novel low cost / high performance nacl – metallic …...novel low cost / high performance nacl –...
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NovelLow Cost / High Performance NaCl – Metallic Sodium Batteries
BroadBit Batteries Oy
April 2018
BroadBit Batteries Confidential and proprietary
BroadBit Batteries Oy
• In development since 2011 with U. of Alicante
• Spun-off from BroadBit Energy Technologies 2015
• First patent granted 2016, many more filed and pending
• Four full-time employees, three of which are PhDs
• Owned by management and private investors
Pioneer in discharge state assembled metallic sodium
batteries
BroadBit Batteries Confidential and proprietary
Summary of BroadBit’s Unique Selling Points
• Higher energy density Gen 1 18650 ~300 Wh/kg possible (Gen 2 ~400 Wh/kg possible)
• Wider operating temperature range
-20C to +60C proven (-30 to +75C possible)
• Safer and simpler to operate
Non-flammable electrolyte, no risk of overcharging, discharged storable
• Lower cost
Cheap, abundant materials, low purity requirements, simple, cheap mfg.
• Can use existing Li-ion production and use infrastructure
BroadBit Batteries Confidential and proprietary
BroadBit’s technical capabilities
• Custom over-pressure resistant test cells for coin and cylindrical cell development
• Nitrogen glove-box, electrochemical characterization and cell preparation tools (incl. cathodes, electrolytes, assembly)
• Electronics / software for massively parallel cell cycle testing in development
• Ramping up small-scale 18650 cylinder cell and roll-to-roll cathode production with partners
BroadBit Batteries Confidential and proprietary
History of metallic anodes in batteries
• Metallic Li anodes long used for primary cells:• Li-manganese dioxide: (MnO2)• Li-thionyl chloride: (SOCl2)• Li-sulfuryl chloride: (SO2Cl2)
• Li-sulfur dioxide: (SO2)
• Chemistries have energy densities between 250-700 Wh/kg
• Rechargeable batteries need reversible charging without dendrites (never achieved with thick metallic lithium-anodes)
BroadBit has achieved this with sodium BroadBit Batteries Confidential and proprietary
• Low tendency to form dendrites• Cheap and widely available• High capacity (1100 mAh/g)• High anode potential (only 0.3 V less than lithium)
• High cell voltage
(with BroadBit’s high-voltage cathode)
4V average cell voltage achieved
• Cell-level bottleneck is cathode capacity (Additional metallic lithium anode capacity gives little improvement in cell-level capacity)
Why metallic sodium anodes?
BroadBit Batteries Confidential and proprietary
Average discharge voltage vs.cycle number
BroadBit’s Gen 1 high-energy sodium battery
• Metallic sodium deposited from NaCl salt crystals onto bare current collector (dendrite free over proprietary substrate)
• No NaCl in cathode when fully charged
• No Na in anode when fully discharged
• Assembled fully discharged
• Highly conductive SO2 based catholyte
(60-80 mS/cm vs. <20 for Li-ion)
BroadBit Batteries Confidential and proprietary
BroadBit’s Gen 1 high-energy sodium battery
• Metallic sodium deposited from NaCl salt crystals onto bare current collector (dendrite free over proprietary substrate)
• No NaCl in cathode when fully charged
• No Na in anode when fully discharged
• Assembled fully discharged
• Highly conductive SO2 based catholyte
(60-80 mS/cm vs. <20 for Li-ion)
BroadBit Batteries Confidential and proprietary
460 mAh/g
1100 mAh/g
2200 mAh/g
Anode
Separator
Na+Na NaCl
NaClNa+Na
Anode
Separator
Na+ Na
NaNa+
Na
Na
Na = Elemental (Metallic) Sodium Na+ = Sodium Ion (in solution) NaCl = Sodium Chloride (crystal)
Sodium-ion batteries use
intercalation to store charge
BroadBit uses electrodeposition &
crystallization to store charge
= Charge = Discharge
~100 Wh/kgFlammable
~300 Wh/kgNon-Flammable
BroadBit’s sodium battery is fundamentally NOT sodium ion
Cath
ode
Cath
ode
Separator
Na+Na NaCl
NaClNa+Na
Separator
Na+ Na
NaNa+
Na
Na
Na = Elemental (Metallic) Sodium Na+ = Sodium Ion (in solution) NaCl = Sodium Chloride (crystal)
Saltwater batteries use
H2O as the electrolyte solvent
BroadBit uses electrodeposition &
crystallization to store charge
