Solid State Battery – Challenges, Present and Perspectives

Tilmann Leisegang1,*
1Technische Universität Bergakademie Freiberg, Institut of Experimental Physics, Energy Materials
*tilmann.leisegang@physik.tu-freiberg.de

Jahresbericht Institut für Experimentelle Physik 2014 | Das Institut für Experimentelle Physik | 7

05 April 2022 Das Institut

Das Institut für Experimentelle Physik arbeitet an

der Schnittstelle von Kristallographie und Festkör-
perphysik zur Entwicklung neuer und innovativer
Blitzlab Funktionsmaterialien vorwiegend im Bereich der
Energie- und Datenspeicher sowie der Bioanwen-
dungen. Mehrere interdisziplinäre Arbeitsgruppen
befassen sich für diese Substanzklassen mit der Syn-
these und der Aufklärung von Struktur-Eigenschafts-
Beziehungen. Dazu beteiligt sich das Institut für Ex- des chemischen Elements Indium. Außerdem sorgte
perimentelle Physik aktiv am Ausbau und Unterhalt er durch Beschaffung einer Kopie des Urmeters aus
des Zentralen Reinraumlabors der TU Bergakade- Paris für die Einführung des metrischen Systems in
mie Freiberg und betreibt die Strukturaufklärung Sachsen.
mittels Röntgenstrahlung mit besonderem methodi-
schen Anspruch. Darüber hinaus ist das Institut in Heimstätte der Physik in Freiberg war zunächst das
ein aktives Kooperationsumfeld eingebunden und Gebäude in der Silbermannstraße. Im Jahre 1956
hat enge Verbindungen zu internationalen Groß- wurde ein zweites Physikalisches Institut eingerich-
 ‣ Energy Materials Team https://tu-freiberg.de/exphys/energiematerialien

Samara Center for

Theoretical Materials
Science

Tilmann Mohammadjafar Yen-Ming Li Manuel Huy Nguyen Anamika

Leisegang Momeni Rothenberger Dang Duc Anand
Team leader Postdoc PhD student Master student Student assistant Student assistant
2
 • Orange: Benchmark systems.

Article

ConductorsA
Mn B Zr Na K V Ca Zn Nb Hf Cr Rb Y W Li Be Sc Ni Mo

ensity Functional Study

ssment of elements.
e Materials,

segang,
fndIonic
Eds. T.The

Stefan
Conductors
evaluate
highest possible
Leisegang,

Adams,
a final system
value
et al., De

Vladislav
or concept,
‣ Topics
is 22. Berlin/Boston (2016).
Gruyter,

A.would
the next step Blatov,
be
on and collation of relevant criteria. This is characterized by a
10.1002/chem.201901438
https://tu-freiberg.de/exphys/energiematerialien

oach, taking into account the entire life cycle from raw material
g, without specific focus. Criteria have been collected in order
dents
Online
of as many relevant stakeholders as possible. There exist
Theoretical methods: GT, BVSE, DFT, ML
a or parameters that are suitable for the characterization of a
ng these, there are numerous dependencies, some of which are
v 31, 737 (2019).
Nestler, et al., Chem. Mater.
ndations *
sı Supporting Information Meutzner, et al., Phys, Sci. Rev. 4, 20180044 (2019).
ereitgestellt von | Technische Universitaet Bergakademie Freiberg Eremin, et al., J. Phys. Chem. C 123, 29533 (2019).
fy Angemeldet
Accepted Manuscript

Heruntergeladen am | 11.02.19 13:10

T)
h- Paper
gMater. 31, 737 (2019).
J. Phys. Chem. C123, 29533 (2019). Ionic conductors: Na /Zn /Al
+ 2+ 3+
Eremin, et al.,
e-lechtweg et al.25 proposed a time-
hydrogen yields from pyroelectro-
3namics of pyroelectrocatalysis by v J. 21, 16601 (2015)
Meutzner, et al., Chem. Eur.
We ally as an RC-circuit with faradaic
ns to be the best model describing Morkhova, et al., J. Phys. Chem. 125, 17590 (2021).
ther accounts for material specifics
er : AlPS
perties in4detail. Thus,
Leisegang, et al., Front. Chem. 7, 268 (2019).
à the accuracy
Zn2+ solid electrolytes
7
stth formal aspects of pyroelectro-
We develop a physical model to
n
emical reactions on pyroelectric Current collectors: LIB, NIB
y.
ropose an appropriate thermo-
O
does) not
m. with
6Eur. migration
require
J. 25, energies
external electric
8623 (2019).
function of the real pyroelectric
of less
Morkhova, than
et al., 0.7 eV/ion.
submitted v (ZF4751502JO9).
(2021). ZIM-Project: LiIonSK
nducting S-containing candidates. Blue spheres: Al, orange spheres: S, grey polyhedra: Tl-S (a), P-S

roach, compared the

ile medium. Estimations of the
value of the
results of different approaches,
dentified by VDP, blue isosurface: percolating Al3+-migration energy structure from BVSE.

