CN114702392A - Metal molecule-free antiferroelectric solid solution, preparation method and application - Google Patents

Metal molecule-free antiferroelectric solid solution, preparation method and application Download PDF

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CN114702392A
CN114702392A CN202210449096.4A CN202210449096A CN114702392A CN 114702392 A CN114702392 A CN 114702392A CN 202210449096 A CN202210449096 A CN 202210449096A CN 114702392 A CN114702392 A CN 114702392A
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cyclohexylmethylamine
solid solution
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cell parameters
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CN114702392B (en
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孙志华
徐豪杰
郭吴倩
罗军华
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Mindu Innovation Laboratory
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Abstract

The invention relates to an antiferroelectric solid solution without metal molecules, a preparation method and application thereof. The general formula of the solid solution is (C)7H16N)BrxI1‑xAnd (C)7H16N)BrxCl1‑x(0≤x<1) And an antiferroelectric phase at room temperature, belonging to an orthorhombic system. The solid solution shows excellent antiferroelectric performance below Curie temperature, wherein the saturation polarization strength of the cyclohexylmethylamine chloride salt can reach 11.4 mu C/cm2. In addition, the solid solution also has nearly zero remanent polarization, large coercive field and high breakdown voltage resistance, and can be used as a candidate material of an energy storage dielectric.

Description

Metal molecule-free antiferroelectric solid solution, preparation method and application
Technical Field
The invention belongs to the field of functional materials, and mainly relates to a metal molecule-free antiferroelectric solid solution, a preparation method and application thereof.
Background
In recent years, due to the excessive use of conventional petrochemical energy sources such as coal, petroleum and natural gas, the problems of global air pollution, energy shortage, climate warming and the like become increasingly prominent. Due to the needs of environmental governance and ecological protection, clean new energy sources such as solar energy, wind energy, geothermal energy and the like are vigorously developed and utilized to replace the consumption of part of conventional energy sources. However, new energy cannot be directly stored, and the new energy needs to be converted into electric energy to be stored, so that solid-state energy storage materials attract more and more attention. As an important functional material, an Antiferroelectric (AFE) material has the structural characteristic of antiparallel arrangement of adjacent sub-lattices, and is a promising candidate for the application of high-efficiency solid state energy storage at present. Thanks to the unique field-induced AFE to ferroelectric phase transition, antiferroelectric material phase transitions are often accompanied by abrupt changes in volume and polarization, resulting in excellent energy storage properties, including ultra-high energy density, fast charge and discharge rates, and excellent fatigue resistance. These energy storage advantages far exceed linear dielectric and ferroelectric materials.
To date, many antiferroelectric materials have been discovered and reported, but still far behind the research on ferroelectric materials, wherein the antiferroelectric materials with potential application value are far less. The conventional inorganic antiferroelectric material has high saturation polarization, small remnant polarization and suitable phase transition electric field, so that the conventional inorganic antiferroelectric material is favored. However, the application of inorganic antiferroelectric materials is often limited by the problems that high-temperature sintering is needed in the preparation process, the preparation cost is expensive, phase separation and precipitation are easily generated, and the like, and meanwhile, lead and other heavy metal elements harmful to the environment are often involved in the synthesis process, so that the development of the inorganic antiferroelectric materials is restricted. Compared with the traditional inorganic material, the molecular antiferroelectric has the characteristics of mild synthesis conditions, easy molecular cutting and structural design and environmental friendliness, and can modify the structure and composition of molecules by the methods of molecular design and crystal engineering, thereby more effectively improving the performance of the molecular antiferroelectric. In addition, molecular antiferroelectric materials are expected to be strong candidates for flexible electronic devices due to their unique advantages in biocompatibility, thin film fabrication, and the like. Therefore, the molecular antiferroelectric is a functional material with development potential, and is expected to provide new opportunities for innovation of energy storage technology and development of electrically ordered materials.
