Energy cooperation in quantum thermoelectric systems with multiple electric currents
1. IntroductionThermoelectric phenomena at the nanoscales have attracted broad research interest for their relevance with fundamental physics, material science, and renewable energy.[1–5] Understanding and harnessing thermoelectric transport at the nanoscales may lead to various applications, including heat and energy detectors,[6–10] heat rectifiers,[11–14] refrigerators,[15–19] and energy transduction.[20] Enhancing the energy efficiency of thermoelectric devices is one of the main challenges in the study of thermoelectrics. Tremendous efforts have been devoted to the optimization of mesoscopic heat engines and refrigerators in both theories[21–35] and experiments,[36–43] which may give insight into the search of high-performance macroscopic thermoelectric materials formed by assembling mesoscopic systems.
The performance of thermoelectric materials is characterized by the dimensionless figure of merit (ZT), which is solely determined by the transport coefficients, ZT = σ S2T/κ.[44] Here T is the temperature, σ, κ, and S are the electric conductivity, the thermal conductivity, and the Seebeck coefficient, respectively. In linear-responses, the maximum energy efficiency is solely determined by the ZT factor as
where
ηC is the Carnot efficiency.
The conventional approaches toward high-performance thermoelectrics include tuning the electronic and vibrational properties in various ways to increase the ZT and the power density (characterized by the power factor PF ≡ σ S2). In most instances, the electric conductivity, the Seebeck coefficient, and the thermal conductivity are correlated, which makes it hard to optimize them independently. Apart from the insight based on Eq. (1), it was recently proposed that in multi-terminal thermoelectric systems, the energy efficiency and output power can be improved through the cooperative effects. The coexistence of multiple thermoelectric effects in those systems enables cooperation between different thermoelectric transport channels, which leads to the enhancement of the thermoelectric performance. In Ref. [45], it was proposed that two coexisting thermoelectric effects induced by the inelastic hopping transport can generate cooperative effects, leading to the enhanced energy efficiency and output power. The generalized thermoelectric figure of merit and power factor for the three-terminal systems which consist of two heat currents and one electric current were introduced as the theoretical framework for the cooperative effect.[45] This study was later extended to three-terminal thermoelectric systems with elastic transport between three electrodes.[46] However, among these studies as well as others, multiple (three or more) heat baths with different temperatures are used, which are difficult to implement in practice.
In this work, we demonstrate that cooperative effects can be exploited to enhance thermoelectric performance even in set-ups with two heat baths. Two prototypes of cooperative thermoelectric devices are illustrated in Fig. 1 where multiple electrodes (with different electrochemical potentials) are mounted onto the two heat baths. The temperatures of the hot and cold baths are kept at Th and Tc, respectively. Due to the multi-terminal geometry, there are multiple thermoelectric effects coexisting in the systems, described by multiple Seebeck coefficients for thermoelectric transport between various pairs of terminals. By making use of the cooperative effects, the thermoelectric performance can be improved, as compared with the situation where only one of them is involved in the energy conversion. Moreover, such cooperative effects exist in a wide parameter region, leading to the considerably enlarged physical parameter space with high thermoelectric performance. Thus, it becomes less demanding to achieve high-performance thermoelectrics in multi-terminal systems when the cooperative effects are exploited. To demonstrate such effects, three-terminal heat engines and refrigerators as well as four-terminal heat engines are studied in this work.
The main part of this paper is organized as follows. In Section 2, we introduce the three-terminal thermoelectric system and its transport properties, give the expressions for the maximum efficiency and maximum power in the linear-response regime. In Section 3, we show that the cooperative effect can enhance the performance of the three-terminal heat engine in the linear-response regime. In Section 4, we study the cooperative effects in a refrigeration set-up. In Section 5, we compare the optimal efficiency and power of a four-terminal thermoelectric heat engine with those of the three-terminal heat engine. Finally, we conclude our study in Section 6 along with our future outlook.
2. Linear-response thermoelectric transport in a quantum three-terminal heat engineWe consider a nanoscale thermoelectric system consisting of triple quantum dots (QDs) coupled to three electrodes (see Fig. 1). One electrode is mounted onto one heat bath and the others are mounted onto another heat bath. The system can function as a heat engine or a refrigerator depending on the voltage and temperature configurations. In the high-temperature regime, the inter-QD Coulomb interaction can be ignored.[47,48] The intra-QD Coulomb interaction, which is not relevant for the essential physics to be revealed in this work, is also neglected. Each QD is coupled to the nearby reservoir. We employ the indices 1/2/3 to identify the leads L/R/P, respectively.
