 1993
Ref2 Kganyago et al., Phys. Rev. B 68, 205111,
2003
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Materials of Choice
However, current carbon/graphite anodes show high
surface area Li-plating when fast recharged
Ref Tarascon et al., Nature 414, 359, 2001
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Motivation for the graphene-based anode

• The reactivity of graphene sheet with Li-ion will
  be different along the plane and also along the
  edges (zig-zag and armchair)
• In graphene based anodes, the Li-ions will be
  adsorbed on the two sides of the sheet and along
  the edges, there by increasing the capacity of
  the anode
• Since the graphene powders are truly disordered,
  so the sheets are randomly oriented making it
  isotropic in all directions. Thus the storage of
  the Li-ion will be isotropic, again enhancing the
  capacity of the anode.
• The disordered nature of the graphene based anode
  will overcome any kinds of pulverization
  effects that is faced by recent high density
  intermatallic anodes, thereby expected to show
  improved rate capabilities
• Reactivity of Li-ion towards graphene oxides or
  graphene-metal composite sheets may be higher
  than towards pure graphene, if so, it can produce
  even more high capacity and high rate capable
  Li-ion batteries

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My Proposal

• To produce high quality graphene-anodes (both
  pure and composites with metals, e.g. Sn)
• Use recently reported high energy LiMn1.5Ni0.5O4
  spinel cathodes and layered LiMn0.5Ni0.5O2
  cathodes
• Fabricate prototype cells using both liquid
  electrolyte (ECDMC with LiPF6 (11)) and PEO
  based solid electrolyte
• 4. Study the charge-discharge behavior of the
  Li-ion in these cells

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High quality graphene and graphene composite
powders
Exfoliation-reintercalation-expansion of graphite
Reducing GO using hydrazine
Dai et al, Stanford
H.Dai et al., Nature Nanotechnology 3, 538, 2008
V. C. Tung et al., Nature Nanotechnology 4, 25,
2009
Electrochemical modification of graphene to
synthesize Graphene-metal (Sn) composite
Solvothermal synthesis and sonification
M. Choucair et al., Nature Nanotechnology 4, 30,
2009
R.S. Sundaram et al., Adv. Mater. 20, 3050, 2008
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Characterization of graphene-based materials
H.Dai et al., Nature Nanotechnology 3, 538, 2008
A.C.Ferrari et al., PRL 97,187401, 2006
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Anode fabrication
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Cell fabrication
Thin film Lithium battery schematic
Coin cell design
HS Test Cell
HS-3E Test Cell
Hand-operated crimping tool for coin cells
http//www.hohsen.co.jp/
(1) J. R. Dahn et al, Electrochimica Acta 38,
1179, 1993 (2) N. J. Dudney et al, Current
Opinion in Solid State and Materials Science 4,
479, 1999
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Other instumentations

1. Battery tester with software and PC
2. Glove box with inert atmosphere facility
3. Vacuum oven
4. Mixer

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Cathode material to be used for cell fabrication
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Polymer electrolyte to be used
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Expected results

• Higher specific capacity for Li-ion batteries
  using graphene based anodes
• Higher rate capabilities
• High capacity retention after repeated cycling
  (over hundred cycles)
• Safe in using in wide variety of applications

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CONCLUSIONS

• Though Carbon is the material of choice for
  anodes in Li-ion batteries for almost last two
  decades, still it has many problems
• Graphene and graphene-based metal composites may
  overcome these obstacles
• Graphene based anodes, being entirely disordered
  in nature and isotropic, is expected to produce
  high energy anodes
• Due to zigzag and armchair configurations and
  exposures of both sides of graphene sheets to
  Li-ion environment, its adsorption of the same
  can be lot higher than the usual carbon or
  graphitic anodes

Acknowledgements I Acknowledge Prof Y. P. Chen
and all the colleagues participating in Carbon
Nanophysics course