CN112373014A - Method for preparing magnetoelectric composite material based on magnetic field assisted 3D printing technology - Google Patents

Method for preparing magnetoelectric composite material based on magnetic field assisted 3D printing technology Download PDF

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CN112373014A
CN112373014A CN202011070742.3A CN202011070742A CN112373014A CN 112373014 A CN112373014 A CN 112373014A CN 202011070742 A CN202011070742 A CN 202011070742A CN 112373014 A CN112373014 A CN 112373014A
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printing
magnetic field
composite material
magnetoelectric
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CN112373014B (en
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魏相霞
刘萌萌
万紫萌
李澳
杜德琪
王玉振
张继光
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Qingdao University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials

Abstract

The invention belongs to the technical field of piezoelectric material preparation and processing, and particularly relates to a method for preparing a magnetoelectric composite material with magnetoelectric coupling performance based on a magnetic field assisted 3D printing technology, and further discloses the prepared magnetoelectric composite material. The preparation method of the magnetoelectric composite material comprises the steps of depositing a printing liquid of a piezoelectric polymer and magnetic nanoparticles layer by layer based on a 3D printing technology to construct a three-dimensional structure, applying a magnetic field for orientation intervention while 3D printing to ensure that the magnetic nanoparticles in the printing liquid can be preferentially oriented and regularly arranged along the direction of the magnetic field to improve the magnetostriction performance of the material, completing the preparation of the material and the orientation of the magnetic field simultaneously, and obtaining the piezoelectric composite material with magnetoelectric coupling performance through one-step processing; the working efficiency is effectively improved, and the device has the advantages of low energy consumption, low cost and wide application range.

Description

Method for preparing magnetoelectric composite material based on magnetic field assisted 3D printing technology
Technical Field
The invention belongs to the technical field of piezoelectric material preparation and processing, and particularly relates to a method for preparing a magnetoelectric composite material with magnetoelectric coupling performance based on a magnetic field assisted 3D printing technology, and further discloses the prepared magnetoelectric composite material.
Background
The magnetoelectric effect is a phenomenon that a material is electrically polarized or magnetized under the action of a magnetic field or an electric field through the coupling action between a ferroelectric phase and a ferromagnetic phase, and is a hot spot of current research and attention. The magnetoelectric material prepared by the magnetoelectric effect can realize the conversion between a magnetic field and an electric field, and is an important functional material, for example, the magnetoelectric composite material which has good flexibility and is easy to process can be prepared by combining an organic material and an inorganic material, and the material is mostly applied to manufacturing micro devices. Compared with the traditional dielectric material or magnetic material, the magnetoelectric composite material has the advantages of high energy conversion efficiency, accurate measurement, low manufacturing cost, high integration level and the like, and the high-performance electromagnetic functional device has wide application prospect and is widely applied to the fields of information storage, magnetic field detection, integrated circuits, magnetoelectric energy conversion and the like.
At present, the processing and preparation of the magnetoelectric composite material generally need to be obtained by compounding a ferroelectric material with piezoelectric property and a magnetostrictive material, and an adjustable surface potential is obtained by utilizing the magnetoelectric coupling property under the action of an external magnetic field. Furthermore, a casting or spin coating forming method can be adopted to prepare the magnetoelectric film, and the film generates surface potential through electric polarization, so that the film can obtain magnetoelectric coupling performance. However, the magnetoelectric composite material of the structure prepared by the above conventional process requires cutting and a large polarization voltage, and thus the conventional method for preparing the magnetoelectric material still needs to be improved, and thus is not widely used. Therefore, the method for preparing the piezoelectric material with the magnetoelectric effect with high efficiency and low energy consumption has positive significance.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a method for preparing a magnetoelectric composite material with magnetoelectric coupling performance based on a magnetic field assisted 3D printing technology, wherein in the printing process, magnetic particles in the material are moved by applying an electromagnetic driving force to obtain the composite material with magnetoelectric effect, and the method has the advantages of high efficiency, low energy consumption, low cost and wide application range;
the second technical problem to be solved by the present invention is to provide the magnetoelectric composite material with magnetoelectric coupling performance prepared by the above method.