The solid solution method is mainly aimed at optimizing and modifying the physical properties of iron-based materialsOrganic oxide materials were first studied and have been used in device development. Unlike metal ions which exhibit good solid solubility, molecules of different sizes, deformations and orientations are difficult to combine in a homogeneous phase, which greatly limits the development of molecular ferrous materials. In recent years, the molecular solid solution method has been paid more attention and made a breakthrough, such as the successful preparation of (TMFM)x(TMCM)1-xCdCl3(TMFM: trimethylfluoromethylammonium; TMCM: trimethylchloromethylammonium, x is 0. ltoreq. x.ltoreq.1) and realizes a large piezoelectric property at a phase boundary close to the morphotropic phase.
In summary, the molecular antiferroelectric crystal material has good application prospects in the fields of large displacement sensors, explosive transducers, energy storage capacitors, infrared pyroelectric sensors, data communication, data storage, nonlinear switches and the like, and the application range of the material is continuously expanded along with the gradual development of the technology. The method for preparing the metal-free molecular antiferroelectric material with high performance by utilizing the molecular solid solution method has important practical value.
Disclosure of Invention
The invention aims to provide a metal molecule-free antiferroelectric solid solution, a preparation method and application thereof. The metal molecule-free antiferroelectric solid solution has good antiferroelectric performance, high saturation polarization strength and moderate coercive field, and is simple in preparation method, low in cost, mild in reaction condition and high in stability, and can be applied to an energy storage.
The invention is realized by the following technical scheme:
scheme I)
An antiferroelectric solid solution without metal molecules, which has the general formula (C)7H16N) X, wherein X ═ BrxI1-xOr BrxCl1-x(0≤x<1) The structure schematic diagram is as follows:
Figure BDA0003616596700000021
(X＝BrxI1-x，BrxCl1-x,0≤x<1)。
further, the solid solutions belong to the orthorhombic system at room temperature, wherein,
(C7H16n) I crystals in the Pbca space group with unit cell parameters of
Figure BDA0003616596700000022
Figure BDA0003616596700000031
α＝β＝γ＝90.0°，Z＝8，
Figure BDA0003616596700000032
(C7H16N)Br0.5I0.5Crystallized in a Pbca space group with unit cell parameters of
Figure BDA0003616596700000033
Figure BDA0003616596700000034
α＝β＝γ＝90.0°，Z＝8，
Figure BDA0003616596700000035
(C7H16N)Br0.8Cl0.2Crystallized in a Pbca space group with unit cell parameters of
Figure BDA0003616596700000036
Figure BDA0003616596700000037
α＝β＝γ＝90.0°，Z＝8，
Figure BDA0003616596700000038
(C7H16N)Br0.4Cl0.6Crystallized in the Pnma space group, with unit cell parameters of
Figure BDA0003616596700000039
Figure BDA00036165967000000310
α＝β＝γ＝90.0°，Z＝4，
Figure BDA00036165967000000311
(C7H16N)Br0.2Cl0.8Crystallized in the Pnma space group, with unit cell parameters of
Figure BDA00036165967000000312
Figure BDA00036165967000000313
α＝β＝γ＝90.0°，Z＝4，
Figure BDA00036165967000000314
(C7H16N) Cl crystals in the Pnma space group with unit cell parameters of
Figure BDA00036165967000000315
Figure BDA00036165967000000316
α＝β＝γ＝90.0°，Z＝4，
Figure BDA00036165967000000317
Furthermore, above the Curie temperature, the solid solution space group is P4/nmm,
(C7H16n) Curie temperature of I is 324K, above the Curie temperature, (C)7H16N) cell parameters of I
Figure BDA00036165967000000318
Figure BDA00036165967000000319
α＝β＝γ＝90.0°，Z＝2，
Figure BDA00036165967000000320
Figure BDA00036165967000000321
(C7H16N)Br0.5I0.5Has a Curie temperature of 349K and above, (C)7H16N)Br0.5I0.5Has unit cell parameters of
Figure BDA00036165967000000322
α＝β＝γ＝90.0°，Z＝2，
Figure BDA00036165967000000323
(C7H16N)Br0.8Cl0.2Has a Curie temperature of 395K, and is above the Curie temperature (C)7H16N)Br0.8Cl0.2Has a cell parameter of
Figure BDA00036165967000000324
α＝β＝γ＝90.0°，Z＝2，
Figure BDA00036165967000000325
(C7H16N) the Curie temperature of Cl is 453K, above the Curie temperature, (C)7H16N) cell parameters of Cl
Figure BDA00036165967000000326
α＝β＝γ＝90.0°，Z＝2，
Figure BDA00036165967000000327
Figure BDA00036165967000000328
In addition, (C)7H16N)Br0.4Cl0.6And (C)7H16N)Br0.2Cl0.8House ofThe interior temperatures are 409K and 443K, respectively.
