solid-state metal anodes (day 1) Ma Mauro Pasta Faraday - - PowerPoint PPT Presentation

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solid-state metal anodes (day 1) Ma Mauro Pasta Faraday - - PowerPoint PPT Presentation

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Proprietary and Confidential SOLBAT: solid-state metal anodes (day 1) Ma Mauro Pasta Faraday Institution 8-monthly meeting 1 WHY SOLID STATE? ENERGY POWER SAFETY 2 HOW SOLID STATE? ENERGY + = + ~1 POWER

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SLIDE 1

SOLBAT: solid-state metal anodes (day 1)

Faraday Institution 8-monthly meeting Ma Mauro Pasta

1

Proprietary and Confidential

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SLIDE 2

WHY SOLID STATE?

ENERGY POWER SAFETY

2

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SLIDE 3

HOW SOLID STATE?

POWER SAFETY ENERGY

𝑒𝑀𝑗+ = 𝐽𝑀𝑗+ π½π‘’π‘π‘’π‘π‘š ~1

3

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SLIDE 4

200 400 600 800

1976 1978 1980 1982 1984 1986 1988 1990 1992 1994 1996 1998 2000 2002 2004 2006 2008 2010 2012 2014 2016 2018

ACADEMIA

Scopus keywords: solid state electrolyte battery

𝑀𝑗10𝐻𝑓𝑄2𝑇12 𝑀𝑗9.54𝑇1.74𝑄21.44𝑇11.7π·π‘š0.3

1976-2018

United States China Japan India Germany South Korea France Canada United Kingdom Italy

125 128 137 202 290 302 314 819 1007 1017

2015-2018

China United States Japan Germany South Korea India Canada France Spain United Kingdom

57 57 58 74 113 168 210 294 525 688

4 Proprietary and Confidential

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SLIDE 5

IN INDUSTRY

β€˜04 β€˜07 β€˜12 β€˜15 β€˜17 β€˜18

+ + + stops manufacturing efforts abandons SAKTI3 patents + + 100M$ +

5 Proprietary and Confidential

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SLIDE 6

SOLBAT

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SLIDE 7

THE TEAM

7

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SLIDE 8

IN INORGANIC CERAMICS

Perovskite (LLTO) 𝑀𝑗3𝑦𝑀𝑏2/3βˆ’π‘¦

1/3βˆ’2π‘¦π‘ˆπ‘—π‘ƒ3

Anti-perovskite (𝑀𝑗3π‘ƒπ·π‘š) NaSICON 𝑀𝐡𝐻𝑄 𝑀𝑗1.3π΅π‘š0.3𝐻𝑓1.7(𝑄𝑃4)3 Garnet (LLZO) 𝑀𝑗7𝑀𝑏3π‘Žπ‘ 

2𝑃12

Thio-LiSICON 𝑀𝑗4βˆ’π‘¦π‘Žπ‘œπ»π‘“1βˆ’π‘¦π‘„π‘‡4 LGPS 𝑀𝑗10𝐻𝑓𝑄2𝑇12 LiSICON 𝑀𝑗14π‘Žπ‘œπ»π‘“4𝑃16 Argyrodite Li6PS5Cl

8

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SLIDE 9

Garnet, Li Li7La La3Zr Zr2O12

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Argyrodite, , Li Li6PS PS5Cl Cl πœπ‘€π‘—+/ S cm-1 1Β·10-3 (Ta doped) 3Β·10-3 Stability vs. Li metal stable ? Electrochemical window wide ? 𝜍 /g π‘‘π‘›βˆ’3 4.89 1.89

Janek, Nazar, Nan, Maier, Armand, Chen et.al., New horizons for inorganic solid state ion conductors, EES (2018)

TWO MODEL SYSTEMS

𝐹/GPa 175.1 22.1 𝐻/GPa 68.9 8.1

9

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SLIDE 10

770 Whl-1 300 Whkg-1 1339 Whl-1 434 Whkg-1

+ 74% vol. + 45% grav.

TECHNOECONOMICS

Conventional l Li-ion Argyrodite, Li6PS PS5Cl Cl

10

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SLIDE 11

770 Whl-1 300 Whkg-1 1339 Whl-1 315 Whkg-1

+ 74% vol. + 5% grav.