In order to solve the technical problems, the method for preparing the magnetoelectric composite material based on the magnetic field assisted 3D printing technology comprises the following steps:
(1) dispersing magnetic nanoparticles in an organic solvent, adding a piezoelectric polymer material, and fully mixing to obtain a polymer printing liquid for later use;
(2) creating a three-dimensional structure digital model, carrying out slicing processing, and setting a proper printing path and a proper printing program;
(3) and (2) transferring the polymer printing liquid prepared in the step (1) into a needle cylinder, carrying out continuous layer-by-layer deposition under the control of a design program, and applying a magnetic field while carrying out 3D printing to orient the magnetic particles along the direction of the magnetic field, so as to construct and obtain the magnetoelectric composite material with the magnetoelectric coupling performance.
Specifically, in the step (1), the piezoelectric polymer material includes at least one of polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (P (VDF-HFP)), or polyvinylidene fluoride-trifluoroethylene copolymer (P (VDF-TrFE)).
Specifically, in the step (1), the magnetic nanoparticles comprise Terfenol-D, Fe3O4、CuFe2O4、NiFe2O4、CoFe2O4At least one of (1).
Specifically, the average diameter of the magnetic nanoparticles is 10-100 nm.
Specifically, in the step (1), the organic solvent includes at least one of N, N-dimethylformamide, N-methylpyrrolidone, or dimethylsulfoxide.
Specifically, the polymer printing liquid is obtained by mixing for 2-4h at 30-60 ℃.
Specifically, in the step (1), the mass content of the piezoelectric polymer material is 15-25 wt% based on the total amount of the polymer printing liquid.
Specifically, in the step (1), the mass ratio of the magnetic nanoparticles to the piezoelectric polymer material is 1: 5-20.
Specifically, in the step (2), the parameters for controlling the slicing processing step are as follows: the moving speed is 10-50mm/s, and the slice thickness is 0.01 mm.
Specifically, in the step (3), in the 3D printing step, the distance between the printing needle head and the collecting bottom plate is controlled to be 1-5mm, and the diameter of the printing needle head is controlled to be 40-400 μm.
Specifically, in the step (3), the magnetic field includes a permanent magnet or an electromagnet, and the magnetic field strength is controlled to be 100Gs to 8000 Gs. Preferably, the magnetic field is a magnetic pole arranged on two sides of the printing platform for providing a magnetic field required by the magnetic material, and the magnetic pole is more preferably a neodymium iron boron permanent magnet capable of generating 200-.
The invention also discloses the magnetoelectric composite material prepared by the method.
The preparation method of the magnetoelectric composite material comprises the steps of depositing a printing liquid of a piezoelectric polymer and magnetic nanoparticles layer by layer based on a 3D printing technology to construct a three-dimensional structure, applying a magnetic field for orientation intervention while 3D printing to ensure that the magnetic nanoparticles in the printing liquid can be preferentially oriented and regularly arranged along the direction of the magnetic field to improve the magnetostriction performance of the material, completing the preparation of the material and the orientation of the magnetic field simultaneously, and obtaining the piezoelectric composite material with magnetoelectric coupling performance through one-step processing; the working efficiency is effectively improved, and the device has the advantages of low energy consumption, low cost and wide application range.
The magnetoelectric composite material takes polymer polyvinylidene fluoride (PVDF) or copolymer thereof with good flexibility and piezoelectricity as a matrix material, additional stress is induced at an interface by adding a magnetic nanoparticle material and introducing an external magnetic field for orientation in the process of forming the composite material, and the crystallization behavior of the PVDF is regulated and controlled through the interface stress coupling effect, so that the piezoelectricity of the PVDF is improved, and the piezoelectric material with magnetoelectric coupling performance is obtained.
