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Biological Engineering
Electrochemistry & Virus-Templated Electrodes
F. John BurpoBiomolecular Materials Laboratory
Massachusetts Institute of Technology
November 30, 2010
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Biological Engineering
Electrochemistry Review
Lithium Rechargeable Batteries
Battery Testing
Outline
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Biological Engineering
1970: Design Choice
Blue Pill: Increase CPU transistor chip density x2,000,000
Red Pill: Increase rechargeable
battery capacity x4
Imagine
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Biological Engineering
Electrochemistry Basics
Cu Zn
e-e-
(-)ions(+)ions –+
Cu2+(aq) +2e- → Cu(s) +0.337 V Zn(s) → Zn2+(aq) +2e- +0.763 V
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) 1.100 V
I
Salt Bridge
I
Capacity = I∙time
V
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Biological Engineering
Standard reduction potentialsHalf reaction Eo, V
F2 (g) + 2H+ + e- 2HF (aq) 3.053Ce4+ + e- Ce3+ (in 1M HCl) 1.280O2 (g) + 4H+ + 4e- 2H2O (l) 1.229Ag+ + e- Ag (s) 0.799
Cu2+ + 2e- Cu(s) 0.3402H+ + 2e- H2 (g) 0.000Pb2+ + 2e- Pb (s) -0.125 Fe2+ + 2e- Fe (s) -0.440Zn2+ + 2e- Zn (s) -0.763Al3+ + 3e- Al (s) -1.676
Li+ + e- Li(s) -3.04
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Biological Engineering
Anode: Zn(s) Zn2+(aq) + 2e- Eo = +0.76 V
What is Eo for the Zn/Cu cell?
Eocell = Eo
cathode - Eoanode= 0.34 – (-0.76) = +1.10 V
Net: Cu2+(aq) + Zn(s) Zn2+(aq) + Cu(s)
Cathode: Cu2+(aq) + 2e- Cu(s) Eo = +0.34 V
Eocell = Eo
cathode ̶ Eoanode
Products ̶̶ ReactantsProduct gets electron
Reactant gives electron
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Biological Engineering
• For a reactant-favored reaction - Electrolytic cell: Electric current chemistry
Reactants Products
DGo > 0 and so Eo < 0 (Eo is negative)
• For a product-favored reaction – Galvanic cell: Chemistry electric current
Reactants Products
DGo < 0 and so Eo > 0 (Eo is positive)
Eo and DGo DGo = - n F Eo
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Biological Engineering
When not in the standard state (Nernst Equation)
DG = - nFE DGo = - nFEo DG = DG0 + 2.303 RT log Q
E = E0 - (RT/nF) ln Q aA + bB cC + dD
• At standard state temperature, Nernst equation
ba
dc
BADC
][][][][log
n 0.0592 - E E 0
Q is the reaction quotient, or the ratio of the activities of products to reactants
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Biological Engineering
= Li+
= LiPF6
Charged state
LiC6 (graphite anode)
Li2O/Coo (cobalt oxide anode)
Anod
e Cathode
FePO4 cathode
CoO2 cathode
e- e-
C (graphite anode)
Co3O4 (cobalt oxide anode)LiFePO4 cathode
LiCoO2 cathode
Discharged stateDischarging
Lithium Rechargeable BatteriesHow They Work
Courtesy Dr. Mark Allen
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Biological Engineering
Energy Density & Capacity
Tarascon, Nature 414, 359-367 (2001)
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Biological Engineering
Energy Density & Capacity
Tarascon, Nature 414, 359-367 (2001)
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Biological Engineering
Lithium plating and dendrites
Xu, K., Chemical Reviews, 2004 4303-4417Tarascon, J.M. & Armand, M., Nature, 414, (2001)
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Biological Engineering
Chemistries of electrodes
• Most common electrode system is that of LiCoO2 and graphite
charge2 1 2discharge xLiCoO Li CoO xLi xe
charge2 1 2 6discharge
6 x xLiCoO C Li CoO Li C
discharge6charge
6 xxLi xe C Li C
3.8-3.9 V vs. Li
0.1 V vs. Li
3.7 V total
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Biological Engineering
Battery Form Factors
Tarascon, Nature 414, 359-367 (2001)
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Biological Engineering
Ubiquitous device demand for energy storage. Need for flexible, conformable, and microbatteries. Micro Power Demand: MEMS devices, medical implants, remote sensors, smart cards, and energy harvesting devices.
