State of Solid-State Batteries
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1 State of Solid-State Batteries Prof. Kevin S. Jones Department of Materials Science and Engineering University of Florida
2 Acknowledgments Dave Danielson Program Director at ARPA-E Scott Faris, Richard Fox, Roland Pitts and Isaiah Oladeji at Planar Energy
3 Outline Introduction Liquid vs. Solid-State Batteries Solid-state Li Ion Batteries Companies Battery Needs for Electric Vehicles BEEST Program Planar Energy Conclusions
4 Typical Li Ion Battery During use (discharge) ions move from anode to cathode Figure courtesy C. Daniel JOM Vol. 60, No.9 pp , 2008
5 Battery Basics Basic terminology Type I vs. Type II Battery: Type II (secondary) is rechargeable Li Metal vs. Li Ion Battery: Based on anode used; Li vs. a compound Capacity: Measure of Li that moves between the anode and cathode (Ah) Cycle Life: Number of recharge cycles before x% of the capacity is lost Energy Density: Energy the battery can deliver per volume (Wh/l) Specific Energy: Energy the battery can deliver per mass (Wh/kg) Specific Power: A measure of the Watts the battery can deliver (W/kg)
6 Existing Battery Types Ragone Plot Higher power and energy are driving the Li Ion battery growth Specific energy is the total energy a battery can deliver in watt-hours per kilogram (Wh/kg) Specific power is the battery s ability to deliver power in watts per kilogram (W/kg).
7 Type II Battery Market $M today Li Polymer Li Ion NiMH NiCd Li Ion dominating the $10B rechargeable battery market Li Ion sales forecast to more than double in the next 10 years Source:
8 Why Li Ion Batteries? Advantages High specific energy (Li is very light) High open circuit voltage (more power at low current) Less memory effect (observed in Ni Cd batteries) Slow self discharge (longer shelf life) Disadvantages Flammable liquids Limited Cell/cycle Life (SEI degradation) Battery life decreases with increasing temperature
9 Outline Introduction Liquid vs. Solid-State Batteries Solid-state Li Ion Batteries Companies Battery Needs for Electric Vehicles BEEST Program Planar Energy Conclusions
10 Types of Li Ion Batteries Liquid Electrolyte LiPF 6 in organic carbonates Li Ion conductivity S/cm Gel/polymer electrolyte Not covered in this talk Solid-state Ceramic Electrolyte Focus of this talk
11 Type II Battery Market $M Li Polymer Li Ion NiMH NiCd Estimated current solid-state battery sales <1% of $8B Li Ion Battery Market* today Source:
12 Why Solid-State Batteries? Advantages over liquid Safety Would eliminate thermal runaway Performance Higher voltages possible Life Much longer cycle life Disadvantages Cost Traditionally very expensive to make Temperature sensitive Low temperature operation can be a challenge
13 Liquid vs Solid-state Li Ion Battery Liquid solvent and polymer separator (not shown) Replaced by solid electrolyte Figure courtesy C. Daniel JOM Vol. 60, No.9 pp , 2008
14 The most common solid-state electrolyte LiPON LiPON is a solid-state electrolyte developed at Oak Ridge National Labs LiPON is an amorphous glass RF Magnetron deposition from Li 3 PO 4 target in N 2 The chemical composition varies from Li 3.3 PO 3.8 N 0.24 to Li 3.6 PO 3.3 N 0.69 * The N increases the Li ion conductivity relative to Li 3 PO 4 Li Ion Conductivity of LiPON is ~2 x 10-6 S/cm still 3-4 orders of magnitude worse than liquid *N.J. Dudney, J. Power Sources, 89, 176, 2000
15 Conventional Solid-State Batteries Vacuum deposition for all layers Cathode: LiCoO 2 or LiMn 2 O 4 or V 2 O 5 Electrolyte: LiPON glass Anode: Li Metal or Sn 3 N 4 Capacity: Typically very low (0.001 to 0.01Ah) Normally LiPON Source:
16 Outline Introduction Liquid vs. Solid-State Batteries Solid-state Li Ion Batteries Companies Battery Needs for Electric Vehicles BEEST Program Planar Energy Conclusions
17 Existing Solid-state Li Battery Companies Cymbet Excellatron Front Edge Infinite Power Sakti3 Seeo Toyota/AIST Planar Energy
18 Cymbet Enerchips Location: Minnesota Based Status: VC funded, selling product Product: Embedded battery back up on PC boards, microcontroller memory, SRAM etc. Electrolyte: LiPON Capacity: Ah batteries Additional features Very low self discharge rates (unlike liquid batteries) Source:
19 Excellatron Location: Georgia Based Status: Private funded, Pilot Line Product: Thin film batteries, Smart cards, RFID implantable medical devices, IC s Electrolyte: LiPON Capacity: Ah batteries Additional features over 50,000 cycles for very thin (0.05µm) cathodes (small capacity) Pulse discharge possible, 1000C rates Source:
20 Front Edge Technology Location: California Based Status: VC funded, selling product Product: NanoEnergy ultra thin battery, smart card, portable sensors, and RFID tag. Electrolyte: LiPON Capacity: Ah batteries Additional features: Thinnest batteries (50 microns), Cycle Life >1000 at 100% discharge Flexible Source: NanoEnergy powering a blue LED
21 Infinite Power Solutions Location: Colorado Based Status: VC funded, Shipping product Product: World leader in Microbatteries (Micro energy cell) wireless sensor, active RFID, powered smart card, medical device, consumer electronic Electrolyte: LiPON Capacity: Ah to Ah Additional features: Cycle life >10,000 Source:
22 SAKTI3 Location: Michigan Based Status: VC funded, R&D Product: solid-state batteries Electrolyte: LiPON? Capacity: aimed at automotive market Additional features: Novel mechanical engineering of vacuum deposition process Not many technical details Source:
23 SEEO Batteries Location: California Based Status: VC funded, R&D Product: solid-state batteries Electrolyte: Solid Polymer Capacity: Goal: grid scale energy storage Additional features: Electrolyte developed at LBL Received DOE ARRA funding from Grid program Source:
24 Toyota/AIST solid-state Battery Location: Japan Status: Collaboration, R&D Product: solid-state Battery Electrolyte: Li Oxide material (LIPON?) Capacity: Ah? Additional features: Using Aerosol deposition (low temperature) Electrolyte conductivity at 3-5 x 10-6 S/cm Source: _research/2010/ / html
25 Solid-state Battery Companies Company Electrolyte Cathode Anode Size Status Cymbet LiPON unknown unknown microbatteries VC: Commercial Excellatron LiPON LiCoO2, LiMn2O4 Li metal or Sn3N4 microbatteries Private: Pilot Front Edge LiPON LiCoO2 Li Metal microbatteries VC: Commercial Infinite Power LiPON LiCoO2 Li metal microbatteries VC: Commercial Sakti3 LiPON? unknown unknown Automotive? VC: R&D or Pilot SEEO Toyota/AIST Solid Polymer Oxide (LiPON?) unknown unknown Grid Scale? VC: R&D LiCoO2 LiMn2O4 Graphite Li4Ti5O12 microbatteries Toyota: R&D Source: Company websites
26 Solid-state Battery Companies Company Electrolyte Cathode Anode Size Status Cymbet LiPON unknown unknown microbatteries VC: Commercial Excellatron LiPON LiCoO2, LiMn2O4 Li metal or Sn3N4 microbatteries Private: Pilot Front Edge LiPON LiCoO2 Li Metal microbatteries VC: Commercial Infinite Power LiPON LiCoO2 Li metal microbatteries VC: Commercial Sakti3 LiPON? unknown unknown Automotive? VC: R&D or Pilot SEEO Toyota/AIST Solid Polymer Oxide (LiPON?) unknown unknown Grid Scale? VC: R&D LiCoO2 LiMn2O4 Graphite Li4Ti5O12 microbatteries Toyota: R&D Planar Energy Thio- LiSICON Source: Company websites CuS SnO2 1-20Ah cells automotive VC: Pilot
