LITHIUM/AIR SEMI-FUEL CELLS: HIGH ENERGY DENSITY BATTERIES BASED ON LITHIUM METAL ELECTRODES

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Steven J. Visco, Eugene Nimon, Bruce Katz, May-Ying Chu, and

Lutgard De Jonghe

PolyPlus Battery Company

2431 5th Street, Berkeley, CA 94710

[email protected]

Scalable Energy Storage: Beyond Li-Ion, Almaden Institute, August 26, 27, 2009

LITHIUM/AIR SEMI-FUEL CELLS: HIGH

ENERGY DENSITY BATTERIES BASED

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Technologies Under

Development

• Lithium/Sulfur - rechargeable (licensed product)

• Lithium/Air - (primary & secondary)

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Water-stable, Li

+

_conductive

solid electrolyte

Li/Aqueous Batteries?

Lithium reacts with water:

Li + H

2

O = LiOH + 1/2 H

2

Unstable to reduction by Li

Li

+

_{electrolyte stable to both}

lithium metal & solid electrolyte

Lithium Electrode

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SOLID ELECTROLYTES

• Lisicon - LiM

2

(PO

4

)

3

σ

=10

-4

to 10

-3

S/cm

• RbAg

4

I

5

σ

=0.27 S/cm

• Na-

β

”

-alumina

σ

=0.2 S/cm (350

o

_C)

• LiI

• Li

2

S

• P

2

S

5

σ

=10

-3

S/cm

• LiPON (Li

3

PO

4

N

x

)

σ

=10

-6

S/cm

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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/cm}2_{; 3) 10 mA/cm}2_{; 4) 15 mA/cm}2_{; 5) 1 mA/cm}2

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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

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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 + O

2

+ 2H

2

O = 4LiOH

Acidic electrolyte: 4Li + O

2

+ 4H+ = 2H

2

O + 4Li

Li/O2 in non-aqueous electrolytes:

Li + O

2

= Li

2

O

2

(peroxide)

Li/Water:

Basic electrolyte: 2Li + 2H

2

O = 2LiOH + H

2

Seawater (pH=8.2): 2Li + 2H

2

O = 2LiOH + H

2

E = 3.45 V

E = 4.27 V

E = 2.96 V

E = 2.22 V

E ~ 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.

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Stability Window for H

₂

O

Conventional Technology

(Conventional vs. Solid Electrolyte Protected Li)

Expanded potential window enables development of stable Li/Air & Li/Water cells

Protected

Anode

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Li/Air Aqueous

Solid-state, non-aqueous, ionic liquid, polymer electrolyte

Solid state/Aqueous Interface

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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 used in Li/Air batteries. Discharge current density: 1) 2.0 mA/cm2_{; 2)1.0 mA/cm}2_{; 3) 0.5 mA/cm}2_{. End of cell}

discharge 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

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Protected Li electrode Li/Air Technology

Flexible seal allows

volume change and

maintains hermetic

enclosure

(Tested to 10,000 psi)

Compliant seal

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Commercial air electrode & Aqueous LiOH electrolyte PolyPlus air electrodes & PolyPlus catholytes

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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/cm}2_{; and 3) 0.2 mA/cm}2

Discharge of Aqueous Li/Air using PLE

Li/Air Cell (800 Wh/kg)

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Li2O2

insoluble

Non-Aqueous Li/Air

Corrosion of Li electrode by water

is unavoidable with this approach

Corrosion of Li electrode is

eliminated with this approach

PolyPlus issued US Patent

Choice of catholytes is limited

Choice of catholytes nearly unlimited

Li2O2

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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}_µ_{m of Li)}

Time, hrs

Cell V

oltage, V

22nd_cycle

5th_cycle

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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

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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

Li

2

O

2

• Develop suitable electrode microstructures

for deep reversible cycling of oxygen electrode

• Demonstrate suitable cycling of lithium

electrode for traction applications

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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)

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Providing Power for Marine Devices

Slide courtesy of Dr. James Bellingham

Monterey 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

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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.

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Discharge of Protected Li Electrode In Seawater at Variety of Rates

Time, days

Anode potential vs. SHE, V

1.0 mA/cm2 0.8 mA/cm2 0.2 mA/cm2 _{0.1 mA/cm}2 ~ 15 months of discharge Li Thickness: 5.1-5.4 mm

End of discharge corresponds to Li depletion

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Discharge of Li/Seawater (O

₂

) Cells

Having Double-Sided Protected Lithium Anodes in 65-L Tank

Cell voltage, V

Time, hrs

End of discharge corresponds to lithium depletion

Glass-ceramic plates 150 µm in thickness

1.0 mA/cm2 _{0.5 mA/cm}2

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

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Discharge of Double-Sided Ceramic-Protected Lithium Anodes

Having Flexible Seal in Seawater

Anode potential vs. SHE, 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 0.5 mA/cm2 0.2 mA/cm2 0.15 mA/cm2

For all cells end of discharge corresponds to lithium depletion

0.1

mA/cm2

105 days of discharge

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Protected Li anode

Li = Li+_{+ e}

-Testing Under Realistic Ocean Conditions

Will Biofouling Occur on Protected Anode?

PolyPlus, MBARI, Scripps

Pacific Ocean

10 meters

Li+ Li+ _Li+ Li+ Lithium Li+ Toxic Non-Toxic

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Deep Water Batteries

Best marine batteries deliver 50 to 250 Wh/kg Li/Seawater should exceed 1000 - 1500 Wh/kg

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MARKETS

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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.

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OHARA

Glass-Ceramic and Tape-Cast Membranes

Glass-ceramic membranes: Ohara Japan Tape-cast membranes: OHARA U.S.

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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.

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NEW OPPORTUNITIES

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IMPLANTABLE

POWER

SUPPLIES

Should last 2 times longer

than Li/I

2

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IMPLANTABLE

POWER

SUPPLIES

Should last 2 times longer

than Li/I

2

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Novel Drug Delivery Systems

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Ionotophoretic Li+ Drug Delivery

Li blood conc

.

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

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-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} Ot her Bio me dic al B a t t e r i e s Li-Seaw ater _Li-P olym er _S olid Sta te Th in M etal Elec tro lyz ers L i-Pa tch Ne w Li - S OCl 2 Li Sulfu r

Li-Air Li -Air

F ilm F uel C ells Secon dary Primary Poly Plu s A no de Pr ot ec tion P

olyPlus Anode Protectio

n P oly Plu s A nod e Pro tecti on Lithiu m (metal) Li Cx (carb on) L_{i M} x (all oys) L ithi um (me tal) Li Cx (c ar bo n) PolyPlus Protected Anode Technology )0#IRCLE INN OVATEP_R OT EC T DEV ELO P

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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

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