@

SOLID STATE BATTERIES:

A STORY ABOUT INTERFACES
PROF. PHILIPPE M. VEREECKEN

Distinguished Member of Technical Staff at imec

Part-time professor at KU-Leuven

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 INTRODUCTION

LITHIUM ION BATTERIES...

IT ONLY JUST BEGAN REALLY

2 CONFIDENTIAL
LITHIUM-ION BATTERY MARKET OUTLOOK
GROWTH POTENTIAL IS LARGE
Fast growing Li-ion battery market because of emerging and growing technologies
Electrical will become the norm for automotive
Further growth of mobile electronics and new additions such as wearables and IOT

Steep growth in use of electric cars

New technologies coming

Storage

EV

Mobile

Source: De Tijd

3 RESTRICTED USE
Li-ION CHEMISTRY HAS THE HIGHEST ENERGY DENSITY

Lithium Li-ion technology

Ion dominates
rechargeable
battery market
for electronics

http://www.houseofbatteries.com/images/Comparison_chart.jpg 5
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 THE BATTERY IS OFTEN THE LIMITING FACTOR
The emergence of Li-ion battery has enabled new applications
which emerged and evolved over the last decade...
Portable electronics Automotive Storage
High Energy
density of Li-ion
= portable
energy source
can be made
small enough

And will continue to do so for future electronics.

Form factor,
Safety, and
Fast charging
are needed for
future
developments

IoT Wearables Health Flexible electronics

6
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APPLICATION SPECTRUM OF Li-ION BATTERIES
Rechargeable Li-ion batteries

Power on board Portable electronics Vehicles

Back-up power chip or PCB

Hobby and power tools Bikes, automotive, aviation, rail,...
Wireless sensor networks
Mobile-IT
Renewable Energy

distributed wireless sensors and communicators...

Wearable and Flexible Smart watch, phones, tablets, PC’s

Home storage, micro-grid storage, grid storage

Smart carts, patches, wearables and flexible electronics...

< mWh < < Wh < < kWh < < MWh
1E-04 1E-03 1E-02 1E-01 1E+00 1E+01 1E+02 1E+03 1E+04 1E+05 1E+06

7
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EVOLUTION IN ENERGY DENSITY OF Li-ION CELL
AND FUTURE SET TARGETS BY INTERNATIONAL COMMUNITY

• Energy density of Li-ion cell

25 years has more than tripled in its
25 years of existence
• Further evolution of
electrode materials and
architectures will continue

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ENERGY STORAGE NEEDS
IT IS MORE THAN ENERGY DENSITY ONLY

Mobile EV GRID

Ene rg y d e nsity Ene rg y d e nsity Sa fe

Fa st re cha rg ing Fa st re cha rg ing Lo ng life time
Sa fe Sa fe Co st
Fo rm fa cto r Lo ng life time Susta ina b le
Co st Co st Hig h Ene rg y d e nsity
Lo ng life time Fo rm fa cto r Fa st cha rg ing
Fo rm fa cto r
Mo re to le ss imp o rta nt RESTRICTED USE
 BUT FIRST,
BACK TO THE BASICS

10 CONFIDENTIAL
Li-ION BATTERY CELL
THE COMPONENTS

negative electrode (anode)

positive electrode (cathode)

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LITHIUM ION CELL WITH LIQUID ELECTROLYTE
THE CELL IS LITERALLY SOAKED WITH LIQUID ELECTROLYTE SOLUTION

- Copper foil State-of-the art liquid cell

Li+ Carbon black

Graphite/Si composite anode
conductive agent

e-
Separator + liquid electrolyte
e-
Particle composite
~100 µm

Cathode impregnated e-
Liquid
with liquid electrolyte
electrolyte Active micro-
fills the e- powder

+
porous
Aluminum foil electrode Binder

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MATERIALS TODAY
Cathode Material V vs. Li+/Li Gravimetric Capacity Volumetric Capacity

LiNi0.8Co0.15Al0.05O2 (NCA) 3.8 V 180-200 Ah/kg 800-890 Ah/L

LiCo1/3Ni1/3Mn1/3O2 (NMC) 3.9V 160-170 Ah/kg 760-810 Ah/L
+ LiCoO2 (LCO) 3.9 V 140 Ah/kg 710 Ah/L
LiFePO4 (LFP) 3.4 V 170 Ah/kg 610 Ah/L

Cell voltage of 3.6V

LiMn2O4 (LMO) 4.1 V 148 Ah/kg 650 Ah/L

Cell voltage of 3.7 V

Liquid Electrolytes
• lithium salts, such as LiPF6, LiBF4 or LiClO4 in an organic solvent, such as ethylene carbonate, dimethyl carbonate,
diethyl carbonate, propylene carbonate and mixtures thereof.
• typical conductivity of about 6-10mS/cm at RT
• the solvent decomposes on initial charging and forms a solid layer at the anode called the solid electrolyte interphase (SEI).

Anode Material V vs. Li+/Li Gravimetric Capacity Volumetric Capacity

Li4Ti5O12 (LTO) 1.55V 160 Ah/kg 650 Ah/L

Li4.4Si (silicon)* 0.27 V 3580 Ah/kg 2190 Ah/L
- LiC6 (graphite) 0.15 V 370 Ah/kg 840 Ah/L
* Currently, only composites of Si(<10%) with graphitic carbon are commercially available
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Li-ION CELL WORKS BY “ION INTERCALATION”
SOLID-STATE ELECTROCHEMISTRY AT WORK

