A kind of tungsten acid manganese hafnium ceramic material based on space and chemical disorder regulation and its preparation method and application

Abstract

The application relates to the technical field of magnetoelectric ceramic materials, in particular to a tungstate manganese hafnium ceramic material based on vacancy and chemical disorder regulation and a preparation method and application thereof. 1‑x Hf x WO4, wherein the hafnium doping amount ranges from 0 < x <= 0.20; in the tungstate manganese hafnium ceramic material Mn 1‑x Hf x WO4, the Hf 4+ Mn 2+ is replaced to introduce vacancy defects and chemical disorder, so as to regulate the magnetoelectric performance of the tungstate manganese hafnium ceramic; the prepared Mn 1‑x Hf x WO4 magnetoelectric ceramic material has a single-phase structure, excellent dielectric performance, significantly improved magnetic transition temperature, expanded ferroelectric polarization temperature range, and obvious magnetic dielectric characteristics, and has very excellent characteristics.

Description

Technical Field

[0001] This invention relates to the field of magnetoelectric ceramic materials technology, specifically to a hafnium manganese tungstate ceramic material based on vacancy and chemical disorder regulation, its preparation method, and its application. Background Technology

[0002] Magnetoelectric materials simultaneously exhibit ferroelectricity and (anti)ferromagnetism, and new effects such as magnetoelectric coupling arise due to the mutual coupling between the two order parameters. Based on their physical properties and manifestations, magnetoelectric materials are generally classified into two categories:

[0003] In Class I multiferroic materials, the ferroelectric and ferromagnetic coupling is weak, which greatly limits their application prospects.

[0004] Type II multiferroic materials exhibit a huge magnetoelectric effect, making them multifunctional materials with significant potential applications; however, their ferroelectricity is relatively weak, and the electromagnetism is not obvious; the magnetoelectric coupling mechanism, especially the ferroelectric mechanism, is still unclear.

[0005] As a typical magnetoelectric material, MnWO4 possesses a simple monoclinic ferroferrometallic structure. Due to complex spin interactions within the system, a three-dimensional long-range antiferromagnetic order is formed. As the temperature decreases, at T... AF3 At ~13.5K, it transitions from a paramagnetic state to a non-commensurate collinear antiferromagnetic phase (AF3), followed by T AF2 Incommensurate elliptical antiferromagnetic order (AF2) forms at ~12.7K, and finally, at T AF1 At ~7.8K, it enters the commensurate collinear antiferromagnetic phase (AF1), in which the incommensurate elliptic antiferromagnetic ordered phase (AF2) exhibits ferroelectric polarization characteristics. Such frequent magnetic structure phase transitions also reflect the intense competition between spin interactions and the high degree of spin structure disorder at low temperatures. The unusual physical implications exhibited by the structurally simple MnWO4, along with its significant magnetoelectric effect, make it a highly promising candidate material for multifunctional magnetoelectronic devices. However, MnWO4 has a low magnetoelectric transition temperature, a narrow ferroelectric temperature range, and weak magnetic / electric properties, making it unsuitable as a good ceramic material. Summary of the Invention

[0006] To overcome the above defects, this invention provides a hafnium manganese tungstate ceramic material based on vacancy and chemical disorder regulation, its preparation method and application, which solves the problems of low magnetoelectric transition temperature, narrow ferroelectric temperature range and weak magnetic / electric properties of existing ceramic materials.

[0007] This invention can be achieved through the following technical solutions:

[0008] A hafnium manganese tungstate ceramic material based on vacancy and chemical disorder regulation, with the chemical formula: Mn 1-xHf x WO4, wherein the hafnium doping amount ranges from 0 to x ≤ 0.20; in manganese manganese hafnium tungstate ceramic materials Mn 1-x Hf x In WO4, the Hf 4+ Perform Mn 2+ The magnetoelectric properties of hafnium manganese tungstate ceramics are modulated by introducing vacancy defects and chemical disorder.

