Redox Flow Batteries for Grid Scale Energy Storage.€¦ · Redox Flow Batteries for Grid Scale...

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Redox Flow Batteries for Grid Scale Energy Storage.

Energy Storage

Vincent SprenklePacific Northwest National Laboratory

August 15, 2017

Energy Exchange: Connect • Collaborate • Conserve2

Challenge for Grid Scale Energy Storage

The value(s) energy storage provides

The ownership cost of the energy storage system over its lifetime

Improving the cost-benefit relationship of energy storage

Energy Exchange: Connect • Collaborate • Conserve

• Grid Scale Energy Storage requires longer cycle life than EV systems

• Grid Scale Energy requires deeper discharge to serve multiple grid applications

• Lithium ion best suited to meet transportation and grid power requirements

• Many chemistries can compete for grid-scale applications

Challenge 1: Reduce Energy Storage Cost

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BATT500

Syst

em C

apita

l Pric

e ($

/kW

h)

# Deep Cycles

EV 2022

1Energy Storage Systems Cost: GTM/ESA US Energy Storage Monitor: Q2 2016

Lead-acid

Li-ion

NaS

LFP

Redox Flow Battery

2030 Stationary Storage Target

Transportation Targets

3-8 X reduction in lifecycle cost required to address multiple grid

storage applications


Challenge - Over 300O utilities Different grid reliability, resiliency, flexibility, renewable integration

challenges Different Market Structure Different cost of electricity Other competing solution approaches besides energy storage

What is needed Requires regional and local analysis of deployed storage technologies

in diverse markets to develop full understanding of monetized and unmonetized benefits

Development of industry standard design tools with fidelity to capture the multi-use value of storage in transmission, distribution, and behind the meter applications.

New business models

Challenge 2: Monetizing Energy Storage Benefits for Multiple Grid Applications

Office of Electricity Delivery and Energy Reliability 5

Strategic Goal:

Mission: To enable energy storage to provide multiple benefits for critical grid applications, DOE is accelerating adoption of energy storage through: improving the technology, field demonstrations, and innovative market design.

Challenges:• Cost competitive energy

storage technologies– Targeted scientific investigations

of key materials and systems

• Validated reliability & safety– Independent testing of

prototypic devices and understanding of degradation.

• Equitable regulatory environment– Enable Industry, Utility,

Developer collaborations to quantify benefits provide input to regulators.

• Industry acceptance – Highly leverage field

demonstrations and development of storage system design tools

Smart Grid

Resiliency

Reliability

Renewables IntegrationAsset Utilization

EV deployment

DOE OE Energy Storage Program


Vanadium Redox Flow Battery

IT Sodium Metal Halide Batteries

Aqueous Soluble Organic RFBsSafety Standards

ESS Performance Protocols

Component Cost Analysis

PNNL – OE Energy Storage Program Activities that support these Challenges

Cost Competitive Technologies

• Mixed acid increases Top by 80%, energy density 70%.

• Additives for sulfate V/V shows similar Top

• 5X stack power without decreasing efficiency

• At higher performance levels, Vanadium 55% of cost.

• Developing engineered molecules that can be drop in replacement for V/V systems

• Decreased Top from 350°C to 190°C improving lifetime.

• DOE-KETEP MOU to leverage PNNL IT chemistry with RIST/POSCO scale-up efforts.

Sodium-ion Batteries• Analog to Li-ion utilizing existing

production capabilities.• Offers potential for longer cycle-life and

lower cost.

Storage use-case analysis• 7MW/15MWh - WA CEF I • EWEB – Eugene, OR (w/ Sandia)• MA DOER - Northampton, MA• WA CEF II (AVISTA, OPALCO) GMLC –

PGE (Salem, OR), GMP (Rutland, VT), EPB (Chattanooga, TN), LMC (Los Alamos, NM)

• Leading OE Safety Codes and Standards Working Group• CSR 101• CSR Inventory • ESS Compliance Guide

• Rev 2 released April - 2016• 8 performance metrics developed for

ESS Applications.• International adoption TEC 120• Basis for new standards from NEMA,

IEE.

Regulatory Support• PNW PUC Workshop July - 2015• Supporting WA and OR dockets on ESS

Market Acceptance


Redox Flow Battery#


Power and Energy are separate enabling greater flexibility and safety. Suitable for wide range of applications 10’s MW to ~ 5 kw Wide range of chemistries available.