Ion transfer at Ion transfer at

electrode/electrolyte Electrolyte/electrode
interface interface

Diffusion though Solid-state diffusion

Solid-state diffusion liquid or solid
electrolyte

e- e-- e- e-
e- e e- e-
e- e- e- e-

Graphite Electrolyte LiCoO2 Li+ ion

Negative Electrode Positive Electrode e- electron
(0.15V) (3.9V) CONFIDENTIAL
THE ROLE OF Li+ ION IS MAINTAIN ELECTRONEUTRALITY
UPON OXIDATION IN ANODE AND REDUCTION IN THE CATHODE
Oxidized state Reduced state
with valence of with valence of
Cobalt (+IV) Cobalt (+III)

𝐿𝐿𝐿𝐿1−𝑥𝑥 𝐶𝐶𝐶𝐶𝑂𝑂2 + 𝑥𝑥𝐿𝐿𝐿𝐿 + + 𝑥𝑥𝑒𝑒 − ⇋ 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝑂𝑂2

−( 𝐶𝐶6 + 𝑥𝑥𝐿𝐿𝐿𝐿 + + 𝑥𝑥𝑒𝑒 − ⇋ 𝐿𝐿𝐿𝐿𝑥𝑥 𝐶𝐶6 )

+

Cell reaction: 𝐿𝐿𝐿𝐿1−𝑥𝑥 𝐶𝐶𝐶𝐶𝑂𝑂2 + 𝐿𝐿𝐿𝐿𝑥𝑥 𝐶𝐶6 ⇋ 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝑂𝑂2 + 𝐶𝐶6

Charged state Dis-charged state
(electrochemical potential (electrochemical potential
difference of ~ 3.7eV) difference of ~ 0 eV)
15 CONFIDENTIAL
THE ROLE OF Li+ ION IS MAINTAIN ELECTRONEUTRALITY
UPON OXIDATION IN ANODE AND REDUCTION IN THE CATHODE
Li+ ions are extracted from Oxidized state Reduced state
the layered LiCoO2 crystal to with valence of with valence of
compensate the gain in Cobalt (+IV) Cobalt (+III)
positive charge upon
oxidation of Co(III) to Co(IV)
𝐿𝐿𝐿𝐿1−𝑥𝑥 𝐶𝐶𝐶𝐶𝑂𝑂2 + 𝑥𝑥𝐿𝐿𝐿𝐿 + + 𝑥𝑥𝑒𝑒 − ⇋ 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝑂𝑂2

Li+ ions are inserted

into the layered LiCoO2
crystal to compensate
−( 𝐶𝐶6 + 𝑥𝑥𝐿𝐿𝐿𝐿 + + 𝑥𝑥𝑒𝑒 − ⇋ 𝐿𝐿𝐿𝐿𝑥𝑥 𝐶𝐶6 )
the loss in positive
charge upon reduction +
of Co(IV) to Co(III)
Cell reaction: 𝐿𝐿𝐿𝐿1−𝑥𝑥 𝐶𝐶𝐶𝐶𝑂𝑂2 + 𝐿𝐿𝐿𝐿𝑥𝑥 𝐶𝐶6 ⇋ 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝑂𝑂2 + 𝐶𝐶6
Charged state Dis-charged state
(electrochemical potential (electrochemical potential
difference of ~ 3.7eV) difference of ~ 0 eV)
16 CONFIDENTIAL
 Li1-xCoO2 Layered structure
Co(IV)  Li(I)Co(III)
(NMC and NCA active materials have layered structure as well)

LiMO2 structures are ordered derivatives of rock

salt (ordering occurs along alternate 111 layers)
Li intercalates into octahedral sites between the
edge sharing CoO2 layers
Good electrical conductor
Lithium de-intercalation varies from 0 ≥ x ≥ 0.5 and
is reversible
Capacity ~ 45 A -h/kg
Voltage ~ 3.7 Volts
Energy density ~ 165 W -h/kg
Cobalt is expensive (relative to Ti, Ni and Mn).

Anisotropic lithiation kinetics (depends on crystal orientation)!

 Li1-xMn2O4 spinel structure
Mn(IV)  Li(I)Mn(III)
Structure type is defect spinel
Mn ions occupy the octahedral sites, while Li+
resides on the tetrahedral sites.
Rather poor electrical conductivity
Lithium de-intercalation varies from 0 ≥ x ≥
1, comparable to Li1-xCoO2
Presence of Mn3+ gives a Jahn-Teller
distortion that limits cycling. High Li content
stabilizes layer like structure.
Capacity ~ 36 A -h/kg
Voltage ~ 3.8 Volts
Energy density ~ 137 W -h/kg
Mn is cheap and non-toxic.

Lithiation kinetics independent on crystal orientation

 NMC = LiNixMnyCozO2

• Ni-rich cathode materials

have higher capacity –
but are more reactive and
unstable
• Increasing the cut-off
voltage gives more
accessible lithium, but
electrolyte stability issues

Source: Kurt Vandeputte (Umicore),

ITF presentation, 23-24 May 2018,
Increasing Ni content
Antwerp, Belgium RESTRICTED USE
NEXT GENERATION HIGH ENERGY CATHODE MATERIALS
Li-rich cathode
“5V” cathode
materials
materials For increased

of liquid carbonate electrolyte

For increased capacity

Electrochemical window
energy Issues with
Issues with electrode stability
electrolyte stability

Current anodes are not stable against the

liquid carbonate electrolyte – however the
decomposition product forms a so-called
SEI layer (solid-electrolyte interphase)
which blocks further decomposition and
as such effectively widens the
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electrochemical window
* Goodenough et al., 2010 (DOI: 10.1021/cm901452z) RESTRICTED USE
(SUB)NANOMETER THIN ARTIFICIAL INTERPHASES
ALD/MLD SYSTEMS FOR COATING INSIDE THE POROUS ELECTRODES
Thin artificial interphase layers are deposited as protective buffer layers in the porous
electrodes to enhance battery performance and life-time
Imec also works on novel thin-film materials for added functionality in the electrode
(dual conductor materials)
Oxides and Li-compounds