compounds, 2 in the BCP is positive and the corresponding

eesented.
@ batterymaterials.info (database).
withInthe
se from O to
s positive. proposal
addition we study ofthe Zn-ion all-solid-state battery
-values are relatively low, ranging from approx. 0.03 (Sr)
to approx. 0.24 (Mo); see supporting material. Hence, the bond
character of Al-X and M-X seems ionic for all 15 combinations
nalcharacteristics was
and material parameters onuploaded to our database
(see supplementary material). The increased Coulomb attraction
BCP) and
119, 18278 (2015).
mpare
and the resulting shorter bond-lengths of X to M with increasing
simulation results to real
covalent or M-valence is the reason why electron density between M and X
nd positive
.ture.
Technol. 52, 1521 (2016). Meutzner, et al., Phys. Sci. Rev. 20180044, 2 (2018).
closed-shell
is steadily increasing. This increase is especially strong for O.
As can be seen in Fig. 1d, there is increasing negative Laplacian,
bond were especially between Al and X, but the distances between M and
decreasing X decrease stronger than for Al and X, suggesting also an
g amount of
roughout all
catalytic threshold
increasing, yet slight covalent character of the bonding.
Batteries: coin/pouch cells, solid state
onally, alkali metal-ion (e.g., Na+, K+) batteries are v 4007 (2016).
Stepniak, et al., RSC Advances 6, D. C. Meyer, T. Leisegang, et al.
d as the most viable alternatives or complements to
nn existing
batteries. However,
thermodynamic cycles high-valent metal-ion (e.g.,
Hanzig, et al. J. Power Sources 267, 700 (2014). (Eds.), Berlin, Boston: De Gruyter,
+ the2+
and , Al3+for
, Zn process ) batteries
the harvesting also appear very promising due
protected by copyright. All rights reserved.
Nestler, et al., Crit. Rev. Solid State Mater. Sci. 44, 298 (2019). 2019.
potential of a pyroelectric particle
ilability and low cost
ater) can be raised only up to a
of raw materials and the higher Nestler, et al. AIP Conf. Proc. 1597, 155 (2014).
heworking ions, which
varying temperature inducesin turn leads to higher energy
A induce
ain recent assessment
surface-bound of elements of the periodic table
charges. Patents: WO2017140581A1, DE102013013785, DE102013013784. 3
electrostatic potential and can
Zn on position 13 as
ace to the surrounding fluid after promising for metal electrode
eZinc as aenergy
activation negative electrode also has a long history,3,9
– is overcome.
ifference required for chemical
ith the voltaic pile, alkaline batteries, and especially
threshold voltage, Vth. Charge
tteries. Whilepotential
reshold reaction Zn−air batteries use oxygen as cathode,
is not
10
carbon battery
ns (high electric is not
resistance rechargeable. The fact that the
of the
Once Vth has been reached, the
in batteries has an
by an infinitesimal temperature
intensive and more-than-200-year
 ‣ Batteries for Electric Vehicles
∼1911

∼2013
Leisegang, et al., Front. Chem. 7, 268 (2019). 4
ntwicklung LiB [GWh p.a.] Marktentwicklung LiB [GWh p.a.]
1000
900
800
LiB Marktentwicklung LiB Marktentwicklung
‣
auf dem Batterieforum gezeigt 2017 2018 2019 2020 2021aufASSB
Batteries: Market Development
700 & Roadmap
dem Batterieforum gezeigt 2017
600
2018 2019 2020
2020 / 2021

Marktentwicklung LiB [GWh p.a.] 500 Marktentwicklung LiB [GWh p.a.]

1000 400 1000
900 900
800 300 800
700
Prognose: 2017 700
Prognose: 2021
200 600
600
500 100 500

Product
400 Watch Report - European Commission 400
300 0 300
2002005 2010 2015 2020 2002005 2025 2010 2015 2020
100 100
0 electric devices (PC, mobile phones, electronic) automotive industrial, stationary
0 otherdevices (PC, mobile phones, electronic)
electric automotive industrial, stationar
2005 2010 2015 2020 2025 2005 2010 2015 2020 2025
new emerging approaches are conducted, and exclude those that are already commercially available
electric devices (PC, mobile phones, electronic) automotive industrial, stationary other electric devices (PC, mobile phones, electronic) automotive industrial, stationary other

e.g.Quelle:
for
19.01.2022
mobile devices.
Avicenne Energy Analysis 2016; Berenberg 2016; SGL Carbon 19.01.2022 Quelle: IHS Markit Update 12/2019, Avicenne Reports 2018 & 2019, research
Quelle: Avicenne Energy Analysis 2016; Berenberg 2016; SGL Carbon
13 reports from major investment banks, SGL Carbon
13
19.01.2022 Quelle: IHS Markit Update 12/2019, Avicenne Reports 2018 & 2019, research reports from major investment banks, SGL Carbon