Scheme two)
The preparation method of the metal molecule-free antiferroelectric solid solution comprises the following steps:
the stoichiometric ratio is x: dissolving (1-x) cyclohexylmethylamine bromide and cyclohexylmethylamine iodide in water or gamma-butyrolactone, or adding the mixture of (1-x) and (2) in stoichiometric ratio of x: dissolving (1-x) cyclohexylmethylamine bromide salt and cyclohexylmethylamine chloride salt in water or gamma-butyrolactone, heating to 80-85 deg.C, maintaining for 24-30 hr, slowly cooling at 0.5-1 deg.C per day, filtering, concentrating, and air drying to obtain colorless sheet (C)7H16N)BrxI1-xWherein 0 is less than or equal to x<1。
Further, the cyclohexylmethylamine bromide salt is prepared by the following method: adding cyclohexylmethylamine into an aqueous solution of hydrobromic acid at room temperature, wherein the molar ratio of the cyclohexylmethylamine to the hydrobromic acid is 1:1, heating to 80-85 ℃, fully stirring until the cyclohexylmethylamine and the hydrobromic acid are completely dissolved, cooling to room temperature at the speed of 0.5-1 ℃/day, and finally filtering, concentrating and naturally air-drying to obtain cyclohexylmethylamine bromide;
the cyclohexylmethylamine iodide salt is prepared by the following method: adding cyclohexylmethylamine into a hydriodic acid aqueous solution at room temperature, wherein the molar ratio of the cyclohexylmethylamine to the hydriodic acid is 1:1, heating to 80-85 ℃, fully stirring until the cyclohexylmethylamine and the hydriodic acid are completely dissolved, cooling to room temperature at the speed of 0.5-1 ℃/day, and finally filtering, concentrating and naturally air-drying to obtain cyclohexylmethylamine iodide;
the cyclohexylmethylamine chloride is prepared by the following method: adding the cyclohexylmethylamine into a hydrochloric acid aqueous solution at room temperature, wherein the molar ratio of the cyclohexylmethylamine to the hydrochloric acid is 1:1, heating to 80-85 ℃, fully stirring until the cyclohexylmethylamine and the hydrochloric acid are completely dissolved, cooling to the room temperature at the speed of 0.5-1 ℃/day, and finally filtering, concentrating and naturally air-drying to obtain the cyclohexylmethylamine chloride salt.
The hydrobromic acid aqueous solution can be 40-48% in mass percentage concentration, the hydrochloric acid aqueous solution can be 40-48% in mass percentage concentration, and the hydroiodic acid aqueous solution can be 40-48% in mass percentage concentration.
Scheme three)
Use of the metal molecule-free antiferroelectric solid solution of claim 1 in an energy storage device prepared from said metal molecule-free antiferroelectric solid solution.
Compared with the prior art, the invention has the following beneficial effects: the metal molecule-free antiferroelectric solid solution disclosed by the invention shows excellent antiferroelectric performance, particularly, the saturation polarization intensity of the cyclohexylmethylamine chloride salt reaches 11.4 mu C/cm2The Curie temperature reached 453K.
Moreover, the reaction is simple and the conditions are mild. The phase transition temperature of the material was determined by Differential Scanning Calorimetry (DSC) and the results showed: the molecular solid solution successfully realizes the wide-range adjustability of the phase transition temperature from 324K to 453K through the amount of the halogen element in the solid solution.
The Sawyer-Tower circuit tests the electric hysteresis loop of the metal molecule-free antiferroelectric solid solution, and the result shows that: the material shows better antiferroelectric performance in an antiferroelectric phase, and has higher saturation polarization strength and moderate coercive field. Especially the cyclohexylmethylamine chloride still has 11.4 mu C/cm at high temperature2And a storage efficiency of about 52%, have potential utility as storage dielectrics.
