On the Route to Solid-State Batteries

Ima ge: Eli sa Mo n te © J LU Gieß en

Jürgen Janek (and teams @JLU & @KIT)

Inst. of Physical Chemistry & Center of Mater. Research, Justus-Liebig University Giessen, Germany & BELLA, Institute of Nanotechnology, Karlsruhe Institute of Technology, Germany

On the Route to Solid-State Batteries

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Foto: Rolf K. Wegst

Coordinators: K. Albe, O. Guillon, H. Ehrenberg, J. Janek, M. Winter

Fuel cells „go solid“ – After a „liquid start“

Alkaline Fuel cells at NASA

From: L. Kordesch, Fuel Cells, Wiley-VCH

Today:

Polymer FC

Solid Oxide FC

3

Benchmarking analysis of SSB literature (materials basis)

LIB (18650)

JLU

S. Randau, et int., F. H. Richter, J. Janek, Nat. Ener. 5 (2020) 259 Samsung cell data from: Y. G. Lee et al, Nat. Ener. 5 (2020) 299

Benchmarking analysis of SSB literature (materials basis)

LIB (18650)

JLU

S. Randau, et int., F. H. Richter, J. Janek, Nat. Ener. 5 (2020) 259 Samsung cell data from: Y. G. Lee et al, Nat. Ener. 5 (2020) 299

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Key Differences – Liquid vs. Solid Electrolytes (SEs)

J. Janek and W. Zeier, Nat. Energy 1 (2016) 16141

Status Quo (liquid EL´s)

• Transport:

Electrode cross-talk by diffusion, single or dual ion motion, electronic partial conductivity,

grain boundaries, temperature dependence

• Thermodynamics:

Stability window, thermal stability, safety

• Mechanics:

Chemo-mechanical coupling (in ceramic ASSB)

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Status Quo 11/2019: „All-Solid State Batteries“ (ASSB)

o LIB are „state-of-the-art“,

still potential for further improvement, but limits are obvious

(fast charging as current challenge).

o ASSB

internationally considered as

attractive concept

for high-E and high-P batteries.

o Japan: LIBTEC

consortium also started in 2018

o China:

Extensive activities

(academic and industrial, JJ at GLABAT meeting in 08/2019)

o Taiwan:

Rapidly increasing activities

(3 new consortia on SSB, JJ at workshop in 11/2019)

o USA:

Yet no national program, but delocalized programs

by ARPA-E (DOE) and EERE-VTO

o Korea:

Diverse programs, including SSB projects

J. Janek and W. Zeier, Nat. Energy 1 (2016) 16141

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Status Quo 11/2019: „All-Solid State Batteries“ (ASSB)

o LIB are „state-of-the-art“,

still potential for further improvement, but limits are obvious

(fast charging as current challenge).

o ASSB

internationally considered as

attractive concept

for high-E and high-P batteries.

o Precise technological and economic evaluation

still open:

o Thiophosphate-based cell concepts

ahead,

due to materials´ properties, but open issues.

o Oxide-based cell concepts

(and hybrid concepts)

on the way, processing issues

o Polymer-based cell concepts

already commercialized,

conductivity remains an issue,

new materials are on their way.

J. Janek and W. Zeier, Nat. Energy 1 (2016) 16141

9

Status Quo 11/2019: „All-Solid State Batteries“ (ASSB)

o LIB are „state-of-the-art“,

still potential for further improvement, but limits are obvious

(fast charging as current challenge).

o ASSB

internationally considered as

attractive concept

for high-E and high-P batteries.

o Precise technological and economic evaluation

still open:

Solid State Batteries – „three speeds“:

o „thio“

– ahead, but stability issues

o „oxide“

– on the way, various issues

o „polymer“

– ahead in processing, but conductivity issue

J. Janek and W. Zeier, Nat. Energy 1 (2016) 16141

10

Status Quo 11/2019: „All-Solid State Batteries“ (ASSB)

o LIB are „state-of-the-art“,

still potential for further improvement, but limits are obvious

(fast charging as current challenge).

o ASSB

internationally considered as

attractive concept

for high-E and high-P batteries.

o Precise technological and economic evaluation

still open.

o Massive industrial efforts

in Japan, Korea,

China and USA:

o Toyota MC, Samsung, LG, Toshiba, CATL, …

o Solid Power, Quantumscape, SolidEnergy, Ionic Materials

o Prologium, et.

o Yet unsolved challenge(s): Which solid electrolyte?

Which cell concept?

J. Janek and W. Zeier, Nat. Energy 1 (2016) 16141

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There is no „best solid electrolyte“ – a

SW

OT analysis

oxides/phosphates

sulfides/thiophosphates

polymers

→ There is

no perfect solid electrolyte!