The system is described by the Hamiltonian[49]
where
Here,
di (
) annihilates (creates) an electron in the
i-th QD with energy
Ei,
t is the hopping strength between the QDs, and
cik (
) annihilates (creates) an electron in the
i-th electrode with energy
εk.
We take the temperature and the electrochemical potential of reservoir R as a reference, we restrict our study to the linear-response regime. We thus define the flowing thermodynamic “forces”
where
e < 0 is the electron charge. We consider the set-up where the electrode
L is connected to the hot bath and the electrodes
R and
P are connected to the cold bath, i.e.,
TL ≡
Th and
TR =
TP ≡
Tc. In this configuration, there is one heat current flowing out of the hot reservoir
L which is
. The corresponding force is
. There are two independent electric currents,
(i.e., the electrical current flowing out of the reservoir
L) and
(i.e., the electrical current flowing out of the reservoir
P).
In the linear-response regime, the charge and heat transports are described by the following equation:[50,51]
where the charge and heat currents flowing out of the left reservoir can be calculated by the Landauer–Büttiker formalism
[52,53]
Here
fi(
E) = {exp[(
E −
μi)/
kBTi] + 1}
−1 is the Fermi–Dirac distribution function and
h is the Planck’s constant. The factor of two comes from the spin degeneracy of electrons.
is the transmission probability from terminal
j to terminal
i[54]
where the (retarded) Green’s function is given by
G(
E) ≡ [
E −
HQD − i
Γ/2]
−1. The QD–electrode coupling
Γ = 2
π∑
k|
Vik|
2δ(
ω −
εik) is assumed to be an energy-independent constant for all three electrodes. Analogous expressions can be written for
, provided that the index
L is substituted by
P in Eq. (
6). The detailed calculation of Onsager transport coefficients
Mij (
i,
j = 1,2,3) can be found in Appendix
A.
The total entropy production accompanying this transport process reads[21]
The second law of thermodynamics, i.e.,
for arbitrary configurations of thermodynamic forces, imposes the following constraints on the linear-transport properties:
as well as the requirement of non-negativeness of the determinant of the 3 × 3 transport matrix in Eq. (
5).
3. Cooperative thermoelectric effects: A geometric interpretationIn this section, we study the cooperative effects in a thermoelectric engine and elucidate such cooperative effects by a geometric interpretation[45,46]
where
is the total “magnitude” of electrical affinities. For our further discussion, we define the effective electrical conductance as a function of the parameter
θ,
[46]
The effective thermoelectric coefficient and the thermal conductance are respectively given by
Using the above relations, we can write the figure of merit
ZT for a given parameter
θ as
[55]
The energy efficiency of the three-terminal thermoelectric heat engine is defined as[54]
which is bounded by the Carnot efficiency
ηC ≡ (
Th −
Tc)/
Th.
The conditional maximum output power is found as[50]
where we have defined
. Here, we call the thermoelectric effect associated with
as the “
L-
R thermoelectric effect”, while the one associated with
as the “
P-
R thermoelectric effect”.
When θ = 0 or π, equation (16) gives the L-R thermoelectric efficiency and power
The P-R thermoelectric efficiency and power are acheived at θ = π/2 or 3π/2, which are given by
In linear-responses, the global maximum energy efficiency and the efficiency at the maximum output power[56–58] of the three-terminal heat engine with the cooperative effects taken into account are respectively given by
It is found that the maximum output power and the output power at the maximum efficiency are
Here,
is a dimensionless parameter which is termed as the “degree of coupling”.
To illustrate how the two thermoelectric effects cooperate}, we plot the energy efficiency η and output power W as functions of the parameter θ in Figs. 2(a) and 2(b). {The efficiencies and powers of the L-R and P-R thermoelectric effects are also respectively marked with red and blue dots for comparison}. It is seen that in the ranges of 0 < θ < π/6 and π < θ < 7π/6, the energy efficiency is greater than both the efficiencies ηL − R and ηP − R when the L-R and P-R thermoelectric effects are considered independently. In the same region of physical parameters, the cooperative output power W is also greater than both the output powers WL − R and WP − R.
