a novel concept for energy storage · 2011. 7. 27. · 1/ g.soloveichik 10/19/2010 grigorii...
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1 /G.Soloveichik10/19/2010
Grigorii SoloveichikGE Global Research
Trans-Atlantic Workshop on Storage Technologies for Power GridsWashington, DC, October 19-20, 2010
A Novel Concept for Energy Storage
This work supported as part of the Center for Electrocatalysis, Transport Phenomena, and Materials for Innovative Energy Storage, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001055
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Acknowledgements
GE EFRC teamP. BonitatibusM. DohertyH. LamL. LewisT. MiebachR. PerryA. PetersJ. PresleyO. SiclovanD. SimoneJ. SteinA. UsyatinskyG. YeagerG. ZappiK. Zarnoch
Yale teamV. BatistaR. CrabtreeS. KoneznyO. LucaT. Wang
Stanford teamC. ChidseyV. ZiadinovA. Hosseini
LBL/Berkeley teamJ. KerrJ. ArnoldT. Devine R. FishK. ClarkD. Kellenberger S. Rozenel
DOE - BESJ. VetranoA. Carim
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Megatrends … fuel cost, emission reduction & digitization
Intermittent renewables, smart grid deployment
Opportunities for an advanced energy storage
Backup PowerTelecom, UPS, Stand Alone Systems
GridRenewable Integration, Power Qality, Smart Grid,
T&D Management
Energy StorageMechanical, Chemical,
Electrical, Electrochemical
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Application Energy Storage Requirements
15 min
30 min
1 hour
5 hrs
1 kWh 10 kWh 100 kWh 1 MWh 10 MWh
Application Energy Level
Application Duration
10 sec
Power Battery
Comm EV
Regional Utility
Grid Utility
Renewable Firming
Micro Grid
PHEV
HEV
OHV &
Marine
Dual Battery
Energy Battery
Telecom
UPS
Energy battery: NaMx now…organic flow battery in future
Flow Battery
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Energy Storage Market
• Global investment in electric power ancillary services systems will reach $6.6 billion by 2019
• Deployment of renewables and smart grid is the strongest driver to push the grid storage market 3 – 5 times by 2016
• The global stationary energy storage business $35 billion by 2020
� 11 competing technologies
� Li ion batteries may be ¼ of revenue
� Compressed air, flywheel and sodium-sulfur batteries follow
• Stationary fuel cells revenue $0.7 – 1.2 billion in 2013
• Stationary energy storage got a boost from transportation energystorage development (market size $19.9 billion in 2012)
Sources: http://www.pikeresearch.com/category/research/energy-storage
http://www.luxresearchinc.com/press/RELEASE_41B_Energy_Storage_Market.pdf
http://www.netl.doe.gov/energy-analyses/
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Electrochemical Energy Storage Options
Secondary batteries
NGK 34 MW NAS alongside 51 MW Wind Farm
Source:http://www.ngk.co.jp/english/products/power/nas/
• Stationary electrode materials• Mature technology (lead acid, NiCd, NiNH, NaS)• Emerging technologies(NaMCl2, Li-ion)• New chemistries(Li-air, Li-S, Zn-air)
Redox flow batteries
VRB (Prudent Energy) PacifiCorp (Moab, Utah) 2 MWh VRB-ESS
Source: http://www.pdenergy.com/
• Flowing electrode materials• Mature technology (zinc-bromine, all-vanadium)• Emerging technologies(cerium-zinc, iron-chromium)• New chemistries(vanadium-bromine, soluble lead)
Regenerative fuel cells
1kW-prototype Regenerative Fuel Cell System
Source: www.apg.jaxa.jp
• Gaseous electrode materials• Emerging technologies(H2-O2 conventional and unitized)• New chemistries(H2-Br2 , H2-H2O2 , NaBH4-H2O2 )
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Electrochemical Energy Storage Comparison
Secondary batteries
• No power-energy separation• Moderate energy density (50 – 240 Wh/kg)• High energy efficiency(65 – 90 %)• Degradation mode –electrode • Linear scalability(small cells)• Moderate cost• Mature technology
Redox flow batteries Regenerative fuel cells
++++ ---- ++++ ----++++ ----++++ ---- ++++ ----
++++ ----Positive