Drawings
FIG. 1 molecular antiferroelectric solid solution (C)7H16N)BrxI1-xAnd (C)7H16N)BrxCl1-x(0≤x<1) The structure is schematic.
FIG. 2 molecular antiferroelectric solid solution (C)7H16N)BrxI1-xAnd (C)7H16N)BrxCl1-x(0≤x<1) Differential scanning calorimetry test curve of (1).
FIG. 3 molecular antiferroelectric solid solution (C)7H16N)BrxI1-xAnd (C)7H16N)BrxCl1-x(0≤x<1) The hysteresis loop of (3).
Fig. 4 is a graph of the relationship between releasable energy storage density and energy loss during discharge.
Detailed Description
The invention is further described below with reference to the accompanying drawings and the detailed description.
Example 1
(C7H16N) the preparation method of I comprises the following steps: dissolving cyclohexylmethylamine iodide in water, heating to 80 deg.C, maintaining for 30 hr, slowly cooling at a rate of 1 deg.C per day, filtering, concentrating, and air drying to obtain colorless sheet (C)7H16N)I。
Example 2
(C7H16N)Br0.5I0.5The preparation method comprises the following steps: mixing a stoichiometric ratio of 0.5: dissolving 0.5 of cyclohexylmethylamine bromide and cyclohexylmethylamine iodide in gamma-butyrolactone, heating to 85 deg.C, maintaining for 24 hr, slowly cooling at 0.5 deg.C per day, filtering, concentrating, and air drying to obtain colorless tablet (C)7H16N)Br0.5I0.5。
Example 3
(C7H16N)Br0.8Cl0.2The preparation method comprises the following steps: mixing the stoichiometric ratio of 0.8: dissolving 0.2 of cyclohexylmethylamine bromide salt and cyclohexylmethylamine chloride salt in gamma-butyrolactone, heating to 80 deg.C, maintaining for 30 hr, slowly cooling at a rate of 1 deg.C per day, filtering, concentrating, and air drying to obtain colorless sheet (C)7H16N)Br0.8Cl0.2。
Example 4
(C7H16N)Br0.4Cl0.6The preparation method comprises the following steps: mixing a stoichiometric ratio of 0.4: dissolving 0.6 of cyclohexylmethylamine bromide salt and cyclohexylmethylamine chloride salt in gamma-butyrolactone, heating to 85 deg.C, maintaining for 24 hr, slowly cooling at 0.5 deg.C per day, filtering, concentrating, and air drying to obtain colorless sheet (C)7H16N)Br0.4Cl0.6。
Example 5
(C7H16N)Br0.2Cl0.8The preparation method comprises the following steps: mixing a stoichiometric ratio of 0.2: dissolving 0.8 of cyclohexylmethylamine bromide salt and cyclohexylmethylamine chloride salt in gamma-butyrolactone, heating to 82 deg.C, maintaining for 24-30 hr, slowly cooling at 0.6 deg.C per day, filtering, concentrating, and air drying to obtain colorless sheet (C)7H16N)Br0.2Cl0.8。
Example 6
(C7H16N) preparation method of Cl comprises the following steps: dissolving cyclohexylmethylamine chloride in gamma-butyrolactone, heating to 85 deg.C, maintaining for 24 hr, slowly cooling at 0.7 deg.C per day, filtering, concentrating, and air drying to obtain colorless sheet (C)7H16N)Cl。
The yield of the solid solution of the above example was more than 98%, and the single crystal diffraction test results are shown in table 1. The molecular structure of the compound is shown in figure 1.
And the solid solution (C) prepared in the above example7H16N)BrxI1-xAnd (C)7H16N)BrxCl1-x(0≤x<1) The method specifically comprises the following steps: (C)7H16N)I、(C7H16N)Br0.5I0.5、(C7H16N)Br0.8Cl0.2、(C7H16N)Br0.4Cl0.6、(C7H16N)Br0.2Cl0.8And (C)7H16N) Cl was subjected to differential scanning calorimetry to give a curve as shown in fig. 2, which shows: (C)7H16N) Curie temperature of I324K, (C)7H16N)Br0.5I0.5Has a Curie temperature of 349K and a Curie temperature of (C)7H16N)Br0.8Cl0.2Has a Curie temperature of 395K and a Curie temperature of (C)7H16N) the Curie temperature of Cl was 453K, (C)7H16N)Br0.4Cl0.6And (C)7H16N)Br0.2Cl0.8Are 409K and 443K, respectively.
