Investigation of critical parameters in Li-ion battery electrodes

Jordi Cabana

Lawrence Berkeley National LaboratoryMay 11th, 2011

ES70_CabanaThis presentation does not contain any proprietary, confidential, or otherwise restricted information

2

• PI joined BATT and LBNL in FY09

• Project start Sep ‘09• Project end Aug ‘11• 80% complete

• Barriers addressed– Gravimetric and volumetric

Energy Density– Cycle life– Safety

• Funding FY09: $420k• Funding FY10: $440k• Funding FY11: $630k

Timeline

Budget

Barriers

• Persson, Doeff, Richardson, Chen, Kostecki, Battaglia (LBNL), Grey (SUNY-SB), Whittingham (SUNY-B)

• A. Mehta, (SSRL, Stanford), M. Casas-Cabanas (Caen, France), M.R. Palacin (ICMAB, Spain), A. Dong (MF, LBNL), M.A. Marcus (ALS, LBNL)

Partners

Overview

33

• To achieve cycle life and energy density targetsusing high voltage (>4.5 V) electrode materials.– Synthesize materials with controlled crystal-chemistry and

microstructure– Establish chemistry-structure-properties correlations that aid in the

design of better materials.– Assess origins of in-cycle and cycling inefficiencies.– barriers: energy density, cycle life, safety

• To understand impact of materials and electrodedesign on performance.– Develop methods to couple electrode performance and

transformations at multiple length scales.– barriers: energy density, cycle life

Relevance - Objectives

44

MilestonesMar. 10 Report the cycling performance of LiNi1/2Mn3/2O4 made solvothermally .

Completed

Jul. 10 Choose promising Cu-M-O (M=transition metal, Al, P, Si) phases and test them. Completed

Sep. 10 Report the characterization of cycled NiO electrodes by NMR, XAS and TEM. Completed

Sep. 10 Synthesize Sn-based nanoalloys with controlled microstructure and report their performance as electrodes. Postponed to FY11

Mar. 11 Report the thermal analysis of cycled LiNi1/2Mn3/2O4 electrodes and the results of annealing using different treatments. Ongoing

Sep. 11 Report the analysis of Sn nanoparticles at different stages of cycling. On schedule

Sep. 11 Report the electrochemical response of NiO when cycled at high temperatures. On schedule

5

• Understand the correlation between crystal structure,microstructure, composition and electrochemical performance inLiNi1/2Mn3/2O4.– Synthesize samples with controlled microstructure, composition, ordering.– Study changes in structural order and composition with synthesis

conditions using a variety of characterization techniques.– Evaluate performance at moderate and high rates. Ultimate goal: 100%

utilization at 2C rate, 85% 1st cycle efficiency and 99.99% steady-stateefficiency at C/2 rate.

• Analyze inefficiencies of high voltage LiNi1/2Mn3/2O4.– Study existence of irreversibility in the lithium intercalation reaction in high

voltage materials and surface layer formation.– Understand the effect of surface modifications.

• Use synchrotron radiation to characterize electrode materials atmultiple length scales.– Spectroscopy to analyze chemical changes at interfaces, surface and bulk

of materials.– Combination of spectroscopy and imaging to evaluate inhomogeneities at

nano as well as macro scale.

Approach/Strategy

6

• Rietveld-refined neutron diffraction data.• Samples synthesized from hydroxide precursors at 500°C≤T≤1000°C for 12 h.

Technical accomplishments:LiNi1/2Mn3/2O4, Neutron Diffraction

500°C 700°C

900°C 1000°C

7

Technical accomplishments:LiNi1/2Mn3/2O4, Ni-Mn ordering

• Clear Ni-Mn ordering transition at 700°C. Diffuse scattering at 600°C and 800°Cdenotes partial ordering.• Patterns at T ≠700°C were refined with disordered cell (Fd-3m). Pattern at T =700°Cwas refined with ordered supercell (P4332): detected partial Ni-Mn exchange.• Consistent with ordering schemes revealed by 6Li MAS NMR.

8

Technical accomplishments:LiNi1/2Mn3/2O4, Chemical composition

• Increase in Mn/Ni ratio upon heating ⇒ increase in Mn3+ + unit cell parameter.• Increase in Mn3+ correlates with electrochemical activity around 4.0 V. Washed outprofile for OH500C could be due to defective/poorly crystallized particles.• No evidence for O vacancies found. Mn enriching is due to segregation of Ni in arocksalt impurity.

Mn K edge XANES(Derivative) Charge in Li cell, C/10

500°C600°C700°C800°C900°C1000°C

500°C900°C1000°C

9

Dark field imaging +

Energy dispersive spectroscopy

Electron diffraction

• Composition by EDS-TEM analysis from ~30 particles.• Rocksalt-type impurity can segregate to the surface of the particles. It contains Mn(not Li1-xNixO), probably in +3 state (deduced from XANES).• The process is exacerbated as the calcination temperature is increased.