TECHNOECONOMICS

Conventional l Li-ion LLZO, Li7La La3Zr Zr2O12

12

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SLIDE 12

Deiseroth et.al. Angew. Chem. Int. Ed. (2008)

ARGYRODITE: HIS ISTORY

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SLIDE 13

Boulineau et.al. Solid State Ionics (2012)

Li Li2S

5

P2S5

1

LiC iCl

2

SYNTHESIS

Li6PS5Cl

13

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SLIDE 14

CHARACTERIZATION

5 mm ΟƒLi+: ~3 mS/cm @ RT E = 15 Β±3 GPa

MICROSCOPY ELECTROCHEMICAL STRUCTURAL MECHANICAL

20 ΞΌm 2 ΞΌm

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SLIDE 15

10 100 0 nm nm

HIG IGH-RESOLUTION PHASE CONSTRAST

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SLIDE 16

1 ΞΌm Li metal Li6PS5Cl Li Li6PS PS5Cl Cl Li Li Li Li6PS PS5Cl Cl

XPS

1200 1700 2200 2700 3200 3700 4200 4700 5200 124 126 128 130 132 134 136 138 140 Intensity (a.u.) Binding Energy (eV)

P 2p

800 1000 1200 1400 1600 1800 2000 2200 2400 124 126 128 130 132 134 136 138 140 Binding Energy (eV)

P 2p

Li3P Li6PS5Cl

reduced P

Li6PS5Cl + Li metal

1000 6000 156 158 160 162 164 166 168 Binding Energy (eV)

S 2p

1800 6800 11800 16800 21800 156 158 160 162 164 166 168 Intensity (a.u.) Binding Energy (eV)

S 2p

PS Li6PS5Cl Li2S Li6PS5Cl PS Li2S + Li metal

1E+0 1E+1 1E+2 1E+3 50 100 150 200 250 300 Resistance / Ξ©βˆ™cm2 or Ξ©βˆ™cm Time / h

Relectrolyte RSEI

SURFACE ANALYSIS

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SLIDE 17

Journal of Power Sources 293 (2015) 941-945

Raman spectra of bare Li6PS5Cl

IN IN-OPERANDO RAMAN

𝑄𝑇4

3βˆ’

Optical Window

50 nm Au/Cu

SE

Li

Laser SS-Back Contact CE/RE Contact pin WE O-ring Cell body

17

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SLIDE 18

Potentiostatic: 15 minutes hold

IN IN-OPERANDO RAMAN

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10 ΞΌm f) 7th Plating Li metal Li6PS5Cl 10 ΞΌm g) 7th Stripping Li metal Li6PS5Cl 10 ΞΌm Li metal Li6PS5Cl c) 1st Stripping 10 ΞΌm a) Pristine Li metal Li6PS5Cl 10 ΞΌm b) 1st Plating Li metal Li6PS5Cl 10 ΞΌm Li metal Li6PS5Cl e) 3rd Stripping d) 3rd Plating Li metal Li6PS5Cl 10 ΞΌm

Solid electrolyte

Li Li

RE

SEM

EFFECT OF PRESSURE

1.0 .0 mA/cm2 1.0 .0 mAh/cm2 3 3 MPa

  • 0.16
  • 0.12
  • 0.08
  • 0.04

0.00 0.04 0.08 0.12 0.16 0.0 0.2 0.4 0.6 0.8 1.0 Voltage / V Areal Capacity / mAhβˆ™cm-2

1.0 mAβˆ™cm-2 3 MPa 1st cycle 6th cycle 7th cycle 8th cycle

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SLIDE 20

EFFECT OF PRESSURE

1.0 .0 mA/cm2 1.0 .0 mAh/cm2 7 7 MPa

20

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SLIDE 21

Effect of Current Density on Fail ilure 7MPa Effect of Applie ied Pressure on Fail ilure 1mA/cm2

7MP 7MPa 50 cycles 3MPa 8 cycles, shorted

Top Bottom

1mA/cm2, 50 cycles 2mA/cm2 failed in 3 cycles 3mA/cm2 failed within 1 cycle

X-RAY TOMOGRAPHY

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SLIDE 22

pri ristin ine

100 100 ΞΌm

Li i meta etal

1st

st stri

rip

18 18 ΞΌm

Li i meta etal

3rd

rd strip

ip

30 30 ΞΌm 47 47 ΞΌm 38 38 ΞΌm

Li i meta etal

7th

th strip

trip

145 145 ΞΌm 75 75 ΞΌm

Li i meta etal

5th

th stri

rip

60 60 ΞΌm 65 65 ΞΌm 105 105 ΞΌm 30 30 ΞΌm

Li i meta etal

VOID EVOLUTION

22

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SLIDE 23

50lambda

electrode . electrolyte electrode

– + + + + – – – – + + + + – – –

0.5 1 1.5 2 Position (nm) 0.2 0.4 0.6 0.8 1 Occupation probability Ideal blocking (i=0)

