Compilation of studies conducted at the Institut des Matériaux de Nantes under the supervision of Dr. Dominique Guyomard between 2008 and 2012.
Focused on solid-state NMR to characterize interphases between positive electrode and electrolyte.
Status of Rechargeable Li-ion Battery Industry 2019 by Yole DéveloppementYole Developpement
E-mobility continues strongly driving the Li-ion battery demand.
More information on https://www.i-micronews.com/products/status-of-rechargeable-li-ion-battery-industry-2019/
Solid electrolytes for lithium ion solid state batteries patent landscape 201...Knowmade
Report’s Key Features
• PDF with > 250 slides
• Excel file > 5,800 patents
• IP trends, including time-evolution of published patents, legal status, countries of patent filings, etc.
• Ranking of main patent assignees
• Patent categorization by type of electrolyte (polymer, inorganic, inorganic/polymer) and inorganic electrolyte materials (sulfide glass ceramics, Thio-LISICON, argyrodite, oxide glass ceramics, NASICON, perovskite, garnet, anti-perovskite, hydride)
• For each technical segment: IP dynamics, ranking of main patent assignees, newcomers, key IP players (leadership, blocking potential, portfolio strength), key patents, and recent development trends
• For each key IP player (100+ companies): Time-evolution of patenting activity, legal status of patents and countries of patent filings, patent segmentation by electrolyte material, IP strengths and weaknesses by electrolyte material
• Excel database containing all patents analyzed in this report, including technology and material segmentations
Part 1 of the tutorial on the Lithium Battery Explorer provides an overview of Li-ion battery technology and the properties that are relevant to battery researchers.
Interested viewers should refer to the following publications for more details:
1) Review: G. Ceder, G. Hautier, A. Jain, S. P. Ong. Recharging lithium battery research with first-principles methods. MRS Bulletin, 2011, 36, 185--191.
2) Computational Electrode Assessment: G. Hautier, A. Jain, S. P. Ong, B. Kang, C. Moore, R. Doe, and G. Ceder. Phosphates as Lithium-Ion Battery Cathodes: An Evaluation Based on High-Throughput ab Initio Calculations. Chemistry of Materials, 2011, 23(15), 3495-3508.
3) Predicting Battery Safety: S. P. Ong, A. Jain, G. Hautier, B. Kang, & G. Ceder. Thermal stabilities of delithiated olivine MPO4 (M=Fe, Mn) cathodes investigated using first principles calculations. Electrochemistry Communications, 2010, 12(3), 427--430.
Batteries are going to be the building block of the smart future currently being envisaged. From a strategic market perspective, a compilation of current and future Li-ion technologies. It is important to understand who are current market leaders in each crucial components of the Li-ion technology and how disruptive technologies will shift the power balance.
Status of Rechargeable Li-ion Battery Industry 2019 by Yole DéveloppementYole Developpement
E-mobility continues strongly driving the Li-ion battery demand.
More information on https://www.i-micronews.com/products/status-of-rechargeable-li-ion-battery-industry-2019/
Solid electrolytes for lithium ion solid state batteries patent landscape 201...Knowmade
Report’s Key Features
• PDF with > 250 slides
• Excel file > 5,800 patents
• IP trends, including time-evolution of published patents, legal status, countries of patent filings, etc.
• Ranking of main patent assignees
• Patent categorization by type of electrolyte (polymer, inorganic, inorganic/polymer) and inorganic electrolyte materials (sulfide glass ceramics, Thio-LISICON, argyrodite, oxide glass ceramics, NASICON, perovskite, garnet, anti-perovskite, hydride)
• For each technical segment: IP dynamics, ranking of main patent assignees, newcomers, key IP players (leadership, blocking potential, portfolio strength), key patents, and recent development trends
• For each key IP player (100+ companies): Time-evolution of patenting activity, legal status of patents and countries of patent filings, patent segmentation by electrolyte material, IP strengths and weaknesses by electrolyte material
• Excel database containing all patents analyzed in this report, including technology and material segmentations
Part 1 of the tutorial on the Lithium Battery Explorer provides an overview of Li-ion battery technology and the properties that are relevant to battery researchers.
Interested viewers should refer to the following publications for more details:
1) Review: G. Ceder, G. Hautier, A. Jain, S. P. Ong. Recharging lithium battery research with first-principles methods. MRS Bulletin, 2011, 36, 185--191.
2) Computational Electrode Assessment: G. Hautier, A. Jain, S. P. Ong, B. Kang, C. Moore, R. Doe, and G. Ceder. Phosphates as Lithium-Ion Battery Cathodes: An Evaluation Based on High-Throughput ab Initio Calculations. Chemistry of Materials, 2011, 23(15), 3495-3508.
3) Predicting Battery Safety: S. P. Ong, A. Jain, G. Hautier, B. Kang, & G. Ceder. Thermal stabilities of delithiated olivine MPO4 (M=Fe, Mn) cathodes investigated using first principles calculations. Electrochemistry Communications, 2010, 12(3), 427--430.
Batteries are going to be the building block of the smart future currently being envisaged. From a strategic market perspective, a compilation of current and future Li-ion technologies. It is important to understand who are current market leaders in each crucial components of the Li-ion technology and how disruptive technologies will shift the power balance.
A feasible way towards safer, better-performing batteries?
Conventional Li-ion battery technologies, based on flammable liquid electrolytes, are continuously improving. However, faster progress towards greater safety, higher performance, and better cost reduction is desired. A next-generation battery technology like solid-state battery, which uses solid electrodes and solid electrolytes, could potentially satisfy these objectives.