Metal molecule free antiferroelectric solid solution (C)7H16N)BrxI1-xAnd (C)7H16N)BrxCl1-x(0≤x<1) Application in the field of energy storage.
The obtained metal molecule-free antiferroelectric solid solution (C) obtained in the above example7H16N)BrxI1-xAnd (C)7H16N)BrxCl1-x(0≤x<1) The method specifically comprises the following steps: (C)7H16N)I、(C7H16N)Br0.5I0.5、(C7H16N)Br0.8Cl0.2、(C7H16N)Br0.4Cl0.6、(C7H16N)Br0.2Cl0.8And (C)7H16N) Cl was subjected to hysteresis loop test as shown in fig. 3 and 4.
In the antiferroelectric phase, the testing frequency is 50Hz, and obvious antiferroelectric characteristics are displayed between the current density and the electric field, and the antiferroelectric phase is prepared from cyclohexylmethylamine chloride (C)7H16N) Cl, which exhibits a large saturation polarization and a moderate coercive field, is an example. Fitting and calculating the electric hysteresis loop to obtain the releasable energy storage density W of the samplere(J/cm3) Total energy storage density Wst(J/cm3) Energy loss Wloss(J/cm3) The energy storage efficiency eta is shown in the table 2, which shows that the metal-free molecular antiferroelectric solid solution has potential application value in the field of energy storage.
TABLE 1 temperature-changing structural parameters of the molecular antiferroelectric solid solutions prepared in accordance with the present invention
Figure BDA0003616596700000071
Figure BDA0003616596700000081
TABLE 2 preparation of (C) according to the invention7H16Performance parameters of N) Cl solid solutions
Performance parameter Wre(J/cm3) Wst(J/cm3) Wloss η
Results of the experiment 0.28 0.54 0.26 52％
The present invention is not limited to the above embodiments, and all alternatives and modifications made in accordance with the principles of the present invention are within the scope of the present invention.

Claims (6)

1. A metal molecule-free antiferroelectric solid solution characterized by: the general formula of the solid solution is (C)7H16N) X, where X ═ BrxI1-xOr BrxCl1-xX is more than or equal to 0 and less than 1, and the structural schematic diagram is as follows:
Figure FDA0003616596690000011
(X＝BrxI1-xor BrxCl1-x,0≤x＜1)。
2. A metal molecule-free antiferroelectric solid solution according to claim 1, characterized in that: the solid solutions belong to the orthorhombic system at room temperature, wherein,
(C7H16n) I crystals in the Pbca space group with unit cell parameters of
Figure FDA0003616596690000012
Figure FDA0003616596690000013
α＝β＝γ＝90.0°，Z＝8，
Figure FDA0003616596690000014
(C7H16N)Br0.5I0.5Crystallized in Pbca space group with unit cell parameters of
Figure FDA0003616596690000015
Figure FDA0003616596690000016
α＝β＝γ＝90.0°，Z＝8，
Figure FDA0003616596690000017
(C7H16N)Br0.8Cl0.2Crystallized in a Pbca space group with unit cell parameters of
Figure FDA0003616596690000018
Figure FDA0003616596690000019
α＝β＝γ＝90.0°，Z＝8，
Figure FDA00036165966900000110
(C7H16N)Br0.4Cl0.6Crystallized in the Pnma space group, with unit cell parameters of
Figure FDA00036165966900000111
Figure FDA00036165966900000112
α＝β＝γ＝90.0°，Z＝4，
Figure FDA00036165966900000113
(C7H16N)Br0.2Cl0.8Crystallized in the Pnma space group, with unit cell parameters of
Figure FDA00036165966900000114
Figure FDA00036165966900000115
α＝β＝γ＝90.0°，Z＝4，
Figure FDA00036165966900000116
(C7H16N) Cl in Pnma space group with unit cell parameter of
Figure FDA00036165966900000117
Figure FDA00036165966900000118
α＝β＝γ＝90.0°，Z＝4，
Figure FDA00036165966900000119