[0009] The beneficial effects of adopting the above technical solution are as follows: This invention uses high-valence nonmagnetic Hf 4+ Ion substitution of Mn 2+ This introduces chemical disorder of Mn vacancies and ions, affecting exchange interaction and magnetoresistance, thus contributing to improved magnetic properties. Furthermore, based on charge compensation effects, lattice distortion, and doping effects, vacancy defects and chemical disorder are introduced into the MnWO4 system, regulating Mn... 1-x Hf x The magnetic transition temperature of WO4 expands the ferroelectric temperature range, while exhibiting high dielectric properties and magnetoelectric effect; the Mn prepared by this invention 1-x Hf x WO4 magnetoelectric ceramic material has a single-phase structure, excellent dielectric properties, significantly increased magnetic transition temperature, expanded ferroelectric polarization temperature range, and obvious magnetoelectric characteristics, exhibiting very superior properties.

[0010] The above-mentioned method for preparing hafnium manganese tungstate ceramic materials based on vacancy and chemical disorder regulation includes the following steps:

[0011] (1) Take manganese dioxide, hafnium dioxide and tungsten trioxide as raw materials, grind them evenly, and pre-calcine them at 550-650℃ for 20-28h;

[0012] (2) Grind the pre-calcined powder obtained in step (1) again until uniform and press it into shape; sinter the pressed material at 900-1000℃ for 20-28h.

[0013] (3) Crush the material obtained in step (2) and place it in a ball mill for 1-3 hours to obtain finely ground powder, and then press it into shape.

[0014] (4) The material obtained in step (3) is sintered at 800-900℃ for 20-28h to obtain hafnium manganese tungstate ceramic material based on vacancy and disorder regulation.

[0015] In one specific embodiment of the present invention, in step (1), manganese dioxide, hafnium dioxide, and tungsten trioxide raw materials are prepared according to Mn 1-x Hf x The range of hafnium doping in WO4 is: 0 < x ≤ 0.20 for batching;

[0016] In one specific embodiment of the present invention, in step (1), grinding is performed in a ball mill for 12-28 hours using an organic solvent as a medium.

[0017] In one specific embodiment of the present invention, the organic solvent is anhydrous ethanol.

[0018] In one specific embodiment of the present invention, in step (1), the ball milling speed is 100-200 rpm and the ball milling atmosphere is argon.

[0019] The beneficial effects of adopting the above technical solution are: ball milling in an argon atmosphere helps retain Mn ions in the material. 2+ This state helps improve the dielectric and magnetic properties of the material.

[0020] In one specific embodiment of the present invention, in step (2), the ball milling time of the pre-calcined powder is 1-3 hours, the ball milling speed is 100-200 rpm, and the ball milling atmosphere is argon.

[0021] In one specific embodiment of the present invention, in step (2), the uniformly ground pre-calcined powder is pressed into shape using a tablet press at 7-15 MPa.

[0022] In one specific embodiment of the present invention, in step (3), the finely grained powder is pressed into shape at 8-12 MPa.

[0023] The beneficial effects of adopting the above technical solution are as follows: by crushing and ball milling the sintered finished product to refine the grains, the magnetic properties are improved, and a hafnium manganese tungstate ceramic material with refined grains controlled by vacancy defects and chemical disorder is obtained, thereby controlling the magnetic, dielectric and magnetodielectric properties of the material.

[0024] The above-mentioned applications of hafnium manganese tungstate ceramic materials based on vacancy and chemical disorder regulation in magnetoelectric sensors, high-capacity sensors, spintronic devices, and novel information storage devices.

[0025] The beneficial effects of this invention are:

[0026] The preparation process of this invention is simple, energy-efficient, and highly reproducible. The resulting ceramic material has a high dielectric constant, low dielectric loss, high magnetic transition temperature, wide ferroelectric temperature range, and obvious magneto-dielectric characteristics. It has important application value in high-performance magnetoelectric sensors, large-capacity capacitors, information storage, spintronic devices, and other fields. Attached Figure Description

[0027] Figure 1 Different Hf samples obtained in Examples 1-4 of this invention 4+ XRD patterns of ceramic samples with substituted MnWO4.