More information on : https://www.i-micronews.com/batteries-energy-mgmt/product/solid-state-battery.html
High energy and capacity cathode material for li ion battriesNatraj Hulsure
Recent development in cathode materials for li-ion batteries drag the industries view towards it due to their high discharge rate compare to older ones.
Polymer/Ionic Liquid Electrolytes and Their Potential in Lithium BatteriesFuentek, LLC
Polymer/Ionic Liquid Electrolytes and Their Potential in Lithium Batteries presented by Allyson Palker and Dean Tigelaar of NASA's Glenn Research Center at an energy workshop on 7/20/2010.
This presentation includes all the information regarding polymer batteries, lithium polymer batteries. Including animations and transitions this PowerPoint presentation is enough for you to understand all about Polymer batteries and cells.
Lithium-ion battery - Challenges for renewable energy solutions - InnoVentum ...Jeff Gallagher
Background on InnoVentum and ADB (Asian Development Bank)
InnoVentum is striving to give Power to the People by making renewable energy affordable and available.
• 1.6 billion people have no access to electricity at all. To start with, InnoVentum is targeting “island economies” like the Philippines, the Maldives and Sri Lanka where most energy today is produced by diesel and gasoline generators.
• InnoVentum is offering a typhoon-resilient solar-wind hybrid solution called the Dali PowerTower and this needs a battery back-up.
• Most human aid organisations today require significant capacity – amounting to 30 kWh per set – and modern Li-
Ion Battery (LIB) technology, but expect lowest possible LCOE (Levelised Cost of Energy) and best possible
sustainability/LCA.
• InnoVentum is using iKnow-Who to organise a collaborative University Competition
A feasible way towards safer, better-performing batteries?
Conventional Li-ion battery technologies, based on flammable liquid electrolytes, are continuously improving. However, faster progress towards greater safety, higher performance, and better cost reduction is desired. A next-generation battery technology like solid-state battery, which uses solid electrodes and solid electrolytes, could potentially satisfy these objectives.
More information on : https://www.i-micronews.com/batteries-energy-mgmt/product/solid-state-battery.html
High energy and capacity cathode material for li ion battriesNatraj Hulsure
Recent development in cathode materials for li-ion batteries drag the industries view towards it due to their high discharge rate compare to older ones.
Polymer/Ionic Liquid Electrolytes and Their Potential in Lithium BatteriesFuentek, LLC
Polymer/Ionic Liquid Electrolytes and Their Potential in Lithium Batteries presented by Allyson Palker and Dean Tigelaar of NASA's Glenn Research Center at an energy workshop on 7/20/2010.
This presentation includes all the information regarding polymer batteries, lithium polymer batteries. Including animations and transitions this PowerPoint presentation is enough for you to understand all about Polymer batteries and cells.
Lithium-ion battery - Challenges for renewable energy solutions - InnoVentum ...Jeff Gallagher
Background on InnoVentum and ADB (Asian Development Bank)
InnoVentum is striving to give Power to the People by making renewable energy affordable and available.
• 1.6 billion people have no access to electricity at all. To start with, InnoVentum is targeting “island economies” like the Philippines, the Maldives and Sri Lanka where most energy today is produced by diesel and gasoline generators.
• InnoVentum is offering a typhoon-resilient solar-wind hybrid solution called the Dali PowerTower and this needs a battery back-up.
• Most human aid organisations today require significant capacity – amounting to 30 kWh per set – and modern Li-
Ion Battery (LIB) technology, but expect lowest possible LCOE (Levelised Cost of Energy) and best possible
sustainability/LCA.
• InnoVentum is using iKnow-Who to organise a collaborative University Competition
Failure is not an option, or, why you need to ask 'Why?" more often.Alessandro Galetto
We should answer a simple question: "Why companies are built and managed in the way we know?".
In this presentation I will give my answer from an historic, scientific and economic perspective, and, at the same, I will try to show why other models are possible.
Different organisational models are not only possible, but needed when the current models are causing so much pain in modern companies.
We need to reinvent the way company works as well as we must reinvent the definition of career in the 21st century.
We have so many tools and the higher amount of technology that we can use to shape the future of our companies. Which is the reason why we are not doing anything about it?
Even if the presentation is definitely focused on the Italian market it contains elements and ideas that have a broader ranged of applicability.
And, as always, it's not too serious.
I used this presentation for my talk at the Better Software 2013 conference in Florence.
Time Resolved IR Spectroscopy (TRIR) combines UV-flash photolysis and fast infrared detection for determining excited states and reaction intermediates, which are often inaccessible to conventional spectroscopy. It is possible to monitor processes within a span of 10-6 s.
Contributed by: Asmita Shrestha & Moumita Bhattacharya (Undergraduate Students)
University of Utah, 2014
Lithium Iron Phosphate: Olivine Material for High Power Li-Ion Batteries - Cr...CrimsonPublishersRDMS
Lithium Iron Phosphate: Olivine Material for High Power Li-Ion Batteries by Christian M Julien* in Crimson Publishers: Peer Reviewed Material Science Journals
CONTROLS OF TOXIC ELEMENTS IN ABIOTIC REDUCTIVE DISSOLUTION OF URANIUM MILL R...Mario Alberto Gomez
U mill tailings in northern Saskatchewan, Canada are alkaline (pH 8 to 10) and often contain elevated concentrations of the elements of concern (EOC) As, Se, Mo and Ni. These EOCs are immobilized within the tailings solids by secondary ferrihydrite (FH). Recent analysis of tailings solids (i.e., neutralized mill raffinates and tailings) also showed the presence of a significant reservoir of a secondary Mg-Al hydrotalcite (HTLC) nano-phase which also has been shown to immobilize EOCs. The bonding via EXAFS of Arsenic on HTLC at the final pH 10 stage of the process in the Key Lake mill samples is also not the same as that found for As-FH at lower pH 4-8 found in the Rabbit Lake mill case.
