PHY 563 Tutorial on Batteries

PHY563 – 10/02/2021

PHY 563 – Tutorial on Batteries

Jean-François Guillemoles

Nathanaelle Schneider

UMR-IPVF 9006 - CNRS

PHY563 – 10/02/2021

Publication

2

General questions:

- Which type of publication is it?

- How important/relevant is the journal? the article?

Specific questions:

- What is the field?

- What are the main claims of the paper?

- Which methods and materials? Preparation (principle, pro/cons)

and Characterization (principle, ex-/in-situ, what is observed)

- What is new since the publication of the article?

PHY563 – 10/02/2021

Publication

Impact factor = 41,845 (2019)

cited 8135 times (Google scholar on 08/02/2021)

22

General questions:

PHY563 – 10/02/2021

Publication

22

Specific questions:

- What is the field?

PHY563 – 10/02/2021

Outline

What is the field? What are the main claims of the paper?

 Main tackled issue

 New electrode material

 New mechanism (nano effect), what are the classical mechanism?

Which methods and materials? Preparation (principle, pro/cons) and

Characterization (principle, ex-/in-situ, what is observed)

 Setups  Voltage-composition profiles  In-situ XRD  TEM/SAED  XANES

•Back-up slides

PHY563 – 10/02/2021

Setups

• Give and explain a schematic representation of classical

mecanisms « Li insertion/desinsertion » and « Li-alloiyng

process »

•Reported mechanism

PHY563 – 10/02/2021

Li-metal

Tarascon, cours Collège de France (2011)

Li-metal > negative electrode = metal Li

J. Rouxel

Reactions during discharge:

Cathode / Reduction : TiS₂ + e- + Li+  TiLiS 2

e-PHY563 – 10/02/2021

20 µm

Cu

Electrolyte

M. Dolle, L. Sannier, B. Beaudoin, M. Trentin, J.-M. Tarascon, Electrochem. Solid State Lett., 5 (12), A286, (2002)

PHY563 – 10/02/2021 Tarascon, cours Collège de France (2011)

Li-ion: electrodes = Li

_{intercalation compounds}

anode

cathode

PHY563 – 10/02/2021

+

Li-ion

PHY563 – 10/02/2021 Tarascon, cours Collège de France (2011)

Li-ion: which electrode materials?

PHY563 – 10/02/2021

Li-ion : exploration of electrode materials

PHY563 – 10/02/2021

13

Conclusions

NATURE | VOL 407 | 28 SEPTEMBER 2000 | www.nature.com

Impact?

Critics?

PHY563 – 10/02/2021

EC methods

14

Principle?

In-situ? Ex situ?

What is observed? What is evidenced?

NATURE | VOL 407 | 28 SEPTEMBER 2000 | www.nature.com

Mesure voltage– composition:

Experimental method Evaluation of curves Specific capacity

PHY563 – 10/02/2021

XRD= X-Ray Diffraction

15

Diffraction – Braggs’s law

d = spacing between diffracting planes

Θ = incident angle n = integer

λ = beam wavelength (1,54A)

Peak height : proportional to the number of incident electron, to the size and number of crystallites

Peak position: depends on the type and the parameter of the primitive cell ( + constraints in the material) Peak width : depends on internal micro-constraints and the size of the crystalline coherence

Principle?

In-situ? Ex situ?

PHY563 – 10/02/2021

Structure identification: XRD

Exemple: XRD zinc-blende structure

- Two atoms per primitive cell A (0,0,0) B (¼, ¼, ¼)

PHY563 – 10/02/2021

XRD

2Θ

Θ

Cubic: (1/d

)² = (h²+k²+l²)/a²

Preferential orientation: (111)

d

= λ/(2 sinθ) = a√3 = 3.12 Å

a = 1.80 Å

PHY563 – 10/02/2021 Secondary electrons: Low energy Superficial layers > Topology Back-scattered electrons: High energy Atomic number sensitive > Chemical homogeneity Auger electrons: Very low energy

> Surface, Chemical bounds X-rays Low energy Superficial layers > Atomic composition, (EDX analysis)

PHY563 – 10/02/2021

TEM/SAED

19

Electronic Microscopy:

TEM (Transmission Electron Microscopy)

and SEAD (Selected Area Electron Diffraction)

NATURE | VOL 407 | 28 SEPTEMBER 2000 | www.nature.com

Principle

PHY563 – 10/02/2021

TEM

20

Electronic Microscopy:

TEM (Transmission Electron Microscopy)

and SEAD (Selected Area Electron Diffraction)

TEM

• Transmitted electrons

• High vacuum system (10-4 _{Pa) to increase} electron mean free path

SAED

• Crystallographic technique that can be performed inside TEM

• Atoms act as diffraction grating to the electrons

• Similar to XRD but smaller samples can be analysed (100 nm vs. cm)

PHY563 – 10/02/2021

SEM

21

Scanning Electron Microscopy: SEM

• Resolution : nm scale

• Conditions: vacuum, ambient T, pre-treatments

• Ex: insulating part (charged) appears bright and conducting part appears dark

PHY563 – 10/02/2021

XANES/EXAFS

XANES (X-ray Absorption Near-Edge Spectroscopy) and EXAFS

(Extended X-ray Absorption Fine Structure)

• Source = synchrotron light

• XANES : electronic state, oxidation state

• EXAFS = oscillations : chemical environment, neighboring atoms (nature, number)

PHY563 – 10/02/2021

Synchrotron tools

• Powerful tunable

light source

 From IR to hard X

Rays

•Based on accelerated

charged particles

PHY563 – 10/02/2021

24

XANES, EXAFS

XANES (X-ray Absorption Near-Edge Spectroscopy) and EXAFS

(Extended X-ray Absorption Fine Structure)

• Excitation source = synchrotron light

• XANES (or NEXAFS) : sensitive to electronic transitions within atoms => electronic state, oxidation state

• EXAFS = oscillations due to interferences with neighboring atoms (of a given atom)=> chemical environment, neighboring atoms (nature, number). Distribution of neighbors requires mathematical fitting

PHY563 – 10/02/2021

25

Size effect

NATURE | VOL 407 | 28 SEPTEMBER 2000 | www.nature.com

IPVF Academic joint Lab UMR

IPVF Academic joint Lab UMR

Lithium batteries

Tarascon, cours Collège de France (2011)

>

Small ionic radius

 rapid diffusion >> Power

>

Works in aqueous medium

>> Thermodynamic limit at

1.2 V

>

Lightest metal (6.9g), d= 0.53g.cm

>

Most electropositive element

>> ΔE 3 – 4V

>

High chemical reactivity (water)

>> Organic electrolytes (non aqueous)

Highest

energy mass

density

IPVF Academic joint Lab UMR

Lithium batteries

IPVF Academic joint Lab UMR

Li-metal

Tarascon, cours Collège de France (2011)

Li-metal > negative electrode = metal Li

J. Rouxel

Décharge:

TiS₂ + e- + Li+  TiLiS 2

e-IPVF Academic joint Lab UMR

Li-polymer

Tarascon, cours Collège de France (2011)

Li-polymer: Li-metal + polymer electrolyte

(flexibilité polymère)

IPVF Academic joint Lab UMR

Li-polymer: Electrolytes

(+) non volatils, Li-metal compatible, low cost, reinforced cells (-) low ionic conductivity (working T 70-80°C)

Polymère gélifié à ilots d’électrolyte liquide

HPE = Hybrid Polymer Electrolyte cryst.: Mechanical stability amorph.: Liquid electrolyte Structured polymer membrane SPE =

Solid Polymer Electrolyte

P(VDF-HFP)- based membrane

IPVF Academic joint Lab UMR _{Tarascon, cours Collège de France (2011)}

Li-ion: electrodes = Li

_{intercalation compounds}

anode

cathode

IPVF Academic joint Lab UMR

Li-ion

IPVF Academic joint Lab UMR _{Tarascon, cours Collège de France (2011)}

Li-ion: which electrode materials?

