阅读说明：本技术 一种高初始磁导率有机无机杂化FeMnZn单晶铁氧体及其制备方法 (Organic-inorganic hybrid FeMnZn single-crystal ferrite with high initial permeability and preparation method thereof ) 是由 吴斌 张朋越 金奕汉 燕杰 赵武奇 赵黎明 楼超艳 李巍霞 于 2021-06-10 设计创作，主要内容包括：本发明公开了一种高初始磁导率有机无机杂化FeMnZn单晶铁氧体及其制备方法。本发明利用溶剂热方法合成具有层状结构的高磁性无机有机杂化单晶铁氧体,以1,3,5-三(4-羧基苯基)苯为有机配体,Mn(NO-(3))-(3)·4H-(2)O、Zn(NO-(3))-(2)、Mn(NO-(3))-(3)·4H-(2)O、FeCl-(3)·6H-(2)O、FeCl-(2)·4H-(2)O中金属阳离子为配位中心,通过控制反应温度及反应物配比,获得了具有0.5mm大小的单晶材料,该材料具有较高的初始磁导率μ-(i),高达1873。(The invention discloses an organic-inorganic hybrid FeMnZn single-crystal ferrite with high initial permeability and a preparation method thereof. The invention utilizes a solvothermal method to synthesize high-magnetism inorganic-organic hybrid single crystal ferrite with a laminated structure, takes 1,3, 5-tri (4-carboxyphenyl) benzene as an organic ligand, and Mn (NO) 3 ) 3 ·4H 2 O、Zn(NO 3 ) 2 、Mn(NO 3 ) 3 ·4H 2 O、FeCl 3 ·6H 2 O、FeCl 2 ·4H 2 Metal cation in O is used as coordination center, and by controlling reaction temperature and reactant ratio, single crystal material with 0.5mm size is obtained and has high initial magnetic permeability mu i Up to 1873.)

1. An organic-inorganic hybrid FeMnZn ferrite with high initial permeability is characterized in that the material belongs to monoclinic system, P2₁A/n space group having unit cell parameters ofα＝90°，β＝98.630°，γ＝90°。

2. A preparation method of organic-inorganic hybrid FeMnZn ferrite with high initial permeability is characterized in that the preparation method can be used for preparing the organic-inorganic hybrid FeMnZn ferrite as claimed in claim 1, and comprises the following steps:

(1) adding 0.0025-0.05 mmol of H₃BTB and 0.02-0.1 mmol Mn (NO)₃)₃·4H₂Dissolving O in 5.0mL of DMAC, and stirring for 30-60 min at 50-80 ℃;

(2) continuously adding 0.001-0.02 mmol Zn (NO)₃)₂、0.01～0.1mmol FeCl₃·6H₂O and 0.01-0.1 mmol FeCl₂·4H₂O, stirring for 30-60 min, filtering out a transparent solution, and transferring the transparent solution into a high-pressure reaction kettle;

(3) and heating the reaction kettle to 110-120 ℃ at the speed of 5-30 ℃/min, keeping the temperature for 36-48 hours, and then cooling to room temperature at the temperature of 5 ℃ per minute to obtain crystals.

Technical Field

The invention particularly relates to an organic-inorganic hybrid FeMnZn single-crystal ferrite with high initial permeability and a preparation method thereof.

Background

The manganese-zinc ferrite material is widely applied to electronic equipment components of communication, electronics, televisions, various digital products and the like at present, and is a soft magnetic ferrite material with large mass production quantity. The manganese-zinc ferrite with high magnetic conductivity is the largest classification of manganese-zinc ferrite, and the most important application of the manganese-zinc ferrite is to prepare main transformers of various high-frequency switching power supplies. The main development trend of switching power supplies is miniaturization and low loss, which requires that the manganese-zinc ferrite as the inner magnetic core of the main transformer should have high saturation magnetic flux density and low power consumption.