Although the tailings are oxic and have remained so for more than 20 years, concern exists as to impact of the development of anaerobic conditions in the tailings and thus the long-term stability of the EOCs. Research suggests ferrihydrite is unstable under moderately reducing conditions (Eh ~ +100 mV) and may undergo phase transformation resuling in redox active species (e.g., Fe, As, and Se) being released into solution. A series of batch abiotic tests were conducted (7 day and 6 months) to investigate the impact of abiotic (via Fe(II)(aq)) reduction
on the sequestered EOCs in neutralized U-mill raffinates and tailings (pH 8 and 10).
Optimization of Coal Blending to Reduce Production Cost and Increase Energy E...inventionjournals
The productivity level of the electricity production is an important indicator in the power plant efficiency. A chase study in this research was choosen at coal power plant PT PJB UP Paiton which is the productivity level of the generated electricity decreases until below the production target level. It due to several factors such as quality of coal and plant design. Depletion of coal heating value (low rank coal) reduce total amount of enerated heat in boiler and finally increase unburned carbon, plant inefficiency, as well as the high production cost. On the other hand, utilizing the high rank coal cause more expensive price. Therefore, the optimiation of coal blending to obtain more plant efficiency and lower production cost is required. This research focus on optimization of low and high rank coal blending that can decrease the production cost and increase plat efficiency. The blending model was built by utilizing Finite Impulse Response Neural Network (FIR-NN) and variable selection is perform using Priciple Component Analys is (PCA) and Partial Least Square (PLS). The result of optimization resulted a decreasing the production cost up to 342 IDR/kWh.
Silicon is of great interest for use as the anode material in lithium-ion batteries due to its high
capacity. However, certain properties of silicon, such as a large volume expansion during the
lithiation process and the low diffusion rate of lithium in silicon, result in fast capacity
degradation in limited charge/discharge cycles, especially at high current rate. Therefore, the
use of silicon in real battery applications is limited. The idea of using porous silicon, to a large
extent, addresses the above-mentioned issues simultaneously. In this review, we discuss the
merits of using porous silicon for anodes through both theoretical and experimental study.
Recent progress in the preparation of porous silicon through the template-assisted approach
and the non-template approach have been highlighted. The battery performance in terms of
capacity and cyclability of each structure is evaluated.
Quantitative electron diffraction tomography for the structure solution of ca...Olesia Karakulina
Here it is shown how the crystal structure of cathode materials can be determined by electron diffraction tomography even after cycling in the electrochemical cell. Moreover, the way to detect and quantify Li is described.
These slides where presented at European Microscopy Congress in Lyon in 2016.
Generating a custom Ruby SDK for your web service or Rails API using Smithyg2nightmarescribd
Have you ever wanted a Ruby client API to communicate with your web service? Smithy is a protocol-agnostic language for defining services and SDKs. Smithy Ruby is an implementation of Smithy that generates a Ruby SDK using a Smithy model. In this talk, we will explore Smithy and Smithy Ruby to learn how to generate custom feature-rich SDKs that can communicate with any web service, such as a Rails JSON API.
Epistemic Interaction - tuning interfaces to provide information for AI supportAlan Dix
Paper presented at SYNERGY workshop at AVI 2024, Genoa, Italy. 3rd June 2024
https://alandix.com/academic/papers/synergy2024-epistemic/
As machine learning integrates deeper into human-computer interactions, the concept of epistemic interaction emerges, aiming to refine these interactions to enhance system adaptability. This approach encourages minor, intentional adjustments in user behaviour to enrich the data available for system learning. This paper introduces epistemic interaction within the context of human-system communication, illustrating how deliberate interaction design can improve system understanding and adaptation. Through concrete examples, we demonstrate the potential of epistemic interaction to significantly advance human-computer interaction by leveraging intuitive human communication strategies to inform system design and functionality, offering a novel pathway for enriching user-system engagements.
Smart TV Buyer Insights Survey 2024 by 91mobiles.pdf91mobiles
91mobiles recently conducted a Smart TV Buyer Insights Survey in which we asked over 3,000 respondents about the TV they own, aspects they look at on a new TV, and their TV buying preferences.
Neuro-symbolic is not enough, we need neuro-*semantic*Frank van Harmelen
Neuro-symbolic (NeSy) AI is on the rise. However, simply machine learning on just any symbolic structure is not sufficient to really harvest the gains of NeSy. These will only be gained when the symbolic structures have an actual semantics. I give an operational definition of semantics as “predictable inference”.
All of this illustrated with link prediction over knowledge graphs, but the argument is general.
GraphRAG is All You need? LLM & Knowledge GraphGuy Korland
Guy Korland, CEO and Co-founder of FalkorDB, will review two articles on the integration of language models with knowledge graphs.
1. Unifying Large Language Models and Knowledge Graphs: A Roadmap.
https://arxiv.org/abs/2306.08302
2. Microsoft Research's GraphRAG paper and a review paper on various uses of knowledge graphs:
https://www.microsoft.com/en-us/research/blog/graphrag-unlocking-llm-discovery-on-narrative-private-data/
Dev Dives: Train smarter, not harder – active learning and UiPath LLMs for do...UiPathCommunity
💥 Speed, accuracy, and scaling – discover the superpowers of GenAI in action with UiPath Document Understanding and Communications Mining™:
See how to accelerate model training and optimize model performance with active learning
Learn about the latest enhancements to out-of-the-box document processing – with little to no training required
Get an exclusive demo of the new family of UiPath LLMs – GenAI models specialized for processing different types of documents and messages
This is a hands-on session specifically designed for automation developers and AI enthusiasts seeking to enhance their knowledge in leveraging the latest intelligent document processing capabilities offered by UiPath.
