Novel Low Cost / High Performance NaCl – Metallic …...Novel Low Cost / High Performance NaCl – Metallic Sodium Batteries BroadBit Batteries Oy April 2018 BroadBit Batteries Confidential

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


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’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


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?


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’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)


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


Saltwater batteries use

H2O as the electrolyte solvent




~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





~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


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)


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


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


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’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’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)


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


1st 18650 Cell

Time (hr:min:sed)

Vo

lts

(V)


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 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’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)



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


Runar Backstrom Grant

Cleantech Award MILstartup Award

Award

Cleantech Award Green Award

Top 30

Top 20

Factory1 Accelerator

WinnerWinnerContact: David Brown, PhD

[email protected]

Never run outB a t t e r i e s

2016T O P 1 0

Winner

Documents

Novel Low Cost / High Performance NaCl – Metallic …...Novel Low Cost / High Performance NaCl – Metallic Sodium Batteries BroadBit Batteries Oy April 2018 BroadBit Batteries Confidential