Electrolyte Tank
Negative
Electrolyte Tank
Bipolar
Flow
Cell
++++ ----++++ ----Positive
Electrolyte Tank
Negative
Electrolyte Tank
Negative
Electrolyte Tank
Bipolar
Flow
Cell
Unitized regenerative
fuel cell
H2O DC power
DC load
O2tank
H2tank
Charge
Discharge
Unitized regenerative
fuel cell
Unitized regenerative
fuel cell
H2O DC power
DC load
O2tankO2tank
H2tankH2tank
Charge
Discharge
• Power and energy separated• Low energy density (10 – 50 Wh/kg)• High energy efficiency(65 – 78 %)• Degradation mode –membrane • Non-linear scalability(cell stacks)• Low cost• Emerging technology
• Power and energy separated• High energy density (450 – 500 Wh/kg)• Low energy efficiency(35 – 50 %)• Degradation mode –catalyst • Non-linear scalability(cell stacks)• High cost• New technology
Energy Power
•Combination of high energy density and efficiency, long cycle life, high DOD, low cost, fire and environmental safety desirable• Main focus on transportation, more efforts on stationary storage needed• New concepts wanted
Energy Power Energy Power
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LQ*H2
LQ
H2-charge liquid (LQ*H2)
H2-depleted liquid (LQ)
Polymer Electrolyte Membrane (PEM)
Backing Layer
Catalyst Layer
Load
H2O
O2 (Air)
Load
Direct organic fuel cell/flow battery concept
• Feed the hydrogenated organic liquid carrier directly into the fuel cell where it will be electrochemically dehydrogenated to a stable, hydrogen depleted organic compound without ever generating gaseous H2 to produce power
• The spent organic carrier may be replenished either mechanically or electrochemically from water splitting
• Minimize the balance of plant by excluding a catalytic reactor and a heat exchanger
• High theoretical energy density (up to 1350 Wh/kg)• Low membrane crossover – high efficiency• Energy conversion and storage separated - low packaging• Reversibility (fuel cell ↔↔↔↔ flow battery)• Excellent safety, zero carbon emission
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Center for Electrocatalysis, Transport Phenomena, and Materials for Innovative Energy StorageDr. Grigorii Soloveichik (GE Global Research)
Electrocatalysis, transport
phenomena and membrane
materials basic research aimed
to three novel components of
an entirely new high-density
energy storage system
combining the best properties
of a fuel cell and a flow battery:
organic carriers,
electro(de)hydrogenation
catalysts, and compatible PEM
an Office of Basic Energy Sciences
Energy Frontier Research Center
Award DE-SC0001055
Focus areas: • C-H bond catalysis/• Electro(de)hydrogenation catalyst • Organic fuel • Low humidity proton exchange membrane
STANFORDUniversity
YaleUniversity
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Electron level material processes
Atom- and energy efficient synthesis
Far from equilibrium processes control
Electrical energy storage
Catalysis for energy
Hydrogen economy
Solar energy utilization
Focus 4Novel proton exchange membrane development
Focus 1Selection and synthesisof organic carriers
Focus 5Modeling of interactions
among components
Focus 3Immobilization and characterization ofelectrocatalystsFocus 2
Discovery ofelectrodehydrogenationand electrohydrogenation
catalysts
Challenges and needs
Program management
EFRCTechnology Applications
High density energy storage organic fuel cell/flow
battery
System integra-tion
Solar energy
Plug-in hybrids
Wind energy
Load leveling
Fundamental research
LQ*H2
LQ
Backing Layer
Load
H2O
O2 (Air)
LoadLoad
LQ*H2
LQ
Backing Layer
Load
H2O
O2 (Air)
LoadLoad
Task interactions and program vision
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Traditional approach
LQHn ⇔ LQ + n/2 H2 ∆H to be minimized
EFRC approach
LQHn + n/4 O2 ⇔ LQ + n/2 H2O∆(GLQHn - GLQ) to be minimized to maximize cell voltageTheoretical cell voltage 0.95 – 1.1 V (depends on organic hydrogen carrier)
Fuel (organic carrier) focus
LQ*H2
LQ
LQ*H2
LQ
