lithium/air semi-fuel cells: high energy...
TRANSCRIPT
Steven J. Visco, Eugene Nimon, Bruce Katz, May-Ying Chu, and Lutgard De Jonghe
PolyPlus Battery Company2431 5th Street, Berkeley, CA 94710
Scalable Energy Storage: Beyond Li-Ion, Almaden Institute, August 26, 27, 2009
LITHIUM/AIR SEMI-FUEL CELLS: HIGH ENERGY DENSITY BATTERIES BASED ON LITHIUM METAL ELECTRODES
Technologies Under Development
• Lithium/Sulfur - rechargeable (licensed product)
• Lithium/Air - (primary & secondary)
• Lithium/Seawater - primary
Water-stable, Li+ conductive solid electrolyte
Li/Aqueous Batteries?
Lithium reacts with water:Li + H2O = LiOH + 1/2 H2
Unstable to reduction by Li
Li+ electrolyte stable to both lithium metal & solid electrolyte
Lithium Electrode
SOLID ELECTROLYTES
•Lisicon - LiM2(PO4)3 σ=10-4 to 10-3 S/cm
•RbAg4I5 σ=0.27 S/cm
•Na-β”-alumina σ=0.2 S/cm (350 oC)
•LiI•Li2S•P2S5 σ=10-3 S/cm
•LiPON (Li3PO4Nx) σ=10-6 S/cm50 microns
Solid-State PLE
Solid-state protected anode - Cycling of solid-state protected anode in 1M LiOH at varying current densities: 1) 1 mA/cm2; 2) 5 mA/cm2; 3) 10 mA/cm2; 4) 15 mA/cm2; 5) 1 mA/cm2
Cu3N/Li3N
U.S. Patent 7,491,458; “Active metal fuel cells,” S.J. Visco; Y.S. Nimon, B D. Katz; and L.C. De Jonghe; filed April 14, 2004
U.S. Patent 7,282,295; “Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture”; S.J. Visco; Y.S. Nimon; , B D. Katz; and L.C. De Jonghe filed April 14, 2004
12th International Meeting on Lithium Batteries, Nara, Japan, June 27th – July 2nd, 2004
1ST PUBLIC PRESENTATION OF THE PROTECTED LITHIUM ELECTRODE (PLE)
“Lithium Metal Aqueous Batteries,” Abstract No. 53,
“Lithium Fuel Cells,” Abstract No. 396
“Lithium Air Batteries,” Abstract No. 397
(S.J. Visco, E. Nimon, B. Katz, L.C. De Jonghe, and M.Y. Chu)
Lithium/Water Chemistry(Low equivalent weight of lithium combined with the high voltage for the Li/Seawater
couple leads to unprecedented energy density for practical Li/Seawater Cells)
Li/O2 in aqueous electrolytes:
Basic electrolyte: 4Li + O2 + 2H2O = 4LiOHAcidic electrolyte: 4Li + O2 + 4H+ = 2H2O + 4Li
Li/O2 in non-aqueous electrolytes:
Li + O2 = Li2O2 (peroxide)
Li/Water:
Basic electrolyte: 2Li + 2H2O = 2LiOH + H2
Seawater (pH=8.2): 2Li + 2H2O = 2LiOH + H2
E = 3.45 VE = 4.27 V
E = 2.96 V
E = 2.22 VE ~ 2.60 V
The gravimetric capacity of lithium is 3800 mAh/g; Li/Seawater batteries make use of both the dissolved oxygen (E=3.45 V) and water reduction (E=2.6 V) leading to a nominal voltage of about 2.8 volts for Li/Seawater battery under discharge. According, the theoretical specific energy is 3800 mA/g x 2.8 V ~ 10,000 Wh/kg.
Stability Window for H2O
Conventional Technology
(Conventional vs. Solid Electrolyte Protected Li)
Expanded potential window enables development of stable Li/Air & Li/Water cells
ProtectedAnode
W. Li, W. R. McKinnon, and J. R. Dahn, J. Electrochem. Soc. 141, 2310 (1994)
Li/Air Aqueous
Solid-state, non-aqueous, ionic liquid, polymer electrolyte
Solid state/Aqueous Interface
Stability of Solid Electrolyte in Aqueous Media
Discharge of Protected Lithium Metal Electrodes
Figure. 5. Discharge of thick protected anodes (Li foil is 5.3-5.6 mm) in aqueous neutral electrolyte usedin Li/Air batteries. Discharge current density: 1) 2.0 mA/cm2; 2)1.0 mA/cm2; 3) 0.5 mA/cm2. End of celldischarge corresponds to Li depletion. Data provided by PolyPlus Battery Company.