27 Why the interest on larger Solid-state Batteries? BEV: Battery Electric Vehicles Significant growth opportunity and need in automotive applications
28 Outline Battery History Liquid vs. Solid-State Batteries Solid-state Li Ion Batteries Companies Battery Needs for Electric Vehicles BEEST Program Planar Energy Conclusions
29 BEEST Program (Batteries for Electrical Energy Storage in Transportation) ARPA-E was created in response to National Academies report Rising above the gathering storm 2009 $400M in funding from Recovery Act Modeled after DARPA BEEST Program was one of the ARPA-E focus areas 10 proposals funded from ~1000 submissions Average funding $3-5M for 3 years The Goal of the BEEST program Developing batteries for PHEVs and EVs that can make a 300- to 500-mile-range electric car a reality Courtesy: ARPA E Website
30 Why do we care about the Electric Car? THE OPPORTUNITY: Reduced Oil Imports Reduced Energy Related Emissions Lower & More Stable Fuel Cost (< $1.00/gallon of gasoline 10 /kwh) THE CHALLENGE: Batteries Low Energy Density (Short Range) High Cost Safety Courtesy: Dave Danielson ARPA -E
31 Do batteries have the potential to rival the energy density of gasoline powered vehicles on a system level? Courtesy: Dave Danielson ARPA -E Specific Energy (Wh/kg)
32 Do batteries have the potential to rival the energy density of gasoline powered vehicles on a system level? Theoretical Max Courtesy: Dave Danielson ARPA -E Specific Energy (Wh/kg)
33 Do batteries have the potential to rival the energy density of gasoline powered vehicles on a system level? Cell level Courtesy: Dave Danielson ARPA -E Specific Energy (Wh/kg)
34 Do batteries have the potential to rival the energy density of gasoline powered vehicles on a system level? Cell Pack Level Courtesy: Dave Danielson ARPA -E Specific Energy (Wh/kg)
35 Do batteries have the potential to rival the energy density of gasoline powered vehicles on a system level? System level including electric motors Courtesy: Dave Danielson ARPA -E Specific Energy (Wh/kg)
36 Do batteries have the potential to rival the energy density of gasoline powered vehicles on a system level? Yes Factor engine and gas weight and Carnot efficiency Courtesy: Dave Danielson ARPA -E Specific Energy (Wh/kg)
37 FACT: Batteries have the potential to rival the energy density of gasoline powered vehicles on a system level Courtesy: Dave Danielson ARPA -E Specific Energy (Wh/kg)
38 Widespread Adoption of EV s Requires RANGE and COST Parity with Internal Combustion Engine (ICE) Vehicles COST: ICE Cost Benchmark ~ 24 /mile RANGE: 250+ mile range needed to eliminate range anxiety In Battery terms the critical factors are: The battery pack price ($/kwh) (cost) The battery pack energy (kwh) (range) The battery pack specific energy (Wh/kg) (weight) Courtesy: Dave Danielson ARPA -E
39 Widespread Adoption of EV s Requires RANGE and COST Parity with Internal Combustion Engine Vehicles COST: ICE Cost Benchmark ~ 24 /mile RANGE: 250+ mile range needed to eliminate range anxiety Ba#ery Pack Cost ($/kwh) Discounted Vehicle Cost per Mile 600 (0.22) (0.27) (0.32) (0.37) (0.42) (0.47) (0.52) 500 (0.21) (0.25) (0.29) (0.34) (0.38) (0.42) (0.46) 400 (0.20) (0.24) (0.27) (0.30) (0.34) (0.37) (0.40) 300 (0.19) (0.22) (0.24) (0.27) (0.29) (0.32) (0.34) 250 (0.19) (0.21) (0.23) (0.25) (0.27) (0.29) (0.32) 200 (0.19) (0.20) (0.22) (0.24) (0.25) (0.27) (0.29) 150 (0.18) (0.19) (0.21) (0.22) (0.23) (0.24) (0.26) Vehicle Range (mi) Pack Energy (kwh) Courtesy: Dave Danielson ARPA -E