Speakers:
👨🏫 Andras Palfi, Senior Product Manager, UiPath
👩🏫 Lenka Dulovicova, Product Program Manager, UiPath
Transcript: Selling digital books in 2024: Insights from industry leaders - T...BookNet Canada
The publishing industry has been selling digital audiobooks and ebooks for over a decade and has found its groove. What’s changed? What has stayed the same? Where do we go from here? Join a group of leading sales peers from across the industry for a conversation about the lessons learned since the popularization of digital books, best practices, digital book supply chain management, and more.
Link to video recording: https://bnctechforum.ca/sessions/selling-digital-books-in-2024-insights-from-industry-leaders/
Presented by BookNet Canada on May 28, 2024, with support from the Department of Canadian Heritage.
DevOps and Testing slides at DASA ConnectKari Kakkonen
My and Rik Marselis slides at 30.5.2024 DASA Connect conference. We discuss about what is testing, then what is agile testing and finally what is Testing in DevOps. Finally we had lovely workshop with the participants trying to find out different ways to think about quality and testing in different parts of the DevOps infinity loop.
Accelerate your Kubernetes clusters with Varnish CachingThijs Feryn
A presentation about the usage and availability of Varnish on Kubernetes. This talk explores the capabilities of Varnish caching and shows how to use the Varnish Helm chart to deploy it to Kubernetes.
This presentation was delivered at K8SUG Singapore. See https://feryn.eu/presentations/accelerate-your-kubernetes-clusters-with-varnish-caching-k8sug-singapore-28-2024 for more details.
How world-class product teams are winning in the AI era by CEO and Founder, P...
Electrode - Electrolyte Interface Studies in Lithium Batteries
1. Electrode/Electrolyte Interface
Studies in Lithium Batteries
Marine Cuisinier
University of Waterloo, Canada
Nicolas Dupré, Dominique Guyomard
Institut des Matériaux Jean Rouxel ‐ Université de Nantes, France
Kouta Suzuki, Masaaki Hirayama, Ryoji Kanno
Tokyo Institute of Technology, Japan
1/29
2. Li-ion & related challenges
Energy (Wh/kg, Wh/l)
Power (W/kg, W/l)
Power (W / kg)
HEV
1000
PHEV, power tools
Li-ion
Safety
Cost
EV
Toxicity
Ni-MH
100
Life
Reactivity at interfaces
Pb-acid
btw. electrodes & electrolyte
10
10
100
1000
Safety
Energy (Wh/kg)
Long term cyclability
Energy
Autonomy
Power
Rate, acceleration
2/33
3. Aging mechanisms of cathode
materials
gas evolution
electrolyte
decomposition
DMC
O
O
EC
dissolution
O
surface layer
formation
O
O
re-precipitation of
new phases
migration of
soluble species
F
Li F P F
F
F
F
ROCO2Li
OPF2(RO)nF
O
LixPOyFz
LiF
Adapted from J. Vetter et al., J. Power Sources 147 (2005) 269
3/33
4. Table of contents
1 CHARACTERIZATION METHODS
Review of interface characterization methods
MAS NMR applied to surface species analysis
2 EXEMPLES: LINI0.5MN0.5O2/ELECTROLYTE INTERPHASE
Aging upon storage in LiPF6 electrolyte
Aging upon cycling in LiPF6 and LiBOB modified electrolyte
3 CASE OF THE LIFEPO4/ELECTROLYTE INTERPHASE
Intrinsic interphasial behavior
Surface aging upon storage: characterization and control
towards improved electrochemical performance
4 GENERAL CONCLUSION & PERSPECTIVES
4/29
5. Classical interface characterization methods
A strategy for R&D of Li and Li-ion batteries.
Study of Electrodes Li, Li-C anodes and LixMOy cathodes.
NMR
Surface Chemistry
in situ & ex situ FTIR, XPS,
EDAX, EQCM
Interfacial properties
EIS, B.E.T. (surface area)
Morphology
in situ AFM (SEM)
Structural analysis
in situ & ex situ XRD (SEM)
Correlation
Performance
Fast tests for cycling efficiency
FTIR
(GCPL)
XPS
MAS NMR
50
40
30
Solution studies
Electrochemical windows, thermal
stability, redox processes:
CV, in situ FTIR, EQCM, EIS, DTA
Optimization of electrolyte
solutions
20
10
Published items each year
Electroanalytical behavior of Li
insertion compounds
PITT, EIS, SSCV
Testing in practical cells
(coin cells and AA cells)
19
9
19 4
9
19 5
9
19 6
9
19 7
9
19 8
9
20 9
0
20 0
0
20 1
0
20 2
0
20 3
0
20 4
0
20 5
0
20 6
0
20 7
0
20 8
0
20 9
1
20 0
1
20 1
1
20 2
13
0
Publication year
From Reuters, Web of Knowledge
5/33
6. Review of interface studies by NMR
< 20 studies in the literature on « passivation layer on LiB materials »
Suitable for: 1H, 7Li, 13C, 19F and
31P in the interphase… or 23Na !