Redox Flow Batteries

#

Key Aspects


Grid Energy Storage Diverse Markets Encourage Bundling and Cost Reduction.

EPRI – Electric Energy Storage Technology Options: A Primer on Applications, Costs & Benefits (2010)

PNNL-23040 Assessment of EnergyStorage Alternatives in the Puget Sound Energy System


• Want energy storage systems that can provide for both:– Fast response balancing services and– Longer duration (2+ hr) deferral and outage mitigation.

Bundled Services: High degree of Flexibility needed from Energy Storage?

Energy price ($/MWh)

Arbitrage only

Arbitrage + Balancing

Arbitrage + Balancing + T&D deferral

Pow

er o

utpu

t (M

W)

Arbitrage + Balancing + T&D deferral + volt/var

PNNL-23040 Assessment of EnergyStorage Alternatives in the Puget Sound Energy System


RFB - Major Challenges

11

Low energy density Large form factor/footprint Limited application

Limited electrolyte stability Capacity decay during cycling Cost

Zhenguo Yang, et. al. Chemical Reviews, 111, 3577, 2011Wei Wang, et. al. Adv. Funct. Mater., , 23, 970, 2013


-1.0 -0.5 0.0 0.5 1.0 1.5 2.0

Standard potential (V) of redox couples

V3+/V2+VO2

+/VO2+

VO2+/V3+

Fe3+/Fe2+

Mn3+/Mn2+

MnO4-/MnO2

Ce4+/Ce3+

Co3+/Co2+

Cu2+/Cu+

TiOH3+/Ti3+

Ti3+/Ti2+

Cr3+/Cr2+

Zn2+/Zn

S/S2-

Br2/Br-

BrCl2-/Br-

Cr5+/Cr4+

Cl2/Cl-

Eo=1.26V

Eo=1.85V

Redox Flow chemistriesOthers:V2+/V3+ vs. Br-/ClBr2

-; Ce4+/Ce3+ vs. V2+/V3+;Fe3+/Fe2+ vs. Br2/Br-;Mn2+/Mn3+ vs. Br2/Br-;Fe3+/Fe2+ vs. Ti2+/Ti4+, …

ZBB: Br-/Br2- vs. Zn2+/Zn

ICB: Fe3+/Fe2+ vs. Cr3+/ Cr2+

VRB: V2+/V3+ vs. VO2+/VO2+

PSB: Br2/Br- vs. S/S2-

Up to 100 kw or multi-MW demonstrated

H2Evolution

O2Evolution


RFB - Early Development

Fe2+ Fe3+ + e–

Cr2+ Cr3+ + e–

Open Circuit Potential (OCP) 1.2 V

significant crossover

requires electrocatalyst


All-Vanadium Flow Battery

V2+

V3+ + e–

crossover is less of an issue

Nafion® membrane

temperature sensitivity

low vanadium concentration/low energy density

graphite

Open Circuit Potential (OCP) 1.5 V

electrolytes influence temperature stability and vanadium concentration

carbon felt


V/V Mixed Acid Redox Flow Battery#


New vanadium chemistry based on SO2-/Cl- electrolytes

Mixed-acids All Vanadium Redox Flow Battery (VRB)

Conventional Sulfate VRB

Mixed AcidVRB


Redox Flow Battery R&D Objectives

Develop the technologies, tools, and system understanding required to move the mixed acid electrolyte chemistry from basic chemistry to cost effective system solution.

Redo

x Sy

stem

Cos

ts

Perf

orm

ance


VRFB 5kW Performance

Stack

Test Parameters

• 780 cm2

• 1-20 cell stacks• 15-85% SOC• Mixed acid electrolyte

• 2M V, 2M S, 5M Cl• Nafion membrane

• 212 (~ 2 mil)• j = 160 -320 mA/cm2

• Modified interdigitated flow design

• 5 KW stack• Chillers to control temperature


Improved Stack Performance can lower parasitic losses

Carbon Felt Electrode

Bipolar Plate

Membrane

Bipolar Plate

Membrane

Bipolar Plate

(Graphite/PP)Outlet

ChannelInlet

Channel


Bipolar Plate

Membrane

Bipolar PlateOutlet

ChannelInlet

Channel



(IDD 1) (IDD 2)(FTD)