[0028] Figure 2 Different Hf prepared according to Examples 1-4 of this invention 4+ Magnetothermal curves of MnWO4 ceramic samples with substitution amount.

[0029] Figure 3 Different Hf prepared according to Examples 1-4 of this invention 4+ Hysteresis loop of the MnWO4 ceramic sample with substitution amount (T = 10K).

[0030] Figure 4 Different Hf prepared according to Examples 1-4 of this invention 4+ Dielectric frequency curves of ceramic samples with substituted MnWO4.

[0031] Figure 5 Mn prepared in Examples 1-4 of this invention 1-x Hf x The variation of the magnetic permittivity MD of the WO4 sample with magnetic field at 10K and 1000Hz. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be described in detail below. Obviously, the described embodiments are merely some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other implementation methods obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0033] Example 1

[0034] Undoped MnWO4 multiferroic ceramic materials were prepared using a solid-state reaction method combined with post-processing techniques.

[0035] (1) The dried raw materials MnO (purity 99.99%) and WO3 (purity 99.99%) are mixed in a 1:1 molar ratio;

[0036] (2) The raw material weighed in step (1) is ground in a ball mill for 24 hours with anhydrous ethanol as the medium. The ball milling speed is 150 rpm and the ball milling atmosphere is argon. The uniformly ground powder is then placed in an air atmosphere at 600°C for 24 hours for pre-calcination.

[0037] (3) The pre-calcined powder obtained in step (2) is ball-milled again for 2 hours at a speed of 150 rpm and in an argon atmosphere.

[0038] (4) The uniformly ground pre-calcined powder is pressed into shape using a tablet press under a pressure of 10MPa.

[0039] (5) The pressed material is sintered at 950°C for 24 hours in an air atmosphere.

[0040] (6) Crush the disc obtained in step (5), put it into a ball mill and ball mill for 2 hours. The ball milling speed is 150 rpm and the ball milling atmosphere is argon to obtain finely grained powder.

[0041] (7) The refined powder is pressed into shape using a tablet press at a pressure of 10MPa.

[0042] (8) The discs obtained in step (7) are sintered at 850°C for 24 hours in an oxygen atmosphere to obtain MnWO4 ceramic material with refined grains controlled by vacancies and chemical disorder.

[0043] The XRD pattern of the MnWO4 multiferroic ceramic material sample prepared using Example 1 is shown below. Figure 1 As shown, from Figure 1 All the observed diffraction peaks are consistent with the monoclinic tungsten manganese iron ore structure of MnWO4, which shows a single-phase structure with no diffraction peaks of the second phase. Figure 2 , Figure 3 , Figure 4 , Figure 5 The magnetic temperature curve, hysteresis loop, dielectric frequency curve, and magnetic dielectric factor of MnWO4 are given respectively; among them, Example 1 is in Figure 1 , Figure 2 , Figure 3 , Figure 4 , Figure 5 The curve represented in the figure is x = 0.00.

[0044] Example 2

[0045] Hafnium tungstate ceramic material Mn was prepared by solid-state reaction combined with post-processing. 0.95 Hf 0.05 WO4: The dried raw materials MnO (99.99% purity), HfO2 (99.99% purity) and WO3 (99.99% purity) are mixed according to the following formula: Mn 0.95 Hf 0.05 The ingredients are prepared according to the stoichiometric ratio of WO4.

[0046] (1) The dried raw materials MnO (purity 99.99%), HfO2 (purity 99.99%) and WO3 (purity 99.99%) are mixed in a molar ratio of 0.95:0.05:1;

[0047] (2) The raw material weighed in step (1) is ground in a ball mill for 24 hours with anhydrous ethanol as the medium. The ball milling speed is 150 rpm and the ball milling atmosphere is argon. The uniformly ground powder is then placed in an air atmosphere at 600°C for 24 hours for pre-calcination.

[0048] (3) The pre-calcined powder obtained in step (2) is ball-milled again for 2 hours at a speed of 150 rpm and the ball-milling atmosphere is argon.