Protective coating on active

material, carbon black and
current collector suppresses
ALD/MLD Picosun R200 integrated in glovebox decomposition of electrolyte

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Al2O3 IS THE MOST COMMONLY APPLIED PROTECTIVE COATING
(FIRST) Al2O3 COATING OF LiCoO2

• Al2O3 coating on
the full electrode
greatly improves
cyclability 
attributed to the
formation of a
artificial CEI

• Al2O3 coating
directly on
particles blocks
electronic access
• Coating cannot be
made too thick as
Al2O3 is an ionic
insulator
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TOO SMALL EC WINDOW LEADS TO DECOMPOSITION ELECTROLYTE
DECOMPOSITION ELECTROLYTE RESULTS IN INTERFACE DEGRADATION

Point-to-point Active Carbon black

binder material conductive agent
e-
e-
e-
e-

The decomposition (oxidation) of electrolyte at high voltage electrodes such as LiNi0.5Mn1.5O2 (LNMO) result in
the formation on undesired interphase layers – known as Cathode Electrolyte Interface (CEI) layers.
The CEI layers form on both the active electrode and carbon conductive additive (which is at the same potential)
These electronically insulating layers eventually hinder electrons from flowing from
the carbon black to the active material and/or
the current collector to the carbon black
25 RESTRICTED USE
TOO SMALL EC WINDOW LEADS TO DECOMPOSITION ELECTROLYTE
DECOMPOSITION ELECTROLYTE RESULTS IN INTERFACE DEGRADATION

Point-to-point Active Carbon black

binder material conductive agent Electrically insulating layer is
e- formed due to decomposition
of electrolyte on active material
e- and carbon black (or current
collector) at higher potentials
e- than EC window

e-

The decomposition (oxidation) of electrolyte at high voltage electrodes such as LiNi0.5Mn1.5O2 (LNMO) result in
the formation on undesired interphase layers – known as Cathode Electrolyte Interface (CEI) layers.
The CEI layers form on both the active electrode and carbon conductive additive (which is at the same potential)
These electronically insulating layers eventually hinder electrons from flowing from
the carbon black to the active material and/or
the current collector to the carbon black
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PROTECTIVE COATINGS HELP AGAINST INTERFACE DEGRADATION
ALD/MLD FOR COATING INSIDE THE POROUS ELECTRODES

Point-to-point Active Carbon black Protective coating on active

binder material conductive agent material, carbon black and
current collector suppresses
decomposition of electrolyte

Solution: deposition of “artificial interphase” layers to prevent the formation of

decomposition layer and maintain good electrical contact for good battery
performance and life time.

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TiO2 IS IONICALLY AND ELECTRONICALLY CONDUCTIVE
SO DOES NOT INHIBIT ION TRANSPORT

Planar thin-film models showed that 5nm TiO2 protective coating layer still does not
inhibit rate performance whereas 1nm Al2O3 does

Thin model
systems are used
to investigate
TiO2
interfaces and
LMO buffer layers as
Pt artificial
interphases – see
Felix Mattelaer, Philippe M. Vereecken, Jolien presentation
Dendooven, and Christophe Detavernier,
Adv. Mater. Interfaces, 1601237 (2017).
“Battery Interface
DOI:10.1002/admi.201601237 platform”

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BLOCKING INTERFACES AND INTERPHASES
STILL A MAJOR ISSUE ALSO FOR SOLID-STATE BATTERIES

Intentional or artificial
INTERPHASE layer

Disconnected
INTERFACES

Un-intentional
INTERPHASE
layer

(source: Toyota R&D announcement)

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SOLID STATE BATTERIES STILL REQUIRE PROTECTIVE COATINGS
EXAMPLE TOYOTA 2016

Kato et al., Nat. Ener., 2016

LiCoO2 cathode reacts with sulfide solid electrolyte (Li9.5Si1.7P1.4S11.7Cl0.3)

LiNbO3 coated LiCoO2 prevents direct reaction with the electrolyte
Enabling battery functionality
LiNbO3 is good ion conductor but poor electronic conductor (bandgap 4 eV)

31 RESTRICTED USE
 THIN-FILM MODEL SYSTEM
TO STUDY INTERFACES AND INTERPHASES
Powder composite electrode Thin-film model system
Zillion e- Carbon-Cathode
poorly interface
defined Electrolyte
interfaces e- One
Li+ ?
Cathode well-defined
X Cathode/Cathode interface
interface
Carbon – Carbon e- Li+
interface
Electrolyte/Cathode
interface

We make experimental model systems using thin film deposition (PVD, ALD) and patterning
to simulate and optimize the individual interfaces and to extract kinetic and transport
properties which can be input for theoretical models

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TF MODEL SYSTEMS ARE USED TO STUDY INTERFACES AND BUFFER LAYERS
PROTECTIVE COATING TO ENHANCE ELECTRODE CYCLABILITY AND RATE PERFORMANCE

Planar thin-film model systems are used to study interfaces and buffer layers
Thin-film LiPON coating on LiMn2O4 cathode improves cyclability by preventing Mn3+ dissolution
Thin-film am-TiO2 coating on LMO enhances the rate performance

B. Put, P. M. Vereecken, N. Labyedh, A. Sepulveda, C. Huyghebaert, I. P. Radu, and A. Felix Mattelaer, Philippe M. Vereecken, Jolien Dendooven, and Christophe
Stesmans, ACS Appl. Mater. Interfaces, 2015. DOI: 10.1021/acsami.5b06386 Detavernier, Adv. Mater. Interfaces, 1601237 (2017). DOI:10.1002/admi.201601237

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 SOLID-STATE AND LITHIUM METAL
FOR NEXT GENERATION BATTERIES

34 CONFIDENTIAL
EVOLUTION IN ENERGY DENSITY OF Li-ION CELL
AND FUTURE SET TARGETS BY INTERNATIONAL COMMUNITY

• Energy density of Li-ion cell

25 years has more than tripled in its
25 years of existence
• Further evolution of
electrode materials and
architectures will continue