40 Widespread Adoption of EV s Requires RANGE and COST Parity with Internal Combustion Engine Vehicles COST: ICE Cost Benchmark ~ 24 /mile RANGE: 250+ mile range needed to eliminate range anxiety Ba#ery Pack Cost ($/kwh) Now Discounted Vehicle Cost per Mile 600 (0.22) (0.27) (0.32) (0.37) (0.42) (0.47) (0.52) 500 (0.21) (0.25) (0.29) (0.34) (0.38) (0.42) (0.46) 400 (0.20) (0.24) (0.27) (0.30) (0.34) (0.37) (0.40) 300 (0.19) (0.22) (0.24) (0.27) (0.29) (0.32) (0.34) 250 (0.19) (0.21) (0.23) (0.25) (0.27) (0.29) (0.32) 200 (0.19) (0.20) (0.22) (0.24) (0.25) (0.27) (0.29) 150 (0.18) (0.19) (0.21) (0.22) (0.23) (0.24) (0.26) Vehicle Range (mi) Pack Energy (kwh) Courtesy: Dave Danielson ARPA -E
41 Widespread Adoption of EV s Requires RANGE and COST Parity with Internal Combustion Engine Vehicles COST: ICE Cost Benchmark ~ 24 /mile RANGE: 250+ mile range needed to eliminate range anxiety Ba#ery Pack Cost ($/kwh) Now Discounted Vehicle Cost per Mile 600 (0.22) (0.27) (0.32) (0.37) (0.42) (0.47) (0.52) 500 (0.21) (0.25) (0.29) (0.34) (0.38) (0.42) (0.46) 400 (0.20) (0.24) (0.27) (0.30) (0.34) (0.37) (0.40) 300 (0.19) (0.22) (0.24) (0.27) (0.29) (0.32) (0.34) Large EV Penetration 250 (0.19) (0.21) (0.23) (0.25) (0.27) (0.29) (0.32) 200 (0.19) (0.20) (0.22) (0.24) (0.25) (0.27) (0.29) 150 (0.18) (0.19) (0.21) (0.22) (0.23) (0.24) (0.26) Vehicle Range (mi) Pack Energy (kwh) Courtesy: Dave Danielson ARPA -E
42 Widespread Adoption of EV s Requires RANGE and COST Parity with Internal Combustion Engine Vehicles COST: ICE Cost Benchmark ~ 24 /mile RANGE: 250+ mile range needed to eliminate range anxiety Ba#ery Pack Cost ($/kwh) Now Discounted Vehicle Cost per Mile 600 (0.22) (0.27) (0.32) (0.37) (0.42) (0.47) (0.52) 500 (0.21) (0.25) (0.29) (0.34) (0.38) (0.42) (0.46) Large EV Penetration 400 (0.20) (0.24) (0.27) (0.30) (0.34) (0.37) (0.40) 300 (0.19) (0.22) (0.24) (0.27) (0.29) (0.32) (0.34) 250 (0.19) (0.21) (0.23) (0.25) (0.27) (0.29) (0.32) 200 (0.19) (0.20) (0.22) (0.24) (0.25) (0.27) (0.29) 150 (0.18) (0.19) (0.21) (0.22) (0.23) (0.24) (0.26) Vehicle Range (mi) Pack Energy (kwh) Courtesy: Dave Danielson ARPA -E
43 Widespread Adoption of EV s Requires RANGE and COST Parity with Internal Combustion Engine Vehicles COST: ICE Cost Benchmark ~ 24 /mile RANGE: 250+ mile range needed to eliminate range anxiety Ba#ery Pack Cost ($/kwh) Now Discounted Vehicle Cost per Mile 600 (0.22) (0.27) (0.32) (0.37) (0.42) (0.47) (0.52) 500 (0.21) (0.25) (0.29) (0.34) (0.38) (0.42) (0.46) 400 (0.20) (0.24) (0.27) (0.30) (0.34) (0.37) (0.40) Large EV Penetration 300 (0.19) (0.22) (0.24) (0.27) (0.29) (0.32) (0.34) 250 (0.19) (0.21) (0.23) (0.25) (0.27) (0.29) (0.32) 200 (0.19) (0.20) (0.22) (0.24) (0.25) (0.27) (0.29) 150 (0.18) (0.19) (0.21) (0.22) (0.23) (0.24) (0.26) Vehicle Range (mi) Pack Energy (kwh) Pack Specific Energy (Wh/kg) Courtesy: Dave Danielson ARPA -E
44 BEEST Program Targets BEEST COST <$250 RANGE >200 Cost needs to drop by 4X Current 4x $1,000 2x 100 Specific Energy needs to double System Cost (/kwh) System Energy (Wh/kg) Courtesy: Dave Danielson ARPA -E
45 Outline Battery History Liquid vs. Solid-State Batteries solid-state Li Ion Batteries Companies Battery Needs for Electric Vehicles BEEST Program Planar Energy Conclusions
46 Solid-state Batteries and Cars Clearly there is a need for high energy, high power, low mass, high cycle number batteries for automotive applications. Solid-state batteries offer the potential for High Energy (higher voltage cathodes possible) High Power (large discharge rates possible) Low Mass (less inert material) High cycle number (10X cycle life of typical Liquid) So why are they not being considered? COST