[0049] (4) The uniformly ground pre-calcined powder is pressed into shape using a tablet press under a pressure of 10MPa.

[0050] (5) The pressed material is sintered at 950°C for 24 hours in an air atmosphere.

[0051] (6) Crush the disc obtained in step (5), put it into a ball mill and ball mill for 2 hours. The ball milling speed is 150 rpm and the ball milling atmosphere is argon to obtain finely grained powder.

[0052] (7) The refined powder is pressed into shape using a tablet press at a pressure of 10MPa.

[0053] (8) The wafers obtained in step (7) are sintered at 850°C for 24 hours in an oxygen atmosphere to obtain Mn with refined grains regulated by vacancies and chemical disorder. 0.95 Hf 0.05 WO4 hafnium manganese tungstate ceramic material.

[0054] Mn prepared using Example 2 0.95 Hf 0.05 XRD patterns of WO4 manganese hafnium tungstate ceramic material samples are as follows: Figure 1 As shown, from Figure 1 All observed diffraction peaks are consistent with the monoclinic tungsten manganese iron ore structure of MnWO4, exhibiting a single-phase structure with no second-phase diffraction peaks, indicating that Hf 4+ Able to completely replace Mn 2+ It enters the MnWO4 lattice; Figure 2 , Figure 3 , Figure 4 , Figure 5 Mn are given respectively 0.95 Hf 0.05 The magnetic temperature curve, hysteresis loop, dielectric frequency curve, and magnetic dielectric factor of WO4; among them, Example 2 is in Figure 1 , Figure 2 , Figure 3 , Figure 4 , Figure 5 The curve represented in the figure is x = 0.05.

[0055] Example 3

[0056] Hafnium tungstate ceramic material Mn was prepared by solid-state reaction combined with post-processing. 0.90 Hf 0.10WO4: The dried raw materials MnO (99.99% purity), HfO2 (99.99% purity) and WO3 (99.99% purity) are mixed according to the following formula: 0.90 Hf 0.10 The ingredients are prepared according to the stoichiometric ratio of WO4.

[0057] (1) The dried raw materials MnO (purity 99.99%), HfO2 (purity 99.99%) and WO3 (purity 99.99%) are mixed in a molar ratio of 0.90:0.10:1;

[0058] (2) The raw material weighed in step (1) is ground in a ball mill for 24 hours with anhydrous ethanol as the medium. The ball milling speed is 150 rpm and the ball milling atmosphere is argon. The uniformly ground powder is then placed in an air atmosphere at 600°C for 24 hours for pre-calcination.

[0059] (3) The pre-calcined powder obtained in step (2) is ball-milled again for 2 hours at a speed of 150 rpm and in an argon atmosphere.

[0060] (4) The uniformly ground pre-calcined powder is pressed into shape using a tablet press under a pressure of 10MPa.

[0061] (5) The pressed material is sintered at 950°C for 24 hours in an air atmosphere.

[0062] (6) Crush the disc obtained in step (5), put it into a ball mill and ball mill for 2 hours. The ball milling speed is 150 rpm and the ball milling atmosphere is argon to obtain finely grained powder.

[0063] (7) The refined powder is pressed into shape using a tablet press at a pressure of 10MPa.

[0064] (8) The wafers obtained in step (7) are sintered at 850°C for 24 hours in an oxygen atmosphere to obtain Mn with refined grains regulated by vacancies and chemical disorder. 0.90 Hf 0.10 WO4 ceramic material.

[0065] Mn prepared using Example 3 0.90 Hf 0.10 XRD patterns of WO4 multiferroic ceramic samples are as follows: Figure 1 As shown, from Figure 1 All observed diffraction peaks are consistent with the monoclinic tungsten manganese iron ore structure of MnWO4, exhibiting a single-phase structure with no second-phase diffraction peaks, indicating that Hf 4+ Able to completely replace Mn 2+ It enters the MnWO4 lattice; Figure 2 , Figure 3 , Figure 4 , Figure 5Mn are given respectively 0.90 Hf 0.10 The magnetic temperature curve, hysteresis loop, dielectric frequency curve, and magnetic dielectric factor of WO4, in which Example 3 is shown. Figure 1 , Figure 2 , Figure 3 , Figure 4 , Figure 5 The curve represented in the figure is x = 0.10.

