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Equilibrium Thermodynamics
Lecture 11: Reconstitution Electrodes
MIT Student (and MZB)
combinations of x− and x+ .
describing free energy, chemical potential and open ciruit voltage (per site)
are:
2
Lecture 11: Reconstitution electrodes 10.626 (2011) Bazant
We know that
ez − e−z
lim tanh z = z
z→∞ e + e−z
1 − e−2z
=
1 + e−2z
≈ (1 − e−2z )(1 − e−2z + e−4z )
≈ 1 − 2e−2z
Thus we can solve for y+ :
˜
y = tanh h̃0 y ≈ 1 − 2e−2h0 y
Recursively substituting this expansion into itself, we get
˜
y+ ≈ 1 − 2e−2h0
Thus,
x+ ≈ 1 − e−2Tc /T . (7)
We can obtain x− by noting that x+ + x− = 1.
3
Lecture 11: Reconstitution electrodes 10.626 (2011) Bazant
0.9
0.8
0.7
0.6
c
T/T
0.5
0.4
0.3
0.2
0.1
T∼Tc
T<<T
c
0
yn+1 = F (yn )
This method converges if F " < 1 at the fixed point. To use this as an
analytic approximation, we observe that substituting the function into itself
and then putting in the guess when sufficently close will give us an arbitrarily
accurate approximation:
˜ 0 · 1)))
y = F (F (F...F (h̃0 y))) ≈ F (F (F...F (h
cleation of the second phase inside the first, to facilitate the transformation.
However, far enough into the miscibility gap– in the spinodal region – spon
taneous instability or “spinodal decomposition” of the uniform, metastable
state will occur.
Imagine some composition fluctuation occurs – see Figure 3. If this
lowers the free energy, then the fluctuation will grow, and phase separation
is spontaneous. Using common tangent construction, this occurs when the
homogenous free energy looses convexity (ḡ "" < 0):
−0.06 −0.142
−0.08
−0.144
−0.09
−0.145
−0.1
g/kT
g/kT
−0.146
−0.11
−0.147
−0.12
−0.148
−0.13
−0.14 −0.149
−0.15 −0.15
0 0.2 0.4 0.6 0.8 1 0.25 0.3 0.35 0.4 0.45 0.5
x x
0.5
(0.08) (0.17) (0.38) (0.50)
0.4
210 mV
0.2
120 mV
85 mV
0.1
(b) (0)
(0.22)
0
0 0.5 1.0
X in LixC6
The Reversible Potential of The Lithium-Graphite
Intercalation Compounds vs. The Composition x in LixC6 Plots
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