Figure 1: Roadmap for High Energy Batteries 2030+

Lithium all solid sate battery (ASSB) roadmap:

Source:
AdvancedThielmann & Neef,
technologies for industry2019
– Product watch, Solid-state-lithium-ion-batteries
for electric vehicles, European Commission, European Union, Brussels, 2021.
Figure 1 shows the development towards high safety all-solid-state batteries as potential enabler for 5Li-
metal anodes and the vision for their performance characteristics. SPE (Solid-polymer-electrolyte) SSBs
have been demonstrated and produced on small scale (Technological Readiness Level (TRL): 7-8).
Market introduction with competitive performance indicators might be possible by 2025+. Hybrid solid
electrolytes and SCE (Solid-ceramic-electrolytes) are in applied research or basic research stage (TRL
ntwicklung LiB [GWh p.a.] Marktentwicklung LiB [GWh p.a.]
1000
900
800
LiB Marktentwicklung LiB Marktentwicklung
‣
auf dem Batterieforum gezeigt 2017 2018 2019 2020 2021aufASSB
Batteries: Market Development
700 & Roadmap
dem Batterieforum gezeigt 2017
600
2018 2019 2020
2020 / 2021

Marktentwicklung LiB [GWh p.a.] 500 Marktentwicklung LiB [GWh p.a.]

1000 400 1000
900 900
800 300 800
700
Prognose: 2017 700
Prognose: 2021
“The development of all-solid-state is one
600
of the most promising and important steps 200
batteries
600
500 100
towards more efficient, sustainable,
500
and safer electric vehicles.”
Product
400 Watch Report - European Commission 400
300 0 300
2002005 2010 2015 (Frank Weber,
2020BMW
2005
200 board member
2025 2010 for development,
2015
May 2021)
2020
100 100
0 electric devices (PC, mobile phones, electronic) automotive industrial, stationary otherdevices (PC, mobile phones, electronic)
electric automotive industrial, stationar
(https://www.electrive.com/2021/05/04/bmw-ford-invest-in-solid-state-battery-specialist-solid-power/)
0
2005 2010 2015 2020 2025 2005 2010 2015 2020 2025
new emerging approaches are conducted, and exclude those that are already commercially available
electric devices (PC, mobile phones, electronic) automotive industrial, stationary other electric devices (PC, mobile phones, electronic) automotive industrial, stationary other

e.g.Quelle:
for
19.01.2022
mobile devices.
Avicenne Energy Analysis 2016; Berenberg 2016; SGL Carbon 19.01.2022 Quelle: IHS Markit Update 12/2019, Avicenne Reports 2018 & 2019, research
Quelle: Avicenne Energy Analysis 2016; Berenberg 2016; SGL Carbon
13 reports from major investment banks, SGL Carbon
13
19.01.2022 Quelle: IHS Markit Update 12/2019, Avicenne Reports 2018 & 2019, research reports from major investment banks, SGL Carbon

Figure 1: Roadmap for High Energy Batteries 2030+

Lithium all solid sate battery (ASSB) roadmap:

Source:
AdvancedThielmann & Neef,
technologies for industry2019
– Product watch, Solid-state-lithium-ion-batteries
for electric vehicles, European Commission, European Union, Brussels, 2021.
Figure 1 shows the development towards high safety all-solid-state batteries as potential enabler for 5Li-
metal anodes and the vision for their performance characteristics. SPE (Solid-polymer-electrolyte) SSBs
have been demonstrated and produced on small scale (Technological Readiness Level (TRL): 7-8).
Market introduction with competitive performance indicators might be possible by 2025+. Hybrid solid
electrolytes and SCE (Solid-ceramic-electrolytes) are in applied research or basic research stage (TRL
 ‣ Battery
parison of conventional lithium-ion battery and all-solid-state lithium battery at the cell, stack, and pack levels with potentials for increased energy density.
or, which consist of the active material, conductive
nder [1]. The ion transfer requires a liquid electrolyte
y composed of aprotic organic solvents and a conductive
he issues that current LIBs are facing can be traced back
electrolyte. Safety concerns, in fact, arise from the
Journal of Power Sources 382 (2018) 160–175
—> increase in energy density/specific energy
—> more charge/discharge cycles
—> higher safety
—> wider temperature range
—> absence of leakage and corrosion
Schnell, et al., J. Power Sources 382, 160 (2018).
6
cell and to reduce the amount of current collectors in the cell stack, as
well as to optimize the packaging design (Fig. 1, image d). Finally, no
cooling system is required for ASSBs due to the lack of flammable or-
ganic components, as depicted in Fig. 1 (image e) and Fig. 1 (image f).
In fact, higher temperatures rather lead to an increased functionality
‣ Resources, Economy
Anode Electrolyte Cathode