47 SOLID-STATE IS PROVEN - BUT DOES NOT SCALE $25 for a 0.001Ah battery that meets specific needs is acceptable $ Ah Courtesy: Scott Faris Planar Energy
48 SOLID-STATE IS PROVEN - BUT DOES NOT SCALE Using current thin film technology the cost of a single 1.1Ah battery would be ~$15,000 One very expensive cell phone $ Ah 1.1 Ah Courtesy: Scott Faris Planar Energy
49 SOLID-STATE IS PROVEN - BUT DOES NOT SCALE Using current thin film technology the cost of a single 20Ah battery would be $100,000 $ Ah 1.1 Ah 20 Ah A high range EV will require Ah cells Courtesy: Scott Faris Planar Energy
50 The Cost Challenge UNDERLYING PROBLEM MANUFACTURING & MATERIALS Traditional solid-state Battery Methodology Electronic Grade Material Complex Equipment Simple Integrated Device THIN FILM SOLID-STATE APPROACH Courtesy: Scott Faris Planar Energy
51 Cost Reduction Avoid semiconductor grade chemicals Develop process around inexpensive chemicals Avoid Vacuum technologies Slows Manufacturing High Capital expense Develop high throughput process e.g. roll to roll
52 Planar Energy Location: Florida Based Status: VC funded, early Prototype development Product: solid-state battery Electrolyte: LiAlGaSPO4 Capacity: 0.1Ah to 20 Ah cells Additional features: Recipient of one of the 10 ARPA E BEEST grants Unique deposition process (SPEED) High conductivity solid-state electrolyte Aggressively pursuing thick cathodes for high capacity batteries Source: Scott Faris, Planar Energy
53 Planar Energy Deposition Approach
54 In Line Scalable Batch Pilot Growth Medium: deionized water Water soluble reagents and complexing agents prevent homogeneous nucleation in solution Heated substrate promotes growth only on hydrophilic surface Result: dense nanoscale grains VP SPEED Gen 3 Courtesy Planar Energy
55 SSE Si SPEED produces self assembled coating New Composition Li Ion Conductivity 1 x 10-4 S/cm vs S/cm for LiPON TiN 7 orders of magnitude difference in ionic and electronic conductivity Rapid switching response of electrolyte Courtesy Planar Energy High Ionic Conductivity
56 Key Challenges Interfaces are always a challenge for solid-state systems Accommodation of current flow across solid-solid interfaces Thick cathodes essential for high energy cells Must reduce impedance of thick cathode materials New Deposition method and chemistries Further optimization of the SPEED process Further optimization of the new thio-lisicon
57 Products Mfg Scale Markets Goal is shipping 1-20Ah cells by 2014 Courtesy Planar Energy
58 SOLID-STATE IS PROVEN - BUT DOES NOT SCALE SPEED greatly reduces the cost of manufacturing solid-state cells. $ Ah Forecast price using SPEED $5-10 Forecast price using SPEED $ Ah 20 Ah Courtesy Planar Energy
59 BEEST Program Targets BEEST Current Planar solid-state Batteries $250/kWh 400Wh/kg COST <$250 4x $1,000 RANGE >200 2x 100 With new Electrolyte and SPEED process Planar believes it can meet the BEEST Targets with a solidstate battery System Cost (/kwh) System Energy (Wh/kg) Courtesy: Scott Faris Planar Energy
60 Conclusions Liquid based Li Ion Batteries dominate the current market Solid-state batteries offer intriguing opportunities for greatly increased cycle life, safety, and energy density To date solid-state batteries have found application primarily in small milliamp hour batteries With recent advances in electrolytes and processing technology, solid-state batteries are poised to contribute to the energy storage challenges on a much larger scale including transportation.
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