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EVOLUTION IN ENERGY DENSITY OF Li-ION CELL
AND FORESEEN ISSUES

• Energy density of Li-ion cell

has more than tripled in its
Expected practical limit wet batteries 25 years of existence
with current set of active materials • Further evolution of
electrode materials and
architectures will continue
• Currently leveling off
towards practical ceiling of
800Wh/L by 2025

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EVOLUTION IN ENERGY DENSITY OF LI-ION CELL
AND ROADMAP TARGETS FOR 2025 AND 2030

Switch to
• Energy density of Li-ion cell
solid-state has more than tripled in its
batteries 25 years of existence
Expected practical limit wet batteries
• Further evolution of
electrode materials and
architectures will continue
• Currently leveling off
towards practical ceiling of
800Wh/L by 2025
• Switch to solid-state needed
to surpass the 800Wh/L
ceiling and reach the goal of
1000Wh/L in 2030

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EVOLUTION IN ENERGY DENSITY OF LI-ION CELL
AND ROADMAP TARGETS FOR 2025 AND 2030

• Energy density of Li-ion cell

Switch to solid-state batteries has more than tripled in its
25 years of existence
Expected practical limit wet batteries • Further evolution of
R&D targets – electrode materials and
5 years ahead
architectures will continue
• Currently leveling off
towards practical ceiling of
800Wh/L by 2025
• Switch to solid-state needed
to surpass the 800Wh/L
ceiling and reach the goal of
1000Wh/L in 2030

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SOLID ELECTROLYTE ENABLES METALLIC LITHIUM
THE PRINCIPLE IS SIMPLE – CREATE MORE SPACE IN THE CELL ARCHITECTURE

Solid electrolyte
650 Wh/L

1000 Wh/L
200 um

20 um 200 um 3. What about the cathode?

200 um 2. Reduction of “separator” thickness

<20 um
50 um 1. Reduction of anode thickness

NMC cathode NMC cathode

Graphite anode Lithium anode

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ELECTRODE MATERIAL SET PRACTICAL UPPER LIMIT
SOLID STATE EXTENDS THE PRACTICAL LIMIT FOR Li-ION CELLS

More cathode material

can be stacked in same
volume through change
SOLID of cell architecture
• Thinner (Li) anode
• Thinner separator
• Denser cathode?
LIQUID

Source: Marcel Meeus and Stéphane Levasseur (Umicore)

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SOLID STATE ENABLES NEXT GENERATION BATTERIES
WITH NANOTECHNOLOGY AND LI METAL ANODES

Solid-state enables increase energy and power density

Through more efficient use of the space in cell and battery
Introduction of high voltage cathodes and lithium metal
Solid-state provides safety
Elimination of the flammable solvent and of the risk of leakage (implants)
However still combustible and risk for poisoning
Solid-state provides form factor
Easier to mold in shape required
Potential for down-sizing for micro-batteries

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SAFETY
Removal of the flammable organic components
Laptop fire at conference First fire in a Tesla Model S burns Samsung Galaxy S7
$600 million off the company's value

Boeing 787 Dreamliner grounded Battery failure Fyra train Hoverboard on fire

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SOLID-STATE HAS STILL SOME CATCHING UP TO DO
target

750 Wh/L
High-energy NMC
>1 hour cells (3.6V):
Li-NiMnCo-oxide chemistry
as cathode C/Si as anode
and liquid electrolyte

Solid-state cells
Fast-charging LTO
First generations of all-
cells (2.4V):
solid state cells with
LiMn-oxide as cathode
inorganic solid electrolyte
LiTi-oxide as anode
have issues with rate
and liquid electrolyte
performance

Thin-film cells:
are solid-state batteries
which give fast charging
but low energy density

10 hours 1hour 6 minutes 36 seconds

44
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 IT STARTS WITH A
SOLID ELECTROLYTE
WITH GOOD ION CONDUCTIVITY

CONFIDENTIAL
CONDUCTIVITY OF ELECTROLYTE DETERMINES ITS THICKNESS
AND THUS THE POSSIBLE CELL ARCHITECTURE Don’t forget,
the electrolyte
is also inside
the porous
For an maximum internal cell resistance of 50Ω.cm2 electrodes!
> 100 μm

< 10 μm
Powder battery
σ >10-3 S/cm > 100 μm

Thin-Film battery
σ >10-7 S/cm < 2.5 μm
< 1 μm
< 2.5 μm

46 RESTRICTED USE
 Room-temperature
MANY SOLID-STATE ELECTROLYTES OUT THERE conductivity between 1and
10 mS/cm is needed to
match current liquid cell
technology
Organic electrolytes (liquid)
Li-salt in carbonate solvent
Li-salt in Ionic Liquid (ILE)
Polymer electrolyte (solid)
Li-salt in PEO
Polymer composite electrolyte
e.g. TiO2 NP in PEO
Polymer-Gel electrolyte
Polymer with added solvent
Inorganic crystalline SE
LiSICON, LLTO, Garnet
Inorganic glass SE
LiPON
Solid Composite Electrolyte (SCE)
Silica and alumina with Li-salt
MOFs