0.5 mA/cm2
1.0 mA/cm2
2.0 mA/cm2
More than 5 mm lithium discharged in in each test at 100% utilization
Protected Li electrode Li/Air Technology
Flexible seal allows volume change and maintains hermetic
enclosure(Tested to 10,000 psi)
Compliant seal
LiM2(PO4)3 Solid electrolyte
Commercial air electrode &Aqueous LiOH electrolyte
PolyPlus air electrodes &PolyPlus catholytes
Gen I Gen II Gen III Gen IV Gen V Gen VI
Discharge of lithium/air cells having double-sided PLEs with compliant seals in aqueous catholyte at varying current density: 1) 1.0 mA/cm2; 2) 0.5 mA/cm2 ; and 3) 0.2 mA/cm2
Discharge of Aqueous Li/Air using PLE
Li/Air Cell(800 Wh/kg)
Li2O2
insoluble
Non-Aqueous Li/AirCorrosion of Li electrode by water is unavoidable with this approach
Corrosion of Li electrode is eliminated with this approach
PolyPlus issued US PatentChoice of catholytes is limited Choice of catholytes nearly unlimited
Li2O2
insoluble
Cycling of Li/Air Cell with Protected Li Anode and Non-Aqueous Catholyte
Li electrode thickness: 40 µm Discharge/Charge: 0.1 mA/cm2 for 10 hrs (~5 µm of Li)
Time, hrs
Cel
l Vol
tage
, V
22nd cycle
5th cycle
Cycling performance of Li/air cell with nonaqueous catholyte comprising LiTFSI in DMF–EG.
Cycling performance of Li/Air cell with non-aqueous electrolyte. Charge/discharge: 0.4 mA/cm2 for 5 hrs; thickness of Li plated and stripped during cycling is ~10 μm
2 mAh/cm2/cycle
Cycling performance of Li/air cell with nonaqueous catholyte comprising LiTFSI in DMF–EG. Charge/discharge: 0.4 mAcm2 for 5 h; thickness of Li plated and stripped during cycling: 10 microns
Rechargeable Li/Air using PLE and non-aqueous catholyte
Rechargeable Li/Air
•Develop thin or wind-able solid electrolyte membranes to increase cell surface area
•Develop electrocatalysts for the non-aqueous oxygen electrode
•Explore non-aqueous electrolytes and complexing agents to increase solubility of Li2O2
•Develop suitable electrode microstructures for deep reversible cycling of oxygen electrode
•Demonstrate suitable cycling of lithium electrode for traction applications
To do list:
ADVANTAGES OF LITHIUM/AIR
• Extremely high specific energy (rivaling that possible for hydrocarbon fuel cells); commercial cells should reach 1000 Wh/kg
• Energy for reaction is not contained in cell; large battery packs may have a safety advantage for that reason
• Environmentally benign system
Li/Air Cell(800 Wh/kg)
Providing Power for Marine Devices
Slide courtesy of Dr. James BellinghamMonterey Bay Aquarium Research Institute (MBARI)
The majority of the oxygen in the earth’s atmosphere is produced from photosynthetic processes occurring in the ocean. This is approximately sixty to seventy percent in total.
The Protected Anode
Fully functional protected lithium electrode; lithium electrode is stable to a broad range of protic and aprotic solvents including water; 2400 Wh/kg with a 2.8 V cathode.
Discharge of Protected Li Electrode In Seawater at Variety of Rates
Time, days
Ano
de p
oten
tial v
s. S
HE,
V
1.0 mA/cm2
0.8 mA/cm2
0.2 mA/cm2 0.1 mA/cm2
~ 15 months of discharge
Li Thickness: 5.1-5.4 mmEnd of discharge corresponds to Li depletion
Rigid Seal
Instrumented 60-liter Tank for Testing Li/Seawater Batteries
Discharge of Li/Seawater (O2) Cells Having Double-Sided Protected Lithium Anodes in 65-L Tank
Cel
l vol
tage
, V
Time, hrs
End of dischargecorresponds to lithium depletion
Glass-ceramic plates 150 µm in thickness
1.0 mA/cm2 0.5 mA/cm2
Discharge at 0.5 mA/cm2: 2268 mAh (1.14 mm Li)Discharge at 1.0 mA/cm2: 2247 mAh (1.13 mm Li)
3.0 V
2.8 V
Discharge of Double-Sided Ceramic-Protected Lithium AnodesHaving Flexible Seal in Seawater
Ano
de p
oten
tial v
s. S
HE,
V
Time, hrs
Sintered ceramic plates 260-270 µm in thickness Lithium thickness: 1.1-1.3 mm (2.2-2.6 mm total)
1.0 mA/cm2
0.5mA/cm2
0.2mA/cm2
0.15mA/cm2
For all cells end of discharge corresponds to lithium depletion
0.1mA/cm2
105 days of discharge
Li/Seawater Batteries are Environmentally Benign
Protected Li anode
Li = Li+ + e-
Testing Under Realistic Ocean ConditionsWill Biofouling Occur on Protected Anode?
