“THIN FILM LITHIUM METAL BATTERY WITH HIGH CAPACITY, ENERGY DENSITY AND CYCLE LIFE”NASA BATTERY WORKSHOP, HUNTSVILLE ALABAMA 2016

Pavel Khokhlov, James Kaschmitter,

Spectra Power, Livermore CA.

Ernest Demaray,

Antropy Tech and DLLC, Portola Valley CA.

Thin Film dielectric ~ 160nm,planarized over topologywith no permeable defects.VSWR< 8E-5gr/m2-day damp heatFor solid state electrolyte

SpectraPower 6.6Ah NCMhigh capacity Li battery

Antropy Tech/Demaray LLC defect free dielectric barrier film

High Capacity Thin Film Lithium Metal Battery

1. SpectraPower High Cellular Energy Density NMC Cathode

2. The 6.6Ah battery with proven high capacity NMC cathode

3. The Thin Film Solid State Electrolyte (TF-SSE) for high cycle life

4. Antropy Tech/Demaray LLC defect Free TF-SSE for protection of the metallic anode

5. High volume manufacturing - cost and Earth Friendly Material

6. Intellectual Property – Integrated thin film high capacity battery

7. Performance Projections and First Results

8. Conclusions

1. SpectraPower Ultra High >480 Wh/kg (cell level) demonstrated

(cathode)

2. Proven SpectraPower High Capacity, High Cellular Energy Density NMC Cathode

(spec for this battery from the provisional)Proven >480 Whr/kg cellular energy density 6.6Ah NMC battery (120x140x1.5) mm3

Cel

l #1

Cel

l #2

Cel

l #3

Cel

l #4

Cel

l #5

…But Limited Cycling Performance of anodeEquivalent Energy

Density in 6.6 Ah cell:

485 Whr/kg

350 Whr/kg

The main cause of limited cycle life is non-uniform lithium deposition on anode(see next slides)

Autopsy Results: Cathode = good

Cathode quality is not affected by cell cycling.

No signs of degradation found on cathode.

Autopsy Results: Anode = bad

Anode failure as a primarily reason for cell degradation:

• Mossy lithium growth during charge, Non-uniform Li stripping during discharge

• Copper roughness promotes lithium dendrite nucleation

• No barrier to dendrites growth into porous electrolyte

• Oxidative degradation of anode• Lithium reduction of anode materials

STMicro Proven high volume manufacturing –low cost, earth friendly material

Wide area production scanning magnetron developed and shipped by Symmorphix to STMicro, 2004 with license for Bias Pulsed DC Sputtering Patents now owned by Demaray LLC.

EnFilm™ µ-battery

2µ-LIPON

3. Start with the solid state micro battery havinga thin film solid state electrolyte (TF-SSE)

the path for high cycle life for high capacity batteries• TF-SSE is proven in manufacturing to efficiently prevent growth of dendritic lithium• Stable cycling is proven in µ-batteries (~ 1 mAh) in production: all based on LIPON

electrolyte as developed by John Bates - ORNL and OakRidge Batteries Inc.

http://ceramics.org/wp-content/uploads/2011/08/energy-ss-batteries-jones.pdfAdv. Energy Mater. 2015, 5, 1401408

Excellatron data> 50 000 cycles

ORNL data – N. Dudney, et. al.> 10 000 cycles

STMicro EnFilmTM Battery4000 cycles

2µ-LIPON

“Solid Electrolyte: the Key for High-Voltage Lithium Batteries” J. Li, C. Ma, M. Chi, C. Liang ,and N. J. Dudney , Adv. Energy Mater. 2015, 5, 1401408https://www.researchgate.net/publication/268578514_Solid_Electrolyte_The_Key_for_High-Voltage_Lithium_Batteries

“Can solid-state batteries fundamentally tackle all the problems in high-voltage lithium (metal) batteries, the unstable cathodes, electro-lytes, and anodes?”

LiNi 0.5 Mn 1.5 O 4 cathode, Lipon solid electrolyte, (0-5.5V)Li metal anode. Disorded spinel-LiNi 0.5 Mn 1.5 O 4 (theoretical capacity 147 mAh g −1 )high-voltage cathode ≈4.7 V

LIPON enabled LiCoO2 Thin Film Batterycourtesy; John Bates circa ~ 2004

• “Biased Pulsed DC Reactive Sputtering of Oxides” - the Reactor • -defect free electrical and optical film production

Reactor Patent has 3 componentsA pulsed DC power supply connected to the sputter target

- more than 5,000 systems have thisA filter to protect the DC supply from the RF supply

– this is required to protect the DC supply An RF bias power supply connected to the substrate

– far more than half of the systems have this

This sputter reactor power configuration is adapted bymore than 5000 production sputter systems in production world wide

RF + DCPlasma

RF Power

Symmorphix-Demaray LLC- LIPON/LiCoO2 TF-uB sputtered at high rate from a conductive ceramic target with system and license for the Infinite

Power Systems (IPS) “Thinergy” battery.

+ =

,

…

2µ LIPON

5µ LiCoO2

.5µ Metal Nitride barrier

Top view crystalline LiCoO2cathode

Structural, defect freeLIPON electrolyte

=

H. Zang - E. Demaraydesigned cluster

tool with 5 chambersfor sputtering of layers

without cross contamination;RF biased Pulsed DC

reactive sputtering, first unite for IPS February 2005.

IPS “Thinergy” TFµB on Cu/Ni foil

Dielectric barrier film 1 ft2 protecting Indium metal coated PEN – 1 hr. boiling water test.

