CN111876136A - Application of iron-doped nickel sulfide material in pressure-driven solid-state refrigeration - Google Patents

Application of iron-doped nickel sulfide material in pressure-driven solid-state refrigeration Download PDF

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CN111876136A
CN111876136A CN202010733902.1A CN202010733902A CN111876136A CN 111876136 A CN111876136 A CN 111876136A CN 202010733902 A CN202010733902 A CN 202010733902A CN 111876136 A CN111876136 A CN 111876136A
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refrigeration
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iron
entropy change
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童鹏
林建超
王萌
宋文海
朱雪斌
孙玉平
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Hefei Institutes of Physical Science of CAS
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    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
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Abstract

The invention discloses an application of an iron-doped nickel sulfide material in pressure-driven solid refrigeration. The material has a hexagonal structure and a chemical formula of Ni1‑xFexS, wherein x is more than 0 and less than 1. The material can generate huge entropy change under the induction of pressure at room temperature, and the entropy change value of the unit volume of the material exceeds that of most of the existing huge pressure card materials. And compared with the existing material of the giant voltage card, Ni1‑xFexThe S heat conductivity is obviously improved, the heat conduction can be fast and efficient, and the heat exchange capacity and the refrigeration efficiency are greatly improved. The material has the advantages of huge entropy change, high thermal conductivity, adjustable working temperature area and low price of raw materials under pressure driving, and has extremely high application prospect in the field of pressure-driven solid refrigeration.

