This paper describes objective technical results and analysis.

Any subjective views or opinions that might be expressed in SAND2022-7808C

the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government.

A Brief Overview of Flow Battery

Construction and Operational
Considerations
Reed Wittman, PhD
Sandia National Labs
[email protected]

Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned
subsidiary of Honeywell International Inc., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525.
Agenda

• Introduction to Flow Battery Operation

• Types of Flow batteries
 Aqueous
 Organic
 Hybrid

• Considerations for Integration and Operation

• Use Cases Comparison
• Conclusion
 Introduction to Flow Batteries

• Charged species is dissolved into

electrolyte
• Pumped from storage tanks to electrode
stacks
• Reaction takes place in the reactor stack
and products are pumped back to
storage tanks

Travis Anderson, Sandia National Laboratories, 2013

4 Key Distinctions from traditional batteries

• Charge carrying species (almost) always remains dissolved in the electrolyte

• Flow batteries flow electrolyte to and from the electrode stack during charge and
discharge
• Electrolyte pumping rates need to be balanced with pumping losses
• Leaks become a larger concern
• Energy and power of the system can be decoupled
• If you you need more energy add more electrolyte
• if you need more power add more stacks

• Low energy density systems but generally lower costs particularly at longer durations
5 Flow Battery Components: Single Cell Ghimire et al, Batteries, 2021

• Single cell is generally composed of two

porous electrodes sandwiching an ion
exchange membrane
• Electrodes are often carbon felts or paper
• Common ion exchange membrane is
nafion
• Bi-polar plates act as current collectors
and distribute electrolyte to the
electrodes
Bi-polar plate Carbon Felt Nafion Ion exchange
membrane

Fuel Cell Store

6 Flow Battery Component: Stack

• Stack is a set of cells connected in

series
• Electrolyte is pumped to each cell in
the stack
• Stacks can vary between10 and 150 Arenas et al, J. Energy Storage, 2017
cells in size
• Power rating will be a function of cell
current and the number of cells in a
stack

Chalamala et al., Proceedings of the IEEE, 2014 Ke et al., Chem. Soc. Rev, 2018
7 Flow Battery Components: Electrolyte Flow System
• Storage tanks for electrolyte
• 1MWh can require up to 20,000 Gallons of
electrolyte

• Tubing to move electrolyte to and from tanks

• Needs to be tolerant of the electrolyte used
• Needs to be sized correctly to achieve desired
flow rates

• Pumps required to move the electrolyte

• Needs to be tolerant of the electrolyte used

Emura, EESAT, 2003

Kim et al, JPS, 2013

 Flow Batteries Come in a Variety of Types

General Types System Type Pros Cons

Aqueous All soluble • No crossover contamination • Limited energy Density

Metal cations and anions • Relatively high efficiency • Relatively high cost
dissolved in acid or bases • Highly Scalable • Low thermal Stability
• Well researched and • Low operating voltage (1-1.5V)
developed

Organic All soluble • High power density • Low long term stability
Organic cations and anions • Low cost • Currently low energy density
dissolved in organic solution • Potentially high energy • Increased flammability
density • Early in development

Hybrid Insoluble and soluble charge • High energy density • Does not scale power and
species • Low cost energy density independently
Generally metal deposited on • High operating voltage (+2V) • Low efficiency
negative electrode • Well researched and • Issues with long term cycling
Usually aqueous systems developed
 General Characteristics of Aqueous Flow Batteries
Most common is Vanadium Redox in sulfuric acid
electrolyte
Power and Energy scale separately
 More power => add more electrode stacks
 More energy => add more electrolyte

System can be easily scaled to meet needs

 Systems can be self contained modules or specifically
designed for a given site

Relatively safe systems

 Thermal runaway generally not an issue
 Gas evolution needs to be monitored

Rated for long life +20 years

 Target +10,000 cycles without significant fade

Low energy density ~20-30Wh/L

Sumitomo 2MW/8MWhr Vanadium Redox Flow Battery system in San Diego, CA
10 General Characteristics of Organic Flow batteries
Similar to aqueous system however uses organic
electrolyte and charge carrying species
Power and Energy scale separately
 More power => add more electrode stacks
 More energy => add more electrolyte
System can be easily scaled to meet needs
 Systems can be self contained modules or
specifically designed for a given site
Safety has yet to be defined
 Thermal runaway and fire are possibilities
Life span has yet to be proven
 Products have rapid decay rate
Increased pumping losses
Higher energy and power density
Reduced active material cost
11 General Characteristics of Hybrid Systems

Zinc-Bromine system is the most common

type currently
Half the system store charge in solution other
half stores charge as a deposited metal
Power and Energy scale do not separately
Safety has yet to be defined
 Thermal runaway and fire are possibilities ZBB Energy Corporation