Drawings
In order that the present disclosure may be more readily and clearly understood, the following detailed description of the present disclosure is provided in connection with specific embodiments thereof and the accompanying drawings, in which,
FIG. 1 is a schematic diagram of the operation of the 3D printing platform of the present invention;
fig. 2 is a hysteresis (M-H) curve of a magnetoelectric composite material prepared based on a magnetic field-assisted 3D printing method in example 7 and based on a conventional spin coating method in comparative example 1;
the reference numbers in the figures denote: 1-air pressure drive pump, 2-needle cylinder material printing device, 3-magnetic pole, 4-spray head, 5-printing model, 6-material receiving plate and 7-printing platform.
Detailed Description
In the following embodiment of the present invention, as shown in the working schematic diagram of the 3D printing platform shown in fig. 1, the prepared polymer printing solution is placed in the syringe material printing device 2, and layer-by-layer printing is performed according to a preset printing program under the control of the air pressure-driven pump 1. The printing platform 7 is provided with a material receiving plate 6 and selected magnetic poles 3 which are horizontally arranged on two sides of the printing platform, and the arrangement distance is not required. In the printing process, polymer printing liquid is extruded by the nozzle 4 and is stacked on the material receiving plate 6 layer by layer to form a printing model 5 in a required preset mode, and magnetic nanoparticles in the polymer printing liquid are oriented in the magnetic field direction under the influence of the magnetic poles 3 to construct and obtain the magnetoelectric composite material with the magnetoelectric coupling performance.
Example 1
The method for preparing the magnetoelectric composite material based on the magnetic field assisted 3D printing technology comprises the following steps:
(1) taking magnetic nano particles Fe3O4Dispersing in an organic solvent N, N-dimethylformamide, and fully dispersing under the assistance of ultrasound; then, adding polyvinylidene fluoride, and mixing for 2 hours at 30 ℃ to obtain the required polymer printing liquid;
wherein the mass ratio of the magnetic particles to the piezoelectric polymer is 1: 20;
the mass content of the polyvinylidene fluoride is 15 wt% based on the total amount of the printing liquid;
(2) according to the 3D printed structure model, a three-dimensional structure digital model is created and is sliced, and a printing path is set; controlling the moving speed to be 10mm/s and the slice thickness to be 0.01 mm;
(3) transferring the polymer printing liquid prepared in the step (1) into a syringe material printing device 2, and performing layer-by-layer deposition printing under the control of a design program, wherein the distance between a printing needle head and a collecting bottom plate is controlled to be 1mm, and the diameter of the printing needle head is controlled to be 40 mu m; and applying neodymium magnet permanent magnetic fields on two sides of the printing platform during printing, wherein the magnetic field intensity is 200Gs, and the magnetic particles in the printing liquid can be oriented along the direction of the magnetic field due to the existence of the applied magnetic field so as to construct the piezoelectric composite material with the magnetoelectric coupling performance.
Example 2
The method for preparing the magnetoelectric composite material based on the magnetic field assisted 3D printing technology comprises the following steps:
(1) taking magnetic nano-particles NiFe2O4Dispersing in an organic solvent dimethyl sulfoxide, and fully dispersing under the assistance of ultrasound; then adding polyvinylidene fluoride-trifluoroethylene copolymer, and mixing for 4 hours at 50 ℃ to obtain the required polymer printing liquid;
wherein the mass ratio of the magnetic particles to the piezoelectric polymer is 1: 10;
based on the total amount of the printing liquid, the mass content of the polyvinylidene fluoride-trifluoroethylene copolymer is 14 wt%;
(2) according to the 3D printed structure model, a three-dimensional structure digital model is created and is sliced, and a printing path is set; controlling the moving speed to be 30mm/s and the slice thickness to be 0.01 mm;
(3) transferring the polymer printing liquid prepared in the step (1) into a syringe material printing device 2, and performing layer-by-layer deposition printing under the control of a design program, wherein the distance between a printing needle head and a collecting bottom plate is controlled to be 3mm, and the diameter of the printing needle head is controlled to be 150 micrometers; and applying neodymium magnet permanent magnetic fields on two sides of the printing platform during printing, wherein the magnetic field intensity is 1500Gs, and due to the existence of the applied magnetic fields, magnetic particles in the printing liquid can be oriented along the direction of the magnetic fields so as to construct and obtain the piezoelectric composite material with the magnetoelectric coupling performance.
