radiation, radionuclides and reactors...march 13 electrolyte stability: pourbaix diagram, band...
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![Page 1: Radiation, Radionuclides and Reactors...March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life. Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state](https://reader031.vdocument.in/reader031/viewer/2022041723/5e4fc93720e6ee0fcc1c2f13/html5/thumbnails/1.jpg)
06 March 2013
1
Radiation, Radionuclides and Reactors
Hydrogen and Electrical Energy Storage
F.M. Mulder & M. Wagemaker
![Page 2: Radiation, Radionuclides and Reactors...March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life. Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state](https://reader031.vdocument.in/reader031/viewer/2022041723/5e4fc93720e6ee0fcc1c2f13/html5/thumbnails/2.jpg)
06 March 2013 2
Program BatteriesLecture 1: History, Applications, basic Electrochemistry and thermodynamics Feb 27 of batteries: Redox reactions, Gibbs free energy, chemical potential,
Nernst.
Lecture 2: Solid state electrode reaction mechanisms, phase diagrams, phase rule, March 6 Gibbs Free energy, voltage profiles, capacities and energy densities.
Li-ion batteries
Lecture 3: Continue topics Lecture 2.March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life.
Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state diffusionMarch 20 Discussion on Science paper 6 seconds discharge.
Lecture 5: Super capacitorsMarch 27 Future systems: Li-air, Li-sulphur
Flow-cellsCosts and Performance comparison batteries/systemsMaterial Abundance
![Page 3: Radiation, Radionuclides and Reactors...March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life. Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state](https://reader031.vdocument.in/reader031/viewer/2022041723/5e4fc93720e6ee0fcc1c2f13/html5/thumbnails/3.jpg)
06 March 2013 3
Practical Issues
Book chapters, scientific literature and sheets will be available on BB
Lecture 1: Electrochemistry 2.3-2.5
Lecture 2: Advanced Batteries: Chapter 1, 2 and 3.1-3.3
Lecture 3: Advanced Batteries Chapter 14.1,14.2,14.B1-4, 16.1-2,16B, Review Goodenough et al. Chemistry of Materials and lecture sheets
Lecture 4: Electrochemistry 3.1-3.3, Lecture sheets
Lecture 5: Lecture sheets, Review Bruce et al. Li-air/Li-sulphur
![Page 4: Radiation, Radionuclides and Reactors...March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life. Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state](https://reader031.vdocument.in/reader031/viewer/2022041723/5e4fc93720e6ee0fcc1c2f13/html5/thumbnails/4.jpg)
06 March 2013 4
From last week…
(1) Table of standard reduction potentials
(2) Derivation Gibbs free energy
(3) Homework
![Page 5: Radiation, Radionuclides and Reactors...March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life. Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state](https://reader031.vdocument.in/reader031/viewer/2022041723/5e4fc93720e6ee0fcc1c2f13/html5/thumbnails/5.jpg)
06 March 2013 5
Equilibrium electrochemistry
During discharge
Think of Battery: we have mass flow in the battery (ions) that cause the charge flow. The mass flow is represents chemical work (moving ions) which is converted to electrical work outside the battery.
chem j jj
W dnIn the battery:
In the Resistance outside the battery:
Elec cellW E dQ
Therefore, besides volume work the battery does chemical work which converted to electrical work outside:
anod
e
cath
ode
e-
Cathions (+)
Anions (-)
- +Resistance
Chem j j cell Elecj
W dn E dQ W
![Page 6: Radiation, Radionuclides and Reactors...March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life. Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state](https://reader031.vdocument.in/reader031/viewer/2022041723/5e4fc93720e6ee0fcc1c2f13/html5/thumbnails/6.jpg)
06 March 2013 6
Application on Daniel element
Anode (-): oxidation Zn(s) -> Zn2+ + 2e-
Cathode (+): reduction Cu2+ + 2e- -> Cu(s)
Total: Cu2+ + Zn(s) -> Cu(s) + Zn2+
O Standard conditions: concentrations 1 mol/l, p=1 bar, T=20oC
Equilibrium electrochemistry
anod
e
cath
ode
- +
Zn2+2e- 2e-Cu2+
NO3-
porousbarrier
Cu(NO3)2Zn(NO3)2
V
2 2
2 2
2 2 2 2
Standard conditions
/ / / /
2
2 2
j jCu Znj Zn Cu
Cell C A
Cu ZnCu ZnCell
o oCell Cu Cu Zn Zn Cu Cu Zn Zn
EzF F
EF F
E
C
j jj
CellEzF
![Page 7: Radiation, Radionuclides and Reactors...March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life. Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state](https://reader031.vdocument.in/reader031/viewer/2022041723/5e4fc93720e6ee0fcc1c2f13/html5/thumbnails/7.jpg)
Discharge Discharge
06 March 2013 7
Electrochemical cells, driving force
Standard reduction potentials are commonly denoted by the symbol °. (means under standard conditions 293 K and 1 bar, 1 molair concentrations)° values for hundreds of electrodes have been determined and are usually tabulated in order of increasing tendency to accept electrons (increasing oxidizing power.)