6/33
7. 7Li
NMR: Li-electron dipolar interaction
Coupling between nuclear spin and
electronic spin (paramagnetic ions)
Distance between Li and
paramagnetic center
0
1
H en
µe .Dij . 3
4
r
Mn4+ t2g (unpaired electron spin)
O
Through space
q
B0
r
Li (nuclear spin)
7/33
8. Using 7Li MAS NMR to selectively DETECT the interphase
T2 para
Distance between Li and
paramagnetic center
B0
0
1
H en
µe .Dij . 3
4
r
y
If r ↓ Hen ↑
x
Surface species = diamagnetic
(Li2CO3, LiF, LixOyPFz etc…)
π/2 pulse
Bulk
Li
Free Induction Decay
Surface
Time
Longer T2
Mn
then T2 ↓
t0
Li
Short T2
acquisition
T2para
DEAD TIME (5-50 s) before acquisition of data
REMOVE Li-bulk SIGNAL
8/33
9. Using 7Li MAS NMR to study electrode/interphase interactions
7Li,
500MHz, 14kHz
FWHM
LiNi0.5Mn0.5O2 with surface Li2CO3
No dead time
If r ↓ Hen ↑ then T2 ↓
If µe ↑ Hen ↑ then T2 ↓
a
Bulk
Dipolar
interaction
Dipolar
interaction
0 ppm
b
Diamagnetic
surface species
Dead time
1
T2
2V
4.5 V
Surface
Li2CO3 c
Li2CO3 powder
3000
2000
1000
40
0
(ppm)
-1000
-2000
20
0
-20
-40
7
Li / ppmm
Ménétrier, M. et al. Electrochem. And Solid State Lett., 2004, 7(6), A140.
Dupré, N. et al. J. Mat. Chem., 2008, 18, 4266
DIPOLAR INTERACTION
THICKNESS / INTIMACY of the interphase with the bulk9/33
10. integrated intensity / NS / RG
integrated intensity / NS / RG (a. u.)
Using MAS NMR to QUANTIFY the interphase
7Li
NMR
50
40
LiFePO4
20
and 31P NMR spectra
calibration curves
LiMn1.5Ni0.5O4
30
7Li, 19F
Si
-1
y = 4.26 10 x
10
LiF / LiPF6 calibration
0
0
25
50
75
100
diamagnetic Li (µmol)
19F
5
NMR
4
LiMn1.5Ni0.5 O4
3
LiFePO4
Si
Works for interphases grown on
≠ electrode materials:
LiMn0.5Ni0.5O2 , LiFePO4 , Si
-2
y = 6.38 10 x
LiF calibration
2
-2
y = 2.80 10 x
1
From known amounts of
diamagnetic nuclei (LiF, LiPF6)
LiPF 6 calibration
Absolute quantification
of interphasial [Li], [F], [P]
in mmol.g-1 or mmol.m-²
0
0
25
50
75
100
diamagnetic F (µmol)
10/33
11. (Li-alkylcarbonates)
O
-1
diamagnetic Li or F (mmol.g )
Interpretation of quantitative NMR results
7Li, 19F
NMR
Total Li
Li
1.4
7
1.2
Li+ O
(7Li
1.4
O
O Li
(Li2CO3)
O
Li in organic
1.0
~ Total Li (7Li) – LiF (19F) ?
F / PF
19
F / LiF
1.0
R
Li
NMR)
19
O
1.2
0.8
0.8
0.6
Fluorophosphates (19F NMR)
0.4
POF3/PO2F2-/ PO3F2-
0.6
0.4
0.2
0.2
0.0
0.0
OX1
RED1
OX5
RED5 OX20 RED20
O
O
F P
R
O
F
or
F P
O Li
F
LiF (19F NMR)
Charge state
O
O
O
O
n
O
O
Non lithiated organic species remain
invisible to our NMR experiments
11/33
12. Need for COMPLEMENTARY analytical tools
0
n
Diamagnetic interphases
m
LiMn0.5Ni0.5O2
interphase
formation
Electrode active material
NMR
Electrode activ
XPS
Diamagnetic interphases
Electrode active material
LiPF6 electrolyte
decomposition
Electrode active material
Electrode active material
In situ EIS
TEM/EELS
Z’’/Ω
5
NMR
Rinterfacial
-50
Nyquist plot
-25
Rel
0
Brookhaven Nat. Lab.
25
50
Z’/Ω
75
100
12/33
13. Table of contents
1 CHARACTERIZATION METHODS
Review of interface characterization methods
MAS NMR applied to surface species analysis
2 EXAMPLES: LINI0.5MN0.5O2/ELECTROLYTE INTERPHASE
Aging upon storage in LiPF6 electrolyte
Aging upon cycling in LiPF6 and LiBOB modified electrolyte
3 CASE OF THE LIFEPO4/ELECTROLYTE INTERPHASE
Intrinsic interphasial behavior
Surface aging upon storage: characterization and control
towards improved electrochemical performance
4 GENERAL CONCLUSION & PERSPECTIVES
13/29
14. Example 1: aging of the LiNi1/2Mn1/2O2 / LiPF6 interphase
upon storage (SEM)
7Li
1 month
NMR
19F
0 ppm
NMR
-205 ppm
LiF
3 days
3 days
1 hour
5 min.
1 min.
30 sec.
1 µm
(a)
Pristine
1000
(b)
500
0
7
Li / ppm
1 µm
normalized / NS / RG /m
1 µm
normalized / NS / RG /m
2 weeks
-500
-1000
(c)
200
0
-200
-400
19F / ppm
Soaking at RT in LiPF6 1M, EC:DMC (1:1)
Surface “film” observation by SEM
19F: LiF only
14/33
15. mmol (Li or F) / g LMN
Example 1: aging of the LiNi1/2Mn1/2O2 / LiPF6 interphase
upon storage (NMR vs XPS)
0.4
7Li, 19F
NMR
0.3
7
Li NMR
One month
0.2
19
0.1
0.0
Li in organic
= Total Li (7Li)
– LiF (19F)
0
10
20
30
F NMR
40
50
60
300 400 500 600 700
Contact time (min)
XPS F1s
XPS C1s
LiF
CC/CH
1 hour
LiF only
XPS: LiF screening
26%
by Li-containing
16% organic species
5 min.