Nature Materials, DOI. 10.1038/NATMAT3066 RESTRICTED USE

TOP-10 REQUIREMENTS FOR SOLID ELECTROLYTE COMPONENT
DIFFERENT SOLID-STATE ELECTROLYTES GIVE DIFFERENT PROPERTIES
1. High ionic conductivity (σi>10-3 S/cm for large capacity batteries)
2. Wide electrochemical window (0 < V vs. Li+/Li < 5.5)
3. Chemical stability (temperature, against electrodes and metallic Li)
4. Wide temperature range (-40C  150C)
5. Negligible electronic conductivity (σe< 10-10 S/cm)
6. Transference number for Li+ close to 1 (tLi+≈1)
7. Resistant to lithium dendrites (mechanically –high Youngs modulus and/or chemically
reaction eliminating Li dendrites)
8. Manufacturable (upscalable, process control)
9. Low toxicity (use of environmentally benign elements)
10. Low cost (use of abundant elements)
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LiPON WAS ONE OF THE FIRST COMMERCIAL SOLID ELECTROLYTES
HOWEVER CAN ONLY BE USED IN THIN-FILM FORMAT BECAUSE OF ITS LOW CONDUCTIVITY

LMO-Li solid-state
thin film battery Lithium

MICA LiPON

LiMn2O4
240 µWh/cm2

1um LMO film has maximum

capacity of 63uAh/cm2

The battery stack consists of a LiMn2O4 cathode layer prepared by RF-sputtering and post treatment annealed, an electrolyte layer
of LiPON prepared by RF-sputtering and an anode layer consisting of a lithium metal thin film prepared by thermal evaporation.
49
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LiPON HAS EXCELLENT CHEMICAL STABILITY BUT LOW σLi

Organic electrolytes (liquid)

Li-salt in carbonate solvent
Li-salt in Ionic Liquid (ILE)
Polymer electrolyte (solid)
Li-salt in PEO
Polymer composite electrolyte
e.g. TiO2 NP in PEO
Polymer-Gel electrolyte
Polymer with added solvent
Inorganic crystalline SE
LiSICON, LLTO, Garnet
Inorganic glass SE
LiPON
Solid Composite Electrolyte (SCE)
Silica and alumina with Li-salt
MOFs

Nature Materials, DOI. 10.1038/NATMAT3066 RESTRICTED USE

NITROGEN-DOPED LITHIUM PHOSPHATE GLASS (LiPON)
PE-ALD LiPON films

Doping of amorphous Li3PO4 with

nitrogen increases enhances the Li+
ion conductivity with 3 orders of
magnitude
Advantage of LiPON is its chemical

Nitrogen doping
stability against metallic lithium and
broad electrochemical window of
[0V  ~5V]
Unfortunately its conductivity is at
least 3 orders of magnitude too
low for application in large capacity
batteries
“Plasma - Assisted ALD of LiPO(N) for Solid State Batteries Lithium-ion Batteries” Brecht
Put, Maarten J. Mees, Norah Hornsveld, Alfonso Sepulveda, Philippe M Vereecken, W. M.
M. Kessels, and Mariadriana Creatore, ECS Trans. 75(20): 61-69 (2017);
doi:10.1149/07520.0061ecst 51 RESTRICTED USE
SOLID-STATE THIN-FILM BATTERIES

on 3D micro-structured substrates for

micro-storage

CONFIDENTIAL
APPLICATION SPECTRUM
SOLID STATE Li-ION MICRO-BATTERIES
Power on board Portable electronics Vehicles

Back-up power chip or PCB

Hobby and power tools Bikes, automotive, aviation, rail,...
Wireless sensor networks
Mobile-IT
Renewable Energy

distributed wireless sensors and communicators...

Wearable and Flexible Smart watch, phones, tablets, PC’s

Home storage, micro-grid storage, grid storage

Smart carts, patches, wearables and

flexible electronics...

< mWh < < Wh < < kWh < < MWh
1E-04 1E-03 1E-02 1E-01 1E+00 1E+01 1E+02 1E+03 1E+04 1E+05 1E+06

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“TRUE” MICRO-DEVICES NEED MICRO-BATTERIES
WHICH THEN URGENTLY NEED TO BE DEVELOPED

Ultimately, the smallest size of a device is limited by its battery

Digital lens Micro drone Implantable glucose sensor Smart pill

54 RESTRICTED USE
COMMERCIAL THIN-FILM BATTERIES
PLANAR GEOMETRY PROVIDES LIMITED CHARGE CAPACITY

(Source: John Bates, Oak Ridge Micro-Energy)

Small <3um
cells with
small
capacity

 Thin films allow fast charging at C-rates >10C (less than 6 minutes)
 Charge Capacity is low (0.01 to 1 mAh) because of thin electrodes.
 Vacuum deposition for all layers, e.g.
o Cathode: LiCoO2
o Electrolyte: LiPON glass
o Anode: Li Metal, SnN3

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THIN-FILM BATTERIES GOING 3D

Higher capacity Lower capacity

2D (Planar)
Slower charging Faster charging
Capacity is increased by
increasing film thickness
but also slows down the
charging (practical limit
around 5um thickness)
3D
High capacity
Fast charging
3D (Microstructured)
Capacity is increased by
increasing the effective
surface area, while the films
can be kept thin for fast
charge/discharge kinetics

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3D THIN-FILM BATTERY FOR HIGH-SPEED MICRO STORAGE

Wet cells Requirements for micro storage

60 -120 mA.h/cm3
 Ultra small form factor: ≤ 1 mL
 High volumetric capacity: 60 -120 mAh/cm3
25-50 mA.h/cm3
 Fast charging: 80% max. capacity in 3 min
charging (20C)
 Safety & Stability
Our solution:
3D Solid-State Thin-Film Batteries
0.5-10 mA.h/cm3
Planar TF

60 RESTRICTED USE
FOOTPRINT CAPACITY > 2mAh/cm2
CAPACITY DENSITY >100mAh/cm3

The 3D thin-film battery could easily match the capacity and energy density of
commercial wet cells, but it should be at much higher C-rates (>10C)

“Towards 3D Thin-Film Batteries: Optimal current-collector design and scalable fabrication of TiO2 thin-film
electrodes" Sébastien Moitzheim, Joan Elisabeth Balder, Riina Ritasalo, Satu Ek, Paul Poodt, Sandeep
Unnikrishnan, Stefan De Gendt, Philippe M. Vereecken, ACS Appl. Energy Mater. 2, 3, 1774-1783 (2019) doi:
10.1021/acsaem.8b01905
61 RESTRICTED USE
Our silicon pillar arrays for micro-structured current collector substrates