[0066] Example 4

[0067] Hafnium tungstate ceramic material Mn was prepared by solid-state reaction combined with post-processing. 0.80 Hf 0.20 WO4: The dried raw materials MnO (99.99% purity), HfO2 (99.99% purity) and WO3 (99.99% purity) are mixed according to the following formula: 0.80 Hf 0.20 The ingredients are prepared according to the stoichiometric ratio of WO4.

[0068] (1) The dried raw materials MnO (purity 99.99%), HfO2 (purity 99.99%) and WO3 (purity 99.99%) were mixed in a molar ratio of 0.80:0.20:1;

[0069] (2) The raw material weighed in step (1) is ground in a ball mill for 24 hours with anhydrous ethanol as the medium. The ball milling speed is 150 rpm and the ball milling atmosphere is argon. The uniformly ground powder is then placed in an air atmosphere at 600°C for 24 hours for pre-calcination.

[0070] (3) The pre-calcined powder obtained in step (2) is ball-milled again for 2 hours at a speed of 150 rpm and in an argon atmosphere.

[0071] (4) The uniformly ground pre-calcined powder is pressed into shape using a tablet press under a pressure of 10MPa.

[0072] (5) The pressed material is sintered at 950°C for 24 hours in an air atmosphere.

[0073] (6) Crush the disc obtained in step (5), put it into a ball mill and ball mill for 2 hours. The ball milling speed is 150 rpm and the ball milling atmosphere is argon to obtain finely grained powder.

[0074] (7) The refined powder is pressed into shape using a tablet press at a pressure of 10MPa.

[0075] (8) The wafers obtained in step (7) are sintered at 850°C for 24 hours in an oxygen atmosphere to obtain Mn with refined grains regulated by vacancies and chemical disorder. 0.80 Hf0.20 WO4 ceramic material.

[0076] Mn prepared using Example 4 0.80 Hf 0.20 XRD patterns of WO4 material samples as follows Figure 1 As shown, from Figure 1 All observed diffraction peaks are consistent with the monoclinic tungsten manganese iron ore structure of MnWO4, exhibiting a single-phase structure with no second-phase diffraction peaks, indicating that Hf 4+ Able to completely replace Mn 2+ It enters the MnWO4 lattice; Figure 2 , Figure 3 , Figure 4 , Figure 5 Mn are given respectively 0.80 Hf 0.20 The magnetic temperature curve, hysteresis loop, dielectric frequency curve, and magnetic dielectric factor of WO4; among them, Example 4 is in Figure 1 , Figure 2 , Figure 3 , Figure 4 , Figure 5 The curve represented in the figure is x = 0.20.

[0077] Experimental Example

[0078] To investigate the phase structure of the hafnium manganese tungstate ceramic material prepared by the method of this invention based on vacancy and chemical disorder regulation, X-ray diffraction (XRD) was used to analyze the phase composition of the samples obtained in Examples 1-4. The results are shown in the figure. Figure 1 As shown; from Figure 1 As can be seen, all samples exhibit a monoclinic tungsten manganese iron ore structure with no second phase formation, indicating that all samples are single-phase structures. With increasing hafnium doping concentration x, the main diffraction peaks shift towards smaller angles, indicating that Hf... 4+ Able to completely replace Mn 2+ It enters the MnWO4 lattice and causes structural distortion.

