Green Sustainable Sugar - Air Batteries (SAB - Sweet Power)

IBA
2013 – 15 March 2013 – Barcelona

© 2013 University of Hawaii
Green Sustainable Sugar-‐Air

Batteries (SAB––Sweet Power)
Bor Yann Liaw

Hawaii Natural Energy Ins6tute, SOEST
University of Hawaii at Manoa
Honolulu, HI 96822
bliaw@hawaii.edu
World Energy Outlook
Driving Force Demand
OECD: Organization for Economic Co-‐operation and Development

Emerging power houses for non-‐OECD: China, India, Brazil… Credit: BP Energy Outlook 2030, January 2013
World Energy Outlook
Demand Resource
toe = tonne of oil equiv. ~ 42 GJ Credit: BP Energy Outlook 2030, January 2013
Energy Resources
n  Primary resources –––

l  Originated from Solar
l  Wind
l  Ocean
l  Hydro
l  Biomass
l  …
l  Indigenous on Earth
l  Fossil
l  Geothermal
l  Nuclear
n  Availability and u6liza6on are constrained by abundance and

loca6on of the source, maturity of the technology, costs of
harnessing (produc6on, distribu6on, and storage), etc.
Take-‐home messages
n  Renewable resources is a major sector of growth for

power genera6on, but not a major player.
n  Problems with fossil fuels are not resources, but
environmental acceptability.
n  Asia Pacific devours deple6ng fossil resources –– We all
need sustainable solu6ons.
n  Conserva6on and efficiency both ma\er.
Energy and Power Sources
n  Need both, but also need to recognize the difference
n  De-‐couple the two might op6mize the overall system efficiency ––
Toyota Prius is an excellent example
n  Energy sources –– Primary è Conversion efficiency, storage capacity,
distribu6on …
l  Primary ba\eries / Fuel cells / Flow ba\eries
l  Fuel –– Engines
l  Solar –– PV or ST / wind / hydro / ocean
l  Geothermal
l  Nuclear
n  Power sources –– Secondary (rechargeable) è Round-‐trip efficiency,

rate capability, peak power …
l  Secondary ba\eries / Rechargeable flow ba\eries
l  Flywheels
l  Ultracapacitors / supercapacitors
l  Pump hydro / heat pumps / CAES
“Energy-‐to-‐Power” – Today’s Op6ons
Power Source kW/kg kWh/kg Example Use
DOE/NASA/0032-28 Mod 2 502 0.30 1.78* Chevrolet Celebrity

cc gas (petrol) Stirling engine 1985
Mazda 13B-MSP Renesis 1.3 L 1.5 Mazda RX-8
Wankel engine
Toyota Brushless AC NdFeB PM 1.37 2.85** Toyota Prius 2004
motor
Energizer 675 Mercury Free 0.00165 0.457 Hearing aids
Zinc-air battery @ 2.24 mA to 0.9 V
A123 Systems 26650 Cell 2.3Ah 3.3 0.108
LiFePO4 Lithium ion battery @ 27C @27C to 2V
Sion Power 2.5Ah Li-S battery 0.672 0.336
@ 2C
Gasoline 12.3
* 12 kWh cruise for 60 miles, 25 mpg

** 40 mpg
S6cky issues
n  Effec6ve primary “energy-‐to-‐power” sources ––

l  Engines –
l  Amazing efficiency & infrastructure support, s6ll going
l  But, where is the “low cost” fuels?
l  PV / ST / wind / … –
l  Cheap ‘fuels’
l  Efficiency? Costs? But, loca6on, loca6on, loca6on … storage,
distribu6on, etc. –– need significant infrastructure upgrade
l  Fuel cells – the same ques6on …
l  Nuclear – $$&??#*^
The outlook is quite grim!!!
Interes6ng proposi6on
n  Electrochemical devices are the most efficient energy

conversion and storage systems – not constrained by Carnot
Cycle efficiency
n  Carbohydrates are the fuels of choice in biological systems

