Nondestructive Diagnostics of Battery Cells by MRI

Alexej Jerschow alexej.jerschow@nyu.edu

predict failures, lifetimes

early non-destructively

quickly

Can we detect dendrites, soft shorts, electrolyte distribution, uneven

SOC, metal particles …?

MRI

In-situ (operando) NMR/MRI

Commercial-type cell analysis •  SOC •  SOH •  Current distribution

Li-dendrite visualization •  7Li MRI / CSI •  1H MRI

Supercapacitors •  1H / 11B MRI

15 -15-5510 0 -10

Chemical Shift (ppm)

PositiveElectrode

Position

NegativeElectrode

15 -15-5510 0 -10Chemical Shift (ppm)

PositiveElectrode

Position

NegativeElectrode

15 -15-5510 0 -10Chemical Shift (ppm)

PositiveElectrode

Position

NegativeElectrode

15 -15-5510 0 -10Chemical Shift (ppm)

PositiveElectrode

Position

NegativeElectrode

15 -15-5510 0 -10Chemical Shift (ppm)

PositiveElectrode

Position

NegativeElectrode

15 -15-5510 0 -10Chemical Shift (ppm)

PositiveElectrode

Position

NegativeElectrode

15 -15-5510 0 -10Chemical Shift (ppm)

PositiveElectrode

Position

NegativeElectrode

15 -15-5510 0 -10Chemical Shift (ppm)

PositiveElectrode

Position

NegativeElectrode

15 -15-5510 0 -10Chemical Shift (ppm)

PositiveElectrode

Position

NegativeElectrode

15 -15-5510 0 -10Chemical Shift (ppm)

PositiveElectrode

Position

NegativeElectrode

-2.0 -1.0 0.0 1.0 2.0

-0.4

-0.2

0.0

0.2

0.4

Voltage (V)

Curre

nt (m

A)

“In real life”

NMR

B0

Chemical shift: varying electron density small changes in frequency

ω = γ B0

NMRandMRIB0

ω +

+ G*z

ω, z

�

ω = γB0

NMRaccessiblenuclei1H

7Li 6Li

11B

Li plating / Li dendrites

Positive electrode Negative electrode (Lithium) In situ TEM of Lead dendrite

Orsini et al, J Pow Src 76, 1998, 19

charging

Hee Jung Chang

e-

Lithium MRI of Batteries

Chandrashekar et al. Nat. Mater., 11, 2012, 311

before charging after charging

x y x

y

Li-dendritesonelectrode

Bhatacharya et al, Nat. Mat. 9, 2010, 504

Orsini et al, J Pow Src 76, 1998, 19

270

260

280 Ch

emic

al s

hift

(ppm

)

1 0 -1 -2 0 2

270

260

280 Ch

emic

al s

hift

(ppm

)

-2 0 2 1 0 -1 y (mm) 1 0 -1 -2 0 2

Li metal

0.3 mm

15 mm

2 mm

B0

7Li CSI of Li-ion batt.

before

after

Chandrashekar et al. Nat Mater, 11, 2012, 311

Superresolution Information: Chemical and Susceptibility shifts

B0

HJ Chang et al., J Phys Chem C, 119 (2015) 16443

Studying dendrite growth models

H.J. Chang et al, JACS 2015, 137, 15209

Indirect MRI of dendrite growth

1H 3D FLASH ‘negative’ image

Ilott et al., PNAS, 2016, 113, 10779-84

~20-fold amplification from field distortions!

Ilott et al., PNAS, 2016, 113, 10779-84

Does not depend on electrode material

Supercapacitors

1H CSI

- - - -

+ + + +

+ + + +

- - - -

Ilott et al., Nat. Comm., 5, 2014, 4536

“In real life”

RF penetration into metal: skin effect

δ = 1πµrµ0σ f skin depth Ilott et al., JMR, 245, 2014, 143-149

Inside-out MRI

Ilott, et al, Nat Comm 9:1776, 2018

B0

B0

Magnetic Susceptibility

B0

By Andy Ilott

Magnetic Susceptibility effects

Magnetic field maps during discharge

Ilott, et al, Nat Comm 9:1776, 2018

State of Charge from Susceptibility

NMC

LCO

Ilott, et al, Nat Comm 9:1776, 2018

Susceptibility Inversion

Ilott, et al, Nat Comm 9:1776, 2018

Samsung battery defects Jan 2017 press release

Battery Prototyping Center Make cells with defects

Defective cells

Ilott, et al, Nat Comm 9:1776, 2018

Current Distribution

Yazdanpour, JECS, 161, 2014, A1953

Current distributions charging charging; short discharging; short

Current distributions with MRI

discharge charge

Current distributions with MRI

discharge charge

Battery Fingerprint Technologies Battery

Diagnostics

In-situ (operando) NMR/MRI

Commercial-type cell analysis • SOC • SOH • Current distribution

Li-dendrite visualization • 7Li MRI / CSI • 1H MRI

Supercapacitors • 1H / 11B MRI

15 -15-5510 0 -10Chemical Shift (ppm)