Life span varies by chemistry

 Low depth of discharge can make dendrites
 Hygiene cycles are required periodically

Higher energy and power density

Relatively low cost
Higher efficiency 10kWh Zn-Br System from Redflow
Primus Power modular Zn-Br, each
unit is 25kW/125kWh
Limitations of Flow Batteries

Low power and energy density

 Narrow voltage range
 Relatively low solubility of charge carriers
Low round trip efficiency
 60-80%
Response time varies
 0.1 sec if pumps operating
 1 min if pumps are not operating
Relatively high material cost
 Membrane
 Redox species Cost break down of a VRFB system,
Energies2016,9, 627
Long term stability of electrolyte and component materials
 Narrow operating temperature window
 Degradation of membrane and electrode materials
 Corrosion of auxiliary equipment by electrolyte
13 Integration considerations: Stack Operation
• Equivalent to a traditional battery cell
module
• Stacks generally are electrically in series
but chemically in parallel
• Flow rate and reactant distribution can
vary through stacks
• Significant imbalance between desired Kim et al, JPS, 2013
current and flow will cause side reactions
and degradation of system
• Shunt currents also need to be managed
• Where chemical reactions take place out
of cell active area
• Result of high electrolyte conductivity
creating current gradients outside the
cells
14 Integration considerations: Electrolyte management
• Electrolyte will crossover the membrane
requiring rebalancing
• In aqueous systems active species can
precipitate out of solution
• Vanadium systems in particularly are
sensitive to temperature

• Organic systems experience rapid

degradation during cycling
M.B. Lim et al., Materials
Science & Engineering, 2021

Fontmorin, Electrochem. Comm., 2021

 15 Integration Considerations: Balance Flow Rate Required with
Pumping Losses

• Flow rate dictates how much reactant is

delivered to the stack/cells which dictates
efficiency
• Higher rates of charge/discharge will required
higher flow rates to maintain efficiency
• As flow rate increases losses from the pumps
increase and may reduce overall efficiency Ma et al, JPS, 2012

• Electrolyte viscosity will vary between systems

and will influence pumping looses
• Need to consider high and low SOC efficiencies Low Low
Efficiency Efficiency

High
Efficiency
16 Integration considerations: Size/scale
• Sizing considerations will vary by system type, desired use and power/energy rating
• Non-hybrid systems generally are designed to provide 4+ hrs of storage to grid
• Require thousands to hundreds of thousands of gallons of electrolyte
• Will take up more physical space than a traditional system
• Energy and power scale independently

• Hybrid systems are often used to provide UPS to critical infrastructure or individual
buildings
• Come as modules with a set power and energy rating
• Power and energy are tied to each other
• Take up less space than non-hybrid system
 Integration considerations: Size/scale
17

Sumitomo 2MW/8MWhr vanadium Redox Flow Battery system in San

Diego, CA
10kWh Hybrid Zn-Br System from Redflow
Footprint: ~4ft2

Primus Power modular hybrid Zn-Br,

each unit is 25kW/125kWh 200MW/800MWh Mixed-Acid Vanadium Redox Flow Battery system
Footprint: ~36ft2 under construction in Dalian China
 How Traditional Batteries Scale

1 cell 35cells ~7,000cells* ~11,500cells* ~5.3 Million Cells*

11.8Wh 422.1Wh 85kWh 232kWh 80MWh
11.4W 614 W 96kW 130kW 20MW

• Adding additional energy or power requires more cells and modules

• Increases battery management costs and system complexity
• Cannot add additional capacity without increasing power and vice versa
• Makes it hard to tailor systems to specific needs particularly long term storage +4hrs

*estimate made based off of Tesla cells

How Non-Hybrid Flow Batteries Scale

From Largo Clean Energy

2 stack containers 2 stack containers 2 stack containers

144,000 Gallons of 192,000 Gallons of 240,000 Gallons of
electrolyte electrolyte electrolyte
6MWh 8MWh 10MWh
1.2MW 1.2MW 1.2MW
• Adding additional energy does not require additional cell stacks
• Battery management costs remain nominally the same
• Can add additional stacks to increase power output without need to add more electrolyte
• Can tailor system to exact demands of energy capacity and power
• Ideal for longer term storage applications +4 hours
How Non-Hybrid Flow Batteries Scale

Cell Cube product spec sheet Sumitomo product spec sheet Invinity product configuration range

• Adding additional energy does not require additional cell stacks

• Battery management costs remain nominally the same
• Can add additional stacks to increase power output without need to add more electrolyte
• Can tailor system to exact demands of energy capacity and power
• Ideal for longer term storage applications +4 hours
21 Integration considerations: Safety Varies by Type and Chemistry

• Aqueous non and hybrid flow have low thermal

runaway risk
• Gas evolution primary concern for aqueous
systems
• Hydrogen for all chemistries
• Other gases depending on electrolyte used (Cl2
from mixed-acid vanadium, Br2 from Zn-Br)