Demand & Capacity
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Biological Engineering
Battery Design Parameters“Design Landscape”
Pressure
Li Dendritic Growth
Cycling Life
Separator permeability
Overpotential
Charge/Discharge Rates
Energy DensityPower Density
Electrode Potentials
Solid Electrolyte Interface
Electrolyte StabilityVolume Swelling
Capacity
Background Objectives Research Design Results
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Biological Engineering
Where to go next?
Background Objectives Research Design Results
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Biological Engineering
Specthrie, J Mol Biol. 228(3):720-4 (1992)
M. Russel, B. Blaber.
M13 Bacteriophage
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Biological Engineering
M13 Bacteriophage
Flynn, Acta Materialia 51, 5867-5880 (2003)(Marvin, J. Mol. Biol. 355, 294–309 (2006)
Background Objectives Research Design Results
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Biological Engineering
Evolving the Battery
Courtesy of Angela Belcher
Background Model Aims Experiments Future
Tarascon, Nature 414, 359-367 (2001)
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Biological Engineering
Bio-Battery ApplicationsUAS Systems
Soldier Load
Plug-in HybridLab on a Chip
Background Objectives Research Design Results
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Biological Engineering
Synthesizing Electrodes
Mix Nanowires with carbon and organic binder
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Biological Engineering
Au or Ag : capable of
alloying with Li up to
AgLi9 and Au4Li15 at very
negative potential
Taillades, 2002, Sold State Ionicshttp://www.asminternational.org/
Alloy forming anodes for Lithium ion batteries
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Biological Engineering
Pure Au viral nanowires
Plateaus: 0.2 and 0.1 V/discharge0.2 and 0.45V/charge
Capacity from 2nd cycle501 mAh/g [AuLi3.69]Diameter: ~40 nm, free surface
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Biological Engineering
Coin Cell Assembly
Lower Assembly
Upper Assembly
Lithium (s)
Steel Spacer
Copper Foil – Current CollectorElectrode
2 x Polymer Separators
PlasticO-Ring
ElectrolyteElectrolyte
Background Design Results Future
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Biological Engineering
Capacity Calculation
8 95484 sec 1 1000 11 3600sec 1 240.8
e X A hour mA moleX X Xmole Amp g
= 881 mAh/g
arg 03 4 2arg
8 8 4 3Disch e
Ch eLi Co O e Li O Co
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Biological Engineering
Calculating capacity for Gold Anodedischarge
charge xAu xLi AuLi Discharge
4 15Charge4Au+15Li 15 Au Lie
Determine the active mass, not everything in the electrode is redox active
2 0.7 0.8 1.12mg X X mg active material
Example: a 2 mg electrode with 20% inactive material (super P and PTFE binder)
1 445.97 11.12 0.4991000 1 1
g mAhmg X X X mAmg g hr
In order to discharge this electrode over one hour, apply -0.499 mA
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Biological Engineering
Battery Testing16 channels for testing batteries
8 coin cell
testers
Celltest program for measurement and
analysis
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Biological Engineering
Au0.9Ag0.1
Discharge/charge curves from the first two cycles
Au0.5Ag0.5
Au0.67Ag0.33
2nd cycle : 499mAh/g459mAh/g
Au0.9Ag0.1
Curve shape similar with AuCapacity at 2nd cycle : 439mAh/g
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Biological Engineering
The Ragone Plot
Gasoline energy density ~12 kWh/kg and nuclear fission yields ~ 25 billion Wh/kg
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Biological Engineering
So What Else Can the Virus Do?
gIII, gVIgVIIIgVII, gIX
Batteries Electrochromics Solar Cells
Fuel Cells Electronics MedicineCarbon Capture
H2O Splitting
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Biological Engineering
Questions ???
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Biological Engineering
Cathode Materials