PositiveElectrode

Position

NegativeElectrode

15 -15-5510 0 -10Chemical Shift (ppm)

PositiveElectrode

Position

NegativeElectrode

15 -15-5510 0 -10Chemical Shift (ppm)

PositiveElectrode

Position

NegativeElectrode

15 -15-5510 0 -10Chemical Shift (ppm)

PositiveElectrode

Position

NegativeElectrode

15 -15-5510 0 -10Chemical Shift (ppm)

PositiveElectrode

Position

NegativeElectrode

15 -15-5510 0 -10Chemical Shift (ppm)

PositiveElectrode

Position

NegativeElectrode

15 -15-5510 0 -10Chemical Shift (ppm)

PositiveElectrode

Position

NegativeElectrode

15 -15-5510 0 -10Chemical Shift (ppm)

PositiveElectrode

Position

NegativeElectrode

15 -15-5510 0 -10Chemical Shift (ppm)

PositiveElectrode

Position

NegativeElectrode

15 -15-5510 0 -10Chemical Shift (ppm)

PositiveElectrode

Position

NegativeElectrode

-2.0 -1.0 0.0 1.0 2.0

-0.4

-0.2

0.0

0.2

0.4

Voltage (V)

Curre

nt (m

A)

“In real life” Inside-out MRI

Relevant Publications •  S.Chandrashekar,N.M.Trease,H.J.Chang,L.-S.Du,C.P.Grey,A.Jerschow,7LiMRIofLiba,eriesrevealsloca3onof

microstructurallithium,NatureMater.,11,311-315,2012,hHp://www.nature.com/doifinder/10.1038/nmat3246.

•  A.J.IloH,S.Chandrashekar,A.Klöckner,H.J.Chang,N.M.Trease,C.P.Grey,L.Greengard,A.Jerschow,VisualizingskineffectsinconductorswithMRI:7LiMRIexperimentsandcalcula3ons,J.Magn.Reson,245,2014,143-149,hHp://dx.doi.org/10.1016/j.jmr.2014.06.013.

•  A.J.IloH,N.M.Trease,C.P.Grey,A.Jerschow,Mul3nuclearinsitumagne3cresonanceimagingofelectrochemicaldouble-layercapacitors,Nat.Comm.5,2014,4536,hHp://dx.doi.org/10.1038/ncomms5536.

•  H.J.Chang,N.M.Trease,A.J.IloH,D.Zeng,L.-S.Du,A.Jerschow,C.P.Grey,Inves3ga3ngLiMicrostructureForma3ononLiAnodesforLithiumBa,eriesbyInSitu6Li/7LiNMRandSEM,J.Phys.Chem.C,2015,119,16443–16451,hHp://dx.doi.org/10.1021/acs.jpcc.5b03396.

•  H.J.Chang,A.J.IloH,N.M.Trease,M.Mohammadi,A.Jerschow,C.P.Grey,Correla3ngMicrostructuralLithiumMetalGrowthwithElectrolyteSaltDeple3oninLithiumBa,eriesusing7LiMRI,J.Am.Chem.Soc.,2015,137,15209–15216,hHp://dx.doi.org/10.1021/jacs.5b09385.

•  A.J.IloH,H.-J.Chang,C.P.Grey,A.Jerschow,Real3me3Dimagingofmicrostructuregrowthinba,erycellsusingindirectMRI,Proc.Natl.Acad.Sci.USA,2016,113,10779-84,hHp://www.pnas.org/content/early/2016/09/06/1607903113.abstract.

•  A.J.IloHandA.Jerschow,Super-resolu3onSurfaceMicroscopyofConductorsusingMagne3cResonance,SciRep.2017,7,5425,hHp://rdcu.be/ubQl,hHps://www.nature.com/ar]cles/s41598-017-05429-3

•  A.J.IloH,M.Mohammadi,C.M.Schauerman,M.J.Ganter,A.Jerschow,Rechargeablelithium-ioncellstateofchargeanddefectdetec]onbyin-situinside-outmagne]cresonanceimaging,NatComm9:1776,2018,hHp://dx.doi.org/10.1038/s41467-018-04192-x

Acknowledgements NYU •  Andy Ilott •  Mohaddese Mohammadi •  S. C. Shekar •  Emilia Silletta

RIT Battery Prototyping •  Christopher Schauerman •  Matthew Ganter