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LG Fuel Cell Systems Program and Technology Update

2015 SOFC Workshop, 14 July 2015Zhien Liu and Cris DeBellis

LG data

Outline 200kW scale demonstration test Cell degradation understanding and mitigation

Primary sources of degradation Improvements for entrance-into-service (EIS) technology

Optimization of LSM-based cathode Single layer anode

Lower ASR cell technology Broad changes of active layers and design for near-

term product Evaluating nickelate cathodes for longer-term

objective

LG data

LG Fuel Cell System Inc. 3

Building on a Solid Foundation

LG data

LGFCS Integrated String Test (IST)

Testing began June 2015 Pipeline natural gas to grid connection 200kW-class pressurized SOFC system Demonstrates functionality of integrated

subsystems: Fuel processing Pressurized SOFC vessel Turbogenerator assembly Power electronics Controls and safety system

Utilizes cell technology developed under LGFCS DOE SECA programs

LG data

Block Performance Testing Prior to the IST UK test rig modified to test block design of IST

Rig accommodates 1 to 3 blocks Design point ASR of 0.32 ohm-cm2 at block midpoint 860C demonstrated

on DSNG 62% anode loop efficiency 78% fuel utilization Block ∆T ~80C

5

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0.50

810 820 830 840 850 860 870 880 890 900 910

Strip

Avg

ASR

, ohm

-cm

2

Temperature, ºC

T1503 (CH4) 22-Apr-15 23:25:19

T1503 (DSNG) 23-Apr-15 13:59:30

LG data

Performance of IST-stage (epsilon) Technology 60 Strips manufactured

Performance and/or OCV quality check of each strip IST block ASR matches single block and expectations from strip

performance QA data LGFCS IP-SOFC ASR similar at scales ranging from penta cell,

bundle, strip, multi-block (150,000x scale up)

6

Strip ASR (1 bar, 860ºC, half load)Average = 0.37 ohm-cm2 @ 860ºCExpected at IST conditions = 0.34 ohm-cm2

0.3920.3840.3760.3680.3600.352

Strip ASR

LSL Target USL

Strip Pass Off Test Results

Block ASR (IST conditions)Average = 0.35 ohm-cm2 @ 860ºC

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810 830 850 870 890 910

Blo

ck A

vera

ge A

SR, o

hm-c

m2

Block Temperature, °C

FCV2 Integrated String Test T1603: Block ASR vs Temperature

FCV2 System Test

T1503 (Single Block on DSNG)

Penta-Cell Average

6/22/15 22:53

LG data

7Natural Gas Variability is Important Factor in System Design

High C2+ Hydrocarbons, v-%: 8.1 - 9.2

Increased risk for carbon fouling in fuel cell NG Contaminants

Total S, ppm-v: 0.3 - 1.5 Sulfur Species, Av. ppm-v: THT 0.32; Et2S 0.14; EtMeS 0.05; Me2S 0.19; Me2S2

0.04; t-BuSH 0.11 Moisture, ppm-v: 300-1000

Selective catalytic sulfur oxidation (SCSO) not affected; passive sorbents impacted

Area Methane Ethane Propane C4+ Nitrogen Carbon

DioxideSpecific Gravity

Wobbe Index

(BTU/ft3)

Gross HV (Dry), BTU/ft3

North Canton 89.6 7.97 0.53 0.28 0.889 0.720 0.615 1367.6 1072.2

US 2013* 95.3 2.79 0.29 0.08 0.582 0.864 0.586 1344.6 1030.7

US 1992* 93.0 3.21 0.66 0.32 1.803 0.845 0.599 1328.8 1027.9

*GTI Surveys

North Canton Natural Gas Variability(October 2014 – May 2015)

LG data

Outline 200kW scale demonstration test Cell degradation understanding and mitigation

Primary sources of degradation Improvements for entrance-into-service (EIS) technology

Optimization of LSM-based cathode Single layer anode

Lower ASR Broad changes of active layers and design for near-

term product Evaluating nickelate cathodes for longer-term

objective

LG data

Degradation Rate Deconvolution - Epsilon technology used in 200 kW IST Test

9

800C: 8,000 – 16,000 hrs 900-925C: 2,500 – 16,000 hrs

Epsilon technology was frozen in 2012 for IST test Lower degradation at low end temperature of block operation Cathode degradation is dominant at high end temperature of block

operation Current status: 13.5 mohm-cm2/1000 hr across block temperatures

(Power deg: 0.55%/1000 h)ASR change:11.0 mohm-cm2/1000 h

(Power deg: 1.18%/1000 h)ASR change:16.1 mohm-cm2/1000 h

LG data

Key Degradation Mechanisms for Cathode

Free MnOx formation and accumulation Cathode densification Chromium contamination Second phase formation was identified near

electrolyte interface after high temperature operation

Three revised LSM-based cathode formulations under evaluation for improved durability

10

LG data

Free MnOx distribution for Epsilon LSM cathodes Mn/La ratio in bulk cathode showed constant level as a

function of operation time. Mn/La ratio at cathode/electrolyte interface increases with time.