Si µ-pillars are Si µ-pillars

fabricated by
lithography
patterning
and deep
reactive ion 2 µm
• pillar diameter: 2 µm
etching on • Inter-pillar spacing: 2 µm
300 mm Si 2 µm • Pillar height: 50-60µm
wafers Area enhancement of 20-25x
5 µm

20 µm
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OUR 3D THIN-FILM STACK
- -
current collector

anode
Solid electrolyte
cathode
current collector

+
Area enhancement of 25x

• Conformal coatings of cathode, anode

and electrolyte thin-films
• Low temperature budget
20 µm
• Industrially scalable techniques
63 RESTRICTED USE
 " Chlorine Doping of Amorphous TiO2 for Increased Capacity and Faster Li+-Ion Storage"
S. Moitzheim, J.E. Balder, P. Poodt, S. Unnikrishnan S. De Gendt and P.M. Vereecken,

PRINCIPLE WORKS Chem. Mater., 29, 23, 10007–10018 (2017) DOI: 10.1021/acs.chemmater.7b03478

PERFORMANCE OF OUR 3D Cl-doped TiO2 THIN-FILM ELECTRODE

Rate-performance Cycling stability

Same rate performance for 3D and planar electrodes but with 24

times higher capacity for the 3D TiO2 electrode
64 RESTRICTED USE
PRINCIPLE WORKS
PERFORMANCE OF OUR 3D LiMn2O4 THIN-FILM ELECTRODE

First demonstration of a 3D LMO electrode

Rate-performance

x21

Same rate performance for 3D and planar electrodes but with 21

times higher capacity for the 3D LMO electrode
68 RESTRICTED USE
 Double the capacity of
3D THIN-FILM ELECTRODES STATUS best planar thin-film
battery and with
LMO AND DOPED TITANIA HALF CELLS PLOTTED TOGETHER ~60mA/cm3 already
better than coin cells
1000

- 0.5mAh/cm2
current collector

TiO2-xCl2x (150nm)

Capacity (µAh/cm2)
Solid electrolyte (100nm)

LiMn2O4 (350nm) 100

current collector

+
100 nm 3D TiO2
Capacity and rate-performance of 3D 350 nm 3D LMO
10
thin-film cathode and anode will match in 0.1 1 10
the final device* C-rate
*Outer electrode will have large volume for same thickness
76 RESTRICTED USE
THIN-FILM ELECTROLYTE
CONFORMAL ELECTROLYTE IS THE BOTTLE NECK IN THE INTEGRATION
-
current collector

TiO2 (150 nm)

Solid electrolyte (100 nm)

LiMn2O4 (350 nm)

current collector

We are working on two approaches for conformal thin-film electrolyte:

• Conformal LiPON thin-films
• Conformal Solid nano-Composite Electrolyte (nano-SCE) thin-films
• Currently, we are working on the integration of the electrolyte in the stack

77 RESTRICTED USE
LiPON THIN-FILM ELECTROLYTE Top

 Conformal LiPON thin-films were

successfully deposited by plasma-enhanced
93 nm
atomic layer deposition (PEALD)
 ~ 80% step coverage was achieved Center
 The LiPON thin-films (planar!) have an ionic
conductivity of 5x10-7 S/cm at 300K 80 nm
 First to demonstrate a planar thin-film
battery with ALD LiPON Bottom
 Next, a full 3D cell will be built
"Plasma-assisted ALD of LiPO(N) for Solid State Batteries" Brecht Put, Maarten J. Mees,
Norah Hornsveld, Alfonso Sepulveda, Philippe M Vereecken, W. M. M. Kessels and 76 nm
Mariadriana Creatore, J. Electrochem. Soc. 166, 6, A1239-A1242 (2019) doi:
10.1149/2.1191906jes
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PLANAR THIN-FILM BATTERY WITH ALD LiPON
Li
70 nm LiPON
• First battery employing ultra thin ALD LIPON
200 nm Li4Ti5O12 • R = 15 Ω.cm2
Pt • Reaches 87 mAh/g
SiO2
• Li metal in contact with 70 nm LiPON is stable

"Plasma-assisted ALD of
LiPO(N) for Solid State
Batteries" Brecht Put,
Maarten J. Mees, Norah
Hornsveld, Alfonso
Sepulveda, Philippe M
Vereecken, W. M. M.
Kessels and Mariadriana
Creatore, J. Electrochem.
Soc. 166, 6, A1239-A1242
(2019) doi:
10.1149/2.1191906jes

79
RESTRICTED USE
 0.30

100 nm THIN-FILM POLYMER-SCE SCE conductivity: > 2×10-7 S/cm

Conductivity ( µS/cm)
0.25 SCE conductance: ~ commercial LiPON
thin film electrolyte
 Two-step deposition for SCE 0.20

0.15
• Deposit porous silica film
0.10

100 nm thick 0.05

mesoporous
silica film 1000 10000 100000
Molecular weight of polymer

120 0.1C
• Fill pores with polymer electrolyte 100 0.1C

Capacity(mAh/cm3)
by spin coating + 80
60 Functional Li/SCE/30nm TiO2
polymer-SCE cell was built
thin film 40
0.5C
1C
20
0
0 5 10 15 20
Cycle No.
“100 nm Thin-Film Solid-Composite Electrolyte for Lithium ion batteries” Xubin Chen and Philippe M. Vereecken, Adv. Mater. Interfaces 4 (4), 1600877 (2017). DOI:10.1002/admi.201600877 83
Xubin Chen, Solid Composite Electrolytes for Lithium Ion Batteries”, Ph.D dissertation, June 2018. RESTRICTED USE
3D-PLANAR HYBRID Li-ION BATTERY
In anticipation of the conformal electrolyte, a functional solid-state Li-ion battery was
demonstrated using our 3D LMO cathode versus a Li-foil using one of our nanocomposite
solid electrolytes (SCE) which is casted from a liquid precursor