= Charge = Discharge
~50 Wh/kg10 hr to charge
~300 Wh/kg0.5 hr to charge
BroadBit’s sodium battery is fundamentally NOT saltwater
Anode
Cath
ode
Anode
Cath
ode
Cath
ode
Separator
Na+Na NaCl
NaClNa+Na
Na = Elemental (Metallic) Sodium Na+ = Sodium Ion (in solution) NaCl = Sodium Chloride (crystal)
BroadBit uses electrodeposition &
crystallization to store charge
= Charge = Discharge
~300 Wh/kg-20C - +60C operating range
BroadBit’s sodium battery is fundamentally NOT molten salt
Cath
ode
Separator
M+ M
MM+
M
M
Molten salt batteries use
melted salt* as the electrolyteM
olt
en M
et a
l M
Molt
en A
l loy M
-N
~300 Wh/kg>300 C operating range
* as in “an ionic compound”
Anode
Anode
BroadBit’s unique cost efficiency
Cheap, abundant, scalable and sustainable raw materials
Simpler dry cathode process
Simpler, cheaper separator
No anode production process
Thick electrode structure
Produced & assembled in air
Combining the above + high energy density = major reduction in cell mfg. costs and $/kWh
BroadBit Batteries Confidential and proprietary
Simpler Cathode Process
No Anode Process
• Demonstrated cells with 100-200 cycle lifetimes
• Near-theoretical discharge capacity (250 mAh/g
of active material) is achieved, along with highly
stable cycling
• Round-trip energy efficiency 70-80%
• 2x energy density with respect to active material
weight than Li-ion technology
Coin cell cycling
Dis
charg
e
Volt
age (
V)
Dis
charg
e
Capaci
ty (
mA
h/g
)
C/5 charging ratecharging up to the nominal capacity
Tolerance to low temperature
Charge-discharge cycle at 20 Celsius Charge-discharge cycle at 0 CelsiusV
olt
ag
e (
V)
Volt
ag
e (
V)
Capacity (mAh) Capacity (mAh)
BroadBit’s Hi-Energy battery specs
• Cathode: Stable 2200 mAh/g (with respect to carbon framework) 70% active material, 30% conductive additive & binder Cathode + catholyte capacity: 270 mAh/g
• Anode: Solid metallic sodium (1100 mAh/g)
• Voltage: Up to 4V average discharge voltage (Max 4.2V, min 2.0V)
• Combined structural-level energy density: Theory: 450 Wh/kg ( 870 Wh/l) @ 3 hr cycling → 365 Wh/kg (700 Wh/l) @ 18650 cell level Current*: 390 Wh/kg ( 780 Wh/l) @ 10 hr cycling → 300 Wh/kg (600 Wh/l) @ 18650 cell level
* extrapolated from coin cell data
Discharge State Assembly (Gen 1 Hi-E chemistry)
BroadBit Batteries Confidential and proprietary
18650 Cell level energy density
High-energy coin cell cycling
Dis
charg
ing
volt
ag
e (
V)
Ch
arg
ing
volt
ag
e (
V)
Charge-discharge voltages (cycle 97) evolution of discharge voltages and capacity at C/10
BroadBit Batteries Confidential and proprietary
Up to 2C charge / discharge possible
100
0
50
Fractional %
High-energy coin cell cycling
Dis
charg
ing
volt
ag
e (
V)
Ch
arg
ing
volt
ag
e (
V)
Charge-discharge voltages (cycle 97) evolution of discharge voltages and capacity at C/10
BroadBit Batteries Confidential and proprietary
Up to 2C charge / discharge possible
100
0
50
Fractional %
BroadBit’s high-energy coin cell cycling
En
erg
y E
fci
en
cy
(%)
NaC
l usa
ge
(% o
f th
eore
tica
l)
Near-theoretical (~90%) NaCl capacity achieved
40-50 cycle formation period 200 cycles demonstrated
Cells cycled at C/3 rate, charging up to nominal NaCl capacity
BroadBit Batteries Confidential and proprietary
BroadBit’s high-energy coin cell cycling
En
erg
y E
fci
en
cy
(%)
Maintenance cycles
NaC
l usa
ge
(% o
f th
eore
tica
l)
Near-theoretical (~90%) NaCl capacity achieved
40-50 cycle formation period 200 cycles demonstrated Can be “revitalized” with occasional
full discharge maintenance cycles Batteries can be stored in fully
discharged state indefinitely
Cells cycled at C/3 rate, charging up to nominal NaCl capacity
Maintenance cycles
BroadBit Batteries Confidential and proprietary
BroadBit’s Next Gen Hi-Energy battery specs
• Cathode: Stable 2200 mAh/g (with respect to Carbon framework) 70% active material, 30% conductive additive & binder Cathode + catholyte capacity: 270 mAh/g
• Anode: Solid metallic Sodium Structural capacity: 1100 mAh/g
• Voltage: 3.7 V average discharge voltage (Max 4.2 V, min 2.0 V)
• Combined structural-level energy density: Theory: 800 Wh/kg (1200 Wh/l) @ 3 hr cycling → 645 Wh/kg (1200 Wh/l) @ 18650 cell level Current*: 410 Wh/kg ( 790 Wh/l) @ 10 hr cycling → 330 Wh/kg ( 600 Wh/l) @ 18659 cell level