11

•Bulk cathode •Cath/Ele interface

Mn/La ratio from EDS analysis

LG data

EIS Cathode Shows Less MnOx Rich Near Cathode/Electrolyte Interface

12

•Cath/Ele interface

EIS cathode has low and stable Mn content near cathode /electrolyte interface up to 8,000 hrs of operation

LG data

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0.35

0 200 400 600 800 1000

ASR

s, Ω

-cm

2

Elapsed Time, hours

Cell ASR - SCT6-149_4x

A1: Ep cathodeA2: EIS1 cathodeB2: EIS2 cathodeB1: EIS3(U) cathode

10% O2 - wet

Anode: bundle inlet fuel

EIS2

Epsilon EIS1

EIS3

EIS Cathode Demonstrated Improved Resistance against Densification during Operation

Footer

At normal operating conditions, densification starts to show up at 8,000 hrs Under accelerated testing conditions, initial densification of epsilon

cathode was observed at 500 hrs. Selected EIS cathode shows more microstructural stability.

Accelerated Test Conditions

LG data

PCT208B2: tested at 925oC for 11,500hr

Second Phase Identified in LSM Cathodes Near Electrolyte Interface

Second phase formed near cathode/electrolyte interface after long term operation at 925oC

La-Zr rich phase No La-rich phase at 800oC Maximum block temperature to be

reduced with in-block reforming

14

PCT89B: 800oC/16,000hr

Epsilon

Epsilon EIS1

•Ele

ctro

lyte

•[PCT189A2]

•La-rich

•Mn-rich

•Mn•LSM

•La

•Zr (YSZ)

PCT189A2: tested at 925oC for 16,000hr

Epsilon

LG data

Understanding Cr Effect on Cathode Performance is One of Key Activities

15

More Cr deposition at cath/Ele interface in strip 1 (inlet) of block testing Cr deposition in bulk cathode and CCC shows no trend vs position Accelerated button cell test to understand Cr effect

Inlet Outlet

Button cell set-up for Cr test

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0 200 400 600 800 1000 1200

Tota

l Rp

(AN

+ C

A) /o

hm-c

m^2

Time (hr)

Ep cathode witout Cr EIS1 without CrEIS2 without Cr EIS1 with CrEIS2 with Cr EIS3 with Cr

w/o Cr source

w/ Cr source

T1314(3,000 hrs)

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0 200 400 600 800 1000 1200

Tota

l Rs /

ohm

-cm

^2

Time (hr)

Ep cathode witout Cr EIS1 without CrEIS2 without Cr EIS1 with CrEIS2 with Cr EIS3 with Cr

w/o Cr

w/ Cr

Epsilon

LG data

Only change from epsilon cell technology was the cathode and PIC material

Average bundle degradation rate at 860oC: 6.0 mohm-cm2/1000 hrs Projects to a 3.0 year life across block temp.

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ASR

, ohm

-cm

2

Elapsed Time, hours

Bundle ASR: ATBT3/6 - Cathode Study Triple Bundle Test

Bundle 1

Bundle 2

Bundle 3•Power degradation rate:

•Bundle 1: 0.35%/1000 hr @ 835oC•Bundle 2: 0.29%/1000 hr @ 860oC•Bundle 3: 0.08%/1000 hr @ 883oC

Candidate EIS Cathode Projects ~3 Year Life 16

1-Bara, Low Cr, Dry air

LG data

0

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0 2000 4000 6000 8000 10000

ASR,

Ohm

cm

2

Time, hours

Epsilon plus anodeSingle layer anode1Single layer anode2

RU ASRs, PCT189-Anode Durability

925oC, 4bar, bundle outlet fuel

10 mohm cm2/1000hr

≤ 2 mohm cm2/1000hr

Single Layer Anode Continues to Show Lower Degradation Rate Degradation rate

Epsilon plus anode : 10 mohm cm2/1000hr Single layer anode: 1.5~2.0 mohm cm2/1000hr

LG data

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1.E-01 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06

-Z"

Frequency, Hz

EIS for PCT247

E+anode_B1_RU_0HrsE+anode_B1_RU_500Hrs

BI, 800, 1Bara

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0.40

1.E-01 1.E+001.E+011.E+021.E+031.E+041.E+051.E+06

-Z"

Frequency, Hz

EIS for PCT234

B1: SL anode, 0 hrB1: SL anode, 500 hrB1: SL anode, 1000 hr

BI,800, 1Bara

Anode

Cathode

Accelerated Anode Testing Helps Database and Decision Making Current density, temperature, and fuel utilization Accelerated testing confirmed single layer anode is more stable than

epsilon plus anode

18

Single layer anodeEpsilon plus anode

AnodeCathode

LG data

Redox Tolerant Anode Benefits System Operation Epsilon plus anode is able to tolerate 4-5 redox cycles Single layer anode being developed for improved redox tolerance