Description

Application of iron-doped nickel sulfide material in pressure-driven solid-state refrigeration
Technical Field
The invention relates to the technical field of solid refrigeration, in particular to application of an iron-doped nickel sulfide material in pressure-driven solid refrigeration.
Background
In the modern society, along with the increasing development of economy, the application of refrigeration technology in the industrial fields of food, medicine, air-conditioning refrigeration and the like and daily life is more and more extensive. The international society for refrigeration has published reports indicating that the amount of electricity consumed by the refrigeration industry accounts for approximately 20% of the total electricity worldwide. However, most of the refrigeration technologies used at present rely on the conventional gas compression cycle, and the refrigerants used have high energy consumption and ozone layer destruction, which are harmful to the ecological environment. In addition, with the gradual approval of the international montreal protocol for ozone depletion substance regulation and the implementation of policies in green and efficient refrigeration in various countries, a consensus that the use of environment-destructive refrigerants is gradually prohibited has been achieved internationally. Therefore, the development of new efficient green refrigeration materials is receiving more and more attention.
The refrigeration technology based on the solid phase change thermal effect is expected to replace the gas compression refrigeration technology. Compared with the traditional gas compression refrigeration material, the solid refrigeration material based on the thermal effect is cleaner and more efficient. The thermal effect accompanying the solid-state phase transition refers to isothermal entropy change or adiabatic temperature change of the material under the action of an external field. According to the difference of the driving external field, the driving external field can be divided into a pressing card, a magnetic card, a spring card effect and the like. The pressure-seizing effect means that the material generates a significant thermal effect under the action of isostatic pressure. Driving the isostatic pressure of the card pressing effect (-10) compared to other thermal effects (e.g. magnetic card, spring card)2MPa) is easier to implement, and the performance of the card pressing material is less affected by cyclic fatigue. In addition, due to the same driving mode, the card pressing refrigeration technology has high compatibility with the current compressed gas refrigeration technology, so that the card pressing refrigeration technology is more expected to be really applied to industry from a laboratory.
To date, a large number of materials have been found to have the giga-card effect, such as magnetic card materials (LaFe)11.33Co0.47Si1.2、Fe49Rh51、Ni2In type compound and Gd5Si2Ge2) Inorganic anti-perovskite structure compound (GaNMn)3And NiNMn3) Organic-inorganic mixed perovskiteMine ([ TPrA)][Mn(dca)3]And [ FeL2][BF4]2) Shape memory alloy (Ni-Mn-Ti), fast ion conductor AgI, ferroelectric compound, high molecular polymer, plastic crystal (neopentyl glycol, NPG) and the like. The thermal conductivity of the currently reported macropressure card materials is generally low, which limits the practical application of the macropressure card materials as refrigerants.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides an application of an iron-doped nickel sulfide material in pressure-driven solid refrigeration.
An application of iron-doped nickel sulfide material in pressure-driven solid refrigeration is disclosed, wherein the material has a hexagonal structure and has a chemical formula of Ni1-xFexS, wherein x is more than 0 and less than 1.
Preferably, in the formula, 0.05. ltoreq. x.ltoreq.0.175.
More preferably, in the formula, x is 0.15.
The application method comprises the following steps: ni in hexagonal structure under isostatic pressure driving1-xFexAnd the S solid material is used as a refrigerating medium for refrigerating.
Wherein Ni of hexagonal structure1-xFexThe S material can be prepared by conventional means, for example, as follows:
mixing Ni powder, Fe powder and S powder at a certain proportion, pressing into sheet, placing in quartz tube, and vacuumizing to 10%- 4Pa, sealing the quartz tube by using oxyhydrogen flame, and sintering for 3 days at 450 ℃; then slowly raising the temperature to 950 ℃, and annealing for 5 days; then taking out the quartz tube, and putting the quartz tube in ice water for quenching; taking out, grinding, tabletting, placing in a quartz tube, vacuum sealing, annealing at 700 deg.C for 8 days, and quenching in ice water to obtain hexagonal structure with chemical formula of Ni1-xFexAnd (3) a material of S.
The invention discloses an application of iron-doped nickel sulfide material in pressure-driven solid refrigeration, wherein the material has a hexagonal structure and has a chemical formula of Ni1-xFexS, wherein x is more than 0 and less than 1. The material can generate huge entropy under the induction of pressure at room temperatureAnd better refrigerating effect is brought. The principle is that the application of pressure can cause huge change of an electronic structure and the synergistic effect of the electronic structure and the lattice entropy, so that a huge pressure-clamping effect is generated, and huge entropy change is generated in the primary nonmetal-metal phase change process.
Table 1 lists the properties of the existing macropressc card materials:
TABLE 1 Properties of the existing megavoltage card materials
Figure BDA0002604461720000031
For a hexagonal structure, the formula is Ni1-xFexS iron-doped nickel sulfide material, and when the applied pressure is only 100MPa, the transformation temperature T is 0.15 in the chemical formulat303K, entropy change value of unit mass can reach 52.8 J.kg-1·K-1The entropy change value of unit volume can reach 0.285J cm-3·K-1Over most of the current materials for the giga-compression card, as shown in Table 1, second only (MnNiSi)0.62(FeCoGe)0.38(0.328J·cm-3·K-1),AgI(0.35J·cm-3·K-1) And NPG (0.425J. cm)-3·K-1) (ii) a Driven by 100MPa pressure, the adiabatic temperature change is slightly larger than 8K. And the thermal conductivity at room temperature can reach 17 W.m-1·K-1In low-temperature non-metallic state, the thermal conductivity can reach 5 W.m-1·K-1. Compared with the existing giant-pressure card material shown in the table 1, the heat conductivity is obviously improved, the heat conduction is rapid and efficient, the heat exchange capacity and the refrigeration efficiency are greatly improved, the high working frequency and the high refrigeration power density of a refrigerator are facilitated, and the application of the material in the field of high-frequency solid refrigeration is particularly facilitated.
At the same time, the transition temperature T of the materialtThe Fe doping amount x is increased, so that the working temperature of the material can be adjusted by changing the Fe doping amount x.