[0079] To investigate the magnetic properties of the hafnium manganese tungstate ceramic material prepared by the method of this invention based on vacancy and chemical disorder regulation, the magnetotemperature curves and hysteresis loops of the samples from Examples 1-4 were measured using the Quantum Design PPMS comprehensive property testing system. The results are shown in [Figure number missing]. Figure 2 and Figure 3 As shown; from Figure 2 As can be seen from this, undoped MnWO4 in T AF3 ~13.5K, T AF2 ~12.7, T AF1 Three magnetic phase transitions occurred at ~7.8K; compared with the undoped sample, Mn 0.95 Hf0.05 WO4 sample T AF3 T AF2 Almost nothing changed, but T AF1 The shift towards the lower temperature range indicates that a hafnium doping concentration of 0.05% expands the temperature range where the ferropolarized AF2 phase exists; compared with Mn... 0.95 Hf 0.05 Compared to WO4 samples, Mn 0.90 Hf 0.10 WO4's T AF3 T AF2 All were improved, T AF1 No detection was found, possibly indicating a shift to lower temperatures. This suggests that with a hafnium doping concentration of 0.10, the magnetic transition temperature of the sample is increased and the temperature range for the presence of the AF2 phase is expanded; compared with Mn... 0.90 Hf 0.10 Compared to WO4 samples, Mn 0.80 Hf 0.20 WO4's T AF3 T AF2 Further improvements were made to T. AF1 The presence of AF2 phase was not detected, indicating that the hafnium doping amount of 0.20 further increases the magnetic transition temperature of the sample and expands the temperature range in which the AF2 phase exists. Figure 3 As can be seen from this, all Mn 1-x HfxWO4 exhibits antiferromagnetism at 10K, but Hf 4+ The maximum magnetization of the doped sample was increased; this is due to the nonmagnetic high-valence state of Hf. 4+ Doping introduces cation vacancies and chemical disorder due to charge compensation effects, because Hf 4+ The valence state is higher than that of Mn 2+ Hf 4+ Replace Mn 2+ To maintain the electroneutrality of a system with an effective charge, negatively charged cation vacancies are introduced to preserve the overall electroneutrality of the material. When the valence state of the doped ion in a crystal differs from that of the substituted ion, the resulting substitution defect carries a certain effective charge. To maintain the electroneutrality of the system, defects with opposite effective charges are generated within the crystal, compensating for the charge carried by the defects created by the doped ion. Simultaneously, due to Hf... 4+ With Mn 2+ Different chemical elements, Hf 4+ Replace Mn 2+ It will cause Mn in the crystal structure of the material 2+ The change in the distribution pattern of lattice elements, that is, the introduction of chemical disorder, leads to lattice distortion, due to Hf 4+ Ionic radius greater than Mn 2+ Hf 4+ Replace Mn 2+Causes MnWO4 lattice expansion, Mn 2+ Interactions and magnetoresistance (magnetoresistance is expressed as the reluctance factor: f = θ) CW / T N Hf 4+ Replace Mn 2+ This causes a decrease in the magnetoresistance of MnWO4, thus altering the magnetic properties of the sample. As can be seen from the above, by adding an appropriate amount of Hf... 4+ Doping can increase the magnetic transition temperature and magnetization of a sample, and extend the ferroelectric polarization temperature range.

[0080] To investigate the dielectric properties of the hafnium manganese tungstate ceramic material prepared by the method of this invention based on vacancy and chemical disorder regulation, the dielectric properties of the samples from Examples 1-4 were measured using an Agilent 4294 A precision impedance analyzer. The results are shown in [Figure 1]. Figure 4 As shown: From Figure 4 As can be seen in (a), the dielectric constant of all samples exhibits a strong frequency dependence, with higher dielectric constants at low frequencies and lower dielectric constants at high frequencies; Hf 4+ After doping, the dielectric constant of the sample was significantly improved; at a test frequency of 1MHz, Mn 0.90 Hf 0.10 The dielectric constant of the WO4 sample is 2387.9, which is 38.5 times that of undoped MnWO4 (62.0). This is similar to that of high-valence Hf. 4+ Doping is related to changes in lattice distortion and local electronic structure; in addition, such as Figure 4 As shown in (b), Hf 4+ The dielectric loss of the doped sample was slightly higher than that of the undoped MnWO4, but the increase in loss value was not significant. Experimental results show that Hf 4+ The doped sample exhibits high dielectric properties in the high-frequency region at room temperature, and the dielectric loss does not increase significantly.