Xn+

O > 45 at.-%*

X > 30 at.-%*

> 20 at.-%* (rest)

*Prototype: All-Solid-state Li-Ion-battery (Schnell et al., J. Power Sources 382, 160 (2018)).
Leisegang, et al., Front. Chem. 7, 268 (2019).
9
‣ Evaluation of Suitable Anode Element

?
10
 solid electrolyte and intercalation electrode X > 30 at.-%*
Metal
metal-electrode
materials must besystems.
identified [3] and synthesized. Z
R > 20 at.-%*
On the basis of the evaluated elements, new sustainable
Rest concepts of electroche-
Leisegang, et al., Front. Chem. 7, 268 (2019).
mical energy storage systems can be developed. In doing so, cathode and solid-

‣
electrolyte
Evaluation
Anode
materials
Material
theoretical
have to
of Suitable be identified.
Anode
Identification
approach for
Element Chapter 4.1 of this book describes a
finding certain materials.
• Strengths and weaknesses analysis of the elements (as anode materials)
25
• Electrochemical (dark) and resource-economic
20 characteristics (light).
• Orange: Benchmark systems.
Figure of merit

15

10

AI Si Mg Fe Ti Mn B Zr Na K V Ca Zn Nb Hf Cr Rb Y W Li Be Sc Ni Mo
0

6). Figure 1.5: Result of

Electrochemical assessment
Storage of elements.
Materials, Eds. T.The highest possible
Leisegang, value
et al., De is 22. Berlin/Boston (2016).
Gruyter,

Electrochemical Storage Materials: From Crystallography to Manufacturing Technology. D. C. Meyer, T. Leisegang, et al. (Eds.), pp. 1–16, Berlin, Boston: De Gruyter, 2019. 11

Identification
In order to describeof
andIonic
Chemistry - A European Journal Conductors
evaluate a final system or concept, the next step would be 10.1002/chem.201901438
the ongoing elaboration and collation of relevant criteria. This is characterized by a
FULL PAPER
comprehensive approach, taking into account the entire life cycle from raw material
‣ Electrolyte and Cathode
Anode Electrolyte Cathode

Xn+

O > 45 at.-%*

X > 30 at.-%*
• Common property: ionic conductivity σ
> 20 at.-%* (rest)

*Prototype: All-Solid-state Li-Ion-battery (Schnell et al., J. Power Sources 382, 160 (2018)).
Leisegang, et al., Front. Chem. 7, 268 (2019).
12
 ‣
Occupied stable Occupied metastable
Transition state
Ionic Conductivity cation site
Vacant stable
cation site
Vacant metastable
Direct
Correlated

REVIEW ARTICLE
cation site cation site

NATU
b Transition
(Meta)stable state (Meta)stable
site site

a implies the absence of regular coordinatio

Mobile ion energy

Vacancy Direct Correlated
interstitial (interstitialcy) long-range migration pathways. Despite dil
theory for conduction in the amorphous s
lished40,41. Nevertheless, elements of the ho
be utilized, but E require a statistical
m ν treatmen
0

a distribution α
of activation energies for hop
one. Pair distribution function analysis of to
0
Migration path

c combination with reverse Monte Carlo ap

Metastable Metastable
Stable
(interstitial) (interstitial)
site
direct visualization of the atomic arrangeme
site site

Occupied stable Occupied metastable

Transition state
ways in amorphous samples43,44. Such ana

Mobile ion energy

cation site cation site
Direct NMR, vibrational and X-ray photoelectron
Vacant stable
cation site
Vacant metastable
cation site
Correlated may serve E to establish the link between stru
m
interstitialcy

ple, the anion framework) and conductivity

Famprikis, et al., Nat. Mater. 18, 1278 (2019). the large system sizes required for satisfact
b Transition
direct probing of ionα dynamics at the ato 0
(Meta)stable state (Meta)stable
site site molecular dynamics α'
Migration calculations
0
path can be d
promising alternatives are being develope 13
ile ion energy

Fig. 3 | Cation migration mechanisms and associated energy profiles.

interatomic
a, The arrows indicate threepotentials
typical migrationderived
mechanisms:from
vacancy,machi
direct
phous
interstitial Li3PO(interstitialcy)
and correlated
4 (ref. ).
47 involving a single or multiple sites
(blue and red, respectively). Circles represent cations in stable (green)
and metastable (orange) sites of a model crystal lattice. Dotted lines
 Figure 1.5: Result of
Electrochemical assessment
Storage of elements.
Materials, Eds. T.The highest possible
Leisegang, value
et al., De is 22. Berlin/Boston (2016).
Gruyter,

‣ Search
Identification
In order to describeof
andIonic
Algorithm
try - A European Journal Conductors
for Ion
evaluate aConductors
final system or concept, the next step would be10.1002/chem.201901438
the ongoing elaboration and collation of relevant criteria. This is characterized by a
L PAPER
comprehensive approach, taking
Zn2+ into account the entire life cycle from raw material
to end-of-life recycling, without specific focus. Criteria have been collected in order
to meet the requirements of as many relevant stakeholders as possible. There exist
more than 60 criteria or parameters that are suitable for the characterization of a
storage system. Among these, there are numerous dependencies, some of which are