→ No class of solid electrolytes can be excluded

based on the current state of research

→ AND: Competitive battery cells may be constructed as

hybrid (multilayered) SE cells?

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Trends in Solid-State Batteries – I. ASSB or hybrid cells

LIB cell

(with porous separator) graphite

anode

intercalation cathode

Hybrid cell (≥ 2 electrolytes): „Protected Li metal anode“

o Reversible Li metal anode enabled by SE separator

o Liquidcatholyte for optimized cathode operation o New SE/LE interface to be optimized (bottleneck) o Protected Li metal anode as new battery component o Key component for Li-sulfur, Li-O₂cells

Separator layer (or bilayer, depending on SE)

o Reversible Li metal anode enabled by SE separator

o Solid catholyte for optimized cathode operation o SE/SE interface to be optimized (kinetically better?) o Protected Li metal anode is implied

o Volume change may be critical

13

Trends in Solid-State Batteries – I. ASSB or hybrid cells

LIB cell

(with porous separator) graphite

anode

intercalation cathode

o Reversible Li metal anode enabled by SE separator

o Solid catholyte for optimized cathode operation o SE/SE interface to be optimized (kinetically better?) o Protected Li metal anode is implied

o Volume change may be critical

All-solid-state cell (≥ 2 electrolytes) – includes protected Li metal anode

All-solid-state cell (≥ 1 electrolyte(s)): SOFC-type concept

o Reversible Li metal anode enabled by SE separator

o Solidcatholyte for optimized cathode operation o SE/SE interface to be optimized (kinetically better?) o Li metal/SE anode composite for faster kinetics

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Trends in Solid-State Batteries – I. ASSB or hybrid cells

LIB cell

(with porous separator) graphite

anode

intercalation cathode

o Reversible Li metal anode enabled by SE separator

o Solid catholyte for optimized cathode operation o SE/SE interface to be optimized (kinetically better?) o Protected Li metal anode is implied

o Volume change may be critical

All-solid-state cell (≥ 2 electrolytes) – includes protected Li metal anode

All-solid-state cell (≥ 1 electrolyte(s)): SOFC-type concept

o Reversible Li metal anode enabled by SE separator

o Solidcatholyte for optimized cathode operation o SE/SE interface to be optimized (kinetically better?) o Li metal/SE anode composite for faster kinetics

o Volume change of Li metal mitigated

Various

options

for advanced cell concepts:

All rely on SE components and SE interfaces

with other (solid) electrolytes or active materials

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Trends in Solid-State Batteries – II. „Anode-free“ cells

Samsung SDI, Oral presentation @AABC Asia, Osaka, Japan, October 28th _{– 31}st ₂₀₁₉

(Avoiding the use of Li metal foils, recent (oral) report by Samsung SDI)

Predicted E_vol= > 900 Wh/L (with Li anode) >1000 Wh/L („anode-free“)

Conclusions

o Anode-free operation possible with suitable

current collector

o Dendrites and external pressure as

remaining problems

Reported (10/2019, AABC Asia)

Capacity = 5.87 Ah

V

= 3.78 V

E

= 921 Wh/L (SOC 100%)

E

= 427 Wh/kg (0.05 C)

Cell configuration (10/2019, AABC Asia):

o High-Ni NCM (>210 mAh/g, 6.8 mAh/cm

_{, LZO coated)}

o Argyrodite Li

PS

Cl, ionic conductivity ≈

2 mS/cm @25 °C

o Anode: Plated Li metal at Ag metal-carbon nanocomposite layer @Cu

Cycling data: S. H. Jung, et int, Y. S. Jung, Chem. Mater. 2018, 30, 8190 Coating graph: S. Culver, et int, J. Janek, Adv. Ener. Mater. (2019)

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Li_3-xB_1-xC_xO₃(30 nm) coating on LiCoO₂, Li₆PS₅Cl

Li-In anode

Trends in Solid-State Batteries: III. Coating for CAM

See next presentation

by Evonik Industries AG (Hanau)

Foto: Raimund Koerver

Thanks

for funding …

Center for Materials Research (LaMa)

HMWK – State Ministry for Science and Art

LOEWE Cluster „STORE-E“, ElCh@LaMa, W2W2B, HGP-E

DFG – German Research foundation

Collab. Project PAK 77 „Lithium high performance batteries“

BMBF – Federal Ministry for Education and Research

Projects „FestBatt“, „FELIZIA“, „BenchBatt“, „EvaBatt“, „CatSE“, „LiSe“

BASF Intern. Network „Electrochemistry & Batteries“

Partners: D. Aurbach, H. Gasteiger, B. Lucht, L. Nazar, P. Novak, S. Komaba, I. Krossing

BELLA – Batteries and Electrochemistry Laboratory, KIT Volkswagen AG