To clarify the enhancement of the thermoelectric performance due to the cooperation effect, we study the maximum efficiency ηmax and the maximum output power Wmax as functions of QD energies E1 and E2. It is seen from Figs. 3(a) and 3(c) that ηmax and Wmax are very sensitive to the QDs energies which can be controlled via gate-voltage in experiments.[11] As shown by the hot-spot regions, the optimal values of ηmax and Wmax are achieved when E1 ≈ E2 > 1.0kBT, reaching to ηmax ≈ 0.6 ηC. Besides, both the efficiency and power are symmetric around the line of E1 = E2 when E3 = 0. Figures 3(b) and 3(d) show that the enhancement of the performance is prominent when E1 ≈ 0. The enhancement factors of the maximum output power Wmax/(WL − R,WP − R) and the maximum efficiency ηmax/(ηL − R,ηP − R) can reach 10 in a wide range of E2. It is also noticed that the enhancement factors of both output power and efficiency are always greater than 1. From the above results, we conclude that the cooperative effects can always enhance the performance of three-terminal thermoelectric engines, which opens a pathway toward high-performance thermoelectric energy conversion in multi-terminal thermoelectric systems.
We now study the problem of optimizing energy efficiency and output power when the three-terminal thermoelectric heat engine is connected to a resistor circuit. As illustrated in Fig. 1(a), we employ a triangular resistance circuit (with three resistors R1, R2, and R3) to harvest the electric power. The resistances, Ri (i = 1,2,3), are tuned to optimize the performance of the three-terminal heat engine. The current–force relation for the triangular resistance circuit is formally written as
where
,
and
are the charge currents flowing out of electrodes
L and
P, respectively, into the resistor circuit. The electrical currents flowing through resistors
Ri (
i = 1,2,3) are given by
According to the Kirchhoff’s current law, we obtain
Using Eqs. (
24)–(
26), we obtain the expression of
as
According to Ref. [
59], we find that the maximum power
Wmax in Eq. (
21) is achieved at
Besides, the maximum energy efficiency
ηmax in Eq. (
21) is achieved at
4. Thermoelectric cooperative effects on a three-terminal refrigeratorThe three-terminal device can also operate as a thermoelectric refrigerator by reversing the electrical currents and exchanging the temperatures of the two heat baths.[11,18,50] In this configuration, there are two electrodes mounted on the hot bath, while one electrode mounted on the cold bath which is to be cooled, i.e., TR(P) = Th, TL = Tc, with Th > Tc, as depicted in Fig. 1(b). The consumed electrical power for the cooling is
while the cooling power is
IQ. The efficiency of the refrigerator is
The Carnot efficiency for the refrigerator is given by
Using Eq. (
5), the cooling heat flux
IQ can be expressed as
which consists of three parts: the heat current
IQ,3 =
M33FQ < 0 due to the (Fourier) thermal conduction, the cooling heat current
as contributed by the
L-
R Peltier effect, and the cooling heat current
as contributed by the
P-
R Peltier effect. The cooling is achieved when the sum of the heat currents
IQ,1 and
IQ,2 exceeds the thermal conduction current |
IQ,3|. Combining Eq. (
11), the effective heat current can be expressed as a function of the parameter
θ,
The above equation indicates that
IQ,1 =
M13Fe cos
θ and
IQ,2 =
M23Fe sin
θ can be tuned effectively by the parameter
θ. When these two currents are of the same sign, i.e.,
IQ,1 > 0 and
IQ,2 > 0, they contribute constructively to the cooling. This cooperative effect leads to enhanced cooling power [as shown in Fig.
4(a)] and the energy efficiency [as shown in Fig.
4(b)]. Explicitly, we find that when 0 <
θ <
π/2, the two cooling heat currents
IQ,1 and
IQ,2 are of the same sign, the cooling power and the energy efficiency are enhanced. In contrast, for
π/2 <
θ < 2
π, the two cooling heat currents are of opposite signs, the cooling power and the energy efficiency are reduced.
5. The optimal efficiency and power of a four-terminal thermoelectric heat engineIn this section, we study the optimal efficiency and output power of a four-terminal thermoelectric heat {engine} and compare the optimal performance of the four-terminal thermoelectric heat engine with that of the three-terminal thermoelectric heat engine.[60–64] As shown in Fig. 5, we focus on the situation where the reservoir 1 is connected to the hot bath and the reservoirs 2, 3, and 4 are connected to the cold bath. In this set-up, there are three independent output electric currents (i = 1,2,3) and only one input heat current flowing out of the hot reservoir 1. In linear-responses, the currents and forces are related to each other through the linear-transport coefficients Mij (i,j = 1,2,3,4) as[50]
where
represents the electric current flowing out of the electrode
i = 1,2,3. The thermodynamic force corresponding to the electric current
is
.
is the heat current flowing out of the electrode 1 with {the corresponding thermodynamic force} given by
. Detailed calculation of the currents and transport coefficients
Mij (
i,
j = 1,2,3,4) can be found in Appendix
B.