• Organic systems have unknown safety

concerns
Chalamala, B. et al. Proceedings of the IEEE, 2014.
• Leaks possible for all systems and need to be
monitored
• Scale and size make safety concerns more
significant
22 Integration considerations: Day to Day Operation and
Maintenance

Operational Equipment
• Stack efficiency vs total system efficiency • Pumps
• Electrolyte temperature • Pipes/checking for leaks
• Min and max SOC range • Stack care
• Electrode
• Min and max currents
• Membrane
• Flow rate • Electrical contacts
• Electrolyte rebalancing • Bi-polar plates

• Start up time before system is ready to • Component corrosion from interactions

provide power with electrolyte or evolved gases

• Hybrid systems require reset cycling • Component corrosion from side

periodically reactions during operation

• Gas buildup in Electrolyte tanks

 Current Development Status

Flow Batteries: Li–ion Batteries:

Varies by chemistry and type • Wide range of established types with new in
development
Few well established companies • Large number of existing vendors to purchase
cells from
~85 systems either announced or operational*
• 600+ systems announced or operation*
 800MW total power
• 2GW total power
Systems are being scaled to MW size • Developed for consumer electronics before grid
 Jumping straight from smaller systems to grid applications
scale • Many issues resolved before systems were
 Leading to growing pains with BESS and system scaled up.
scale up
 AMO just funded projects on this last fall

*Systemand power numbers are from DOE OE Global Energy storage

Database: https://www.sandia.gov/ess-ssl/global-energy-storage-
database-home/
 What is the Right Fit for Each Technology?
Storage system Target discharge Minimum
Applications
size duration cycles/year
Energy arbitrage 1 – 500 MW Up to 8 hours 250+
Renewable energy time-shift 1 kW – 500 MW 3 – 5 hours
Electric supply capacity 1 – 500 MW 2 – 6 hours 5 – 100
Load following 1 – 500 MW 2 – 4 hours
Area regulation 10 – 40 MW 15 minutes – 1 hour 250 – 10,000
Operating reserve (spinning, non-
spinning, and supplementary) 10 – 100 MW 15 minutes – 1 hour 20 – 50

Voltage support 1 – 10 MVAR 15 minutes – 1 hour N/A

Black start 5 – 50 MW 15 minutes – 1 hour 10 – 20
Load following, ramping support for
renewables 1 – 100 MW 15 minutes – 1 hour N/A

Transmission upgrade deferral 10 – 100 MW 2 – 8 hours 10 – 50

Transmission congestion relief 1 – 100 MW 1 – 4 hours 50 – 100
Transmission stability damping
control 10 – 100 MW 5 seconds – 2 hours 20 – 100

Distribution upgrade deferral and

voltage support 500 kW – 10 MW 1 – 4 hours 50 – 100

Reliability and resilience 0.2 kW – 10 MW 5 minutes – 1 hour

Power quality
100 kW – 10 MW 10 seconds – 15 minutes 10 – 200

Time-of-use energy cost

management 1 kW – 1 MW 1 – 6 hours 50 – 250

Demand charge management 50 kW – 10 MW 1 – 4 hours 50 – 500

Alvaro Bastos, https://www.sandia.gov/ess-ssl/global-energy-storage-database-home/

Albertus et al., Joule 4, 21-32, January 15, 2020

How Might Flow Batteries Work on the Grid?

Use case for hybrid VRFB and Li-ion system planned

for Energy Superhub Oxford

From Invinity Energy Systems

 Conclusions
• Flow batteries are unique energy storage technologies that require new
considerations for operation
• They have lower power and energy density compared to other systems
• Flow batteries can scale energy storage capacity with ease making them attractive
for longer duration storage needs +4 hours
• Integration of flow batteries to the grid need to consider a number of things
traditional batteries do not have
• Flow system (Pumps, and piping)
• Electrolyte health
• Integrated stack of cells
• Balance pumping losses with flow rate
• Scaling of system to desired application

• IEEE standard P1679.3 has more information, currently being revised

If you have any questions please reach out at: [email protected]

Comparison Performance and Cost Characteristics

Energy Lifetime Number of Round trip Self Duration of $/KWh $/kW

Density (Years) cycles Efficiency Discharge discharge
(Wh/L)
VRFB 16-35 20+ 15,000+ 60-80% Near 0 4+ Hours 121-810 486-1,215

Li-ion 150-250 10 5,000 90% .1-5% Min to 4hr 486-3,078 729-3,240

per month
Lead- 80-90 12 1,300 77% ~5% per 30sec to 2hr 521-643 1,042 – 1,286
Acid month

• VRFBs are relatively low power and energy density storage devices
• Setup for long duration charge and discharge cycles
• Long cycle and calendar life help make total life time cost relatively low