n  Is it possible to improvise a ba\ery using widely accessible,
indigenous materials for power genera6on?
l  If so, the ba\ery must be low cost and widely accessible –– a
solu6on to overcome scarcity of resources
n  How much power can we get?
l  Enable simple architecture and high efficiency
Bio-‐fuels shall have opportuni6es
n  Carbon neutral è renewable

n  High volume to drive costs down, ease to handle
(produc6on, distribu6on & storage) è liquids or solids
n  Three universal candidates:
l  Alcohols — costly, low efficiency
l  Urea — cheap, but low energy
l  Carbohydrates ???
A few examples . . .
Microbial Fuel Cells
P: 0.2–0.3 mW/cm2
Logan & Rabaey, Science 337 (2012) 686 Rabaey & Verstraete, Trends in Biotech. 23 (2005) 291
Enzyma6c Bio-‐fuel Cells
fundamentals
Utilization of
Complex Biofuels
Bioengineering of
Enzyme Electrocatalysts
engineering
Electron Transfer Immobilization and
Fundamentals Surface Architectures
applications
P. Atanassov et al. “Fundamentals and bioengineering of enzymaPc fuel cell” AFOSR program review, 2007.
Electrode Design and Engineering
Micro-scale Control
●  Deposition Rate
●  Monomer
Concentration Microstructure
●  Porosity, Pore Size &
Distribution, Surface Area
●  Techniques ●  Morphology
●  Concentration & ●  Thickness
Ratio
Performance
●  Charge Transfer
Immobilization
Efficiency
●  Loading Efficiency
●  Limiting Mechanism
●  Loading Density
●  Current Density
●  Power Density
Nano-scale Control Macro-scale Control

Bio-‐implantable Design
Mano & Heller

2003
Sony’s Sugar Ba\ery
Pushing Power Limit
Sony Sugar Bio-‐ba\ery
Sakai et al. EES 2 (2009) 113

Inspira6ons of Green Tech
Sugar is a naturally occurring energy

source produced by plants through
photosynthesis. It is therefore
regenerative, and can be found in
most areas of the earth, underlining
the potential for sugar-‐based bio
batteries as an ecologically-‐friendly
energy device of the future.
– Nokia promotes
green phone
with similar
concept!
1.45 ±0.24 mW/cm2 @ 0.3 V
Complicated and delicate ! http://www.daizizheng.com/projects.htm

Abio6c Sugar–Air Fuel Cell / Ba\ery
ScoS & Liaw, Energy Environ. Sci. 2 (2009) 965
No GO catalyst
No membrane
RT quiescent mode
Game-‐Changing Technology
No GO catalyst
No membrane
Open to air
H2O OH¯ˉ
Wide temp range
Low Cost
Catalyst
n  Flexible configuration

n  Flexible geometry (soft packaging)
n  Flexible fuels
n  Low cost materials
n  Reliable
Glucose: 2.5 mW/cm2 @0.3 V
n  Easy to set up Fructose: 3.8 mW/cm2 @0.25 V
Abio6c Glucose-‐Air Ba\ery
n  Carbon felt anode & air-breathing cathode for O2

reduction
2 e− In the solution:

β-‐D-‐glucose + 2 MV2+ + 2 OH¯ˉ
− +
→ δ-‐gluconolactone + 2 H2O
Reducing + 2 MV•+
Oxidized sugar
dye OH−
On the anode:
MV•+ ↔ MV2+ + e¯ˉ

On the cathode:
O2 O2 + 2 H2O + 4 e¯ˉ → 4 OH¯ˉ
Reduced H2O
dye Oxidation
product Cell:
Carbon MnO2
felt catalyzed 2 β-‐D-‐glucose + O2 →
current air
collector electrode 2 δ-‐gluconolactone + 2 H2O
Cell Performance
n  3 M KOH, 2 M glucose, and 28 mM methyl viologen (MV)

n  Max. power of 2.5 mW/cm2 (~ 8.5 mA/cm2 @ 0.3 V)
700 3
Power Density (mW/cm2 ) .