In conclusion, the material has the advantages of huge entropy change, high thermal conductivity, adjustable working temperature area under pressure driving, low price of raw materials, and extremely high application prospect in the field of pressure-driven solid refrigeration.
Drawings
Fig. 1 is an XRD image of a sample where x is 0.05, 0.125, 0.15, 0.175.
Fig. 2 shows the thermal conductivity of 0.05 and 0.125 samples.
FIG. 3a is the thermal curve dQ/dT of the sample with x being 0.05, 0.125, 0.15, 0.175 under normal pressure, and FIG. 3b is the thermal curve dQ/dT of the sample with x being 0.05, 0.125, 0.15, 0.175 under normal pressure, TtThe entropy change of (c).
FIGS. 4a-4d are dQ/dT curves (0.1 MPa, 20MPa, 40MPa, 60MPa, 80MPa, 100MPa from right to left) measured during temperature increase for samples with x being 0.05, 0.125, 0.15, 0.175 at different applied pressures; FIGS. 4e-4h show the temperature T of samples with x being 0.05, 0.125, 0.15, 0.175 under different applied pressurestNearby entropy change Δ Sp(0.1 MPa, 20MPa, 40MPa, 60MPa, 80MPa, 100MPa from right to left).
Fig. 5 shows that the samples with x being 0.05, 0.125, 0.15 and 0.175 are respectively from normal pressure (p)00.1MPa) to different applied pressures p (20 MPa, 40MPa, 60MPa, 80MPa, 100MPa in order from low to high)BC(T)。
FIG. 6 is the relative Refrigeration Capacity (RCP) and adiabatic temperature change Δ T at an applied pressure of 100MPa for samples with x being 0.05, 0.125, 0.15, and 0.175, respectivelyad。
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
Preparation of a sample:
mixing Ni powder, Fe powder and S powder at a certain proportion, pressing into sheet, placing in quartz tube, and vacuumizing to 10%- 4Pa, sealing the tube by oxyhydrogen flame, and sintering for 3 days at 450 ℃; then slowly raising the temperature to 950 ℃, and annealing for 5 days; then taking out the quartz tube, and putting the quartz tube in ice water for quenching; taking out, grinding, tabletting, placing in quartz tube, vacuum sealing, annealing at 700 deg.C for 8 days, quenching in ice water,obtain hexagonal structure and chemical formula of Ni1-xFexAnd (3) a material of S.
Samples were prepared as described above with x being 0.05, 0.125, 0.15, 0.175, respectively.
Example 2
Measurement of physical Properties of the sample:
x-ray diffraction (XRD) tests were performed on samples of X0.05, 0.125, 0.15, and 0.175, respectively, and the results are shown in fig. 1.
The thermal conductivity of the sample, x being 0.05 and 0.125, was measured by a Thermal Transport Option (TTO) on a comprehensive Physical Property Measurement System (PPMS), and the results are shown in fig. 2.
As can be seen from fig. 2, the sample has a higher thermal conductivity whether the temperature is above or below the phase transition temperature.
Example 3
And (3) testing the refrigeration performance of the sample:
(1) adjustability of the working temperature range
Measurement of the Heat Curve dQ/dT at Normal pressure for samples with x ═ 0.05, 0.125, 0.15, 0.175 by Differential Scanning Calorimetry (DSC), in which the non-metal to metal transition temperature TtDefined as the highest peak point in the thermal curve; t is obtained by integrating the heat Q (P, T) after deducting the base linetEntropy change of (Δ S)t) (this entropy change only takes into account phase changes). The results are shown in FIG. 3.
FIG. 3a is the heat curve dQ/dT of the sample at normal pressure, and FIG. 3b is the heat curve T of the sample at TtThe entropy change of (c). As shown in fig. 3a, the non-metal to metal transition temperature TtThe Fe doping amount x is increased, so that the working temperature of the material can be adjusted by changing the Fe doping amount; as shown in FIG. 3b, Δ StExhibit a correlation with TtSimilar trend, Δ S, increasing with increasing x and obtained by heating and cooling processestThe absolute values all exceed 50 J.kg-1·K-1。
(2) Sticking coefficient and entropy change
The samples with x being 0.05, 0.125, 0.15 and 0.175 are sealed in the high-pressure sample cell, and the reference sample cell is put into the sample cavity of the mu DSC7 together, and the height is utilizedA gas compression control template, wherein nitrogen is introduced to keep the gas pressure constant (the applied pressure is 0.1MPa, 20MPa, 40MPa, 60MPa, 80MPa and 100MPa respectively), the gas is heated to 338K from 260K at the heating rate of 2K/min, and a heat curve is measured; under the external pressure of 0.1MPa, 20MPa, 40MPa, 60MPa, 80MPa and 100MPa, the calculated temperature is TtA change in entropy of (b); then passes through the formula Δ SBC(T,p0→p)＝ΔS(T,p)-ΔS(T,p0) Calculating the pressure from atmospheric pressure (p)00.1MPa) to an applied pressure p, the induced entropy change Δ SBC. The results are shown in FIGS. 4 and 5.
FIGS. 4a-4d are dQ/dT curves (0.1 MPa, 20MPa, 40MPa, 60MPa, 80MPa, 100MPa, from right to left) measured during temperature increase of a sample under different applied pressures; FIGS. 4e-4h show the temperature T of the sample under different applied pressurestChange in entropy of (Δ S)p(0.1 MPa, 20MPa, 40MPa, 60MPa, 80MPa, 100MPa from right to left). As shown in fig. 4a-4d, the non-metal to metal transition temperature T increases with increasing external pressuretMoving to a low temperature. dT may also be derived using the data of FIGS. 4a-4dtThe value of/dp (sticking coefficient). For example, for samples where x is 0.05 and x is 0.175, the derived dTtThe values of/dp are-0.0881K/MPa and-0.0947K/MPa, respectively. It can be seen that the sample has a high Kpa coefficient, comparable to other Kpa materials.
Fig. 5 shows that the samples with x being 0.05, 0.125, 0.15 and 0.175 are respectively from normal pressure (p)00.1MPa) to different applied pressures p (20 MPa, 40MPa, 60MPa, 80MPa, 100MPa in order from low to high)BC(T). As shown in fig. 5, in the samples where x is 0.05, 0.125, 0.15, and 0.175, the peak of entropy change increases with the increase of pressure; peak of entropy change for samples with x 0.05, 0.125, 0.15, 0.175 at 100MPa pressure
Figure BDA0002604461720000071
Are 39.5 J.kg respectively-1·K-1,49.4J·kg-1·K-1,52.8J·kg-1·K-1,46.7J·kg-1·K-1. Wherein x is 0.15 sample unit volumeThe entropy change value of (A) is 0.285J-cm-3·K-1。
(3) Relative cooling capacity (RCP) and adiabatic temperature change Δ Tad
According to sample Δ SBC(T) peak and half-peak width in the curve, calculating relative Refrigerating Capacity (RCP) at an applied pressure of 100MPa with x being 0.05, 0.125, 0.15, 0.175, and passing through the formula Δ Tad(T,p0→p)＝T(T,p)-T(T,p0) Using the resulting entropy-change curve Δ Sp(T), deriving the adiabatic temperature variation DeltaTad. The results are shown in FIG. 6.
FIG. 6 is the relative Refrigeration Capacity (RCP) and adiabatic temperature change Δ T at an applied pressure of 100MPa for samples with x being 0.05, 0.125, 0.15, and 0.175, respectivelyad. As shown in FIG. 6, the adiabatic temperature change Δ T at a pressure of 100MPa was measured for the samples where x was 0.05, 0.125, 0.15, and 0.175adThe peaks are all greater than 8K.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (4)