The more positive the half-cell EMF, the smaller the tendency of the reductant to donate electrons, and the larger the tendency of the oxidant to accept electrons
oxidant(electron acceptor)
reductant(electron donor) E°, volts
Na+ + e- -> Na(s) –2.71Zn2+ + 2e- -> Zn(s) –.76Fe2+ + 2e- -> Fe(s) –.44Cd2+ + 2e- -> Cd(s) –.40Pb2+ + 2e- -> Pb(s) –.126
2 H+ + 2e- -> H2(g) 0.000AgCl(s) + e- -> Ag(s) + Cl–(aq) +.222
Hg2Cl2(s) + 2e- -> 2Cl–(aq) + 2Hg(l) +.268Cu2+ + 2e- -> Cu(s) +.337I2(s) + 2e- -> 2 I–(s) +.535Fe3+ + e- -> Fe2+(aq) +.771Ag+ + e- -> Ag(s) +.799
O2(g) + 4H+ + 4e- -> 2 H2O(l) +1.23Cl2(g) + 2e- -> 2 Cl–(g) +1.36
Zn(s) + Cu2+ -> Zn2+ + Cu(s), cell = Cu/Cu2+– Zn/Zn2+ = 0.337 – (-0.76) = 1.097 V
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ht
What is the potential difference (Volt, V=J/C) build up?
![Page 8: Radiation, Radionuclides and Reactors...March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life. Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state](https://reader031.vdocument.in/reader031/viewer/2022041723/5e4fc93720e6ee0fcc1c2f13/html5/thumbnails/8.jpg)
06 March 2013 8
Equilibrium electrochemistry
What is the influence of concentrations (activities) on the electrode potential?
We already found for the potential of a redox reaction:
Using = + RT lnc (derived for ideal gas, dilute solutions) this leads to the Nernst equation:
Where K is the equilibrium constant of the redox reaction
j jj
CellEzF
0 0ln ln( )Cell jRT RTE E c E KzF zF
![Page 9: Radiation, Radionuclides and Reactors...March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life. Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state](https://reader031.vdocument.in/reader031/viewer/2022041723/5e4fc93720e6ee0fcc1c2f13/html5/thumbnails/9.jpg)
06 March 2013 9
From last week…
(1) Table of standard reduction potentials
(2) Derivation Gibbs free energy
(3) Homework
![Page 10: Radiation, Radionuclides and Reactors...March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life. Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state](https://reader031.vdocument.in/reader031/viewer/2022041723/5e4fc93720e6ee0fcc1c2f13/html5/thumbnails/10.jpg)
06 March 2013 10
Basic thermodynamicsFundamental equation of reversible thermodynamics (combination laws 0-2 and work):
Relevant for batteries (add pressure volume work and chemical work):
Note: determining U by integration is not easy because the natural variables of U are S and V, which are not easy to control! (n: number of moles reacted is easy to control)
Change natural (dependent) variables to p and T (easy to control and constant during battery operation) by Legendre transformation. Define new state variable Gibbs free energy F:
i ii
dU Q W TdS Y dX
i ii
dU TdS pdV dn
G U TS pV
![Page 11: Radiation, Radionuclides and Reactors...March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life. Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state](https://reader031.vdocument.in/reader031/viewer/2022041723/5e4fc93720e6ee0fcc1c2f13/html5/thumbnails/11.jpg)
06 March 2013 11
i ii
i ii
G U TS pVdG dU TdS SdT pdV VdpdG TdS pdV dn TdS SdT pdV Vdp
dG Vdp SdT dn
Basic thermodynamics
i ii
dU TdS pdV dn
Constant p and T
j j j jj j
dG Vdp SdT dn dn
0 0
( )
chem elec j jj
dG W W dn EdQ
G E Q znFE nG zFE
Integrate over n moles
Standard conditions, 1 mol, RT, 1bar