13%
CO
CO3 CO
2
1 month
LixPFy
LixPOyFz
1 month
1 hour
5 min.
Contact time (h)
26%
33%
37%
19F:
15/33
16. Example 1: aging of the LiNi1/2Mn1/2O2 / LiPF6 interphase
upon storage (EELS)
EELS
100
%F
F-K
atomic %
O-K
8
8
7
6
5
4
3
Mn-L
Ni-L
2,3
500
2,3
600
700
800
900
Energy Loss (eV)
80
60
40
20
% Mn
%O
0
8
7
6
5
4
3
spot number
Interphase growth scenario:
LiPF6
O
PF5 + LiF
O
O
O
Li+ O
O
R
LMN½
5
Salt decomposition
Solvents decomposition
Contact time
16/33
18. RED1
0.3
140
120
0.2
100
10
15
0
0.1
20
5
Cycle number
0.0
0.0
OX5 RED5 OX20 RED1 OX5
PRISTINEOX1 RED20
Charge state
Li+ O
O
R
O
F P
O Li
F
70
60
50
100 RED 1
Q charge
Q discharge
75
Coulombic efficiency
10
R902 V
ct
80
70
50
OX 1
60
25
Cycle number
200
15
0
0
2019
5
50
-200
10
125
100
75
50
25
F / ppm
Cycle number
-400
0
15
0.0
RED5 OX20 RED20
Charge state
O
80
100
Rct 4.5 V
NMR
Charge transfer resistance ()
0.1
5
0
0.4
Coulombic efficiency
160
125
Coulombic efficiency (%)
100
0.2
)
-1
0.2
90
19F
normalized / NS / RG /m
120
0.5
Q charge
180
Q discharge
Charge transfer resistance ()
0.4
0.3
140
200
100
Coulombic efficiency (%)
0.6
0.4
160
0.6
T2(Li) (ms)
0.8
0.5
Capacity (mA.h.g
1.0
)
-1
1.2
F / LiF
19
200
F / PF
7
180
Li
220
0.6
T2(Li) (ms)
220
19
1.4
Capacity (mA.h.g
LiF
PF
diamagnetic Li/F (mmol/g)
Example 2: aging of the LiNi1/2Mn1/2O2 / LiPF6 interphase
upon cycling (2)
Appearance of fluorophosphates
Electrochemical formation of the
interphase?
Indirect electrochemical oxidation: oxygen transfer
from the oxide surface to the solvent molecules
S.-W. Song et al., JES, 151, A1162 (2004)
18/33
19. 1.4
1.2
1.0
0.6
19
F / LiF
19
F / PF
7
Li
0.4
0.8
0.3
0.6
0.2
0.4
0.2
0.1
0.0
0.0
PRISTINEOX1
RED1
OX5
Li-poor interphase:
LiF + non-lithiated species
T2(Li): No evolution of the
AM /interphase intimacy
Stable (resistive)
LiF-based interphase
+ growing non-lithiated
(PEO type + phosphates)
0.5
T2(Li) (ms)
diamagnetic Li/F (mmol/g)
Example 2: aging of the LiNi1/2Mn1/2O2 / LiPF6 interphase
upon cycling (3)
Li-free organic
RED5 OX20 RED20
Charge state
Organic species
Fluorophosphates
LiF
O
O
O
O
n
O
O
O
LMN½
M. Cuisinier et al. Solid State Nucl. Magn. Reson. 42, 51 (2011)
LMN½
F P
R
O
F
19/33
20. Example 3: aging of the LiNi1/2Mn1/2O2 / LiPF6 interphase
upon cycling (effect of LiBOB additive)
Cathode protecting agent
Mn-containing insoluble
surface layer [*]
No LiBOB
LiBOB
30
19F / LiF
19F / PF
7Li
1.2
1.2
1.0
0.8
0.6
0.6
0.4
0.4
20
15
10
0.2
0.0
PRISTINE OX1
RED1
OX5
RED5
OX20
5
0.0
0.2
BOB-1ox
BOB-5ox
BOB-20ox
25
1.0
0.8
200
1.4
Z'' / (mmol/g)
diamagnetic LiOhm
1.4
Z'' / Ohm
diamagnetic Li (mmol/g)
1.4
0
RED20
Charge state
1.2
150
5
10
15
20
Z' / Ohm
25
30
19F / LiF
19F / PF
7Li
PF6-1ox
PF6-5ox
PF6-20ox
1.2
1.0
1.0
0.8
0.8
100
0.6
0.6
0.4
0.4
50
0.2
0.0
0
1.4
0.2
0
PRISTINE OX1 RED1
0
50
0.0
OX5
100
RED5
OX20 RED20
150
200
Z' / Ohm
Charge state
Composition of interphase is different:
Presence of Li in org. species / fluorophosphates
Less resistive interphase
« good » interphase
[*] Chen, Z. et al., Electrochim. Acta 51 (2006) 3322.
