silicon based nano-scoops for high-power lithium-ion ... · rahul mukherjee (graduate student)...
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Silicon based Nano-Scoops for High-Power Lithium-Ion Battery Anodes
Si
Al
C
10%
94%280%
C
AlSi
Before Lithiation
After Lithiation
10%
94%280%
C
AlSi
10%
94%280%
10%
94%280%
C
AlSi
Before Lithiation
After Lithiation
Rahul Mukherjee(Graduate Student)
Department of Mechanical,Aerospace and Nuclear Engineering
Rensselaer Polytechnic Institute110 8th Street, Troy,
New York, USA.
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Research Objective• Need for a power source
that can provide high power density and high energy density
• Research aim: To design electrode nano-architectures that can retain mechanical integrity over hunderds of cycles while providing a high capacity even when cycled at very high C-rates (> 20C)
Source: M. Winter, R. J. Brodd, Chem. Rev. 2004, 104, 4245.
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Li-ion Cell Structure
Cathode: It is the source of Lithium.Ex: LiCoO2, LiFePO4
Anode: It is a host material for insertion of Li+.Ex: Graphite, porous carbon
Electrolyte: It offers a medium for the transport of Li+.Ex: solution of lithium-salt electrolytes, such as LiPF6, LiBF4, or LiClO4, in an organic solvent such as alkene carbonates
Source: R. Teki, M. K. Datta, R. Krishnan, T. C. Parker, T. –M. Lu, P. N. Kumta, N. Koratkar, Small, 2009, 5, 2236.
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Is there room for improvement ?• Charge / discharge capacity: It is a measure of the total charge per unit
weight stored or recovered from the electrode material. The standard units for specific capacity are (mAh/g). The specific capacity is also a measure of the “Energy Density” of the battery.
• C-rate: A rate of nC corresponds to a full discharge in 1/n hours. This parameter monitors rate of charge/discharge as well as magnitude of current. It captures the “Power Density” of the battery.
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Alternative Anode Materials: Quest for Higher Energy Density !
Alloy Capacity (mAh/g) Volumetric change (%)
Li22Si5 4200 400
Li3As 840 201
Li3Sb 564 147
LiAl 993 94
LiC6 372 10
Silicon has been proposed as the anode instead of carbon.Higher the Li capacity, larger the accompanying volumetric change
Source: A. Patil, V. Patil, D. Shin, J. Choi, D. Paik, S-J. Yoon, Mater. Res. Bull. 2008, 43, 1913.
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Prior Art: Silicon Films as AnodeAdvantage: High theoretical charge capacity of 4200 mAh/g (10 times larger than carbon) Disadvantage: 400 % volume expansion leading to pulverization and delamination of the electrode films.
(a) Specific capacity plotted as a function of cycle number. (b) Stress-induced cracking of the film after a few cycles. (c) Delamination and peeling of the film from the collector electrode after extended cycling [2]
Source: J. P. Maranchi, A. F. Hepps, A. G. Evans, N. T. Nuhfer, P. N. Kumta, J. Electrochem. Soc. 2006, 153, A1246.
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Nano-Silicon Reports
(a) Scanning electron micrographs of the porous Si particles indicating a pore wall size of ~40 nm. (b) Capacity vs. cycle number.
Source: H. Kim, B. Han, J. Choo, J. Cho, Angew. Chem. 2008, 47, 10151.
(a) Concept schematic of Si nanowire electrode (b) Scanning electron micrograph of Si nanowires that comprise the device anode. (c) Capacity vs. cycle number. Source: C. K. Chan, H. Peng, G. Lin, K. McIlwrath, X. F. Zhang, R. A. Huggins, Y. Cui, Nat. Nanotechnol. 2008, 3, 31.
0.05C
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Our Concept: Strain graded carbon-aluminum-silicon nano-scoop anode architecture
• C nanorods – oblique angle flux (85° from normal)
• Al and Si scoops – normal flux incidence
• Tested at 40C (51.2 A/g), 60C (76.8 A/g), 100C (128 A/g)
10%
94%280%
C
AlSi
Before Lithiation
After Lithiation
10%
94%280%
C
AlSi
10%
94%280%
10%
94%280%
C
AlSi
Before Lithiation
After Lithiation
200 nm
Si
Al
C100 nm
Si wafer 200 nm
Si
Al
C100 nm
Si wafer 200 nm
Si
Al
C100 nm
200 nm200 nm
Si
Al
C100 nm
Si wafer
Coin cell testing
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C-Al-Si Nanorods: Oblique Angle Deposition (OAD) C-Al-Si Nanorods: Oblique Angle Deposition (OAD)
+Ar
Sputter target (Pt)
Pt atoms
Substrate
Oblique angle θ
will reach the target point
Obliquely incident particles
hθ
will be captured by the tall
surface feature
Incident atoms preferentially land on taller islands due to the shadowing effect:physical self-assembly!
will reach the target point
Obliquely incident particles
hθ
will be captured by the tall
surface feature
Incident atoms preferentially land on taller islands due to the shadowing effect:physical self-assembly!
Growth mechanism:
+Ar
Sputter target (Pt)
Pt atoms
Substrate
Oblique angle θ
+Ar
Sputter target (Pt)
Pt atoms
Substrate
Oblique angle θ
will reach the target point
Obliquely incident particles
hθ
will be captured by the tall
surface feature
Incident atoms preferentially land on taller islands due to the shadowing effect:physical self-assembly!
will reach the target point
Obliquely incident particles
hθ
will be captured by the tall
surface feature
Incident atoms preferentially land on taller islands due to the shadowing effect:physical self-assembly!
Growth mechanism:
Sputter Target (C, Al, Si)
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Results: Specific Capacity vs. Cycle Index
C-rate: 40C
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Evidence of Li Insertion into C-Al-Si Anode Unlithiated
Lithiated: 1C
Lithiated: 40C
Direct Physical Evidence ofLi+ insertion intoThe Si Scoops
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Effect of Strain Gradation
CAlSiSi
Cr Vs.(0%)
(280%)
(10%)
(94%)(280%)
CAlSiSi
C Vs.
(280%)
(10%)(10%)
(94%)(280%)
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Results: Ragone Plot
Advantages:
Energy density of 100 Wh/kg at C-rate of 40C
Power density as high as 250 kW/kg
Stability in performance
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Journal Publication: Nano Letters
5th Highest Downloaded Paper on Nano Letters Web-site in Jan/Feb 2011
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Current Work : Mass Scalable Geometry
ISSUES
POOR DIFFUSIVITY OF LITHIUM IN MICRON-
LONG SILICON SPRINGS
POOR CONDUCTIVITY OF SILICON SPRINGS
HINDERING ELECTRON TRANSFER
Research Objective :Mass Scalable Silicon geometry for Li-ion batteries
Approach :Deposition of micron long Silicon springs
(a) (b)
(a) Cross-Section SEM Image of Silicon arm-based spiral. (b) Cross-Section SEM image of Si-Al helical spiral
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