[0081] To investigate the magnetic dielectric properties of the hafnium manganese tungstate ceramic material prepared by the method of this invention based on vacancy and chemical disorder regulation, the magnetic dielectric properties of samples from Examples 1-4 were measured using a precision impedance analyzer manufactured by Agilent Technologies, connected to a Quatum Design PPMS. The results are shown in [Figure 1]. Figure 5 As shown; from Figure 5 As can be seen, all samples exhibit a magnetoelectric effect, and this effect increases with the increase of the applied magnetic field. Hf 4+ The magneto-dielectric effect of the doped sample is significantly enhanced, which is related to the high valence state of Hf. 4+ The increase in vacancies, chemical disorder, and lattice distortion caused by doping are related to the increase in magnetoelectric coupling effect in MnWO4 samples; experimental results show that Hf4+ Doping enhances the magnetoelectric effect of the MnWO4 sample.

[0082] In summary, the present invention provides a manganese hafnium tungstate ceramic material Mn based on vacancy and chemical disorder regulation. 1- x Hf x WO4, via Hf 4+ Doping induces vacancies and chemical disorder, which can significantly improve the magnetic and magnetoelectric properties of hafnium manganese tungstate ceramics. Meanwhile, Hf... 4+ Doped MnWO4 exhibits high dielectric properties and is a promising novel multiferroic material for further research and exploration. Finally, it should be noted that the embodiments described herein are merely illustrative of the technical implementation of this material and not intended to limit it. Although the invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the invention without departing from the spirit and scope of the invention, and all such modifications and substitutions should be covered within the scope of the claims of the invention.

Claims

1. A hafnium manganese tungstate ceramic material based on vacancy and chemical disorder regulation, characterized in that, Its chemical formula is: Mn 1- x Hf x WO4, wherein the hafnium doping amount ranges from 0 to x ≤ 0.20; in manganese manganese hafnium tungstate ceramic materials Mn 1-x Hf x In WO4, Hf 4+ Perform Mn 2+ The magnetoelectric properties of hafnium manganese tungstate ceramics are modulated by introducing vacancy defects and chemical disorder. The hafnium manganese tungstate ceramic material based on vacancy and chemical disorder regulation is prepared by the following steps: (1) Take manganese dioxide, hafnium dioxide and tungsten trioxide as raw materials, grind them evenly, and pre-calcine them at 550-650℃ for 20-28h; (2) Grind the pre-calcined powder obtained in step (1) again until uniform and press it into shape; sinter the pressed material at 900-1000℃ for 20-28h. (3) The material obtained in step (2) is crushed and placed in a ball mill for 1-3 hours to obtain finely ground powder, which is then pressed into shape. (4) The material obtained in step (3) is sintered at 800-900℃ for 20-28h to obtain hafnium manganese tungstate ceramic material based on vacancy and disorder regulation.

2. The hafnium manganese tungstate ceramic material based on vacancy and chemical disorder regulation according to claim 1, characterized in that, In step (1), the grinding is carried out in a ball mill for 12-28 hours using an organic solvent as a medium.

3. The hafnium manganese tungstate ceramic material based on vacancy and chemical disorder regulation according to claim 2, characterized in that, The organic solvent is anhydrous ethanol.

4. The hafnium manganese tungstate ceramic material based on vacancy and chemical disorder regulation according to claim 1, characterized in that, In step (2), the uniformly ground pre-calcined powder is pressed into shape using a tablet press at 7-15 MPa.

5. The hafnium manganese tungstate ceramic material based on vacancy and chemical disorder regulation according to claim 1, characterized in that, In step (3), the finely grained powder is pressed into shape at 8-12 MPa.

6. The application of the hafnium manganese tungstate ceramic material based on vacancy and chemical disorder regulation as described in claim 1 in magnetoelectric sensors, high-capacity sensors, spintronic devices, and storage devices.

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