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Equilibrium electrochemistry: Relation cell voltage and Gibbs Free energy
0 0
chem j j elecj
W dG dn EdQ W
G E QG zFE
Zn(s) + Cu2+ -> Zn2+ + Cu(s), cell = Cu/Cu2+– Zn/Zn2+ = 0.337 – (-0.76) = 1.097 V
Application on Daniel element (standard conditions)
0 0 2 96500 1.1 212.3 kJ/molG zFE
G<0 Reaction occurs spontaneous (battery discharge)
General: G<0 : E>0 : discharge exothermicG>0 : E<0 : charge, endothermic
(0 standard conditions, p=1 bar, T=293 K, 1 molair concentrations )
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06 March 2013 13
From last week…
(1) Table of standard reduction potentials
(2) Derivation Gibbs free energy
(3) Homework
![Page 14: Radiation, Radionuclides and Reactors...March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life. Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state](https://reader031.vdocument.in/reader031/viewer/2022041723/5e4fc93720e6ee0fcc1c2f13/html5/thumbnails/14.jpg)
06 March 2013 14
Home assignments
Read Chapters 1 and 2 Advanced Batteries
Practice Electrochemistry:
Plot the voltage of the daniel element as a function of [Zn2+] concentration Assuming starting concentration cZn2+ =0.1 mol/l and cCu2+ =1.0 mol/l (assume cZn(s)=cCu(s)=1, and the cell volume 0.01 l).
How much chemical energy was converted to electrical energy?
Consider the following redox reaction: Cu(s) + Ag+(aq) → Cu2+
(aq) + Ag(s)What is the Gibbs free energy change under standard conditions? (Use standard reduction potentials)
![Page 15: Radiation, Radionuclides and Reactors...March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life. Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state](https://reader031.vdocument.in/reader031/viewer/2022041723/5e4fc93720e6ee0fcc1c2f13/html5/thumbnails/15.jpg)
06 March 2013 15
Examples of using = (C - A) = O – RT/zF [ln cj] = O – RT/zF ln(
Example 1: How does the electrode potential of the reaction Cu2+ + 2e- -> Cu(s) depends on the concentration
For Cu2+ + 2e- -> Cu(s) we find: cCu2+ , =-1, cCu(s), =1
So: K = cCu(s) / cCu2+
Hence: = OCu/Cu2+ - RT/2F [ln (cCu(s)/cCu2+)]= 0.337 - 0.013 [ln (cCu(s)/cCu2+)]
where we used R=8.31 J·mol-1·K-1, F=9.65 104 C ·mol-1
Similar for Zn2+ + 2e- -> Zn(s) :
= OZn/Zn2+ - RT/2F [ln (cZn(s)/cZn2+)]= -0.76 - 0.013 [ln (cZn(s)/cZn2+)]
Equilibrium electrochemistry
![Page 16: Radiation, Radionuclides and Reactors...March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life. Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state](https://reader031.vdocument.in/reader031/viewer/2022041723/5e4fc93720e6ee0fcc1c2f13/html5/thumbnails/16.jpg)
06 March 2013 16
0 lnCell jRTE E czF
Home assignments
Cu2+ + Zn -> Cu(s) + Zn2+
z=2, Cu2+=-1, Zn=-1, Cu=1, Zn2+=1
R=8.31 J·mol-1·K-1, F=9.65 104 C ·mol-1, T=293 K
Eo= OCu/Cu2+ - O
Zn/Zn2+ = 0.337 – (-0.76)=1.097
2 2
2 2
( )
( )
1.097 0.013ln 1.097 0.013lnCu s Zn ZnCell
Zn s Cu Cu
c c cE
c c c
![Page 17: Radiation, Radionuclides and Reactors...March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life. Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state](https://reader031.vdocument.in/reader031/viewer/2022041723/5e4fc93720e6ee0fcc1c2f13/html5/thumbnails/17.jpg)
06 March 2013 17
Plot the voltage of the daniel element as a function of [Zn2+] concentration Assuming starting concentration cZn2+ =0.1 mol/l and cCu2+ =1.0 mol/l (assume cZn(s)=cCu(s)=1, and the cell volume 0.01 l).