In recent years, digital cameras, digital video cameras, mobile communication devices, and the like have become popular in daily life, and these devices are generally operated at 45 ℃ or lower, and therefore, the optimum operating temperature of various internal electronic components is required to be 45 ℃ or lower, and switching power supplies are no exception. This requires that the manganese-zinc ferrite material in the main transformer of the switching power supply have a minimum power consumption below 45 c. Therefore, the development of the manganese-zinc ferrite with the lowest power consumption and high saturation magnetic flux density below 45 ℃ has wide market application prospect.

At present, the temperature range of the lowest power consumption of most of power manganese zinc ferrite is generally within 60-100 ℃, and the power consumption value under the test conditions of 100kHz and 200mT is generally more than 300kW/m³In order to adapt to the development of digital equipment, the power consumption value of the manganese-zinc ferrite is required to be lower than 245kW/m³To be made ofTo achieve the purpose, some researchers usually add nanoscale auxiliary components into the manganese-zinc ferrite, change the preparation process and the like, but all have the problems of high raw material preparation cost, difficult control of the technology and the like.

Therefore, aiming at the products in the field of digital equipment, the product which is not required to be added with nano assistance, has the lowest power consumption at about 45 ℃ and the power consumption value lower than 245kW/m³And power manganese zinc ferrite having a high saturation magnetic flux density has been the focus of research.

Disclosure of Invention

Aiming at the situation, in order to overcome the defects of the prior art, the invention provides an organic-inorganic hybrid FeMnZn single-crystal ferrite with high initial permeability and a preparation method thereof.

In order to achieve the purpose, the invention provides the following technical scheme:

an organic-inorganic hybrid FeMnZn ferrite with high initial magnetic conductivity, belonging to monoclinic system, P2₁A/n space group having unit cell parameters ofα＝90°，β＝98.630°，γ＝90°。

A preparation method of an organic-inorganic hybrid FeMnZn ferrite with high initial permeability can be used for preparing the organic-inorganic hybrid FeMnZn ferrite, and comprises the following steps:

(1) adding 0.0025-0.05 mmol of H₃BTB and 0.02-0.1 mmol Mn (NO)₃)₃·4H₂Dissolving O in 5.0mL of DMAC, and stirring for 30-60 min at 50-80 ℃;

(2) continuously adding 0.001-0.02 mmol Zn (NO)₃)₂、0.01～0.1mmol FeCl₃·6H₂O and 0.01-0.1 mmol FeCl₂·4H₂O, stirring for 30-60 min, filtering out a transparent solution,transferring the mixture into a high-pressure reaction kettle;

(3) and heating the reaction kettle to 110-120 ℃ at the speed of 5-30 ℃/min, keeping the temperature for 36-48 hours, and then cooling to room temperature at the temperature of 5 ℃ per minute to obtain crystals.

The invention has the beneficial effects that:

the invention utilizes a solvothermal method to synthesize high-magnetism inorganic-organic hybrid single crystal ferrite with a laminated structure, takes 1,3, 5-tri (4-carboxyphenyl) benzene as an organic ligand, and Mn (NO)₃)₃·4H₂O、Zn(NO₃)₂、Mn(NO₃)₃·4H₂O、FeCl₃·6H₂O、FeCl₂·4H₂Metal cation in O is used as coordination center, and single crystal material Zn with the size of 0.5mm is obtained by controlling different reaction temperatures and reactant ratios_xFe²⁺ _yMn_zFe₂O₄(x + y + z is 1), the photoelectric property (10) is initially explored^-7) Has photocurrent response and electrical bistable property (10)²) Meanwhile, the material is found to have higher initial permeability mu_iUp to 1873.

Drawings

FIG. 1 is a view of a structure of a single crystal.

FIG. 2 is a single crystal pxrd pattern.

Detailed Description

In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be described and illustrated below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments provided in the present application without any inventive step are within the scope of protection of the present application.

Reference in the specification to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the specification. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of ordinary skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments without conflict.