Li
SCE

LiMn2O4
84 RESTRICTED USE
NOW BACK TO THE
LARGE CAPACITY
SOLID-STATE CELLS

CONFIDENTIAL
CONDUCTIVITY OF ELECTROLYTE DETERMINES ITS THICKNESS
AND THUS THE POSSIBLE CELL ARCHITECTURE

For an maximum internal cell resistance of 50Ω.cm2

> 100 μm

< 10 μm
Powder battery
σ >10-3 S/cm > 100 μm

Thin-Film battery
σ >10-7 S/cm < 2.5 μm
< 1 μm
< 2.5 μm

86 RESTRICTED USE
OXIDIC SOLID ELECTROLYTES WITH ION CONDUCTIVITY <1 mS/cm

Organic electrolytes (liquid)

Li-salt in carbonate solvent
Li-salt in Ionic Liquid (ILE)
Polymer electrolyte (solid)
Li-salt in PEO
Polymer composite electrolyte
e.g. TiO2 NP in PEO
Polymer-Gel electrolyte
Polymer with added solvent
Inorganic crystalline SE
Perovskite, Garnet, LiSICON, LLTO
Inorganic glass SE
LiPON
Solid Composite Electrolyte (SCE)
Silica and alumina with Li-salt
MOFs

Nature Materials, DOI. 10.1038/NATMAT3066 RESTRICTED USE

PEROVSKITE – Li0.5La0.5TiO3 OR LLTO
RECORDHOLDER FOR MANY YEARS WITH RT ION CONDUCTIVITY ~1mS/cm

Li-ions can move through channels in the

crystal to leave or occupy Li-sites similarly
as it is the case in electrode materials
However, small EC window as it is unstable
below 1.5V vs. Li+/Li

RESTRICTED USE
GARNET – Li7La3Zr4O12 OR LLZO
RT ION CONDUCTIVITY BETWEEN 0.1-1mS/cm FOR CUBIC STRUCTURE

High conductivity cubic structure

can be stabilized by doping with
substitution of La and Zr
Large EC window and stable against
metallic lithium

RESTRICTED USE
SULFIDIC SOLID ELECTROLYTES WITH ION CONDUCTIVITY >10 mS/cm

Organic electrolytes (liquid)

Li-salt in carbonate solvent
Li-salt in Ionic Liquid (ILE)
Polymer electrolyte (solid)
Li-salt in PEO
Polymer composite electrolyte
e.g. TiO2 NP in PEO
Polymer-Gel electrolyte
Polymer with added solvent
Inorganic crystalline SE
LiSICON, LLTO, Garnet
Inorganic glass SE
LiPON
Solid Composite Electrolyte (SCE)
Silica and alumina with Li-salt
MOFs

Nature Materials, DOI. 10.1038/NATMAT3066 RESTRICTED USE

THIO-LISICON AS NEW FAMILY OF SUPERIONIC CONDUCTORS
Li10GeP2S12 WITH RT ION CONDUCTIVITY OF ~10 mS/cm

S is larger than O and thio-LiSICON have

more open crystal structure than oxidic
LiSICON
3D framework with Li diffusion in a, b, and c
directions
Large EC window though some stability
issues are remaining

RESTRICTED USE
 Li-SULFIDE TYPE CRYSTALLINE MATERIAL (THIO-LISICON)
LATEST CLASS OF SUPERIONIC CONDUCTOR

World record of 25
mS/cm at room
temperature has been
achieved by Japanese
groups by substitution
and doping of the
superionic conductor
Li10GeP2S12 (LGPS)
resulting in a crystal
structure with widely
accessible channels for
Li-ion transport

Yuki Kato et al. High-power all-solid-state batteries using sulfide superionic

conductors, Nature Energy (2016). DOI: 10.1038/nenergy.2016.30
RESTRICTED USE
SOLID ELECTROLYTE AS “POWDER” LIMITS PERFORMANCE
LOWER CATHODE DENSITY AND “POINT” CONTACTS
Anode electrolyte cathode

Source: PhD thesis of X.

Chen, KU-Leuven (2018)

Solid electrolyte powder has to be mixed with electrode powder

Typically as pressed pellet even though also wet coated is possible
Porosity in the powder pellets/coatings is “lost space”
Particle size of the electrolyte powder limits the density of the active electrodes
Ionic interaction only at direct “particle-to-particle” contacts
93 RESTRICTED USE
ALSO FOR INORGANIC/CERAMIC SOLID ELECTROLYTES
INTERFACE ENGINEERING FOR “TRANSPARENT” INTERFACES

Pressing and sintering connects the individual particles at certain “contact points” only
and thermal (spark) process may create in-diffusion and blocking interfaces
(b) Electrolyte
particles

LLZO pellet
(Advanced Materials
29(22):1606042 (2017))

Interface

Contact area with potentially

an ionically blocking interfaceRESTRICTED USE
LIMITED CONTACT AREA AND BLOCKING INTERFACES
ALSO FOR CERAMIC SOLID-STATE COMPOSITE ELECTRODES

Electrolyte
particles
e- Cathode
particles
Carbon e-
Li+ ?
black e-
conductor X
Li+
e-

Limited contact area for ion

Electronic contact with carbon can be access with potentially
(source: Toyota R&D announcement) also compromised by interface layers blocking interface
due to sintering process e.g. Similar
story for cathode/cathode interface,
RESTRICTED USE
POOR RATE PERFORMANCE
PARTICLE-TO-PARTICLE CONTACT