1. SEM fracture cross section of 180nm oxide barrier film over Indium metal on PEN

2. TEM cross section of oxide barrier film over indium on PEN

3. 1Ft square sample of barrier film shown in 1&2 after 1 hr boiling water immersion

S

1

2

3

4. Defect free single layer oxide barrier film developed to protect metallic Ca anode for OLED tested in damp heat.

• Ca is more reactive to Oxygen and water vapor than Li metal. Ca is necessary as an electron injection anode layer for OLED light emission.

• Single point defects develop and can be located and sized for water vapor permeation rate as they form a region of oxidation of the Ca that grows in time quantitatively as the thickness of the Ca film is known. The OLED grows dark where the Ca is oxidized.

• Defect free barrier films were first demonstrated by Symmorphix and Dupont under a U.S. Display Consortium grant, 2003-4 by H.Zhang and E. Demaray. Their work independently tested by Dupont resulted in the demonstration of active Ca anode OLED devices surviving 1654 hours in damp heat. This work resulted in the award of a patents claim US7,262,131B2 and US7,205,662,B2, Dielectric Battier Layer, 2007 with allowed claims for a barrier with permeable defect concentration less than ~ 1 per cm2, including a barrier over a soft metal.

5.Low Ionic Resistance from solid state thin film electrolyte comparable to Liquids

Li+ Ion Conductivity Thin Film Li+ ion conductivity

• e.g. c-Li6.4Ga0.2La3Zr2O12 solid state electrolyte;

• 4 e-4 S/cm conductivity ~

• .25 e4 Ohm-cm resistivity, so for

• 1micron = e-4 cm

• (.25e4Ohmcm) (e-4cm) =

250mOhms resistance

[1] cubic c-Li6.4Ga0.2La3Zr2O12 solid state electrolytes, σ∼4.0 × 10−4 S cm−1 at 20 °C “..garnet-type fast Li-ion conductors for all-solid state batteries”, S. Afyon, et, al.J. Mat. Chem. A, I36, 2015.

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Demaray LLC Core Patents; Biased PDC and RF Sputter Applications US6,533,907 Method of producing amorphous silicon for hard mask and waveguide applicationsUS8,105,466 Biased pulse DC reactive sputtering of oxide filmsUS7,413,998 Biased pulse DC reactive sputtering of oxide filmsUS7,544,276 Biased pulse DC reactive sputtering of oxide filmsUS7,381,657 Biased pulse DC reactive sputtering of oxide films US7,378,356 Biased pulse DC reactive sputtering of oxide films

High Rate Deposition of crystalline LiCoO2 cathode

US8,636,876 B2 Deposition of LiCoO2 2014 3.• China ZL200580042305, 2010, • EU 1825545, 2009, • Japan 5095412, 2012, • South Korea 10-1021536, 2011, • Taiwan 1346403, 2011, • France 1825545, 2009, • Germany 6020050175 12.1, 2009, • Italy 1825545, 2009, UK 1825545, 2009• China published

6. DLLC Solid State, Thin Film Battery (TFB) Intellectual Property

1. RF biased RF deposition of

glassy conformal defect free LIPON

2. reactive BPDC conductive barrier for metal foil

Infinite Power Solutions (IPS) & Apple TFB

Oxidation of metals- Gibbs free energy of oxidation

Ellingham DiagramOxides stable to reduction

By Li metal

Only Ca, Mg and Be oxides are stable to reduction by Li metal.

Earth abundant, non-toxic Ca and Mg are the only metals available as oxides to contain metallic Li.

Binary Oxides CaxMg(1-x)0 are a little more stable.

Nitrides are sometimes more exothermic but susceptible to moisture, e.g.,

Mg3N2 + 3H2O = 2NH3 + 2NH3

7. LTFB Performance Projections

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LTFB energy density is equivalent to high powerICE power and exceeds all published

gravimetric energy density goals. High power may eliminate

Some applications for supercapacitors. Low resistivitysolid state thin film electrolyte, e.g. 5-7 mOhms

provides low temperature as well as low temperature ambient

Operation.

confidential

LTFB plots “off the chart” for volumetric energy density, J. Electrochem. Soc. 162 (4) A722-A726 (2015) “A High-Throughput Approach…for All-Solid-State Lithium Batteries”, C. Yada, et. al. Adv. Tech 1, Toyota Motor, Zaventem, Belgium

http://jes.ecsdl.org/content/162/4/A722.full

First Thin Film HC LI Metal First Cell Results

8. Conclusions

• SpectraPower has demonstrated >480 Wh/kg (cell level) rechargeable “anode-less” battery with capacity 6.6 Ah

• Demaray LLC Thin Film micro battery; production proven to > 10,000-50,000+ cycle with defect free thin film electrolyte and surface planarization for amorphous solid state electrolyte.

• Each technology component has been independently demonstrated. New high conductivity oxide electrolytes are available with Li metal durable and earth abundant solid state oxides and nitrides.

• Integrated process has demonstrated equivalent ~ 500Wh/kg with lithiation of oxide solid state electrolyte and uniform plating of ductile Li metal on the passivated thin film anode.

• Cost; ~ $100/kWh full production opens large scale cost sensitive applications for batteries with service life = > product life.

• Low self discharge and high temperature operation provide safe, secure, on demand power with charging latency of many years.

• ~ 20 allowed Biased Pulsed DC sputtering patents for planarized and amorphous thin films granted for proprietary market franchise and license.

• New Provisional Patent; “THIN FILM BATTERY WITH HIGH CAPACITY, ENERGY DENSITY AND CYCLE LIFE” USPTO Application no. 62333782, Pavel Khokhlov, James Kaschmitter, Ernest Demaray, May 2016.

• Contact Ernest Demaray, ed@edemaray.com, +1 650-283-7765 cell/text