Equivalent or better than epsilon bi-layer structure Able to tolerate more redox cycles without significant ASR change

No of redox cycles

LG data

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ASR

, ohm

-cm

2

Elapsed Time, hours

Scale-Up of Epsilon Performance and Durability

T1411 - Epsilon TechnologyT1314 - Epsilon TechnologyT1315 - Improved PIC and Cathode Block

860ºC Nominal Temperature6.4 Bara

20Lower ASR Technology was Demonstrated in Block Level High conductive interconnect plus EIS cathode Average block ASR: 0.28 ohm-cm2 vs 0.35 ohm-cm2 for epsilon

technology Stable performance in 700 hrs of operation with 15.7 kW output

EpsilonEpsilon

Improved PIC & cathode

Improved PIC & cathode

860oC

0.05

LG data

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0.35

0.40

0.45

0.50

760 780 800 820 840 860 880 900 920

PTT-Epsilon technologyPTT6: Low ASR PIC+EIS cathode+Thin wall tubePoly. (Low ASR PIC)

RU A

SR ,

Ω

Temperature,

4 Bara, system conditions

Pressurized full tube testing

Further ASR Reduction - Thin Wall Tube Thin wall tube could reduce fuel diffusion resistance

ASR reduction 0.02 to 0.03 ohm-cm2 by subscale cell Feasibility was demonstrated by pressurized full tube test

21

-0.20-0.18-0.16-0.14-0.12-0.10-0.08-0.06-0.04-0.020.00

0.00 0.10 0.20 0.30 0.40ASR, ohm-cm2

Z"

144A: st. tube144B: thin wall

0.262 0.291

830C, bundle inlet, air

ASR reduction: 0.029 ohm-cm2

Subscale cell

Epsilon

Thin wall tube w/ improvedPIC & cathode

LG data

Shorter PIC for Further ASR Reduction 22

Smaller PIC dimension has lower ASR contribution Shorter PIC will increase active cell area Model calculation indicates increase in power

output up to 6% Shorter PIC was demonstrated by subscale cells

Meaningful lower ASR Stable performance in test to 4,500 hrs

Via-based interconnect design

P-Value = 0.096 P-Value = 0.013

LG data

Significant Effort on Nickelate Cathode Screening

23

Extensive composition matrix was evaluated using cathode symmetric cells A site doped nickelate B site doped nickelate Composite nickelate

Some compositions show much lower polarization than LSM-based cathode

•Rp and Rs increase

•EIS1 •cathode

LG data

Nickelate Cathode Shows ASR benefits against LSM-Based Cathode Across Block Temperature Range

Nickelate cathode has lower ASR than EIS LSM cathode Statistic data show the difference is meaningful

24

Nickelate at 860CEIS1 at 860C

0.30

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0.10

Cell

ASR

, ohm

-cm

^2

0.240

0.192

Boxplot of ASR of EIS1 vs Nickelate Cathodes

Estimated difference: ~0.055 (for means)

P-value = 0.000

ASR vs temperature Statistic analysis

Nickelate

EIS1

LG data

Lower Degradation Rate during Short-term durability Test

25

High order nickelate cathodes showed lower degradation rate even though initial Rp is higher

Some composite nickelate cathodes showed both lower ASR and degradation rate – chosen for subscale tube testing

•EIS

1 ca

thod

e

LG data

Long-term Durability of Nickelate Cathodes at 860oC is Promising

26

Selected Nickelate cathode has low degradation rate, similar to LSM-based cathode

Good repeatability Longer term durability is on-going

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1.0

0 1000 2000 3000 4000 5000

Cel

l ASR

, ohm

-cm

2

Time, hours

bundle mid-point fuel, wet air. 1 bara, 860oC

PCT222B1PCT238A1

Nickelate composite A

ASR deg. rate: 9.8 mohm-cm2/1000 hrs

LG data

Phase Composition of Nickelate Cathode is Manageable

Composite nickelate cathode shows more uniform chemistry in nickelate phase after aging 870oC/500 hrs

27

Pure Nickelate Cathode (n=1) Ni-depleted phase on ageing

Nickelate CompositeComposite phases retained, some minor Ni dissolution

Nickelate 2nd ionic phase

LG data

Summary 200 kW-scale system test performed

Pipeline natural gas to grid connection Demonstrating product architecture for commercial

systems Testing and analysis supporting cell technology showing

an extension in service life Lower ASR technology in the pipeline for near-term and

longer-term validation → cost and efficiency gains

28

LG data

Acknowledgements Special thanks to NETL program management

team: Shailesh Vora, Patcharin Burke, Heather Quedenfeld, Briggs White, Brittley Robbins

Case Western Reserve University University of South Carolina

LG data

Acknowledgements_Continued This material is based upon work supported by the U.S. Department

of Energy, National Energy Technology Laboratory under Award Number DE-FE0012077 and DE-FE0023337.

Disclaimer: This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of the authors expressed herein do not necessarily state or reflect those of the United States Government of any agency thereof.