Bereitgestellt von | Technische Universitaet Bergakademie Freiberg

Angemeldet

nuscript
Heruntergeladen am | 11.02.19 13:10

Nestler, et al., Chem. Mater.TOPOSPRO

Nestler, et al., Chem. Mater. 31, 737 (2019).
31, 737 (2019).Paper
SoftBV
Leisegang, et al., Front. Chem. 7, 268 (2019).
Eremin, et al., J. Phys. Chem. C 123, 29533 (2019).

defined.Blatov,
Mostet al.,
Eremin, et al.,
Schlechtweg et al.25 proposed aChen,
Cryst. Growth Des. 14, 7, 3576 (2014).
recently,
J.et al.,
time-
Phys. Chem.
Acta Crystallogr. C123,
B, 75.1, 29533 (2019).
18 (2019). 14

pendent model to predict hydrogen yields from pyroelectro-

alysis. They describe the dynamics of pyroelectrocatalysis by
 Figure 1.5: Result of
Electrochemical assessment
Storage of elements.
Materials, Eds. T.The highest possible
Leisegang, value
et al., De is 22. Berlin/Boston (2016).
Gruyter,

‣ Search
Identification
In order to describeof
andIonic
Algorithm
try - A European Journal Conductors
for Ion
evaluate aConductors
final system or concept, the next step would be10.1002/chem.201901438
the ongoing elaboration and collation of relevant criteria. This is characterized by a
L PAPER
comprehensive approach, taking
Zn2+ into account the entire life cycle from raw material
to end-of-life recycling, without specific focus. Criteria have been collected in order
to meet the requirements of as many relevant stakeholders as possible. There exist
more than 60 criteria or parameters that are suitable for the characterization of a
storage system. Among these, there are numerous dependencies, some of which are
Collection of cathode & solid electrolyte materials: https://batterymaterials.info

Bereitgestellt von | Technische Universitaet Bergakademie Freiberg

Angemeldet

nuscript
Heruntergeladen am | 11.02.19 13:10

Nestler, et al., Chem. Mater.TOPOSPRO

Nestler, et al., Chem. Mater. 31, 737 (2019).
31, 737 (2019).Paper
SoftBV
Leisegang, et al., Front. Chem. 7, 268 (2019).
Eremin, et al., J. Phys. Chem. C 123, 29533 (2019).

defined.Blatov,
Mostet al.,
Eremin, et al.,
Schlechtweg et al.25 proposed aChen,
Cryst. Growth Des. 14, 7, 3576 (2014).
recently,
J.et al.,
time-
Phys. Chem.
Acta Crystallogr. C123,
B, 75.1, 29533 (2019).
18 (2019). 14

pendent model to predict hydrogen yields from pyroelectro-

alysis. They describe the dynamics of pyroelectrocatalysis by
‣ Solid State Battery: From Materials to Design

Morkhova et al., J. Phys. Chem. 125, 17590 (2021).

15
‣ Solid State Battery: From Materials to Design
J. Schnell et al. Jou

Fig. 2. Composit
energy ASSBs wit
100 μm thick NM
solid electrolyte,
30 μm thick lithiu
density of 1177 W
kg−1 for a sulfid
based ASSB, resp
osities in the elec
reduce the overa

Schnell, et al., J. Power Sources 382, 160 (2018). 15

challenges from the perspective of production engineering and devel- 2.1. Product requirements
oping possible production scenarios for the fabrication of ASSBs.
After an investigation of the requirements and properties of ASSBs To meet the demands for automo
−1
 ‣ Solid State Battery: Multiscale Ion Transport & Microstructure
NATURE MATERIALS REVIEW ARTICLE
σGBi ASR charge
transfer

rtic e
pa thod
le
Ca
Contact
σcrystal area

Composite
cathode
ASR xface
σamorphous
ZSSB

σmeso
Micro Device σmacro
(nm) (mm) SE
EHop, νHop Metal
anode

Atomic Macro Solid-state battery (cm)

(Å) (µm)
Famprikis, et al., Nat. Mater. 18, 1278 (2019).