PolyPlus, MBARI, Scripps
Pacific Ocean10 meters
Li+Li+ Li+
Li+Lithium Li+
Toxic Non-Toxic
Deep Water Batteries
Best marine batteries deliver 50 to 250 Wh/kgLi/Seawater should exceed 1000 - 1500 Wh/kg
MARKETSLithium/Air & Lithium/Seawater Technologies
MANUFACTURING
The Protected Anode
Fully functional protected lithium electrode; lithium electrode is stable to a broad range of protic and aprotic solvents including water; 2400 Wh/kg with a 2.8 V cathode.
OHARAGlass-Ceramic and Tape-Cast Membranes
Glass-ceramic membranes: Ohara Japan
Tape-cast membranes: OHARA U.S.
MANUFACTURING
• PolyPlus is working with Quallion LLC, a potential manufacturer of Li/Air and Li/Seawater batteries.
• Quallion is now developing pack designs for commercial Li/Air products.
NEW OPPORTUNITIES
Deep ocean New Battery Chemistry Drug Delivery
IMPLANTABLE POWER SUPPLIES
Should last 2 times longer than Li/I2
IMPLANTABLE POWER SUPPLIES
Should last 2 times longer than Li/I2
Novel Drug Delivery Systems
Bipolar Disorder
Ionotophoretic Li+ Drug Delivery
Li b
lood
con
c.
Time
oral lithium
therapeutic
toxic
Electrochemical drug delivery (iontophoresis)ultra-compact Li source
+
_
Biological medium
Live pig skin
Protected Li Electrode
Ag/AgCl Electrode
Li+
Li + AgCl = LiCl + Ag
e-
Intellectual Property (IP) Assets
Intellectual Property Assets
• Innovate & Protect IP‣ 72 Issued Patents & 60 Pat. Apps.‣ Domestic and foreign patent coverage‣ Internal IP Circle leads to new innovations
• Solidify Core IP ‣ Employee Retention = IP Retention‣ Internal IP Circle strengthens core protection
• Monetize IP Assets‣ Leverage IP (JV, Gov’t funding, strategic alliances)‣ License secondary IP (field of use)‣ Sell prepackaged secondary IP portfolios ‣ New IP = New Business
E N E R G Y T E C H N O L O G Y
Other
B
iomed
ical
B a t t e r i e s Li-Seawater Li-Polymer Solid State Thin Metal Electrolyzers L
i-Patch
New
Li
- SO
Cl 2 L
i - Su
lfur
Li-
Air Li -Air
Film Fuel Cells
Secondary Primary
PolyPlus Ano
de Pr
otec
tion
P
olyPlus Anode Protection PolyPlus Anode Protection
Lithiu
m (metal) Li Cx (carbon) Li M
x (alloys) Lithium (metal) Li
Cx (c
arbo
n)
PolyPlusProtected Anode
Technology
U.S. Patent Application No. U.S. Patent Application Title
20070172739 COMPOSITE SOLID ELECTROLYTE FOR PROTECTION OF ACTIVE METAL ANODES
20070117007 LI/AIR NON-AQUEOUS BATTERIES
20070051620 Polymer adhesive seals for protected anode architectures
20070037058 Compliant seal structures for protected active metal anodes
20060078790 Solid electrolytes based on lithium hafnium phosphate for active metal anode protection
20050175894 Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture
20050100793 Active metal electrolyzer
20050100792 Active metal fuel cells
20040197641 Active metal/aqueous electrochemical cells and systems
20040191617 Ionically conductive membranes for protection of active metal anodes and battery cells
20040142244 Ionically conductive composites for protection of active metal anodes
20040131944 Compositions and methods for protection of active metal anodes and polymer electrolytes
20040126653 Ionically conductive composites for protection of active metal anodes
20030088971 Encapsulated alloy electrodes
20020182508 Coated lithium electrodes
20010041294 Plating metal negative electrodes under protective coatings
Relevant PolyPlus U.S. Patent Applications
Fish love lithium
