diff --git a/Physlib.lean b/Physlib.lean index 58db66fdb..efa95d934 100644 --- a/Physlib.lean +++ b/Physlib.lean @@ -29,6 +29,7 @@ public import Physlib.ClassicalMechanics.Vibrations.LinearTriatomic public import Physlib.ClassicalMechanics.WaveEquation.Basic public import Physlib.ClassicalMechanics.WaveEquation.HarmonicWave public import Physlib.CondensedMatter.Basic +public import Physlib.CondensedMatter.Thermoelectric.Basic public import Physlib.CondensedMatter.TightBindingChain.Basic public import Physlib.Cosmology.Basic public import Physlib.Cosmology.FLRW.Basic diff --git a/Physlib/CondensedMatter/Thermoelectric/Basic.lean b/Physlib/CondensedMatter/Thermoelectric/Basic.lean new file mode 100644 index 000000000..8bbbcf8b6 --- /dev/null +++ b/Physlib/CondensedMatter/Thermoelectric/Basic.lean @@ -0,0 +1,213 @@ +/- +Copyright (c) 2026 Giuseppe Barbalinardo. All rights reserved. +Released under Apache 2.0 license as described in the file LICENSE. +Authors: Giuseppe Barbalinardo +-/ +module + +public import Mathlib.Data.Real.Basic +public import Mathlib.Tactic.Ring +public import Mathlib.Tactic.Positivity +/-! + +# Thermoelectric figure of merit + +## i. Overview + +A thermoelectric material converts a temperature difference into electrical +power. In the linear-response (Onsager) regime, the coupled transport of +charge and heat in an isotropic material is governed by the constitutive +relations + + J = σ (E − S ∇T), q = T S J − κ ∇T, + +so a thermoelectric material is characterized by exactly four transport +coefficients: the Seebeck coefficient `S`, the electrical conductivity `σ`, +and the thermal conductivity `κ = κl + κe`, split into its lattice (phonon) +and electronic contributions because the two channels respond independently +to material design. These four coefficients are collected in the structure +`ThermoelectricMaterial`, and everything in this file is stated on it. + +The performance of the material at absolute temperature `T` is captured by +the dimensionless figure of merit + + zT = σ S² T / (κl + κe), + +whose numerator groups into the power factor `PF = σ S²`. Temperature is a +state variable, not a material property, so `T` enters as an argument rather +than a field. The four coefficients of a real material are themselves +temperature-dependent, so a `ThermoelectricMaterial` should be read as a +material at an operating point, its coefficients evaluated at the same +temperature at which `zT` is evaluated. + +In this file all quantities are real numbers in a fixed consistent system of +units, following the convention of `Physlib.Thermodynamics.IdealGas.Basic`. + +## ii. Key results + +- `ThermoelectricMaterial`: the four linear-response transport coefficients + of a thermoelectric material, with their physical sign constraints. +- `powerFactor`: the thermoelectric power factor `σ S²`. +- `totalThermalConductivity`: the total thermal conductivity `κl + κe`. +- `figureOfMerit`: the dimensionless figure of merit `zT`. +- `figureOfMerit_eq`: the flat form `zT = σ S² T / (κl + κe)`. +- `figureOfMerit_pos`: positivity of `zT` for a material with a nonzero + Seebeck coefficient at positive temperature. +- `figureOfMerit_le_of_le`: lowering the lattice thermal conductivity raises + `zT`, the phonon-glass electron-crystal design principle. + +## iii. Table of contents + +- A. The thermoelectric material +- B. The power factor +- C. The total thermal conductivity +- D. The figure of merit + - D.1. Equalities for the figure of merit + - D.2. Positivity of the figure of merit + - D.3. Monotonicity in the lattice thermal conductivity + +## iv. References + +- Ioffe, A.F., *Semiconductor Thermoelements and Thermoelectric Cooling*, + Infosearch (1957). +- Snyder, G.J., Toberer, E.S., *Complex thermoelectric materials*, + Nature Materials 7, 105–114 (2008). + +-/ + +@[expose] public section + +noncomputable section + +namespace CondensedMatter + +/-! + +## A. The thermoelectric material + +The four fields are the complete set of linear-response coefficients for +coupled charge and heat transport in an isotropic material: no