3. The metal molecule-free antiferroelectric solid solution according to claim 1, wherein: above the Curie temperature, the space groups of the solid solution are all P4/nmm,
(C7H16n) Curie temperature of I is 324K, above the Curie temperature, (C)7H16N) cell parameters of I
Figure FDA00036165966900000120
Figure FDA00036165966900000121
α＝β＝γ＝90.0°，Z＝2，
Figure FDA00036165966900000122
Figure FDA00036165966900000123
(C7H16N)Br0.5I0.5Has a Curie temperature of 349K and above, (C)7H16N)Br0.5I0.5Has unit cell parameters of
Figure FDA0003616596690000021
α＝β＝γ＝90.0°，Z＝2，
Figure FDA0003616596690000022
(C7H16N)Br0.8Cl0.2Has a Curie temperature of 395K and above (C)7H16N)Br0.8Cl0.2Has a cell parameter of
Figure FDA0003616596690000023
α＝β＝γ＝90.0°，Z＝2，
Figure FDA0003616596690000024
(C7H16N) the Curie temperature of Cl is 453K, above the Curie temperature, (C)7H16N) cell parameters of Cl
Figure FDA0003616596690000025
α＝β＝γ＝90.0°，Z＝2，
Figure FDA0003616596690000026
Figure FDA0003616596690000027
4. A method for producing a metal molecule-free antiferroelectric solid solution according to claim 1, characterized in that:
the stoichiometric ratio is x: dissolving (1-x) cyclohexylmethylamine bromide and cyclohexylmethylamine iodide in water or gamma-butyrolactone, or adding the mixture of (1-x) and (2) in stoichiometric ratio of x: dissolving (1-x) cyclohexylmethylamine bromide salt and cyclohexylmethylamine chloride salt in water or gamma-butyrolactone, heating to 80-85 deg.C, maintaining for 24-30 hr, slowly cooling at 0.5-1 deg.C per day, filtering, concentrating, and air drying to obtain colorless sheet (C)7H16N)BrxI1-xWherein x is more than or equal to 0 and less than 1.
5. The method for producing a metal molecule-free antiferroelectric solid solution according to claim 4, wherein: the cyclohexylmethylamine bromide salt is prepared by the following method: adding cyclohexylmethylamine into an aqueous solution of hydrobromic acid at room temperature, wherein the molar ratio of the cyclohexylmethylamine to the hydrobromic acid is 1:1, heating to 80-85 ℃, fully stirring until the cyclohexylmethylamine and the hydrobromic acid are completely dissolved, cooling to room temperature at the speed of 0.5-1 ℃/day, and finally filtering, concentrating and naturally air-drying to obtain cyclohexylmethylamine bromide;
the cyclohexylmethylamine iodide salt is prepared by the following method: adding cyclohexylmethylamine into a hydriodic acid aqueous solution at room temperature, wherein the molar ratio of the cyclohexylmethylamine to the hydriodic acid is 1:1, heating to 80-85 ℃, fully stirring until the cyclohexylmethylamine and the hydriodic acid are completely dissolved, cooling to room temperature at the speed of 0.5-1 ℃/day, and finally filtering, concentrating and naturally air-drying to obtain cyclohexylmethylamine iodide;
the cyclohexylmethylamine chloride is prepared by the following method: adding the cyclohexylmethylamine into a hydrochloric acid aqueous solution at room temperature, wherein the molar ratio of the cyclohexylmethylamine to the hydrochloric acid is 1:1, heating to 80-85 ℃, fully stirring until the cyclohexylmethylamine and the hydrochloric acid are completely dissolved, cooling to the room temperature at the speed of 0.5-1 ℃/day, and finally filtering, concentrating and naturally air-drying to obtain the cyclohexylmethylamine chloride salt.
6. Use of the metal molecule-free antiferroelectric solid solution of claim 1 in an energy storage device, wherein: the energy storage is prepared from the metal molecule-free antiferroelectric solid solution.
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