Unless defined otherwise, technical or scientific terms referred to herein shall have the ordinary meaning as understood by those of ordinary skill in the art to which this application belongs. Reference to "a," "an," "the," and similar words throughout this application are not to be construed as limiting in number, and may refer to the singular or the plural. The present application is directed to the use of the terms "including," "comprising," "having," and any variations thereof, which are intended to cover non-exclusive inclusions; reference to "connected," "coupled," and the like in this application is not intended to be limited to physical or mechanical connections, but may include electrical connections, whether direct or indirect. Reference herein to "a plurality" means greater than or equal to two. "and/or" describes an association relationship of associated objects, meaning that three relationships may exist, for example, "A and/or B" may mean: a exists alone, A and B exist simultaneously, and B exists alone. Reference herein to the terms "first," "second," "third," and the like, are merely to distinguish similar objects and do not denote a particular ordering for the objects.

(one) Crystal preparation

A preparation method of high-permeability organic-inorganic hybrid FeMnZn single-crystal ferrite comprises the following steps:

(1) h is to be₃BTB (0.0025 to 0.05mmol, 0.001 to 0.02g) and Mn (NO)₃)₃·4H₂Dissolving O (0.02-0.1 mmol, 0.005-0.025 g) in 5.0mL of DMAC, and stirring at 50-80 ℃ for 30-60 min;

(2) continued addition of Zn (NO)₃)₂(0.001～0.02mmol，0.001～0.04g)、FeCl₃·6H₂O (0.01 to 0.1mmol, 0.001 to 0.05g) and FeCl₂·4H₂O (0.01-0.1 mmol, 0.0015-0.06 g), stirring for 30-60 min, filtering out a transparent solution, and transferring into a polytetrafluoroethylene high-pressure reaction kettle;

(3) and heating the reaction kettle to 110-120 ℃ at the speed of 5-30 ℃/min, keeping the temperature for 36-48 hours, and then cooling to room temperature by a program of 5 ℃ per minute to obtain brown crystals. Washed with DMAC and dried under vacuum for 24 hours (with Mn (NO)₃)₃·4H₂The calculated yield of O is 30-41.4%).

(II) measurement

(1) Single crystal Apex Duo CCD X-ray diffractometers (Mo target, K alpha radiation, 40kV, 25Ma,) The single crystal structure is tested. Both the initial structure and the refinement of the crystals were done using the SHELX-97 structure resolution procedure.

TABLE 1 cell parameters after refinement

Different from the traditional spinel cubic crystal system, the crystal prepared by the invention belongs to a monoclinic crystal system through single crystal XRD test, P2₁A/n space group having a cell parameter ofα＝90°， β＝98.630°，γ＝90°。

In FIG. 1, gray represents a carbon atom, red represents an oxygen atom, black represents a hydrogen atom, green represents an iron atom, and purple representsA manganese atom. As seen from the single crystal structure diagram of FIG. 1, the coordination numbers of the metal cations are all 6, and an octahedral structure with distortion is formed. Three metals (zinc, iron and manganese) form a trinuclear metal oxygen cluster in a mode of sharing a vertex, and the trinuclear metal oxygen cluster is taken as a node and passes through a bridge chain organic ligand H₃BTB expands in three dimensions, forming a single crystal material with a three-dimensional structure. The single crystal material prepared by the invention is a new substance, the conventional preparation method in the prior art can only produce polycrystal FeMnZn ferrite, and the single crystal FeMnZn material and the preparation method thereof are not reported. The single crystal ferrite prepared by the invention has the characteristics of single crystal structure (phase purity), no crystal boundary, no impurities and point defects and the like, so that the magnetic property, particularly the magnetic conductivity is higher.

(2) Powder XRD of the compounds was carried out on a Rigaku-Miniflex II powder diffractometer using a Cu Ka targetAnd (6) scanning.