Example 3
The method for preparing the magnetoelectric composite material based on the magnetic field assisted 3D printing technology comprises the following steps:
(1) taking magnetic nano-particles CoFe2O4Dispersing in an organic solvent N, N-dimethylformamide, and fully dispersing under the assistance of ultrasound; then adding polyvinylidene fluoride-trifluoroethylene copolymer, and mixing for 4 hours at 50 ℃ to obtain the required polymer printing liquid;
wherein the mass ratio of the magnetic particles to the piezoelectric polymer is 1: 5;
based on the total amount of the printing liquid, the mass content of the polyvinylidene fluoride-trifluoroethylene copolymer is 16 wt%;
(2) according to the 3D printed structure model, a three-dimensional structure digital model is created and is sliced, and a printing path is set; controlling the moving speed to be 40mm/s and the slice thickness to be 0.01 mm;
(3) transferring the polymer printing liquid prepared in the step (1) into a syringe material printing device 2, and performing layer-by-layer deposition printing under the control of a design program, wherein the distance between a printing needle head and a collecting bottom plate is controlled to be 4mm, and the diameter of the printing needle head is controlled to be 200 mu m; and applying neodymium magnet permanent magnetic fields on two sides of the printing platform during printing, wherein the magnetic field intensity is 2000Gs, and the magnetic particles in the printing liquid can be oriented along the direction of the magnetic field due to the existence of the applied magnetic field so as to construct the piezoelectric composite material with the magnetoelectric coupling performance.
Example 4
The method for preparing the magnetoelectric composite material based on the magnetic field assisted 3D printing technology comprises the following steps:
(1) dispersing magnetic nanoparticles Terfenol-D in an organic solvent N-methyl pyrrolidone, and fully dispersing under the assistance of ultrasound; then, adding polyvinylidene fluoride, and mixing for 4 hours at 20 ℃ to obtain the required polymer printing liquid;
wherein the mass ratio of the magnetic particles to the piezoelectric polymer is 1: 10;
the mass content of the polyvinylidene fluoride is 20 wt% based on the total amount of the printing liquid;
(2) according to the 3D printed structure model, a three-dimensional structure digital model is created and is sliced, and a printing path is set; controlling the moving speed to be 50mm/s and the slice thickness to be 0.01 mm;
(3) transferring the polymer printing liquid prepared in the step (1) into a syringe material printing device 2, and performing layer-by-layer deposition printing under the control of a design program, wherein the distance between a printing needle head and a collecting bottom plate is controlled to be 1mm, and the diameter of the printing needle head is controlled to be 350 micrometers; and applying neodymium magnet permanent magnetic fields on two sides of the printing platform during printing, wherein the magnetic field intensity is 3500Gs, and the magnetic particles in the printing liquid can be oriented along the direction of the magnetic field due to the existence of the applied magnetic field so as to construct the piezoelectric composite material with the magnetoelectric coupling performance.