* extrapolated from coin cell data
Charge State Assembly (Gen 2 Hi-E chemistry)
BroadBit Batteries Confidential and proprietary
18650 Cell level energy density
Cylindrical Cell Production
Spiral in rolling machine Spiral ready for anode tab weld
Spiral complete Test cell ready for fill Filled & sealed 18650 cell
BroadBit Batteries Confidential and proprietary
1st 18650 Cell
Time (hr:min:sed)
Vo
lts
(V)
BroadBit Batteries Confidential and proprietary
BroadBit has successfully scaled from coin to spiral cells
Volt
age (
V) • Tools and processes for scalable electrode production and cell assembly validated
• Spiral cell behavior corresponds to coin cell
• Improved NaCl usage observedTime
N
aC
l usa
ge
(%
of
theore
tica
l)
Cycle
Current focus to modify anode and demonstrate Gen 1 high energy density 18650 cellsShort term target is 200 Wh/kg cells. Production target is 300 Wh/kg (18650 cell level)
• Spiral
• Coin
BroadBit Batteries Confidential and proprietary
BroadBit can use standard Li-Ion infrastructure
Standard USB power source
Standard Li-Ion charger chip
Standard 18650 cell flashlights
Standard 18650 cells (size, voltage and current)
First product demos
The Kapsch CEN DSRC / GNSS hybrid on-board units (OBUs) are the in-vehicle parts of the Kapsch TrafficCom Satellite Tolling system designed to facilitate distance based road charging schemes. The DSRC interface can be used to communicate with the vehicle from mobile or fixed compliance checking facilities.
BroadBit Batteries – Kapsch demo at the
ITS-World Congress 2017
BroadBit Gen-1 Hi-Energy 18650 Cell in a Kapsch On-Board Unit
Remaining obstacles to reaching energy density targets
300 Wh/kg (18650 cells, Gen 1 Hi-E chemistry) • Optimize: Ratio between anode, cathode, separator thicknesses
Separator / current collector design
Cathode NaCl concentration
Cycling algorithm
• Establish repeatable/controllable large area cathode production• Improve packaging: Wind cells tighter, remove dead spaces, etc.
400 Wh/kg (21700 cells, Gen 2 Hi-E chemistry) • All of the above +• Establish repeatable/controllable pre-sodiated anode production
BroadBit Batteries Confidential and proprietary
BroadBit’s Hi-Endurance battery specs
• Cathode: Stable 150 mAh/g (with respect to active material) 85% active material, 15% conductive additive & binder Cathode + catholyte capacity: 270 mAh/g
• Anode: Solid metallic Sodium Structural capacity: 1100 mAh/g
• Voltage: 3.35 V average discharge voltage (Max 3.6 V, min 3.2 V)
• Combined cell-level energy density: 140 Wh/kg ( 220 Wh/l) @ 18650 cell 175 Wh/kg ( 270 Wh/l) @ larger cell
Discharge State Assembly (Gen 1.5 chemistry)
BroadBit Batteries Confidential and proprietary
BroadBit Batteries Confidential and proprietary
New robust/high endurance cathode
New robust/high endurance cell(operated in high-efficiency mode 140 Wh/kg)
Cou
lom
bic
Ef
cien
cy
(%)
Cap
aci
ty R
ete
nti
on
(%
)Stable capacity
High efficiency
Low self discharge
48 hrs
0.09%
Cell
Volt
ag
e
(V)
Cell
Volt
ag
e
(V)
Stable Voltage
Cycle #Cycle #
Cycle #
New robust/high endurance cell(operated in high-energy mode 210 Wh/kg)
Cou
lom
bic
Ef
cien
cy
(%)
Cap
aci
ty R
ete
nti
on
(%
)Stable capacity
Medium efficiency
Cell
Volt
ag
e
(V)
Cell
Volt
ag
e
(V)
Stable Voltage
Cycle #Cycle #
Cycle #
Summary
• Novel Hi-Performance, Low-Cost sodium battery proven in coin cells
– Hi-Energy:
• Gen 1 18650: >300 Wh/kg, Gen 2 18650: > 400 Wh/kg
– Hi-Endurance:
• Hi-Efficiency 18650: >140 Wh/kg, Hi-Energy 18650: > 210 Wh/kg
– -20 C to +60 C operational temperature range, non-flammable
– Plug and replace for Li-ion in terms of voltage and charging
– Target mass production price below 70$/kWh
• Optimizing structure & chemistry reach demoed 18650 performance
• Preparing for small scale production in Q1 2019
BroadBit Batteries Confidential and proprietary
Runar Backstrom Grant
Cleantech Award MILstartup Award
Award
Cleantech Award Green Award
Top 30
Top 20
Factory1 Accelerator
WinnerWinnerContact: David Brown, PhD
Never run outB a t t e r i e s
2016T O P 1 0
Winner