Organic fuel requirements•Minimal ∆∆∆∆G dehydrogenation of organic carriers via molecular modeling guidance
• Scalable synthesis of aromatic precursors and hydrogenation to saturated carriers (high pressure lab)
• Liquid at ambient conditions, low vapor pressure
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Comparison of dehydrogenation energies for model and promising fuelsin kcal/mol H2 by DFT calculation (method B3LYp, basis set 6-311++G**)
Electrooxidation of model fuels on Pt electrode
First dehydrogenation step most critical
NN
N N N
28.4 7.5
22.9
15.4
N N
14.8
OH O
13.9
18.2
Single-bond and multiple-bond model and promising fuels selected based on computational modeling
Organic fuels molecular modeling
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C-H bond catalysis focusHomogenous C-H bond activation and electron transfer
Catalyst requirements• Catalytic activity in the C-H bond activation and further dehydrogenation of saturated hydrocarbons
• Redox activity in target electrochemical potential windows• Microscopic reversibility (dehydrogenation/hydrogenation)• Ability to transfer multiple electrons and protons• Tunable redox potentials to selected organic fuels
catalystLHn - n e
- ⇔⇔⇔⇔ L + n H+
Utilize defined metal centers for catalysis understanding
Rh-based pincer complex
M=Ni M=Co
no decalinwith decalin
no decalinwith decalin
M=Ni M=Co
no decalinwith decalinno decalinwith decalin
no decalinwith decalinno decalinwith decalin
Organic catalyst for electrodehydrogenation
First electrocatalytic oxidation of cycloalkane on a metal complex
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I II
IVVVI
VII
VIII
(equatorial)(equatorial, cis)
III
(cis)
C.M. Jensen, 1999,A.S. Goldman, 2003
Alkane dehydrogenation mechanism
-2e-
-2H+
No sacrificial olefin
Iridium pincer dihydride primary target for e/chem study
Computational simulation of catalytic cycle
Yale
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Electrocatalysis focusElectrocatalysis for dehydrogenation and hydrogenation
Electrocatalyst requirements
• Fast electron transfer from metal centers through a linker to electrode viastudy of the transport mechanism and determination of controlling factors
• Fast proton transport to PEM via structured catalyst/support
• Robust catalyst that tolerant to impurities/reaction products- design catalyst ligand environment for selectivity- use nanosized metal alloys catalysts supported on carbon
electrodeLHn - n e
- ⇔ L + n H+
EtOH, CH3Cl Rinse
N
N
N
N
N
N
+
_
+
_N
NN
N
NN
1) IN3 in hexanes2) , Cu(I)
CH3Cl, DMSO,
H2O Rinse
catalyst
catalystcatalyst
Chronoamperometry of baseline RVC (blue) and functionalized RVC (red)
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Proton exchange membrane focus
Membrane requirements•Water free PEM (H2O detrimental to anode chemistry) • Low fuel and products solubility – mechanical integrity • Proton conductivity 10-3 S/cm @ 120 oC• High oxidative stability at 120 oC • Thermal stability (> 150 oC)
F2C
O2SN
SO2F3C
N
N
N
N
Imidazole H+
solvating groupImide Anion
H NN
H
+H
H
N
N
N
NHN
NH
H
Pore
Diameter
Phase separated Polymer Backbone
Phase separated Polymer Backbone
Proton Moves
Traditional approach EFRC approach
SO O
O
O n
O
SiHSi O
O2S
F F
F F FF
F F
LiN
O2S CF3+
THF
[Pt]
70C
SO O
O
O n
O
Si
Si
O
O2S
NLi
F
FF
FFF F
F
O2S
CF3
SO O O
O
O
S
O
O
O
OO
N
N
CPh3
0.3 0.7
Si
Si
OSO2
FF
FFFF
FFLiN
O2SF3C
SO O O
O
O
S
O
O
O
OO
HN
HN
0.3 0.7
Si
Si
OSO2
FF
FFFF
FF
HN
O2SF3C
THFTFA
basic
acidic
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Direct organic hydride fuel cell testing Fuel Cell Testing Station
Fuel Cell AssemblyMembrane Electrode Assembly (MEA)
Cyclohexane/air cell
Membrane dehydration,new membranes needed
• 5 cm2 active area• Anode: 4mg/cm2 60% PtRu/C, C-cloth anode GDL
• Cathode: 2 mg/cm2 40% Pt/C •115 Nafion membrane
Significant current observed for tetralin
Use of liquid hydrocarbon fuel in fuel cell demonstrated
Temperature. oC
95 o
Tetralin as Fuel