600 2.5
Cell Voltage (mV) .
500
2
400
1.5
300
1
200
100 0.5
0 0
0 2 4 6 8 10
Current Density, i (mA/cm2 )
Addi6onal Performance Merits
n  Glucose is the fuel

n  Long durability
n  Easy to stack
n  Insensitive to impurity
n  Work on a variety of
reducing sugars & dyes
0.6 10 mM Aliquots of glucose

0.5
0.4
I (mA) .
0.3
0.2
0.1
0
0 2000 4000 6000 8000
Time (sec)
Reac6on Mechanism
D-‐Gluconic acid δ-‐lactone
OH− OH−
Ene-‐diol
H2O
MV2+ MV•+
D-‐Glucose Gluconic acid
Carbon felt anode

[KOH] Dependence
Scan rate: 10mV/s

With [OH] é
▶  Dimer side reactions involvement ê
▶  Reversibility in kinetics é
What Glucose Contributes?
Scan rate: 10mV/s ▶  Dimer formation suppressed

in reduction
▶  Dimer actively involved in
charge transfer in oxidation
Polariza6on and Limi6ng Mechanism
n  Peak power density and short-‐circuit current is limited by the
mediator transport in the solu6on
n  Mediator does not catalyze GO, but perturb equilibrium
700 Conc ratio in 3

Glucose:MV:KOH
600
Power Density (mW/cm2 )

2.5
Cell Voltage (mV).
500
2
400
0.5:0.028:3
1.5
300
1
200
2:0.005:3
2:0.01:3
1:0.028:3
2:0.028:3
100 0.5
0 0
0 2 4 6 8 10
Role of KOH
n  KOH concentra6on affects solubility, electrolyte conduc6vity,

oxida6on kine6cs and mass transport; thus, max power point
and peak power density
700 3 M KOH 3
1 M KOH
600
Power Density (mW/cm2 )

0.5 M KOH 2.5
Cell Voltage (mV).
500
2
400
1.5
300
1
200
100 0.5
0 0
0 2 4 6 8 10
Mass Transport Issue
n  Mechanical s6rring improves mass transport; thus, increases

peak power density and short-‐circuit current
Voltage, unstirred cell
700 Voltage, stirred cell
Power, unstirred cell 600
600 Power, stirred cell
Power Density (µW/cm 2)

Cell Voltage (mV) .
500
400
400
300
200 200
100
0 0
0 0.5 1 1.5 2 2.5
Current Density (mA/cm2)

Peculiarity with Mass Transport Limi6ng
n  Although mass transport is limi6ng the power genera6on, the
insensi6vity of power profile with dye concentra6on indicates
that this phenomenon is peculiar to understand
Power Density (µW cm-2)

Current Density (mA cm-2) !
Dye–C Electrode Interac6ons
In situ Spectroscopic Imaging Ellipsometry + QCM + CV/EIS

Forward scan
0.002 1 mV/s
0.000
I/mA
-‐0.002
-‐0.004
-‐1.4 -‐1.2 -‐1.0 -‐0.8 -‐0.6

E/V vs. S CE
-‐0.4 -‐0.2 0.0
Crystals appear
-‐0.3 V -‐0.6 V -‐1.04 V -‐1.10 V -‐1.20 V -‐1.30 V
Reversed scan
All crystals
disappear
-‐1.00 V -‐0.94 V -‐0.84 V -‐0.80 V -‐0.72 V -‐0.60 V

Background becomes darker, crystals start to dissolve
Transient IE+QCM+CV
n  In situ & operando

characteriza6ons
Svoboda & Liaw, Pure Applied Chem. 80 (2008) 2439

Modeling of Poly-‐MG Deposition
! © 2013 University of Hawaii
!" #$
!" #% &
!" #&
!" # +
'
,- . . /01 2 3 45 3 6
$
# reduction
!
)
$ !" #
!" # $
!
% oxidation
(!
!"# !"$ !"% %"& %"' %"# %"$ %"% (%"$ (%"# (%"'
7 8 9:-2 ;/<. "/= 2 4= 2 > 9/07 6
3
4
Measured @ -0.5V:
Measured @ 1.2V: D=127.991 Y =34.2896
D=123.7806 Y =32.9262
Simulated:
Simulated: D=127.9940 Y =34.2894
D=123.8002 Y =32.7326 d=300.16 nm
d=154.33 nm
MG solution n=1.3342 k=0.0010