1. The application of the iron-doped nickel sulfide material in pressure-driven solid refrigeration is characterized in that the material has a hexagonal structure and has a chemical formula of Ni1-xFexS, wherein x is more than 0 and less than 1.
2. Use according to claim 1, characterized in that, in the formula, 0.05. ltoreq. x.ltoreq.0.175.
3. Use according to claim 1 or 2, wherein in the formula x is 0.15.
4. The use according to any one of claims 1 to 3, wherein the method of application is: in isostatic pressure drivingIn the hexagonal structure of Ni under dynamic conditions1-xFexThe S material is used as a refrigerating medium to realize the refrigeration of the external environment.
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Cited By (2)

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CN113652203A (en) * 2021-07-23 2021-11-16 中国科学院金属研究所 Application of halogen compound containing ammonium ion in solid refrigeration
WO2022110508A1 (en) * 2020-11-30 2022-06-02 中国科学院金属研究所 Use of material with abnormal piezocaloric effect in solid-state refrigeration and/or heat storage

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022110508A1 (en) * 2020-11-30 2022-06-02 中国科学院金属研究所 Use of material with abnormal piezocaloric effect in solid-state refrigeration and/or heat storage
CN113652203A (en) * 2021-07-23 2021-11-16 中国科学院金属研究所 Application of halogen compound containing ammonium ion in solid refrigeration
CN113652203B (en) * 2021-07-23 2022-10-04 中国科学院金属研究所 Application of halogen compound containing ammonium ion in solid refrigeration
WO2023001018A1 (en) * 2021-07-23 2023-01-26 中国科学院金属研究所 Application of ammonium ion-containing halogen compound in solid-state refrigeration

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