• In liquids, the active material

particles are have maximum
contact with electrolyte which
is “all around”
• In case of a solid powder
(a) (b)
electrolyte, the active Electrode
electrode particles have particle
limited contact points Electrolyte
particle
(sintering step to increase the Interface
density and contact area)
Solid/Solid Solid/Liquid
point contacts All-around contact
"Solid and Solid-Like Composite Electrolytes for Lithium Ion Batteries: Engineering the ion conductivity at interfaces", Xubin Chen
96
and Philippe M. Vereecken, Advanced Materials Interfaces, 2018; doi: 10.1002/admi.201800899 RESTRICTED USE
HIGH Li-ION CONDUCTIVITY SOLID ELECTROLYTES

Organic electrolytes (liquid)

Li-salt in carbonate solvent
Li-salt in Ionic Liquid (ILE)
Polymer electrolyte (solid)
Li-salt in PEO
Polymer composite electrolyte
e.g. TiO2 NP in PEO
Polymer-Gel electrolyte
Polymer with added solvent
Inorganic crystalline SE
LiSICON, LLTO, Garnet
Inorganic glass SE
LiPON
Solid Composite Electrolyte (SCE)
Silica and alumina with Li-salt
MOFs

Nature Materials, DOI. 10.1038/NATMAT3066 RESTRICTED USE

SOLID NANO-COMPOSITE ELECTROLYTE (NANO-SCE)
ENHANCED ION TRANSPORT AT THE LARGE INTERNAL SURFACE

SCE = Ionic liquid electrolyte

confined in mesoporous silica

SCE monolith pellets

What’s unique? The Li-ion conductivity in the composite is

enhanced beyond the ion conductivity of the individual Li-
ion electrolyte confined in the pores of the porous oxide
nanocomposite due to formation of surface adsorbed layer
TEM of nanoporous oxide matrix after removal of the electrolyte or “mesophase” layer
99 RESTRICTED USE
LIQUID PRECURSOR FOR SOLID ELECTROLYTE
SIMILAR CELL ARCHITECTURES AND SIMILAR MANUFACTURING METHODS

Can be manufactured on similar manufacturing tool set as for wet batteries

Similar cell architectures and thus performance
Source: PhD thesis of X.
Chen, KU-Leuven (2018)

Li

SCE

powder electrode Impregnated with After solidification and

liquid precursor lamination with anode
RESTRICTED USE
IMEC PROCESS FOR NEXT GENERATION BATTERIES
MADE POSSIBLE BY HIGH CONDUCTIVITY NANOCOMPOSITE SOLID ELECTROLYTE

Click on link
https://www.imec-int.com/en/articles/imec-reaches-milestone-for-next-gen-solid-
For 2min movie state-batteries-to-power-future-long-range-electrical-vehicles

RESTRICTED USE
STATUS SOLID-STATE LI CELLS
AND CATHODE AND ANODE COMBINATIONS UNDER DEVELOPMENT

300
NCA
Li NMC811
Volumetric capacity [Ah/l]

250
Li
> 550 Wh/L
200 @ 0.02C NMC811
Graphite-Si
150 > 150 Wh/L LFP
@ 0.02C NMC811
Li Graphite
100
LFP
LTO > 210 Wh/L
50
@ 0.5C
Based on specs commercially available electrode foils
0
1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Cell voltage [V]

RESTRICTED USE
 IT’S (OVER)TIME FOR CONCLUSIONS

110 CONFIDENTIAL
IMEC WORKS ON TWO SOLID-STATE ARCHITECTURES
Rechargeable Li-ion batteries

Power on board Portable electronics Vehicles

Back-up power chip or PCB

Hobby and power tools Bikes, automotive, aviation, rail,...
Wireless sensor networks
Mobile-IT
Renewable Energy

distributed wireless sensors and communicators...

Wearable and Flexible Smart watch, phones, tablets, PC’s

Home storage, micro-grid storage, grid storage
(2) Solid-state 3D micro battery (1) Powder-based Large Energy cells
with thin-film materials with imec’s wet-casted
Smart carts, patches, wearables and flexible electronics... Solid nanoComposite Electrolyte (SCE)

< mWh < < Wh < < kWh < < MWh
1E-04 1E-03 1E-02 1E-01 1E+00 1E+01 1E+02 1E+03 1E+04 1E+05 1E+06

111
RESTRICTED USE
CURRENTLY: HIGH ENERGY DENSITY OR FAST CHARGING

High-energy NMC
700 Wh/L SSB
cells (3.6V):
> 1 hour
Li-NiMnCo-oxide chemistry
3D TFB
as cathode C/Si as anode
and liquid electrolyte

Fast-charging LTO
cells (2.4V):
LiMn-oxide as cathode
LiTi-oxide as anode
and liquid electrolyte

Thin-film cells:
are solid-state batteries
Solid-state cells
which give fast charging
First generations of all-
but low energy density
solid state cells with
inorganic solid electrolyte
have issues with rate 10 hours 1hour 6 minutes 36 seconds
performance
112
RESTRICTED USE
ACKNOWLEDGEMENTS
Estore team, imec-Leuven
Nathalie Hendrickx
Nick Clerckx
Dr. Maarten Mees
Dr. Brecht Put
Dr. Xubin Chen
Dr. Maarten Debucquoy
Dr. Knut Gandrud
Nouha Labyedh
Stanislaw Zankowski
Simon Hollevoet
Louis De Taeye
Eva Vandaele
Dr. Yongho Kee
Andrea Pitillas Martinez
Keerthi Reddy
Genis Vanheusden
Dr. Sergey Remizov
Akihiko Sagara
Bart Onsia, Dr. Geoffrey Pourtois, Prof. Paul Heremans
Prof. Christophe Detavernier and team, University Ghent 113
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114 CONFIDENTIAL