SGL TF6Graphite sheet

SGL PPG 86Graphite/PP

PVC

Fram

e

PVC

Fram

e

PVC

Fram

e

Carbon Felt

Flow direction


Comparison of ID Designs – 320 mA/cm2

IDD 1 IDD 2s

• IDD 2s design attains a higher capacity at a given cut off window.• IDD 1 has a much higher charge/discharge overpotential at a lower capacity


Develop material and system enhancements to resolve key cost and performance challenges for energy storage devices.

goal

5X increase in power density since start of program while improving energy efficiency at targeted condition.

Vanadium Cost

Mixed Acid VRFB Performance


Can Flow Batteries provide Frequency Regulation Services?

*DC only

FR duty cycle determined from PJM balancing signal for year 2011

Signals grouped into low, average and high standard deviations

Representative 2-hour intervals with average standard deviation and 2-hour intervals with high standard deviation chosen

• each being energy neutral

Duty cycle consisted of three 2-hour average standard deviation (SD) signals followed by one 2-hour high SD signals, three 2-hour average standard deviation (SD) signals followed by one 2-hour high SD signals and four 2-hour average SD signals

21 cell VRFB stack under Frequency Regulation protocol


Remaining Challenges - Cost Reduction#


Gritsevski and Nakicenovic, Energy Policy 28 (2000) 907-921

24

Technology Learning rates

• Learning rate (LR) is defined as the % drop in cost as production volume doubles.

• Based on previous development of PV, windmills and gas turbines

• Learning rate of -20% during early stage development/commercialization.

• - 10% LR for full scale manufacturing.


Redox Flow and Li-ion Battery Price Projections

Flow2014 - $1200 - 1500/kWh2017 - $600-$800/kWh

LR > 25%

Li-Ion $1200/kWh in 2011 based on ~ 1 GWh in EV/PHEV sales

Li-ion First commercialized 1991

~ 15% LR 2011-2015 all EV/PHEV

• $1200/kWh in 2011 – 1.06 GWh1

• 2014 – projected 7.5 GWh1,2

• ~15% LR

• 2014 – Actual ~ 9 GWh4

To maintain 15% LR requires 27.6 GWhin 2015

Stationary storage market:

• 6.6 GWh by 20253

1. Technology Roadmap, Electric and plug-in electric vehicles, IEA, Updated June 20112. Electric and plug-in hybrid vehicle roadmap, IEA, 20103. Source for stationary storage projected production rates: http://cleantechnica.com/2014/08/26/energy-

storage-market-rises-50-billion-2020-according-lux-research/4. http://evobsession.com/ev-battery-manufacturer-sales-market-share-march-2015/

Redox• @ 20 - 25% LR for redox, can achieve ~ $500 kWh with 4

GWh of installed capacity.

http://cleantechnica.com/2014/08/26/energy-storage-market-rises-50-billion-2020-according-lux-research/

http://evobsession.com/ev-battery-manufacturer-sales-market-share-march-2015/


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2010 2011 2012 2013 2014 2015 2016

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August 22, 2017

Chemicals36%

PCS10%

Felt8%

Membrane33%

80 mA/cm2

$465/kWhr

Chemicals

51%PCS13%

240 mA/cm2

$347/kWhr

Chemicals

55%

400 mA/cm2

$275/kWhr

Where to Next with Redox Flow Systems

26


Advantage: Low-cost redox couple; Low-cost supporting

electrolyte; No resource constraints; Less corrosive and toxic.

A Total Organic Aqueous Redox Flow Battery


Conclusions

The flexibility of redox flow battery technology offers the potential to capture multiple value streams from a single storage device.

Current research has demonstrated high power conditions can be achieved with minimal impact in stack efficiency.

Next generation RFB technology based on Aqueous Soluble Organics (ASO) being developed to replace vanadium species.

Continued cost reductions in Li-ion technology will be driven by EV/PHEV deployments. RFB maybe able to achieve similar cost targets at ~ 100X lower production volume.


Acknowledgements

Support from US DOE Office of Electricity Delivery & Energy Reliability - Dr. Imre Gyuk, Energy Storage Program Manager

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