cCu2+=1.1 - cZn2+ [ 0.1 ≤ cZn2+ ≤1.1]
2
2
1.097 0.013ln 1.097 0.013ln 0.1 1.127Start ZnCell
Cu
cE
c
Home assignments
2
2
1.097 0.013ln1.1
Start ZnCell
Zn
cE
c
0.0 0.2 0.4 0.6 0.8 1.00.8
1.0
1.2
Cel
l
cZn2+ [mol/l]2
1.0
20.1
C l V mol2 96500 0.01 1.1 1 [ ] 2 kJmol l
Cell
Zn
Cell Zn
dG dQdQ zFVdc
G zFV dc
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06 March 2013 18
Home assignments
Consider the following redox reaction: Cu(s) + Ag+(aq) → Cu2+
(aq) + Ag(s)What is the Gibbs free energy change under standard conditions? (Use standard reduction potentials)
![Page 19: Radiation, Radionuclides and Reactors...March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life. Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state](https://reader031.vdocument.in/reader031/viewer/2022041723/5e4fc93720e6ee0fcc1c2f13/html5/thumbnails/19.jpg)
Discharge Discharge
06 March 2013 19
Electrochemical cells, driving force
Standard reduction potentials are commonly denoted by the symbol °. (means under standard conditions 293 K and 1 bar, 1 molair concentrations)° values for hundreds of electrodes have been determined and are usually tabulated in order of increasing tendency to accept electrons (increasing oxidizing power.)
The more positive the half-cell EMF, the smaller the tendency of the reductant to donate electrons, and the larger the tendency of the oxidant to accept electrons
oxidant(electron acceptor)
reductant(electron donor) E°, volts
Na+ + e- -> Na(s) –2.71Zn2+ + 2e- -> Zn(s) –.76Fe2+ + 2e- -> Fe(s) –.44Cd2+ + 2e- -> Cd(s) –.40Pb2+ + 2e- -> Pb(s) –.126
2 H+ + 2e- -> H2(g) 0.000AgCl(s) + e- -> Ag(s) + Cl–(aq) +.222
Hg2Cl2(s) + 2e- -> 2Cl–(aq) + 2Hg(l) +.268Cu2+ + 2e- -> Cu(s) +.337I2(s) + 2e- -> 2 I–(s) +.535Fe3+ + e- -> Fe2+(aq) +.771Ag+ + e- -> Ag(s) +.799
O2(g) + 4H+ + 4e- -> 2 H2O(l) +1.23Cl2(g) + 2e- -> 2 Cl–(g) +1.36
Cu(s) + 2Ag+ -> Cu2+ + 2Ag(s), cell = Ag/Ag+– Cu/Cu2+ = 0.799 – 0.337 = 0.462 V
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0 0 2 96500 0.462 89.2 kJ/molG zFE
![Page 20: Radiation, Radionuclides and Reactors...March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life. Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state](https://reader031.vdocument.in/reader031/viewer/2022041723/5e4fc93720e6ee0fcc1c2f13/html5/thumbnails/20.jpg)
06 March 2013 20
Program BatteriesLecture 1: History, Applications, basic Electrochemistry and thermodynamics Feb 27 of batteries: Redox reactions, Gibbs free energy, chemical potential,
Nernst.
Lecture 2: Solid state electrode reaction mechanisms, phase diagrams, phase rule, March 6 Gibbs Free energy, voltage profiles, capacities and energy densities.
Li-ion batteries
Lecture 3: Continue topics Lecture 2.March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life.
Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state diffusionMarch 20 Discussion on Science paper 6 seconds discharge.