Nuclear magnetic resonance Impedance spectroscopy

• Various physiochemical and electrochemical transport phenomena occurring at multiple length and time scales.
Molecular dynamics Continuum modelling 16

Diffraction, pair distribution function analysis

Electron microscopy
 ‣ Solid State Battery: Fundamentals & Challenges
REVIEW ARTICLE NATURE MATERI
• Evolution of chemical potential:
REVIEW ARTICLE
• Mechanical degradation:
(equation (4)) , and other researchers have expanded th
65

Vcathode Oxidation to Li-poor μLi, cathode Na (ref. 84) and Mg (ref. 85) creating effective libraries of st
interphase?
windows. In practice, such computed stability windows mP
T
extended due to stabilizing kinetic effects. A certain ‘overp
Fracture i
Electrolyte μLi, SE tial’ beyond the K lc thermodynamic stability limit is often requid
stability window
drive the atomic rearrangements associated with decompositio b
example, about ±0.5 V in the case of Na3PS4 (ref. ). The m 83
i
tude of this required overpotential +
could be
Solid electrolyte linked to the mob g
Vanode
μLi, anode charged species in the electrolyte , which
Li 86
ESE, GSE would explain thee
Reduction to Li-rich
interphase? for the most conductive electrolytes to decompose most ea
contact with electrodes. S
The high-voltage oxidation Electrode stability of solid electrolytes is l
r
+ m
Anode Cathode
set by the anion Liframework E E , Gand
E specifically its propensity to gp
Li reservoir Li sink electrons,
σ adh ,typically
γ xfc limited by the anion with the
ε electrochemical
Li
+ lowest ioni
h
potential following the order N3− < P3− < H− << S2− < I− a
< Br −
< Cl− << F− (ref. 65). Inversely, the
Adhesion
stability against redo
Delamination

is set by the propensity of the solid electrolyte to accept elecn

Solid electrolyte Vacancy accumulation
Fig.accounted
6 | Mechanical bydegradation
the Famprikis,
electron of a affinity
solid-stateofbattery.
the (non-mobile)
The mechanicalcation r
Vacancy depletion et al., Nat. Mater. 18, 1278 (2019).
(Interstitial accumulation) thickness (nm) (Interstitial depletion) properties (Young’s
note that the and shear moduli,
electron affinityE and
canG,berespectively, by the specificr
affectedfracture
Positive space-charge Negative space-charge toughness KIc) of the solid characteristics.
electrolyte (SE) andFor electrode (E) dictate the
ture and bonding example, a phosphorus
response of the system to the strain (εelectrochemical) during cycling. The 17
will be reduced more easily if weakly bonded to sulfur atomse
Fig. 4 | Evolution of chemical potential across the solid electrolyte in adhesion of different solid phases in the composite can be quantified m
pared with when strongly bonded to oxygen species, as exemc
through the adhesion strength σadh and interfacial energy γxfc.
contact with an anode and a cathode. The y axes denote the voltage (V, by the increased stability of Li3PO4 compared with Li3PS4 (ra
increasing) and the chemical potential (μ, decreasing) (see equation (4)) Indeed, consequences,
the stability such against reduction
detrimental as the formationhas been experime
of fractures and f
 ‣ Manufacturing of TF-SSB: SSB Meets FLA
• Thin-film solid-state batteries: low-power devices such as wearable sensors, implantable medical devices, RFID, …
ACS Applied Energy Materials www.acsaem.org Letter

T > 700 °C

Figure 1. Processing steps for fabrication of TF-SSBs on Al foil.

Metallic substrates offer lower material cost, present phase and electrochemical performance while avoiding damage
flexibility, and do not require an additional current collector to the Al foil. To estimate the temperatures reached on the
layer unlike polymer and ceramic substrates. Conventional Li- surface Chen,
of the LCO
et al.,layer, the SimPulse
ACS Appl. Energy software
Mater. 4,was
5408used. The
(2021).
ion batteries employ Cu and Al as substrates for anode and simulation results are shown in Figure 2. On the surface of the
cathode, respectively. Surface-passivated Al foil is electro- cathode, annealing temperatures ranging from 700 to 900 °C
chemically stable against high voltage cathodes and cost- were estimated. Thicker films demand a higher surface
effective from an industrial perspective. However, the use of Al temperature to ensure sufficient crystallization for good18
foil as a substrate for TF-SSBs is impeded by its melting point electrochemical performance of the cathode. Simultaneously,
g for (a,b) Figure
0.7, (c,d) 1.2, and
2. Simulated (e,f) 3.3 μm LCO
°C and profiles
of 660temperature films on
the cross-diffusionAl foil,
of FLA microsecond of Al and cathode
processing the Al
for (a,b) 0.7, (c,d) 1.2,substrate
and (e,f) remained
3.3 μm LCO below
filmsthe
onmelting
Al foil, point of the Al foil
terface, andrepresenting
in the bulk temperatures
of the Al foil.reached
Left plots show threesurface,
enlarged
re profile during
on the LCO at
components that degrade the electrode performance. the LCO/Al interface, and in the (660 °C) for most of the experiments. This simulation
bulk of the Al foil. Left plots show three enlarged
pulsesthe processing.
after 42 sNovel
processing, and right
photonic plots show
methods forthecathode
completecrystallization
temperature profile during theconfirms
have processing.that the LCO films can be annealed without
 ‣ Manufacturing of TF-SSB: SSB Meets FLA
ied Energy Materials www.acsaem.org
ACS Applied Energy Materials
Letter

A
E

Chen, et al., ACS Appl. Energy Mater. 4, 5408 (2021).