For a multi-terminal machine, the steady-state heat-to-work conversion efficiency η4T is defined by the ratio between the output power W4T and the heat current , i.e.,
Here,
η4T ≤
ηC is dictated by the second-law of thermodynamics, i.e., the total entropy production rate
. The maximum energy efficiency and the efficiency at the maximum output power are respectively found to be
Besides, the maximum output power and the output power at the maximum efficiency are respectively found to be
Here,
is the so-called degree of coupling.
denotes the 3 × 3 charge conductivity tensor.
and
are the 3 × 1 and 1 × 3 matrices, respectively, describing the Seebeck and Peltier effects.
MQQ represents the heat conductivity.
We first examine the optimal efficiency and output power of the four-terminal heat engine and then compare them with those of the three-terminal heat engine. As shown in Fig. 6, we plot the maximum efficiency and the efficiency at the maximum output power η4T(Wmax as functions of the QD energy E4. From Figs. 6(a) and 6(c), we find that both of and η4T(Wmax) achieve their maximum values at E4 ≈ 1.2kBT. Especially when E2 = −2kBT, the maximum efficiency is found to be 0.4ηC. As shown in Figs. 6(b) and 6(d), both of the maximum efficiency and the efficiency at the maximum power of the four-terminal heat engine are greater than those of the three-terminal heat engine in the range of 0.2kBT < E4 < 4kBT. These comparisons illustrate that the heat engine with multiple output electrical currents {offers} accesses to better performance.
In order to verify the above results, we further study the maximum energy efficiency, the energy efficiency at the maximum power, the maximum output power, and the output power at the maximum efficiency as functions of QD energies E3 and E4. Both of the efficiencies and powers are symmetric around the line of E3 = E4. The improvements are especially pronounced when E3 > 1kBT and E4 > 1kBT with the optimal energy efficiency of the four-terminal thermoelectric heat engine reaching to 0.5ηC. Figure 8 shows the comparisons of the optimal performances between the four-terminal and three-terminal set-ups, it is found that the energy efficiency and output power are considerably enhanced by using the four-terminal set-up, particularly when 0.5kB T < E4 < 1.5kBT, E3 < 0, as well as E3 > 2kBT.
Finally, we come to the realistic situations where the four-terminal heat engine is connected to a resistor circuit. The thermoelectric energy is used by the resistor network, as shown in Fig. 5. The relation between the currents and forces of the resistor circuit can be expressed by the Onsager transport matrix
where
and
(
i = 1,2,3,4) is the electric current flowing out of electrode
i into the resistor circuit.
is the corresponding thermodynamic force. The electric currents
Ji flowing through the resistors
Ri (
i = 1,2,3,4) are given by
According to the Kirchhoff’s current law for the resistor circuit, we have
Combining Eqs. (
44)–(
46), the expression of
is found to be
In addition, the Kirchhoff’s current law for the electrodes requires that
Then we obtain
The electric power consumed by the resistor circuit is given by
And the heat current is given by
The energy efficiency of the four-terminal heat engine is then defined as
. Through the modification of
, the maximum output power is achieved at
and the maximum energy efficiency is obtained at
It is noticed that the above formulas of the optimal energy efficiency and output power are consistent with Eqs. (
39) and (
41).
6. ConclusionIn this work, we show that cooperative effects can be a useful way to improve the energy efficiency and output power of the multi-terminal quantum-dot thermoelectric heat engines with multiple output electric currents. Each pair of terminals (including a hot terminal and a cold terminal) yields a thermoelectric effect. The cooperation between the coexisting multiple thermoelectric effects leads to improved thermoelectric performance. Through the calculation of the thermoelectric transport coefficients using the Landauer–Büttiker formalism, we find that both the efficiency and power can be considerably improved by the cooperative thermoelectric effect, as compared with that using each thermoelectric effect independently. Such improvements are as effective for good thermoelectrics as that for bad thermoelectrics. Therefore, the region of physical parameters with high thermoelectric performance is considerably increased by the thermoelectric effects. By comparing the thermoelectric performance of four-terminal and three-terminal thermoelectric engines, we find that more output electric currents can further improve the performance of quantum heat engines in a certain range of parameters. Our results offer useful guidelines in the understanding of optimal behaviors of the multiple-terminal heat engine in the linear response regime. Nonlinear effects, which may yield interesting effects, deserve future studies.