Lecture 5: Super capacitorsMarch 27 Future systems: Li-air, Li-sulphur
Flow-cellsCosts and Performance comparison batteries/systemsMaterial Abundance
![Page 21: Radiation, Radionuclides and Reactors...March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life. Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state](https://reader031.vdocument.in/reader031/viewer/2022041723/5e4fc93720e6ee0fcc1c2f13/html5/thumbnails/21.jpg)
06 March 2013 21
Overview
Book chapters, scientific literature and sheets will be available on BB
Lecture 1: Electrochemistry 2.3-2.5
Lecture 2: Advanced Batteries: Chapter 1, 2 and 3.1-3.3
Lecture 3: Advanced Batteries Chapter 14.1,14.2,14.B1-4, 16.1-2,16B, Review Goodenough et al. Chemistry of Materials and lecture sheets
Lecture 4: Electrochemistry 3.1-3.3, Lecture sheets
Lecture 5: Lecture sheets, Review Bruce et al. Li-air/Li-sulphur
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Modern batteries: Solid state reaction mechanisms in batteries Electrolyte concentrations of charge carrying ions does not change=> Nernst is useless determining the voltage=> Structural and morphological changes in the electrodes
LiFePO4
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Solid state reaction mechanisms in batteries
Reconstitution reactions: Formation reactions: A+B = ABDisplacement reactions: A+BX = AX + B
Insertion reactions: xA + BX = AxBX
(1) Morphology change/phase diagrams(2) Relation morphology and voltage shape(3) Capacity and Energy density
Apply to Li-ion batteries:
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Solid state reactions
Left: A = A+ + e-
Right: B + A+ + e- = ABTotal: A + B + A+ + e- = AB + A+ + e-
A + B = AB
Gfo < 0
Requires A and B diffusion through AB
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Question electrochemistry 4
Left: A = A+ + e-
Right: B + A+ + e- = AB
13. What is the anode and what reaction occurs at the anode?(a) Right, oxidation(b) Right, reduction(c) Left, oxidation(d) Left, reduction(e) no clue
http://www.edupinion.nl/c954
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Question electrochemistry 4
13. What is the anode and what reactionoccurs at the anode?
Left: A = A+ + e- => oxidation/anode c)Right: B + A+ + e- = AB
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Reconstitution-formation reactionsA+B = AB
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DischargeLi -> Li+ + e- (oxidation/anode)Si+ 4.4Li+ + 4.4e- -> Li4.4Si (reduction/cathode)
Total Si + 4.4Li -> Li4.4Si
Reconstitution-formation: Example Si
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06 March 2013 30
3800
Reconstitution-formation: Example Si
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06 March 2013 31
Intermezzo: Strategies Alloy anode
Space for Li4.4Sn volume expansion No loss of contact due to confinement in Carbon sphere
(2) Nano sized Sn particles encapsulated in hollow carbon spheres
Space for Li4.4Si volume expansion Only 10 cycles reported
(1) Nano Si wires
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Reconstitution-formation reactions
General characteristics:
Host structure is radically changed due to alloying reaction, huge volume changes, short cycle life
Relatively large amount of Li per host atom, relatively high specific capacities (high energy density)
Usually metals (Si, Sb, …) good electronic conductivity (next lectures)
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Reconstitution-displacement reactionsA+BX = AX + B
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06 March 2013 34
Reconstitution-displacement reactions: Example: RuO2
Capacity of graphite
(a) Li+ + e- + RuO2 -> LiRuO2 (Li-insertion, see later)
(b) 3Li+ + 3e- + LiRuO2 -> 2Li2O + Ru (reconsititution-displacement)
(c1) Li+ + e- + electrolyte -> SEI(Li) (supercapacitive behavior, later)
SEI: Solid electrolyte interface: forms during first (dis)charge cycles, decomposed electrolyte(later)
Host material decomposes in Li2O and metal
A+BX = AX + B4Li + RuO2 -> 2Li2O + Ru
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06 March 2013 35
Reconstitution-displacement reactions: Example: RuO2
Nano structured RuO2
(a) Li+ + e- + RuO2 -> LiRuO2
(b) Li+ + e- + LiRuO2 -> 2Li2O + Ru
(c1) Li+ + e- + electrolyte -> SEI(Li)
SEI: Solid electrolyte interface: forms during first (dis)charge cycles, decomposed electrolyte
Host transforms in new compound Extra capacity Huge structural changes (after first cycle it remains nano-structured) Only reversible because of nano distances Ru-O in Li2O/Ru mixture