↑ electrochemical performance
20/33
21. Table of contents
1 CHARACTERIZATION METHODS
Review of interface characterization methods
MAS NMR applied to surface species analysis
2 EXEMPLES: LINI0.5MN0.5O2/ELECTROLYTE INTERPHASE
Aging upon storage in LiPF6 electrolyte
Aging upon cycling in LiPF6 and LiBOB modified electrolyte
3 CASE OF THE LIFEPO4/ELECTROLYTE INTERPHASE
Interphase dynamics upon voltage variations
Interphase modeling using ideal 2D films
Interphase evolution upon extended cycling
4 GENERAL CONCLUSION & PERSPECTIVES
21/29
22. -1
diamagnetic Li or F (mmol.g )
Evolution of the LiFePO4 interface with voltage
7
3.0
Li
3.0
19
F/PF
19
2.5
F/LiF
2.5
2.0
2.0
1.5
1.5
1.0
1.0
0.5
0.5
0.0
0.0
4.0 V
4V
4.5 V
4.5V
2.0 V
2V
2.7 V
2.7V
2.7 V
2.7V
Charge state
7Li/19F:
clarify XPS
stable inorganic interphase
+ fluctuating organic species
FePO4
F. Croce et aL., J. Power Sources, 43 (1993) 9
Oxidized state
4.5 V
4.5V
Interphase model:
Solid Polymer Layer
Li-organic species
Fluorophosphates
LiF
LiFePO4
Reduced state
22/33
23. Modeling the interphase architecture (1)
100
Elemental percentage (%)
EELS
%O
%F
% Fe
80
60
40
20
-20
0
20
40
60
80
100
Distance from the surface (nm)
F-K
O-K
#12: 14 nm
#11: 19 nm
#10: 18 nm
Fe L2,3
500
550
600
650
700
#6: AM
750
800
Energy loss (eV)
EELS: Any multi-layered model is abusive !
(at least on powder samples)
23/33
24. a- oriented LiFePO4 thin films
d / g·cm-3
Model surface: a- oriented LiFePO4 thin films
Thickness
l / nm
20.36
-
Roughness
t / nm
glue
Pulsed Laser
(a)
(b)
Deposition: 20-80nm
thick LiFePO4 4epitaxial
LiFePO
film on SrTiO3 (010)
1.33
1.06
0.55
1.08
690
520 525 530 535 540 545 550 555
700
710
720
730
energy loss (eV)
energy loss (eV)
(d)Pristine film:Surface
LiFePO4
SrTiO3
(c)
structurally homogeneous
layer
O
740
Possibility to monitor fine surface
Density
2.11
3.62
5.12
structure changes upon Li (de)intercalation
d / g·cm-3
Thickness
a- oriented LiFePO4 thin films
SrTiO substrate
1.33
20.36
Roughness
t / nm
1.06
0.55
l / nm
3
-
TEM-EELS
1.08
O-K
Fe-L2,3
energy loss (e
Pulsed
(d)Pristine film: structurally hom
(b)
Ideal 2D surface
Deposition: 20-80nm
= model interphase
Possibility to monitor fine
thick LiFePO4 4epitaxial
LiFePO
structure changes upon
film on SrTiO3 (010) Subjected to storage in LiPF6 Li (d
Pulsed Laser
electrolyte and cycling
Pristine film: structurally homogeneous
Deposition: 320-80nm
SrTiO substrate
Validate to monitor fine surface
Possibility the interphase model?
thick LiFePO epitaxial
glue
Laser
520 525 530 535 540 54
520 525 530 535 540 545 550 555
energy loss (eV)
4
film on SrTiO3 (010)
690
700
710
720
730
740
energy loss (eV)
structure changes upon Li (de)intercalation
Hirayama et al., Electrochemistry (Tokyo), 5 (2010) 413
24/33
25. Modelingthe interphase architecture
Modeling the interphase architecture (2)
XPS
Electron
detector
Electron
detector
X-ray
X-ray
XPS
)
(θ
in )
. s (θ
n
3λ si
.
λ
3
)
(θ
s
o
.c
3λ
θ
Penetration depth = 3λ.cos(θ)
Penetration depth = 3λ.sin(θ)
with λ ~λ~27Å
with 22 Å
θ
θ varied from 0° to 60°
I(θ)= Iinf . exp(-d/λ.cosθ)
3λ
3λ
Bulk
Bulk
Surface
Surface
Interphase depth profile:
ln C(Fe 2p1/2)
1.6
1.4
1.2
0.8
surface
5
Average λ (inelastic mean free path) is inaccurate !
air contact
4.5V 1st charge
2.5V 1st discharge
0.6
0.4
0.2
1.0
0.8
-0.2
-d
0
0.6
LiF
PF
CO
CO2
Confirms NMR and EELS results:
1.0
1.2
1.4
1.6
1.8
2.0
Inner LiF, covered by fluorophosphates
1/cosq -1
and a dynamic Solid Polymer Layer (SPL)
0.4
d (nm)
4
Pristine
3
1
0.44
1st ox. 4.5 V
3.5
bulk
dried
PO
Fe
4.5 V
2.5 V
4.5V 1st charge
2.5V 1st discharge
4.5
LN(P-O)
LN(surface/bulk)
1
d, the interphase thickness
1.4
1st
1.2
1.4
1.6
1/cos(q)
red 2.5 V
0.25
1.8
% 26
pristine
4.5V
2.5V
0.8 nm
1.7 nm
1.2 nm
Voltage dependance of the interphase thickness
25/33
26. 2
Modeling the interphase architecture (3)
XPS
LiF
F 1s
)
((θ)
θ
sn
i
.