No elements being:



Dangerous



Expensive



Heavy



Rare earth



Noble

gases

IPVF Academic joint Lab UMR

IPVF Academic joint Lab UMR

LiMnO₂/LiCoO₂ : 10% less capacity

advantage : cost & green

to achieve higher capacities : design materials in which the metal-redox oxidation state can change reversibly by 2 units :

Mn+2_/Mn

Preserving frame work structure

Molecular masses similar to 3d metal-layer oxides (ex : LiMnO₂ or LiCoO₂)

 Not W, Mo ou Nb : heavy

V-based oxides L₃V₂O₅-Li₃V₃O₈

 Cr6+_/Cr3+

LiMnO₂ : structural instability upon cycling : substitution by Cr : Li_1+X Mn_0.5Cr_0,5O₂

Capacity : 190 mAhg-1

Mn : stabilize the layered structure

Cr : large capacity due to oxidation state that changes from +3 to +6 But Cr : presents major toxicity & pricing issues

IPVF Academic joint Lab UMR

Li₂MnO₃

LiCoO₂ LiNi_1/2Mn_1/2O₂

LiNi_1/3Mn_1/3Co_1/3O₂ Chosen to be the next generation of + electrode material in lithium-ion batteries

Li(

Co

Li

Mn

)O

Li(

Ni

Li

Mn

)O

Li(Co

Ni

Mn

)O

(4) Z.H. Lu, D.D. MacNeil, and J.R. Dahn, ESSL., 4(11), A191 (2001)

(5) K. Numata, C. Sakaki and S. Yamanaka, Solid State Ionics, 117, 257 (1999) (1) Y. Makimura and T. Ohzuku, J. Power Sources, 119, 156 (2003)

(2) N. Yabuuchi and T. Ohzuku, J. Power Sources, 119, 171 (2003) (3) Z.H. Lu, D.D. MacNeil, and J.R. Dahn, ESSL., 4(12), A200 (2001)

The Li(Co_1-xNi_x/2Mn_x/2)O₂ systems :

 High capacity

 High cycleability

 Larger safety (vs. LiCoO₂)

 Lower cost (vs. LiCoO₂)

The Li(Co_1-xNi_x/2Mn_x/2)O₂ systems :

 High capacity

 High cycleability

 Larger safety (vs. LiCoO₂)

 Lower cost (vs. LiCoO₂)

IPVF Academic joint Lab UMR 50 75 100 125 150 175 200 0 10 20 30 40 50 Cycle Number Q (mAh/g) LiCoO2 3.5-4.25V, 0.5C, 25°C LiNi1/3Co1/3Mn1/3O2 3.0-4.3V, 0.5C, 25°C LiNi1/3Co1/3Mn1/3O2 3.0-4.5V, 0.5C, 25°C LiNi1/3Co1/3Mn1/3O2 3.0-4.7V, 0.5C, 25°C

Q

Discharge capacity (mAh)

0.2 C

2 C

Li (Co_.33Ni_.33Mn_.33) O₂

94% retained capacity at 2C

(design not optimized for high power applications)

Excellent capacity retention up to 4.5-4.6V

Reversible capacity of 170mAh/g at 4.5V







Technical Data Cellcore® MX- Kindly provide by UMICORE

IPVF Academic joint Lab UMR

a

b

(001)

Structure olivine

J. Goodenough and K. Padhi, 1996

Cheap, safe



Triphylite



From P. Poizot, LRCS

Li-ion: LiFePO

₄

Coating + nanostructuration : cœur-courrone

strategy

IPVF Academic joint Lab UMR

Li-ion: LiFePO

₄

– carbon coating

C. Wurm; C. Masquelier – LRCS, Amiens

15% de carbone

IPVF Academic joint Lab UMR

Li-ion: LiFePO

₄

– nanstructuration

500 nm

Taille des particules (nm)

0 20 40 60 80 100 120 140 160 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8 1-10 1 2-10

Capacité Spécifique mAhg

Poten

ti

el

Li

vs.

Li (V)

C. Delacourt, P. Poizot et al. , Electrochem Solid State Lett 9(7) A352-55(2006).

LRCS-Umicore Patent (2006)

IPVF Academic joint Lab UMR

Li-ion: Nanostructuration

IPVF Academic joint Lab UMR

nature materials | VOL 4 | MAY 2005 |