“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.

Antropy Tech/Demaray LLC SpectraPower 6.6Ah NCM defect free dielectric barrier film high capacity Li battery

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

Cell Cell #1

Cell Cell #2

Cell Cell #3

Cell Cell #4 Cell Cell #5 …But Limited Cycling Performance of anode

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

2µ-LIPON

EnFilm™ µ-battery 3. Start with the solid state micro battery having a 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. STMicro EnFilmTM Battery Excellatron data ORNL data – N. Dudney, et. al. 4000 cycles > 50 000 cycles > 10 000 cycles

2µ-LIPON

http://ceramics.org/wp-content/uploads/2011/08/energy-ss-batteries-jones.pdf Adv. Energy Mater. 2015, 5, 1401408 “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, 1401408 https://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 Battery courtesy; John Bates circa ~ 2004 • “Biased Pulsed DC Reactive Sputtering of Oxides” - the Reactor • -defect free electrical and optical film production

Reactor Patent has 3 components A pulsed DC power supply connected to the sputter target - more than 5,000 systems have this RF + DC A filter to protect the DC supply from the RF supply Plasma – 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 by RF Power more than 5000 production sputter systems in production world wide 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

Structural, defect free LIPON electrolyte Top view crystalline LiCoO2 + = 5µ LiCoO2 cathode .5µ Metal Nitride barrier …

H. Zang - E. Demaray designed cluster tool with 5 chambers for 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 S Dielectric barrier film 1 ft2 protecting Indium metal coated PEN – 1 hr. boiling water test.

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3

2

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 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

−4 −1 [1] cubic c-Li6.4Ga0.2La3Zr2O12 solid state electrolytes, σ∼4.0 × 10 S cm at 20 °C “..garnet-type fast Li-ion conductors for all-solid state batteries”, S. Afyon, et, al. J. Mat. Chem. A, I36, 2015. 6. DLLC Solid State, Thin Film Battery (TFB) Intellectual Property Demaray LLC Core Patents; Biased PDC and RF Sputter Applications US6,533,907 Method of producing amorphous silicon for hard mask and waveguide applications US8,105,466 Biased pulse DC reactive sputtering of oxide films US7,413,998 Biased pulse DC reactive sputtering of oxide films US7,544,276 Biased pulse DC reactive sputtering of oxide films 1. RF biased RF deposition of US7,381,657 Biased pulse DC reactive sputtering of oxide films glassy conformal defect free LIPON US7,378,356 Biased pulse DC reactive sputtering of oxide films

2. reactive BPDC conductive barrier for metal foil High Rate Deposition of crystalline LiCoO2 cathode US8,636,876 B2 Deposition of LiCoO2 2014 3. • China ZL200580042305, 2010, • EU 1825545, 2009, Infinite Power Solutions (IPS) & Apple TFB • 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

17 Oxidation of metals- Gibbs free energy of oxidation Ellingham Diagram Oxides 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 confidential 7. LTFB Performance Projections

LTFB energy density is equivalent to high power ICE power and exceeds all published gravimetric energy density goals. High power may eliminate Some applications for supercapacitors. Low resistivity solid state thin film electrolyte, e.g. 5-7 mOhms provides low temperature as well as low temperature ambient Operation.

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

19 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, [email protected], +1 650-283-7765 cell/text