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Reconstitution-displacement reactions
General characteristics:
Host structure is radically changed due to alloying reaction, huge volume changes, segregation metal and Li2O short cycle life
Relatively large amount of Li per host atom, relatively high specific capacities (high energy density)
Good electronic conductivity metal, but poor electronic and ionic mobilityLi2O. To make this reversible requires very short Metal-Li2O distances
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Insertion reactionsxA + BX = AxBX
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Insertion reactions
06 March 2013 38
Li-ions intercalate into a host material
Usually host is crystalline transition metal oxide/phosphate/silicate
Transition metal provides redox couple
Requirements host material:
• Ionic and electronic conductor• Large specific Li-ion capacity• High voltage difference• Stable • Cheap• Abundant• Non-toxic
(+) Li0.5CoO2 + 0.5Li+ + 0.5 e- LiCoO2 (~3.9 V vs Li-metal)
(-) LiC6 6C + Li+ + e- (~0.3 V vs Li-metal)
~ 3.6 V battery. This is ~3 times higher than that of NiCd and NiMH (-> high energy density)
discharge
chargedischarge
charge
Anode and Cathode are intercalation compounds(rocking chair system):
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06 March 2013 39
Insertion Reaction Example: LiFePO4
LiFePO4 current alternative for LiCoO2
o Very stable (high cycleability, safe)o Cheap, abundant and environmentally friendlyo High Voltage, but less than LiCoO2 (3.6 versus Li-metal)o Reasonable capacityo Constant voltage
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06 March 2013 40
Volume change: ~ 5 %
“Host reaction” Example: LiFePO4
LiFePO4FePO4
Voids for Li-ions
Fe3+ -> Fe4+ (3.6 V vs Li-metal)
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Insertion Reactions
General characteristics:
Host structure provides framework, if volume change is small, long cycle life
Host structure is extra weight to carry, relatively low specific capacities (low energy density)
Metals have no voids, insertion hosts are usually semi conductors, poor electronic conductivity (next lectures)
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Phase Diagrams
What are they, how they work
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Binary Phase Diagrams
• The components A and B are completely miscible
• A and B have a different melting point
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Binary Phase Diagrams, lever rule
Composition Solid A0.95B0.05 Composition Liquid A0.35B0.65
SL
Phase fraction Liquid: FL= L/(L+S)~0.75, Phase fraction Solid: FS= S/(S+L)~0.25
Back calculation overall composition: AxB1-x with x=0.95xFS+0.35xFL=0.5
A0.5B0.5
T
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Question Phase Diagram 1
T14. Suppose we cool down what will happen:
a) nothingb) contents A of liquid phase will decreasec) contents B of liquid phase will decreased) no clue
http://www.edupinion.nl/c474Result
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Question Phase Diagram 1
14. Suppose we cool down what will happen =>
In liquid phase B increases so A decreases (also in the solid phase!) => b)
TSL
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Example Insertion Phase diagram: LiFePO4
T: LiFePO4H: FePO4
Voids for Li-ions
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06 March 2013 49
This is a Phase Transition
The two phases coexist
T: LiFePO4H: FePO4
Li-ion insertion
~5% Volume increase
FePO4
FePO4LiFePO4
FePO4LiFePO4
LiFePO4
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Question phase diagram 2
15. How is the material best described in point A?
a) homogeneous composition with Si/(Li+Si) between 0.24 and 0.3b) constant composition Li7Si3c) coexisting Li7Si3 and Li13Si14d) no clue
A
http://www.edupinion.nl/c269Result
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Example Reconstitution-formation phase diagram: Li-Si
(1)(2)(3)(4)
(1) 7Si + 12Li = Li12Si7(2) Li12Si7 + 13/3Li = Li7Si3(3) Li7Si3 + 11/4Li = Li13Si4(4) Li13Si4 + 23/5Li = Li22Si5
Total: Si + 4.4Li = Li4.4Si
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Relation Voltage Profile with Phase Diagram
Gibbs phase rule
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Example, the Lithium Iodine Cell
Anode (Ox): Li = Li+ + e-
Cathode (Red): Li+ + ½ I2 + e- = LiI
Total: Li + ½ I2 = LiI
Note LiI is the electrolyte!