Technical accomplishments:LiNi1/2Mn3/2O4, Chemical composition (II)

10

Technical accomplishments:LiNi1/2Mn3/2O4, Impurity vs. performance

• Li extraction is not possible from rocksalt impurity ⇒ cripples performance,especially if it accumulates on the surface of spinel particles.• Minimization is desirable. Important implications when annealing is used to increaseparticle size, which is needed for better performance.

BM

exMnO2

exMnCO3

exMnCO3 BM900C

(J. Cabana, 2010 AMR)

Li cells, 1C900°C1000°C

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0 20 40 60 80 100 120 140 160

3.6

3.8

4.0

4.2

4.4

4.6

4.8

5.0

Capacity (mAh/g)0 20 40 60 80 100 120 140 160

3.6

3.8

4.0

4.2

4.4

4.6

4.8

5.0

Capacity (mAh/g)

0 20 40 60 80 100 120 140 160

3.6

3.8

4.0

4.2

4.4

4.6

4.8

5.0

Capacity (mAh/g)

Volta

ge (V

)

Technical accomplishments:LiNi1/2Mn3/2O4, Effect of annealing

900°C 500°C700°C

• Samples synthesized from hydroxide precursors: heated in air at 900°C, 1 h + 12 h at500 or 700°C.• No notable changes in particle size/morphology observed (consistent with absence ofmajor coarsening below 800°C, vid. J. Cabana – 2010 AMR )• Annealing at 700°C: mechanism of ordered spinel. Smaller Mn3+ signal.• Annealing at 500°C: mechanism of disordered spinel. Similar Mn3+ signal.• Decouple microstructure from crystal-chemistry: higher capacity/efficiencies at 900°C(under study).

Li cells, C/10

100 nm(scale bar)

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Full Li-ion cell:BM,900°C vs. MCMB

Li half cell, 1C rateBM,900°C

• Unacceptable capacity loss of 75% in Li-ion cell after 100 cycles.• The low coulombic efficiencies observed (~99.5%) even upon extended cycling likely producelosses in the negative electrode that cripple the lifetime of the battery.• Coulombic efficiency appears to be a pressing issue.

Technical accomplishments:LiNi1/2Mn3/2O4, Full Li-ion cells

13

Technical accomplishments:LiNi1/2Mn3/2O4, Electrochemical reversibility

20 40 60 800

200

400

600

800

1000

1200

1400

1600

In

tens

ity (a

rb. u

nit)

Scattering Angle (2θ )

1st Charge

1st Discharge

2nd Charge

2nd Discharge

(111

)

(311

)

(222

) (400

)

(331

)

(333

)

(440

)

(531

)

(533

)(6

22)

**

Pouch: *

After 1st cycle

After 2nd cycle

Pristine

• Synchrotron XRD patterns (referenced to Cu Kα) collected during 2 cycles of Li/LiNi0.5Mn1.5O4at 900°C.•Multiple processes are observed during lithium extraction/reinsertion.

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0 100 200 300 400 500 6001.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

Volta

ge (V

vs.

Li/L

i+ )

Capacity (mAh)

1st Charge 1st Discharge 2nd Charge2ndDischarge

7.85

7.90

7.95

8.00

8.05

8.10

8.15

8.20

8.25

La

ttice

Con

stan

t (A)

43 44 45 46 470

200

400

600

800

1000

1200

64 66 68

(4

00)

(440

)

1stCharge

1stDischarge

2ndCharge

2ndDischarge

Inte

nsity

(arb

. uni

t)

2Ѳ

After 1st cycle

After 2nd cycle

Pristine

Technical accomplishments:LiNi1/2Mn3/2O4, Electrochemical reversibility (II)

• Single phase - 2 phase - single phase - 2 phaseprocesses on charge. Reversible on discharge.• Changes in cell parameter (~2% volume change)and phase distribution are largely reversible evenafter 2 cycles.

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Technical accomplishments:LiNi1/2Mn3/2O4, Crystal-chemical inefficiency?

36 38 40 42 44 46

Scattering Angle (2θ )

20 30 40 50 60 70

Scattering Angle (2θ )

pristine1 cycle

Pristine

1 cycle

2 cycles

*

*

*: Pouch

• ∆Qirrev is not related to crystallographic or chemical inefficiencies: structure and Ni2+ contentrecovered after 1 cycle.• ~130 mAh/g discharge capacity ⇒ ~88% theoretical capacity. Is Li completely removed uponcharge?

