Review of the molecular dynamics of molten salt thermal physical properties

doi:10.19799/j.cnki.2095-4239.2023.0708

Abstract

Abstract:

As a high-temperature heat transfer and storage medium, molten salt is widely used for solar thermal power generation and the flexible transformation of thermal power plants. First, the potential functions of the molecular dynamics of molten salt were summarized and analyzed. This indicated that to reduce simulation errors, the Buckingham potential with coulomb force is more suitable for nitrate and the BMH potential is more suitable for carbonate and chloride salt. Second, an analysis of the thermal properties of molten salt indicated that the addition of Ca²⁺ to solar salt decreased its melting point and increased its viscosity, and the specific heat capacity of nitrate decreased with increasing NO^2- concentration. Increased Li⁺ concentrations increased the specific heat capacity and thermal conductivity of chloride salt but also increased the simulation error; however, with increased K⁺, the specific heat capacity error decreased and the error when calculating residual heat properties increased. The carbonate simulation error was relatively small, which is consistent with experimental results. The simulation errors were large with the addition of K⁺ or Li⁺, and the increased potential energy between ions led to the loss of some particles. It was found that the influence of the boundary effect after the introduction of a boundary condition increased the error; however, the error was reduced by increasing the number of molecules, the potential energy truncation distance correction, and the simulation time step. Currently, studies on the molecular dynamics of molten salt with the same cation and different anions are rare. Exploring the influence of nanofluids on molten salt molecular dynamics, reducing the simulation error of molecular dynamics, and conducting research on the corrosion characteristics of molten salt based on molecular dynamics is the next research direction of molten salt molecular dynamics.

Key words: molten salt, molecular dynamics, potential function, thermophysical property

CLC Number:

TK 512

Dianwei FU, Cancan ZHANG, Heya NA, Guoqiang WANG, Yuting WU, Yuanwei LU. Review of the molecular dynamics of molten salt thermal physical properties[J]. Energy Storage Science and Technology, 2023, 12(12): 3873-3882.

Figures/Tables 10

Fig. 1

Fig. 2

Table 1

Molten salt molecular dynamic simulation potential functions"

氯化物、硝酸根和碳酸根熔盐的模拟势函数
序号	势函数名称	应用类型	公式
1	Born-Mayer-Huggins-Tosi-Fumi^[24] (BMHFT)	$N a C l$	$ϕ i j r = Z i Z j e 2 r + A i j e x p B σ i + σ j - r - C i j r 6 - D i j r 8$	(1)
1	Born-Mayer-Huggins-Tosi-Fumi^[24] (BMHFT)	$N a C l$	$A i j = A i A j 12, C i j = C i C j 12, 2 ρ i j = 1 ρ i + 1 ρ j$	(2)
2	Born-Mayer-Huggins-Tosi-Fumi^[25](BMHFT)	$N a C l$	$Φ = Z i Z j e 2 4 π ε ε 0 r + B i j e x p - r - σ i j β i j - C i j r 6 - D i j r 8$	(3)
3	Born-Mayer-Huggins^[26](BMH)	$N a C l$ $- K C l$	$E i j = A i j e σ i j - r i j ρ - C i j r i j 6 - D i j r i j 8$	(4)
4	Born–Mayer–Huggins^[27-28](BMH)	$N a C l$ $- L i C l$ $- K C l$ $L i C l$ $- K C l$ $N a C l$ $- K C l$ $N a 2 C O 3$ $- K 2 C O 3$	$U i j = q i q j r i j + A i j e x p σ i j - r i j ρ - C i j r i j 6 - D i j r i j 8$	(5)
5	Born-Mayer^[29]	$N a 2 C O 3$ $- K 2 C O 3$ $L i 2 C O 3$	$u r i j = z i z j e 2 r i j + b 1 + z i n i + z j n j e x p α σ i + σ j - r i j$	(6)
6	Busing^[30]	$Z n C l 2$ $Z n C l 2$ $- K C l$	$φ i j = - Z i Z j r i j + f ρ i + ρ j e x p R i + R j - r i j ρ i + ρ j$	(7)
7	Buckingham^[31]+Coulomb^[32]	$N a N O 3$	$U B u c k i n g h a m = ∑ i ∑ i ≠ j A i j e - r i j ρ i j - C i j r i j 6, r i j < r c$	(8)
7	Buckingham^[31]+Coulomb^[32]	$N a N O 3$	$U C o u l o m b = ∑ i ∑ i ≠ j q i q j ε r i j, r i j < r c$	(9)
8	Buckingham^[33]	$N a N O 3$ $- K N O 3$ $K 2 C O 3$ $- L i N O 3$ $N a N O 3$ $- K N O 3$ $- N a N O 2$	$E = A i j e - r i j ρ i j - C i j r i j 6 + q i q j 4 π ε 0 r i j$	(10)
9	Lennard-Jones^[34](LJ)	$N a N O 3$ $- K N O 3$ $N a C l$	$E r = q i q j r + 4 ε σ r 12 - σ r 6$	(11)
9	Lennard-Jones^[34](LJ)	$N a N O 3$ $- K N O 3$ $N a C l$	$σ i j = σ i + σ j 2, ε i j = ε i ε j$	(12)

Table 1

Table 2

Correlation formula"

序号	名称	公式
1	径向分布函数RDF	$g α β r = 1 4 π ρ β r 2 d N α β r d r$	(13)
2	配位数N(r)	$N α β r = 4 π ρ β ∫ 0 r m i n g α β r r 2 d r$	(14)
3	均方位移MSD	$M u t = r t - r 0 2$	(15)
4	自扩散系数D^[35]	$D u = 16 d M u t d t$	(16)
5	角分布函数ADF	$θ i j k = c o s - 1 r i j 2 + r i k 2 - r j k 2 2 r i j r i k$	(17)
6	密度^[36]	$ρ = N M V N A$	(18)
7	比热容	$C p = Q / Δ T$	(19)
8	剪切黏度^{[24, 37]}	$η = 1 k B T V ∫ 0 ∞ P x y 0 P x y t d t$	(20)
8	剪切黏度^{[24, 37]}	$P x y t = ∑ i = 1 N m i v x i v y i + 12 ∑ j ≠ i x i j f y r i j$	(21)
9	热导率	$j z = - λ T ∂ T ∂ z$	(22)
9	热导率	$λ T = - ∑ t r a n s f e r m 2 v h o t 2 - v c o l d 2 2 t L x L y ∂ T / ∂ z$	(23)
10	离子电导率^[38]	$λ z = 1 3 V k B T ∫ 0 ∞ J z 0 J z t d t$	(24)
11	键能^[39]	$E = K b (r - r 0) 2 + K a (θ - θ 0) 2 + K u b (r - r u b) 2$	(25)

Table 2

Fig. 3

Fig. 4

Table 3

Fig. 5

Fig. 6

Fig. 7

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熔点	介孔尺寸
熔点	3 nm	4 nm	6 nm
实验结果/K	485.45	488.71	499.16
模拟结果/K	492	493	503

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