Example 5
The method for preparing the magnetoelectric composite material based on the magnetic field assisted 3D printing technology comprises the following steps:
(1) taking magnetic nano particles Fe3O4Dispersing in organic solvent N-methyl pyrrolidone, and fully dispersing under the assistance of ultrasound; then, adding polyvinylidene fluoride, and mixing for 3h at 30 ℃ to obtain the required polymer printing liquid;
wherein the mass ratio of the magnetic particles to the piezoelectric polymer is 1: 5;
the mass content of the polyvinylidene fluoride is 20 wt% based on the total amount of the printing liquid;
(2) according to the 3D printed structure model, a three-dimensional structure digital model is created and is sliced, and a printing path is set; controlling the moving speed to be 40mm/s and the slice thickness to be 0.01 mm;
(3) transferring the polymer printing liquid prepared in the step (1) into a syringe material printing device 2, and performing layer-by-layer deposition printing under the control of a design program, wherein the distance between a printing needle head and a collecting bottom plate is controlled to be 2mm, and the diameter of the printing needle head is controlled to be 400 mu m; and applying neodymium magnet permanent magnetic fields on two sides of the printing platform during printing, wherein the magnetic field intensity is 4000Gs, and the magnetic particles in the printing liquid can be oriented along the direction of the magnetic field due to the existence of the applied magnetic field so as to construct the piezoelectric composite material with the magnetoelectric coupling performance.
Example 6
The method for preparing the magnetoelectric composite material based on the magnetic field assisted 3D printing technology comprises the following steps:
(1) taking magnetic nano-particles NiFe2O4Dispersing in an organic solvent N, N-dimethylformamide, and fully dispersing under the assistance of ultrasound; then, adding polyvinylidene fluoride, and mixing for 2 hours at 40 ℃ to obtain the required polymer printing liquid;
wherein the mass ratio of the magnetic particles to the piezoelectric polymer is 1: 20;
the mass content of the polyvinylidene fluoride is 15 wt% based on the total amount of the printing liquid;
(2) according to the 3D printed structure model, a three-dimensional structure digital model is created and is sliced, and a printing path is set; controlling the moving speed to be 30mm/s and the slice thickness to be 0.01 mm;
(3) transferring the polymer printing liquid prepared in the step (1) into a syringe material printing device 2, and performing layer-by-layer deposition printing under the control of a design program, wherein the distance between a printing needle head and a collecting bottom plate is controlled to be 3mm, and the diameter of the printing needle head is controlled to be 400 mu m; and applying neodymium magnet permanent magnetic fields on two sides of the printing platform during printing, wherein the magnetic field intensity is 5000Gs, and the magnetic particles in the printing liquid can be oriented along the direction of the magnetic field due to the existence of the applied magnetic field so as to construct the piezoelectric composite material with the magnetoelectric coupling performance.
Example 7
The method for preparing the magnetoelectric composite material based on the magnetic field assisted 3D printing technology comprises the following steps:
(1) taking magnetic nano-particles CoFe2O4Dispersing in an organic solvent dimethyl sulfoxide, and fully dispersing under the assistance of ultrasound; then adding polyvinylidene fluoride, and mixing for 3h at 50 ℃ to obtain the required polymer printing liquid;
wherein the mass ratio of the magnetic particles to the piezoelectric polymer is 1: 5;
the mass content of the polyvinylidene fluoride is 20 wt% based on the total amount of the printing liquid;
(2) according to the 3D printed structure model, a three-dimensional structure digital model is created and is sliced, and a printing path is set; controlling the moving speed to be 20mm/s and the slice thickness to be 0.01 mm;
(3) transferring the polymer printing liquid prepared in the step (1) into a syringe material printing device 2, and performing layer-by-layer deposition printing under the control of a design program, wherein the distance between a printing needle head and a collecting bottom plate is controlled to be 4mm, and the diameter of the printing needle head is controlled to be 340 mu m; and applying neodymium magnet permanent magnetic fields on two sides of the printing platform during printing, wherein the magnetic field intensity is 6500Gs, and the magnetic particles in the printing liquid can be oriented along the magnetic field direction due to the existence of the applied magnetic field so as to construct the piezoelectric composite material with the magnetoelectric coupling performance.
Comparative example 1
The raw materials for preparing the magnetoelectric composite material in the comparative example are the same as those in example 7, and the difference is only that the preparation method adopts the traditional spin coating method to prepare the magnetoelectric film.