19
) Picture of an array of TF-SSBs on a bendable Al foil. (b) Cross-sectional SEM image of the TF-SSB with FLA-processed LCO. (c)
ffractograms of an as-sputtered LCO film and FLA-crystallized LCO films with different thicknesses (0.7, 1.2, and 3.3 μm). (d) ToF-
profile of an Al/1.2 μm LCO stack after FLA.

capacity of 49 and 85 μA h cm−2, respectively. That ance to conventional TF-SSBs is the one fabricated on a
 ‣ Manufacturing of TF-SSB: SSB Meets FLA
ied Energy Materials www.acsaem.org Letter

A
E

Chen, et al., ACS Appl. Energy Mater. 4, 5408 (2021).

19
) Picture of an array of TF-SSBs on a bendable Al foil. (b) Cross-sectional SEM image of the TF-SSB with FLA-processed LCO. (c)
ffractograms of an as-sputtered LCO film and FLA-crystallized LCO films with different thicknesses (0.7, 1.2, and 3.3 μm). (d) ToF-
ammetry measurement of a FLA-processed LCO film. (b) Charge−discharge curves at different C-rates of T
profile of an Al/1.2 μm LCO stack after FLA.

ms of different
capacity of 49 and 85 μAthicknesses.
h cm , respectively.(c)
−2
That Normalized discharge
ance to conventional TF-SSBscapacity over 100
is the one fabricated on a cycles. (d) Ragone plot comparing the
 x y
Partikeln eine deformierte Struktur aufzeigen. Das Erscheinungsbild der FLA-Proben-
oberfläche wird im Folgenden nur noch als Blumenkohl-Struktur“ bezeichnet. Die
”
Mischphase kann anhand der deformierten Partikel identifiziert werden. Betrachtet
man Abb. 15 (b) etwas genauer so erkennt man, dass die Si-Bereiche von den Cux Siy -
Mischphasen umgeben bzw. begrenzt werden. Wird dieser Sachverhalt auf die noch

‣ Manufacturing of Electrode: Anode Meets FLA

zu beantwortende Frage angewandt, so erho↵t man sich von dem FLA-Prozess, dass
die Cux Siy -Phase die Volumenexpansion des umgebenden Si während der Interkalation
abfedert.

(a) (b)

SiO2

5 Ergebnisvorstellung 37 Cu-Si

sorgt dafür, dass nach 100 Zyklen alle Materialien aus der Si-FLA-Reihe einen Verlust
von > 91 % zu verzeichnen haben.

Abb. 15: Rasterelektronenmikroskopieaufnahme (REM) 120 der Oberfläche einer F1-Probe mit 1000 fa-
cher Vergrößerung (a) und mit 6500 facher Vergrößerung
110 (b). Die hervorgehobenen Bereiche 1 und
2 wurden mittels ortsaufgelöster, energiedispersiver100 FLA-F1
Röntgenfluoreszenzspektroskopie (EDX) auf ihre
FLA-F2
Entladekapazität C (mAh g-1)

Zusammensetzung untersucht. 90 FLA-F3

80 FLA-F4

70 identische Blumenkohl-artige-Struktur
FLA-Cu-F4 DE102016001949A1/WO2017140581A1.
Die REM-Aufnahme der Probe F2 zeigt eine
wie die F1-Probe (s. Abb. 27 im Anhang). Aus60Abb. 27 sowie aus dem EDX geht hervor,
50
dass die F2-Probe ebenfalls Si- und Cux Siy -Bereiche
40
aufweist, die sich in der Größe nicht
unterscheiden. 30
Die REM-Aufnahme sowie das EDX der 20 F3-Probe sind in Abb. 28 im Anhang zu
sehen. Hier kann aus der REM-Aufnahme ein 10 noch nicht vollständig ausgewachsener

Cux Siy -Bereich beobachtet werden. Die Partikel 0 der Si-Bereiche sind kleiner im Ver-
0 10 20 30 40 50 60
gleich zur F1 und F2-Probe. Zudem besteht der Bereich 1 nur noch zu70rund
80
4890 100
% aus
Zyklenzahl n
Cu. Das sind
L. Wolf, ungefThesis,
Bachelor ähr 20 %TUweniger Cu im(2019).
BA Freiberg Vergleich zu den F1 und F2-Proben. 20
Abb. 16 (a) zeigt die Oberfläche einer F4-Probe. Auf den ersten Blick können wieder
Abb. 17: Lebensdauertest der Si-FLA-Proben F1, F2, F3, F4 und Cu-F4. Als Elektrolyt wurde 1 M
verschiedene strukturierte Bereiche
LiClO4 infestgestellt
PC verwendet. werden. Vergleicht man die Aufnahme
mit Abb. 15 (b), so fällt auf, dass die Partikel in Abb. 16 (a) kleiner sind. Die F4-Probe
zeigt im Bereich 1 einen au↵ällig niedrigen Cu-Gehalt von rund 12 %. Charakteristisch
 ANALYSIS
‣ Summary
a Ambient temperature 20 °C–30 °C
• Batteries: High upcoming materials demand (resources & raw materials) 103
By cell mass

Randau, et al., Nat. Energy 5, 259 (2020).