further +material parameter enters the steady-state thermoelectric equations, and +`zT` is a function of exactly these four together with the temperature. +The sign constraints are physical: a thermoelectric material conducts +charge (`0 < σ`) and its lattice conducts heat (`0 < κl`), while the +electronic heat channel can be negligible but never negative (`0 ≤ κe`). +The Seebeck coefficient is unconstrained: its sign records the carrier +type (negative for electrons, positive for holes), and it vanishes at +compensation points. + +-/ + +/-- A thermoelectric material in the linear-response regime, characterized by +its four transport coefficients. -/ +structure ThermoelectricMaterial where + /-- The Seebeck coefficient `S`: the voltage developed per unit temperature + difference. Its sign records the dominant carrier type. -/ + S : ℝ + /-- The electrical conductivity `σ`. -/ + σ : ℝ + /-- The lattice (phonon) contribution `κl` to the thermal conductivity. -/ + κl : ℝ + /-- The electronic contribution `κe` to the thermal conductivity. -/ + κe : ℝ + σ_pos : 0 < σ + κl_pos : 0 < κl + κe_nonneg : 0 ≤ κe + +namespace ThermoelectricMaterial + +/-! + +## B. The power factor + +-/ + +/-- The thermoelectric power factor `PF = σ S²` of a material. -/ +def powerFactor (M : ThermoelectricMaterial) : ℝ := M.σ * M.S ^ 2 + +/-- The power factor is positive when the Seebeck coefficient is nonzero. -/ +lemma powerFactor_pos {M : ThermoelectricMaterial} (hS : M.S ≠ 0) : + 0 < M.powerFactor := by + unfold powerFactor + -- `positivity` does not look through the projection, so name the field. + have hσ := M.σ_pos + positivity + +/-! + +## C. The total thermal conductivity + +-/ + +/-- The total thermal conductivity `κl + κe` of a material, the sum of the +lattice (phonon) and electronic contributions. -/ +def totalThermalConductivity (M : ThermoelectricMaterial) : ℝ := M.κl + M.κe + +/-- The total thermal conductivity is positive. -/ +lemma totalThermalConductivity_pos (M : ThermoelectricMaterial) : + 0 < M.totalThermalConductivity := + add_pos_of_pos_of_nonneg M.κl_pos M.κe_nonneg + +/-! + +## D. The figure of merit + +-/ + +/-- The dimensionless thermoelectric figure of merit +`zT = PF · T / (κl + κe)` of a material at absolute temperature `T`. -/ +def figureOfMerit (M : ThermoelectricMaterial) (T : ℝ) : ℝ := + M.powerFactor * T / M.totalThermalConductivity + +/-! + +### D.1. Equalities for the figure of merit + +-/ + +/-- The figure of merit in its standard flat form +`zT = σ S² T / (κl + κe)`. -/ +lemma figureOfMerit_eq (M : ThermoelectricMaterial) (T : ℝ) : + M.figureOfMerit T = M.σ * M.S ^ 2 * T / (M.κl + M.κe) := by + unfold figureOfMerit powerFactor totalThermalConductivity + ring + +/-! + +### D.2. Positivity of the figure of merit + +-/ + +/-- The figure of merit is positive at positive temperature when the Seebeck +coefficient is nonzero. -/ +lemma figureOfMerit_pos {M : ThermoelectricMaterial} {T : ℝ} + (hS : M.S ≠ 0) (hT : 0 < T) : + 0 < M.figureOfMerit T := + div_pos (mul_pos (powerFactor_pos hS) hT) M.totalThermalConductivity_pos + +/-! + +### D.3. Monotonicity in the lattice thermal conductivity + +-/ + +/-- Lowering the lattice thermal conductivity raises the figure of merit: if +`M.κl ≤ κl'` then the material with lattice conductivity `κl'` (all other +coefficients equal) has the smaller `zT`. This is the phonon-glass +electron-crystal design principle: scatter phonons without degrading +electronic transport. Note the hypotheses: no condition on the Seebeck +coefficient is needed, since monotonicity only requires the numerator +`σ S² T` to be nonnegative. -/ +lemma figureOfMerit_le_of_le (M : ThermoelectricMaterial) {κl' T : ℝ} + (hpos : 0 < κl') (h : M.κl ≤ κl') (hT : 0 ≤ T) : + figureOfMerit { M with κl := κl', κl_pos := hpos } T ≤ M.figureOfMerit T := by + unfold figureOfMerit powerFactor totalThermalConductivity + have hnum : (0 : ℝ) ≤ M.σ * M.S ^ 2 * T := by + have hσ := M.σ_pos + positivity + have hden : 0 < M.κl + M.κe := add_pos_of_pos_of_nonneg M.κl_pos M.κe_nonneg + gcongr + +end ThermoelectricMaterial + +end CondensedMatter