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0 50 100 150 200
Current Density (mA/cm2)
Po
ten
tia
l (V
)
tetralin
1M Methanol
Tetralin/air cell
Liquid fuel cells OCV, VFuel Theory Exp.MeOH 1.21 0.73Decalin 1.10 0.55Tetralin 1.08 0.66
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Conclusions
• Smart grid development and deployment of intermittent renewables requireperformance and cost effective energy storage
• New concept of high energy densitystorage system combining a PEM fuel cell and a flow battery suggested
• Energy Frontier Research Center targets major components of this system: organicfuel, electrocatalyst and low humidity PEM
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Backup slides
-
Secondary batteries
FZ Sonick SA, GE-1352.58NaNiCl2
-
20
34
27
20
Demo scale, MW
350
75 - 200
150 -240
50 - 75
30 - 50
Energy density, Wh/kg
2.2
3.3 –4.2
1.78 –2.07
1.29
2.04
Cell voltage, V
SION Power, PolyPlusLiS
A123, Ener1, Altair Nanotechnologies, Saft
Batteries
Li-ion
NGK Insulators Ltd.NaS
Saft Batteries, Storage Battery Systems
NiCd
C&D Battery, Exide Technologies, Hagen BatterieAG, Storage Battery Systems
Lead acid
Major playersType
Advantages:•Mature technology • High round trip efficiency• High power or high energy •Modular design
Major technical challenges:• High cost for advanced batteries• Linear scalability (kW to MW)• No deep cycling• Electrode degradation, short lifetime• Corrosion (high temperature batteries)• Safety
++++ ---- ++++ ----
Energy
Power
Cell resistance
-
Flow batteries
65
66
73
77
78
Energy efficiency, %
No membrane
Ion-selective
PEM
Porous diaphragm
Ion-selective
PEM
Membrane
2.04
1.18
2.48
1.85
1.36
1.26
Cell voltage, V
General AtomicsSoluble lead acid
Deeya Energy Iron-chromium
PlurionCerium-zinc
ZBB Energy, Premium Power, Primus Power
Zinc-bromine
Prudent Energy (IP holder)
Polysulfide-bromine
Prudent Energy, Sumitomo, VFuel
Pt
All-vanadium
Major playersType
++++ ----Positive
Electrolyte Tank
Negative
Electrolyte
Tank
Bipolar FlowCell
++++ ----++++ ----Positive
Electrolyte Tank
Negative
Electrolyte
Tank
Negative
Electrolyte
Tank
Bipolar FlowCell
Advantages:• Separation of energy and power • Non-linear scalability (kW to MW)• High round trip efficiency•Modular design • Long lifetime• Low cost
Major technical challenges:• Low energy density (25 – 70 Wh/kg)• Corrosion, expensive plumbing• Environmental issues
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Regenerative H2/O2 fuel cells
D. Bents et al., NASA Glenn Research Center, 2008http://gltrs.grc.nasa.gov
Major players:Giner, Proton Energy Systems
H2tank
O2tank
Electrolyzer Fuel cellH2ODC power DC load
Charge Discharge
H2tank
O2tank
Electrolyzer Fuel cellH2ODC power DC load
Charge Discharge
Conventional design Unitized design
Unitized
regenerativefuel cell
H2O DC power
DC load
O2tank
H2tank
Charge
Discharge
Unitized
regenerativefuel cell
Unitized
regenerativefuel cell
H2O DC power
DC load
O2tankO2tank
H2tankH2tank
Charge
Discharge
F. Mitlitsky et al., LLNL https://www.llnl.gov/str/Mitlit.htmlF. Barbir et al., IEEE A&E Systems Magazine, 2005500 Wh/kg with roundtrip efficiency of 34%.
Major players:EnStorage URFC
Major technical challenges:• Dual function oxygen electrode (unitized FC)• Low roundtrip energy efficiency• Low energy density storage system• Cost
Advantages:• High energy density (500 Wh/kg)• Separation of energy and power• Long lifetime• No environmental issues
-
Electrochemical energy storage systems
yes
yes
yes
no
no
no
no
Deep cycling
Flammable+kWhlong?35 - 50450RFC
Toxic, corrosive
MWhlong5007370ZBB
Corrosive, toxic
+MWhlong8007835VRB
Thermal runaway
+kWhmoderate130060 - 80130Li-ion
Molten NakWhmoderate40075135Na/MCl2
Thermal runaway
MWhlong45072120Na/S
Toxic, corrosive
+kWhshort1507841Lead acid
EHS issuesResponse time
ScaleCycle lifeCost, $/kWh
Round trip efficiency, %
Energy density, Wh/kg
System
• Solid electrodes – degradation, liquid electrodes – low energy density