400 Wh kg–1 Target region
• SSBs:
250 Wh kg–1
+ solid-electrolytes more tolerant to changes in temperature, physical

Specific energy, Em/Wh kg–1

102
damages, to overcharging, deep discharging
+ higher safety, more resource efficient
– creating effective solid electrolyte/active material interfaces, overall 101

reduction of the amount of solid electrolyte

– interfaces electrochemically (and chemically) stable at both anodic

C
100
and cathodic limit to avoid formation of unfavorable passivation or

4
10–1 100 101 102 103 104
reaction layers Specific power, Pm/W kg–1
– mass market processing techniques to achieve the internal resistance ASSBs with thiophosphate electrolyte
Intercalation-type CAM Intercalation-type CAM Conversion-ty
and current density requirements for high energy and high power

www.electrive.com
and lithium metal and graphite and lithium m
Cell type 1 Nam et al.15, pouch Yamada
• Flash Lamp Annealing: Formation of crystalline phases and dedicated Cell type 2 Nam et al.15, pellet Yao et a
Whiteley et al.19 Yamamoto et al.25 Zhang e
microstructure, infiltration/mixing of materials, … Zhang et al.20 Sakuda et al.16
Woo et al.21 Kato et al.3, high power
Xie et al.22 Kato et al.26, high energy
Ulissi et al.23 Ito et al.27
Choi et al.24 Kim et al.28
Kraft et al.29

Fig. 1 | Ragone plots for cells cycled at different temperatures. a,b, Ambient (
indicate targets for specific energy and C-rate. The area in blue depicts the targ
 ANALYSIS
‣ Summary
a Ambient temperature 20 °C–30 °C
• Batteries: High upcoming materials demand (resources & raw materials) 103
By cell mass

Randau, et al., Nat. Energy 5, 259 (2020).

400 Wh kg–1 Target region
• SSBs:
250 Wh kg–1
+ solid-electrolytes more tolerant to changes in temperature, physical

Specific energy, Em/Wh kg–1

102
damages, to overcharging, deep discharging
+ higher safety, more resource efficient
– creating effective solid electrolyte/active material interfaces, overall 101

reduction of the amount of solid electrolyte

– interfaces electrochemically (and chemically) stable at both anodic

C
100
and cathodic limit to avoid formation of unfavorable passivation or

4
10–1 100 101 102 103 104
reaction layers Specific power, Pm/W kg–1
– mass market processing techniques to achieve the internal resistance ASSBs with thiophosphate electrolyte
Intercalation-type CAM Intercalation-type CAM Conversion-ty
and current density requirements for high energy and high power

www.electrive.com
and lithium metal and graphite and lithium m
“…excluding
• Flash cell casing,
Lamp Annealing: ASSBsofwith
Formation specific
crystalline energy
phases beyond 400 Whkg
and dedicated
1 , energy
Cell type −1 density
Nam et al.15, pouchbeyond Yamada
Cell type 2 Nam et al.15, pellet Yao et a
1,000 Whl−1 and more than 90 % energy efficiency at a 1C Whiteley
rate etare
al. withinYamamoto
reach…” et al.
19 25 Zhang e
microstructure, infiltration/mixing of materials, … Zhang et al. 20
Sakuda et al.16

(Randau, et al., Nat. Energy 5, 259 (2020))Woo et al.21 Kato et al.3, high power
Xie et al.22 Kato et al.26, high energy
Ulissi et al.23 Ito et al.27
Choi et al.24 Kim et al.28
Kraft et al.29

Fig. 1 | Ragone plots for cells cycled at different temperatures. a,b, Ambient (
indicate targets for specific energy and C-rate. The area in blue depicts the targ
 ‣ Acknowledgements
• Vladislav Blatov Samara Center for
Theoretical Materials Science
• Artem Kabanov
• Stefan Adams
Marek Haiduk
Willkommen
• Yaroslav
Welcome
envenue
Romanyuk Thank you!
• elfolion GmbH
film battery group

EMPA meeting - 25.08.2021

Romanyuk
Financial Support:
for Thin Films and Photovoltaics
ss Federal Laboratories for Materials Science and Technology
• German Federal Ministry of Education and Research
übendorf, Switzerland
w.empa.ch/web/s207/thin-film-batteries
(CryPhysConcept: 03EK3029A, R2RBattery: 03SF0542A)
• Forschungsnetzwerk Mittelstand – AIF
(LiIonSK: ZF4751502JO9)
22