As can be seen from fig. 2, the experimentally determined powder XRD pattern is consistent with the simulated powder XRD pattern, which indicates that the crystalline material prepared by the present invention has a higher purity.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

Example 1

Different reaction temperature tests: (100 ℃ C.)

Controlling reactant ratio BTB^2-:Mn²⁺:Fe³⁺:Fe²⁺＝1:1:2:1

(1) 0.0025mmol of H₃BTB (1,3, 5-tris (4-carboxyphenyl) benzene) and 0.02mmol Mn (NO)₃)₃·4H₂Dissolving O in 5mL of DMAC (dimethylacetamide), and stirring at 80 ℃ for 30 min;

(2) further addition of 0.001mmol Zn (NO)₃)₂、0.001mmol FeCl₃·6H₂O and 0.01mmol FeCl₂·4H₂O, stirring for 30min, filtering out a transparent solution, and transferring the transparent solution into a polytetrafluoroethylene high-pressure reaction kettle;

(3) heating the reaction kettle to 100 ℃ at the speed of 18 ℃/min, keeping the temperature for 48 hours, reducing the temperature to 30 ℃ at the speed of 5 ℃ per minute, and after the reaction is finished, clarifying the solution in the reaction kettle without finding the existence of the product.

Example 2

Different reaction temperature tests: (120 ℃ C.)

Controlling reactant ratio BTB^2-:Mn²⁺:Fe³⁺:Fe²⁺＝1:1:2:1

(1) 0.02mmol of H₃BTB and 0.05mmol Mn (NO)₃)₃·4H₂Dissolving O in 10mL of DMAC, and stirring for 60min at 50 ℃;

(2) further addition of 0.02mmol of Zn (NO)₃)₂、0.1mmol FeCl₃·6H₂O and 0.1mmol FeCl₂·4H₂O, stirring for 60min, filtering out a transparent solution, and transferring the transparent solution into a polytetrafluoroethylene high-pressure reaction kettle;

(3) the reaction kettle is heated to 120 ℃ at the speed of 10 ℃/min, the temperature is kept for 38 hours, the temperature is reduced to 30 ℃ at the speed of 5 ℃ per minute, brown crystals appear in the reaction kettle, but more brownish red precipitate substances are generated at the same time.

Example 3

Different reaction ratios are tested: BTB^2-:Mn²⁺:Fe³⁺:Fe²⁺＝1:1:1:1

(1) 0.03mmol of H₃BTB and 0.05mmol Mn (NO)₃)₃·4H₂Dissolving O in 8mL of DMAC, and stirring for 30min at 80 ℃;

(2) further addition of 0.01mmol of Zn (NO)₃)₂、0.08mmol FeCl₃·6H₂O and 0.08mmol FeCl₂·4H₂O, stirring for 30min, filtering out a transparent solution, and transferring the transparent solution into a polytetrafluoroethylene high-pressure reaction kettle;

(3) the reaction kettle is heated to 115 ℃ at the speed of 10 ℃/min, the temperature is kept for 48 hours, the temperature is reduced to 30 ℃ by a program of 5 ℃ per minute, and brown powder appears in the reaction kettle.

Example 4

Different reaction ratios are tested: BTB^2-:Mn²⁺:Fe³⁺:Fe²⁺＝1:1:2:2

(1) 0.04mmol of H₃BTB and 0.08mmol Mn (NO)₃)₃·4H₂Dissolving O in 8mL of DMAC (dimethylacetamide), and stirring at 80 ℃ for 30 min;

(2) further addition of 0.015mmol of Zn (NO)₃)₂、0.015mmol FeCl₃·6H₂O and 0.015mmol FeCl₂·4H₂O, stirring for 30min, filtering out a transparent solution, and transferring the transparent solution into a polytetrafluoroethylene high-pressure reaction kettle;

(3) the reaction kettle is heated to 120 ℃ at the speed of 30 ℃/min, the temperature is kept for 48 hours, the temperature is reduced to 30 ℃ by a program of 5 ℃ per minute, and brown powder appears in the reaction kettle.