MG solution n=1.3342 k=0.0010
adsorbed MG: d2= 300.16 nm

n= 1.3050 k= 0.0266
adsorbed MG:
d2= 154.33 nm
n= 1.3186 k= 0.0269
polyMG: n= 1.2422 k= 0.1464 d1= 31.87 nm
polyMG: n= 1.2422 k= 0.1464 d1= 32.74 nm
Pt: n= 1.517 k= 2.898
Pt: n= 1.517 k= 2.898
Broader Perspec6ve
n  Sugar is renewable

n  Cellulose/semi-cellulose could be a useful energy
source; cheap
n  C-neutral –– we need balance between human activities
and the environment; sustainability
Specific merits –––

n  5.5 M: 200 Wh/kg; 200–400 Wh/L
l  Comparable to LIB: 100–160 Wh/kg; 250–360 Wh/L
n  Technologically viable ––
l  Unique way to harness energy efficiently;
l  Simplicity in mechanics making it cost effective
Poten6al Applica6ons
n  Portable/mobile power — cell phones, iPods, Bluetooth

devices, media storage devices with BT, (devices that
run on batteries), underwater vehicles…
l  Need cost-effective, convenient, reliable charging
infrastructure & support (i.e., primary energy source)
n  Emergency power — disaster relief, energy security…
l  Need readily available, easy-to-transport, reliable, high-
energy-content power source
n  Safe power — for hazardous areas (e.g., mining facility,
explosive storage…), space/underwater applications,
biomedical applications….
n  Green power — renewable & sustainable
l  Need sustainable, indigenous, easy-to-store, reliable
energy source
Poten6al to an Untapped Market
The Bo\om Line –– Essence of Significance
& Broad Impact
n  Costs of electricity:

California levelized energy costs for different generation
technologies in US dollars per megawatt hour (2007)

Technology Cost (USD/MWh)
Advanced Nuclear 67
Coal 74–88
Gas 87–346
Geothermal 67
Hydro power 48–86
Wind power 60
Solar 116–312
Biomass 47–117
Fuel Cell 86–111
Wave Power 611

SAB 250-‐550
Conclusions
n  A novel sugar–air battery without oxidation catalyst or

membrane
l  High concentration of reducing sugars
l  Wide temperature range
l  High alkaline concentration ► better conductivity ► higher
(highest) power
l  Flexible cell configuration
n  Best performance among all glucose-oxygen fuel cells /
batteries
n  Work with many reducing sugars & inexpensive dyes
n  Long durability of operation
n  Mediator acts like a shuttle medium not a catalyst
n  Immobilization and stabilization of mediator is a key
issue
Acknowledgements
n  D.M. Scott & Ellipsometer (Accurion/Nanofilm) —–

Intelligence Community Postdoctoral Fellow Research
Program (Nano- and Micro- Enzymatic Power Sources,
HM1582-04-1-2013)
n  S. Li, N. Zhao, V. Svoboda, R. Eustis, D. Sun, W.
Johnston, C.C. Chiu —– Hawaii Energy & Environmental
Technology (HEET) initiative funded by ONR
(N00014-09-1-0709 and N00014-10-1-0310)
n  M.J. Cooney, A. Konash, C. Lau, M. Windmeisser –––
AFOSR MURI project (led by Prof. P. Atanassov of Univ.
New Mexico) on “Fundamentals & Bioengineering of
Enzyme Fuel Cells” (FA9550-06-1-0264)
Thank you!