Ni K edge XANES

∆Qirrev

16

Technical accomplishments:µ-XAS as a technique to study electrode inhomogeneities

• Small (down to 1x1 µm) spot size on the sample allows collection of multiple X-ray absorptionspectra with spatial resolution ⇒ good for complex inhomogeneous samples.• Three detectors available: total electron yield (probes ~10 nm), fluorescence yield (

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0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

0.0 0.5 1.0 1.5 2.0 2.5 3.0

V v

s. L

i+ /Li

0 (V

)

x Li equivalents reacted

1

2

X

X

X

XXpristine

DoD1Li

red0V

SoC2V

1 cycle

pristine

red0V

1cycle

NiOLi2ONi

Technical accomplishments:µ-XAS, NiO as proof of concept

Li2ONiOred0V1 cycle

• NiO + 2Li ↔ Ni + Li2O ⇒ reversible conversion reaction that leads to high storage capacity.• Ni species involved are easily resolvable ⇒ good model system to test the efficacy of thetechnique.

O K edge EELS

Ni LII,III edge XANES

Electron Diffraction

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0 1 2 3 4 5 6 7 8 9 100

102030405060708090

100

% m

etal

ic Ni

ckel

spot

NiTFY NiTEY

0 2 4 6 8 100

102030405060708090

100 NiTEY NiTFY

% m

etal

lic N

ickel

spot

NiNiO

0 1 2 34

56

7 8 9 10

0,1

2

34 5 67,8

9,10

Technical accomplishments:µ-XAS, Identification of homogeneities

73% NiO+15% CB+12% PVDFDischarged halfway, 1C

• Inhomogeneities in the phase transformation identified at mm scale. Aggravated as rate isincreased ⇒ risk of capacity losses, overdischarge, localized heat.•Methodology can be extended to other systems (including those showing amorphous phases)→ generate input for electrode design.

0.08mm

73% NiO+15% CB+12% PVDFDischarged halfway, C/20

NiONi

1919

Collaboration and Coordination with Other

Institutions• Within BATT:

– Dr. V. Battaglia (LBNL): testing of spinel electrodes in Li-ion cells.– Dr. M. M. Doeff (LBNL): XAS and XRD of electrode materials.– Dr. R. Kostecki (LBNL): understanding surface reactivity in cathode materials.– Prof. C.P. Grey (SUNY-SB): MAS-NMR of electrode materials.– Prof. Whittingham (SUNY-Binghamton): magnetic susceptibility of spinels.

• Outside BATT:– Dr. M. Casas-Cabanas (ENSICaen, France): neutron diffraction and electron

microscopy of electrode materials.– Dr. A. Mehta (SSRL): XAS and XRD of electrode materials.– Dr. M.A. Marcus (LBNL): µ-XAS of electrode materials.– Dr. A. Dong (LBNL): synthesis of materials with controlled nanostructures.

20

• Continue to understand parameters that control performance ofLiNi1/2Mn3/2O4 (within BATT Focus Group):– Continue using NMR (with Grey group) as core technique for analysis of

ordering.– Collaboration has been established with Whittingham group to analyze Mn3+

content using magnetic susceptibility.– Establish sensitivity of XANES to small amounts of Mn3+.– Analyze role of crystal-chemistry on electrode performance in samples

where microstructure effects are decoupled.• Continue to investigate sources of coulombic inefficiency in

LiNi1/2Mn3/2O4 (within BATT Focus Group):– Samples at full charge: Is there Li+ left? Is there Ni4+? Are holes created

into O 2p bands? What is the composition of electrolyte decompositionlayers on surface of electrode? Use combination of soft and hard XAS.

– Analyze the effect of simply adding inorganic additives to electrode oncoulombic efficiency. Compare to traditional coatings.

• Extend µ-XAS method to commercially relevant systems (alloys,intercalation).

Future Work

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• LiNi1/2Mn3/2O4 crystallizes in a variety of patterns of with different Ni/Mnordering. Ni/Mn mixing can be found in samples showing unit cellsuperstructures.

• All samples made in this study show Mn over-stoichiometry, but noevidence of O2- vacancies. Mn3+ is due to a preferential segregation of Niin a rock salt impurity, which also contains Mn.

• Amounts of impurity and Mn3+ increase with synthesis temperature.Impurity is detrimental to performance; needs to be minimized duringmaterial preparation.

• Annealing of samples prepared at high temperature leads to decouplingof microstructure from ordering/composition.

• Poor performance of LiNi1/2Mn3/2O4 in Li-ion cell, most likely due tocoulombic inefficiencies. These are not related to crystal-chemicalirreversibilities.

• Developed a µ-XAS method to evaluate charge distribution with highspatial resolution. Analyzed discharge inefficiency dependence on ratefor conversion model system.

Summary

Investigation of critical parameters in Li-ion battery electrodes Slide Number 2Slide Number 3MilestonesSlide Number 5Slide Number 6Slide Number 7Technical accomplishments:�LiNi1/2Mn3/2O4, Chemical compositionSlide Number 9Slide Number 10Slide Number 11Slide Number 12Slide Number 13Slide Number 14Slide Number 15Slide Number 16Slide Number 17Slide Number 18Collaboration and Coordination with Other InstitutionsSlide Number 20Slide Number 21