The hysteresis (M-H) curves of the magnetoelectric composites prepared in inventive example 7 and comparative example 1 are shown in fig. 2. It can be seen that the invention is based on the influence of the magnetic field assisted 3D printing on the hysteresis loop of the magnetoelectric film, and proves that the composite film generates Magnetoelectric (ME) coupling. As can be seen from fig. 2, the saturation magnetization of the magnetic field-assisted 3D printed material is significantly increased, indicating that there is strong magnetoelectric coupling in the magnetoelectric composite material, which is mainly achieved by orienting and magnetizing the magnetic particles of the material by printing while applying a magnetic field. Therefore, the magnetoelectric composite material prepared by the method has higher magnetoelectric voltage coefficient and better magnetoelectric coupling performance, and can be used for processing storage and magnetoelectric sensor parts.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (10)

1. A method for preparing a magnetoelectric composite material based on a magnetic field assisted 3D printing technology is characterized by comprising the following steps:
(1) dispersing magnetic nanoparticles in an organic solvent, adding a piezoelectric polymer material, and fully mixing to obtain a polymer printing liquid for later use;
(2) creating a three-dimensional structure digital model, carrying out slicing processing, and setting a proper printing path and a proper printing program;
(3) and (2) transferring the polymer printing liquid prepared in the step (1) into a needle cylinder, carrying out continuous layer-by-layer deposition under the control of a design program, and applying a magnetic field while carrying out 3D printing to orient the magnetic particles along the direction of the magnetic field, so as to construct and obtain the magnetoelectric composite material with the magnetoelectric coupling performance.
2. The method of claim 1, wherein in step (1), the piezoelectric polymer material comprises at least one of polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (P (VDF-HFP)), or polyvinylidene fluoride-trifluoroethylene copolymer (P (VDF-TrFE)).
3. The method for preparing magnetoelectric composite material based on magnetic field assisted 3D printing technology according to claim 1 or 2, wherein in the step (1), the magnetic nanoparticles comprise Terfenol-D, Fe3O4、CuFe2O4、NiFe2O4、CoFe2O4At least one of (1).
4. The method for preparing a magnetoelectric composite material based on the magnetic field assisted 3D printing technology according to any one of claims 1 to 3, wherein in the step (1), the organic solvent comprises at least one of N, N-dimethylformamide, N-methylpyrrolidone or dimethylsulfoxide.
5. The method for preparing a magnetoelectric composite material based on the magnetic field assisted 3D printing technology according to any one of claims 1 to 4, characterized in that in the step (1), the piezoelectric polymer material is 15 to 25 wt% based on the total amount of the polymer printing liquid.
6. The method for preparing a magnetoelectric composite material based on the magnetic field assisted 3D printing technology according to any one of claims 1 to 5, wherein in the step (1), the mass ratio of the magnetic nanoparticles to the piezoelectric polymer material is 1: 5-20.
7. The method for preparing magnetoelectric composite material based on magnetic field assisted 3D printing technology according to any one of claims 1 to 6, wherein in the step (2), the parameters for controlling the slicing processing step are as follows: the moving speed is 10-50mm/s, and the slice thickness is 0.01 mm.
8. The method for preparing magnetoelectric composite material based on magnetic field assisted 3D printing technology according to any one of claims 1 to 7, characterized in that in the step (3), in the 3D printing step, the distance between the printing needle head and the collecting bottom plate is controlled to be 1-5mm, and the diameter of the printing needle head is controlled to be 40-400 μm.
9. The method for preparing magnetoelectric composite material based on magnetic field assisted 3D printing technology according to any one of claims 1 to 8, characterized in that in the step (3), the magnetic field comprises permanent magnets or electromagnets, and the magnetic field strength is controlled to be 100Gs-8000 Gs.
10. A magnetoelectric composite material produced by the method according to any one of claims 1 to 9.
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