ECell =-Gr /zFGr = Gf(LiI) = -269.7 kJ/mol at 25 oC ECell =2.8 V
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Example, the Lithium Iodine Cell
Why is the voltage constant?
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Gibbs Phase Rule
F = C – P + 2
F: Number of degrees freedomC: Number of components (e.g. elements)P: Number of phases present in this system
Number of degrees freedom: Number of intensive thermodynamic parameters that must be specified to define the system.
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Question Thermodynamics 3
16. Examples of Intensive thermodynamic parameters are:(a) G, (b) G, S, U(c) T, p, (d) no clue
http://www.edupinion.nl/c573Result
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Question Thermodynamics 3
16. Examples of Intensive thermodynamic parameters are:(a) G, (b) G, S, U(c) T, p, (d) No clue
Intensive variables do not scale with the system => c)
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F = C – P + 2
F: Number of degrees freedomC: Number of components (e.g. elements)P: Number of phases present in this system
LiI becomes the electrolyte
Li-metal, negative electrode: C = 1, P = 1 => F=2
I2, positive electrode: C = 1, P = 1 => F=2
If p, T are specified, the chemical potential is defined (fixed)
Example, the Lithium Iodine Cell
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2 22
22 2
1 12 2
constant2
j j Li ILi Ij
Cell C A
I I LiLiCell
EzF F
EF F
Example, the Lithium Iodine Cell
Anode (Ox): Li = Li+ + e-
Cathode (Red): Li+ + ½ I2 + e- = LiI
Total: Li + ½ I2 = LiI
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Example, the Lithium Iodine Cell
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Question Gibbs Phase Rule 1
17. How many relevant components are present in this phase diagram?
a) 1b) 2c) 3d) 4e) no clue
http://www.edupinion.nl/c391Result
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Question Gibbs Phase Rule 1
17. How many components?
a) 1b) 2c) 3d) 4e) no clue
2 components: Li and FePO4 => answer b)
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Question Gibbs Phase Rule 2
18. What is true in the region H+T?
a) The voltage variesb) The voltage is constantc) Nothing can be said about the voltaged) no clue
http://www.edupinion.nl/c195Result
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LiFePO4FePO4
Voids for Li-ions
F = C – P + 2 = 2 (Li and FePO4) – 2 (H and T) + 2 = 2, T,p specified => Ecell = constant => b)
Question Gibbs Phase Rule 2
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Question Gibbs Phase Rule 2
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06 March 2013 70
Program BatteriesLecture 1: History, Applications, basic Electrochemistry and thermodynamics Feb 27 of batteries: Redox reactions, Gibbs free energy, chemical potential,
Nernst.
Lecture 2: Solid state electrode reaction mechanisms, phase diagrams, phase rule, March 6 Gibbs Free energy, voltage profiles, capacities and energy densities.
Li-ion batteries
Lecture 3: Continue topics Lecture 2.March 13 Electrolyte stability: Pourbaix diagram, band structure solids, Cycle life.
Lecture 4: Kinetics, Buttler-Volmer, diffusion, solid state diffusionMarch 20 Discussion on Science paper 6 seconds discharge.
Lecture 5: Super capacitorsMarch 27 Future systems: Li-air, Li-sulphur
Flow-cellsCosts and Performance comparison batteries/systemsMaterial Abundance
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06 March 2013 71
Practical Issues
Book chapters, scientific literature and sheets will be available on BB
Lecture 1: Electrochemistry 2.3-2.5
Lecture 2: Advanced Batteries: Chapter 1, 2 and 3.1-3.3
Lecture 3: Advanced Batteries Chapter 14.1,14.2,14.B1-4, 16.1-2,16B, Review Goodenough et al. Chemistry of Materials and lecture sheets
Lecture 4: Electrochemistry 3.1-3.3, Lecture sheets
Lecture 5: Lecture sheets, Review Bruce et al. Li-air/Li-sulphur
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To do for next weekRead Chapters 2.5 and 2.6 Electrochemistry
Read Advanced Batteries Chapter 14.1,14.2,14.B1-4, 16.1-2,16BReview Goodenough et al. Chemistry of Materials
Consider the following phase diagram for a cathode, and assume that the anode has a constant voltage independent of the composition:
a) Apply the Gibbs Phase Rule along T1 in the regions and is the potential constant?
b) Sketch the voltage diagram