cλos
.3
3λ
X-ray
k
1.0
θ
C.P.S
Electron
detector
1.2
θ
3λ
Bulk
q = 60°
q = 55°
q = 48°
q = 37°
q = 0°
0.8
LixPOyFz
0.6
0.4
0.2
0.0
Surface
-0.2
C %(60)
1.0
C %(0)
1.2
690
686
684
682
P
Binding energy (eV)
1st Ox
4.5 V
0.8
688
0.6
CH2CO2Li, ROCO2Li
0.4
1st Red
2.5 V
0.2
0.0
OPF2OMe, OPF2(OCH2CH2)nF
LiF
LiFePO4
FePO4
-0.2
PO Fe
LiF PF CO2 CO
--
Inner interphase: stable / inorganic
Outer interphase : dynamic / polymeric
26/33
27. 100
180
100
1 ox 4.5 V
5 ox 4.5 V
20 ox 4.5 V
1 red 2V
5 red 2V
20 red 2V
Pristine - 4.5 V
80
Stable impedance,
60
no resistive film
140
120
100
Pristine - 2 V
80
60
-Z'' /
160
-Z'' /
Discharge capacity (mA.h.g
-1
)
Interphase data upon cycling for bare LFP
5
40
40
80
0
20
40
60
80
20
1
20
20
20
250 Hz
100
100 Hz
0
cycle number
0
0
20
40
60
80
100
0
Z' /
-1
diamagnetic Li or F (mmol.g )
7Li, 19F
0.5
NMR
Accumulation of
0.5
interphase species
7
Li
F / PF
19
F / LiF
19
0.4
0.4
0.3
0.3
0.2
0.2
0.1
0.1
0.0
0.0
1 ox 1 red 5 ox 5 red 20 ox 20 red
OX1
RED1
OX5
RED5
Charge state
1
5
5 kHz
Charge transfer
6 kHz
OX20
RED20
20
40
60
80
100
Z' /
Stable performance vs Li
No resistive film
Lots of Li outside LiF,
in LixPOyFz (?),
in Li-organic (1H NMR, XPS)
O
F P
O Li
F
O
Li+ O
O
R
27/33
28. 0.0
x 20 red
0.4
0.3
0.3
7
0.2
0.2
0.1
0.1
T2(Li) (ms)
-1
T2(Li) (ms)
0.4
0.0
0.4
0.5
0.3
NMR
0.2
7Li
0.1
Interphasial Li (mmol.g )
Interphase growth scenario for bare LFP
0.0
1 ox 1 red 5 ox 5 red 20 ox 20 red
Stable performance vs Li
No resistive film
Li-rich porous interphase
Interphase growth by
stacking
Li-organic species
Fluorophosphates
LiF
FePO4
M. Cuisinier et al. J. Power Sources, 224, 50 (2013)
T2(Li): decreasing intimacy
Signal integration:
accumulation of surface Li
Non blocking interphase,
But no passivation:
Oxidized state
Li+
Li+
LiFePO4
Reduced state
28/33
29. The case of LiFePO4: summary vs. LiMn1/2Ni1/2O2
Stable performance
require a Li-rich organic
interphase
How to stop Li
consumption in it?
STABLE REVERSIBLE “BREATHING”
FP
LFP
STABLE PERFORMANCE
Poor performance of our LMN
material might be assigned to a
“bad” interphase: no Li mobility,
growing Li-free matrix on Organic species
LiF-rich inner interphase Fluorophosphates
Li-free organic
O
O
O
O
n
LiF
O
O
O
LMN½
M. Cuisinier et al. J. Power Sources, 224, 50 (2013)
M. Cuisinier et al. Solid State Nucl. Magn. Reson. 42, 51 (2011)
LMN½
F P
R
O
F
29/33
30. Table of contents
1 CHARACTERIZATION METHODS
Review of interface characterization methods
MAS NMR applied to surface species analysis
2 EXEMPLES: LINI0.5MN0.5O2/ELECTROLYTE INTERPHASE
Aging upon storage in LiPF6 electrolyte
Aging upon cycling in LiPF6 and LiBOB modified electrolyte
3 CASE OF THE LIFEPO4/ELECTROLYTE INTERPHASE
Intrinsic interphasial behavior
Surface aging upon storage: characterization and control
towards improved electrochemical performance
4 GENERAL CONCLUSION & PERSPECTIVES
30/29
31. GENERAL CONCLUSION & PERSPECTIVES
Battery performance is driven by surface chemistry
Need for powerful analytical tools
Validation of NMR for interphase studies (perspectives)
Use for full cells and negatives: Si or intermetallics
Use for the exploration of Na interphasial chemistry
(NaClO4 NaTFSI?) even more critical at the negative
T1/T2(Li) mapping = principle of MRI !
use to localize liquid/confined/solid state Li in the battery
31/33
32. GENERAL CONCLUSION & PERSPECTIVES
Battery performance is driven by surface chemistry
Interphase evolves upon voltage variations, depending on the AM
No general formation mechanism
Complex architecture/composition conducting properties
Good interphase = SEI-like
Li-O-rich to be conducting
Dense to passivate the AM surface
Thin to limit Li consumption
Not straightforward tailor with additives or new electrolytes
NMR for the diagnostic evaluation of detrimental phenomena
Cross-talk between the negative and positive interphases
Need for parallel studies on both electrodes
32/33
33. Acknowledgments
Nicolas Dupré, Dominique Guyomard but also L. Lajaunie, J.-F.
Martin, P. Moreau, Z.-L. Wang (co-workers)
R. Kanno, M. Hirayama, K. Suzuki, S. Taminato (Tokyo Tech collab.)
K. Edström (Uppsala), T. Épicier (INSA Lyon), L. Croguennec,
M. Ménétrier & A. Wattiaux (ICMCB), J.-M. Tarascon (LRCS),
J. Cabana (LBNL) for fruitful discussions and experimental
contributions
MESR, METSA (funding)
marine.cuisinier@gmail.com
nicolas.dupre@cnrs-imn.fr
33/33