0.32 V 0.24 V 0.16 V 0.08 V

Li+ depletion β€˜jamming’ (signature of Fermi statistics) uniform conc. in the bulk 0.08 V 0.32 V

position (nm) Lithium-site occupancy x

0.5 1 1.5 2 Position (nm)

  • 600
  • 500
  • 400
  • 300
  • 200
  • 100

Pressure p-p (MPa) Ideal blocking (i=0) 0.08 V 0.16 V 0.24 V 0.32 V

pressure p–pref (MPa) tens ensio ion O O (0. (0.1 GP GPa)

10-2 100 102 104 Current density i (A/m2) 102 104 106 108 p (Pa) 303 K 343 K 373 K 403 K 433 K

c= 3 kPa

current density i (A/m2) stress (Pa)

A simple predictor: Space charging (screening) in double layers produces large forces at the interface β€˜Critical current’ or β€˜critical stress’?

data = β€’ from Sharifi et al., J. Power Sources 302 302 (2016) 135

Tran ansport model l out utput

position (nm)

ELECTRO-CHEMO-MECHANICS

Guanchen Li

23

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SLIDE 24

ALL-SOLID-STATE: LTO| Li

Li6PS PS5Cl|LTO

Li4+xTi5O12/Li Li6PS PS5Cl Cl/Super P (3:6:1, mass)

1st discharge

50 mV

400 800 1200 1600 2000 400 800 1200 1600 2000

  • Z " (W)

Z ' (W)

1st 7th

0.00 0.04 0.08 0.12 0.16 0.20

  • 0.4
  • 0.2

0.0 0.2 0.4

Voltage (V) Areal capacity (mAh cm-2)

PreLTO : LiPSC : C (3: 6 : 1 by mass ) 100 um Li6PS5Cl 588 um PreLTO : LiPSC : C (3: 6: 1 by mass ) 100 um

100 um

Stack pressure: 2.5 MPa Current density: 0.1 mAβˆ™cm-2 (0.1 mA g-1)

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SLIDE 25

5 10 15 20 80 90 100 110 120 130 140 150 160

Discharge Capacity (mAh g

  • 1)

Cycle number

20 40 60 80 100 120 140 160 1.2 1.4 1.6 1.8 2.0

Voltage (V) Specific Capacity (mAh g

  • 1)

17.5mA g-1 (0.1 C)

1st 5th, 10th, 15th

Li4+xTi5O12/Li Li6PS PS5Cl Cl/Super P (Cathode =3:6:1, mass)

ALL-SOLID-STATE: LTO| Li

Li6PS PS5Cl|Li

Active material Solid electrolyte Li metal Ying Zhao

25

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PROBE-STRUCTURE BASED DIS ISCOVERY

10 20 30 40

Mo_2 (ο‚°)

Li2MgCl4 Li7Mg5Cl15S Li15Mg9Cl31S Li13Mg10Cl31S Li6Mg5.5Cl15S Li11Mg11Cl31S Li13Mg11Cl29S3 Li3Mg3Cl7S

Li Li-Mg Mg-P-S-Cl Cl

Paul Sharp

26

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SLIDE 27

0.0 Al 0.05 Al 0.1 Al 0.015 Al

Al O Al Al Zr

0.5 mo mol per er f.u. . Ti Ti- dop

  • ped LLTO

0.5 mo mol per er f.u. . Zr Zr- dop

  • ped LLTO

Al Al-doped LLZTO Ti Ti and Zr Zr-doped LLTO

OXIDES: LLZO

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DEVICE FABRICATION

Mihkel Vestli

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SLIDE 29

IN INDUSTRIAL IN INTERACTION

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PDRA PRESENTATIONS

  • Dr. Guanchen Li
  • Prof. Monroe’s group

University of Oxford

Den endrite nuc nucle leatio ion in n polycrysta tall llin ine lith thiu ium- conductive ceramic ics

  • Dr. Ying Zhao
  • Prof. Fleck’s group

University of Cambridge

  • Dr. Mihkel Vestli
  • Prof. Irvine’s group

University of St. Andrews

  • Dr. Paul Sharp
  • Prof. Rosseinsky’s group

University of Liverpool

Towards an an Opti timiz ized Composite e Cat athode Str tructure Tap ape-casti ting of f NASICON-based solid id state ba batt ttery Using ng Probe Structures to to Explo lore the e Li-Mg Mg-P-S-Cl l Phase Field ld with th ChemDASH

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SLIDE 31

SOLBAT: solid-state metal anodes (day 1)

Faraday Institution 8-monthly meeting Mauro Pasta

31