Example 5

Different reaction ratios are tested: BTB^2-:Mn²⁺:Fe³⁺:Fe²⁺＝1:1:3:2

(1) 0.035mmol of H₃BTB and 0.035mmol Mn (NO)₃)₃·4H₂Dissolving O in 10mL of DMAC, and stirring for 30min at 70 ℃;

(2) 0.018mmol Zn (NO) was added continuously₃)₂、0.018mmol FeCl₃·6H₂O and 0.1mmol FeCl₂·4H₂O, stirring for 30min, filtering out a transparent solution, and transferring the transparent solution into a polytetrafluoroethylene high-pressure reaction kettle;

(3) the reaction kettle is heated to 110 ℃ at the speed of 20 ℃/min, the temperature is kept for 48 hours, the temperature is reduced to 30 ℃ by a program of 5 ℃ per minute, and reddish brown powder appears in the reaction kettle.

The experimental result shows that when the reaction temperature is 120 ℃, the reactant proportion is BTB^2-:Mn²⁺:Fe³⁺:Fe²⁺1:1:2:1 favors the formation of crystalline material.

And (3) testing:

(1) after the sample is wound around the enameled wire, an inductance L and a quality factor Q of the sample at different temperatures and different frequencies are measured by using a JS4225LCR automatic measuring instrument, and corresponding initial magnetic permeability and specific loss factors are calculated. The material has high initial magnetic permeability mu_iUp to 1873.

(2)

1. Test environmental conditions

Temperature: (25-100) DEG C;

relative humidity: (45-75)%;

air pressure: (86 to 106) kPa.

2. Conditions of test

The test conditions for the materials or cores should comply with the relevant regulations in table 5.

TABLE 5 test conditions

3. Test sample

And measuring the electromagnetic property of the material by using an annular sample. Size:or

Material testing coil: the measuring coil is uniformly wound along the magnetic circuit, and the wire diameter is selectedHigh temperature resistant wire with 20T turns_S. Magnetic core test coil: wire diameter selectionHigh temperature resistant wire with 8T turns_S。

4. Magnetic neutral state

The electromagnetic property of the material is generally treated by magnetic neutral state treatment before the test.

The method comprises the following steps: the 50Hz sine wave is applied to two ends of the coil, the amplitude is increased from zero to a maximum value and then is monotonously adjusted to zero from the maximum value, and the time of the latter process is not less than 5 s. The maximum value of the current is selected at the position of the magnetization curve HC corresponding to 5-10 times of the magnetic field, and the sample is placed for 24 hours after being in a magnetic neutral state to be measured.

In addition, if the same sample is subjected to two or more consecutive measurements, the measured value can be regarded as unchanged, and the magnetic neutral state treatment can be omitted.

The magnetic core test, unless otherwise indicated, may eliminate the need for a magnetically neutral conditioning treatment.

The time interval between two consecutive tests of either the material sample or the magnetic core sample must not be less than 4 hours.

TABLE 2 Single Crystal Zn_xFe²⁺ _yMn_zFe₂O₄Power consumption Pcv test results

Remarking: frequency-f/kHz; magnetic flux density-B/mT; power consumption-Pcv/(mW/cm)³)。

TABLE 3 Single Crystal Zn_xFey²⁺ _yMn_zFe₂O₄Saturation magnetic flux density Bs test results

Remarking: saturation magnetic flux density-Bs/mT; magnetic field intensity-H/(A/m).

TABLE 4 Single Crystal Zn_xFey²⁺ _yMn_zFe₂O₄Initial permeability mu_iTest results

Remarking: frequency-f/kHz; magnetic flux density-B/mT; initial permeability mu_i。

It should be understood by those skilled in the art that various features of the above-described embodiments can be combined in any combination, and for the sake of brevity, all possible combinations of features in the above-described embodiments are not described in detail, but rather, all combinations of features which are not inconsistent with each other should be construed as being within the scope of the present disclosure.

The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application.