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IBA

2013 – 15 March 2013 – Barcelona

Green Sustainable Sugar-­‐Air

Bor Yann Liaw

Driving Force Demand

OECD: Organization for Economic Co-­‐operation and Development

n Primary resources –––

n Availability and u6liza6on are constrained by abundance and

n Renewable resources is a major sector of growth for

n Power sources –– Secondary (rechargeable) è Round-­‐trip eﬃciency,

Power Source kW/kg kWh/kg Example Use

DOE/NASA/0032-28 Mod 2 502 0.30 1.78* Chevrolet Celebrity

* 12 kWh cruise for 60 miles, 25 mpg

n Eﬀec6ve primary “energy-­‐to-­‐power” sources ––

n Electrochemical devices are the most eﬃcient energy

Bio-­‐fuels shall have opportuni6es

n Carbon neutral è renewable

Nano-scale Control Macro-scale Control

Mano & Heller

Sakai et al. EES 2 (2009) 113

Sugar is a naturally occurring energy

1.45 ±0.24 mW/cm2 @ 0.3 V

Complicated and delicate ! http://www.daizizheng.com/projects.htm

n Flexible configuration

n Carbon felt anode & air-breathing cathode for O2

2 e− In the solution:

n 3 M KOH, 2 M glucose, and 28 mM methyl viologen (MV)

Power Density (mW/cm2 ) .

n Glucose is the fuel

0.6 10 mM Aliquots of glucose

D-­‐Gluconic acid δ-­‐lactone

Carbon felt anode

Scan rate: 10mV/s

Scan rate: 10mV/s ▶ Dimer formation suppressed

700 Conc ratio in 3

Power Density (mW/cm2 )

n KOH concentra6on aﬀects solubility, electrolyte conduc6vity,

Power Density (mW/cm2 )

n Mechanical s6rring improves mass transport; thus, increases

Power Density (µW/cm 2)

Current Density (mA/cm2)

Power Density (µW cm-2)

In situ Spectroscopic Imaging Ellipsometry + QCM + CV/EIS

-­‐1.4 -­‐1.2 -­‐1.0 -­‐0.8 -­‐0.6

-­‐0.3 V -­‐0.6 V -­‐1.04 V -­‐1.10 V -­‐1.20 V -­‐1.30 V

-­‐1.00 V -­‐0.94 V -­‐0.84 V -­‐0.80 V -­‐0.72 V -­‐0.60 V

n In situ & operando

Svoboda & Liaw, Pure Applied Chem. 80 (2008) 2439

MG solution n=1.3342 k=0.0010

adsorbed MG: d2= 300.16 nm

n Sugar is renewable

Specific merits –––

n Portable/mobile power — cell phones, iPods, Bluetooth

n Costs of electricity:

n A novel sugar–air battery without oxidation catalyst or

n D.M. Scott & Ellipsometer (Accurion/Nanofilm) —–

Das könnte Ihnen auch gefallen

Green Sustainable Sugar-‐Air

OECD: Organization for Economic Co-‐operation and Development

n  Primary resources –––

n  Availability and u6liza6on are constrained by abundance and

n  Renewable resources is a major sector of growth for

n  Power sources –– Secondary (rechargeable) è Round-‐trip eﬃciency,

n  Eﬀec6ve primary “energy-‐to-‐power” sources ––

n  Electrochemical devices are the most eﬃcient energy

Bio-‐fuels shall have opportuni6es

n  Carbon neutral è renewable

n  Flexible configuration

n  Carbon felt anode & air-breathing cathode for O2

n  3 M KOH, 2 M glucose, and 28 mM methyl viologen (MV)

n  Glucose is the fuel

D-‐Gluconic acid δ-‐lactone

Scan rate: 10mV/s ▶  Dimer formation suppressed

n  KOH concentra6on aﬀects solubility, electrolyte conduc6vity,

n  Mechanical s6rring improves mass transport; thus, increases

-‐1.4 -‐1.2 -‐1.0 -‐0.8 -‐0.6

-‐0.3 V -‐0.6 V -‐1.04 V -‐1.10 V -‐1.20 V -‐1.30 V

-‐1.00 V -‐0.94 V -‐0.84 V -‐0.80 V -‐0.72 V -‐0.60 V

n  In situ & operando

n  Sugar is renewable

n  Portable/mobile power — cell phones, iPods, Bluetooth

n  Costs of electricity:

n  A novel sugar–air battery without oxidation catalyst or

n  D.M. Scott & Ellipsometer (Accurion/Nanofilm) —–